BİLDİRİLER - PRESENTATIONS 22 -23 Mart / March 2016 İstanbul

6th International Paint, Paint Raw Materials, Construction Chemicals, Adhesives and Raw Materials, Laboratory and Production Equipments Exhibition and Congress 2016

www. ww com www.turkcoat-paintistanbul.com / www.paintistanbul-turkcoat.com

PAINTISTANBUL TURKCOAT 2016

CONGRESS BOOK

Organizer With the cooperation of

Main Sponsor Sponsors

www.turkcoat-paintistanbul.com / www.paintistanbul-turkcoat.com Congress Scientific and Organization Committees / Kongre Bilimsel Kurulu & Fuar Düzenleme Kurulu

Name Institution

Hakan İ. FİDAN - Chairman of BOSAD Exhibition/Congress Palet Kimya San. Tic. Ltd. Şti.

Congress Scientific Committee / Kongre Bilimsel Kurulu Name Institution

Dr. Engin ÇÖRÜŞLÜ - Chairman of the Congress Scientific Committee Kansai Altan Boya San. Tic. A.Ş. Prof. Dr. Emin ARCA - Vice Chairman of the Congress Scientific Committee Marmara Üniversitesi A. Burhan ÖZDEMİR - Vice Chairman of the Congress Scientific Committee Polisan Boya San. Tic. A.Ş. Prof. Dr. Ahmet AKAR İstanbul Teknik Üniversitesi Alptekin AKGÜMÜŞ İba Valresa Boya A.Ş. Prof. Dr. Atilla GÜNGÖR Marmara Üniversitesi Beyhan GÖZOĞUL Dow Türkiye Kimya San. Tic. Ltd. Şti. Dr. Clifford K. SCHOFF Schoff Associates Ebru Ergüven ÇAKMAK Kayalar Kimya San. Tic. A.Ş. Prof. Dr. Ersin SERHATLI İstanbul Teknik Üniversitesi Handan AYDIN DYO Boya Fabrikaları San. Tic. A.Ş. Prof. Dr. İskender YILGÖR Koç Üniversitesi Prof. Dr. Mehmet Ali GÜRKAYNAK İstanbul Üniversitesi Mehmet AYABAKAN Kimya Mühendisleri Odası İstanbul Şubesi Mesut EREN Betek Boya ve Kimya San. Tic. A.Ş. Mustafa TUNÇGENÇ AkzoNobel Kemipol Kimya San. A.Ş. Prof. Dr. Nergis ARSU Yıldız Teknik Üniversitesi Sibel ALTINOK Organik Kimya San. Tic. A.Ş. Dr. Sonja SCHULTE Vincentz Network Dr. Tahir ALTUNBULDUK İshakol Boya San. Tic. A.Ş. Prof. Dr. Yusuf MENCELOĞLU Sabancı Üniversitesi

Organization Committee / Fuar Düzenleme Kurulu Name Institution Hakan ÜNEL - Chairman of Organization Committee Luma Kimya San. Tic. Ltd. Şti. Ahmet Faik BİTLİS Polisan Kimya San. Tic. A.Ş. Arif AKYOL Turkuaz Kimya San. Tic. A.Ş. Deniz BÖLÜKBAŞI Organik Kimya San. Tic. A.Ş. Erol ÖZER Clariant Türkiye Boya ve Kim. Mad. San. Tic. A.Ş. Ersin YILDIRIM Mikron’s Mikronize Mineral End. Tic. A.Ş. Gürses ÖNER Sudarshan Chemical Industries Limited İlker EMİROĞLU Kalekim Kimyevi Mad. San. Tic. A.Ş. M. Akın AKÇALI Akçalı Boya ve Kimya San. Tic. A.Ş. Mert SOMTÜRK Betek Boya ve Kimya San. Tic. A.Ş. Murat YASA Mas Kimya San. Tic. Ltd. Şti. Nilay MİDİLLİ Univar Kimya San. Dış. Tic. Ltd. Şti. Onur L. AYDEMİR BASF TÜRK Kimya San. Tic. Ltd. Şti. Onur KARACA Artkim Fuarcılık Tic. A.Ş. Şebnem ÇEÇEN Artkim Fuarcılık Tic. A.Ş. Tezel KÖKDEMİR Arkem Kimya San. Tic. A.Ş. Yasemin GEZGİNER DYO Boya Fabrikaları San. Tic. A.Ş. Zafer KAYALAR Kayalar Kimya San. Tic. A.Ş.

Secretariat General of BOSAD / BOSAD Genel Sekreterliği Name Institution O. Tufan ÇINARSOY Secretary General Bilge ÇETİN Research Expert Türkan UZUNER Assistant of Secretary General

KÜNYE Graf ik ve Tasarım: CHEM AJANS (Kimya Medya Yayıncılık ve İnsan Kaynakları Tic. A.Ş.) Baskı : Bilnet Matbaacılık ve Ambalaj San. A.Ş. Telefon: 0 (212) 324 00 00 Baskı Yeri: İstanbul E-mail: [email protected] www.chemajans.com Tarih: Ağustos 2016 Congress Scientific and Organization Committees / Kongre Bilimsel Kurulu & Fuar Düzenleme Kurulu

MAIN SECTORAL TARGETS AND SERVICE THEMES OF BOSAD

The foundation process of BOSAD has started in February 2003 by the participation of representatives coming from nine companies targeting to build the national and international sectoral representation and cooporation power. After the completion of the related legal procedures by 2 June 2003, BOSAD started its activities to meet the demand for sectoral cooperation and representation which was lacking throughout the years both in national and international areas.

Main target of BOSAD, as also stated in its Rules and Regulation Book, is to collect the main Turkish manufacturers, providers and side industry companies under a single sectoral roof; to provide the coorperation of the participant companies appropriate to national issues, to express the problems of the paint sector from a common language and to protect the sectoral rights and benef its.

The companies and individuals in the sector are obliged to continue production according to all the related laws and regulations and have accepted the responsibility of taking part and contribute in the sector under several obligations such as providing the necessary technical and hygienic working conditions, obeying sectoral rivalry rules, protecting the consumer and manufacturer rights and not giving harm to the environment.

Besides, BOSAD also carries out several professional studies which aims to increase the paint consumption in Turkey according to national and international standarts, to provide healthy and good quality paint and to make the sector get more conscious about the ongoing issues. On the other hand, BOSAD desires to provide closer relationships within the participant companies and members in the sector to enable better cooperation and professional support.

The number of participant members has increased on the basis of participant companies by March 2016 and has taken a large production power under its roof. The sectoral production power of participant companies has exceeded %85 of national capacity.

BOSAD is being represented by the powerful companies and members in the paint sector concerning national and internation legal standarts, and respectful to environment issues and consumer rights.

BOSAD is a member of CEPE (European Council of Paint, Printing Ink and Artists' Colours Industry) and IPPIC (International Paint and Printing Ink Council).

Registered Trademarks of Bosad

Address: Selim Ragıp Emeç Sok. Kafaoğlu Apt. No:13/5 Suadiye / Kadıköy / İSTANBUL - TÜRKİYE Tel: +90 216 384 74 53 +90 216 384 74 93 www.bosad.org.tr [email protected] / [email protected]

03 BOSAD BOYA SANAYİCİLERİ DERNEĞİ'NİN TEMEL SEKTÖREL AMAÇLARI VE HİZMET TEMALARI

BOSAD (Boya Sanayicileri Derneği) Türk Boya ve Hammaddeleri Sanayiinin sektörel alanda işbirliği ve temsil gücünü ulusal ve uluslararası alanlarda oluşturmak amacıyla boya sektöründe faaliyet gösteren dokuz üretici kuruluşun temsilcileriyle meydana gelen kuruluş sürecini 2003 yılının Şubat ayında başlatmış, 02 Haziran 2003 tarihinde tüm yasal sorumluluklarını yerine getirerek faaliyete geçmiştir.

Bosad Ana Tüzüğü'nde belirtildiği üzere temel amacı; Türk Boya Sanayiinin üretici, tedarikçi ve yan sanayici kuruluşlarını sektörel bir çatı altında toplayarak, dernek üyeleri arasında ulusal mevzuata uygun işbirliği sağlamak, boya sanayiimizin sorunlarını tek çatı altında dile getirmek, sektörel hak ve menfaatlerini korumaktır.

Bu temel sektörel alanlarda faaliyette bulunan gerçek ve tüzel kişiler tüm yasa ve ilgili mevzuat hükümleri doğrultusunda üretim yapmak, işyerlerinde gerekli teknik ve hijyenik şartları taşımak, sektörel rekabet kurallarına uymak, tüketici ve üretici haklarını korumak ve çevreye zarar vermemek ana kuralları çerçevesinde çalışmaya ve bu temel faaliyetlere katkı sağlama sorumluluğunu taşımayı amaç edinmişlerdir.

Ayrıca BOSAD ( Boya Sanayicileri Derneği ) ülkemizde ulusal ve uluslararası standartlı boya tüketimini arttırmak, tüketicilere sağlıklı, kaliteli boya sanayi ürünlerinin sunulmasını sağlamak üzere Türk Boya Sanayii hakkında gerekli sektörel bilgilendirmeyi ve bilinçlendirmeyi sağlamak amacıyla mesleki çalışmalar yapmaktadır. Diğer yandan BOSAD, tüm boya sektöründe faaliyet gösteren kişi ve kurumlar arasında yakın bir işbirliği ve mesleki dayanışmayı gerçekleştirmek arzusundadır.

2016 yılı Mart ayı itibari ile önemli bir temel güce ulaşmış ve boya sektörünün değerli bir üretim gücünü bünyesine almıştır. Katılımcı firmaların üretim gücü ulusal kapasitenin %85’ini aşmıştır.

BOSAD (Boya Sanayicileri Derneği), boya sektörünün güçlü, ulusal ve uluslararası yasal standartlara sahip çevre ve insan sağlığı, tüketici haklarına saygılı bir üye profiline ve bu anlayışa sahip kuruluşlarca temsil edilmektedir.

BOSAD; Avrupa Boya, Matbaa Mürekkepleri ve Sanat Boyaları Endüstrisi Birliği (CEPE) ve Uluslararası Boya ve Matbaa Mürekkepleri Birliği (IPPIC) üyesidir.

Bosad'ın Tescilli Markaları

Adres: Selim Ragıp Emeç Sok. Kafaoğlu Apt. No:13/5 Suadiye / Kadıköy / İSTANBUL - TÜRKİYE Tel: +90 216 384 74 53 +90 216 384 74 93 www.bosad.org.tr [email protected] / [email protected]

04 THE BOARD OF BOSAD BOSAD YÖNETİM KURULU 2015-2017

Ahmet F. YİĞİTBAŞI Yönetim Kurulu Başkanı Chairman of the Board

M. Akın AKÇALI Kenan BAYTAŞ Hakan İ. FİDAN Yönetim Kurulu Başkan Vekili Yönetim Kurulu Başkan Vekili Yönetim Kurulu Başkan Vekili Vice Chairman of the Board Vice Chairman of the Board Vice Chairman of the Board

Altuğ AKBAŞ Ahmet Faik BİTLİS Mustafa DERYAL Yönetim Kurulu Muhasip Üye Yönetim Kurulu Üyesi Yönetim Kurulu Üyesi Accounting Member of the Board Member of the Board Member of the Board

R. Şükrü ERGÜN Semih KILIÇ Levend KOKULUDAĞ Yönetim Kurulu Üyesi Yönetim Kurulu Üyesi Yönetim Kurulu Üyesi Member of the Board Member of the Board Member of the Board

Tayfun KÜÇÜKOĞLU Erol MİZRAHİ Serdar ORAN Yönetim Kurulu Üyesi Yönetim Kurulu Üyesi Yönetim Kurulu Üyesi Member of the Board Member of the Board Member of the Board

A. Selçuk PAKSOY Feridun UZUNYOL Yönetim Kurulu Üyesi Yönetim Kurulu Üyesi Member of the Board Member of the Board

05 Dear Congress Participants,

The Association of the Turkish Paint Industry, BOSAD, has maintained its professional and leading work in the sector since 2003. The growth and the development of the paint industry, both in the region and in the domestic market, positions it as a new centre the production the investment. In this regard, it aims to proactively develop and to increase sectoral cooperation opportunities in the international context, with the particular emphasis on CEPE (European Council of Paint, Printing Ink and Artists' Colours Industry) and IPPIC (International Paint and Printing Ink Council).

6th International Paint, Paint Raw Materials, Construction Chemicals, Adhesives and Raw Materials, Laboratory and Production Equipments Exhibition and Congress / Paintistanbul & Turkcoat 2016, held on 22-26 March 2016, has been organized within the frame work of the promising growth targets of the Turkish paint and related raw materials industry and with the contributions of the leading sectoral companies and the institutions.

Paintistanbul & Turkcoat 2016 project will be accessible to all related fields of the paint industry, covering the whole value chain from raw materials producers, paint manufacturers to consumers. It has also been organized in the line with the concept of the international congresses and the fairs.

Paintistanbul & Turkcoat 2016 Exhibition and Congress offers different groups of presentation headings including paint, varnish, ink, adhesives, coating raw materials and auxiliary products, new types of coatings, innovative technologies and their application methods. The Congress programme and the activities have been organized for the participants who are coming from the universities, coating and raw material producers, as well as from the other industrial areas, which are directly integrated into our paint industry.

The preparation for this Congress has been carried out by the Congress Scientific Committee, which has been formed from the body of BOSAD. The Committee has held joint meetings over the last year, in conjunction with the distinguished academics and the prominent representatives of the industry.

Within the content of the Congress programme invited the prominent national and international speakers, who will make their contributions to the technological and scientific body of the paint and raw materials sectors. Profession-related and technological work groups will also be made. In addition, various scientific and technical presentations will run parallel to the Congress, exploring issues which refer to the production and the application methods of paint.

I would like to primarily to thank valuable Chairman and members of the Congress Scientific Committee, also the BOSAD employees, BOSAD Technical Work Groups and our Congress partner Vincentz Network for their outstanding contributions and their constructive supports to our project.

I believe that this Congress will provide a forum to reach successful results and will bring the opportunity to share the latest developments, both the academic and technological and innovations in line with the dynamic growth of our sector. I extend my thanks and respect on behalf of myself and BOSAD for your contributions.

Best regards,

Hakan İ. FİDAN Vice Chairman of the Board Chairman of BOSAD Exhibition/Congress and Chemicals Working Group

06 Değerli Kongre Katılımcıları,

BOSAD ( Boya Sanayicileri Derneği), Türk Boya ve Hammaddeleri Sanayiinin; yurt içi ve uluslararası bölgesel gelişimine yönelik, yeni üretim ve yatırım üssü olarak büyüme hedefi doğrultusunda mesleki ve sektörel çalışmalarını 2003 yılından bu yana sürdürmektedir. Bu bağlamda, IPPIC (Dünya Boyacılar Birliği) ile CEPE (Avrupa Boyacılar Birliği) başta olmak üzere uluslararası değişik platformlarda mesleki işbirliği imkânlarının arttırılması hedeflenmektedir.

Türk Boya ve Hammaddeleri Sanayiinin geniş ölçekli gelişim hedefleri çerçevesinde; sektörel kurum ve kuruluşlarımızın katkıları ile 22-26 Mart 2016 tarihlerinde 6. Uluslararası Boya, Boya Hammaddeleri, Yapı Kimyasalları, Yapıştırıcı ve Hammaddeleri, Laboratuvar ve Üretim Ekipmanları Fuar ve Kongresi/Paintistanbul & Turkcoat 2016 düzenlenmiş bulunmaktadır.

Paintistanbul & Turkcoat 2016 projesi ülkemizde geniş sektörel katılımla boya üretiminden tüketicilere kadar boya ile ilgili tüm değer zincirini içeren kuruluşlara açık olarak düzenlenmekte olup, uluslararası kongre ve fuar konseptine uygun bir içerikle organize edilmektedir.

Paintistanbul & Turkcoat 2016 Fuar ve Kongresi; boya, vernik, mürekkep, yapıştırıcılar, boya hammaddeleri ve yardımcı maddeler, yeni boya türleri, teknolojik gelişmeler ve uygulama yöntemleri gibi sektörel uzmanlık alanlarında farklı uluslararası kongre sunum başlıkları ile gerçekleştirilecektir.

Uluslararası katılımlı Kongre programı ve etkinlikleri; üniversiteler, araştırma kurumları, boya ve hammadde üreticileri ile birlikte sektörümüzün entegre olduğu diğer sanayi alanlarından oluşan kongre katılımcılara yönelik olarak düzenlenmektedir.

Kongre çalışmalarımız, BOSAD bünyesinde oluşturulan Kongre Bilimsel Kurulu tarafından, ülkemizin ve uluslararası kuruluş temsilcilerinin bu alandaki değerli akademisyenleri ile sanayi temsilcilerinin bir yılı aşkın süredir yaptıkları ortak toplantılar ile gerçekleştirilmiştir.

Kongre programı kapsamında, boya ve hammadde sektörümüzün teknolojik ve bilimsel yapısına katkı sağlayacak ulusal ve uluslararası değerli davetli konuşmacıların yanı sıra, mesleki ve teknik konuları kapsayan atölye çalışmalarına, yine kongre konularına paralel boya ile ilgili üretim ve uygulama tekniklerini içeren geniş ölçekli bilimsel ve teknik sunumlara yer verilmektedir.

Kongre Bilimsel Kurulumuzun başta değerli Başkan ve üye katılımcıları olmak üzere ilgili etkinliğimize çok yönlü destek veren BOSAD Genel Sekreterlik çalışanlarına, BOSAD Teknik Çalışma Gruplarımıza ve sektör partnerimiz Vincentz Network temsilcilerine projemize yönelik yaptıkları değerli katkılardan dolayı BOSAD ve şahsım adına teşekkürlerimi sunarım.

Sektörümüzün büyüme dinamikleri doğrultusunda, akademik ve teknolojik son gelişmeleri ve yenilikleri paylaşacağımız Kongremizin, sektörümüz açısından başarılı sonuçlar doğuracağı inancı ile saygılarımı sunarım.

Saygılarımla,

Hakan İ. FİDAN Yönetim Kurulu Başkan Vekili BOSAD Fuar & Kongre ve Kimyasallar Çalışma Grubu Başkanı

Dear Congress Participants,

The Association of the Turkish Paint Industry, Bosad, maintains its function as the representative of the sector since its foundation. The growth of the paint market, both in the region and in the domestic market, positions Turkey as a new center of production and investment. In this regard, Bosad aims to proactively develop and increase sectoral cooperation opportunities in various international platforms.

Paintistanbul & Turkcoat 2016 International Congress on Paints, Organic Coatings, Polymers and Raw Materials held on 22-23 March 2016, has been organized within the framework of the promising growth targets of the Turkish paint and raw materials industries and with the contributions of the leading sectoral companies and institutions.

Paintistanbul & Turkcoat 2016 Exhibition and Congress were intended to serve all related fields of the sector, covering the whole value chain, from raw material producers to paint manufacturers and to end users. These two events have been organized in line with the concept of international congresses and fairs. Two keynote speeches and 30 presentations focusing on practically all aspects of paint technology will be made during the Congress in ten different sessions. There will be also a session for posters.

The Congress program and activities have been organized taking into consideration the needs and demands of the participants coming from the universities, research institutes, coatings and raw materials producers, as well as from the other industrial areas related to the paint industry, directly or indirectly.

Paintistanbul & Turkcoat 2016 Congress has been organized with the cooperation of Vincentz Network who have significant experiencein organizing international congresses. The preparations for the Congress have been carried out by the Congress Scientific Committee which was formed by Bosad with the participation of distinguished members from the academia and the industry.

We would like primarily to thank the valuable members of the Congress Scientific Committee and particularly the BOSAD General Secretariat and their employees for their outstanding contribution and support to the Congress.

We believe that, this Congress has provided a forum to share the developments and the innovations in paint and the related industries. We appreciate the contributions of the participants in making the Congress a fruitful organization.

Best regards,

Dr. Engin ÇÖRÜŞLÜ Chairman of Paintistanbul & Turkcoat 2016 Scientific Committee

08 Değerli Kongre Katılımcıları,

Boya Sanayicileri Derneği, BOSAD, kurulduğu günden bu yana sektörün temsilcisi olarak işlevini sürdürmektedir. Hem bölgedeki pazarın hem de yurt içindeki boya pazarının büyümesi, Türkiye'yi üretim ve yatırımın yeni bir merkezi olarak konumlandırmaktadır. Bu bağlamda, BOSAD çeşitli uluslararası platformlarda sektörel işbirliği imkanlarının arttırılmasını ve proaktif bir şekilde geliştirilmesini hedeflemektedir.

22-23 Mart 2016 tarihlerinde düzenlenen Paintistanbul & Turkcoat 2016 Boya, Organik Kaplama, Polimer ve Hammaddeleri Uluslararası Kongresi boya ve hammadde sanayimizin gelecek vaadeden gelişim hedefleri çerçevesinde, önde gelen sektörel kurum ve kuruluşların katkılarıyla düzenlenmektedir.

Paintistanbul & Turkcoat 2016 Fuar ve Kongresi’nde, hammadde üreticilerinden boya üreticilerine ve son kullanıcılara kadar sektörün tüm değer zincirini kapsayarak alanlarına hizmet vermek hedeflenmiştir. Bu iki etkinlik uluslararası kongre ve fuar konsepti doğrultusunda düzenlenmektedir. Kongrede boya teknolojilerinin hemen hemen tüm yönlerine odaklanan iki açılış konuşması ve 30 sözlü sunum, 10 farklı oturumda yapılacaktır. Ayrıca posterler için de bir oturum mevcuttur.

Kongre programı ve etkinlikler üniversiteler, araştırma enstitüleri, boya ve hammadde üreticileri, doğrudan ya da dolaylı olarak boya sanayii ile ilgili olan diğer endüstriyel alanlardan gelen katılımcıların ihtiyaçları ve talepleri dikkate alınarak organize edilmiştir.

Paintistanbul & Turkcoat 2016 Kongresi uluslararası kongreler düzenleme konusunda önemli deneyimlere sahip olan Vincentz Network ile işbirliği içinde düzenlenmektedir. Kongre hazırlıkları akademi ve sanayiden seçkin üyelerinin katılımı ile BOSAD tarafından kurulan Kongre Bilimsel Kurulu tarafından yürütülmektedir.

Kongre Bilimsel Kurulu’nun değerli üyeleri başta olmak üzere, Bosad Genel Sekreterliği ve çalışanlarına Kongre’ye olan önemli katkıları ve destekleri için teşekkür ederim.

Kongremizin boya ve ilgili sektörlerdeki gelişme ve yenilikleri paylaşmak için bir forum oluşturduğuna inanıyoruz. Kongreyi değerli bir organizasyon yapan katılımcılara katkılarından dolayı müteşekkiriz.

Saygılarımla,

Dr. Engin ÇÖRÜŞLÜ Paintistanbul & Turkcoat 2016 Bilimsel Kurulu Başkanı

09 CONTENTS / İÇİNDEKİLER

12 Keynote Speeches Session Moderator: Dr. Clifford K. Schoff 13 Research and Development in Germany - The Role of Academia and Industry, Prof. Dr. Wolfgang Bremser, Paderborn University, Germany 15 Collaborations Between Industry and Academia: Navigating a Complicated Landscape, Dr. Victoria Gelling, Valspar Paint, USA

16 Novel Raw Materials (I) Session Moderator: Prof. Dr. Mehmet Ali Gürkaynak 17 Acure: Ultra-Fast Drying, Low VOC, Isocyanate Free Technology for 2K Coating Systems, Dr. Ir. Fred van Wijk, Nuplex Resins BV, Netherlands 31 Improved Industrial & Protective Coatings Enabled by Siloxane Resins, Dr. David Pierre, Dow Corning Europe SA, Belgium 35 Optimization and Investigation of Solvent Based Dyes Including Boron Chemicals in Metal Industry, Tuğba Çifte, Yıldız Technical University, Turkey

42 Functional Coatings (I) Session Moderator: Prof. Dr. Ahmet Akar 43 The Current Use and the Future Prospects of Nano-Sized Materials in Surface Coatings, Prof. Dr. Güngör Gündüz, Middle East Technical University, Turkey 55 Mimicking from Nature: Synthesis of Superhydrophobic and Superolephobic Coatings, Prof. Dr. H. Yıldırım Erbil, Gebze Technical University, Turkey

56 Novel Raw Materials (II) Session Moderator: Prof. Dr. Atilla Güngör 57 Stimuli Responsive Polymeric Materials for Antifouling Applications, Prof. Dr. Yusuf Z. Menceloğlu, Sabancı University, Turkey 59 Serendipity to Rational Design: Discovery and Development of Novel Inorganic Pigments for Art and Industry, Prof. Dr. Mas Subramanian, Oregon State University, USA

66 Functional Coatings (II) Session Moderator: Prof. Dr. Ayşen Önen 67 Functional Composites of an Ionic Salt in a Hydrophobic Polymer Matrix, Doç. Dr. Seda Kızılel, Koç University, Turkey 69 Antifouling Activity of Sea Cucumber Extracts, Nazlı Mert, Dokuz Eylül University, Turkey 73 Polymer Coated Fertilizers as Nutrient Management, Prof. Dr. Emin Arca, Marmara University, Turkey

80 Novel Raw Materials (III) Session Moderator: Mustafa Tunçgenç 81 Unique Solutions for the Cobalt and MEKO Regulatory Concerns Affecting the Coatings Industry, Dr. Franjo Gol, OMG Borchers, Germany 91 Synthesis and Film Properties of Novel Acrylic Modified Water Reducible Alkyd Resin, Nagihan Akgün, Istanbul University, Turkey

98 Architectural Coatings Session Moderator: Prof. Dr. Nergis Arsu 99 Glossy Coatings with Good Water Vapor Transmission - Made Possible by a New Cobinder Technology, Markus Vogel, Evonik Resource Efficiency GmbH, Germany 107 Rheology Modifiers for Improved Applied Hide and Smooth Finish in Low VOC Emulsion Paints, Dr. Anne Koller, Dow Chemical Company, France

114 Sustainable Technologies & Regulatory Issues (I) Session Moderator: Prof. Dr. Ersin Serhatlı 115 The First Bio-Based Aliphatic Polyisocyanate for High Performance Polyurethane Coatings, Dr. Abdullah Ekin, Covestro LLC, USA 117 Bringing Polyurethanes Coatings to the Next Level with Bio-Based Polyols and Enhanced Performance, Eric Brouwer, Croda Nederland BV, Netherlands 119 Bio-Based UV Curable Coating Systems, Prof. Dr. Hüseyin Deligöz, Istanbul University, Turkey

120 Processing & Testing of Coatings (I) Session Moderator: Dr. Ali Önen 121 Preparation and Characterization of Alkyd Resin Nanocomposites, Alican Güler, Alfa Kimya, Turkey 129 The Use of Rheology in Evaluating and Optimizing the Paint Performance, Dr. Funda İnceoğlu, Kalekim Kimyevi Mad. A.Ş., Turkey 131 Extensional (Elongational) Viscosity, Dr. Clifford K. Schoff, Schoff Associates, USA

134 Sustainable Technologies & Regulatory Issues (II) Session Moderator: Handan Aydın 135 BPR and Biocidal Product Authorisations? What You Need to Know?, Paul Wood, Dow Microbial Control, Switzerland 141 Renewable Micronized Powders for Coatings & Inks, Tobias Niederleitner, Clariant Produkte GmbH, Germany 143 Influence of Paint Quality on the Environmental Footprint of Architectural Paints, Dr. Steven De Backer, Chemours Belgium BVBA, Belgium

148 Processing & Testing of Coatings (II) Session Moderator: Dr. Tahir Altunbulduk 149 Designing Pigment Dispersing System to Reduce Total Cost of Ownership, Norbert Kern, Bühler AG, Switzerland 151 Fluorescent Pigments and Their Diverse Applications, Darren D. Bianchi, Brilliant Group, USA 157 Matting of Solvent Free UV-Curable Coatings, Peter Lederhos, Evonik Resource Efficiency GmbH, Germany

158 Paint School-1 159 Architectural Coatings, Dr. Anne Koller, Dow Chemical Company, France

160 Paint School-2 161 Adhesives and Sealants, Dr. Matthias Popp, Fraunhofer IFAM, Germany CONTENTS / İÇİNDEKİLER

162 Paint School-3 163 The Basics of Pigment Dispersion, Dr. Clifford K. Schoff, Schoff Associates, USA

164 Paint School-4 165 Biocides and Current Regulations, Dr. Annette Bitsch, Fraunhofer ITEM, Germany

166 Poster Presentations

167 Characterization of Urethane-Modified Polyester in The Coating System with Ftir and Pyrolyser-Gcms, Adalet Ayça Biçen İbik, Kansai Altan Boya A.Ş., Turkey

169 Investigation of Different Hardeners in Epoxy Systems and Hardening Mechanisms in Coatings, Betül Tok, Yildiz Technical University, Turkey

173 Effect of Boron Acrylate Monomer Content and Multi Arm Boron Acrylate on Adhesive Performance for Water Borne Acrylic Polymers Coated on Bopp Film, Cansu Akarsu Dülgar, Istanbul Technical University, Turkey

187 Investigation with 3d Optic Profilometer of the Tribological Behaviors Alkaline Zinc and Zinc-Nickel Alloy Electrocoatings, Doç. Dr. Feza Geyikçi, Ondokuz Mayıs University, Turkey

195 Synthesis, Characterization and Photophysical Properties of Novel Dye Water Soluble Zinc-Phthalocyanines, Dr. Bahadır Keskin, Yıldız Technical University, Turkey

199 Low Cost Flame Retarder in Interior Wall Paints, Hatice Begüm Murathan, Gazi University, Turkey

207 Investigation of Dilution Ratio Effect on Film Properties of Acrylic Modified Water Reducible Alkyd Resin, Özge Naz Büyükyonga, Istanbul University, Turkey

215 Production and Application of Decorative Paints Containing Rust in Art, Sema Ayvaz, Yildiz Technical University, Turkey

219 Determination of Drying Agents for the Resins Used in the Coating Film, Prof. Dr. Sevgi Ulutan, Ege University, Turkey

223 AMMETM Technology for Dry Film Preservation - Advanced Micro Matrix Embedding, Katia Padoan, THOR Specialties, Italy

227 Removal of Acid Red 336 Dye Using Green Tea Adsorbent, Yrd. Doç. Dr. Selcan Karakuş, Istanbul University, Turkey

229 The Potential Use of Pumice Powder as Paint Filler, Yrd. Doç. Dr. Ömer Edip Kuzugüdenli, Erciyes University, Turkey

231 Effect of Solvent-Filler Surface Compatibility on Paint Drying Speed, Yrd. Doç. Dr. Ömer Edip Kuzugüdenli, Erciyes University, Turkey Keynote Speeches

Prof. Dr. Wolfgang Bremser

Paderborn University Germany

Wolfgang Bremser studied chemistry in Mainz, Germany. His PhD-thesis in physical chemistry was about the synthesis, characterization and the mobility of nano- and microgels. In 1991 he joined the research of BASF Coatings. Main topics have been cathodic electrodeposition coatings and the development of a modular System with solvent free dispersions. In 2004 he went to Paderborn University to chair the group “Coatings, Materials, Polymers”. Since 2013 he is member of the Institute for light weight construction ILH.

The areas of interest are the organization of colloidal materials, their physical properties and their technical application – the material science of polymers.

Different fields are investigated: Anti fouling coatings, corrosion, modification of particles, fiber-composites. He enjoys an enhanced physical but graphical view on matter.

RESEARCH AND DEVELOPMENT IN GERMANY: THE ROLE OF ACADEMIA AND INDUSTRY

Prof. Dr. Wolfgang Bremser Paderborn University Germany

Abstract What are the factors for a successful development of innovative products? This simple question has unfortunately an unsatisfactory complex, unclear and subjective answer. The answer becomes even more complex and diffuse, if considered from a national perspective and for a complete industrial segment. In Germany the coatings industry is rather strong and the technological progress is based on an interplay between academia, industry, research institutes and governmental influence. The German educational and academic research system is rather differentiate. It offers all levels of education and professional development. This addresses all levels of a product development and technical support, from daily trouble to strategic developments. All those interactions are established and are forming a system with an own tradition and an own mentality.

The strength and the weaknesses of the German system will be analyzed and are compared with US and Chinese systems. Specific examples of successful developments between industry and and academia are given.

13 Keynote Speeches

Dr. Victoria J. Gelling

Valspar Paint USA

Dr. Gelling is a Technical Director in Performance Coatings at The Valspar Corporation in Minneapolis, MN. At Valspar, she is has responsibilities in the Electrocoating, Liquid Advanced Platforms, and corrosion laboratories. Before her time at Valspar, she was an Associate Professor in the Department of Coatings and Polymeric Materials at North Dakota State University. She gained a B.S. in Chemistry at the University of North Dakota then completed a doctorate in Chemistry at North Dakota State University. Her principal research interests are the use of electrochemistry to monitor the health and degradation of polymeric materials and the transitioning of laboratory electrochemical techniques to the field. During her career, she has studied various coating systems from the traditional to the novel, such as electroactive conducting polymers. She has experience with numerous lightweight metal alloys from her research concentrating on aluminum and magnesium corrosion inhibition; focusing on environmentally compliant non-chromate coatings.

14 COLLABORATIONS BETWEEN INDUSTRY AND ACADEMIA: NAVIGATING A COMPLICATED LANDSCAPE

Dr. Victoria J. Gelling Valspar Paint USA

Abstract Developing a successful collaboration between industrial coating companies/organizations with academic institutions can be challenging; however the rewards often outweigh the challenges encountered during setting up the collaboration. Oftentimes, differences in goals, timelines, publishing rights, and budgets can be a cause of frustration for both the academic and industrial partners. These issues can result in lengthy delays in the negotiation process as well as a complete failure to agree to a path forward that will allow for the collaboration to occur. When both sides understand the inherent challenges and limitations that impact the other party, a decrease in the time of negotiations may be observed with an increased likelihood that the negotiations end with a successful outcome.

During this presentation, a review on common academic budget considerations for industrially funded projects will be provided. Additionally, a discussion on the academically- important negotiated publication rights will be given. Finally, an overview of the various forms of Intellectual Property (IP) that are often negotiated for joint-development projects will be provided.

15 Novel Raw Materials (I)

Dr. Ir. Fred Van Wijk

Nuplex Resins B.V. Netherlands

Fred van Wijk studied Molecular Sciences at Wageningen University, The Netherlands, and received his PhD in molecular physics in 1987. He then worked for Akzo Nobel in various positions. In 2000 he joined Akzo Nobel Resins, now Nuplex Resins, heading the product development for automotive and performance coatings in EMEA. Since July 2015 he is global business R&D manager for Acure systems.

16 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

F. Van Wijk Nuplex Resins B.V. Netherlands

Abstract Two component urethane topcoats are well established in coatings applications. There is a need, however, for systems with increased productivity coupled with environmental and health and safety friendliness. Here we present a new, low VOC, isocyanate and tin free, breakthrough technology which meets these needs. The system is built on a novel blocked catalyst and kinetic control additive package used in conjunction with Michael Addition chemistry. Prototype paint formulae highlight the low VOC capability (<250 g/l) of this very fast drying 2K system (<15 minutes, ambient) and the unique decoupling of dry time and potlife (>5 hours), expected to trigger new paint and process solutions. The chemistry of the system and comparative results versus other topcoats are presented. The results show that the system has significant potential to displace existing two component topcoats in Marine and Protective and Industrial OEM market applications, without compromise. Introduction Driven by changes in HSE legislation, competition on paint application costs and coating performance, today’s paint technology continues to develop in the direction of higher solids, lower curing temperatures and faster painting processes. Meeting these combined requirements is very challenging and encounters the limits of versatility of presently available cure chemistries. Michael Addition chemistry [1] offers a perspective for making steps beyond those limits.

17 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

Michael Addition (MA) has been explored before for coating applications [2], although it has never established itself as a mainstream cure technology, most likely because it is too reactive. The key components of a MA system are electron deficient C=C double bonds (e.g. an acryloyl, the acceptor), acidic C-H bonds (as present in acetoacetate and malonate moieties, the donor), and a base catalyst strong enough to abstract the proton of this C-H bond yielding a nucleophilic carbanion that can add to the double bond. A carbon-carbon link is formed between the two moieties. The second proton of the donor species is available for reaction with similar reactivity (Scheme 1).

Scheme 1. The Michael Addition reaction between malonate and acryloyl

Relevant features derived from the characteristics of MA chemistry include • The need for a base strong enough to abstract a proton from the donor species. The pKa of an acetoacetate C-H is around 10.7, for a malonate it is even higher (>13). • The absence of acidic species that will deactivate the catalyst. • The very high reactivity of the carbanions formed, especially when using malonate species as the donor. In paint formulations it is easy to create conditions under which a MA reaction between malonate and acryloyl species can essentially be completed within minutes. In this instance, both malonate and acryloyl may coexist in the uncatalyzed paint and present good shelf stability. • The nature of the carbon-carbon links formed; not leading to weak spots in durability. • Michael addition technology opens a window to using non-polar, low equivalent weight crosslinking components that can lead to very low solvent demand formulations capable of creating high crosslink density polymer networks.

We have expanded the options of MA chemistry by focusing on ways to control the inherent reactivity of a malonate-acryloyl system by using its high reactivity potential, whilst creating both a long potlife and a workable open time. Combined with specially developed resins, the obtained benefits are so profound that it may be recognized as a new type of curing technology, finding use in many different markets and applications. We will refer to this new chemistry hereinafter as ‘Acure’.

Controlling pot life and drying Very high reactivity cannot easily be combined with a good pot life. However, a solution was found in the reversible blocking of a strong base catalyst with dialkylcarbonate as depicted in Scheme 2a. Strong bases will form alkyl carbonate anions with a basicity low enough to not initiate the MA reaction. These carbonates are inherently unstable, and through protonated species will form an equilibrium with free CO2 and alcohol (Scheme 2b).

Scheme 2. Blocked catalyst formation and activation; HA represents a proton donor 18 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

After mixing in a container (with a relatively low surface area / volume ratio) there is no fast CO2 release and long pot lives are observed (vide infra). Upon applying the paint however, large surface areas will be created facilitating easy escape of solvent and especially CO2. This shifts the equilibria, followed by rapid de-blocking of the basic species which triggers the full reactivity potential of the malonate acryloyl system. This de-blocking process will be accelerated when HA becomes more acidic, shifting equilibrium 2b to the right. The net result is the combination of a very long pot life with very fast drying. Workable pot lives of at least 4 hours are easily obtained, and if needed can be formulated to be counted in days. At the same time we can observe tack free times down to 10 minutes after application, and phase 4 (scratch free) drying recorder times not much longer. Figure 1 shows the different pot life / drying speed balance for Acure versus isocyanate based systems.

Figure 1: Figure 1: Generalized picture of potlife – drying balance. Blue area: the ‘world’ of OH and NH isocyanate curing; red area: the field of operation for Acure based paints. Overlapping area denotes the ‘aspartates’ region (NHisocyanate).

The effect of adding alcohols to Acure paints is given in Figure 2, showing the pot life prolongation without significantly affecting dry times. When following the acryloyl conversion upon application with FTIR (809 cm-1), we see that conversion can easily reach values above 80% in the first 10 minutes (figure 4). This indicates not only a rapid physical dry state of the film but also a very rapid crosslink density development with the associated beneficial early coating performance of both chemical and mechanical robustness. The potential reactivity may also be used at temperatures below ambient: dry times of less than an hour have been observed at application temperatures as low as 15ºC. In terms of its practical use, this system may be used as a 2K coating with both reactive components (malonate polymer and acryloyl oligomer) premixed and the catalyst being added as an activator.

Figure 2. Effect of volatile alcohols added to the paint on potlife (left) and drying time (tack-free - right); weight % on solid binder (malonate polymer + acryloyl); potlife as double viscosity.

ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

Complications arising from very fast cure Paint systems with drying times this short may bring complications not normally recognized for ‘slow’ systems.

Firstly, such drying times become competitive with the ability of the solvents to escape from the film. Under ambient curing conditions the glass transition temperature (Tg) of the wet coating rises due to solvent release and reaction. When the Tg reaches room temperature (RT) the system will vitrify: both solvent diffusion and chemical reactivity become severely retarded. If such vitrification in the surface of the coating, becoming tack free, occurs much earlier than in the deeper layers, some solvent may be retained in those deeper layers which cannot then easily escape through this closed surface. I.e. further solvent release will be significantly slowed down. The upside to this picture is that solvents are excellent plasticizers. This means that the crosslink conversion is able to rise further while the reaction is not yet impeded by a high Tg and it is then easier to reach full conversion. However, an excess of entrapped solvent may cause the Tg in deeper layers to remain lower in which case a lower pendulum hardness may be observed. Kiil modelled the competition between chemical reaction and solvent escape [3].

Secondly, ultrafast drying may lead to reduced appearance as a very narrow time window for levelling remains. One may see such fast drying systems struggle with releasing entrapped air and picking up overspray. Under some conditions, a rapid surface cure on top of a still mobile sublayer can even give rise to wrinkling phenomena, furthermore telegraphing defects are more likely to occur.

It is clear that combining a very fast dry profile with very good pot life is not a guarantee for an application profile without significant complications. The challenge we addressed, was how to save the fast dry time profiles, and simultaneously mitigate the problems described above. The solution we’re presenting is found in the use of special kinetic control additives to create an induction period in the crosslink reaction, and so create a tuneable ‘open time’ window.

Creating an ‘open time’

The concept used revolves around the presence of HA species in the formulation that can add to the acryloyl acceptors by a Michael addition after deprotonation, but differing from malonate in that: a. HA is significantly more acidic than the malonate C-H; i.e. the base will deprotonate HA much more readily than malonate, postponing the fast addition of malonate onto acryloyl. b. The conjugate anion (A-) has a significantly lower reactivity towards the acryloyl: the consumption of these species by the MA reaction is slow, i.e. already low concentrations of HA will have a significant effect on early kinetics. c. Ideally, the generated HA-acryloyl adduct does not significantly increase viscosity of the paint. This implies that HA is preferably a low molecular weight, mono-functional component; guaranteeing the wet layer’s ability to wet, level, de-gas, toolbox is available for easy optimization of Acure paints to meet specific application performance demands.

20 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

A beneficial consequence of using a relatively acidic species HA is that reaction b in Scheme 2 will shift to the right, increasing the concentration of weak acid (A-) and in particular CO2. The latter will now diffuse out of the paint layer more readily. Because of its low reactivity (compared to malonate) the higher concentration of Adoes not neutralize the positive effect of the ‘newly created’ open time. However, if all HA is consumed and CO2 mostly expelled then the maximum concentration of MA reactive anionic species is present in the paint. The malonate then becomes deprotonated and the full potential of the ultra-fast Michael addition is released as if there never was a blocked catalyst (see Figures 3 and 4 and Scheme 3). Acure chemistry can therefore be summarized as in Table-1. Table-1. Suitable kinetic control additives; pKa’s from [4] Scheme 3, where a tetrabutyl ammonium cation counters the blocked base with succinimide as an example kinetic control additive (HA). The paint components controlling the reactions 1 and 2 in Scheme 3 are different species, allowing both the pot life and open time to be tuned independently, while accepting only a limited compromise in drying time. Simultaneously, very significant advantages in pendulum hardness development and appearance are obtained (see figures 5 – 8 and Table 2). For layer thicknesses above 40 μm we found that both 1,2,4-triazole and succinimide are needed for optimum results.

Scheme 3. Reactivity control of Acure chemistry. MA: Michael Addition. Reaction (1): potlife control. Reaction (2): open time control. Reactions (3) and (4): crosslinking. Both malonate hydrogens react with acryloyl

21 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

Figure 3. Effect of blocking the catalyst and adding an excess (relative to catalyst) of kinetic control additives on the conversion of acrylic double bonds (FT-IR, 809 cm- 1) by Michael addition. Cat conc.: 40 μeq/g resin solids for all curves apart for the purple dashed one. The 40 μeq/g was used to allow for proper FT-IR experimenting purposes. The dashed arrow indicates the open time tuning window (here taken as max 15% crosslink conversion). For thicker (³ 40 μm) high gloss layers both succinimide and 1,2,4-triazole are combined in Acure paints to yield optimal performance (orange dashed line - See the text for more information).

Figure 4. Idem Figure 3, showing the effect of CO2 expulsion (Scheme 2-b)

Table 2. Acure with and without catalyst additives Figure 5. Effect on appearance impacted by Acure kinetic control additives. Entrapped air (left) is minimized in the formulation with increased open time (right).

Figure 6. Contours represent the drying time (min.) as function of 1,2,4-triazole and succinimide concentrations in the Acure paint.

22 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

Figure 7. Appearance (short wave values) as function of Figure 8. Persoz hardness as function of 1,2,4- triazole and 1,2,4-triazole and succinimide concentrations in Acure paint. succinimide concentrations in Acure paint. Note that 1,2,4- triazole only (without succinimide) cannot yield low SW values.

Durability In general, accelerated weathering tests yield results very comparable to high quality (4% OH) HS urethane coatings. Figures 9a and b show the results of various white Acure top coatings (typically 40 – 60 μm) on commercial epoxy amine primers exposed to UV-B and Xenon. Note: The Acure catalyst may be incompatible with some UV absorbers. Figure 10 shows that Acure coatings also behave very comparably to urethanes in Florida exposure testing.

Figure 9. Gloss retention under accelerated weathering. Left (9a): UV-B exposure (4h/4h, 313 nm), the blue field indicates a large variety of urethane top coats without HALS. Right (9b): Xenon exposure.

Figure 10. Gloss retention during Florida exposure (2012-2013) of Acure white top coat formulations over epoxy amine primer compared to three different urethane coatings of comparable performance quality.

23 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

Adhesion

In the General Industrial, Marine, Protective, and ACE markets, topcoats are usually applied over an epoxy-amine primer. Adhesion studies of Acure coatings were carried out over 11 different types of commercially available epoxy-amine primers used in a wide field of end use applications including general industry, ACE and protective coatings. The different epoxy primer types included new build, holding, fast-cure, surface tolerant, low temperature cure and zinc rich types. Good to excellent adhesion was found on more than 80% of these primers, which can be explained by chemical bond formation between remaining free amine groups on the substrate and acryloyl groups from the Acure paint (see Figure 11).

Figure 11. Chemical adhesion of Acure hardeners on epoxy-amine primers [5]

Obtaining chemical adhesion with Acure paints on substrates not containing NH-moieties can be more difficult. However, we have found that the presence of 1,2,4-triazole, apart from its function as kinetic control additive, also helps as an adhesion promoting agent on metallic substrates. Well-known [6] metal pre-treatment methods with silanes also exhibited excellent adhesion with Acure top coats.

Comparing Acure Technology with isocyanate-containing systems Below we have shown comparative data obtained from various TiO2-white paint formulations; one Acure and four high solids isocyanate containing systems. All paints were optimized for high gloss industrial top coat use and are based on commercially available components. 4% OH-NCO paint A is a “state-of-the-art” very fast RT drying top coat system, paints B and C are intended for elevated temperature curing (B: 60°C, C: 80°C). All paints have identical pigment / binder ratios. The Acure paint composition is given in Table 3 and is based on DTMPTA (ditrimethylolpropane tetra acrylate) as acryloyl acceptor. The malonate functional resin A is a specially designed polyester resin with a number average molecular weight of about 1780 Da and a malonate equivalent weight of 350 g/mole solid resin. The resin is at 85% solids in butyl acetate and has a viscosity of 5-10 Pa.s. Table 3. Acure paint composition The malonate functional resin B is the same resin; however modified with 1.4% succinimide on solids.

24 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

We have focused on leveraging our control of the cure chemistry in systems with relatively high concentrations of functional groups. Consequently, Acure coatings with very high crosslink densities (XLD) of typically 2.5 - 3 mmole/cc are obtained. These XLDs are higher by a factor of around 3 relative to high end, e.g. 4% OH – isocyanate based systems, even when using high isocyanate levels (see Table 4 comparing isocyanate levels in this study). XLD is amongst others, tuned by the acryloyl –malonate hydrogen ratio, see Figure 12, showing the resistance to MEK dramatically improve when A/M > 0.9. Figure 13 shows that in order to avoid thermal (dark) yellowing of the coating, the A/M ratio should also be > 0.9 and then it may even out-perform isocyanate based systems.

Table 4 compares the appearance data, including the effect of thermal (dark) ageing. Note that Acure paint was applied at the highest spray viscosity (DIN-4). The aspartate coating deteriorated significantly with time when exposed to 24 hrs 120°C. An additional advantage of Acure chemistry is its relative insensitivity of appearance as a function of the applied layer thickness. Unlike OH-isocyanate-containing systems there are no foam generating reactions with water and subsequent pin-holing risk. In our lab we have applied Acure paints at over 240 μm DFT that still exhibit very good appearance. Table 5 shows the comparative potlife – drying balance for these paints at room temperature. Acure II differed from Acure I only in that the former contains half the amount of succinimide and 20% more catalyst compared to the latter to match the cure speed of the aspartate paint. Note the very long pot lives for both Acure paints.

Table 6 shows the Persoz hardness development for the various coatings. Note that paints B and C were cured at the recommended elevated temperature (30 min 60°C and 80°C respectively). Yet the early hardness cannot compete with Acure and aspartate. Table 7 shows the mechanical test results. The very good mar (scratch) resistance is consistent with the high crosslink density present in the Acure coating. Resistance to various chemicals is equal to or better than the references for Acure coatings. Resistance to acid etch, was found to out-perform the reference coatings. In Figure 14 the DMTA behaviour of the pigmented top coats is shown. The rubber modulus (lowest E’ above Tg) was used to derive the crosslink density. For Acure this is about 2.5 – 3 times higher than the references. Although cured at room temperature the Tg of the aspartate is much higher than that of the other coatings.

Figure 12: Resistance to 4 min. MEK exposure (cotton soaked under Figure 13. Hardness (65 μm) after one day RT (B) and thermal yellowing a watch glass) as function of acryloyl / malonate hydrogen ratio (after 24hr 120 °C) depend on the ratio between acryloyl groups and (using DTMPTA as XL) on a scale of 1 (bad) to 5 (no visible damage, malonate hydrogen in Acure paint. DTMPTA was used as XL. perfect).

25 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

Table 4. Appearance directly after application and after ageing (DFT: 45 ± 4 μm on Q-panel)

Table 5. Comparing potlife – drying balance at room temperature

Table 6. Comparing hardness (Persoz)

Table 7. Comparing mechanical properties

26 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

Table 14. DMTA (dynamic mechanical thermal analysis) results from the coatings used in Tables 4 – 7 above. Note the high rubber modulus for Acure in comparison with the other coatings. Data generated using a modified Rheovibron (Toyo Baldwin, type DDV-II-C) at a frequency of 11 Hz with a dynamic strain of 0.03%. The heating rate was of 5°C/min.

VOC, Health and Safety Acure paints consist of malonate functional polyesters and acryloyl functional oligomers, both of whichare compounds of low polarity with no appreciable hydrogen bonding. Consequently the intrinsic viscosity of the paint is significantly lower than when using hydroxyl functional binders. The Acure paintused in Tables 4 to 7 contained about 245 g/l VOC; no effort was made to optimize for low VOC. Acure is base catalysed; it does not require an organotin or any other organometallic catalyst, nor does it release formaldehydes. Depending on the type of selected acryloyl oligomers the paint can be formulated without skin sensitizing compounds; e.g. di-trimethylol propane tetraacrylate (DTMPTA). If this is not a requirement more cost effective alternatives are available (e.g. TMPTA).

Summarizing Acure Performance and Outlook Acure, based on Michael addition chemistry, extended with the kinetic toolbox developed and put to work with dedicated malonate polyesters, has yielded an impressive combination of attractive performance parameters. We expect these innovations to form the basis for a next generation of novel high performance coatings capable of providing significant improvements in application cost efficiency. Key features and benefits include: • very fast drying, with fast crosslink density development, and a very long potlife • application at ambient temperatures, or even below • very low solvent content (VOC < 250 g/L) • excellent appearance • thick layer application (> 150 μm) possible • very good chemical resistance • very good mar resistance • excellent flexibility • good outdoor durability • isocyanate, formaldehyde and organotin-free cure chemistry

As such, Acure presents a system that can combine many premium characteristics through an unprecedented control over the cure kinetics. Of course, being a base catalysed system, it also encounters some inherent limitations, especially in terms of

27 ACURE: ULTRA-FAST DRYING, LOW VOC, ISOCYANATE FREE TECHNOLOGY FOR 2K COATING SYSTEMS

sensitivity to acidic components that may interact with the catalyst system. Care must be taken when selecting additives in order to avoid those that can potentially cause acid contaminations, e.g. dispersants, rheology control agents, etc. With a proper choice of additives, complications can be avoided. As an alternative to acidic rheology additives, Nuplex also provides malonated polyesters equipped with urea nanocrystal based rheology agents (SCA’s) that are compatible with this technology. Cure inhibition complications can also arise when applying Acure paints onto substrates containing mobile acid species, such as WB base coatings used in automotive applications.

We have presented our first observations in this paper based on a limited set of malonated binders. We expect considerable room to decrease the viscosity of the binders and develop lower VOC Acure paints. Likewise variations in e.g. polarity, malonate equivalent weight, or resin Tg and the nearly unlimited variations in paint formulation will further add to the potential for Acure in a broad range of application fields. E.g. we have already shown in our lab that ‘quasi 1K’ paint systems (pot lives extending over days) are possible whilst still retaining the cure speed by increasing the amount of alcohols.

References 1- Michael, A. (1887). “Ueber die Addition von Natriumacetessig- und Natriummalonsäureäthern zu den Aethern ungesättigter Säuren”. Journal für Praktische Chemie 35: 349–356. 2- A. Noomen, Progress in Organic Coatings, 32 (1997), 137-142 3- S. Kiil, J. Coat. Technol.Res., 7 (5), (2010), 569-586. 4- http://www2.lsdiv.harvard.edu/pdf/evans_pKa_table.pdf 5- Adhäsion, Theoretische und Experimentelle Grundlagen, C. Bischof und W. Possart, Akademie Verlag Berlin, 1983; Adhesion Science and Engineering – 2, Surfaces, Chemistry & Applications, Ed. M. Chaudhury & A. Pocius, Elsevier 2002. B) R. Dillingham, C. Moriarty, Journal of Adhesion 2003, 79(3), 269 – 285. 6- T.S.N. Sankara Narayanan, Rev. Adv. Mater. Sci. 9 (2005), 130 – 177

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29 Novel Raw Materials (I)

Pınar Çetin

Dow Corning Corporation Turkey

Education: 2006 – 2008 Koç University, Istanbul - M.S. in Material Science & Engineering 2001 – 2006 Boğaziçi University, Istanbul - B.S. in Chemistry 2004 – 2009 Eskişehir Anadolu University - B.S. in Business Administration

Experience: 2006 - 2008 Koç University - Teaching and Research Assistant 2008 – 2010 Eczacibasi Esan - Business Develop. Specialist since 2010 Dow Corning • Technical Development – 2010 - 2012 • Application Engineer and Technical Service – High Performance Building Solutions and Coatings – since 2012

30 IMPROVED INDUSTRIAL & PROTECTIVE COATINGS ENABLED BY SILOXANE RESINS

Pınar Çetin Dow Corning Corporation Turkey

Abstract Silicon-based technologies comprise a growing portion of modern coatings. Used solely, in simple cold-blend combinations, or copolymerized into organic hybrids, Silicon-based technologies are utilized as the primary binder in applications where for instance heat or/and UV resistance, flexibility, adhesion are required. 2K Epoxy-Amine systems are well- known in the Protective coating market; a new generation of amino functional Silicon-based materials is proposed to formulators, combining the reactivity of the amine and the benefits of siloxane. The siloxane backboned binder will be described as an impactful component on the final properties of the paint: heat and chemical resistance, flexibility, adhesion….. The effects of this material will be described through different examples and descriptions. Furthermore, siloxanes with substituents of other chemistries such as alkoxies are used in the heat resistance area, where different factors can impact the resistance of the coating.

31 IMPROVED INDUSTRIAL & PROTECTIVE COATINGS ENABLED BY SILOXANE RESINS

Silicones do have a general structure - fig.1 - that clearly shows the possibilities to create long/short, linear or tri-dimensional polymeric chains, with different organic substituents.

Figure 1. R1 and R2 can be: SiO, -NH2, -F, -Phe …..

When used as main (and only) binder in coatings, with 2 specific reactions, siloxanes can lead to durable film formation (fig.2). Films that were achieved can present excellent heat resistance, up to 650°C when combined with suitable pigments and fillers, but also UV resistance and water repellent character (Water Contact Angle >90°). Showing lower viscosities than organic binders, siloxanes binders allow lower VOC formulations.

Figure 2: Crosslinking reactions for siloxanes.

In parallel, siloxanes can be used as co-binders in hybrids (= organic+silicone systems), where both chemistries can bring their benefits. Amino-epoxy systems, commonly used on the market, can then be enhanced by the used of amino siloxanes – fig.3a and 3b -.

32 IMPROVED INDUSTRIAL & PROTECTIVE COATINGS ENABLED BY SILOXANE RESINS

Another application of siloxanes in coatings is the heat resistant paint market. When exposed to heat (>350°C), carbon-based polymers are completed oxidized (into CO2 and H2O), siloxanes binders will generate a silica layer (SiO2) and pigments around the substrate.

Domestic stoves are painted with Si-based coatings .

Finally, there is a growing trend pushing for waterborne systems; Siloxanes emulsions are available on the market and do lead to very elastomeric films at ambient temperature. These materials can be blended to organic systems (latexes) and will improve their end-properties: vapor permeability, flexibility,….

For each type of application, Si-based materials can bring a benefit to the coating. This no-so-new chemistry still remains an unknown area for a lot of formulating chemists, but their interest is growing!

33 Novel Raw Materials (I)

Tuğba Çifte

Yıldız Technical University Turkey

She was born in Istanbul in 1991. She graduated from Chemical Engineering Department -Yildiz Technical University in 2015. She has been studying in master of science about titled “Dyes in metal industry” in Yildiz Technical University. She has international articles on dyes.

34 OPTIMIZATION AND INVESTIGATION OF SOLVENT BASED PAINTS INCLUDING BORON CHEMICALS IN METAL INDUSTRY

Tuğba Çifte, Nil Acaralı, Abdullah Bilal Öztürk, Hediye İrem Özgündüz, Havva Gizem Kandılcı, Hanifi Saraç Yıldız Technical University Turkey Abstract From the perspective of Turkey’s geology, our country is very rich in terms of boron minerals. There are variety of boron minerals having different physical properties and chemical composition in Turkey (Kütahya, Eskişehir, Balıkesir, etc.). Nowadays, boron minerals are being used to improve flame retardant properties in different materials. Especially in recent years, there has been increasing demand for the use of paints that can provide some important features. These features are used in metal industry such as shipbuilding, automotive and aircraft industry for corrosion-resistance, flame retardance, high impact resistance and antibacterial protection. In this study, the received boron chemicals (boric acid, boron oxide) from various regions triturated certain size to fineness, in the specified different rates, a suitable polymeric binding in paint homogenization. After optimization studies, the most effective parameters were determined using the Taguchi method of experimental statistics. This method is expected to serve as an alternative to the conventional optimization method. Consequently, it was seen that corrosion resistance, flame retardance and hydrophobic feature were obtained by using boron chemicals, natural minerals and herbal resources in paints. As a result, the paints containing additives will be provided for use in a variety of metal industries.

Keywords: Taguchi, boron, paint, corrosion, hydrophobic

35 OPTIMIZATION AND INVESTIGATION OF SOLVENT BASED PAINTS INCLUDING BORON CHEMICALS IN METAL INDUSTRY

Introduction Turkey is one of the world’s leading countries with the quality of boron reserves and ore. Using flame retardant and smoke suppressant additive is expected in plastic, wood and textile products, paint and various construction materials for reducing life and property loss.

Our country is the global market leader in the production of boron chemicals in addition to having the highest quality boron source. An important issue that must be addressed to expand the applications of boron chemicals sector in order to contribute to the evaluation of these benefits.

Turkey, The United States and The Russian Federation are the countries that have the largest boron mineral reserves in the world. Turkey has 72% of the total boron reserves [1]. The boron are widely used in the industry for two main reasons. Firstly, boron is harmless. In normal conditions, borates have not toxic effects on nature, people or others. In recent years the harmful effects of boron are mentioned but it could not be substantiated in anyway. The second reason is that the boron is useful in terms of environmental health and safety advantages.

In the literature, there are studies for conventional paints including various additives. Different from literature, Taguchi method was used to improve quality and to provide low cost.

Taguchi method, based on the partial factorial experimental design methods, robust design with orthogonal arrays and experimental design method, is based on the principles of quality development [2]. Taguchi provides an opportunity to select an appropriate level orthogonal array, depending on the number of them. The benefit of using a fractional factorial approach is radically to reduce the number of experiments [3].

In one study, Ökenek (2013) studied some alkaline borate compounds (calcium metaborate, potassium metaborate and sodium tetraborate) during the formulation of the acrylic paint as physical [4]. Kayran (2013) focused on the manufacture of paint containing zinc borate in different combinations. As a result of tests (LOI, smoke density, etc.), paint additives added have already been shown to affect in a positive way [5].

In another study, Yıldırım (2013) examined the flame retardant properties of the plastic coating materials [6]. Within this context, the environment-friendly paint materials (halogen-free), boric acid compounds etc. are used by adding different amounts of composite materials. The purpose of these studies were also made of composite materials with flame retardant properties to determine the candle flame test. Tests showed excellent flame retardant properties. Karakas et al. (2011) provided significant fire retardant properties by using water-based paints containing colemanite [7].

Durgun (2010) investigated characterization of synthetic calcium borate compounds and the effects of flame retardation properties in laboratory conditions [8].

36 OPTIMIZATION AND INVESTIGATION OF SOLVENT BASED PAINTS INCLUDING BORON CHEMICALS IN METAL INDUSTRY

In this study, pumice, lady’s mantle and various boron minerals were added in solvent based paints. Optimum parameters were determined according to the Taguchi method. Consequently, it was seen that corrosion resistance, hydrophobicity and flame retardation tests showed the positive results to evaluate the paints in metal industry.

Experimental Materials Solvent based paints, Al plates, pumice, lady’s mantle and boron minerals (boron oxide, boric acid) were provided from Kayalar Chemistry, YTU-Workshop, YTU-Civil Engineering Department, Herbalist and Eti Mine Works, respectively. Methods The paint, pumice, lady’s mantle, boron chemicals were homogenized by using mechanical stirrer (Fig. 1). The paint with the additives was stirred at 1000 rpm for 3 minutes. Zebra papers (the surface chequered with black and white colours) were used for the visual test. According to Taguchi method a specially constructed aluminum plates were prepared as 2 sets for paint application. These sets are given in the following tables (Table 1, Table 2).

Figure 2: Mechanical stirrer

Pumice Lady’s mantle Boron oxide Pumice Lady’s mantle Boric acid 1 1 1 1 1’ 1 1 1 2 1 2 2 2’ 1 2 2 3 1 3 3 3’ 1 3 3 4 2 1 2 4’ 2 1 2 5 2 2 3 5’ 2 2 3 6 2 3 1 6’ 2 3 1 7 3 1 3 7’ 3 1 3 8 3 2 1 8’ 3 2 1 9 3 3 2 9’ 3 3 2 10 1 1 3 10’ 1 1 3 11 1 3 1 11’ 1 3 1 12 3 1 1 12’ 3 1 1 Table 1. First Paint Set Prepared by Taguchi Method Table 2. Second Paint Set Prepared by Taguchi Method

37 OPTIMIZATION AND INVESTIGATION OF SOLVENT BASED PAINTS INCLUDING BORON CHEMICALS IN METAL INDUSTRY

The first set is for the lady’s mantle, pumice [9], and boron oxide; the second set is for the lady’s mantle, pumice, boric acid according to Taguchi method’s certain proportions. The paints were applied on different plates by using applicator.

Results and Discussion Taguchi method The Taguchi method [10] is the conventional approach used in off-line quality control. However, most previous Taguchi method applications have dealt only with a single-response problem. The multi-response problem has received only limited attention. Proposes an effective procedure on the basis of the quality loss of each response so as to achieve the optimization on multi- response problems in the Taguchi method [11]. In this study, Taguchi method was performed for 3 parameters and 3 levels at 9 different experiments. As a result of Taguchi Method, optimum experimental paint mixtures were obtained as 5 and 5’ samples (Fig. 2, Fig. 3).

Figure 2: S/N ratios for set 1

38 OPTIMIZATION AND INVESTIGATION OF SOLVENT BASED PAINTS INCLUDING BORON CHEMICALS IN METAL INDUSTRY

Figure 3: S/N ratios for set 2

Visual Tests Hydrophobicity Wettability is an important property of solid surfaces from both fundamental and practical aspects. Given the limited contact area between solid surface and water, chemical reactions or bonding formation through water are limited on a superhydrophobic surface. Hydrophobic material was added to solvent-based paint content. Water was dropped on the dry coating film a period of time as a volume of 0,1 ml pipette. As a result, surface was hydrophobic in the dry paint film (Fig. 4).

Figure 4: Hydrophobicity test

39 OPTIMIZATION AND INVESTIGATION OF SOLVENT BASED PAINTS INCLUDING BORON CHEMICALS IN METAL INDUSTRY

Corrosion Samples prepared for corrosion testing in 5% NaCl solution were waited for 3 hours. Consequently, Any deformation was not seen on plates (Fig. 5).

Figure 5: Corrosion test Flame Retardation Ash oven was used to determine ash percentage by burning sample and obtain raw quality and to analyze the resistance of the sample to temperatures. At 375°C, the color of paint applied to the plates changed by bringing blackening. Optimum flame retardation value was 375°C (Fig. 6, 7).

Figure 6: Samples before ash oven test

40 OPTIMIZATION AND INVESTIGATION OF SOLVENT BASED PAINTS INCLUDING BORON CHEMICALS IN METAL INDUSTRY

Figure 7: Samples after 375°C

Conclusion In this study, the physical properties of the paints containing pumice, lady’s mantle, boron oxide and/or boric acid were investigated in detail. As a result, it was seen that corrosion, hydrophobicity and flame retardation tests showed positive results to evaluate the paints in metal applications and industry. Acknowledgement We thank for the contributions of Kayalar Chemistry and Tubitak Project-2209B (2241A) Industry Oriented Support Program.

References 1- Yenmez, N., (2009), The Importance of Boron Minerals in Turkey as a Strategic Mine, Istanbul University Geography Journal, 19, 59-94. 2 - Bayrak, Z., (1996), Applying Taguchi Method in the Sield of Practising Quality Control, Master Thesis, Kocaeli University, Kocaeli. 3- Canıyılmaz, E., (2001), Taguchi Method in Quality Improving and an Application, Master Thesis, Gazi University, Ankara. 4- Okenek, F., (2013), Investigation of Flame Retardant Feature of Alkaline- Alkaline/Earth, Borates Additives in Water Based-Styrene Acrylic Paints, Master Thesis, Gazi University, Ankara. 5- Kayran, B., (2013), Flame Retardant, Smoke Suppression and Antibacterial Efficiencies of Zinc Borates Additives at the Water Based-Styrene Acrylic Paints, Master Thesis, Gazi University, Ankara. 6- Yıldırım, S. (2013), Production and Industrial Application of Nanostructured Flame Retardant Reinforced Composite Materials, Master Thesis, Dokuz Eylül University, Izmir. 7- Karakas, F., Çelik, İ.Y., Çelik, M.S., (2011), Use of Colemanite as an Extender in Architectural Waterborne Paints, International Symposium on Boron, Borides and Related Materials, Istanbul, Turkey, September 11-17. 8- Durgun, Z.G., (2010), Synthesis of Various Calcium Borates Characterization and Investigation of Flame Retardant Efficiencies, Master Thesis, Ankara University, Ankara. 9- Oz, E., (2007), Avaliability of Acidic Light Pumice as Concrete Aggregate around Nevsehir, Master Thesis, Cukurova University, Adana. 10- Tong, L.I., Su, C.T., Wang, C.H., (1997), The Optimization of Multi-Response Problems in the Taguchi Method, Int. J. Qual. Reliab. Manage., 14(4), 367–380. 11- Gures, S., Baran Acaralı, N., Kandilci, H.G., Ozgunduz, H.İ., Yıldırım, F., Bayram, M., Vergül, H., Sarac, H., Investigation of Parameters Affecting Thermal Insulation for Decorative Insulated Interior Paint, PaintIstanbul 2014, Istanbul-Turkey.

Functional Coatings (I)

Prof. Dr. Güngör Gündüz Middle East Technical University (METU) Turkey

Experience: 1975-present: METU, teaching, academic advising 1975-1976: Anadolu University, part time, teaching 1976-1977: Gazi University, part time, teaching 1982-1983: Teaching in Center for Nuclear Studies, Memphis State University, Memphis, Tennessee, USA 2002-2003: Teaching in Materials Science and Engineering Department, Iowa State University, USA, teaching, research

Referral Work: Chimica Acta Turcica, Cement & Concrete World, Journal of Aplied Polymer Science, Industrial Crops and Products, Journal of Mathematical Sociology, Sociological Theory, Physica A, Physica D, Physics Letters A, Materials Letters, J. Nanoscience and Nanotechnology, Journal of Composite Materials, Polymer Engineering & Science, Materials Chemistry and Physics

Fields Of Research Past : Neutron activation analysis, Plasma turbulence, Polymer-concrete composite materials, Nuclear shielding materials, Steel-fiber reinforced polymer concrete composites, Food irradiation, In-core fuel management in nuclear reactors, Phenol - formaldehyde resins, Flame retardant polymers, Polymer composites, Nuclear fuels

Present (last ten years): Mechanical properties of polymers, Advanced ceramics (CVD and plasma assisted CVD), Polymer chain statistics, Flame retardant paints, Water dispersed paints, Carbon nanotubes, Dendritic and hyperbranched polymers, Polymeric & ceramic nanofibers (electrospinning technique), Functional polymers, Functionalized nano materials with inorganic core, Nano composites, Zirconium tungstate composites with tuned thermal expansion, Patterns and fractals, Production of nanocables, Special effect pigments, Modeling of evolutionary network relations (such as wars, financial markets, music) by physical concepts and laws.

42 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

Prof. Dr. Güngör Gündüz Middle East Technical University (METU) Turkey

Abstract Nano-sized materials usually have finite geometries or shapes which offer a specific chemical potential associated with that geometry. Nano-sized materials usually have rigid structures such that their shape and the associated chemical potential do not change, and thus they function properly. It is possible to make appropriate changes on the shape and tune the function of the nano material. In other words, in nano materials the chemical potential is well stabilized against the changes in the medium, and thus the property associated with it is always well-defined, and such a material is said to have “functionality”. The nano materials are important not because they are small size materials but they usually perform specific jobs. Any functionality actually represents a kind of “information”. The smart materials which perform specific duties, when produced at nano size, are said to be nano-sized smart materials.

The use of nano-materials in coatings can result in crucial new developments in achieving special properties and making functional coatings. Special effect pigments, opaque hollow polymer pigments, and self-cleaning coatings have nano sized structures.

Such materials have already been in use in improving adhesive, cohesive, and surface properties, and a greater number of special purpose paints will be available in the market in near future. For instance, effect pigments are actually nano-pigments and are in use since last two decades. The use of nano-sized resins such as dendrimer/hyperbranched polymers can introduce much better solution to solvent-free coatings.

Keywords: Nano material, functionality, surface coating, resin, pigments, smart paint,

43 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

1- Introduction Nano materials are used in paint technology for different purposes, as to modify paint properties, filling materials, to create special structures such as the use of surfactants in making emulsions, but especially to produce functional coatings and smart materials. Nano-sized additives in paint like nano-silica, nano-clay, nano-zinc, nano-alumina, carbon nano-tubes, etc. increase glass transition temperature, modulus, tensile strength, elongation at break, hardness, adhesion, scratch resistance, toughness, and the resistance to water penetration. There are also some other important outcomes of using nano materials. For instance, if the size of an emulsion droplet is reduced to nano size, uniform particle size and structure are obtained. Boehmite, silica, titania nanoparticles function as a kind of reservoir for the corrosion inhibitors. Nano zinc oxide absorbs UV light effectively and it can be added even to varnishes since it is transparent at nano size. Nano materials are successfully used in making effect pigments, opaque hollow pigments, self-cleaning coatings, self-healing coatings, and low viscosity resins.

The physical and chemical properties of materials highly depend on the chemical structures or the chemical potentials of the reactant materials, and on the macro structure such as the cohesiveness of the material, the pores formed, and the interactions between different phases, namely, as resin-pigment interactions. The cohesiveness of the paint affects the strength and the duration, whereas weak cohesion increases the adhesion of the coating film onto the surface of the substrate. However, the color of the pigments is not affected from the cohesion in the polymer phase.This is because, color originates from the chromophores which absorb certain frequencies of visible light at atomic scale. For instance, consider the following pigments of different colors.

Toluidine red Maroon

Isoindoline Copper phthalocyanine

44 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

where chromophores like >N=N<, >C=O, and create the color. Most organic pigments have aromatic structure which introduces molecular stability so that the type of the color does not change under an external stimulus such as temperature. In fact, different shades of color are usually obtained by changing the substituents in the periphery of the organic molecule. In the In the case of phthalocyanines, the type of the metal at the center determines the color. For instance, the blue color of copper phthalocyanine turns into green on substitution of copper by zinc [1].

In coating industry nano materials with sheetlike structures are used quite often to modify the properties of paints or to make pigments. Mica, sheet-like alumina (boehmite), synthetic symectite, and organo modified montmorillonite which have sheetlike structures are used as additives, and also in making effect pigments. Graphene which has mono-layered sheet structure is expected to find important applications in coating technology probably in conductive surface coatings.

Nano materials which have other shapes also find large applications in surface coating. For instance, surface modified fullerenes or carbon nano tubes can be incorporated into coating materials.

2. Nano-Size Structured Pigments 2.1 Pearlescent Effect Pigments: These pigments are manufactured by coating inorganic flakes having nano thickness such as mica, alumina, and glass flakes by a compound with high refractive index such as titania [1-6]. Light beam incident on the surface of titania is partly reflected and partly refracted. The refracted component is reflected back from the surface of mica and interferes with the reflected light from the surface of titania leading to constructive interference. Therefore, the light emitted becomes enhanced in intensity, and it becomes very bright. To influence the color other metal oxides also may be deposited on mica. By changing the thickness of the coated layer one may obtain different colors. The following colors are revealed with the change of thickness when (i) titania, and (ii) magnetite is coated on mica [7].

The use of mixed oxides in the coating layer gives further varieties and more enhanced colors. For example, coprecipitation of cobalt oxide with titania produce pearlescent blue and violet colors, whereas, magnetite produces gold color [8]. Depending on the angle of view, the pigment may have one or two colors.

Mica-titania pigments have excellent thermal stability up to 800oC. In addition, they have very high chemical stability against acidic or alkali media. However, it is usually difficult to obtain large variety of colors by using inorganic ingredients. They usually have different coprecipitation behavior and also different calcination/sintering temperatures, and it becomes a hard work to get the right color. Instead, working with organic pigments offers large variety of colors if they could be adhered on the surface of titania. It was shown that copper phthalocyanine can be successfully deposited on mica-titania to produce combination pigment [9]. Copper phthalocyanine can be deposited at varying temperatures between 25 to 125°C, and the size of crystals form on the surface of titania increases with deposition temperature.

45 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

In Fig.1, the micrograph on the left shows copper phthalocyanine crystals deposited on mica-titania, and the diagram on the right shows the L*a*b* value of different copper phthalocyanine coated samples compared onto mica-titania. The symbol such as CuPhM005 means “copper phthalocyanine deposited onto mica-titania pigment containing 0.005 g copper phthalocyanine and ‘0.3 g mica-titania+10 ml DMF in the medium’. The darkest blue color is achieved with CuPhM010, and it does change at CuPhM020, but further increase to CuPhM040 shifts the color to red region.

The luminescence properties of mica-titania pigments can be further improved by coating the titania surface with fluorescent compounds. For instance, zinc phthalocyanine is a fluorescent molecule and can be deposited on mica-titania to produce fluorescent mica-titania pigment.

Figure 1: Left: copper phthalocyanine crystals on mica-titania effect pigment. right: the comparative color properties of combination pigments based on different amounts of copper phthalocyanine deposition.

2.2 Hollow Polymer Pigments: Hollow polymer pigments are new pigments with an opaque appearance, and they are obtained from transparent polymers. Hollow polymers have core-shell structure with the polymer as the shell and the void as the core. The size of the void must be at submicron level so that it matches the wavelength range of visible light. The incident light is refracted at the shell, it propagates in the void, and it is refracted once more when leaving the void. The diffracted diffuse light waves interfere with each other and give opaque white color [10-12].

The well known procedure is first to prepare seed from the mixture of methyl methacrylate (MMA), methacrylic acid (MA) and dimethacrylate at appropriate proportions by emulsion polymerization. It is mixed with MMA, MA, and the butyl acrylate, and copolymerized. Styrene and divinyl benzene are copolymerized to make the shell. The MA is neutralized with an alkali, which, in turn, causes osmotic swelling of the core, and thus void is created.

46 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

Figure 2: The SEM and TEM micrographs of single-hollow polymer pigment [13].

Figure 2 shows the SEM and TEM micrographs of single-hollow polymer pigments created by this procedure. The polymer pigments thus obtained having a particle size of 350 nm particle depicted 93.8% opacity that of titania.

Multi-hollow polymer pigment particles can have quite high opacity due to a cascade of scatterings inside several hollows. It naturally increases the extent of diffractions in the pigment. The multi-hollow particles can be produced by multi-emulsion technique. In this procedure, usually water is dispersed in monomer forming a water-in-oil (W/O) system. It is then dispersed in water by agitation or sonication to form a complex water-in-oil-in-water (W/O/W) system. It is of primary importance to attain stability in a double emulsion system (i.e. W/O/W), otherwise they can easily break down [14-17].

The W/O phase can be prepared by using the monomers MMA and ethylene glycol dimethacrylate (EGDM) in equal amounts, and also a radical initiator such as 2,2’ azobisisobutyronitrile. As surfactant ‘Span 80 + Tween 80’ can be used, and their ratio is adjusted to have an HLB (Hydrophilic-Lipophilic-Balance) value appropriate for making the emulsion. After sonication another surfactant solution such as Triton-X 405 is added and stirred mechanically for 3 min. The W/O/W system thus formed is stabilized with 1% solution of poly(vinyl pyrrolidone) and then polymerized at 55oC.

The TEM micrograph of multi-hollow polymer pigment is shown in Fig.3. A relatively larger picture is given on the left on-site at the bottom where five hollows can be identified. It is possible to get opacity as high as 96.1% that of titania. The hollows in a multi-hollow system are not of same size, and the process parameters as well as the chemicals used determine the average size and the size distribution. If the stability of the W/O/W can not be well accomplished it is likely to have mostly single-hollow particles [18].

47 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

Figure 3: Multi-hollow polymer pigment particles.

2.3 Self-Cleaning Pigments: Self-cleaning is important not only in coatings but also in windshields of vehicles, window glasses, all kinds of walls, and textiles. Self-cleaning can be achieved by either chemical or physical means. Chemical method depends on the degradation of organic materials by the photocatalytic activity of UV radiation which is a part of solar radiation. The photocatalytic activity is revealed by using a semiconductive material which creates electron-hole pair when illuminated. The most widely used semiconductor is the anatase form of titania. The photocatalytic activity depends on particle size, surface area, and the method of preparation, and high performance is achieved with nano-sized particles. The activity is improved by doping titania with silver, and it can be incorporated into the structure during sol-gel synthesis [19]. The cations with higher oxidation states than that of titania (e.g. Ti+4) like Mo5+, Nb5+, and W6+ increase the photocatalytic activity whereas the ones with lower oxidation states like Fe3+, Co2+ and Ni2+ reduce it [20].

Superhydrophobic materials also can keep coatings clean as any foreign material cannot adhere onto the surface. Such materials were prepared by mimicking the structure of Lotus leaf which has very high super hydrophobicity. It has micropapillae of 3–10 μm long and epicuticular waxy material covering the whole surface with the dimension of around 120 nm. Water droplet touches the tips of micropapillae where there exists the waxy material. When the surface is tilted very slightly just few degrees the water droplet rolls down and sweeps away the dust or dirt. Micro- and nano-silica particles are quite often used to produce Lotus-effect coating, and it is possible to achieve a contact angle of 165o and sliding angle of 2.5°. There are a variety of materials and processes to make super hydrophobic materials [21]. Fluoro and silanol functionalized polyhedral oligomeric silsesquioxane (POSS) draws significant attention in recent years. After creating micrometric roughness by silica or some other materials, the second layer is produced by silicones and fluorocarbons. Silanes can be directly incorporated the polymers to improve hydrophobicity and to get

48 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

better corrosion protection [22]. A sol solution having water, methanol, and methyltriethoxysilane gives a hydrophobic coating with the water contact angle of 155° and sliding angle of 7° [23].

2.3 Self-Healing Coatings: Self-healing coatings are of great importance in coating technology as they have extended lifetime by repairing themselves. They are smart coatings and respond whenever the damage occurs at the film. Smart materials react to an external stimulus which can be temperature, pressure, pH, or electrical field, and the piezoelectric, photochromic, thermochromic, electrochromic, and shape memory materials are classified as smart materials.

In self-healing coatings an anticorrosive agent or healing agent can be microencapsulated by emulsion techniques and then mixed with the coating [24-26]. The capsules act as a kind of micro- or nano-tank, and any crack propagating in the film raptures the capsules and the released healing agent fills the gap created. Linseed oil is the most extensively used material for self-healing as it dries in atmospheric conditions upon exposure to air, but urethanes and epoxies also can be used for this purpose [27-31].

Nano containers which have a kind of core-shell structure containing anticorrosive agents in the core can be used in the primers [32]. It is also possible to hold the anticorrosive agent like benzotriazole in a sol-gel protective coating. However, in such systems activity of the anticorrosive agents may reduce in time, so nano tanks are more efficient than such systems [33, 34].

3. Hyperbranched Polymers The polymers or resins are the vehicles which carry all the ingredients, but in order to disperse them uniformly the polymer chains must surround all the materials. This is well accomplished by using a solvent which dissolves the polymer chains and provides a homogeneous mixing of all the ingredients. However, organic solvents are not desired due to environmental considerations, and there are strict regulations set down by the governments on solvent-based surface coating materials. The widespread solution to this problem was to develop water-based paints but they usually did not meet the high quality of solvent-based paints. Anyway, water-based paints were well accepted and they have been in use for decades. In both solvent based and water-based paints about one third of the material which is solvent or water goes off after application. So, it is actually an inefficient way of consuming paints. Solvent- or water-free surface coatings such as powder coating and UV coating protective systems find an increasing trend of acceptance, but they have some other problems. Powder coating needs special devices such as corona-charged and tribo-charged systems, and curing is needed at high temperatures. In addition sharp geometrical shapes may not be effectively coated, and usually small size items are preferred in powder coating. UV curing also needs special instrumentation and application unit. Its main advantage is that monomers and oligomers are used in coating, but the curing unit cannot be very large, and usually small items are coated.

A different class of polymers so-called dendrimers or hyperbranched polymers can introduce significant change of the vehicle used traditionally. Such polymers have already been in use in coating technology as raw materials to synthesize oligomeric or nano sized additive materials. They can also be used as vehicle in coating technology.

49 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

Hyperbranched resins which are expected to look similar in properties to the alkyd resins can be synthesized starting with a polyol such as dipentaerythritol as the core molecule. It can be esterified with dimethylol propionic acid (DMPA) by using p-toluene sulfonic acid as catalyst to second or third order generations. A second order generation is usually sufficient to synthesis resins with low viscosity.

Then it is esterified with fatty acids. The fatty acid composition can be adjusted on purpose. Linseed oil fatty acids impart high unsaturation but usually give dark color. So they can be mixed with the sun flower oil fatty acids or whatever is desired. The use of castor oil fatty acids which have around 85% ricinoleic acid introduces hydroxyl groups into the structure. A typical structure of a hyperbranched polymer synthesized using linseed oil and castor oil fatty acids, is shown below. This type of hyperbranched polymer can be used in making new products by blending with other polymers [35, 36].

The core can be made from other chemicals also, for instance like hexamethylol melamine. It can also be reacted with DMPA and fatty acids to obtain different products [37].

50 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

The core can be made from other chemicals also, for instance like hexamethylol melamine. It can also be reacted with DMPA and fatty acids to obtain different products [37].

It can be dried by adding driers, preferably at an elevated temperature, or it can be hardened under UV radiation since there in an intense unsaturation on the molecule. Figure 4 shows two different curing, one at an elevated temperature, and the other under UV curing.

Figure 4: left: cured at 120°C, right: cured under UV radiation [37].

UV curing resulted in extensive wrinkling, and it may be used in decorative coatings.

4. Conclusions The use of nano materials in coating technology covers a very wide range of applications. Nano-sized materials find applications in pigments, additives, polymers and resins, and property modifying agents. The main purpose of using nano materials is to introduce a kind of new function to the already existing form, or to produce new products with new functionalities so that a new performance is accomplished. In this respect nano materials contain new information originating from their shape. In future, it is possible to develop coatings with more complex structures having higher number of functionalities.

51 THE CURRENT USE AND THE FUTURE PROSPECTS OF NANO-SIZED MATERIALS IN SURFACE COATINGS

References 1. G. Gündüz, Chemistry, Materials, and Properties of Surface Coatings, DEStech publications, Inc., 2015. 2. H. Giesche and J. Disper. Sci. Technol., 19 (1998) 249–265. 3. A.N. Alexandrova and W.L. Jorgensen, J. Phys. Chem. B, 111 (2007) 720–730. 4. N. Bayat, S. Baghshahi, and P. Alizadeh, Ceram. Int., 34, (2008) 2029–2035. 5. C. Çağlar, Yüksek Lisans Tezi, Anadolu Üniversitesi, 2004. 6. B.B. Topuz, G. Gündüz, B. Mavis, and Ü. Çolak, Dyes Pigments, 90 (2011) 123–128. 7. G. Pfaff, Special Effect Pigments, Vincentz Network, 2008. 8. C. Jing and S.X. Hanbing, Dyes Pigments, 75 (2007) 766–769. 9. B.B. Topuz, G. Gündüz, B. Mavis, and Ü. Çolak, Dyes Pigments, 96 (2013) 31–37. 10. R.E. Harren, J. Coat. Technol. Res., 55(707) (1983) 79–81. 11. D.M. Fasano, J. Coat. Technol. Res., 59 (1987) 109–116. 12. M. Peng, H. Wang, and Y. Chen, Mater. Lett., 62(10-11) (2008) 1535–1538. 13. E. Karakaya, M.Sc. Thesis, Middle East Technical University, Ankara, 2013. 14. C.J. McDonald and M.J. Devon, Adv. Colloid. Interfac., 99(3) (2002) 181–213. 15. T. Schmidts, D. Dobler, C. Nissing, and F. Runkel, Journal of Colloid and Interface Science, 338 (2009) 184–192. 16. J. Jiao and D.J. Burgess, Multiple Emulsion Stability: Pressure Balance and Interfacial Film Strength, in Multiple Emulsions, ed.: A. Aserin, John Wiley & Sons Inc., 2007, p. 1–27. 17. D. Myers, Emulsions, in Surfactant Science and Technology, ed.: D. Myers, John Wiley & Sons Inc., 2005, p. 280–322. 18. S. Asmaoğlu, M.Sc. Thesis, Middle East Technical University, Ankara, 2012. 19. T. Zhang, L. You, and Y. Zhang, Dyes Pigments, 68 (2006) 95–100. 20. I.P. Parkin and R.G. Palgrave, J. Mater. Chem., 15 (2005) 1689–1695. 21. V.A. Ganesh, H.K. Raut, A.S. Nair, and S. Ramakrishna, J. Mater. Chem., 21 (2011) 16304–16322. 22. M.R. Bagherzadeh, A. Daneshvar, and H. Shariatpanahi, Surf. Coat. Tech., 206 (2012) 2057–2063. 23. A.V. Rao, S.S. Latthe, S.A. Mahadik, and C. Kappenstein, Appl. Surf. Sci., 257 (2011). 24. R.A.T.M Benthem, W.M. Ming, and G.B. de With, Self Healing Polymer Coatings, in Self Healing Materials, An Alternative Approach to 20 Centuries of Materials Science, ed.: S.van der Zwaag, Springer, 2007. 25. 110. T. Szabó, L.M. Nagy, J. Bognár, L. Nyikos, and J. Telegdi, Prog. Org. Coat., 72 (2011) 52–57. 26. D.S. Xiao, Y.C. Yuan, M.Z. Rong, and M.Q. Zhang, Polymer, 50 (2009) 2967–2975. 27. M. Huang and J. Yang, J. Mater. Chem., 21 (2011) 11123–11130. 28. T. Nesterova, K.D. Johansen, and S. Kiil, Prog. Org. Coat., 70 (2011) 342–352. 29. S.H. Boura, M. Peikari, A. Ashrafi, and M. Samadzadeh, Prog. Org. Coat., 75 (2012) 292–300. 30. N. Selvakumar, K. Jeyasubramanian, and R. Sharmila, Prog. Org. Coat., 74 (2012) 461–469. 31. A. Pilbáth, T. Szabó, J. Telegdi, and L. Nyikos, Prog. Org. Coat., 75 (2012) 480–485. 32. N.K. Mehta and M.N. Bogere, Prog. Org. Coat., 64 (2009) 419–428. 33. S.V. Lamaka, M.L. Zheludkevich, K.A. Yasakau, R. Serra, S.K. Poznyak, and M.G.S. Ferreira, Prog. Org. Coat., 127–135. 34. M.L. Zheludkevich, D.G. Shchukin, K.A. Yasakau, H. Möhwald, and M.G.S. Ferreira, Chem. Mater. 19 (2007) 402–411. 35. E. Bat, G. Gündüz, D. Kısakürek, and İ.M. Akhmedov, Prog. Org. Coat., 55 (2006) 330-336. 36. Karakaya C., G. Gündüz, L. Aras, and İ.A. Mecidoğlu, Prog. Org. Coat., 59 (2007) 265-273. 37. N. Keskin, M.Sc. Thesis, Middle East Technical University, Ankara, 2011.

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53 Functional Coatings (I)

Prof. Dr. H. Yıldırım Erbil

Gebze Technical University Turkey

Education: BSc. and MSc. in Chemical Engineering (1972-1977) Istanbul University, Turkey. MSc. in Chemistry & Technology of Polymers (1977-1978) The University of Aston in Birmingham, U.K. Ph. D. in Physical Chemistry (1982-1985) Istanbul Technical University, Turkey

Professional Experience: A) Academic History: 1979-1988: Researcher in TUBITAK (Turkish National Science and Technology Research Council) 1992-1998: Senior Researcher and Research Advisor in TUBITAK. 1998-2004: Professor of Physical Chemistry in Kocaeli University, Faculty of Sciences and Arts, Department of Chemistry. 2004-2005: Professor in Gebze Institute of Technology, Faculty of Engineering, Department of Energy Systems Engineering. 2005-...... : Professor in Gebze Institute of Technology, Faculty of Engineering, Department of Chemical Engineering. B) Work History: 1975 (2 months): Training Engineering Student, Textile Dyeing Division, BAYER A.G., Leverkuzen, Germany. 1979 (5 months): Project Engineer for Low Density Polyethylene Plant, PETKIM Petrochemicals, Turkey. 1979 - 1985: Assistant Research Scientist, Marmara Research Center, TUBITAK, Turkey. 1985 - 1988: Research Scientist, TUBITAK, Turkey. 1988 - 1992: Research Director and Consultant: TUT Adhesives Co., ENYAP Adhesives Co., Gumussuyu Carpets Co., Turkey. 1992 - 1998: Part Time Senior Research Scientist, Marmara Research Center, TUBITAK and Part time Consultant to Turkish Private Sector, Turkey. 1998 - 2004 : Professor of Physical Chemistry, Kocaeli University, Faculty of Sciences and Arts, Department of Chemistry, Izmit, Kocaeli, Turkey. 2004-2005: Professor in Gebze Institute of Technology, Faculty of Engineering, Department of Energy Systems Engineering. 2005-...... : Professor in Gebze Institute of Technology, Faculty of Engineering, Department of Chemical Engineering.

54 MIMICKING FROM NATURE: SYNTHESIS OF SUPERHYDROPHOBIC AND SUPEROLEPHOBIC COATINGS

Prof. Dr. H. Yıldırım Erbil Gebze Technical University Turkey

Mimicking from nature is an useful method to develop novel materials such as superhydrophobic (water repellent) surfaces having water contact angles larger than 150o with a very small tilt angle (less than 5o). Water droplets roll off from these surfaces while removing dust and other materials.1 Similarly, superoleophobic (oil repellent) surfaces are designed to remove hydrocarbons and oils from surfaces. Micro-rough surfaces coated by materials having low surface free energy can show superhydrophobic property. Silicone or fluorine containing polymers and other chemicals are such kind of materials. Lotus leaves, butterfly wings and duck feathers are the examples showing this property in the nature. Superhydrophobic surfaces could be synthesized from expensive materials by time consuming methods after 1999, however it was shown that a cheap commercial polymer such as polypropylene can be used for this purpose by the application of a phase separation process in 2003.2 This method was applied to 1200 different polymers afterwards. On the other hand, the manufacture of superoleophobic surfaces is more difficult because the surface tension of oils and hydrocarbons (20-25 mN/m) are much smaller than the surface tension of water (72.8 mN/m).3-6 The synthesis conditions and characterization methods for superhydrophobic and superoleophobic surfaces, as well as

their new application fields in industry will be discussed in this presentation.3-8

References: 1- Surface Chemistry of Solid and Liquid Interfaces, H. Y. Erbil, Blackwell Publishing, Oxford, UK, 2006. 2- Transformation of a Simple Plastic into a Super-Hydrophobic Surface, H. Y. Erbil, A. L. Demirel, Y. Avci and O. Mert, Science, 299, 1377-1380 (2003). 3- Progess in superhydrophobic surface development, P. Roach, N. J. Shirtcliffe and M. I. Newton, Soft Matter, 4, 224–240 (2008). 4- Design principles for superamphiphobic surfaces, H.J. Butt, C.Semprebon, P. Papadopoulos, D. Vollmer, M. Brinkmann, M. Ciccotti, Soft Matter, 9, 418–428 (2013). 5- Superamphiphobic surfaces, Zonglin Chu and Stefan Seeger, Chem. Soc. Rev., 43, 2784 (2014) 6- “Rubbery superhydrophobic and oleophobic surfaces” S. Ozbay and H. Y. Erbil, accepted by Colloids and Surfaces A, April, 2015. 7- “Range of Applicability of the Wenzel and Cassie-Baxter Equations for Superhydrophobic Surfaces”, H. Y. Erbil and C. E. Cansoy, Langmuir, 25, (24), 14135-14145, (2009). 8- The debate on the dependence of apparent contact angles on drop contact area or 3-phase contact line: A review”, H. Y. Erbil, Surface Science Reports, 69, 325-365, (2014).

55 Novel Raw Materials (II)

Prof. Dr. Yusuf Ziya Menceloğlu Sabanci University Turkey

2000 - present : Professor of Materials Science and Engineering, Sabanci University 1994 - 2000 : Various positions including product manager, R&D manager and deputy general manager (technical), GEMSAN (Genel Endustri Maddeleri Sanayi A. S.) Istanbul, Turkey 1991 - 1994 : Post doctoral research associate; Chem. and Mat. Sci., Univ. of North Carolina, Chapel Hill NC/USA Education: PhD in Polymer Chemistry Department at Istanbul Technical University, 1991 MSc in Polymer Chemistry Department at Istanbul Technical University, 1987 BSc in Chemistry Department at Karadeniz Technical University, 1983

Research Areas: Polymer synthesis; characterization, modification and structure/property/application relationship, and polymerization kinetics; florinated polymers, oligomers and surfactants (synthesis and characterization); reactions and extractions in supercritical carbon dioxide; formulation of performance chemicals.

56 STIMULI RESPONSIVE POLYMERIC MATERIALS FOR ANTIFOULING APPLICATIONS

STIMULI RESPONSIVE POLYMERIC SYSTEMS FOR SMART COATING APPLICATIONS IN MARINE INDUSTRY

Prof. Dr. Yusuf Ziya Menceloğlu Sabancı University Turkey

Biofouling, which can be described as the colonization of marine organisms such as microorganisms, barnacles and seaweeds on submerged surfaces, is the fundamental problem in Marine industry since it causes to increased hydrodynamic drag resulting in significantly increased fuel consumption and greenhouse gas emissions. In antifouling applications, the challenge is to develop cost-effective design approaches rely on the eco- friendly materials that should be highly efficient in various types of organisms. From a physical point of view, the trend is moving towards to understand the fundamental driving forces that are able to eliminate surface interaction between microorganisms and surface. On this basis, rational design of stimuli responsive polymeric materials is the key concept towards solving this problem since it enables us to create complex molecular assemblies and interfaces that can be controlled by an external stimuli within desired time scales in various environmental conditions. The main objective of this study is to reconcile the key parameters in antifouling applications and the smart coating solutions offered by stimuli responsive materials. From this perspective, principles architectures and mechanisms will be reviewed in a comprehensive manner under the consideration of reconstructable surfaces and applications in Marine industry. Furthermore, the structure-property behavior of supramolecular assemblies in thin films, such as polymer brushes, and the stimuli responsive nanoparticles, such as core-shell particles, and the hybrid systems consisting of those polymers and particles will be discussed in detail. The concepts emphasized in this study will be helpful to introduce novel design strategies and bring new insights into the field of antifouling coatings that enables us to find out sustainable solutions for enviromental and economical concerns in Marine industry.

57 Novel Raw Materials (II)

Prof. Dr. Mas Subramanian Oregon State University USA

Professor Mas Subramanian received his PhD (1982) from Indian Institute of Technology, Madras, India. Subsequently, he was a NSF postdoctoral fellow at Texas A&M University. From 1984 to 2006 he was a scientist at DuPont Company. In 2006, he joined Oregon State University as a Milton Harris Endowed Chair Professor of Materials Chemistry. Professor Subramanian’s research focuses on discovering new inorganic solid state functional materials for emerging applications in electronics, energy conversion and environment. His discoveries were highlighted in several leading magazines/newspapers all over the world including The New York Times and National Geographic Magazine, Professor Subramanian has authored more than 300 publications and holds 54 US patents. Professor Subramanian has received several awards and honors for his outstanding contributions to science including Charles Pedersen Medal awarded by DuPont Company for Excellence in Scientific and Technical Achievement (2004) and F.A. Gilfillan Memorial Award from Oregon State University for Distinguished Scholarship in Science (2014).

58 NOVEL INORGANIC PIGMENTS BASED ON OXIDES WITH CHROMOPHORE IONS OCCUPYING TRIGONAL BIPYRAMIDAL COORDINATION

Prof. Dr. Mas Subramanian Oregon State University USA

Abstract The discovery of a brilliant-blue color upon the introduction of Mn3+ into the trigonal- bipyramidal (TBP) sites in hexagonal YInO3 has led to a search for other hosts for Mn3+ with TBP coordination. An obvious choice would be hexagonal YAlO3; however, Mn3+ substitutions into citrate-prepared YAlO3 have failed to produce the anticipated blue color due to the destruction of TBP sites caused by carbonate incorporation. Blue color is developed when Mn3+ is substituted into YbFe2O4-related layered oxides containing TBP coordination. We conclude that the resulting blue color is a consequence of both the crystal field splitting associated with the trigonal bipyramidal coordination and the short apical Mn-O bonds. Introducing chromophore ions other than or in addition to Mn3+ into the TBP sites in YInO3 can produce various colors from orange to purple. All indium-containing pigments show excellent near infrared reflectance comparable to that of commercial TiO2.

Keywords: Blue pigments, Mn-containing pigments, In-containing pigments, Trigonal bipyramidal coordination, Optical properties, Cool pigments *Corresponding author: mas.subramanian@ oregonstate.edu Introduction

From Egyptian blue (CaCuSi4O10) to Chinese Han blue (BaCuSi4O10), synthetic blue pigments have been known for thousands of years. Current commercial inorganic blue pigments, such as ultramarine (Na7Al6Si6O24S3), cobalt blue (CoAl2O4), Prussian blue (Fe4[Fe(CN)6]3) and

59 NOVEL INORGANIC PIGMENTS BASED ON OXIDES WITH CHROMOPHORE IONS OCCUPYING TRIGONAL BIPYRAMIDAL COORDINATION

azurite [Cu3(CO3)2(OH)2], all suffer from environmental and/ or durability issues. A serendipitous discovery in 2009 made by our research group at Oregon State University addressed all of those concerns.[1] While exploring a new class of manganese containing inorganic oxides for applications in electronics as magnetic capacitors, we discovered a surprisingly intense blue color when introducing Mn3+ into the trigonal bipyramidal (TBP) sites of hexagonal YInO3 (Fig. 1). Both end members, YInO3 and YMnO3, crystalize in an acentric hexagonal structure consisting of alternating layers of edge-shared YO6 octahedra and corner-shared MO5 (M = In, Mn) trigonal bipyramids (Fig.1). Despite the large size mismatch between In3+ and Mn3+ we were still able to prepare a complete YIn1-xMnxO3 solid solution. We attribute this complete miscibility to the similar In-O and Mn-O basal-plane distances in isostructural hexagonal YInO3 and YMnO3. The large size difference between In3+ and Mn3+ is manifested only in the apical distances. The crystal field splitting of the d-orbital energies in trigonal bipyramidal (TBP) coordination is shown in Figure 1. The e’ to a” energy excitation depends sensitively on the apical M-O bond length through its influence on the energy of the dz2 orbital (Fig.1).

This intense Mn-containing blue is the first new inorganic blue pigment in 200 years! It is safer to produce, much more durable, and more environmentally benign than any being used now or in the past. And it can survive at extraordinarily high temperatures and does not fade after a week in an acid bath. As an added bonus, this pigment shows the highest heat reflectance ever seen in a blue pigment (in near infrared region of the electromagnetic spectrum) and making it ideal for painting energy efficient roofs of buildings and cars.[2] In addition, it can function as a more effective UV stabilizers than the commercial cobalt blue to suppress photo-degradation of polymers and paints.[3] Dr. Philip Ball, a science writer who has written books on colors and pigments and a former consultant editor for Nature journal, categorized our blue pigment as the new “Blue Standard”.[4]

So far the “happy accident” of our new blue has led to discoveries of a “rainbow” of colors through rational design as shown in Figure 2. Starting from the hexagonal parent compound YInO3, substituting a small amount of iron for indium produces intense orange colors, replacing some or all indium with titanium and copper makes green colors and swapping some of the manganese in blue pigments with a combination of zinc and titanium gives violet to purple colors.[1,5-7] Most of these novel pigments show high durability and good heat reflecting properties similar to the Mn-containing blue pigments.

We have also demonstrated that a blue color can be obtained when Mn3+ is introduced into the TBP sites in layered oxides other than the hexagonal YInO3. When substituting Mn3+ into YbFe2O4-related oxides a blue or

Figure 2: A “rainbow” of colors are created through various substitutions into the TBP sites of the hexagonal YInO3. [6] 60 NOVEL INORGANIC PIGMENTS BASED ON OXIDES WITH CHROMOPHORE IONS OCCUPYING TRIGONAL BIPYRAMIDAL COORDINATION

bluish-purple color occurs for host materials such as LuGaMgO4.[8] Although Mn-substitution also produces a navy blue color in the hexagonal YAlO3, it is not as bright as the expected color associated with the TBP site.[9] We found that the centric hexagonal structure for YAlO3 reported in 1963 with Al in TBP coordination cannot be correct based on its unit cell dimensions and bond- valence sums.[10] Our studies indicate instead that all, or nearly all, of the Al in this compound has a coordination number of 6. The compound long assumed to be a hexagonal form of YAlO3 is actually an oxycarbonate with the ideal composition Y3Al3O8CO3. The absence of bright color is presumably due to the destruction of TBP sites in the presence of carbonate groups. Experimental Most of the polycrystalline samples were prepared by conventional solid state synthesis. The Fe- and Al-rich samples however were synthesized by a citrate route.[11] For solid state reactions, stoichiometric amounts of chemicals were weighed and thoroughly ground using an agate mortar and pestle. The mixed powders were pressed into pellets and calcined at 1000~1200°C for 12 hr in air, and then at 1050~1350°C for 12 hr once or twice with intermediate grinding. The Y2O3 and Lu2O3 were first heated at 850°C overnight to remove any moisture. For sol-gel synthesis, the procedure described in reference [11] was followed and amorphous precursors were heated at 750−930°C in air for 10−18 h. To obtain pure Al-rich phases, the precursor was placed in a preheated furnace (900~950°C) and quenched after heating for 20~30 min. X-ray powder diffraction patterns were obtained with a Rigaku MiniFlex II diffractometer using Cu Kα radiation. Powder neutron diffraction data were collected on the high-resolution diffractometer BT-1 at the Center for Neutron Research at the National Institute of Standards and Technology. Diffuse reflectance spectra of powdered samples were measured using a homemade UV-VIS spectrophotometer. Near-infrared reflectance (NIR) data were collected using a Jasco V-670 Spectrophotometer. Results And Discussion An entire solid solution of YIn1-xMnxO3 can be made with colors going from intense blue to dark blue (Fig.1). Yellow to bright orange YIn1-xFexO3 phases were prepared by standard solid-state reactions for x = 0.0 to 0.3. Red brown YIn1-xFexO3 phases were synthesized through the solution route for x = 0.7 to 1.0. Neither approach was successful for intermediate x values. Green powders of YM1-x(Cu0.5Ti0.5)xO3 (M = Al, Ga, In) all showed impurity phases for x < 0.8, while powders of YIn1-2x(CuxTix)O3 (x<0.3) are nearly pure with intense light green to green colors. Violet to purple colors were obtained for YIn1-x-2yMnxTiyZnyO3 compositions by solid state synthesis. The representative powder XRD patterns are shown in Figure 3. A weak reflection near 20º 2θ indicating the 102 peak that arises from the ferrielectric form (space group P63cm) for all the patterns.

The impact of B-site substitution upon cell edges of hexagonal YInO3 are illustrated in Figure 4 using the blue YIn1-xMnxO3 solid solution as an example. Both the c lattice parameter and the c/a ratio decrease dramatically with x as a result of the short apical Mn-O distances. It is clear that the basal-plane bond lengths similar to the end members lead to a weak variation of cell edge a across the solid solution series.

3+ Figure 3: X-Raydiffraction Patterns of Y[InM] O3 (M=Mn, Mn/Ti/Zn, Fe, Cu/Ti) with various colors. 61 NOVEL INORGANIC PIGMENTS BASED ON OXIDES WITH CHROMOPHORE IONS OCCUPYING TRIGONAL BIPYRAMIDAL COORDINATION

The YAlO3-YMnO3 system is explored in consideration of replacing indium with cheaper aluminum for producing Mn-containing blue pigments. The crystal structure of YAlO3 was reported to be centric P63/mmc, a hexagonal structure similar to that of YMnO3.[10] The conventional solid-state synthesis approach was successful only for the preparation of YMnO3 and Al-poor phases YAl1-xMnxO3 (x > 0.9). The complete solid solution of YAl1-xMnxO3 (x = 0~1) can be prepared using a citrate sol-gel method. XRD analysis reveals a centric structure for YAl1-xMnxO3 phases when x < 0.9. The superstructure reflections in YMnO3 due to the ferroelectric distortion remain present at x ≥ 0.9. Although a blue color develops with Mn substitution, it is not as intense as what was observed for YIn1-xMnxO3 phases due to the destruction of the TBP coordination caused by carbonate incorporation.[9] The carbonate content was verified by thermogravimetric analysis coupled with mass spectrometry, magic- angle-spinning 27Al NMR, Fourier transform infrared, and transmission electron microscopy. Refinement of neutron diffraction data indicates a composition of Y3Al3O8CO3 for the long assumed to be a hexagonal “YAlO3”. Powder XRD patterns confirmed that purplish-blue ScAlMgO4, ScGaMgO4, ScGaZnO4, LuGaMgO4, and LuGaZnO4 have the YbFe2O4-type structure consisting of edge-shared double layers of trigonal bipyramids. And LuGaO3(ZnO)2 is isostructural with LuFeO3(ZnO)2 which contains single layers of trigonal bipyramids. m (hexagonal setting). A similar trend of cell edge variation upon substitution as shown in Figure 4 is observed for Mn-substituted YAlO3 and YbFe2O4-type of phases. To understand the origin of the resulting colors, we measured diffuse reflectance spectra for all the powder samples. Taking YIn1-xMnxO3 solid solution as an example (Fig.5), at low doping concentrations there is a strong, narrow (~1 eV width) absorption centered at ~2 eV that absorbs in the red-green region of the visible spectrum. The absorption then decreases between 2.5 and 3 eV before a second onset near 3 eV. The absence of absorption in the 2.5-3 eV (blue) region of the spectrum results in the blue color. As the concentration of Mn is increased, the lower-energy absorption peak broadens and the higher- energy onset shifts to lower energy, consistent with the gradual darkening of the samples toward navy blue. In pure YMnO3, absorption occurs throughout the entire visible region, resulting in the black color. According to DFT calculations, the peak at ~2 eV arises from the transition between the valence-band maximum, consisting of Mn 3dx2-y2 and dxy states, and the lowest unoccupied energy level, which in lightly Mn-doped YInO3 is a narrow band formed from the Mn 3dz2 state that lies in the band gap of YInO3 (Fig.1). Notably, in the local D3h symmetry of the trigonal bipyramids, the d-d component of this transition (between symmetry labels a' and e' in Fig.1) is formally symmetry-allowed according to the Laporte selection rule, whereas the e" to a" transition is symmetry-forbidden. This results in a high transition probability and intense absorption. We assign the higher-energy peak (~3 eV) to the onset of the transition from the O 2p band to the Mn 3dz2 band. With increasing Mn concentration, our calculations indicate that the Mn 3d levels (particularly the 3dz2 band) broaden substantially, causing the absorption peaks to become broader. Similar absorption features are observed for other solid solutions mentioned above, with certain shifting and broadening for both the low- and high-energy absorption peaks. Although for TBP coordination the structural features correlating with colors are mainly the apical M-O distances that determine the energy level of the dz2 state, oxygen-to-metal charge transfer would also make its contribution to the color change.

62 NOVEL INORGANIC PIGMENTS BASED ON OXIDES WITH CHROMOPHORE IONS OCCUPYING TRIGONAL BIPYRAMIDAL COORDINATION

Roughly 50% of the solar energy is from the near infrared (NIR) region (wavelength 700~2500 nm). The NIR-radiation strikes the earth in the form of heat and results in heat build-up on objects painted with normal pigments. Due to their high NIR reflectance, the so-called “Cool Pigments” are desired in commercial applications such as vinyl siding, cool roofing, automotive applications and industrial coatings for reducing solar heat and saving energy. In Figure 6, the reflectance spectra over a wavelength range of 300~2500 nm were recorded for our In-containing pigments of blue, orange and purple colors. The spectra of commercial TiO2 and Co blue were also collected for comparison. As we can see within nearly the whole NIR range our In-containing pigments exhibit extremely high reflectance comparable to that of the TiO2, especially above 900 nm. Commercial Co blue, on the other hand, displays a large absorption band between 1200 and 1550 nm and much lower reflectance across the entire NIR range compared with our pigments. In general, the percentage of NIR reflectance decreases with increasing chromophore concentration, but not to a very large extent. Great NIR reflectance of our In-containing samples makes them promising candidates for “Cool Pigments” applications which could help to reduce cooling costs and energy consumption. Figure 6: Comparison of NIR reflectance spectra. The stability and durability of these samples were also evaluated by high temperature annealing and acid/base tests. Compared with commercial cobalt blue, which partially decomposes and/or fades in color, our Mn-containing blue pigment is superior in every respect. The stability of our blue pigment is further confirmed in form of pigmented acrylic resin to be heat stable, light stable, weather-proof and chemically innert by The Shepherd Color Company.[3] Conclusions In summary, we have shown for the first time that an intense bright-blue color occurs through most of the YIn1-xMnxO3 solid solution. We have confirmed that blue pigments can be designed by introducing Mn3+ into various structures containing TBP coordination and is not limited to hexagonal AMO3 phases. Thus, we conclude that the blue color is a general characteristic of Mn3+ in a TBP site when the oxide structure can accommodate the required short Mn-O apical bonds, and this should be particularly favorable in layered structures. Substitution of chromophore ions other than Mn into the TBP sites of hexagonal YInO3 can tune the color from blue to various colors across the electromagnetic spectrum (except for red). We expect that our results will lead to routes for the development of inexpensive, earth-abundant, environmentally benign, highly stable inorganic pigments. Acknowledgement This research was supported by National Science Foundation (DMR – 1508527). We acknowledge support of the National Institute of Standards and Technology, U.S. Department of Commerce, in providing the neutron research facilities used in this work.

63 NOVEL INORGANIC PIGMENTS BASED ON OXIDES WITH CHROMOPHORE IONS OCCUPYING TRIGONAL BIPYRAMIDAL COORDINATION

References: 1- Smith, A. E.; Mizoguchi, H.; Dlaney, K.; Spaldin, N. A.; Sleight, A. W.; Subramanian, M. A. J. Am. Chem. Soc. 2009, 131, 17086. 2- National Geographic Magazine, 2013, February issue, p. 19. 3- Smith, A. E.; Comstock, M. C.; Subramanian, M. A. Spectral properties of the UV absorbing and near-IR reflecting blue pigment, YIn1-xMnxO3. Dyes and Pigments, 2016. 4- Ball, P. Royal Society of Chemistry magazine, Chemistry World, 2012; http://www.rsc.org/chemistryworld/2012/09/blue-pigment-paint-chemistry 5- Jiang, P.; Li, J.; Sleight, A. W.; Subramanian, M. A. Inorg. Chem. 2011, 50, 5858−5860. 6- Li, J.; Lorger, S.; Stalick, J. K.; Sleight, A. W.; Subramanian, M. A. From Serendipity to Rational Design: Tune Blue to Violet and Purple through B-Site Substitution in Hexagonal YInO3-YMnO3 Solid Solution, Inorg. Chem. 2016, submitted. 7- Smith, A. E.; Sleight, A. W.; Subramanian, M. A. Mate. Res. Bull. 2011, 46, 1–5. 8- Mizoguchi, H.; Sleight, A. W.; Subramanian, M. A. Inorg. Chem. 2011, 50, 10–12. 9- Li, J.; Smith, A. E.; Jiang, P.; Stalick, J. K.; Sleight, A. W.; Subramanian, M. A. Inorg. Chem. 2015, 54, 837−844. 10- Bertaut, F.; Mareschal, J. C. R. Hebd. Seances Acad. Sci. 1963, 257, 867−870. 11- Li, J.; Singh, U. G.; Schladt, T. D.; Stalick, J. K.; Scott, S. L.; Seshadri, R. Chem. Mater. 2008, 20, 6567−6576.

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65 Functional Coatings (II)

Doç. Dr. Seda Kızılel Koç University Turkey

Seda Kızılel is an Associate Professor in Chemical and Biological Engineering program at Koc University, Istanbul, Turkey. Seda Kizilel received her BS and MS degrees from Chemical Engineering, Boğaziçi University, and PhD degree from Illinois Institute of Technology. She completed her postdoctoral work at the University of Chicago in December 2007, and moved to Koc University in 2008. She was awarded with "Charles Huggins Most Outstanding Research" in 2006 at the University of Chicago, and L’OREAL Young Women in Science Award in 2009.

Research Interests: Her scientific interests are related to the design of novel scaffolds with spatial and temporal responsive properties, nanoparticles for targeted delivery of therapeutics, multifunctional hydrogels as immunoactive barriers for pancreatic islets.

66 FUNCTIONAL COMPOSITES OF AN IONIC SALT IN A HYDROPHOBIC POLYMER MATRIX

Doç. Dr. Seda Kızılel Koç University Turkey

Polymer composites consisted of small hydrophilic pockets homogeneously dispersed in a hydrophobic polymer matrix are important in many applications where controlled release of the functional agent from the hydrophilic phase is needed. As an example, a release of biomolecules or drugs from therapeutic formulations or release of salt in anti-icing application can be mentioned. Here, we report a method for preparation of such a composite material consisted of small KCOOH salt pockets distributed in the styrene-butadiene-styrene (SBS) polymer matrix and demonstrate its effectiveness in anti-icing coatings. The mixtures of the aqueous KCOOH and SBS-cyclohexane solutions were firstly stabilized by adding silica nanoparticles to the emulsions and, even more, by gelation of the aqueous phase by agarose. The emulsions were observed in optical microscope to check its stability in time and characterized by rheological measurements. The dry composite materials were obtained via casting the emulsions onto the glass substrates and evaporations of the organic solvent. Composite polymer films were characterized by water contact angle (WCA) measurements. The release of KCOOH salt into water and the freezing delay experiments of water droplets on dry composite films demonstrated their anti-icing properties. It has been concluded that hydrophobic and thermoplastic SBS polymer allows incorporation of the hydrophilic pockets/ phases through our technique that opens the possibility for controlled delivering of anti-icing agents from the composite.

67 Functional Coatings (II)

Nazlı Mert Dokuz Eylül University Turkey

Nazlı Mert graduated from Hacettepe University, Department of Biolgy in 2012. She hold her master of science degree from Department of Biotechnology of Dokuz Eylul University in 2012. Her main research interests are Marine Biotechnology, isolation and characterization of secondary metabolites from living organisms, biofouling-antifouling processes and in silico biology. She is currently a Ph.D. student in Department of Biotechnology of Dokuz Eylul University.

68 ANTIFOULING ACTIVITY OF SEA CUCUMBER EXTRACTS

Nazlı Mert Prof. Dr. Levent Çavaş Dokuz Eylül University Turkey

Abstract Settlement of micro and macro fouling organisms on artificial surfaces in sea ecosystems is defined as biofouling. Although biofouling is a natural process, it has many disadvantages on the marine transportation [1]. Current antifouling paints formulations contain toxic synthetic biocides which are very harmful to the sea ecosystems. Thus, development of ecologically friendly version of booster biocides is of great importance. Sea cucumbers secrete triterpene glycoside based secondary metabolites from their skins. These molecules have biological activities such as antifungal, antiproliferative, anti-inflammatory, antithrombic, antibacterial, apoptotic, cytotoxic, hemolytic, cytostatic and immunomodulatory activities [2-4]. In this study, sea cucumber (Holothuria tubulosa and H. polii) extracts based antifouling paints were prepared and their antifouling performances were evaluated in İzmir-Turkey for 30 days. Zinc pyrion was used as a positive control. According to the results, the most effective formulation contains methanol-dicholoromethane extract. The results show that sea cucumber extracts are promising natural booster biocides which could be alternative to toxic synthetic biocides. The studies on the organic synthesis of these secondary metabolites are strongly recommended by authors.

Keywords: Antifouling, booster-biocide, extraction, natural sources, sea cucumber.

69 ANTIFOULING ACTIVITY OF SEA CUCUMBER EXTRACTS

References 1- Yebra, D., Kiil, S., Dam-Johansen, K., 2004. Review. Antifouling technology- past, present and future steps towards efficient and environmentally friendly antifouling coatings. Progress in Organic Coatings 50 (2), 75-104. 2- Han, H., Yi, Y., Li, L., Liu, B., La, M., Zhang, H., 2009. Antifungal active triterpene glycosides from sea cucumber Holothuria scabra. Acta Pharmacologica Sinica 44 (6), 620-624. 3- Haug, T., Kjuul, A., Styrvold, O., Sandsdalen, E., Olsen, O., Stensvag, K., 2002. Antibacterial activity in Strongylocentrotus droebachiensis (Echinoidea), Cucumaria frondosa (Holothuroidea), and Asterias rubens (Asteroidea). Journal of Invertebrate Pathology 81, 94-102. 4- Acevedo, M. S., Puentes, C., Carreño, K., León, J. G., Stupak, M., García, M., Pérez, M., Blustein, G., 2013. Antifouling paints based on marine natural products from Colombian Caribbean. International Biodeterioration & Biodegradation 83, 97-104.

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71 Functional Coatings (II)

Prof. Dr. Emin Arca Marmara University Turkey

Emin Arca is a Professor in the Chemical Engineering Department at Marmara University where he has been a faculty member since 2003. He completed his undergraduate studies in the Chemical Engineering Department of the Middle East Technical University, Turkey (1976- 1981) and his Ph.D. on Polymer Technologies at the Chemical Engineering Department of the Hacettepe University, Turkey (1981-1987).

He joined Dr. Peter. Munk's research group at University of Texas at Austin, USA, where he focused on self organizing polymers with Dr. Z.Tuzar and Dr. S.E.Webber (1992-1994).

In 1995, joined Polisan A. S., as technical operations manager. Between the years 1998-2003 he was the Dean of the Engineering Faculty and Founder Proffesor of Chemical Engineering Department at Kocaeli University. He is one of the founders of Mavi Kimya A.Ş., Tuzla İstanbul. His research interests includes polymer technologies related to, polymer coatings, cement and concrete additives, and slow release fertilizers.

72 POLYMER COATED FERTILIZERS AS NUTRIENT MANAGEMENT

Prof. Dr. Emin Arca Marmara University Turkey Coating of Fertilizers: Coating of fertilizers is a process where surface treatment is applied to solid fertilizers to improve its performance. The coating can be in liquid form (such as oil), solid form (such as clay, talk) or thermoplastic mixtures (resins, wax, polymers etc.) and polymer systems (crosslinking on top of surface). Types of coating and their advantages are summarized in Table 1.

Coating is used to preserve the quality of manufactured fertilizers throughout the shipping, storage, handling and increase performance of nutrient release. Nonetheless, it cannot correct inherent problems. For instance, if the granular form of the fertilizer is damaged concerning its integrity or stability (poor shape and surface, excessive porosity, softening over time, high moisture content and poor process control or excessive rates) coating the fertilizer would not fix the existing damage. However; in some cases, process additives can help to mitigate the above problems, as well as process modifications.

The function of coating is to minimize dust emission, enhance flowability acting as anti-caking agent, minimize moisture pickup to stabilize the surface, improve compatibility for end uses and enhance nutrient release in order to control its performance for nutrient management. Controlled/Slow Release Fertilizers: There has been exponential growth in the earth's population that has now reached approximately 7.0 billion and is expected to approach 9.5 billion by 2050. Global food requirements have also risen and the expected per capita food requirement is likely to double by 2050 . Meanwhile, arable lands diminish due to industrialization, urbanization, desertification and land degradation from heavy flooding . These pressuring aspects t threaten

73 POLYMER COATED FERTILIZERS AS NUTRIENT MANAGEMENT

global food security and demand a effective response. Multidimensional steps have already been taken worldwide to meet the challenge of food security with modifications to improve agricultural systems. To meet the increasing food demands, the agricultural sector is obligated to employ huge quantities of fertilizers that have thus far demonstrated undesirable environmental impacts. Hence, it is of outstanding importance to develop systems that increase production and mitigate environmental problems. Controlled release fertilizers may be one such solution as they are believed to enhance nitrogen use efficiency (NUE) while reducing the environmental pollution caused by the hazardous emissions (NH3, N2O etc.) from current fertilizer applications . (Baber Azeem, et al., 2014

All plants require nitrogen (N) to complete their life cycles It is often the primary limiting factor for plant growth due to high demand to facilitate essential biochemical processes, and the fact that soluble soil N is easily lost to the surrounding environment due to its mobile nature (Chatterjee, 2012). Without adequate concentrations of N, plants produce less chlorophyll and proteins, which results in decreased growth and increased susceptibility to pests and diseases (Marschner, 2012).

Types of Coating Advantages and Disadvantages

Particulates (sometimes called parting agents), Good for followability and caking, but Increases dust, clay, talc, etc. high amount is needed Good for dust, not so good for caking Coating oils (fuel oil, asphaltic oils, refined oils, natural oils, fats) Good for dust, not so good for caking Thermoplastic mixtures (wax, waxy surfactants, sulfur, resins, polymers) Good for dust and caking, somewhat higher cost Water-soluble liquids (glycerin, molasses, For special applications where solubility is surfactant solutions, polymer solutions) needed Polymer systems (polymerized film via reaction with surface or crosslinking on top Costly, difficult process, but high performance of surface)

Table 1: Advantages and disadvantages of coating types.

Plants require N but fertilizer mismanagement can lead to N pollution in the environment. Controlled-release (CRFs) and slow-release (SRFs) fertilizers are commonly used to supply N to plant while mitigating N loss. The use of controlled-release fertilizers (CRFs) is starting to evolve in a promising direction, offering an excellent means to improve management of nutrient application causing significant decrease in environmental threats while maintaining high crop yields of good quality.

Under practical conditions, nitrogen use efficiency (NUE) can be considered as the amount of nutrients taken up from the soil by plants and crops within a certain period of time compared with the amount of nutrients available from the soil or applied during the same period of time. Because a considerable proportion of applied Fertilizer-N is lost during the year of application, N application and crop management must be fine-tuned in order to maximize system-level NUE. In general, the utilization rate of N in mineral fertilizers is about 30-70% in the first year.

74 POLYMER COATED FERTILIZERS AS NUTRIENT MANAGEMENT

The fertilizer industry faces a continuing challenge to improve its products with an increased efficiency, particularly nitrogen fertilizers, and to minimize any possible adverse environmental impact. This is done either through improvement of fertilizers which are already in use, or through development of new specific fertilizer types . Types of new products developed as CRFs are outlined in Figure 1. (Baber Azeem , et al., 2014).

Figure 1: Classification of slow/controlled Release Fertilizers

Heavy applications of N-based fertilizer are often used to ensure high crop yields and to compensate for losses due to N lost from the soil. The application process of fertilizers is often inefficient, leading towards a waste of natural resources and money. Also it often results in N lost as a pollutant to the environment through ammonia volatilization, nitrate leaching, and by-products of denitrification, such as nitrous oxide. Nitrogen lost in the various mobile forms contributes to issues in the atmosphere and hydrosphere that ultimately affect human and animal health (Olson et al., 2009; Mulvaney et al., 2009).

Hydrolysis of urea fertilizer and decomposition of soil organic matter and organism residues result in ammonification— conversion of R-NH2 to ammonia [NH3 (g)] and then to ammonium (NH4+). However, the gaseous form volatilizes quickly into the atmosphere,

75 POLYMER COATED FERTILIZERS AS NUTRIENT MANAGEMENT

especially if the ammonification occurs at or near the soil surface (Schlesinger and Harley, 1992). If the NH4+ is formed and captured by soil, it can be retained relatively well. However, under typical soil conditions, NH4+ is rapidly nitrified—oxidation to nitrate (NO3-). Nitrate is easily lost by leaching due to its high solubility and anionic repulsion from similarly charged soil colloids. It can also be denitrified into the nitrous oxide [N2O (g)] form and subsequently released to the atmosphere, especially under anaerobic conditions. A portion of the N is also lost as N2O during nitrification.

Control release fertilizers (CRFs) and/or slow-release fertilizers (SRFs) are often used to increase nitrogen-use efficiency (NUE) and to allow for the provision of N over extended periods of time. As compared to “quick release” fertilizers, CRFs and SRFs are designed to release N over an extended period of time, rather than all at once, in an attempt to better match plant N needs throughout the growing season and to reduce time of exposure for N losses to the environment.

Control release fertilizers and SFRs primarily differ in their mode of release. (Curtis, J.R., 2014).

Slow- release fertilizers release through a variety of methods including: microbial processes, chemical reactions, or bursting of a coating due to water vapor infiltration resulting in high internal pressures. Once a point of the coating breaks, the urea becomes exposed and left accessible to be hydrolyzed and further converted to other N forms. This process is relatively more unpredictable compared to CRFs, making additional applications necessary during growing seasons and decreasing N use efficiency (Ellison et al., 2013). This group of fertilizers includes denitrification/nitrification inhibitors, long chain molecules requiring microbial decomposition, and granules coated in a substance to restrict water movement through hydrophobic or hydrophilic attractions (Aviv, 2001).

Control release fertilizers have been developed using a coating around individual granules of fertilizer materials, such as urea. A variety of coatings have been applied to fertilizer particles to control their solubility in soil. Controlling the rate of nutrient release can offer multiple environmental, economic, and yield benefits.

The commonly used polymer coating has micro pores that allow soil moisture to diffuse through the coating to dissolve the urea. Urea is a larger molecule than water and, as such, does not immediately cross the membrane into the soil. As the temperatures increase, it is thought that the coating warms up and expands, increasing the size of the micro pores and allowing the urea to eventually reach the soil solution through diffusion. The rate of diffusion follows first-order kinetics with an approximate doubling of the diffusion rate for every 10oC increase (Adams et al., 2013).

By altering the thickness of the coating, the rate of N diffusion is reduced. Knowing the plant’s N needs and the average soil or air temperature, an appropriate combination of coating thicknesses can be used to match plant N needs.

A wide range of materials have been used as coatings on soluble fertilizers. Coatings are most commonly applied to granular or prilled nitrogen (N) fertilizer, but multi-nutrient fertilizers are sometimes used. Since urea has the highest N content of common soluble fertilizers, it is the base material for most coated fertilizers.

76 POLYMER COATED FERTILIZERS AS NUTRIENT MANAGEMENT

Coating Techniques Elemental sulfur (S) was the first widely used fertilizer coating. It involved spraying molten S over urea granules, followed by an application of sealant wax to close any cracks or imperfections in the coating. An improvement in this process was later adopted when the S layer was covered with a thin layer of organic polymer.

Other coated fertilizers are made by reacting various resin-based polymers on the surface of the fertilizer granule. Another technique is to use low permeability polyethylene polymers in combination with high permeability coatings. The coating materials and coating processes vary among manufacturers.

The composition and thickness of the fertilizer coating is carefully adjusted to control the nutrient release rate for specific applications. The duration of nutrient release from specific fertilizers can vary from several weeks to many months, as described on the product label. An additional expense is associated with adding a coating to a fertilizer particle, as a result coated fertilizers are costlier than the non-coated materials.

Coating selection criteria: reasonable cost per ton of product, reliable supply and reliable supplier, safety, toxicity, environmental fate, service and knowledge of supplier, performance criteria (does it work in the field), customer acceptance. Coating techniques for coating of fertilizers are summarized in Table 2.

Application Techniques Coating Drums Spray inside drum Blenders Spray or inject coating during blending Screw conveyers Cut flight conveyers Spraying Spraying at drop point of conveyers Special processes Sulfur coated urea

Table 2: Application Techniques for fertilizer coating.

Coated fertilizers in agricultural use, their management practices and the possible use of the products in different areas are explained.

Agricultural Use: Coated fertilizers are used in a variety of agricultural and horticultural situations. They provide a prolonged supply of nutrients that may offer many benefits. These include:

- Sustained nutrient release that may decrease leaching and gaseous losses. - Labor and application costs may be reduced by eliminating the need for multiple fertilizer applications. - Greater tolerance of seedlings to closely placed fertilizer. - Prolonged nutrient release may provide more uniform plant nutrition, better growth and improved plant performance.

The maximum benefit from coated fertilizer is only achieved when the duration of nutrient release is synchronized with the periods of plant nutrient uptake.

Management Practices: Predicting the pattern of nutrient release from coated fertilizers in wide-ranging soil and cropping conditions is complex, since the release is controlled by a variety of environmental factors. For example, many coated fertilizers release more rapidly with increased moisture and soil temperature. Some products depend on soil microbial activity for nutrient release.

77 POLYMER COATED FERTILIZERS AS NUTRIENT MANAGEMENT

An understanding of the mechanism of nutrient release is helpful for getting the maximum value from coated fertilizers. Some coating materials are relatively brittle and are subject to abrasion and breaking under harsh environments. Excessive handling should be avoided when possible.

Possible Uses of Controlled-Release Products: The higher cost of controlled-release products generally excludes their use in cases where conventional N fertilizers can perform the same function adequately. Most growers of commodity row crops who use controlled-release products likely apply most of their CRF needs with conventional products and only use controlled- release products to supplement their primary N fertilization program.

Also lack of proper legislation in most parts of the world is to restrict the use of soluble fertilizers. Today only about 0.25 % of the total fertilizer consumption in such products are used in high technology coatings (controlled-release, etc.) but used only for horticulture, orchards. The other disadvantages of CRFs may be inadequate sources of nutrients in situations with low ambient and soil temperatures. Issues related to better NUE and more environment friendly utilization of CRFs deserve greater attention and deeper insights, as listed below:

- Improved utilization of advanced technologies to prepare CRFs. - Better understanding of the mechanisms controlling release rate and pattern - Better assessment of expected benefits to the environment by using CRFs - Development of soil degradable coatings - Improved quantification of economic advantages

Conclusion: Will the advancement in the coating technology help the fertilizer industry to create a new market? Also will the advancement in the coating technology be economical enough be in the market? Can advanced coating technology be more economical to ensure market grow? When the coating and fertilizer sectors come together and unite their valuable accumulated knowledge then new environment friendly products with high nitrogen use (NUE) efficiency will be produced.

78 POLYMER COATED FERTILIZERS AS NUTRIENT MANAGEMENT

References: Adams, C., J. Frantz, and B. Bugbee. 2013. Macro- and micronutrient-release characteristics of three polymer-coated fertilizers: Theory and measurements. J. Plant Nutr. Soil Sci. 176: 76-88. Babar, A.,Kuzilati, K., Zakaria, B., Abdul,B., Trinh,T., 2014 , Review on materials & methods to produce controlled release coated urea fertilizers, Journal Of Controled Release, 181: 11-21 Aviv, S. 2001. Advances in controlled-release fertilizers. Adv. Agron. 71: 1-49. Chatterjee, A. 2012. Reducing denitrification loss of nitrogen fertilizer. Crop and Soil Magazine: 45: 14-15. Ransom, Curtis J., (2014). "Nitrogen Use Efficiency of Polymer-Coated Urea" Theses and Dissertations., Brigham Young University - Provo Marshchner, P. 2012. Mineral nutrition of higher plants (3rd ed.). San Diego, CA: Elsevier. Schlesinger, W.H. and A.E. Hartley. 1992. A Global Budget for Atmospheric NH3. Biogeochemistry: 15: 191-211.

79 Novel Raw Materials (III)

Dr. Franjo Gol Omg Borchers Germany

Franjo Gol gained a master’s degree in chemistry and a Dr. rer. nat. in inorganic and organophosphorus chemistry at Wuppertal University. He has worked in the chemical industry for almost 30 years, initially on the development of water-borne binders for coatings for Herberts and then on binders, metal carboxylates and paint additives for Abshagen and now OMG Borchers.

80 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

Richard Najdusak, Dr. Franjo Gol Omg Borchers Germany

Introduction Being a formulator is becoming more and more difficult in light of increased regulatory pressures on common raw materials. Formulators who develop coatings based on oxidatively cured (alkyd) binders face major regulatory obstacles for two of their key ingredients: methyl ethyl ketoxime (MEKO) anti skinning additive and Cobalt based driers. MEKO’s volatility makes it difficult to meet safe exposure limits due to its toxicity. Cobalt carboxylates are being pressured to be classified as carcinogens.

In this paper we will discuss potential non-toxic alternatives to both of these problems with supporting test results. Coatings Based on Binders that Cure via Oxidation Drying oils and alkyd resins have many advantages over other binders used in the coatings industry. They are bio-renewable, inexpensive and extremely stable compared to other organic binder systems. They can be used to formulate coatings which have long open times, relatively hard films, require minimal surface preparation and provide good stain blocking properties, particularly over water based stains. These binders have also been modified to be used in water and solvent based systems to meet the end user’s needs. They are found in architectural, light duty industrial, wood care, printing inks and maintenance coatings.

All of these binders have certain things in common. They all contain some degree of unsaturation (double bonds) and hydroxyl/carboxyl functionality. In the example of common

81 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

vegetable oils the triglyceride contains various amounts of different organic acids which have different degrees of unsaturation. Those with more potential crosslinking sites like linolenic acid can be expected to dry faster and yield harder finishes than those based on oleic acid, for example, which only has one unsaturation site.

Why do we need driers? Atmospheric oxygen reacts spontaneously with the unsaturated fatty acid components of oils and alkyd resins causing free radical reactions to form films (Autoxidation), but if unaided, the reaction rates will be slow. Surface (or oxidative) driers catalyze reactions by deactivating the natural antioxidants found in drying oils by forming hydroperoxides, accelerating oxygen absorption and peroxide formation via catalytic activity, reacting with oxygen or hydroperoxides to form complexes that catalyze oxidation reactions, and acting as oxygen carriers. Surface driers are also susceptible to redox reactions which can decompose hydroperoxides and promote crosslinking.

82 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

Metal Catalyzed Reactions Adding metal catalysts greatly improves the oxidation rate of the binder. When a metal catalyst is present, the activation energy for oxygen uptake is only 10% of the amount needed when none is present. Peroxide formation also proceeds more rapidly. Metal catalysts aid in the decomposition of the peroxides which accelerates the free radical formation to promote crosslinking.

Metals capable of being used in Oxidative (Surface) driers There are only few metals that promote oxidative or surface curing in some form. Cobalt is the most common oxidative drier and has been commercially available since the early 1900’s. It exists in the two valance states noted in the above examples which helps it form coordination complexes with oxygen and organic molecules. The activity of cobalt driers is inhibited by lower temperatures and its use in high humidity drying conditions may promote film wrinkling. Manganese is more efficient than cobalt at low temperatures and also when used in baking finishes but not at ambient temperatures. It is mainly used in drying oils in combination with cobalt. As a cobalt replacement, manganese requires the addition of a drier accelerator like 1,10 phenanthroline or 2,2’ bipyridyle chelating additives to approach the activity level of manganese. Films may develop a brown hue on ageing due to the color of the manganese drier. Iron has no function in air drying finishes at room temperature but it is more active than cobalt at baking temperatures (130°C). The dark red color of iron driers restricts their usage in coatings. Vanadium is efficient at lower temperatures but has a tendency to impart a greenish stain to films. Unlike cobalt, vanadium is more stable in its higher valence state which inhibits its role in oxidative curing and complex formation. Higher levels are generally needed. Cerium can promote oxidative curing at elevated temperatures but is primarily used as a through or coordinate drier.

A new unique organic iron complex has yielded an oxidative drier which magnifies the drying activity of iron so that it is effective over a wide range of temperatures and drying conditions. This new Iron Complex technology is more active than cobalt, has a very light color and provides both surface and through drying activity in a wide range of binders.

83 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

Potential Cobalt Re-Classification Cobalt driers have been a regulatory concern for over 20 years. Reproductive concerns and the long term adverse effects on aquatic organisms have been well known and documented. As described above, cobalt driers are true catalysts in the oxidation process of air drying binders in that they do not become part of the molecular structure. Cobalt driers have some water solubility and will eventually leach into the ground water supply when the films come in contact with water. There is also the growing concern that cobalt carboxylates will be classified as a carcinogen. A lot of European paint manufacturers have already replaced cobalt driers in their formulations in anticipation of one or all of these concerns being realized.

Cobalt Replacement Strategies Few viable options exist to replace cobalt in alkyd and other air drying systems. As noted above, only manganese and iron complexes can approach cobalt’s activity level. Conventional iron, vanadium and cerium driers are not effective replacements. “Accelerated” manganese driers improve the activity somewhat but may affect the color of light tinted coatings over time. However, a new iron complex drier has been developed to equal or exceed the drying performance of cobalt at reduced levels. The catalytic reaction mechanisms of cobalt and the iron complex driers have been shown to be the same.

Iron Complex Drier - FeLT® The new Iron Complex drier has been shown to be a highly effective oxidative drier in a wide variety of binder systems, particularly alkyd emulsions. The graph below shows the surface dry time and Koenig Pendulum Hardness test results of a variety of cobalt and manganese based driers compared to the iron complex in a long oil alkyd based coating.

The rates of dry were tested initially and after a one week accelerated shelf life test at 40ºC. Pendulum hardness tests were run after one week cure. Note that the new Iron Complex developed faster surface drying results at ambient temperatures than any of the other products tested. However, cobalt based enamels developed harder films faster than any of the cobalt replacements.

84 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

Hardness development depends not only on the drier metal. The fatty acid residues of the alkyd also influence hardness due to the higher degree of crosslinking. A high amount of linolenic acid (e.g. from linseed oil fatty acid) leads to harder films no matter which drier is used.

A major concern about alkyd and drying oil films is their tendency to yellow in the absence of UV light. The higher the amount of highly unsaturated fatty acids in the alkyd, the stronger the tendency to yellowing will be. Typically a cocktail of through driers is necessary to reduce yellowing by forming coordinate bonds with the chromophores that are generated during the curing process. The additional through drying property of the Iron Complex drier greatly reduces the film’s tendency to yellow as seen in the following graph. As a consequence, less yellowing will be noted when using the iron complex drier to replace cobalt in alkyds with highly unsaturated fatty acids.

85 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

A major advantage of the iron complex drier is its ability to promote improved oxidative cure under marginal drying conditions which typically affect conventional surface driers. In this example the iron complex drier was not only more effective than cobalt or accelerated manganese based driers under standard drying conditions but also was virtually unaffected in low temperature/ high humidity environments.

Summary of Cobalt Replacement Driers No other metal carboxylate drier can approach the oxidative activity of cobalt. However, the Iron Complex drier is a sustainable alternative to Cobalt driers. This product is not CMR classified, can provide equal surface dry times to cobalt at low levels under standard drying conditions, has improved efficiency in promoting surface curing under low temperature/high humidity conditions and, due to its additional through drying properties, can reduce long term film yellowing. Due to its low tendency to yellowing, highly unsaturated fatty acids can be used to achieve hard films without negative by-effects.

Using Anti Skinning Additives in Paints Oxidatively cured binders without driers rarely dry fast enough to cause “skinning” issues. However, as soon as we add driers to improve the drying times of our coatings we also increase the ability of the coating to begin the curing process prematurely any time after it comes in contact with air. This includes during the manufacturing, filtering and filling processes as well as long term storage in the can. Adding driers also means that less oxygen is needed so skinning is more likely to occur. The coatings industry developed anti skinning additives to delay the curing process to prevent skin formation. The main methods to prevent skinning are inhibiting the metal carboxylate to block its catalytic effect temporarily or to prevent oxygen from coming in contact with the catalyst/binder.

The first method involves using a volatile material which forms unstable complexes with the metal in the drier to block catalytic activity until the inhibitor evaporates during application leaving the metal to function. The most common chemical used for

86 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

this is methyl ethyl ketoxime (MEKO) or oximes in general. They are especially effective with cobalt however their high volatility makes them a health concern. Methyl ethyl ketoxime and cyclohexanone oxime exhibit very similar toxic effects. For both chemicals, the major toxicity is to erythrocytes and the hematopoietic system. Each chemical causes similar lesions in the olfactory epithelium. Hyperplasia of the urinary bladder transitional epithelium was observed in mice exposed to methyl ethyl ketoxime but not cyclohexanone oxime. For methyl ethyl ketoxime, the no observed-adverse-effect level (NOAEL) for erythrotoxicity is 312 ppm in the drinking water for rats and 2,500 ppm for mice (see National Toxicology Program, Toxicity Report Series, Number 51, July 1999, NIH Publication 99-3947).

Below is part of the SDS for MEKO with regards to Health Hazards (2.1) and Label Elements (2.2).

The second method involves using non-volatile antioxidants to chemically remove oxygen from the immediate area of the coating. However, these can severely inhibit oxidation and affect curing and film appearance. The coating can only cure after the antioxidant has been consumed (with oxygen) or leaves the film through evaporation or being driven off during the bake cycle (if part of the curing system). These consist of substituted phenolics, hydroquinones, aromatic amines, sterically hindered aliphatic amines and hydroxyl amines.

The most preferred anti skinning additive would be non-toxic, have no regulatory concerns, have no effect on the cured film and still prevent skin formation. Methyl Ethyl Ketoxime (MEKO) Replacement Most antioxidants are unsuitable for architectural and industrial applications due to their side effects of dry inhibition, color contribution and odor. However, a proprietary aminic compound has been developed which is volatile and consumes oxygen. The complex has been dissolved in glycolic solvents for primary applications in highly polar solvent and waterborne formulations.

87 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

Another version has been dissolved in fatty acid esters making them effective for general use including low VOC/high solids coatings and printing inks. This “Advanced Antioxidant” provides a controlled retardation of surface dry resulting in improved through dry without affecting the film hardness. Another advantage is that its activity is independent of the drier metal. This new product is more volatile than other types of antioxidants but not as volatile as MEKO. It can also be used in clear and pigmented systems, is non-hazardous and has no labeling issues. More importantly, the technology has been successfully marketed since 2002. Aminic Complex The health hazards associated with this new product are minimal compared to MEKO as noted on its current SDS.

Unlike MEKO, the proprietary aminic complex is not harmful to humans and only in concentrated form can be harmful to aquatic life if discharged directly into watercourses.

Comparative testing to MEKO These “Advanced Antioxidants” were evaluated for In-Can Preservation, Film Surface Drying and Film Hardness Development testing vs MEKO. MEKO is completely volatile and does not interfere with curing while all antioxidants remain, at least for a period of time, in the film to function properly. In our tests, we chose a simple clear alkyd formula based on a long oil alkyd resin and used a drier package consisting of 0.04% Cobalt and 0.1% Calcium metal based on resin solids.

88 UNIQUE SOLUTIONS TO THE REGULATORY CONCERNS AFFECTING COBALT AND MEKO IN THE COATINGS INDUSTRY

Skin Prevention

Although not as effective as MEKO with this drier package the Advanced Antioxidants at low levels provide anti skinning properties to this test system.

Hardness Development (Koenig Pendulum Hardness Method)

The overall hardness and integrity of the dried film has not been compromised initially or after one week using the Advanced Antioxidant complex at any levels tested. This confirms that it does not remain in the film for long periods of time to interfere with crosslinking and final cure.

Hardness Development (Koenig Pendulum Hardness Method)

There is a slight loss of surface dry using the Advanced Antioxidant complex which is probably due to its volatility being slightly slower than MEKO and the different mechanism for inhibiting oxidation. Excessive amounts should be avoided for these reasons.

Summary – MEKO Replacement These less toxic alternatives to phenolic and oximic antioxidants require less than half the level of MEKO in most coatings systems to provide effective anti-skinning properties. They perform independently of the oxidative metal drier and are recommended in cobalt replacement strategies. These “Advanced Antioxidants” are suitable for clear and pigmented coatings with no discoloration. However, the optimum level should be experimentally determined as excessive amounts may lead to longer dry times due to their volatility being less than MEKO. 89 Novel Raw Materials (III)

Nagihan Akgün Istanbul University Turkey

Nagihan Akgün works as a scholarship student in TUBITAK project which number is 214M660 at Istanbul University, Chemical Engineering Department, Chemical Technologies Sub Department.

Akgün received her BSc in Chemical Engineering in 2014 from Istanbul University, Istanbul, Turkey, and she is still MSc student at Istanbul University, Chemical Engineering Department, Chemical Technologies Sub Department. She has published 2 papers and her research interests are polymer synthesis and applications, and plastic recycling.

Akgün is a member of Chamber of Chemical Engineers (CCE).

90 SYNTHESIS AND FILM PROPERTIES OF NOVEL ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Nagihan Akgün, Özge Naz Büyükyonga, Işıl Acar, Gamze Güçlü Istanbul University Turkey

Abstract In this study, novel four-component water reducible acrylic modified alkyd resins containing different ratios of acrylic copolymer were synthesized with different method. In this novel method, water reducible acrylic modified alkyd resins were synthesized with fatty acid method in four stages. The final content of solids in the water reducible acrylic modified alkyd resins was 50% by weight. After the modified alkyd resin films had been prepared and cured at 150oC for 1 h, physical/chemical surface coating properties and thermal behaviors were investigated. In conclusion, according to all experimental data we can deduce that, the optimum acrylic copolymer ratio is 30% of the equivalent amount of acrylic copolymer to alkyd resin at this dilution ratio. Keywords: alkyd resin; acrylic modification; water reducible coating; film properties. Introduction Alkyd resins are defined as polyesters which formed by the polycondensation reactions of polyhydric alcohol and polybasic acid and modified with fatty acids or fats [1-2]. Alkyd resins are widely used as binder in large variety of products in the coating and paint industry [3- 4], and they are generally characterized by good adhesion, excellent gloss, flexibility, good heat and solvent resistances [4-5]. However, alkyd resins have some disadvantages such as relatively low water, acid and alkaline resistances [5].

91 SYNTHESIS AND FILM PROPERTIES OF NOVEL ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Alkyd resins can be modified with many other resins or chemicals, and these modifications affects the final properties of the alkyd resins [6]. In addition, alkyd resin is one of the most popular components for waterborne coating systems [7], and most types of modified alkyds can be turn into water reducible form [8]. For this purpose, the free acid functional groups of alkyd resin are neutralized with amine compounds when preparing the water reducible alkyd coating systems [4, 9-11].

In the present study, water reducible acrylic modified alkyd resins were synthesized with a different method from literature. Furthermore, 1,3-propanediol (1,3-PDO) was used to synthesis of four-component alkyd resin, for the first time. A literature survey has not yielded any research on the 1,3-PDO based alkyd resin synthesis. 1,3-PDO is a bio-based diol, and it is used production of poly (trimethylene terephthalate) [12-13].

Eventually, four-component water reducible acrylic modified alkyd resins based on 1,3-PDO containing different two ratios of acrylic copolymer were synthesized with novel method, for the first time. In this novel method, water reducible acrylic modified alkyd resins were synthesized with fatty acid method in four stages. Then, the effect of different ratios of acrylic copolymer on the surface coating properties and thermal behaviors of water reducible alkyd resins was investigated. Experimental Materials Tall oil fatty acid (TOFA) and trimethylol propane (TMP) were obtained from Arizona Chemicals and Perstorp, respectively. 1,3-propandiol (1,3-PDO), phthalic anhydride (PA), methacrylic acid (MA), fumaric acid (FA) and diethanolamine (DEA) were synthesis or analytical grade. Isopropyl alcohol (IPA) was used as technical grade. Driers for water reducible alkyd resins was kindly provided by AKPA Kimya (Turkey).

Preparation of acrylic modified water-reducible alkyd resins Preparation of acrylic modified water-reducible alkyd resins were performed in four stages. All stages were presented in below.

Synthesis of acrylic copolymer: The copolymer synthesis reactions of MA and FA in xylene were carried out in a glass reactor equipped with a mechanical stirrer, a condenser, a gas bubbler and a thermometer. At the end of the reaction, the copolymer, which has been collapsed in xylene, was filtered, and it was dried under vacuum at 40oC. The acid value (AV) of synthesized acrylic copolymer was determined by titration of sample dissolved in pyridine with 0.1 N potassium hydroxide solution [14].

Synthesis of alkyd resin: Four-component alkyd resins, formulated to have an oil content of 50%, were prepared using TOFA, PA, TMP and 1,3-PDO. The “K alkyd constant system” was used for the formulation calculations of the alkyd resins [15]. The reactions were realized in a glass reactor equipped with a mechanical stirrer, a gas bubbler, a thermometer and a condenser containing a Dean-Stark piece. The alkyd synthesis reactions were allowed to continue until the AV of the alkyd resin was approximately 40-45 mg KOH/g. At the end of the reaction, the hydroxyl value (HV) of synthesized alkyd resin was determined by acetylation method [16].

92 SYNTHESIS AND FILM PROPERTIES OF NOVEL ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Synthesis of acrylic modified alkyd resin:In this stage, the alkyd resin was reacted with the acrylic copolymer. Thus, acrylic modified alkyd resins, which containing 30% and 40% acrylic copolymer ratios of the equivalent amounts of acrylic copolymer to alkyd resin, were prepared. Modification reactions were carried out in a glass reactor equipped with a mechanical stirrer, a condenser containing a Dean-Stark piece, a gas bubbler and a thermometer. The reaction was allowed to continue until the AV of the acrylic modified alkyd resin was approximately 30-40 mg KOH/g.

Preparation of water reducible acrylic modified alkyd resin: To obtain water reducible form of alkyd, synthesized acrylic modified alkyd resin was neutralized with DEA, dissolved in IPA and then diluted with distilled water. The final content of solids in the water reducible acrylic modified alkyd resin was 50%, by weight. Driers (1% Zn, 0.1% Co based on the alkyd) were added with water to the alkyd solution. The combination of water reducible acrylic modified alkyd resins are given in Table 1.

Table 1: The combinations of water reducible acrylic modified alkyd resins

Alkyds Acrylic copolymer (AC) content* Final solid content % (by weight) WRAlkyd30 30 50 WRAlkyd40 40 50

*Acrylic modified alkyd resins, which containing 30% and 40% AC ratios of the equivalent amounts of AC to alkyd, were prepared.

Physical surface coating properties Drying time (or degree) was determined by an Erichsen Drying Time Tester, according to DIN 53150. The drying time is estimated by the adherence or non-adherence of paper or glass beads. There are 7 drying stages and the max. drying stage is 7, in this standard. Hardness was determined by the Sheen König Pendulumaccording to DIN 53157. The procedure of hardness determination is based on the measurement of the damping of a pendulum oscillating on the paint film. Adhesion strength was determined by the Erichsen Cross-Cutter according to ASTM D3359. The principle of this method is to cut through the coating with a series of several cuts at right angles. Square pattern occured on the film surface can be compared with schematic representations in the standard. Abrasion resistance was determined by an Erichsen Sand Abrasion Tester according to ASTM D968. In this test, sand is dropped down a vertical tube onto the panel that is mounted at a 45o angle, and test results are given as the amount of sand required to remove a certain thickness of coating. Impact resistance was determined by a BYK Gardner Impact Tester according ASTM D2794. In this test, the standard steel cylinder testers in different weights are dropped from different heights through a cylindrical guide tube onto the metal panel. The test was repeated by increasing the height from which the object falls till the film was cracked or detached. Gloss was determined by Sheen Mini Glossmeter at 60o angle according to ASTM D523. The gloss value of coating by this test method is obtained by comparing the specular reflectance from the specimen to that from a black glass standard [17-19]. Chemical surface coating properties Alkaline, acid and salt resistance properties of the films were determined according to ASTM D1647 and ASTM D1308. In these tests, films were prepared on glass test tubes or glass test panels for alkaline and acid/salt water resistance tests, respectively. Then, oven cured glass test tubes/panels were immersed in alkaline (3% NaOH, wt), acid (3% H2SO4, wt) and salt (5% NaCl, wt) solutions for, alkaline, acid and salt resistance tests, respectively. The glass tubes/panels were removed from the solutions after

93 SYNTHESIS AND FILM PROPERTIES OF NOVEL ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

immersion for at given time intervals, and the appearances of the films were investigated visually [20-21]. Water resistance properties of the films was determined according to ASTM D1647. In this test, films were prepared on tin test panels and they oven cured. Then, these tin panels were immersed in distilled water at room temperature for 18 h. At the end of the 18 h, the appearances of the films were determined after wiping dry, 20 min later, 1 h later and 2 h later [20-21]. Solvent resistance test was also performed as follows. Alkyd resin films were prepared on glass panels and they oven cured. Then, a piece of solvent (i.e., acetone, methanol, toluene and ethyl acetate) impregnated absorbent gauze was put on an alkyd resin film coated glass panel. The glass panel was covered with petri dish and kept at room temperature for 30 min. At the end of this time, the appearances of films were visually evaluated [22]. Thermogravimetric analysis Thermogravimetric analyses (TGA) of alkyd films were carried out by a Seiko SII Exstar 6000 Termogravimetric/Differential Thermal Analysis system under air at a rate of 10oC/min. Result And Discussion Physical surface coating properties Physical surface coating properties of water reducible acrylic modified alkyd resin films are given in Table 1. As shown in table, both alkyd films have excellent drying properties after being oven cured. Before the determination of drying degree, alkyd films were kept on room temperature for 24 h. At the end of the 24 h, no alkyd resin films had reached the dry-to-touch stage. The dry-to-touch stage is defined as when no mark is left when the film is touched by a finger [23]. There by, alkyd films have been cured at 150oC for 1 h. Alkyd films reached to stage 7 after being oven cured. The change of AC ratio has not affected the drying property after being oven cured. Hardness values of films were determined as 14 and 47 König second for WRAlkyd30 and WRAlkyd40, respectively. Hardness values increased with the increasing of AC ratio. At the end of the acrylic modification quite soft alkyd films were obtained. As it seen from table, the percentages of the adhesion strength of the both alkyd films were determined as 100% after being oven cured. The change of AC ratio did not cause any negative effect on the adhesion strength. As expected, the abrasion resistance test results were also obtained parallel with to the hardness test results. Abrasion resistance values of films were determined as 3000 and 2000 mL sand for WRAlkyd30 and WRAlkyd40, respectively. Abrasion resistance values decreased with the increasing of AC ratio. When these results are considered together, it can be said that, the alkyd films gained a flexibility decreasing of AC ratio. In addition, both alkyd films have very good impact resistance values after being oven cured. Oven curing process did not cause any negative effect on the impact resistance values. Gloss test results of alkyd films, which also determined after being oven cured. Gloss values of alkyd films increased with the increasing of AC ratio.

Alkyds Drying Hardness Gloss b Adhesion Abrasion resistance Impact resistance c degree a (König s.) (%) (mL sand) (kg.cm)

WRAlkyd30 7 14 34 100% 3000 >200 WRAlkyd40 7 47 48 100% 2000 >200

a after 1 h 150˚C, b at 60˚ angle, c for weight of 2 kg Table 2: Physical surface coating properties of water reducible acrylic modified alkyd resin films

94 SYNTHESIS AND FILM PROPERTIES OF NOVEL ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Chemical surface coating properties Alkaline, acid / salt, solvent and water resistance test results of alkyd films are given in Table 3, Table 4, Table 5 and Table 6, respectively.

The results of the alkaline resistance test indicated that, alkyd films have been affected alkaline solution. Whole dissolution of alkyd films in 3% wt NaOH solution were observed within 48h and 54h for WRAlkyd30 and WRAlkyd40, respectively.

Alkyds Alkaline Resistance Dissolution started Whole dissolution WRAlkyd30 23 hours 48 hours WRAlkyd40 6 hours 54 hours

Table 3: Alkaline resistance test results of water reducible acrylic modified alkyd resin films

As it seen from Table 4, WRAlkyd40 film have been affected acid and salt solutions. Dissolution have been started within the first 6 hours in 3% wt H₂SO₄ and 5% wt NaCl, solutions. However, WRAlkyd30 films have excellent acid and salt resistance.

Alkyds Acid Resistance 6 hours 48 hours 96 hours WRAlkyd30 No change No change No change WRAlkyd40 Dissolved Dissolved Dissolved Salt Resistance 6 hours 48 hours 96 hours WRAlkyd30 No change No change No change WRAlkyd40 Dissolved Dissolved Dissolved

Table 4: Acid and salt resistance test results of water reducible acrylic modified alkyd resin films

As shown in Table 5 and Table 6, both alkyd films have excellent solvent and water resistance. The change of AC ratio did not have a negative effect on the water and solvent resistances of resins.

Alkyds Solvent resistance acetone Methanol toluene ethyl acetate WRAlkyd30 No change No change No change No change WRAlkyd40 No change No change No change No change

Table 5: Solvent resistance test results of water reducible acrylic modified alkyd resin films

95 SYNTHESIS AND FILM PROPERTIES OF NOVEL ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Alkyds Water resistance after wiping dry* 20 minutes 1 hour 2 hours WRAlkyd30 Transparent Transparent Transparent Transparent WRAlkyd40 Transparent Transparent Transparent Transparent

* The appearance of film after 18 hours immersed in distilled water Table 6: Water resistance test results of water reducible acrylic modified alkyd resin films

Thermal oxidative degradations of the water reducible acrylic modified alkyd resin films were investigated by TGA under an air atmosphere. TGA thermograms are presented in Figure 1. The TGA curves indicate that, both alkyd resins show almost the same degradation behaviors.

Figure 1: TGA thermograms of alkyd films The temperatures required for reaching to certain weight losses (%) were obtained from TGA curves and are listed in Table 7.

Alkyds Temperature (oC) 10% 20% 30% 40% 50% 60% 70% 80% 90% WRAlkyd30 265 290 308 322 338 365 426 444 446 WRAlkyd40 259 284 302 316 332 362 424 440 442

a The temperature where various weight loss has occurred.

As it seen from Table 7, increasing the amount of AC caused a slight decrease in the degradation temperature. That is, increasing the AC ratio in the alkyd resin structure caused a slight decrease in the thermal stability. Conclusions As a result, for the synthesis of water reducible acrylic modified alkyd resin with the best physical, chemical, and thermal properties, the optimum AC ratio is 30% of the equivalent amount of AC to alkyd resin at this dilution ratio. Acknowledgments This work is supported by TUBITAK (The Scientific and Technological Research Council of Turkey) with Project number 214M660.

96 SYNTHESIS AND FILM PROPERTIES OF NOVEL ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

References 1. K. Manczyk, P. Szewczyk, Prog. Org. Coat. 44, 99 (2002). 2. A.I. Aigbodion, F.E. Okieimen, Ind. Crops Prod. 13, 29 (2001). 3. D.S. Ogunniyi, T.E. Odetoye, Bioresour. Tech. 99, 1300 (2008). 4. E.U. Ikhuoria, A.I. Aigbodion, F.E. Okieimen, Prog. Org. Coat. 52, 238 (2005). 5. O. Saravari, P. Phapant, V. Pimpan, J. Appl. Polym. Sci. 96, 1170 (2005). 6. V.C. Patel, J. Varughese, P.A. Krishnamoorthy, R.C. Jain, A.K. Singh, M. Ramamoorty, J. Appl. Polym. Sci. 107, 1724 (2008). 7. E. Akbarinezhad, M. Ebrahimi, S.M. Kassiriha, M. Khorasani, Prog. Org. Coat. 65, 217 (2009). 8. F.N. Jones, Alkyd resins in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Verlag GmbH & Co. KGaA, Weinheim, 2, 430 (2003). 9. R. van Gorkum, E. Bouwman, Coordin. Chem. Rev. 249, 1709 (2005). 10. A.I. Aigbodion, C.K.S. Pillai, Prog. Org. Coat. 38, 187 (2000). 11. I. Acar, A. Bal, G. Güçlü, Can. J. Chem. 91, 357 (2013). 12. Z.-L. Xiu, A.-P. Zeng, Appl. Microbiol. Biotechnol. 78, 917 (2008). 13. T. Willke, K. Vorlop, Eur. J. Lipid Sci. Technol. 110, 831 (2008). 14. C.A. Lucchesi, P.J. Secrest, C.F. Hirn, Chapter 37, Volume 2, Standard Methods of Chemical Analysis, F.J. Welcher, Ed., Robert E. Krieger Publishing Co. Inc., Huntington, New York(1975). 15. T.C. Patton, Alkyd Resin Technology, Wiley, New York (1962). 16. R.H. Pierson, Chapter 32, Volume 2, Standard Methods of Chemical Analysis, F.J. Welcher, Ed., Robert E. Krieger Publishing Co.Inc., Huntington, New York (1975). 17. G.G. Sward, Paint Testing Manual, ASTM Special Technical Publication 500, 13th Edition, American Society for Testing Materials, Philadelphia (1972). 18. A. Bal, I. Acar, G. Güçlü, J. Appl. Polym. Sci. 125, E8-E92 (2012). 19. H.S. Patel, B.K. Patel, K.B. Patel, S.N. Desai, Int. J. Polym. Mater. 59, 25 (2010). 20. M. Tahmaz, I. Acar, G. Güçlü, Res. Chem. Intermed. 41, 27 (2015). 21. E. Bulak, I. Acar, Polym. Eng. Sci. 54, 2272 (2014). 22. T. Mizutani, K. Arai, M. Miyamoto, Y. Kimura, Prog. Org. Coat. 55, 276 (2006). 23. J.V. Koleske, Paint Coating Testing Manual, 14th Edition of the Gardner-Sward Handbook, ASTM International, Ann Arbor (1995).

97 Architectural Coatings

Markus Vogel Evonik Industries AG Germany

Markus Vogel is Senior Manager of Applied Technology for the Architectural Coatings department in the business unit Coating Additives at Evonik Resource Efficiency GmbH. After studying in the field of paint and coatings technology at Niederrhein University, he began as an application engineer at an epoxy resin producer. In 2007 he joined Evonik Tego Chemie GmbH, where he worked as technical service manager in the field of architectural coatings and later on in the field of pigment concentrates.

98 GLOSSY COATINGS WITH GOOD WATER VAPOR TRANSMISSION MADE POSSIBLE BY NEW CO-BINDER TECHNOLOGY

Jürgen Kirchner, Florian Hermes, Oliver Peters Evonik Industries AG Germany

Exterior paints are the outer shell of the building. Although they play only a minor part in the total construction, they have a tough job: protect the building from the influence of weather and the environment. In many countries, this mainly means protection from the influence of water. Ideally, wall constructions should be dry and free of water or moisture. In reality, this is not usually the case. During the lifetime of a building, the walls will occasionally contain more water or moisture than is desirable, necessitating “smart” exterior coatings. This coating must protect the exterior wall from water, but it should also offer a smart management of moisture in the wall. Once moisture is in the wall, the exterior paint has to let it pass by evaporation. These two criteria – water protection and moisture management – can be described and tested by the measurement of capillary water absorption according to DIN EN 1062-3 (w-value) and the measurement of water vapor diffusion according to EN ISO 7783-2 (sd- value). These parameters must maintain a certain ratio in order to provide the best protection of the construction. In the best case, both values – the value for capillary water absorption (w-value) and the value for water vapor diffusion (sd-value) – are as low as possible.

99 GLOSSY COATINGS WITH GOOD WATER VAPOR TRANSMISSION MADE POSSIBLE BY NEW CO-BINDER TECHNOLOGY

Diagram 1: Displays the relation of w- and sd-values of different exterior paint technologies.

Low-PVC (pigment volume concentration) gloss or semi-gloss dispersion paints give low values in capillary water absorption. This means they provide very good protection against water penetration into the wall. However, low PVC formulations do have restraints: limited water vapor diffusion capabilities. Consequently, the ability to allow moisture to pass through the coating or evaporate from inside the wall is hindered, resulting in pressure which creates blisters and, in a later stage, cracking of the film, as shown in Diagram 2.

Diagram 2: Low water vapor diffusion creates crack and blistering

Opting to formulate high-PVC exterior paints (which offer a matte finish) instead results in completely different performance with regard to capillary water absorption and water vapor diffusion. However, in high-PVC paints with a low amount of binder, the voids between pigments and fillers are not completely filled. Thus the films of these paints have a microporous structure, which provides excellent completely filled. Thus the films of these paints have a microporous structure, which provides excellent

100 GLOSSY COATINGS WITH GOOD WATER VAPOR TRANSMISSION MADE POSSIBLE BY NEW CO-BINDER TECHNOLOGY

water vapor diffusion. Unfortunately, the microporous structure within the film offers poor protection against water from the outside (such as rain), resulting in high values for capillary water absorption. The common solution for the dilemma of balancing good performance in both capillary water absorption and in water vapor diffusion is the formulation of high-PVC coatings utilizing hydrophobing agents, as in silicone resin paints. This concept of formulation achieves excellent water vapor diffusion, which is generated by the inherent microporosity of the high-PVC formulation as well as the low capillary water absorption generated by hydrophobizing the microporous capillary system of the pigment and fillers with a silicone resin. The drawback is that this formulation concept only allows the formulation of matte paints.

Our new binder technology of core-shell dispersions, TEGOVAPRO®, allows the formulation of gloss and semi-gloss exterior paints with low capillary water absorption as well as high water vapor diffusion.

The new technology of core-shell dispersions enables the improvement of water vapor diffusion of low-PVC coatings by creating domains that will allow water vapor to pass without causing defects in the dried coating film, resulting in a lower sd-value of the whole coating film. To do so, the new coreshell dispersion needs to be used as a partial replacement of the dispersion binder within the formulation. A typical ratio for the replacement should be on a level of approximately 20%, calculated on the solid content of the binder. Diagram 3 shows the effect of the new core-shell dispersion on the sd-value of a low-PVC acrylic paint.

By exchanging 20% of the acrylic binder (calculated on solid content of binder) with the new core-shell dispersion, a significant increase of the water vapor diffusion has been achieved, reducing the sd-value by 60%. Additionally, the value for capillary water absorption remains unchanged, as shown in Diagram 4.

Diagram 4: High water vapor diffusion without sacrificing capillary water absorption

101 GLOSSY COATINGS WITH GOOD WATER VAPOR TRANSMISSION MADE POSSIBLE BY NEW CO-BINDER TECHNOLOGY

The effectivity of the new core-shell dispersion in reducing the sd-value strongly depends on the PVC of the formulation and therefore the binder content of the formulation as shown in Diagram 5.

Diagram 5: Strongest effect on water vapor diffusion at lower PVC

The lower the PVC of the coating, the more pronounced the effect on water vapor diffusion. In formulations with higher PVC, respectively lower binder content, the effect is greatly minimized. As the new core-shell dispersion technology partially replaces the binder, the total concentration of the new core-shell dispersion is lower compared to a binder-rich formulation Thus, as the concentration is lower, the effect diminishes until it reached a negligible level at a PVC value of 50 to 60%.

Other paint properties such as gloss, wet abrasion resistance, and artificial and outdoor weathering have been tested as well. The results of all tests are shown in Table 1.

Table 1

The use of the new core-shell dispersion minimally influences these parameters compared to the original formulation. The usage of the new core-shell dispersion does result in an increase of paint viscosity, making a correction of the thickener package necessary. Tests show that the new core-shell dispersion works with all common thickeners.

102 GLOSSY COATINGS WITH GOOD WATER VAPOR TRANSMISSION MADE POSSIBLE BY NEW CO-BINDER TECHNOLOGY

Diagram 6 shows a photograph taken with a transmission electron microscopy (TEM).

Diagram 6: Unlike high PVC paints – the new core shell emulsion provides better water vapor diffusion without pores in the film

To make the new core-shell dispersion particles visible, the acidic groups of the polymer have been marked with ruthenium tetroxide. The photo shows a coating film that has 10% of the dispersion binder (calculated on solid content of binder) exchanged with the new core-shell dispersion. Although it provides domains allowing for higher water vapor diffusion, it does not cause voids or defects in the coating film. Rather, these domains are filled with polymer of a lower density than the surrounding polymer. To create these domains, a special treatment of the new core-shell dispersion during manufacturing of the paint is necessary.

The new technology is founded on a core-shell dispersion with an extendable core of polyacrylic acid and a shell made from a film forming polymer as shown in Diagram 7.

Diagram 7: The technology

103 GLOSSY COATINGS WITH GOOD WATER VAPOR TRANSMISSION MADE POSSIBLE BY NEW CO-BINDER TECHNOLOGY

In the final formulation, the extended core creates domains of higher water vapor diffusion compared to the surrounding polymer film. The film forming shell of the dispersion provides a good integration in the coating film. Supplying the new core- shell dispersion in its most effective form requires some minor adjustments in the handling and incorporation into the final formulation.

The important step when formulating with the new core-shell dispersion is that the polymer needs to be extended by the addition of an inorganic base, such as caustic soda solution or caustic potash solution. Diagrams 8 and 9 explain how the new core-shell dispersion needs to be handled in the production process.

Diagram 8: 1. Preparation of the mill-base with an excess of inorganic neutralizing agent

Diagram 9: 2. Addition of the new core shell emulsion during the let-down stage

A standard procedure for the formulation of dispersion paints is the preparation of the mill-base with wetting and dispersing additives, pigments and fillers, and other ingredients. Quite often this step is followed by the addition of the neutralizing agent to the formulation. As the new core-shell dispersion requires the addition of an inorganic base to display its full potential, the dispersion should be added after the standard neutralization takes place. The amount of base necessary for extension of the

104 GLOSSY COATINGS WITH GOOD WATER VAPOR TRANSMISSION MADE POSSIBLE BY NEW CO-BINDER TECHNOLOGY

dispersion can be taken from the technical data sheet and is approx. 3.2g of 10% caustic soda solution per 100g of the new core-shell dispersion. After the addition of the inorganic base in the letdown step, the dispersion binder can be added and the formulation can be completed by the addition of the new core-shell dispersion as well as optional materials such as coalescing agents, thickeners etc. (Note: A pH adjustment after addition of the new core-shell dispersion needs to be avoided as it may cause instability.) In summary, the following advice should be followed when handling the new core-shell dispersion:

• The new core-shell dispersion works exclusively with inorganic neutralizing agents (e.g. NaOH, KOH). Organic amines and ammonia should be avoided. • Avoid over-neutralization. Do not add more neutralizing agent than recommended in the technical data sheet. • Do not adjust pH after addition of the new core-shell dispersion. • Prepare mill-base with an excess of inorganic neutralizing agent as indicated in the technical data sheet. • Add the new core-shell dispersion in the let-down stage.

The new core-shell dispersion offers the possibility to overcome the limitations of glossy low-PVC exterior paints with regard to their poor water vapor diffusion performance. By increasing the water vapor diffusion without impairing the low capillary water absorption, low-PVC glossy exterior paints can now be formulated on a comparable level to silicone resin paints with regard to weather protection properties. In the past, in markets where matte exterior paints (e.g. silicone resin paints) were used due to their advantages in weather protection, the use of the new core-shell dispersion enables the formulator to now also develop paints with similar performance and glossy appearance. Thanks to the new core-shell dispersion technology, TEGOVAPRO®, market segment formulations of predominately low-PVC exterior coatings can now provide strongly increasing water vapor diffusion directly translating to improved building protection.

105 Architectural Coatings

Dr. Anne Koller The DOW Chemical Company France

Dr. Anne Koller has worked for The DOW Chemical Company since 1986 both at the Research facility in Springhouse, PA, USA and at the European Laboratories, Valbonne, France. She is currently an applications scientist developing new binders for architectural coatings.

106 RHEOLOGY MODIFIERS FOR IMPROVED APPLIED HIDE AND SMOOTH FINISH IN LOW VOC EMULSION PAINTS

Dr. Pol Storme, Dr. Anne Koller The DOW Chemical Company, France

Introduction One of the decorative paints market needs is the achievement of maximum hiding with a minimum of paint coats. There are several tools designed to maximize hiding such as the use of polymeric opacifiers (Ropaque™ technology) and pre-composite polymers which adsorb onto titanium dioxide to optimize its efficiency (Evoque™ technology).

New DOW HEURS and HASE rheology modifiers were also developed to improve flow and leveling and therefore improve applied hiding, i.e. the opacity that the end user perceives. These rheology modifiers are efficient from low to high shear rate viscosity. The applied hiding of a paint is represented by the following equation in Figure 1.

Figure 1 107 RHEOLOGY MODIFIERS FOR IMPROVED APPLIED HIDE AND SMOOTH FINISH IN LOW VOC EMULSION PAINTS

It is the sum of intrinsic opacity brought by the level of titanium dioxide and the polymeric technologies such as the Ropaque™ and Evoque™ plus the paint thickness which is controlled by rheology. To this equation, one must substrate the negative effect due to lack of leveling which creates low spots in the dry paint film leading to low opacity.

Newly developed DOW Acrysol™ rheology modifiers were designed to maximize paint leveling and surface smoothness and improve applied hiding.

A) Intrinsic hiding Intrinsic hiding in a paint is determined by the level of titanium dioxide, the paint porosity and polymeric technologies such as Ropaque™ opacifier and Evoque™pre-composite technology. For Ropaque™ technology, the light scattering and hiding come from the difference of refractive index between encapsulated air in the dry stage and the surrounding components of the paint (figure 2)

Figure 2: Ropaque™ technology

Evoque™ latex

TiO2

Figure 3: Evoque™ technology

This adsorption prevents TiO2 particle to crowd and therefore leads to improved light scattering and hiding. Figure 4 shows that when TiO2 PVC of a paint increases, contrast ratio values for Evoque™ paints are higher than for standard non Evoque™ paints.

108 RHEOLOGY MODIFIERS FOR IMPROVED APPLIED HIDE AND SMOOTH FINISH IN LOW VOC EMULSION PAINTS

Figure 4: Contrast ratios

B) Film build and paint pattern B-1) Technologies to analyze paint film surface smoothness Now we are investigating the influence of the second part of the equation described in Figure 1, i.e. the influence of rheology on applied hiding. In order to link applied hiding to the paint surface smoothness, we took pictures of its surface as a function of paint drying time. A light box in which the paint film was freshly applied by roller is lit up from behind and pictures are taken during drying. Figure 5 shows the diversity of roller pattern obtained. On the left side (paint 1), paint film is leveling well during the 0-10 minute time lapse. On the right side, on the contrary, paint 2 is not as leveled and shows more pronounced hills and valleys.

Figure 5: Time Lapse Imaging

109 RHEOLOGY MODIFIERS FOR IMPROVED APPLIED HIDE AND SMOOTH FINISH IN LOW VOC EMULSION PAINTS

Figure 6: Profilometry

B-2) New DOW rheology modifiers for improved applied hiding DOW has developed low VOC HEUR and HASE rheology modifiers for low and mid shear viscosity (Brookfield and Krebs Stormer types) which offer the right balance between leveling and sagging resistance yielding to high applied opacity. Some of these new rheology modifiers use the DOW « Acid Suppression™ » technology.

Those rheology modifiers are supplied at low pH. At low pH, the hydrophobic end groups are tertiary amines which do not associate leading to easy to use, low viscosity rheology modifier solutions. When used in a paint where pH is generally high (>8), hydrophobic groups will be able to associate and fill their thickening role.

• Example A: low shear viscosity builder Acrysol™ RM-998 HEUR rheology modifier New low shear viscosity builder Acrysol™ RM-998 which utilizes the «Acid suppression™ » technology is developed to offer better paint film leveling at same sagging resistance than existing technologies. Figure 7A shows that Acrysol™ RM-998 offers better paint film leveling than a conventional commercial rheology modifier at same low shear paint viscosity adjusted at 10000 cps. This improved leveling characteristics is coupled with same sagging resistance as conventional HEURS as shown in Figure 7B.

110 RHEOLOGY MODIFIERS FOR IMPROVED APPLIED HIDE AND SMOOTH FINISH IN LOW VOC EMULSION PAINTS

Figure 7A

Figure 7B A semi-gloss paint formulated at 30% PVC, containing a hydrophobically modified HEC (HMHEC) and standard HEUR is reformulated with Acrysol™ RM-998 at same rheology. Figure 8 shows a visual comparison of the two paints applied with a roller. The paint formulated with Acrysol™ RM-998 has better leveling characteristics and better applied hiding.

Figure 8: Improved applied hiding with Acrysol™ RM-998

111 RHEOLOGY MODIFIERS FOR IMPROVED APPLIED HIDE AND SMOOTH FINISH IN LOW VOC EMULSION PAINTS

• Example B: New mid shear builder Acrysol™ DR-180 HASE rheology modifier for partial replacement of cellulosic thickeners Styrene acrylic paints were prepared at PVC 71%. Paints were applied with a leveling blade on normalized charts. Figure 9 shows that at higher paint thickness, Acrysol™ DR-180 provides better paint leveling than a paint prepared with a mixture of HEC and low shear HASE.

Figure 9 also shows that in order to control sagging resistance, it is recommended to combine Acrysol™ DR-180 with a low shear HASE thickener or HEC.

Figure 9: Acrysol DR-180 as partial replacement of HEC

Paints were applied with a brush in order to assess applied opacity. Figure 10 shows that paint containing Acrysol™ DR-180 has better leveling than paint prepared with cellulosic thickener after both one and two coats. The visual result is better applied opacity for the paint containing Acrysol™ DR-180.

Figure 10: Improved applied hiding with Acrysol™ DR-180

112 RHEOLOGY MODIFIERS FOR IMPROVED APPLIED HIDE AND SMOOTH FINISH IN LOW VOC EMULSION PAINTS

Conclusion In this article we detailed the available technologies to improve paint film applied hiding. Intrinsic opacity depends on TiO2 PVC and film porosity. Polymeric technologies such as organic opacifiers (Ropaque™) and adsorbing polymers reducing TiO2 crowding (Evoque™) are available to the paint formulator to improve intrinsic hiding.

For the end user what counts is visual opacity which also depends on paint film rheology and its ability to level without sagging in order to minimize low paint spots. Newly developed Acrysol™ rheology modifier technologies maximize paint film leveling and surface smoothness leading to better applied opacity.

Acknowledgements: I would like to thank Dow scientists Pol Storme and Inge De Preter (DOW Belgium), Tara Conley, David Fasano, James Maher, John Rabasco and Mark Langille (DOW USA), for their contributions.

113 Sustainable Technologies & Regulatory Issues (I)

Dr. Abdullah Ekin

Covestro LLC USA

Abdullah Ekin is a senior scientist at Covestro (formerly Bayer MaterialScience) in Pittsburgh, PA, USA since 2007. Dr. Ekin received his BS in chemistry in 2002 from Koç University, Istanbul, Turkey. During his undergraduate studies, he did research on thermoplastic polyurethanes and polyureas. Later, he received his Ph.D. in Coatings and Polymeric Materials in 2007 from North Dakota State University, Fargo, ND USA. During his Ph.D. he did research on thermoset silicone-polyurethane coatings for underwater marine applications. He has 8 US patents and 7 pending patent applications. He has published 14 peer-reviewed papers and several preprints.

114 THE FIRST BIO-BASED ALIPHATIC POLYISOCYANATE FOR HIGH PERFORMANCE POLYURETHANE COATINGS

Dr. Abdullah Ekin1, Dr. Gesa Behnken2, Nusret Yuva2, Dr. Berta Vega Sánchez2, Andreas Hecking2 1Covestro LLC, Pittsburgh USA 2Covestro Deutschland AG Germany

A new bio-based pentamethylene diisocyanate (PDI) based polyisocyanate was developed and its properties were compared to existing hexamethylene diisocyanate (HDI) polyisocyanates. The properties of bio-based PDI polyisocyanates coatings are comparable (or better) than HDI polyisocyanates.

Bio-based PDI polyisocyanate has 70% bio-content that is from field corn, a feed and industrial crop that is not intended for human consumption. Bio-based PDI polyisocyanates can be complimentary hardeners for bio-based polyols and may form high-performance polyurethane coatings that are derived from nature without sacrificing any coating properties: High performance enabled by nature.

Coating formulations, application and performance of the bio-based PDI polyisocyanates will be discussed. In addition to comparable performance of bio-based PDI to HDI, some unique features of bio-based PDI polyisocyanates will be presented.

115 Sustainable Technologies & Regulatory Issues (I)

Eric Brouwer Croda Nederland B.V. Netherlands

Academic Background: Graduation: Master degree Chemical Engineering Course: Polymer Chemistry Institution: Eindhoven University of Technology (TU/e), Eindhoven, The Netherlands Graduated: 1993

Professional Experience: Since 2011 with Croda Coatings & Polymers as Applications Specialist for industrial coatings, Eric has 20 years of experience in R&D departments of coatings, polymers and adhesives producing companies. Currently responsible for technical support in Europe.

116 BRINGING POLYURETHANES COATINGS TO THE NEXT LEVEL WITH BIO-BASED POLYOLS AND ENHANCED PERFORMANCE

Eric Brouwer Croda Nederland B.V. Netherlands

Traditionally PU coatings have been based on polyether and polyester polyols from non- renewable sources. With a trend towards more sustainable raw materials, bio-based polyols are being developed. Besides sustainability, these polyols can offer clear performance benefits over traditional raw materials.

To meet market needs for polyols with improved properties like moisture resistance and flexibility, a bio-based range of polyols has been developed. Besides being more sustainable themselves, these polyols can meet the requirements of the coating producers that are currently not fulfilled by PTMEG or adipates. Properties like flexibility, low viscosity and affinity for substrates such as plastics, steel and wood can be found. This also makes the final coating more durable and provides a sustainable solution. Typical applications include PUDs. The polyols have shown good soft feel and good adhesion to a wide variety of substrates.

These polyols are widely applicable, so not only in coatings but also in adhesives, as will be shown.

117 Sustainable Technologies & Regulatory Issues (I)

Prof. Dr. Hüseyin Deligöz Istanbul University Turkey

Professor Deligoz received his B.S. in Chemical Engineering from Istanbul University (IU) in 1994 and he earned his PhD in 2002 from IU. After obtaining his PhD, he joined the team of Professor Werner Mormann from University of Siegen/Germany in 2003 and then joined the workgroup of Professor Bernd Tieke from University of Cologne/Germany in 2004-2005 as post-doctoral associate. He was also at University of Cologne/Germany in 2012 as visiting Professor. He is currently working in Chemical Engineering Department of Istanbul University as Professor from July 2014.

His main researches include polymer chemistry, polymer composites, nano functional surfaces and coatings. Professor Deligoz serves as an editorial board member of International Journal of Membrane Science (IJMST) and acts as reviewer and evaluator for TUBİTAK supported projects. He has published over 40 SCI papers and more than 100 congress presentations.

118 BIO-BASED UV CURABLE COATING SYSTEMS

Prof. Dr. Hüseyin Deligöz Istanbul University Turkey In the paint industry, it has been realized that the presence of volatile organic compounds (VOCs) in the atmosphere can lead to serious air pollution problems. The key is to formulate coatings with reduced or no solvent levels. A way to attain high solid coatings is to use reactive diluents which are very low molecular weight polymers instead of the conventional use of solvents to thin coatings to correct application viscosity. These diluents react to become part of the coating matrix and do not evaporate [1]. Energy also is a big concern, particularly, the consumption of fossil fuel resources since polymer and coatings fields rely mainly on petrochemical products derived from crude oil which will become scarce in the future. As a result, new technologies were invented and many efforts have been directed toward the area of renewable resources. In the last decade, UV-curing technology has attracted a great attention for the satisfaction of these requirements. This technology can be considered as a kind of high solid system. Studies have demonstrated that UV-curing coatings reduce energy consumption and hazardous emissions over conventional coatings [2-3].

In this study, a series of UV-curable tung oil alkyd (UVTA) was prepared from tung oil-based alkyd synthesized via the monoglyceride process and then reacted with acrylate via Diels-Alder cycloaddition reaction. Acrylate compound was added to the alkyd formulation in different proportions to adjust the performance of final product. The tung oil-based alkyd (UVTA) was characterized using FTIR, H-NMR and C-NMR. Then the UV-curable alkyd was formulated with some diluents and commercial photo-initiators to form a UV-curable paint. Then, the coating performances of UV-curable paints/films on glass and wood substrate were tested in terms of curing time, hardness and adhesion and contact angles. In conclusion, cure and surface cure assessment showed that the use of modified resin (MR) in the alkyd formulation lead to faster curing and the product was fully cured in 112 seconds. The paints/films exhibited good coating properties including impact resistance, hardness and adhesion.

Acknowledgements This study was financially supported by TUBITAK, Project Number: 513007. The authors also wish to express their appreciation for the cooperation of KAYALAR KIMYA San. ve Tic. A.Ş. References 1- Johnson, Jeffery W.; Matheson, Robert R.; White, Donald A.; Drysdale, Neville Everton; Corcoran, Patrick Henry; Lewin, Laura Ann. Polymerization of acrylic polymers in reactive diluents. PCT Int. Appl. (2008) 2- Golden, Ronald. Low-emission technologies: A path to greener industry. RadTech Report (2005), 19(3): p. 14-18. 3- Mehnert, R., Pincus, A., Janorsky, I., Stowe, R., Berejka, A., UV & EB Curing Technology & Equipment, John Wiley and Sons Inc., 1998, New York.

119 Processing & Testing of Coatings (I)

Alican Güler Alfa Kimya Turkey

Alican Güler studied chemical engineering at Yıldız Technical University in Istanbul. After graduated from Bs. in 2013, started to MSc. in Chemical Engineering at the same university. His MSc. thesis is about ''Preparation and Characterization of Alkyd Resin Nanocomposites''. He is working as a Technical Sales Engineer in Alfa Kimya since 2013.

120 PREPARATION AND CHARACTERIZATION OF ALKYD RESIN NANOCOMPOSITES

Alican Güler1 Sennur Deniz2 1 Alfa Kimya, 2 Yıldız Technical University Turkey Abstract In this study, synthesis of alkyd-nanosilica nanocomposites, investigation of phsyical, chemical and optical properties were studied. As nanosilica, hydrophobic and hydrophilic silicas were used. Alkyd nanocomposites were synthesized as a benzoic modified alkyd in a different ratio of (% 0.1 to %3) nanosilica containing. Benzoic modified alkyd nanocomposites were produced in a reactor at 240°C and was diluated with xylene to % 60 percent of solid. The quick drying paint from benzoic modified rapid alkyd was produced. Different ratio of nanosilica containing alkyd nanocomposite paints were charachterizated with gloss, gloss retention, scratch resistance, corrosion resistance, adhesion properties, hardness and drying tests. All test results were compared with alkyd resin which is not including nanosilica and were investigated the effects of hydrophobic and hydrophilic nanosilica amount. Using %0.1 hydrophilic silica has very good scratch resistance, corrosion resistance, adhesion properties and flexibilty. So, alkyd resins containing hydrophilic nanosilica are suitable for manufacturing of industrial rapid coatings.

121 PREPARATION AND CHARACTERIZATION OF ALKYD RESIN NANOCOMPOSITES

1. Introduction Alkyd is a kind of polyester resin produced by polycondensation reaction of polyhydric alcohols and dibasic acids, modified with oil or fatty acids. The name “alkyd” comes from ingredients; alcohols and acids. These resins are polyesters modified with monobasic fatty acids [1]. Coatings made from alkyd resins dry quickly and their properties are sufficient for decorative purpose [2] The coatings of standard conventional alkyds are solvent based resins, and these resins are diluted with an organic solvent such as toluene, xylene, white spirit, solvent naphta, solvesso 100, excol D40 and a mixture of these solvents. The emission of volatile organic compounds (VOC) from solvent based alkyd resins causes many environmental problems[3-4].. In all over the World, usage of solvent borne binders are under serious restrictions. However, especially in industrial coatings, alkyd resins are widely used due to their outstanding performance and easy application.

Nano particle additives are very important for the paint industry. The inorganic nanoparticles used for the polymeric coatings are SiO2, TiO2, Al2O3, CaCO3, ZnO,Fe2O3 and organoclay [5-14]. Especially silica based nanocomposites are widely used in coatings. In this study, synthesis of alkyd-nanosilica nanocomposites, investigation of phsyical, chemical and optical properties were studied. As nanosilicas, hydrophobic and hydrophilic silicas were used. All test results were compared with alkyd resin which is not including nanosilica and were investigated the effects of hydrophobic and hydrophilic nanosilica amount. 2. Experimentals 2.1 Materials Sunflower oil was used in preparation of alkyd resins. Oil was obtained from Sam Yagcilik. Phthalic anhydride was obtained from Petkim, pentaerythritol was from MKS, benzoic acid from RMS and xylene from Gadiv. As a hydrophobic silica, Evonik AEROSIL® R 972 , as a hydrophilic silica Evonik AEROSIL® 200 was used.

Characteristic physico-chemical datas of Evonik AEROSIL® R 97 Properties Unit Amount Specif ic surface area m2/g 175-225 pH value (in %4 dispersion) 3,7 - 4,5 Loss on drying (2 hours at 105°C') % <0,5 SiO2 Content % >99,8

Table 1

Characteristic physico-chemical datas of Evonik AEROSIL® 200 Properties Unit Amount Specif ic surface area m2/g 90-130 pH value (in %4 dispersion) 3,6 - 5,5 Loss on drying (2 hours at 105°C') % <0,5 SiO2 Content % >99,8

Table 2

122 PREPARATION AND CHARACTERIZATION OF ALKYD RESIN NANOCOMPOSITES

2.2 Preparation of alkyd nanocomposites Alkyds have %27 oil content and prepared with sunflower oil, phthalic anhydride, pentaerythritol, benzoic acid and nanosilica. The temperature of reactions are approximately 240°C. Alkyds were produced with monoglicerid process. Hydrophobic and hydrophilic silicas were added different ratio of %0,1 to %3. At the end of the reaction, alkyds were diluated to %60 solid content with xylene.

2.3 Paint formulation In paint formulation alkyd ratio is %56,1. As a dispersion agent Disperbyk 107, as a TiO2 Dupont R902 was used. All driers were obtained from Ege Kimya.

Paint formulation Product Amount ALFAKYD O27 X60 (with nanosilica modif ied) 561g Dispersing/Wetting Agent 8g Titan R 259g Cobalt (6) 2,5g Ca (4) 13,6g Zr(12) 12g Anti skinning agent 2,5g Xylene 141,4g Total 1000g

Table 3

2.4 Testing of Paint Samples Different ratio of nanosilica containing alkyd nanocomposite paints were charachterizated with gloss, gloss retention, scratch resistance, corrosion resistance, adhesion, toughness and drying tests. Paint films were applicated by 100 µm applicator. All test results were made in first and seventh day. Gloss and gloss retention test was made on TS_4318_EN_ISO_2813 reference. Konig test was made according to DIN 53157. Adhesion test was determined by cross-cut method according to ASTM D-3359- 76. Corrosion resistance tests were made in %3 NaCl solution for 28 days. 3. Results and Discussions Rapid alkyd resins of acid values (max 12) were prepared from phthalic anhydride, pentaerythritol, benzoic acid , hydrophobic nanosilica ( %0,1 - %0,5 - %1 ) and hydrophilic nanosilica ( %0,1 - %1 - %3 ). All paints were preapared from paint formulation on Table 3.

3.1 Mechanical and Optical Properties 3.1.1 Adhesion Properties Fig. 1 shows the adhesion properties of the coating as a function of a concentration hydrophobic and hydrophilic nanosilica in first and seventh day. From this figure, it can be appeared that coating with hydrophilic nanosilica effects on adhesion well. A coating system with Evonik Nanosilica 200 which has amount of %0,1 nanosilica has the best performance from the rest of systems.

123 PREPARATION AND CHARACTERIZATION OF ALKYD RESIN NANOCOMPOSITES

When the amount of hydrophilic nanosilica increased, adhesions properties decreased. Although it has %3 nanosilica, has better adhesion than without nanosilica sample. From the figure, it can be seemed that alkyd without nanosilica has better adhesion than all hydrophobic nanosilicas in first day ( %0,1 - %0,5 - %1 ). In seventh day, it balanced on Gt-5.

Fig 1. Adhesion properties of the coating as a function of a concentration hydrophobic and hydrophilic nanosilica

Adhesion properties Cross Alkyd Evonik Evonik Evonik Nanosilica Nanosilica Nanosilica Cut (without Aerosil Aerosil Aerosil 200 %0,1 200 %1 200 %3 Results silica) R972 %0,1 R972 %0,5 R972 %1

1st day Gt-2 Gt-5 Gt-5 Gt-5 Gt-1 Gt-2 Gt-2 7th day Gt-5 Gt-5 Gt-5 Gt-5 Gt-2 Gt-3 Gt-4

Table 4 3.1.2 Scratch Resistance Fig. 2 shows the scratch resistance of the coating as a function of a concentration hydrophobic and hydrophilic nanosilica in first and seventh day. It can be appeared that coating with hydrophilic nanosilica contributes to sctratch resistance. It was found that small amount of hydrophilic silica which are %0,1 and %1 increase scratch resistance. Also, addition of hydrophobic nanosilica showed worse performance than paint which produced from alkyd without nanosilica.

Fig 2. Scratch resistance of the coating as a function of a concentration hydrophobic and hydrophilic nanosilica 124 PREPARATION AND CHARACTERIZATION OF ALKYD RESIN NANOCOMPOSITES

Scratch Resistance Scratch Alkyd Evonik Evonik Evonik Nanosilica Nanosilica Nanosilica resistance (without Aerosil Aerosil Aerosil 200 %0,1 200 %1 200 %3 silica) R972 %0,1 R972 %0,5 R972 %1 1st day A-5 A-4 A-2 A-3 A-5 A-5 A-5 7th day A-2 A-3 A-1 A-1 A-5 A-5 A-3

Table 5

3.1.3 Hardness Hardness test results were given in Table 6 as Konig second for air dried films. Films were determined by Konig Pendelum according to DIN 53157. As it is seen on Table 6 that using hydrophilic silica increased flexibility of films. Increasing the hydrophobic silica amount to %1 causes an increment about %10 in hardness value of films.

Hardness Properties Hardness Alkyd Evonik Evonik Evonik Nanosilica Nanosilica Nanosilica (without Aerosil Aerosil Aerosil 200 %0,1 200 %1 200 %3 silica) R972 %0,1 R972 %0,5 R972 %1 Konig 1st day 22 21 25 28 22 21 20 Konig 7th day 47 48 52 53 48 46 38

Table 6

3.1.4 Gloss and Gloss Retention It shows that using %1 hydrophobic nanosilica decreasing gloss and gloss retention about 8 gloss in 60° angle. The results show that hydrophilic nanosilica has no effects on gloss properties.

Gloss and gloss retention properties Alkyd Evonik Evonik Evonik Nanosilica Nanosilica Nanosilica Gloss (without Aerosil Aerosil Aerosil 200 %0,1 200 %1 200 %3 silica) R972 %0,1 R972 %0,5 R972 %1

20° 90,8 84,3 75,8 65,2 91,5 87,9 85,9 1st day Gloss 60° 95,5 94,2 91,5 88,4 95,7 94,7 94,6 85° 100 99,1 98,4 98 100 99,8 99,2 20° 88,2 83 73,9 61 89,4 87,2 84,6 7th day Gloss 60° 94,5 93,8 90,9 86,5 94,8 94,5 94 85° 99 99,9 99,9 98,5 99 99,7 99,7

Table 7

125 PREPARATION AND CHARACTERIZATION OF ALKYD RESIN NANOCOMPOSITES

3.1.5 Corrosion Resistance %3 NaCl solution was prepared. All panels were kept in this solution for 28 days. As it is seen on Figure 3, %3 hydrophobic nanosilica has a very good anticorrosive properties.

Fig. 3 Corrosion resistance of hydrophobic and hydrophilic nanosilica

3.1.6 Drying Properties Each nanosilica addition has not shown a negative effect on drying time.

Hardness Properties Product Alkyd Evonik Evonik Evonik Nanosilica Nanosilica Nanosilica (without Aerosil Aerosil Aerosil 200 %0,1 200 %1 200 %3 silica) R972 %0,1 R972 %0,5 R972 %1 Drying (Touch dry) 10' 10' 10' 10' 12' 10' 10'

4. Conclusion After the films dried, chemical and phyical properties of the films were investigated. Nanosilica addition has not shown a negative effect on drying time. While hardness values of films decreased with the increasing of hydrophilic nanosilica,adhesion, anticorrosive properties and scratch resistance increased, gloss and gloss retention wasn’t change In addition to gloss values of films were decreased with increasing hydrophobic nanosilica amounts and in case of %1 Evonik Aerosil R972 content, gloss reduced more than %9. Using hydrophobic silica has a negative effects on scratch resistance and adhesion. No effects on corrosion resistance.

In conclusion, %0,1 hydrophilic nanosilica usage increased adhesion, scracth resistance, corrosion resistance and flexibility and has no effects on drying and gloss properties. So, alkyd resins containing hydrophilic nanosilica are suitable for manufacturing of industrial rapid coatings.

126 PREPARATION AND CHARACTERIZATION OF ALKYD RESIN NANOCOMPOSITES

References: 1. G.P.A. Turner, Introduction to Paint Chemistry and Principles of Paint Technology, 2nd ed., Chapman and Hall, New York, 1980. 2. K. Mańczyk, P. Szewczykb, “Highly branched high solids alkyd resins’’, Progress in Organic Coatings, 2002, 99–109. 3. A.A. Yousef i, M. Pishvaei, A. Yousef i, Prog. Color Colorants Coat. 4 (2011) 15–25. 4. S.K. Dhoke, T.J.M. Sinha, P. Dutta, A.S. Khanna, Prog. Org. Coat. 62 (2008)183–192. 5. Dhoke S.K., Khanna A.S.: Effect of nano-Fe2O3 particles on the corrosion behavior of alkyd based waterborne coatings. Corrosion Science, 2009; 51: 6-20. 6. Dhoke S. K., Bhandari R., Khanna A.S.: Effect of nano-ZnO addition on the silicone-modified alkydbased waterborne coatings on its mechanical and heatresistance properties. Prog. Org. Coat. 2009; 64: 39-46. 7. Allen N. S., Edge M., Ortega A., Sandoval G., Liauw C.M., Verran J., Stratton J., McIntyre R.B.: Degradation and stabilization of polymers and coatings: nano versus pigmentary titania particles. Polym. Degrad. Stab. 2004; 85: 927-946. 8. Tahmaz M., Acar I., Güçlü G.: Synthesis and film properties of long oil alkyd resin/organo clay nanocomposite coatings. Res. Chem. Intermed. 2015; 41: 27-42. 9. Kurt İ., Acar I., Güçlü G.: Preparation and characterization of water reducible alkyd resin/colloidal silica nanocomposite coatings. Prog. Org. Coat. 2014; 77: 949-956. 10. Bal A., Acar I., İyim T.B., Güçlü G.: A Novel Type of Organo clay containing alkyd-melamine formaldehyde resins, Int. J. Polym. Mater. Polym. Biomater. 2013; 62, 309-313. 11. Bal A., Güçlü G., Acar I., İyim T.B.: Effects of urea formaldehyde resin to film properties of alkyd-melamine formaldehyde resins containing organo clay, Prog. Org. Coat. 2010; 68, 363-365. 12. Bal A., Acar I., Güçlü G., İyim T.B.: Effect of organo clay on film properties of alkyd-phenol formaldehyde resins, Pigment & Resin Tech. 2012; 41/2, 100-103. 13. Bal A., Acar I., Güçlü G.: A novel type nanocomposite coating based on alkyd-melamine formaldehyde resin containing modified silica: Preparation and film properties, 2012; J. Appl. Polym. Sci. 125, E85-E92. 14. Bal A., Acar I., Güçlü G.: Thermal oxidative degradation kinetics of nanocomposite alkyd-melamine formaldehyde resin containing modified silica, Ins. Sci. & Tech. 2014; 42,345-356.

127 Processing & Testing of Coatings (I)

Dr. Funda İnceoğlu Kalekim Kimyevi Maddeler San. Tic. A.Ş. Turkey

Dr. Funda İnceoğlu obtained her BSc and MSc degrees in Chemistry at Middle East Technical University and her PhD in Material Science and Engineering at Sabanci University. After obtaining her PhD, she continued her studies mainly on polymer processing as a Postdoc researcher at Sabanci University. She then worked as a Research Engineer at Arkema-France until 2010. Since then, she has been working for Kalekim Chemicals as an Applied Research Group Leader.

128 THE USE OF RHEOLOGY IN EVALUATING AND OPTIMIZING THE PAINT PERFORMANCE

Dr. Funda İnceoğlu, Nazife Uğur, Volkan Kırmızı, Melek Övet, Gülden Tombaş Kalekim Kim. Mad. San. Tic. A.Ş. Turkey

Abstract Many different paint properties; like consistency, storage stability, brush drag, spattering, leveling, sagging are related to flow behavior. Rheological measurement is necessary to characterize the flow behavior of paint formulations, because it covers a wide range of shear rates that are associated with different paint properties. For example, storage and transportation are low-shear processes and the viscosity requirement for these processes is high, while rolling and spraying are high shear processes and low viscosity is necessary for these applications. On the other hand, flow curve at different shear rates obtained from rotational measurements is not enough to evaluate all the paint properties. Since most of the paints are viscoelastic materials, oscillatory measurements have to be performed as well.

The present work includes the study of rheological profile of various paint formulations prepared using different thickeners. Rheological test measurement includes both rotational and oscillatory tests. In order to establish the correlation with rheology, the paint formulations were also evaluated in terms of application, performance and in-can properties. The results showed that rheological measurements provided valuable insight into the important paint properties and minimized the need for real application trial which is time consuming, expensive and human dependent.

129 Processing & Testing of Coatings (I)

Dr. Clifford K. Schoff Schoff Associates USA

Cliff Schoff has spent 40 years doing research and problem solving related to coatings. He holds B.S. and M.S. degrees in Chemistry from the University of Idaho and a Ph.D. in Polymer Chemistry from the University of St. Andrews in Scotland. Before joining the coatings industry, he was a Peace Corps science teacher in Nigeria and on the research staffs at Glasgow and Princeton Universities. From 1974 until 2002, he did research and problem solving in many areas for PPG Industries, including surface defects, rheology, mechanical properties, corrosion and pigment dispersion. Cliff has published more than 40 papers and articles plus more than 100 one-page “Coatings Clinic” articles for JCT Coatings Tech. He has given lectures and taught short courses on a number of coatings subjects in the U.S. and overseas. He has been active in the Pittsburgh Society for Coatings Technology and Committee D01 on Paints and Related Materials of ASTM for many years. He is Chair of the Publications Subcommittee for the American Coatings Association and is one of the Technical Editors for the Journal of Coatings Technology and Research. He has received the Mattiello and Tess awards for outstanding contributions to coatings science and technology.

130 EXTENSIONAL (ELONGATIONAL) VISCOSITY

Dr. Clifford K. Schoff Schoff Associates USA

When we measure or specify viscosity in the coatings industry, we virtually always are dealing with shear viscosity and laminar flow. Processes such as brushing, spraying, roll coating, pipe flow and pigment dispersion involve shearing deformation such that one layer of material slides over another and over the substrate, pipe or pigment particle. When measured under the right conditions with devices such as flow cups and rotational viscometers, shear viscosity enables us to meet specifications and predict or confirm that our coatings will apply properly, flow and level adequately and not sag noticeably.

However, there is another type of viscosity called extensional or elongational viscosity. Extensional flows occur when fluid deformation is the result of a stretching motion. Well- known examples of such flows include the spinning of fibers for textiles, extrusion of polymer melts and blow-molding of plastic bottles. Stretching also occurs in coatings, particularly during the breakup of droplets in spray atomization, the splitting of paint between a brush and the substrate and the splitting of paint between the roller and the substrate in roll coating (architectural and industrial coatings). Less obvious stretching undoubtedly occurs in sagging and surface tension driven flows. Unlike shear viscosity, extensional viscosity has no meaning unless the type of deformation is specified. The three types of extensional viscosity are uniaxial, biaxial, and pure shear. However, uniaxial viscosity is the only one used to characterize fluids. For a Newtonian fluid, the uniaxial extensional viscosity is three times the shear viscosity: (ηe) uni = 3η and for non-Newtonian fluids it can be many times higher.

131 EXTENSIONAL (ELONGATIONAL) VISCOSITY

Extensional viscosity is related to the stress required for the stretching. This stress is defined as that necessary to increase the distance between two material entities in the same plane when the separation is s and the relative velocity is ds/dt. The deformation rate is the extensional strain rate, which is given by the equation ė = 1/s (ds/dt).

The problem with the extensional viscosity of paints and inks is that it is difficult to measure.

Historically, extensional viscosity measurements have been done on polymer melts and concentrated solutions with homemade instruments. Commercial instruments have come and gone and one or two are currently available. Most devices stretch a filament at a constant deformation rate and measure the force necessary to do so along with the diameter of the filament. The methods are limited to spinnable fluids, which do not include paints and inks unless they are highly thickened. However, a number of adhesives and sealants probably could be tested with these instruments. Two rheometers that hold promise for measuring extensional viscosities of paints and inks are the Haake Capillary Breakup Extensional Rheometer (CaBER 1) and the Vilastic V-E Rheometer with the extensional viscoelastic attachment. They both claim wide shear viscosity ranges that go down to 5-10 mPa•s (cPs), which should allow testing of just about all paints and inks. They have been shown to work with low viscosity materials, but only those having a considerable viscoelastic component. Unfortunately, I have never had the opportunity to work with either one of these instruments and have not yet seen any paint or ink data from them.

There is a rheometer that works for a wide range of fluids. It is an opposed jets device invented by G.G. Fuller. Opposing nozzles suck or blow out fluid. Extensional viscosity is measured from the force required to keep the nozzles at a fixed distance apart as a function of time. Unfortunately, if you want such an instrument, you must build it yourself. Rheometrics marketed one version, the RFX, but must not have sold enough of them to justify continuing to manufacture them. I had a few automotive clearcoats that showed differences in sprayability run on the RFX, but the extensional viscosities were not as different as I expected. Before we could do more measurements and, perhaps, optimize the conditions, management stopped the project.

With such measurement difficulties, why should we worry about extensional viscosity, much less try to measure it? It turns out that high extensional viscosity contributes to roller spatter, roll coat ribbing and misting, poor spray atomization (large droplets, stringing and cobwebbing) and poor knitting of spray droplets on the work piece. Extensional viscosity is related to viscoelasticity, so one way to get at extensional viscosity is to measure or estimate the degree of elasticity of the fluid. Measurement of viscoelasticity is not easy either and requires an oscillatory rheometer for precise measurements, but a lot can be learned from careful observations during rheological measurements and paint formulation. For example, a viscoelastic fluid tends to push up the cone of a cone/plate viscometer or cause chattering (bouncing) of the cone. It also is liable to climb up stirrer shafts during polymerization or mixing and during viscosity measurement in a concentric cylinder viscometer. A viscoelastic fluid shows extrusion swell from a syringe that can be observed by eye or, better, with a microscope. What causes viscoelasticity? In solventborne coatings, it is likely to be high molecular weight resin, often just a small amount that shows up in Gel Permeation Chromatography (GPC) as a high MW “tail.” Waterborne coating elasticity also may be due to high MW material or to solvent swelling of the latex or dispersion resin.

In conclusion, extensional viscosity is a frustrating parameter. It is important, but we are not likely to be able to measure it. However, we can measure or estimate elasticity and there are tell-tale signs when a paint has significant elasticity. The resin and/or solvent blend may have to be changed to prevent or reduce elasticity.

132 EXTENSIONAL (ELONGATIONAL) VISCOSITY

Relevant References

• J.E. Glass, J. Coatings Technol., 50 (641), 56 (1978). • G.G. Fuller et al, J. Rheol., 31, 235 (1987). • D.A. Soules, R.H. Fernando and J.E. Glass, J. Rheol. 32, 181, 199 (1988). • J. Meadows, P.A. Williams and J.C. Kennedy, Macromolecules, 28, 2683-2692 (1995). • A. Lindner, J. Vermant and D. Bonn, Physica A: Statistical Mechanics and its Applications, 319 (3), 125-133 (2003). • J.H. Yu, S.V. Fridrikh and G.C. Rutledge, Polymer 47, 4789-4797 (2006). • K. Niedzwiedz et al, Applied Rheol., 19 (4), 41969-1 (2009). • L. Campo-Deaño and C. Clasen, J. Non-Newt. Fluid Mech., 165, 1688-1699 (2010). • O. Arnold et al, Rheol. Acta, 49, 1207-1217 (2010).

133 Sustainable Technologies & Regulatory Issues (II)

Paul Wood Dow Microbial Control Switzerland

Customer Application Specialist – CEET region, Dow Microbial Control, part of the Dow Chemical Company, based in Horgen, Switzerland. With over twenty five years experience in the biocides industry initially holding laboratory based roles in research and development and customer service, and then in sales and marketing. For the last twelve years I have been the technical support for biocides covering a wide range of different industries covering many different countries. Author of many technical papers and review articles.

134 BPR AND BIOCIDAL PRODUCT AUTHORISATIONS ? WHAT YOU NEED TO KNOW?

Paul Wood Dow Microbial Control Switzerland

1 - Regulatory Changes Legislation, legislation and more legislation! Confused by the new EU Biocidal Products Regulation ( BPR ) and the 2nd ATP of the CLP and how this impacts the sale of your products both in Turkey and your exports to Europe today, tomorrow and also in the future. This paper will explain the complexities of the BPR with regards to Treated Articles, Article 95 and the ECHA approved list suppliers of biocidal actives as well the subject of Product Authorisations. Turkey will adopt the CLP ( GHS system ) in 2016 – how will this affect your current preservation system? 2016 will see the milestone launch of a new biocidal active from Dow Microbial Control the first in over twenty years to help with your compliance to all the above legislation.

Whilst the subject of changes in European legislation have been extensively covered in my previous papers the consequences for the Turkish coatings industry when exporting to the EU are such that is vitally important to re-visit these complex pieces of legislation, for example Treated Articles and more recently Product Authorisations. 1. Biocidal Products Regulation 1.1. Introduction Biocides are regulated under the Biocidal Products Regulation (BPR, Regulation (EU) 528/2012) which repeals the Biocidal Products Directive (Directive 98/8/EC). [3] The EU Biocides Regulation 528/2012 (EU BPR) contains provisions which apply not only to biocidal products but also to all articles which have been treated or incorporate a biocidal product. In particular, articles can only be treated with active substances which have been approved in the EU for

135 BPR AND BIOCIDAL PRODUCT AUTHORISATIONS ? WHAT YOU NEED TO KNOW?

that purpose. This is a significant change to the previous requirements under the Biocidal Products Directive (BPD), where articles imported from outside the EU could be treated with substances not allowed in the EU. Article 3 of the EU Biocides Regulation 528/2012 (EU BPR) defines a treated article as “any substance, mixture or article which has been treated with, or intentionally incorporates, one or more biocidal products”.

1.2. What are the Requirements for Treated Articles? The requirements for treated articles can be found in Article 58 of EU BPR and these apply to treated articles that are not themselves biocidal products. EU BPR prohibits placing on the market, including the importation, of the treated article unless all active substances in the biocidal product it was treated with/incorporates are approved for relevant Product Type and use under EU BPR, and any specified conditions or restrictions of all the active substances are met. Therefore, before placing the treated article on European market, the manufacturer of the treated article will need to ensure that the active substance is either approved for that Product Type, or is under review for that Product Type. Approved suppliers can also only sell in the Product Type where they have notified and supported their active ingredients. ECHA published a list of all approved suppliers that is publically accessible [2]. As of September 2015 only approved suppliers can sell in the EU. http://echa.europa.eu/documents/10162/17287015/active_substance_suppliers_en.pdf

Manufacturers and importers of treated articles are also required to label the articles when they make a claim that the treated article has biocidal properties; and/or the conditions of the approval of the active substance(s) use to treat the article require specific labelling provisions to protect public health or the environment. Finally, anyone placing a treated article on the market must provide, free of charge when requested, information on the biocidal treatment of the treated article. This information must be provided within 45 days (article 58 (3)).

1.3. What Information should be Included on the Labelling of a Treated Article? The label on a treated article must contain the following information: a. a statement that the treated article incorporates biocidal product(s); b. where substantiated, the biocidal property attributed to the treated article; c .the name of all active substances contained in the biocidal products; d. the name of all nanomaterials contained in the biocidal products, followed by the word ‘nano’ in brackets; e. any relevant instructions for use, including any precautions to be taken because of the biocidal products with which a treated article was treated or which it incorporates. f. any relevant instructions for use, including any precautions to be taken, if this is necessary to protect humans, animals and the environment.

The key is to understand what type of claim is made to the finished products in order to understand the labelling or even the need to register the finished product as a biocidal product. There is still the distinction between a treated article having a biocidal property and a biocidal function. For example, a paint containing an in-can biocide shall be considered as a treated article. If the paint producer is not making any claims, then the biocide added in this case is considered to be an internal effect and does not need any labelling, except if the active substance approval requires it.

136 BPR AND BIOCIDAL PRODUCT AUTHORISATIONS ? WHAT YOU NEED TO KNOW?

•A dry film biocide (Product Type 7) added in a paint but where the paint producer does not make any claim also does not need any labelling, except if the active substance approval requires it •A dry film biocide (Product Type 7) added in a paint but where a claim is made needs to be labelled “Paint contains biocidal products + name of substances”. Claim can be of the type “This paint is protected against disfigurement caused by fungi and algae”. • A paint where a biocide is added to bring an external effect and where the claim is in the order of antibacterial properties (e.g. hygiene claim), this would make the paint a biocidal product and therefore falls under Product Type 2. The labelling requirements mentioned in Article 58 (3) applies to treated articles placed on the EU market from 1 September 2013.

1.4. Product Authorisations Once an active ingredient has been approved and placed on the EU list of Approved Substances for use in specific Product Types there is a short-time frame, typically eighteen months whereby formulated biocides and if applicable customer formulations need to be registered. Registrations will only be granted for suppliers who are on the ECHA approved suppliers list with active ingredients which are approved in the product types and accompanied with an extensive full dossier containing information as specified in the BPR Technical Guidance notes. Registration fees are applaicable not only for the Member State where registration is sought but also for all Member States where the product will be sold. These fees are still under but could vary between 0.50 and 2.00% of the annual turnover of the product in each Member State. 2. 2nd Adaptation to Technical Progress: definition and solutions - CLP 2.1. Definition In Europe, a new EU regulation (EU) No 286/2011 the 2nd Adaptation to Technical Progress (ATP) to the CLP Regulation. CLP is Regulation (EC) No. 1272/2008 on classification, labelling and packaging (CLP) of substances and mixtures. It introduced a new rule for the labelling of preparations used in industrial products containing a skin sensitising substances. Indeed, for sensitising substances with a specific concentration limit lower than 0.10 %, the concentration limit for elicitation (EUH 208) should be set at one tenth of the specific concentration limit.

A higher concentration in a preparation will trigger the EU H208 warning phrase: “Contains (name of sensitising substance). May produce an allergic reaction.” This labelling requirement came into force on 1st of June 2015 and was applicable for all sensitising substances – not just biocides. Today there are 100`s substances classified as a skin sensitizer in the CLP with an official classification limit. There also 100`s substances classified as a skin sensitizer but with no “official“ classification limit in the CLP. The limit for these substances is the inventor/prime manufacturers “Self-classification Limit ( SCL) ” which is then adopted as the default value. EUH208 limits reduce considerably the dosage of some well-known molecules in the market (e.g. BIT, MIT, etc). This change creates opportunities for new or existing molecules to be used in different combinations for the paints & coatings and household industries.

137 BPR AND BIOCIDAL PRODUCT AUTHORISATIONS ? WHAT YOU NEED TO KNOW?

1. On the basis of ongoing review within BPD, and as part of the CLP notification scheme, different SCL proposals have been made for DCOIT. Based on the data available, DMC suggests to use an SCL of 250 ppm, but the final SCL is yet to be set up by the ECHA committee in charge of classification and labelling. It should be noted that when DCOIT is formulated in polymers (e.g., in paints), the SCL may be higher. 2. On the basis that the current proposal from Slovenia RMS for MIT under BPD active substance evaluation is to propose a sensitising limit from 1000ppm and for BIT, Spain has proposed a sensitising limit of 500 ppm. Final SCL will be set up by the ECHA committee in charge of classification & labelling. 3. IPBC decision to not assign

Table 1: EUH 208 limits from biocidal active substances used for paint and coatings and household

3.1. Dow Microbial Control‘s Sustainable Future Solution: mBIT The registration process to introduce a new active ingredient under the EU BPR demands a multimillion Euros commitment over a multi-year time-frame. As anticipated, the largest financial investment for the registration of N-methyl-1,2-benzisothiazol- 3(2H)-one, mBIT (figure 1) which can be considered as this Century’s First New Biocidal Active for Coatings [3] was the toxicology data package, which accounted for more than 90% of the costs. The introduction of this new active on to the market in Japan has already led to significant commercial success. The active ingredient offers robust protection against bacteria, yeasts and mould fungi in many different types of applications: EU BPR registration of this new active ingredient is expected late in 2016 as the active ingredient has been classed as new active ingredient which requires a different registration procedure.

Figure 1: N-methyl-1,2-benzisothiazol-3(2H)-one (mBIT)

138 BPR AND BIOCIDAL PRODUCT AUTHORISATIONS ? WHAT YOU NEED TO KNOW?

4. Conclusions In conclusion it is very clear that customers must form a strong relationship with a biocide supplier who not only understands the legislation but one who actually abides by and fulfills all the requirements and who have fully supported their actives through the BPR. Additionally, only those suppliers who are listed on the ECHA List of Approved Suppliers will be able to supply, whilst remembering that this list also limits active ingredients to Product Types as defined in the BPR. This will mean no more “free-riders“ and no more traders that do not own necessary the BPR dossiers or Letter of Access to a substance dossier for the biocide substance or biocide products they place onto the European market. I would to thank Dr. Rodolphe Querou, European Regulatory Director, Dow Microbial Control and Mrs. Emmanuelle Yvon for their help and advice in the preparation of this paper.

References 1. http://echa.europa.eu/view-article/-/journal_content/c89bdb13-09e9-497c-8e73-ddae13a842c8 2. http://echa.europa.eu/information-on-chemicals/active-substance-suppliers 3. PCI Magazin, April 2014, New Biocidal Active, Effectively Preserves Paint, Latex, Colorants and Mineral Slurries, by Beth Ann Browne

139 Sustainable Technologies & Regulatory Issues (II)

Tobias Niederleitner Clariant Produkte GmbH Germany

Tobias Niederleitner studied Chemical and Biology Engineering in the Friedrich Alexander University Erlangen/Nuremburg and joined the Clariant Corporation in the year 2008. He started his career in the Technical Marketing department and was responsible for hotmelt adhesive applications. Since 2009 Tobias Niederleitner has been working for the Technical Service waxes for Coatings/Inks/Adhesives and Formulators.

140 RENEWABLE MICRONIZED POWDERS FOR COATINGS & INKS

Tobias Niederleitner Clariant Produkte GmbH Germany

Clariant presents the latest renewable-based polymers combining demand for more natural, sustainable products with state-of-the-art performance. The micronized innovations for wood coatings are based on renewable raw materials in different particle size distributions. The coarser version of this additive for wood coatings creates a protected and smooth surface with the pleasant feel of untreated wood. The micronized polymer increases coefficient of friction in combination with outstanding scratch resistance performance in water-based formulations.

The fine grind of the renewable based micronized polymer combines smoothness with very high scratch resistance. The high matting efficiency, together with the above mentioned properties, enables the manufacturer to formulate more sustainable coatings with top quality.

The revolutionary predominantly bio based additive for printing inks offers the possibility to reduce the wax with no compromise on performance. Its mix of flexible but still tough polymeric characteristics makes a powerful rub resistance additive for all kind of ink systems.

141 Sustainable Technologies & Regulatory Issues (II)

Dr. Steven De Backer Chemours Belgium BVBA Belgium

Steven De Backer graduated in 1993 as a masters in physical chemistry at the university of Leuven, Belgium. During his Ph. D. he investigated interactions between solvents and polymers via time resolved lasertechnologies. In 1998 he worked for 5 years in the quality department of Innogenetics, a Belgian pharmaceutical company where he was responsible for the quality control of the raw materials. After that he started his career at DuPont de Nemours in Mechelen, Belgium, where he worked for 4 years as a formulating chemist of waterborne automotive coatings. Since about 6 years he is technical consultant for DuPont Titanium Dioxide Technology serving the EMEA coatings market.

142 INFLUENCE OF PAINT QUALITY ON THE ENVIRONMENTAL FOOTPRINT OF ARCHITECTURAL PAINTS

Dr. Steven De Backer, Johan Rommens, Shaibal Roy Chemours Belgium BVBA Belgium

Introduction Coatings provide both protection and aesthetic appeal. Just a thin layer of paint can extend the useful life of everyday objects and thus avoid the environmental burden that would come with an early replacement. Consequently, the sustainability of coatings should be assessed over the entire product life cycle in order to adequately capture the impact of coatings performance in a given application.

Coatings are formulated products, i.e. they are made from a blend of ingredients such as resins, pigments, filler and additives. Choosing the right ingredients are essential to achieving the desired product specifications in commonly used performance metrics such as opacity, hiding power, washability, scrub resistance, and others. With their embedded environmental footprint, ingredients also influence the environmental impact profile of coatings. Life Cycle Assessment (LCA) forms a solid basis for holistic formulation choices, where ingredients are not judged in isolation, but in consideration of their impact on the on the performance throughout the life cycle of the ultimate article [1].

143 INFLUENCE OF PAINT QUALITY ON THE ENVIRONMENTAL FOOTPRINT OF ARCHITECTURAL PAINTS

Figure 1: LCA cycle for a typical architectural paint.

In this work, a novel formulation tool will be demonstrated that integrates LCA with a predictive model of coatings performance for flat and low sheen interior wall paints. The LCA approach mimics the definitions and assumptions of the CEPE Eco footprint tool [2], which is widely used in the coatings industry. In accordance with the emerging guidelines for the product environmental footprinting of paint, the functional unit for fair comparisons addresses the key aspects of how much surface is coated by a certain quality of paint for how long. Paint properties are estimated with a mixture design model that is calibrated with comprehensive laboratory test data.

Figure 2: Schematic representation of the formulation tool that allows predictability of a variety of paint properties (including environmental footprints) based on the ingredients.

144 INFLUENCE OF PAINT QUALITY ON THE ENVIRONMENTAL FOOTPRINT OF ARCHITECTURAL PAINTS

This integrated formulation tool drastically reduces the experimental effort to develop new paints. It effectively guides the formulator towards the blend of paint ingredients that deliver the right performance at the lowest overall cradle to grave environmental footprint. As an example, we compared two formulations for the same type of flat interior wall paint across the full range of environmental indicators defined in the CEPE Eco footprint tool [3]. The formulation corresponds to a high quality interior architectural coating (PVC above CVPC and a TiO2 loading of more than 14%). One formulation uses universal TiO2 pigments designed for diverse paint applications, whereas the other uses a highly treated TiO2 pigments, specially developed for paints above critical PVC in combination with high TiO2 loadings.

Figure 3: Microscopic pictures of highly treated TiO2 (Ti-Pure TS 6300, left), and a universal type (Ti-Pure R902+, right)

Experimentally validated and externally peer reviewed results show that both paints meet the same quality requirements, like scrub (or washability), gloss, dirt pick up. However, the paint with the specialized pigment enables reductions in the cradle-to- grave environmental footprint on the order of 20% across the board.

Working Mechanism of highly treated TiO2 Figure 4 shows that as the distance between two TiO2 particles decreases, the scattering efficiency of these particles is reduced significantly.

Figure 4: Relative scattering power as a function of TiO2 particle separation.

145 INFLUENCE OF PAINT QUALITY ON THE ENVIRONMENTAL FOOTPRINT OF ARCHITECTURAL PAINTS

This phenomenon is well understood and often referred to as the “crowding” effect. This explains the lower TiO2 efficiency at high TiO2 concentrations. Alternatively, spacing the TiO2 under these conditions will result in an increase in TiO2 efficiency and consequently increase hiding power. One way to create this spacing is encapsulating the TiO2 particles in a thick layer, providing the necessary sterical hindrance. In practice this can be realized by depositing special forms of silica and alumina on the pigment surfaces to envelop them with a porous, voluminous coating. These thick, porous coatings function as spacers to keep the TiO2 particles separated from one another, minimizing the overlap of TiO2 scattering volumes and vastly improving the TiO2 scattering strength. Highly treated TiO2 grades are most effective in flat coatings formulated near or above Critical PVC (CPVC) and are therefore sometimes referred to as “flat” grades. This, in contrast to more conventionally treated TiO2 grades that can be used in many different coatings applications, are referred to as “universal” grades.

The oxides deposited on the surface of the highly treated TiO2 grades must be porous to minimize the dilution of the TiO2 in the pigment (a non-porous coating of similar thickness would result in a pigment with over 80% oxide coating and less than 20% TiO2 by weight). Because this oxide layer is so porous, these pigments have higher oil absorption than universal grade TiO2 pigments, which decreases the CPVC significantly. This effect on CPVC is shown in Figure 2, where the hiding power (spread rate) versus TiO2 volume concentration curve for a series of paints (TiO2 and resin only) made with a universal TiO2 grade is compared to that of a series of paints made with a highly treated flat TiO2 grade. The CPVC value decreases from 41.1 for the universal TiO2 to 32.4 for the highly treated TiO2.

Figure 5: Impact on hiding power of universal and highly treated TiO2 grades

This figure also illustrates the PVC range that benefits from highly treated grades of TiO2. At low PVC values (below the CPVC), universal grades outperform the highly treated grades because of their higher TiO2 content. Said differently, a liter of universal pigment has more TiO2 particles – thus more light scattering centers – than an equal volume of the highly treated pigment).

146 INFLUENCE OF PAINT QUALITY ON THE ENVIRONMENTAL FOOTPRINT OF ARCHITECTURAL PAINTS

Above the CPVC, there is not enough resin available to fill up all volume between the particles (TiO2 and extenders) and air pores are generated as the paint dries. As air has a low refractive index, the average refractive index of the coating decreases, thereby increasing the efficiency of the TiO2. Additionally if these air pores have the correct diameter they also can contribute to the total dry hiding power by scattering of light. As a consequence, the dry hiding power increases significantly for paints with a PVC above the CPVC. Figure 5 suggests that in this part of the formulation space, the highly treated grades outperform the universal grades, despite their lower TiO2 content. As a consequence, the hiding power of paints formulated with the highly treated grade will be higher and the environmental impact per m2 painted surface will decrease (see figure 6).

Figure 6: Impact of universal and highly treated TiO2 grades on hiding power and carbon footprint.

Acknowledgements The authors would like to thank Dr. Johan Rommens, Stephane Cappelle and Carina Alles for their substantial contributions to the data and interpretation presented in this paper. Special thanks go to Chris Michiels and Vicky Fisher who generated all the experimental data points.

References 1. CEPE, 2012 Charter for Sustainable Development in the Paint and Printing Ink industry; http://www.cepe.org/EPUB//easnet.dll/GetDoc?APPL=1&DAT_IM=105FF1&DWNLD=Charter_ Sustaini bility.pdf 2. CEPE, 2013-2014; CEPE LCI Project and CEPE Ecofootprint tool; http://www.cepe.org/efede/public.htm#!HTML/29121 3. C. Alles, S. DeBacker, M. Sauder, 2015 Value Chain Sustainability Benefits of Specialized TiO2 Pigments for Flat and Low Sheen Paints Proceedings of the European Coatings Conference; Nuremberg, Germany

*The information set forth herein is furnished free of charge and based on technical data that Chemours believes to be reliable. It is intended for use by persons having technical skill, at their own risk. Since conditions of use are outside our control, we make no warranties, expressed or implied and assume no liability in connection with any use of this information. Nothing herein is to be taken as license to operate under or a recommendation to infringe any patents.

147 Processing & Testing of Coatings (II)

Norbert Kern Bühler AG Switzerland

Norbert Kern, is as Head of Process Engineering in Buhler Grinding and Dispersing Technologies (GD) Business Unit responsible for worldwide Technology support. Norbert joined Buhler after graduating at Zurich University in Winterthur as process engineer in 2001. He started as a process technologist in the central Grinding and Dispersing lab in Switzerland. Developing of different continuous flushing processes for the printing ink industry was one of his main task from 2001 to 2005. Later he took over the responsibility of building up local competence in Grinding and Dispersing in Japan, this included also establishing the first RADEC (Regional Application, Development and Education Center) for the Business Unit in Yokohama. From 2006 to 2010 he was also partially responsible for Sales in the Region North America and Middle East. Since two years he’s now in charge for the RADEC’s in North America, Japan and China and the Center of Competence in Switzerland and Germany.

148 DESIGNING PIGMENT DISPERSING SYSTEM TO REDUCE TOTAL COST OF OWNERSHIP

Norbert Kern Bühler AG Switzerland

Energy Savings in Grinding and Dispersing Unit operation grinding on agitated bead mills To understand the function and effect of the production parameters in the grinding and dispersing process, it is necessary to understand the forces acting between single beads as a function of beads, mill and product. The most important parameter related to the grinding process is of course the bead diameter, as many investigations into grinding efficiency have shown.

To meet the requirements of today’s production in regard to efficiency, achievable quality and scalability there are three main drivers in the design of a bead mill: » High flow capability to fulfil the requirement for high recirculation turnovers » Separation of the smallest beads » Scalability, by keeping significant parameters constant

149 Processing & Testing of Coatings (II)

Darren D. Bianchi Brilliant Group USA

Mr. Bianchi serves as President at NANOGAP USA of Nanogap Sub-NM-POWDER S.A. Mr. Bianchi has over twenty years of technical management and business development in the specialty chemicals field to NANOGAP. He has spent much of his career developing specialty fluorescent polymers and bringing them to market. He was President of Radiant Color (USA), President of Dane Group North America and founder and Chief Executive Officer of Brilliant Group. Mr. Bianchi has a Bachelor of Science degree in Chemistry from Illinois State University, a Master of Science degree in Environmental Management from the University of San Francisco, and has completed the Advanced Management Program at the University of California, Berkeley, Haas School of Business.

150 FLUORESCENT PIGMENTS AND THEIR DIVERSE APPLICATIONS

Darren D. Bianchi Brilliant Group USA

Introduction Fluorescence is a process of photo-luminescence by which light of short wavelengths, either in the ultraviolet or the visible regions of the electromagnetic spectrum, is absorbed and re-radiated at longer wavelengths. The re-emission occurs within the visible region of the spectrum and consequently is manifested as color.

The commercial development and sale of fluorescent pigments and colorants dates back to the 1940s in the field of graphic arts. Development was initially centered around the application of point-of-purchase displays, advertising, safety and identification. To date, fluorescent materials have gained widespread acceptance in a myriad of applications, including toys, fashions, and packaging.

Fluorescent pigments are often used in specific applications where a particular appeal is desired. Studies have been conducted with children and adults showing that fluorescent products are noticed earlier and seen longer than their conventional counterparts. As a result, designers have incorporated the use of fluorescent products in many creative ways to enhance product sales.

The unique brightness of a fluorescent may be employed alone when one is trying to set their product apart from the rest in a competitive situation. In addition, fluorescents can be used as an accent in contrast to a more drab color, or they may be added to conventional pigments to brighten an otherwise dull color.

151 FLUORESCENT PIGMENTS AND THEIR DIVERSE APPLICATIONS

Due to the specialty of this market, only three domestic and four foreign manufacturers have enjoyed any real success in the manufacture of fluorescent colorants. Nature of Fluorescent Pigments As those who have processed fluoresce know, they differ significantly from conventional pigments not only in color but in chemistry as well. Conventional pigments can be organic or inorganic substances and are of extremely limited solubility. Their dispersion is usually achieved and enhanced by the application of shear and the pigment particles tend to be more opaque in nature.

Daylight fluorescent pigments, however, are comprised of a solid state solution of fluorescent dyes in a friable polymeric resin. Once the dyes are incorporated into the resin, they are ground into a fine powder for use as a pigment or colorant. As these pigments are resinous solutions of dyes, they tend to be transparent in nature. Manufacturing Processes The techniques employed to make the fluorescent pigments have varied over the years. The original method used was the bulk polycondensation reaction of melamine, formaldehyde, and toluene sulfonamide. The resulting products were tailored to various applications by being thermoplastic or thermoset depending upon the mole ratios of the polymer's raw materials. As the fluorescent products evolved and certain shortcomings of the above products were noted, similar bulk condensation polymerization methods were carried out to make polyesters[1] and polyamides[2]. These are currently the most widely used fluorescent colorants for plastics. The polyesters allow for lower processing temperatures (<400°F) for bright, clean colors while the polyamides allow for higher processing temperatures (>400°F) and greater shear to achieve color development.

Another method developed in the 1970's to manufacture a pigment similar to the first by using suspension polymerization.3 This technique offered pigments which combined bright colors and excellent inertness. This was due to the high degree of polymerization which was achievable in the droplet state. Until recently, this technique yielded colorants with poor color strength and high price and were thus not welcomed into the marketplace.

Another important component of fluorescent colorants are the dyestuffs used. Fluorescent pigments, as noted, are solid solutions of fluorescent dyes which do not fluoresce in an undissolved state. The dyes used in are predominately rhodamine (magenta) and coumarin (yellow) types. The fluorescent spectrum from yellow to magenta is achieved by combining the dyes at different ratios. The popular green color is made by adding yellow dye and phthalo green to the resin carrier. The blue is a combination of phthalo blue and optical brighteners of the benzopyranone type.

152 FLUORESCENT PIGMENTS AND THEIR DIVERSE APPLICATIONS

Environmental Considerations We have seen the recent rise of environmental legislation regarding packaging materials. As a result, designers and users are required to be increasingly more selective about which materials they use as they incorporate their awareness of environmental issues.

Most, if not all, fluorescent pigments do not contain any of the commonly regulated heavy metals (cadmium, lead, mercury, and hexa–valent chromium). In fact, to the author's knowledge, no heavy metals are used in the manufacture of any fluorescent colorants.

In addition, many of the fluorescent products have been tested for skin irritation and acute toxicity. As a result, those that have been tested are classified as “essentially non-irritating” with a Draize Score of 0, and “essentially non-toxic” with an oral LD50 (rat) >5000 mg/kg.

Quality Control The quality control testing of fluorescent colorants by the manufacturers has been based upon attempted simulation of the end user’s testing. Fluorescent pigments are commonly tested by the manufacturer in solvent-based coating, plastisol screen ink, textile ink, flexo ink, lithographic ink or in plastics. In most cases, they are tested in both masstone and tint. In plastics, the colorants are commonly injection molded in HDPE for observation. Carefully trained technicians perform visual observations while those in the fluorescent industry await the development of technology which will allow for adequate computerized color measurement. Incorporation Into Paints, Inks And Plastics Once the fluorescent colorant passes quality control testing, it is then made useful for more specific applications by industrial users. The industrial users are commonly ink makers, paint manufacturers, masterbatch manufacturers, paper coaters, crayon manufacturers, to name a few. By use of these methods and materials, one is allowed to create products for markets such as crafts, toys, detergent boxes and bottles, traffic cones and safety equipment, among others. There is not a great deal of work done with fluorescents in architectural or automotive applications due to the inherently poor lightfastness and low tinting strength of these materials.

153 FLUORESCENT PIGMENTS AND THEIR DIVERSE APPLICATIONS

Processing Challenges There are some challenges that processors may face when handling fluorescent colorants. Because they are polymeric in nature, unlike organic and inorganic pigments, they do not tolerate high shear. In this case, the polymer will heat and fuse, causing unusably large agglomerates. Further, many fluorescent pigments are not resistant to highly polar solvents and the dyes used can migrate out of the article. There are certain grades which are resistant to these phenomenon and should be sought out if these specific properties are desired. Also, as mentioned, fluorescent pigments are inherently poor in terms of lightfastness. The best way to prolong the life of a fluorescent article is to color it with high loadings of fluorescent pigment, with as thick a film as possible, and then follow with an over-coat of clear containing UV absorber. The addition of UV absorbers into the system is not a terribly effective way to improve the performance in this regard.

In plastics, many grades of fluorescent pigments suffer from the occurrence of plate-out. This phenomenon occurs when organic material, such as oligomeric species or fluorescent dyestuffs, thermally decompose and separate from the compounding mixture. Thus, these materials deposit on screws and other metal processing equipment.

Steps have been taken to address this problem by both the colorant manufacturers and the compounders. Manufacturers have worked to shift the molecular weight distribution of the colorants and reduce the lower molecular weight species[4]. Thus, reducing the likelihood of separation and decomposition. Compounders and additive suppliers have developed additive packages to reduce plate-out.

Other challenges in processing fluorescents may be heat instability or incompatibility of the colorants with the various resins. The manufacturers of fluorescent colorants are continually looking at ways to improve their processability in these regards. Conclusions The use of fluorescent pigments and colorants in a broad range of applications has experienced sustained growth over the past few decades. Research and development efforts continue in the pursuit of more thermally stable, more lightfast and plate-out resistant fluorescent colorants with greater tinting strength and opacity. As these qualities are achieved and improved upon, we should see the use and growth of fluorescent pigments and colorants into more diverse applications well into the future.

References 1. U.S. Patent No. 3,922,232, Alan K Schein, November 25, 1975. 2. U.S. Patent No. 3,915,884, Zenon Kazenas, October 28, 1975. 3. U.S. Patent No. 3,945,980, Tsuneo Tsubakimoto, Iwao Fuzikawa, March 23, 1976. 4. U.S. Patent No. 5,094,777, Thomas C. DiPietro, March 10, 1992. 5. International Patent No. WO 9310191, Kenneth Wayne Hyche, May 27, 1993.

154 FLUORESCENT PIGMENTS AND THEIR DIVERSE APPLICATIONS

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155 Processing & Testing of Coatings (II)

Peter Lederhos Evonik Resource Efficiency GmbH Germany

Peter Lederhos is Technical Market Manager for Evonik Resource Efficiency GmbH, Silica Business Line. He is a graduate coating technician and has been responsible for the technical aspects of using silica products in different coating applications for eight years. Besides conventional coating he is also responsible for silica use in Printing Inks applications. Peter is part of a team that covers the EMEA and South America regions.

156 MATTING OF SOLVENT-FREE UV- CURABLE COATINGS

Peter Lederhos Evonik Resource Efficiency GmbH Germany

Abstract Conventional coating systems with volatile components, including water and solvent- based UV-curable coatings, are easy to mat because of their emissions-related vertical film shrinkage. On the other hand, solvent-free coatings, such as 100% UV-curable coatings are difficult to mat because there is no film shrinkage by evaporation of volatile compounds. The task of the coating formulator is to make up for the lack of vertical film shrinkage with suitable mechanisms to achieve a roughening of the coating film surface and, consequently, an adequate degree of matting.

One option is to select the particle size of the matting agent so that it largely corresponds to the thickness of the applied coating. The second possibility is to strengthen the volumetric shrinkage of the coating film caused by radical polymerization of the acrylate oligomers and monomers and make optimum use of this. Important in this context is that the matting agent matrix, consisting of silica particles distributed evenly in the liquid coating, shrinks less than the surrounding binder matrix during the curing process.

157 Paint School 1

Dr. Anne Koller

The DOW Chemical Company France

158 BASICS ON ARCHITECTURAL COATINGS

Dr. Anne Koller Paderborn University Germany

Architectural Coatings tutorial will detail performance requirements for Interior wall paints, exterior masonry paints and paints for wooden substrates such as trim and exterior house paints. Typical testing procedures will be explained.

Examples of paint formulations will be given with discussions on the effects of raw materials such as binders, pigments, fillers and additives (dispersants, rheology modifiers...) on performance properties.

159 Paint School 2

Dr. Matthias Popp Fraunhofer-IFAM Germany

Studies of Chemistry at the University of Bremen. After finishing the PhD-thesis in 1997 working for a midsize company in Hannover dealing with textile coatings. From 2000 to 2006 project leader at the Fraunhofer-IFAM in Bremen in the field of research “instrumental analysis” and “adhesive formulations”. From 2006 to 2010 development specialist at 3M in Neuss, working in the area of epoxy adhesive development. Since October 2010 group leader “adhesive compositions” at the Fraunhofer-IFAM.

160 FORMULATING ADHESIVES AND SEALANTS

Dr. Matthias Popp Fraunhofer-IFAM Germany

Bonding – it is part and parcel of everyday life. There is hardly another field as chemically and technically diverse as that of adhesives and sealants. This tutorial will familiarise you with the most important types, focusing on the composition and ingredients of the different kinds of adhesive with their chemical structures and functional groups, so that you will be able to clearly deduce the resulting properties. Using practical formulation tips, you will analyse guide recipes and patent examples and learn to calculate key recipe parameters step by step. At the end of the tutorial, you will be able to formulate confidently and competently!

161 Paint School 3

Dr. Clifford K. Schoff Schoff Associates USA

162 THE BASICS OF PIGMENT DISPERSION

Dr. Clifford K. Schoff Schoff Associates USA This tutorial is aimed at teaching the basics of pigment dispersion in terms of the principles involved, how they fit into paint manufacture, some of the problems that occur and how to prevent them. It begins with an overview of the dispersion process and goes on to give a series of definitions related to pigments. It then discusses pigment wetting, which is the key step at the beginning of the process, followed by deagglomeration and stabilization. It is surprisingly easy to initially disperse pigments, but difficult to stabilize that dispersion and keep it stabilized. Stabilization is done through the use of dispersants and dispersing resins. These are described along with the testing of dispersions and paints including by microscope techniques. Flocculation is discussed and illustrated. The letdown step in paint manufacture is where a pigment paste and the rest of the paint formula (the let down) are mixed. Poor letdown practices can ruin a good pigment paste and produce a flocculated paint. Ways to prevent this are discussed. Different types of plant dispersing equipment are described along with their use. The presentation ends with a set of conclusions and a list of references.

163 Paint School 4

Dr. Annette Bitsch Fraunhofer-ITEM Germany

Bitsch studied biology with a focus on biochemistry at the University Hannover and worked thereafter for several years in the topic of chemical induced carcinogenesis and adaptive responses at the Institute of Toxicology of the University Würzburg. In 1996 she successfully absolved the final examinations to a certified expert in toxicology. Since 2001 she is working at Fraunhofer ITEM in the field of chemical risk assessment.She is head of the division “Chemical risk assessment, databases and expert systems” and group manager “Biocides” in the Fraunhofer Institute for Toxicology und experimental Medicine (ITEM) in Hannover, Germany. Here she is amongst others responsible for hazard and risk evaluation of biocides and organises the correspondence with competent authorities and within task forces of companies. Recent research projects where she is involved include projects on the definition of chemical categories and on read-across approaches. A. Bitsch is member the BfR Committee for “Food Additives, Flavourings and Processing Aids” and the working group for probabilistic exposure assessment.

164 UNDERSTANDING BIOCIDES AND THEIR LATEST REGULATIONS

Dr. Annette Bitsch Fraunhofer-ITEM Germany

Inadequate preservation of paints and surface coatings leads to visual contamination. In-can bacterial contamination can lead to undesired liquefaction, odors, gassing and discoloration. The use of biocides is indispensable to avoid this process. This tutorial covers all you need to know about the use of biocides. Additionally, you will learn about the current changes that have to been made to the Biocides Directive in Europe.

165 Poster Presentations

Adalet Ayça Biçen İbik, Gizem Kurşunluoğlu Kansai Altan Boya A.Ş. Turkey

Ayça BİÇEN received her B.S. degree from the University of Dokuz Eylül, in Izmir in 1996. In 2000 she earned her M.S. degree from the Dokuz Eylul University Institute of Science. She researched “Investigation of Relationship Between Antioxidant Enzyme Activities and Some Secondary Metabolites Production in Urtica Dioica Depending On The Medium Conditions”. Currently, she has worked for over ten years in Kansai Altan Boya San. A.Ş. at analysis laboratuary. As a specialist, she has focused on characterization of structural coating and raw materials by using analytical methods & coating technology. She has extensive technical knowledge on all steps of analytical processes. More specificially, she has well- versed using spectroscopic and chromatographic analytical instruments such as FTIR, UV- spectrophotometer, GC, Pyrolyzer-GC, GPC, HPLC.

Gizem Kurşunluoğlu was born in Denizli, Turkey, on Semptember 21, 1987. She graduated from Dokuz Eylül University, Faculty of Science and Letters / Chemistry Department in 2010. After then, she has continued her education and recieved her Master’s degrees in the Dokuz Eylül University, The Graduate School of Natural and Applied Sciences / Chemistry Department as a master's student in order to improve her quantitative research skills. During her master education, she has been in The University of Perpignan Via Domitia, as an Exchange Student (project researcher) for six months and improved her analytical ability at the different advanced laboratory

166 CHARACTERIZATION OF URETHANE- MODIFIED POLYESTER IN THE COATING SYSTEM WITH FTIR AND PYROLYSER-GCMS

Adalet Ayça Biçen İbik, Gizem Kurşunluoğlu, Rüyam Alev Parıldar Kansai Altan Boya A.Ş. Turkey

Polyesters are widely used in one or two components coating systems. Most coating polyesters which are made by diols and dibasic acids have amorphous and branched structure. Polyesters have the advantages for coating systems in terms of physical and chemical properties such as adhesion, toughness, abrasion resistance, durability, dispersibility, flexibility, stress release. They can be designed with combination and modification of different materials such as urethane, acrylic, silicone, polyamide to improve the mechanical properties. One of these well-designed types is urethane modification. The coating including the urethane-modified polyester resin composition has improved exceptional mechanical strength and adhesion between the basecoat and a substrate or topcoat film and has enhanced processibility, impact resistance and flexibility. Urethane-modified polyester can be designed by reacting a polyester resin with an isocyanate compound. Types of diols, dibasic acids and isocyanates which are used in polyester resin have great importance in respect to variety properties given to coating systems. In this study, we aim to determine qualitatively the monomer composition of the polyester system which can be cross-linked melamine formaldehyde resins by FT-IR and pyrolyser-GCMS. Initially, we have obtained whether or not there is urethane modification in polyester resin by using FT-IR. After then, diols, dibasic acids monomers and isocyanate types have been identified by pyrolyser-GCMS. This research improves the characterization of polyester monomers and urethane types with different analytical method.

167 Poster Presentations

Betül Tok Yıldız Technical University Istanbul

Betül Tok was born in Istanbul in 1993. After completing her primary education at Pertevniyal High School, she graduated from Chemical Engineering Department - Yildiz Technical University in 2016.

168 INVESTIGATION OF DIFFERENT HARDENERS IN EPOXY SYSTEMS AND HARDENING MECHANISMS IN COATINGS

Betül Tok, Pelin Akveren, Nil Acaralı, Hanifi Saraç Yıldız Technical University Istanbul

Abstract Epoxy resins are nowadays widely used in many applications that range from common adhesives to high-performance composite materials, industrial and protective coatings. Epoxy resin based on bisphenol A and bisphenol F are cured by using a hardener. Kinetics of the curing reaction and morphology of epoxy systems, using a hardener at different weight contents was widely investigated in literature. In this study, the effects of different hardeners (polyamide, polyamine, phenylalkylamine etc.) with epoxy resins were compared. The optimum parameters were investigated by using Taguchi optimization method for 3 parameters and 3 different ratios. Consequently, the test results showed that using different types and ratios of epoxy hardeners provide different physical and chemical properties.

Keywords: Epoxy, hardener, coatings, resin, curing

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171 Poster Presentations

Cansu Akarsu Dülgar Istanbul Technical University Turkey

B.Sc. degree in Chemistry from Istanbul Technical University in 2008; M.Sc. degree in Polymer Science & Technology Program from Istanbul Technical University in 2010 and continues to study for Ph.D in the same program. Currently working as R&D Chief in Organik Kimya San. ve Tic A.Ş. Formerly, Research Engineer in Teklas Kauçuk San. ve Tic A.Ş and Research assistant in Wacker - Chair of Macromolecular Chemistry in Technische Universitat München. Research interests are latex technology, emulsion polymerization, controlled free-radical polymerization, paper impregnation and pressure-sensitive adhesives.

172 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

Cansu Akarsu Dülgar, Tuba Çakır Çanak, İ.Ersin Serhatlı Istanbul Technical University Turkey

Abstract The interest in water based pressure sensitive acrylic adhesives grew with the need to solve solvent emission problems and they are used in wide range of applications such as the automotive, aerospace, construction and electrical markets, either in the form of tapes or as adhesive coatings on other backings. Thus, in some cases even the adhesive should reduce the flammability. For increasing the flame retardancy of polymeric materials the use of borates was probed earlier in the 20th century and they are adventageous due to being a halogen free alternative. In this study the influence of boron acrylates as functional monomer on adhesive and cohesive performance of water borne pressure sensitive adhesives coated on bi-orientated polypropylene (BOPP) has been investegated. A series of pressure-sensitive adhesives (PSAs) with different monomer composition was prepared using emulsion polymerization. The monomers were butyl acrylate (BA); methyl methacrylate (MMA); acrylic acid (AA); boron acrylate (BoA) and multiarm boron methacrylate (muliarm-BoMA). The adhesive performance was studied at 0%, 1.3% and 3.9% of boron acrylate monomer content based on total monomer (BOTM) composition and 1% of multi arm boron methacrylate. The adhesives obtained with constant thickness were coated onto a bi-orientated polypropylene (BOPP) and evaluated for the performance by measuring the tackiness, peel strength and shear strength on several

173 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

surfaces including stainless steel (SS), glass, aluminum (Al) and low density polyethylene (LDPE). Results showed that addition of boron acrylate was slightly increasing the adhesion and cohesion performance on nonpolar surfaces. While it did not show any dramatic decrease on the adhesive performance for different surfaces, the decomposition temperature showed slightly increase on TGA analysis.

Keywords: emulsion polymerization; acrylic coating; water based; pressure sensitive adhesive; boron acrylate; flame retardant. *Correspondance to: İ.E.Serhatli ([email protected]) 1. Introduction Adhesives are defined as materials that bond other materials, mainly on their surfaces through adhesion and cohesion. Pressure sensitive adhesives (PSAs) are ensure instantaneous adhesion by application of a light pressure and can be organic solventborne, water-borne (dispersions), or in a solvent-free form (e.g. hot melt).1,2 Water-borne adhesives comprise acrylics, natural & synthetic rubber latexes, and ethylene vinyl acetate dispersions. In commercial applications, emulsion acrylic copolymers have the fastest growth in the market share. The interest in aqueous acrylic dispersions PSA grew with the need to solve solvent emission problems.3 Emulsion polymerization is a preferred process for industrial preparation, due to obtaining high molecular weight polymers and no or negligible volatile organic compounds (VOC).4

Adhesives based acrylate copolymers have been investigated since years. Many research results for the poly(BA-co-MMA) based PSA and polar group containing polymers were already published5-9 in order to vary chemical and physical properties of the adhesives and also improve the adhesives’ mechanical properties such as cohesion. In several researches, the work on PSAs has been reported by using different type of monomers in various formulations. According to those researches a PSA must be soft and tacky. Thus, its glass transition temperature (Tg) should be low, ranging from –20°C to –60°C. Polymers with low Tg typically from a class of alkyl acrylates such as poly (butyl acrylate) and poly (2-ethylhexyl acrylate) are inherently soft and tacky but do not possess adequate shear strength.10-13 Acrylate copolymers containing functional groups are used in the form of emulsions in coatings, adhesives. Polar monomers are used in copolymerization in order to vary the chemical and physical properties of the adhesives improve the adhesives’ mechanical properties such as cohesion. Their inclusion increases the Tg and this may be explained by increasing dipole interaction, or enhanced hydrogen bonding. Polar groups in polymers increase intermolecular forces thus reduce free volume and increase Tg.9

Recent developments and an outlook for opportunities with flame retardant pressure sensitive hot melt adhesives have been given in an article.14 Adhesive tapes and self-adhesive coated materials are used in various industries and in multiple applications such as the automotive, aerospace, construction and electrical markets, either in the form of tapes or as adhesive coatings on other backings. For many of these applications, good flame retardant properties have considerable importance. The demand for halogen-free flame retardant adhesives, which do not emit toxic fumes during a fire, resulted with the studies focus on to phosphate, silisium, nitrogen, boron containing structures and varied modifications.15-18

For increasing the flame retardancy of polymeric materials the use of borates was probed earlier inthe 20th century. It was found that inorganic boron compounds promote char formation in the burning process. In a previous work, the physical and

174 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

mechanical properties of UV-curable boron containing epoxy acrylate coatings were investigated. The boron acrylate used in current study, has been synthesized according to section 2.5 of the previous study19; HEA has been used instead of HEMA.

Figure 1: Boron acrylate

Hydrogen bonding and Van der Waals attractions are particularly strong with the borates forming hydrates, double salts and polymers. In all cases except for the comparatively few mono- and diborates, B-O grouping tends to form one or more ring structures, allowing electrons to resonate around the ring, thus strengthening its bonds. Ring structures can also form with borates and many organic compounds especially those with adjacent OH or groups that are similar (=O, -COOH, etc.) Borates also keep the rings stable while they are cleaved and OH and H groups from water during dehydration, thus creating more complex structures.20 Effect of crosslinkers on PSA performance has also been studied by several researchers.21-23 It is known that an acrylate copolymer which has no crosslinking or is crosslinked only by hydrogen bonds has insufficient thermo-mechanical stability. The generated, crosslinked connections extensively inhibit the mobility of polymer molecules by chemical bonding the network of the polymeric PSA and undergoes a decomposition above a certain temperature.24 Crosslinking behavior could be determined via swelling parameters as mentioned in the literature.25 In this study, beside the evaluation of boron acrylate monomer, 4,4'-(2,2'-oxybis(ethane- 2,1-diyl)bis(oxy)) bis(10-methyl-9-oxo-3,5,8-trioxa-4-boraundec-10-ene-4,1-diyl) bis (2-methylacrylate) (multi arm BoMA) was synthesized by the esterfication reactions of boric acid, HEMA and diethyleneglycol and used as crosslinking monomer.

Figure 2: Multi arm boron methacrylate

As it is known, adhesion is not only related to the chemical composition of adhesive polymer. The structure of substrate and the surface has a huge impact on adhesion properties.7 Surface characteristics are based on physical properties such as roughness, surface energy, mechanical properties or the chemical composition of the surface. Good wettability of a surface is a mandatory to provide good bonding which is related to the surface energy which was studied in several researches. Wetting is determined as the spreading and contact of a liquid (adhesive) over a solid surface (substrate). If contact is sufficiently achieved between the two phases, a physical attraction from inter-molecular forces occurs. Influence of substrate SFE on tack the adherents with the same surface roughness.32-34 Among SS, glass, Al and LDPE, the poorest wettability surfaces are HDPE and LDPE due to their low surface energy which has critical surface tensions of wetting of about 35 mJ/m2 or less.35,36 PVC has surface energy around 39 mJ/ m2.32 Aluminum, glass and stainless steel are mentioned as high surface energy materials with the surface energy above 38 mJ/ m2.33,34 Surface energy of aluminum is around 850 mJ/m2, glass is between 250 to 500 mJ/m2 and SS is 700-1000 mJ/m2.35,36 175 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

For solvent based film deposition a non-homogeneous distribution of the different parts of the copolymers along the film normal was reported.37,38 Near-surface enrichment of particular monomer types were found and assigned to the adhesive behavior. For the present study such non-homogeneous distribution is also likely although mobility might be less. Stainless steel (SS), glass, aluminum (Al) and low density polyethylene (LDPE) are very different in surface roughness. As shown in literature39, besides surface energies also the surface roughness has an important effect on the adhesive bonding. Independently of the bonding mechanism (cohesive or adhesive failure) in case of a rough probe, the cavity growth rate significantly decrease with increasing shear modulus of PSA, in case of a smooth probe, this characteristic quantity is insensitive to the viscoelastic properties of the PSA. Comparing the cavitation process for uncrosslinked and crosslinked copolymers with different Mw, including various polar comonomers reveals, that the cavity growth rate decreases with increasing modulus on the rough substrate, but is independent of the modulus on the smooth substrate.40 The effects of the roughness increase with the elastic modulus of the polymer film. The strength of an adhesive bond directly or indirectly reflects the energy dissipated in the joint as a whole during failure. Surface roughness can increase this energy dissipation by increasing the tack.34

In this study, it has been focused on the effect of BoA (boron acrylate) and multi arm BoMA as co-monomer in the emulsion process and on the adhesive performance of poly (BA-co- MMA-co-AA) latexes. The amount of BoA co-monomer has been studied at 0%, 1.3% and 3.9% based on total monomer composition and multi arm BoMA was used as 1% together with 3.9% BoA. Other materials used for this research were the monomers mentioned as butyl-acrylate (BA), methyl meth acrylate (MMA), acrylic acid (AA), surfactants; ammonium persulfate, NaHCO3 and deionized water. The anionic surfactant system has been used, the composition cannot be revealed for proprietary reasons. Boron acrylate monomers were synthesized by esterification reaction.19 The aim of the study is to investigate the influence of BoA and multi arm BoMA co-monomers on pressure sensitive adhesive performance of the resultant polymers through measurement of shear strength, loop tack and peel strength on different surfaces such as SS, glass, Al, PVC, HDPE and LDPE. 2. Experimental 2.1 Materials All the reagents were used as supplied. BA, MMA and MAA monomers were all commercial grades available from Arkema and Evonik. Boron acrylate and multi arm boron methacrylate were synthesized as refered in 19,44. The initiator used was ammonium persulfate obtained from Hebei Jiheng. Tert-butyl hydroperoxide was obtained from Gliss Chemicals. Sodium hydrogen carbonate and sodium formaldehyde sulfoxylate were obtained from Bruggemann. Deionized water was used throughout the polymer preparations. The polymerization surfactants were two different type of anionic surfactant with different HLB content. The surfactant system employed was referred to as surfactant A in the pre-emulsion. Surfactant composition cannot be revealed for proprietary reasons.

2.2 Characterization, Analysis and Testing The thermal properties of the polymers were measured by differential scanning calorimeters (Mettler Toledo, DSC 821e) in a flowing air atmosphere from -80oC at scanning rate of 10oC/min.

Thermo gravimetric analysis was performed in a TA TGA Q50instrument under the nitrogen atmosphere at a heating rate20oC/ min in the temperature range of 30–850oC. The weights of sample are 10–13 mg in all cases.

176 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

Solid content was measured by drying the polymer films at 150 0C for 20 minutes after filtered from 60 micron filter. Weight of polymer (wt1) and dried latex (wt2) has been calculated by the following equation.

Solid % = wt2 / wt1 ×100

Coagulum content of polymer latex was measured after filterable solids of any runs were dried at room temperature for 24 hours. Then coagulum content was measured by the weight of filterable solid in 1 liter of polymer dispersion. (ISO 4576) Free monomer measurements were performed by HS-GC (Perkin Elmer, HS 40 XL, Auto System XL) with FID detector and N2 was used as carrier gas. Viscosity was measured by Brookfield viscosimeter under room conditions by LVT 3/60 (ISO 3219). pH of polymers has been determined under room temperature according to ISO 976 by calibrated pH meter. Surface tension of polymer dispersions has been measured by Du Nouy ring method according to ISO 1409. Swelling behavior has been determined by the preparation of 1 mm thickness samples by gradual evaporation of water from the emulsion at room temperature. The films were coated on the Teflon plates and then dried at room temperature for 7 days. Then, films were cut into square pieces in order to obtain similar weights around 0.59gr ± 0.03. Dry weights (W0) of the cut samples were taken before immersion into the acetone containing bottle. The study of the swelling behavior of films was followed gravimetrically by measuring the weight gain with the time of immersion into the acetone. The bottles were placed in a climatized room (at 23 oC, %50 relative humidity) to maintain a constant temperature for 24 hours. Wet surfaces were quickly wiped using tissue paper and re-weighted (W1). Polymer films were dried at 70 C for 3 hours and weighed immediately (W2). Acetone in-soluble parts and swelling indexes have been calculated.

Swelling index = (W1-W0)/W0 Insoluble Fraction % = W2/W0*100

The adhesive polymer was coated on BOPP film as 50 μ with applicator and was dried at 70°C for 10 min. The adhesive coated samples were left for 24 hours in a controlled environment (23±2°C, 50±5 relative humidity) chamber prior to testing the adhesive properties. A specimen of 25 × 400 mm was cut in the machine direction and laminated onto the clean stainless steel test plate using finger pressure. The average force to peel the specimen from test plate was recorded. In FINAT technical handbook, peel adhesion is defined as force required removing pressure sensitive coated material, which has been applied to a standard test plate under specified conditions from the plate at a specified angle and speed. In this study, peel adhesions were tested according to FTM1 on stainless steel (SS), glass, aluminum (Al) and low density polyethylene (LDPE) as 180° at 300 mm/ min by Adhesion Release Tester AR-1000. Test conditions were at 23 ± 2°C, 50 ± 5 % relative humidity.40

Shear strength is the internal cohesion and the resistance to shear from a standard surface and gives an indication of the mode of adhesive or cohesive failure. Static shear test was applied according to FTM 8 on stainless steel (SS), glass and low density polyethylene (LDPE), at 23°C and the test equipment was 10 Bank Shear RT-10.40 Loop tack value of PSAs is expressed as the force required separating, at a specified speed, a loop of material which has been brought into contact with a specified area of a standard surface (FTM 9). Loop Tack measured on stainless steel via Loop Tack Tester LT-1000.40

177 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

Loop tack value of PSAs is expressed as the force required separating, at a specified speed, a loop of material which has been brought into contact with a specified area of a standard surface (FTM 9). Loop Tack measured on stainless steel via Loop Tack Tester LT-1000.40 2.3 Synthesis of 4,4'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(10-methyl-9 oxo 3,5,8- trioxa-4-boraundec-10-ene-4,1-diyl)bis(2-methylacrylate) (Multiarm Boron Methacrylate) 23.3 ml toluene, 79 μl hydrophosphorus acid solution, 6.15 ml diethyleneglycol, 5 g of boric acid, 0.078 g methylhydroquinone and 14.7 g HEMA were added to a 100 ml two-necked round bottom flask equipped with a Dean-Stark and a condenser respectively. The reaction mixture was stirred and heated to reflux temperature and the water was removed by azeotrope distillation with Dean-Stark. End of the reaction was determined by monitoring amount of removed water. The solvent was removed by vacuum distillation. The product was transparent, colorless and viscous liquid. 2.4 Synthesis of Acrylic PSA Using Delayed Addition Radical Emulsion Polymerization 2.4.1 Preparation of monomer emulsions 16.4 g surfactant A was dissolved in deionized water and placed in a vessel equipped with stirrer. 667 g butyl acrylate, 33,5g methyl methacrylate, acrylic acid and boron acrylate were added respectively. BoA amounts were given in Table 1 based on total monomer composition (BOTM). The water-surfactant mixture was placed under high shear agitator at 200 rpm. The monomer mixtures were slowly added into the water-surfactant mixture under sufficient stirring to make a monomer pre-emulsion. The mixing time required was 10 minutes for all the trials. The resulting monomer emulsions were homogenous, viscous and milky in appearance. The emulsion polymerizations were carried out at 84 - 86 °C for 3 hour.

BoA Multi arm BoA Trial (%, BOTM) (%, BOTM)

1 - -

2 1.3 -

3 3.9 -

4 3.9 1.0

Table 1: Monomer compositions (based on total monomer*, % weight).

* Total monomer amount was calculated regarding only BA amount. The water-surfactant mixture was placed under high shear agitator at 200 rpm. The monomer mixtures were slowly added into the water-surfactant mixture under sufficient stirring to make a monomer pre-emulsion. The mixing time required was 10 minutes for all the trials. The resulting monomer emulsions were homogenous, viscous and milky in appearance.

2.4.2 Preparation of starting and delayed initiator The initial initiator was prepared by adding 2.0 g of ammonium persulfate into 10 g of deionized water and stirred in using a

178 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

magnetic bar. For the delayed initiator, 1 g of ammonium persulfate and 2g of sodium hydrogen carbonate were solved in 70g of deionized water and added into the reactor by 3 hours of feeding.

2.4.3 Polymerization procedure Delayed radical emulsion polymerization was used for the initiation. All polymerizations were carried out using deionized water (DI). For the polymerization procedure; starting initiator and water were initially charged into the reactor. The monomer emulsion and delayed initiator were fed in two streams having both the same feeding time, 3 hours, using a peristaltic pump via silicone tubing, and the feed rate monitored volumetrically. The reactions were performed in a 2 liter, glass made, and round-bottomed reactor flask with a mechanical agitator and stirred at 180 rpm. The reactor flask was equipped with reflux condenser, thermocouple and metallic stirrer. Polymerization temperature was maintained at 84–86°C, and agitation rate was increased if necessary. After feed, the monomer mix beaker was flushed with water, and was post-heated for 30 min. The reaction mixture was then cooled to 55°C and post redox reaction was applied. A redox post polymerization process provides lower residual monomer levels and/or lower volatile organic compound levels for emulsion systems. t-Butyl hydroperoxide / sodium salt of an organic sulfonic acid derivative as redox couple were selected. In neutralization step, ammonia solution (28%) was used to adjust the pH around 8.0±0.5. Then the polymer was filtered into a suitable container.

2.5 Film Preparation A 50 μ film of the sample is applied on BOPP "corona" treated >36 Din by automatic coater with the coating rate of 150mm/ min. Applied film was placed in an oven at 70°C for 15 minutes. For each sample at least 3 coated samples have been prepared and whole performance tests have been repeated 3 times. The average of the performance graphics has been obtained as result in order to minimize the errors. 3. Results And Discussion Adhesive polymers were prepared by emulsion polymerization due its advantage of reducing the volatile organic content. Solid content of all polymers were calculated in the range of 59±1%, pH has adjusted around 7.5-8.

The results of polymer characterization and performance analysis are summarized in Table 2.

Polymer Solid pH Viscosity Tg Surface Coagulum % (cps.)a ( 0C ) Tension Weight (mN/m) (g/lt) 1 59.8 7.5 140 -39.0 37.7 0.06

2 59.4 7.4 130 -38.5 37.4 0.12

3 59.7 8.0 140 -35.0 34.2 0.08

4 59.0 8.0 150 -36.5 36.9 0.14

Table 1: Monomer compositions (based on total monomer*, % weight). aLatex viscosity measured using Brookfield LVT viscometer using speed : 60 rpm, spindle : No. 3, and temperature:250 C.

According to the results in Table 2, the addition of BoA has slightly decreased the surface tension. Coagulated part was around 0.1 for all the reactions and the total amount of unreacted monomer was below 250ppm, which showed that the polymerization was completed successfully.

179 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

Polymer Peel Peel Peel Peel Peel Peel Strength, Strength, Strength, Strength, Strength, Strength, SS Glass Al PVC LDPE HDPE (N/cm)a (N/cm)a (N/cm)a (N/cm)a (N/cm)a (N/cm)a

1 2.5 1.9 2.3 2.2 0.4 1.0 2 2.3 2.2 2.3 2.3 0.6 1.0 3 2.1 2.2 2.4 2.7 0.6 1.1 4 2.0 2.2 2.7 3.2 0.7 0.8

Table 3: Adhesion performance on SS, Glass, Al, PVC, LDPE and HDPE.

a The result quoted is the average of three determinations. Peel adhesions were tested according to FTM1 on stainless steel, glass, aluminium and low density polyethylene as 180° at 300 mm/min by Adhesion Release Tester AR-1000. Test conditions were at 23 ± 2°C, 50 ± 5 % relative humidity.

Figure 3: Comparison of peel strength

Increasing BoA content in the dispersion decreased the adhesion on SS, however slightly increased the adhesion on glass, aluminum, PVC and PE due to its chemical structure and surface tension. The multi arm BoA especially increased the interaction between adhesive and the substrate in case of Al and PVC.

180 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

Polymer Shear Shear Shear Initial Initial Initial Strength, Strength, Strength, Track Track Tack, SS Glass LDPE Glass LDPE HDPE (hrs.)a (hrs.)a (hrs.)a (N/cm)b (N/cm)b (N/cm)b 1 4020 7500 2400 10000 11.4 3.2 2 1680 5460 3300 10000 11.9 3.6 3 1380 5400 4080 10000 11.3 3.6 4 2800 6700 5800 10000 8.5 2.6

Table 4: Shear strength and loop tack results for the adhesive films. a The result quoted is the average of three determinations. Static shear test was applied according to FTM 8 on stainless steel, glass and low density polyethylene at 23°C and the test equipment was 10 Bank Shear RT-10. Test conditions were at 23 ± 2°C, 50 ± 5 % relative humidity. bThe result quoted is the average of three determinations. Initial tack values were tested according to FTM9 on glass, and low density polyethylene by Loop Tack Tester LT-1000. Test conditions were at 23 ± 2°C, 50 ± 5 % relative humidity.

Figure 4: Comparison of shear strength

Figure 5: Comparison of shear strength 181 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

Tack values did not show a significant effect on glass, however tack on HDPE and LDPE was slightly increased.

In acetone test, the amount of insoluble part was increased by the increase on boron acrylate content. The highest value has been obtained by the usage of the multi-arm boron acrylate monomer which also decreased the swelling and showed a crosslinking behavior as expected.

Polymer W0 W1 W2 Swelling index Insoluble (gr.) (gr.) (gr.) (W1-W0)/W0 Fraction % W2/W0*100

1 0.57 12.47 0.41 20.9 72 2 0.62 15.34 0.48 23.7 77 3 0.56 15.76 0.46 27.1 82 4 0.60 10.81 0.51 17.0 85

Table 5: Swelling and solubility in acetone As shown in the TGA results boron acrylate content, increased the decomposition temperature for the same amount of weight loss. When compared to the polymer sample without boron acrylate, boron acrylate containing polymer samples has higher residue at 700oC due to its in organic structure and strong bonding especially in case of multi arm boron methacrylate.

Polymer 50% Weight Loss Residue at 700oC Temperature (0C) (%)

1 410 0.2 2 416 2.0 3 423 1.8 4 418 3.5

Table 6: TGA results

Figure 6: TGA results

182 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

4. Conclusions Pressure-sensitive adhesives (PSAs) were prepared from acrylate monomers (BA, MMA, BoA and multi arm BoMA) by using emulsion polymerization. Analysis results of solid and coagulum content as well as low residual monomer results from GC showed that synthesis of co-polymers had been properly achieved. The small differentiations on the Tg based on the structure of co-monomer had an influence on tackiness, because it determines the softness of the polymer. Adhesion and cohesion is affected by the co-monomer due its effect on the bonding strength and wettability. The highest adhesion was obtained when bonded onto the polar surfaces such as Al, glass and SS. However, increasing BoA showed a positive effect on LDPE both for adhesion and cohesion, while both performances showed a decrease on SS. The use of a rough substrate reduces the adhesion of a PSA to the substrate. BoA content mainly affected the non-polar and plastic surfaces which have surface energy below 40mN/m. Multi arm BoMA enhanced the crosslinking of the PSA. According to the TGA results, decomposition temperature has been increased by the increase on boron content in the adhesive and the thermal stability was enhanced by boron acrylates. This study shows that boron acrylate content in a water borne pressure sensitive adhesive may provide flame retardancy as well as keeping the adhesive and cohesive performance in a line for several substrate surfaces. Acknowledgement The authors would like to express their gratitude to Istanbul Technical University Research Fund and Organik Kimya San. ve Tic. A.Ş. for their technical and financial support. (ITUAYP- 2014-6) References 1. Czech, Z.; Pełech, R., Progress in Organic Coatings, 65 84–87 (2009). 2. Benedek, I. Marcel Dekker Inc. and Newyork Basel, 2nd ed. (2004) 3. Demarteau, W.; Loutz, J.M., Progress in Organic Coatings, 27 33-44 (1996). 4. Bakhshi, H.; Zohuriaan-Mehr, M.J.; Bouhendi, H.; Kabiri, K., Polymer Testing, 28 730– 736 (2009). 5. Xu, H.; Wang, N.; Qu, T.; Yang, J.; Yao, Y.; Qu, X.; Lovell, P., J. Appl. Polym. Sci., 123 (2012) 1068–1078. 6. Qie, L.; Dube, M.A., Int. J. Adhes. Adhes., 30 (2010) 654–664. 7. Sun, S.; Li, M.; Liu A., Int. J. Adhes. Adhes., 41 (2013) 98–106. 8. Dhal, K.; Deshpande, A.; Babu, G.N., Polym., 23 (1982). 9. Comyn, J., Adhesion Science, 1 (1997) 14-15. 10. Ismail, H.; Ahmad, Z.; Yew, F. W., J. Phys. Sci., 22 (2011) 51–63. 11. Gower, M. D.; Shanks, R. A., J. Appl. Polym. Sci., 93 (2004) 2909–2917. 12. Jovanovic, R.; Ouzineb, K.; McKenna, T. F.; Dube, A. M., Macromol. Symp., 206 (2004) 43–56. 13. Stephane, R.; Dube, A. M., Polym., 47 (2006) 799–807. 14. Blickenstorfer, B.; Nookala, R.K., Collano AG, https://www.pstc.org/files/public/Nookala08.pdf, (n.d). 15. Petrie, E.M., Adhesives & Sealants Industry Magazine, (2007) 16. Parsons, K.P.; Buckingham, M.R.; Diamond, J.H.; Ilkka, S.J, Nowak, P., US 5851663 A, (1998). 17. Esmay, D., US 4599265 A, (1986) 18. Nishimura, H.; Sakai, T.; Nate, K., US 20050227065 A1, (2005). 19. Canak, T. C.; Kaya, K.; Serhatlı İ.E., Progress in Organic Coatings, 77 11 (2014) 1911- 1918. 20. Garrett, D. E., Academic Press, (1998). 21. Kajtnaa, J.; Golobb, J.; Krajncb, M., International Journal of Adhesion and Adhesives, 29 (2009) 186-194. 22. Czech, Z., Journal of Adhesion Science and Technology, 21 (2007) 625-635. 23. Asahara, J.; Hori, N.; Takemura, A.; Ono, H., Journal of Applied Polymer Science, 87 (2003) 1493–1499 24. Czech, Z., Polym. Int., 52 (2003) 347–357. 25. Ahmed1,K.; Nizami, S.S; Raza1, N. Z.; Shirin1, K., Advances in Materials Physics and Chemistry, 2 (2012) 90-97. 26. Duncan, B.; Mera, R.; Leatherdale, D.; Taylor, M.; Musgrove, R.; NPL Report (2005). 27. Piltonen, P.; Stoor, T.; Niinimaki, J., Int. J. Adhes. Adhes., 36 (2012) 15–19. 28. Kowalski, Z.; Czech, Z., Int. J. Adhes. Adhes., (2015).

183 EFFECT OF BORON ACRYLATE MONOMER CONTENT AND MULTI ARM BORON ACRYLATE ON ADHESIVE PERFORMANCE FOR WATER BORNE ACRYLIC POLYMERS COATED ON BOPP FILM

28. Kowalski, Z.; Czech, Z., Int. J. Adhes. Adhes., (2015). 29. Groves, J.D., United States Patent, US 5677376 A (1997). 30. Broje, V.; Keller, A., J. Col. and Int. Sci., 305 (2007) 286–292. 32. 3M, http://multimedia.3m.com/mws/media/755526O/innovations-in-bonding-to-lowsurface-energy-white-paper.pdf, (n.d). 33. Kowalski, A.; Czech, Z.; Byczy , ., Coat. Technol. Res., 10 (2013) 879–885. 34. Peykovaa, Y.; Lebedevaa, O.V; Diethertb, A.; Buschbaumb, P.; Willenbachera, N., Int. J. Adhes. Adhes., 34 (2012) 107–116. 35. Tecman, http://tecmanuk.com/news/bonding-low-surface-energy-lse-materials, (2016). 36. 3M, http://www.markingsystems.com/pdf/3mfundamentals_of_adhesion.pdf, (n.d.). 37. Diethert, A; Eckert, K.; Peykovaa, Y.; Willenbacher, N., Buschbaum, P, ACS Appl. Mater. Interfaces, 3 (2011) 2012-2021. 38. Diethert, A.; Lebedeva, O.; Willenbacher, N., Buschbaum, P., ACS Appl. Mater. Interfaces, 2 (2010) 2060-2068. 39. Peykova, Y.; Lebedeva, O.; Diethert, A.; Buschbaum, P.; Willenbacher, N., Int. J. Adhes. Adhes., 30 (2010) 245-254. 40. FINAT Technical Handbook, 9th edition.

184 35 Poster Presentations

Doç. Dr. Feza Geyikçi Ondokuz Mayıs University Turkey

She was born in Samsun in 1966. She graduated from Istanbul University Faculty of Engineering Department of Chemical Engineering in 1988. She completed the Master's and doctoral education in Environmental Engineering Department, worked as a research assistant at the same department. Later she worked 15 years in Province Bank as the chemical engineer in charge at Drinking Water Analysis Laboratory. In 2005, she was appointed as an Assist. Prof. in the Department of Chemical Engineering in 19 Mayıs University, Faculty of Engineering. In 2014, she received the title of Assoc. Prof. of Chemical Engineering. She has 16 Turkish, 52 foreign registered, 16 of 52 in Science Citation Index "published papers/ works", in the following fields; dyes, nanotechnology, biodegradable polymers, leaching and adsorption. She took place as the head in 4 of the 5 completed projects, one as a researcher. She still continues to academic study as a lecturer in the same department.

186 INVESTIGATION WITH 3D OPTIC PROFILOMETER OF THE TRIBOLOGICAL BEHAVIORS ALKALINE ZINC AND ZINC-NICKEL ALLOY ELECTROCOATINGS

Doç. Dr. Feza Geyikçi, Muhammet İskender Ondokuz Mayıs University Turkey Abstract Zinc and zinc alloy coatings have increased in importance to extend the lifetime of components and materials that exposure to wear and corrosive effects in accordance with the work environment, especially have a risk of safety in the automotive and industrial sectors. In accordance with this importance in this study; tribological behaviors of NaOH-based non-cyanide zinc and NaOH-based zinc-nickel electrocoating were searched. In this study, X-Ray Fluorescence (XRF) spectrometry was used to determine the elemental composition of the coating thickness and scanning electron microscope (SEM) was used to examine the cross sectional area of coatings. Tribological behaviors were tested linear reciprocating in tribological device and surface topography were examined by 3D Optical Profilometer. Coefficient of friction of coatings were compared after the heating at 120 °C 24 hours and 200 oC 24 hours with unheated. When examined wear resistance of coatings Zn/Fe and ZnNi/Fe (%14,34 Ni) that thickness was 13 µm, coefficients of friction of zinc nickel alloy coating were determined 0.55,0.49,0.45 at unheated,120 oC,200 oC ,while coefficients of friction of alkaline zinc coating were determined 0.5,0.6,0.7 at unheated,120 oC,200 oC. Experimental results showed that increased of wear resistance of alkaline zinc-nickel coating, whilst decreased of wear resistance of alkaline non-cyanide zinc coating after heating.

Key Words: alkaline non-cyanide zinc coating; alkaline zinc-nickel coating; tribological behaviors; coefficient of friction; 3D optical profilometer

187 INVESTIGATION WITH 3D OPTIC PROFILOMETER OF THE TRIBOLOGİCAL BEHAVIORS ALKALINE ZINC AND ZINC-NICKEL ALLOY ELECTROCOATINGS

1. Introduction In the industrial field, particularly in iron and ferro-alloys, it is necessary to take precautions against the corrosive environment causing economic damage. Wear resistance, thermal stability and mechanical properties are also improved and should be controlled. Zinc and zinc alloy coating systems have an important role in meeting this demand in recent years. Taking into account the environment and human health, according to the desired conditions are continuing to improve. Zinc alloy plating and post created specially layers (passivation, sealing etc.) meets the demands which are corrosion resistance, hardness and thermal stability in the automotive and aerospace industry. Thermal stability and wear resistance of the component or parts which especially close motor assembly are quite important. In this study, tribological behaviors of NaOH-based zinc and NaOH- based zinc-nickel alloy electroplating were investigated with 3D optical surface imaging after linear reciprocating wear testing. Heat treatment effect to zinc and zinc-nickel coating layers were tested. 2. General Information 2.1 Tribological System Third bodies are generated between the two contact surfaces during wear of materials, The third bodies are generally classified tribo film, transfer film and wear debris. In terms of a counterface versus coating tribosystem, a tribo film is mechanically or chemically modified layer at the coating surface, which may also consist of wear debris. [1-3]. Wear debris is generally considered as any removed portion of the coating or counterface that is not part of the transfer film or tribo film. A schematic representation of linear reciprocating mechanism which carried out in tribology are shown in Figure 2.1. Abrasive environment and abrasive equipment must be ready before starting the tribology test.

Figure 2.1: Schematic of the linear wear test.

188 INVESTIGATION WITH 3D OPTIC PROFILOMETER OF THE TRIBOLOGİCAL BEHAVIORS ALKALINE ZINC AND ZINC-NICKEL ALLOY ELECTROCOATINGS

As shown in Figure 2.2 , the tribological behavior of the coating layer has changed in the film layer dimension during the test process [4].

Figure 2.2: Contact conditions encountered during in situ tribology testing of the investigated coatings

2.2 3D Non-Contact Optical Profilometer The axial chromatism technique uses a white light source, where light passes through an objective lens with a high degree of chromatic aberration. The refractive index of the objective lens will vary in relation to the wavelength of the light. In effect, each separate wavelength of the incident White light will re-focus at a different distance from the lens (different height). When the measured sample is within the range of possible heights, a single monochromatic point will be focalized to form the image. Due to the confocal configuration of the system, only the focused wavelength will pass through the spatial filter with high efficiency, thus causing all other wavelengths to be out of focus. The spectral analysis is done using a diffraction grating. This technique deviates each wavelength at a different position, intercepting a line of CCD, which in turn indicates the position of the maximum intensity and allows direct correspondence to the Z height position [5].

Unlike the errors caused by probe contact or the manipulative Interferometry technique, White lightAxial Chromatism technology measures height directly from the detection of the wavelength thathits the surface of the sample in focus. It is a direct measurement with no mathematical software manipulation [5].

Figure 2.3: Schematic of a 3D non-contact optical profilometer and a recessed surface measurement. 189 INVESTIGATION WITH 3D OPTIC PROFILOMETER OF THE TRIBOLOGİCAL BEHAVIORS ALKALINE ZINC AND ZINC-NICKEL ALLOY ELECTROCOATINGS

3. Materials And Method Zinc and zinc nickel plating was carried out to the plate in 60 x 60 x 5,0 mm. Non heating and after 120 oC 24 hours and 200 oC 24 hours heating treatment was carried out for zinc (13 μm thickness of coating ) and zinc nickel (13 μm thickness of coating ve Ni %14,34 ) platings . Then the plates were subjected to tribology test in accordance with the standard ASTM G133 [6]. Tribology tests was made in a dry place at room temperature and under low oscillations in computer-controlled device in Bruker UMT. Shematic of tribological test was given in Figure 3.5 . The surface of the sample polished and both abressive ball and disk was cleaned in pure ethanol before test. After different tries for zinc coating, test method for wearing period was determined like as amount of normal force 2 N, 15 mm/s speed, 10 mm movement distance ve 480 cycles (linear reciprocating total 20 mm wear distance was equal 1 cycle) [7]. Test method for zinc nickel plating which amount of normal force 4 N, 15 mm/s speed, 10 mm movement distance ve 600 cycles was determined. 440-C Stainless Steel Balls, Dia. 9,5 mm(3/8”) was used for abresive balls. Surfaces of different plates was analyzed by 3D optical profilometer after wear test. Examining the surface profile of the wear areas was obtained data such as wear area, volume and depth. Helping suitable fringes ,1.2 mm surface imaging on abraded area of plate were obtained with VSI mode on the 3D non-contact profilometer.

4. Results And Discussion 4.1 Coating Characterization The cross-sectional SEM of the zinc and zinc nickel coatings are shown in Figure 4.1. Zinc nickel coating consisted of through- thickness microcracks which is a typical of intermetallic γ-ZnNi. The zinc coating consisted of more uniform cross section devoid of microcracks.

Figure 4.1: SEM cross-sectional morphologies of the investigated coatings; a) zinc b) zinc nickel (a) (b) 190 INVESTIGATION WITH 3D OPTIC PROFILOMETER OF THE TRIBOLOGİCAL BEHAVIORS ALKALINE ZINC AND ZINC-NICKEL ALLOY ELECTROCOATINGS

4.2 Coefficient of Friction and 3D Optical Surface Imaging Friction coefficient versus cycle number and 3D optical surface images are shown in Figure 4.2 and 4.3 for the zinc nickel alloy and zinc coating. Coefficient of friction of the coatings were compared that without heating and after heating at a constant temperature 120 °C for 24 hours with at 200 °C for 24 hours. Coefficient of friction decreased with heating at alkaline zinc nickel coating , while coefficient of friction increased with heating at alkaline zinc. For 13.0 mm thickness of the Zn / Fe and ZnNi / Fe (14.34% Ni) ,summary of wear testing and analysis of wear area were shared n Table 4.1. Coefficient of friction of zinc-nickel alloy coating without heating, 120 ° C and 200 ° C respectively, 0.55, 0.49, and 0.45 were identified, while the coefficient of friction of alkaline non-cyanide zinc 0.50, 0.60, 0.70 were identified. ZnNi/Fe Zn/Fe Non 120 ºC 200 ºC Non 120 ºC 200 ºC heating 24 hours 24 hours heating 24 hours 24 hours

Transfer Film Stability 80 90 100 75 75 50 (cycles) Coating Life (cycles) 600 600 600 200 200 200 Coefficient of friction 0,55-0,70 0,49-0,61 0,45-0,55 0,5-0,60 0,60-0,65 0,70-0,80 Volume of wearing areas (mmᶟ) 0,0261 0,0250 0,0126 0,0346 0,3690 0,3700 Width of wearing areas (mm) 0,2127 0,2085 0,1046 0,2883 0,3077 0,3081

Table 4.1: Summary of wear testing and analysis of wear area. 4. Conclusions The nature of transfer film formation and stability, wear debris generation is observed to be different for zinc and zinc nickel coating. Comparing wear resistance of coatings, zinc nickel alloy coating is observed to be higher. Coefficient of friction of zinc-nickel alloy coating without heating, 120 ° C and 200 ° C respectively, 0.55, 0.49, and 0.45 are identified, while the coefficient of friction of alkaline non-cyanide zinc 0.50, 0.60, 0.70 are identified. With heating wear resistance increases for alkaline zinc nickel coating , while with heating wear resistance decreases for alkaline zinc coating.

191 INVESTIGATION WITH 3D OPTIC PROFILOMETER OF THE TRIBOLOGİCAL BEHAVIORS ALKALINE ZINC AND ZINC-NICKEL ALLOY ELECTROCOATINGS

Non heating 120 oC 24 hours 200 oC 24 hours

Figure 4.2: The development of the coefficient of friction wear test process and 3D image of wearing areas - ZnNi/Fe coating.

Non heating 120 oC 24 hours 200 oC 24 hours

Figure 4.3: The development of the coefficient of friction wear test process and 3D image of wearing areas - Zn/Fe coating.

References 1. Barcelo G., Sarret M., Muller C., Pregonas J., 1998. Corrosion resistance and mechanical properties of zinc electrocoatings, Electrochimica Acta, 13–20. 2. Jahanmir S., Abrahamson Ii E. P., Suh N. P., 1976. Sliding wear resistance of metallic coated surfaces, Wear report, 75–84. 3. Khurshudov A. G., Olsson M., Kato K., 1997. Tribology of unlubricated sliding contact of ceramic materials and amorphous carbon, Wear report, 11-101. 4. Siniawski M. T., Harris S. J., Wang Q., 2007. A universal wear law for abrasion, Wear report 83-88. 5. Petzin J., Coupland J., 2013. The measurement of rough surface topography using coherence scanning interferometry, Applied optics, 1554-1563. 6. ASTM G133, 2010.Standard test method for linearly reciprocating ball-on-flat sliding wear. 7. Evin E., Tomáš M., Kollárová M., Antoszewski B., 2014. Some tribological aspects of Fe-Zn coated steel sheets at stamping processes, Acta Metallurgica Slovaca, Vol. 20, No. 2, 189-199.

192

Poster Presentations

Dr. Bahadır Keskin

Yıldız Technical University Turkey

Education: Academic Degree Doctorate: Inorganic Chemistry, Department of Chemistry, Faculty of Science, Yıldız Technical University, Turkey, 2009 Academic Degree Master: Inorganic Chemistry, Department of Chemistry, Faculty of Science, Yıldız Technical University, Turkey, 2003 Academic Degree Bachelor: Department of Chemistry Teacher, Faculty of Education, Uludag University, Turkey, 1994

Experience: Visiting Scientist, Department of Chem.& Biochemistry, University of Minessota Duluth, USA, 2011 Postdoctoral Fellowship, Department of Chem.& Biochemistry, North Dakota State University, USA, 2010 / 2011 Position Research Assistant, Chemistry Department, Yıldız Technical University, Turkey, 2000 / ~

Research Interests: Phthalocyanine - Porphyrazine - Ferrosen derivatives - Electrochemical Analysis - Organometallics - Photodynamic Theraphy, Cancer Drugs, Synthesis and Characterization

194 SYNTHESIS, CHARACTERIZATION AND PHOTOPHYSICAL PROPERTIES OF NOVEL DYE WATER SOLUBLE ZINC-PHTHALOCYANINES

Dr. Bahadır Keskin Yıldız Technical University Turkey

Phthalocyanines (Pcs) are functional dyes with an extended conjugated network of π-electrons. Pc blue is a bright, greenish-blue crystalline synthetic blue pigment from the group of phthalocyanine dyes [1]. It has the appearance of a blue powder, insoluble in water and most solvents. Although metallophthalocyanines (MPcs) possess great potential in electrochromic applications due to their good chemical stability and rich color changes, they are practically insoluble in common organic solvents and aqueous media, thereby minimizing their applications. Quaternized ammonium groups are especially useful to achieve solubility within a wide pH range [1]. Their outstanding dye properties and the ability to self-assemble, by means of π-π interactions, into highly ordered arrays can be tuned by careful design of their periphery such as quinoline moiety [2].

In this work, water soluble derivative (3) of tetra-1-chloro-3,4-dicyano-6-quinolin-8-yloxy substituted novel zinc(II) and titanium(IV) phthalocyanine dye complexes were synthesized and characterized by UV-Vis, FTIR, 1H NMR, Fluorescence and Mass Spectroscopies [3]. This study was supported by Scientific Research Projects Unit of Yildiz Technical University (P.No: 2015-01-02-GEP01).

195 SYNTHESIS, CHARACTERIZATION AND PHOTOPHYSICAL PROPERTIES OF NOVEL DYE WATER SOLUBLE ZINC-PHTHALOCYANINES

References: 1. Lever, A.B.P.; Leznoff, C.C.; “Phthalocyanines and their applications”, Wiley, Vol 4, 1996 2. Michal Juricek, Paul H. J. Kouwer, Juraj Rehak, Joseph Sly, and Alan E. Rowan, J. Org. Chem. 74 (2009) 21–25. 3. V. Çakır, D. Çakır, M. Göksel, M. Durmuş, Z. Bıyıklıoglu, H. Kantekin, J. Photochemistry and Photobiology A: Chemistry, 299 (2015) 138–151.

196 35 Poster Presentations

Hatice Begüm Murathan

Gazi University Turkey

Hatice Begüm Murathan was born in Yenimahalle/Ankara in 1992. She graduated from Gazi University Department of Chemical Engineering in 2014. She received M.Sc degree in 2016 at Gazi University Department of Chemical Engineering. Currently she is attending Gazi University Department of Chemical Engineering as PhD student.

198 LOW COST FLAME RETARDER IN INTERIOR WALL PAINTS

Hatice Begüm Murathan Atilla Murathan Gazi University Turkey

Abstract There are many dangers with fire origin for human and environment health. This subject is important in daily life according to the "Regulations on the Protection of Buildings from Fire". In this study, PVA based interior wall paint was used as control sample and the same dye with boric acid in powder was used as flame retardant. At the end of the ignition test results due to Dixon statistical calculation method (ISO 4589-2), limited oxygen indexes of the control sample and the dye with boric acid were obtained as 27% and 30% respectively. Also, use of boric acid may be advantageous in paint sector as a cheap and environmental friendly flame retardant material because of high capacity of boron ore in Turkey.

Key words: construction paint; boric acid; flame retardant Introduction Uncontrolled fires indoors can kill people at the same time can make buildings unusable. In our country, the number of fires that occur each year increased as a result of rapid population growth, rapid urbanization and industrialization. Indoor fires are important to intervene in the first five minutes. Loss of life from the fire origin can be minimize with non-combustible or flame retardant materials [1]. Flame retardant and smoke suppressant materials, additives and reagents are divided into two main groups. The flame retardants do not react with the additive fillers. Halogens may be released poisonous gas when used in the flame retardant additive compositions. These auxiliaries help plastic manufacturing (mixing, drawing or during casting viscosity modifiers, plasticizers, mold, relaxers, etc.) also provides requirements the same time as the final product in strength, stiffness, flexibility and resistance to the conditions. Flame retardant and smoke suppression inorganic minerals/compounds play an important role and also should not be damage of the core material. Certain extent by addition of various flame

199 LOW COST FLAME RETARDER IN INTERIOR WALL PAINTS

retardant additives and easily flammable base material for reduce to oxygen [2]. Especially aluminum trihydrate and magnesium hydroxide are used as fire retardant materials. Besides boron derivatives, brominated, chlorinated and phosphorescent chemicals are also used. In recent years, using of the combination of these products has been studied for example zinc borate and antimony trioxide. But brominated, chlorinated, phosphorus and antimony gas output due to toxic chemicals is prohibited in accordance with European Union Directive. LOI (Limited Oxygen Index) Test There is variety of tests to determine of flame resistance of materials. These tests are related with the type of material, shape and size. For example materials wood, paper coatings, textile products and different types of polymers suitable test methods are available. LOI test method, where the oxygen and nitrogen in a gas mixture, in the continuation of combustion after ignition of measuring the minimum oxygen concentration, is the most commonly used in flammability test. LOI test determines the oxygen necessary for combustion of the sample. ASTM D2863 standard experimental procedures performed for LOI test [3]. Standard test method of TS 11162-2 EN ISO 4589-2 is also useful [4]. Various types of materials in different dimensions can be prepared for the test sample, an oxygen and nitrogen mixture upward through a chimney.

ISO 4589-2 is technically equivalent when using the gas measurement and control device with direct oxygen concentration measurement. At different oxygen concentrations, with a series of experiments using test sample, the minimum required oxygen concentration value is calculated for a statistical method using the up and down of Dixon method. According to Dixon’s up and down method, burning time after ignition must be over 180s. The procedures are repeated, using oxygen concentration changes of any convenient step size, until two oxygen concentrations, in percent volume, have been found that differ by 1.0 % and of which one gave an “O” response and the other an “X” response. From this pair of oxygen concentrations, are noted that which gave the “O” response as the preliminary oxygen concentration level. The two results, at oxygen concentrations 1.0 % apart, which give opposite responses, do not have to be from successive specimens. At times, the concentration that gave the “O” response will not be lower than that which gave the “X” response. Such apparent inconsistencies, that are likely to be caused by the variability of the test, the equipment, or the material, are not uncommon.

LOI value, the percentage by volume calculated from the following equation:

LOI = Cƒ +k x d

Cf; Recently attempts oxygen concentration applied to the test sample d; Step size k; Dixon's “up and down” of the determination made by the method used to calculate the concentration of oxygen index factor (Table 1).

200 LOW COST FLAME RETARDER IN INTERIOR WALL PAINTS

1 2 3 4 5 6 Values of k for which the first NL determinations are

Responses for Responses for the Last Five O OO OOO OOOO the Last Five Measurements Measurements*

XOOOO -0.55 -0.55 -0.55 -0.55 OXXXX XOOOX -1.25 -1.25 -1.25 - 1.25 OXXXO XOOXO 0.37 0.38 0.38 0.38 OXXOX XOOXX -0.17 -0.14 -0.14 -0.14 OXOXX XOXOO 0.02 0.04 0.04 0.04 OXOXX XOXOX -0.50 -0.46 -0.45 -0.45 OXOXO XOXXO 1.17 1.24 1.25 1.25 OXOOX XOXXX 0.61 0.73 0.76 0.76 OXOOO XXOOO -0.30 -0.27 -0.26 -0.26 OOXXX XXOOX -0.83 -0.76 -0.75 -0.75 OOXXO XXOXO 0.83 0.94 0.95 0.95 OOXOX XXOXX 0.30 0.46 0.50 0.50 OOXOO XXXOO 0.50 0.65 0.68 0.68 OOOXX XXXOX -0.04 0.19 0.24 0.25 OOOXO XXXXO 1.60 1.92 2.00 2.01 OOOOX XXXXX 0.89 1.33 1.47 1.50 OOOOO First NL determination results **X XX XXX XXXX Responses for *Values of k for which the first NL determinations are ** X, XX, the Last Five XXX, and XXXX are as given in Table 1 opposite he appropriate Measurements response in Column 6, but with the sign of k reversed, that is:

OI = CF − kd

Table 1: Determination of k value by using Dixon’s up and down method [5] LOI results, some plastic materials under controlled laboratory conditions provides a sensitive measure of combustion properties and therefore may be useful for quality control purposes which finds extensive use exterior paint and coating materials and so on. Play a role in many areas of the polymeric material they are susceptible to flame, low flame retardants, thermal and mechanical properties are improved by the addition of various additives. Polymerization is achieved by the addition of dye or pigment additives [5]. Silicon-based binder developed using both binder and pigment in high temperature paint is resistant to high temperatures, so they can be used as fireproof paint [6]. Classification of the flame retardants was given in Table 2 [7].

LOI values, % combustion condition < 24 combustible, flammable 24-28 limited flame retardant 29-34 flame-retardant > 34 flame retardant extra Table 2: Classification based flame retardants according to LOI 201 LOW COST FLAME RETARDER IN INTERIOR WALL PAINTS

Experimental Method Interior white paint which based on PVA obtaining by Kardelen Paint and Chemical Co.Ltd./Ankara, was used in the experiments. Paint formulation was given in Table 3. These first group samples were taken as control samples. Examples of the dye formulation in the second group experiments were performed by adding 1.0 %, w/w H3BO3 (in 60% purity from Eti Mine Facility). Aluminum molds were prepared in 11x4x4 cm3 dimension (Figure 1). Then petroleum jelly to the inside of the plaster mold was applied for separated easily and the paint samples including five double molds. Thick of each test specimen was at least 3.0 mm and the specimen were conditioned for 40 h at 23±2°C and 50±5 % relative humidity. After conditioning, limit oxygen index tests due to the ASTM D 2863 were obtained.

Table 2: Classification based flame retardants according to LOI

Chemicals %, w/w Water 20 Calgon 0.25 Ammonia 0.004 Defoamer 0.3 Dispersion Agent(P-90) 0.32 TiO2 10 Calcite (2μm) 28.84 Calcite (5μm) 23.33 Hidroxy ethyl celulose 0.3 Glue 16.66 Texanol 1 Toxic 0.2 Acrisol 2.5 Table 3: Interior white paint formulation

LPG fuel was used as ignition source and Dynisco LOI apparatus was given in Figure 2. The remaining outer part of the sample perpendicular to the shaft of at least 100 mm center to be mounted. At a rate of 23 ± 2°C containing the desired oxygen concentration from the oxygen / nitrogen mixture 40 ± 2 ml/s to be fed into the heating zone. To maintain the flow of flue gas flow during ignition and combustion with no change in each sample is provided ignition for at least 30 seconds.

202 LOW COST FLAME RETARDER IN INTERIOR WALL PAINTS

Figure 2: Dynisco LOI apparatus

X and O with a range of movement between the 0.2 step again has decided to perform observation. The flow rate of oxygen and nitrogen are calculated and these values together with the experiments were repeated. OXOOO movement for control samples, OOXOO for sample k value was calculated based on its movement. The results were verified by calculating the standard deviation of the values and the validity of the results were checked, calculations were given as follows: for dye samples

LOI = Cƒ+ k x d LOI =29.94 + (-0.30x0.2) = 30.00 for dye sample with boric acid

Results Successive change in the oxygen concentration of 0.2% was used for the step size. The flow rates of oxygen and nitrogen have been calculated as given in the Table 4 and Table 5, respectively.

O2 (%) 26.2 26.4 26.6 26.8 27 N2 (%) 26.2 26.4 26.6 26.8 27 ml/s 65.5 66 65 67 67.5 ml/s 87.7 87.4 87.1 86.6 86.5

Table 4: Calculated O flow rates 2 Table 5: Calculated N2 flow rates O2 concentration in the range of movement of a pair of X and O for oxygen concentration determination for control dye sample and dye sample with boric acid were given in Table 6 and Table 7 respectively.

O2 flow rate of flow rate of combustion movement of a pair of X (%) O (ml/s) N (ml/s) time and O 2 2 (second) 21 53 94.5 no ignition O 22 55.5 93 27.3 O 23 57.5 91.5 38.5 O 24 60 90.5 41.7 O 25 52.5 89 99.2 O 26 65 88 58.8 O 27 67.5 86.5 >180 X

Table 6: O2 concentration in the range of movement of a pair of X and O for oxygen concentration determination (control dye sample) 203 LOW COST FLAME RETARDER IN INTERIOR WALL PAINTS

As seen from Table 6, values for control sample correspond to 27 percent oxygen. In this Table, meaning of O movement is non combustion, meaning of X movement is combustion.

O2 flow rate of flow rate of combustion movement of a pair of X (%) O (ml/s) N (ml/s) time and O 2 2 (second) 27 67.5 86.5 no ignition O 28 70 85.5 157.3 O 29 72.5 84 180.6 O 30 75.5 82.5 230 X

Table 7: O2 concentration in the range of movement of a pair of X and O for oxygen concentration determination (dye sample with boric acid)

As seen from Table 7 for the specimen with boric acid values correspond to 30 percent oxygen. According to these results control dye sample group with limited flame retardant, boric acid flame retardant group is located in non-limited flame retardant. As a result, boric acid can be take place as a non-toxic and inexpensive flame retardant material in industrial paint sector.

References 1. “Regulations on the Protection of Buildings from Fire”, Official Gazette, September 9, Issue: 27344, 2009. 2. S EN 13501-1+A1, Fire classification of construction products and building elements - Part 1: Classification using data from reaction to fire tests, 2010. 3. ASTM D 2863, Standard Test Method for Measuring the Minimum Oxygen Concentration to Support Candle-Like Combustion of Plastics (Oxygen Index), 2009. 4. Durak, D., Synthesis and Characterization of Some Metal Borates, M.Sc. Thesis, University of Kırıkkale, 109 s, 2007. 5. TS 11162-2 EN ISO 4589-2, Plastics- Determination of burning behaviour by oxygen index- Part 2: Ambient- Temperature test, 2001. 6. Carpentier, F., Bourbigot, S., Bras, M.L., Delobel, R., Foulon, M., “Charring of fire retarded ethylene vinyl acetate copolymer – magnesium hyroxide / zinc borate formulations”, Polymer Degradation and Stability, 83 – 92, 2000. 7. Kaya, M., and Oz, D., Mineral-Based Flame Retardant and Smoke Suppression Additives Agents, 3, Industrial Raw Materials Symposium, Izmir, Turkey, 1999. 8. Schmidt, R., “In the Line of Fire-Flame Retardants Overview”, Industrial Minerals, 37-41, 1999.

204 35 Poster Presentations

Özge Naz Büyükyonga

Istanbul University Turkey

206 INVESTIGATION OF DILUTION RATIO EFFECT ON FILM PROPERTIES OF ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Özge Naz Büyükyonga, Nagihan Akgün, Gamze Güçlü, Işıl Acar Istanbul University Turkey

Abstract In this study, the effects of two different dilution ratios on film properties of acrylic modified water reducible alkyd resin were investigated. For this purpose, 1,3-propanediol based alkyd resin was synthesized with fatty acid method. This alkyd resin was modified with 40% acrylic copolymer of the equivalent amount of acrylic copolymer to alkyd resin. Synthesized acrylic modified alkyd resin was dissolved in isopropyl alcohol to 70% solid content by weight, and then diluted with distilled water with different ratios. In this way, the final contents of solids in the water reducible acrylic modified alkyd resins were obtained as 50% and 60% by weight according to water. Then, alkyd resin films had been prepared and cured at 150°C for 1 h. After that, physical film properties of these alkyd films were comparatively investigated. As a result, the optimum final content of solids in the water reducible acrylic modified alkyd resin was determined as 60% according to water by weight.

Key words: water reducible coatings; alkyd resins; acrylic modification; dilution ratio; film properties.

207 INVESTIGATION OF DILUTION RATIO EFFECT ON FILM PROPERTIES OF ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Introduction Alkyd resin is known as one of the most important binders in the coating industry [1]. Alkyds are polyester resins which modified with fatty acids or fats and they are characterized by good adhesion, flexibility, solvent resistance, durability, excellent gloss and low cost [2]. However, the disadvantages of alkyds are their low water, acid and alkali resistances [3-5]. These disadvantages can be improved by different modification reactions [2, 6]. In the literature, there are several study about modified alkyd resins such as epoxy, vinyl, acrylate, urethane, styrene, phenolic and silicone modified alkyds [7]. During the process of coating, volatile organic solvents (VOCs) are released into the atmosphere and cause too many environmental problems [8]. VOC is injurious to human health and it is also perceived to be a contributory factor to global warming and depletion of the ozone layer [9]. To overcome these problems, the volatile organic solvents replace by water [8]. Water based coatings are more economically attractive and thus gaining prominence due to cheapness of water and the restrictive area of application of the other coating types [9]. In this work, the effects of different dilution ratios on physical film properties of acrylic modified water reducible alkyd resin were investigated and the optimum dilution ratio was determined. Experimental Materials Tall oil fatty acid (TOFA) and trimethylol propane (TMP) were obtained from Arizona Chemicals and Perstorp, respectively. 1,3-propandiol (1,3-PDO), phthalic anhydride (PA), methacrylic acid (MA), fumaric acid (FA) and diethanolamine (DEA) were synthesis or analytical grade. Isopropyl alcohol (IPA) was used as technical grade. Driers for water reducible alkyd resins was kindly provided by AKPA Kimya (Turkey).

Preparation of Acrylic Modified Water-Reducible Alkyd Resins Acrylic modified water-reducible alkyd resins were prepared in four stages. These stages were presented in below. In first stage, acrylic copolymer synthesis reaction of FA and MA in xylene was carried out in glass reactor system. At the end of the reaction, the system was cooled at room temperature and the copolymer was filtered and dried under vacuum. The acid value (AV) of synthesized acrylic copolymer was determined according to related standard [10].

In second stage, four-component alkyd resins containing 50% oil were synthesized in glass reactor system including “Dean-stark piece” using with TOFA, PA, TMP and 1,3-PDO. The “K alkyd constant system” was used for the formulation calculations of the alkyd resins [11]. Reaction was continued until the AV of the alkyd resin was approximately 40-45 mg KOH/g. At the end of the reaction, the hydroxyl value (HV) of synthesized alkyd resin was determined according to related standard [12].

In third stage, acrylic modified alkyd resin was synthesized. That is, the alkyd resin was reacted with the acrylic copolymer (AC). Thus, acrylic modified alkyd resins, which containing 40% AC ratios of the equivalent amounts of AC to alkyd resin, were prepared. The reaction was continued until the AV of the acrylic modified alkyd resin was approximately 30-40 mg KOH/g.

In fourth stage, water reducible acrylic modified alkyd resin was prepared in two steps which are neutralization and dilution. Firstly, DEA was added acrylic modified alkyd resin for neutralization. Then, the acrylic modified alkyd resins were dissolved in slowly added IPA to 70% (wt) solid content. The pH was adjusted to be slightly alkaline. In second step, desired amount of deionized water was added for dilution. Thus, the water reducible acrylic modified alkyd resins having different final solid contents by weight (50% and 60%) were obtained. Symbols and the combinations of water reducible acrylic modified alkyd resins were given in Table 1.

208 INVESTIGATION OF DILUTION RATIO EFFECT ON FILM PROPERTIES OF ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Solid content after adding Final solid content after adding water Alkyds IPA % (by weight) % (by weight)

WRAlkyd70/50 70 50 WRAlkyd70/60 70 60

Table 1: The combinations of water reducible acrylic modified alkyd resins

The Preparation of Water Reducible Acrylic Modified Alkyd Resin Films Driers (1% Zn, 0.1% Co based on the alkyd) were added to alkyd resins and then stirred vigorously. The alkyd films prepared on glass and metal test panels using applicator. Alkyd films were kept at room temperature for 24 hours and then they cured at 150°C for 1 hour.

Physical Surface Coating Properties of Water Reducible Acrylic Modified Alkyd Resin Films “Drying time”, “hardness”, “adhesion strength”, “abrasion resistance”, “impact resistance”, and “gloss” tests were performed to determine the physical film properties of water reducible acrylic modified alkyd resin films. These physical surface coating tests were determined according to related ASTM and DIN standards.

Drying time (or degree) was determined by an “Erichsen Drying Time Tester (Model 415)”, according to DIN 53150. There are 7 drying stages (or degree) and the maximum drying stage is 7, in this standard. Stage 1 is determined with glass beads, and the other stages are determined with disks of typewriter paper under loads range from 5 to 5000 g/cm2. The glass beads remain on film for 10 s, and the loads on the disks remain for 60 s [13-14].

Hardness was determined by the “Sheen König Pendulum” according to DIN 53157. Hardness determination is based on the measurement of the damping of a pendulum oscillating on the film. The oscillations of a standardized König pendulum placed on the test surface are damped in proportion to the “softness” of the coating [13-14]. Adhesion strength was tested by the “Erichsen Cross-Cutter” according to ASTM D3359. The adhesion of a coating is a mechanical property defining the bond between film and substrate [15]. In this method, adhesion strength is determined by cutting through the coating with a series of several cuts at right angles. A square pattern occurred on the film surface can be compared with schematic representations in the standard [13-14].

Abrasion resistance was determined by an “Erichsen Sand Abrasion Tester (Type 2511-11)” according to ASTM D968. In this test, sand is dropped down a vertical tube onto the panel that is mounted at a 45° angle. Test results are given as the amount of sand required to remove a certain thickness of coating [13-14].

Impact resistance was determined by a “BYK Gardner Impact Tester” according to ASTM D2794. The standard steel cylinder testers in different weights (1 kg and 2 kg) are dropped from different heights through a cylindrical guide tube onto the metal panel. The test was repeated by increasing the height from which the object falls till the film was cracked or detached [14, 16].

209 INVESTIGATION OF DILUTION RATIO EFFECT ON FILM PROPERTIES OF ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Gloss was determined by “Sheen Mini Glossmeter” at 60o angle according to ASTM D523. The gloss value of coating by this test method is obtained by comparing the specular reflectance from the specimen to that from a black glass standard [14]. Results And Discussion In this work, the effect of two different dilution ratios on physical film properties of acrylic modified water reducible alkyd resin were investigated and the optimum dilution ratio was determined.

“Drying degree/ hardness test results”, “adhesion strength / abrasion resistance test results” and “impact resistance / gloss test results” of water reducible acrylic modified alkyd resin films are given in Table 2, Table 3 and Table 4, respectively.

Alkyds Drying degree Hardness (König second)

WRAlkyd70/50 7 47 WRAlkyd70/60 7 17

Table 2: Drying degree and hardness test results of water reducible acrylic modified alkyd resin films

As it seen from Table 1, both alkyd films have excellent drying properties after being oven cured. Both alkyd films were kept on room temperature for 24 hours before the determination of drying degree. At the end of the 24 h, no alkyd films had reached the dry-to-touch stage. Then, it has been decided that, curing of alkyd films at 150oC for 1 h. As a result, the change of dilution ratio has not affected the drying property after being oven cured. Hardness values of films were determined as 47 and 14 König second for WRAlkyd70/50 and WRAlkyd70/60, respectively. Hardness values changed with the changing of dilution ratio. At the end of the acrylic modification soft alkyd films were obtained.

Alkyds Adhesion strength (%) Abrasion resistance (mL sand)

WRAlkyd70/50 100 2000 WRAlkyd70/60 100 8000

Table 3: Adhesion strength and abrasion resistance test results of water reducible acrylic modified alkyd resin films

As it seen from Table 2, the percentages of the adhesion strength of the both alkyd films were determined as 100% after being oven cured. The change of dilution ratio did not change the adhesion strength. As expected, the abrasion resistance test results were also obtained parallel with to hardness test results. Abrasion resistance values of films were determined as 2000 and 8000 mL sand for WRAlkyd70/50 and WRAlkyd70/60, respectively.

Alkyds Impact resistance (kg.cm) Gloss (Gloss Unit)

WRAlkyd70/50 > 200 48 WRAlkyd70/60 > 200 61

Table 4: Impact resistance and gloss test results of water reducible acrylic modified alkyd resin films

In addition, both alkyd films have very good impact resistance values after being oven cured. Gloss test results of alkyd films, which also determined after being oven cured as 48 and 61 for WRAlkyd70/50 and WRAlkyd70/60, respectively.

210 INVESTIGATION OF DILUTION RATIO EFFECT ON FILM PROPERTIES OF ACRYLIC MODIFIED WATER REDUCIBLE ALKYD RESIN

Conclusions The effects of two different dilution ratios on the physical surface coating properties of water reducible alkyd resins were investigated. For this purpose, alkyd resin based on 1,3-PDO was synthesized with fatty acid method. This alkyd resin was modified with 40% AC of the equivalent amount of AC to alkyd resin. Then it was dissolved in slowly added IPA to 70% solid content by weight, and then diluted with distilled water. Thus, the water reducible acrylic modified alkyd resins having different final solid contents by weight (50% and 60%) were obtained. These alkyd resin films had been prepared and cured at 150°C for 1 h. After that, physical film properties of these alkyd films were comparatively investigated.

The following conclusions can be drawn from the obtained results:

• Both alkyd films have excellent drying, adhesion strength and impact resistance. In case of same IPA ratios, increasing of water ratio on total amount by weight has led to increase of hardness and decrease of abrasion resistance. In addition, gloss values of alkyd films increased, in spite of decreasing water ratio on total amount by weight at the same IPA ratios. • When results are considered all together, the optimum final contents of solids in the water reducible acrylic modified alkyd resins were obtained as 60% according to water by weight, in respect to physical surface coating properties. In conclusion, low-VOC content water reducible acrylic modified alkyd resins which yielded to soft and flexible films are suitable for manufacturing of surface coating binders.

Acknowledgments This work is supported by TUBITAK (The Scientific and Technological Research Council of Turkey) with Project number 214M660.

References 1. L. Liang, C. Liu, X. Xiao, S. Chen, A. Hu, J. Feng, Prog. Org. Coat., 77 (2014), 1715. 2. Ö. Tuna, A. Bal, G. Güçlü, Polym. Eng. Sci., 53 (2013), 176. 3. O. Saravari, P. Phapant, V. Pimpan, J. Appl. Polym. Sci., 96 (2005), 1170. 4. A. Bal, I. Acar, T.B. İyim, G. Güçlü, Int. J. Polym. Mater. Biomater., 62 (2012), 309. 5. E.U. Ikhuoria, A.I. Aigbodion, F.E. Okieimen, Prog. Org. Coat., 52 (2005), 238. 6. M. Bajpai, S. Seth, Pigm. Resin Technol., 29(2) (2000), 82. 7. F.N. Jones, Alkyd Resins in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Verlag GmbH & Co. KGaA, Weinheim, 2 (2003). 8. A.A. Yousefi, M. Pishvaei, A. Yousefi, Prog. Color Colorants Coat., 4 (2011), 15. 9. A.I. Aigbodion, F.E. Okieimen, E.O. Obazee, I.O. Bakare, Prog. Org. Coat., 46 (2003), 28. 10. C.A. Lucchesi, P.J. Secrest, C.F. Hirn, Chapter 37, Volume 2, in Standard Methods of Chemical Analysis, F.J. Welcher, Ed., Robert E. Krieger Publishing Co.Inc., Huntington, New York (1975). 11. T.C. Patton, Alkyd Resin Technology, Wiley, New York (1962). 12. R.H. Pierson, Chapter 32, Volume 2, in Standard Methods of Chemical Analysis, F.J. Welcher, Ed., Robert E. Krieger Publishing Co. Inc., Huntington, New York (1975). 13. I. Kurt, I. Acar, G. Güçlü, Prog. Org. Coat., 77 (2014), 949. 14. G.G. Sward, Paint Testing Manual, ASTM Special Technical Publication 500, 13th Edition, American Society for Testing Materials, Philadelphia (1972). 15. I. Acar, M. Orbay, Polym. Eng. Sci., 51 (2011), 746. 16. H.S. Patel, B.K. Patel, K.B. Patel, S.N. Desai, Int. J. Polym. Mater. 59 (2010), 25.

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213 Poster Presentations

Sema Ayvaz Yıldız Technical University Turkey

214 PRODUCTION AND APPLICATION OF DECORATIVE PAINTS CONTAINING RUST IN ART

Sema Ayvaz1, Nil Acaralı1, Lütfü Kaplanoglu2, Hanif i Sarac1

1 Chemical Engineering Department, 2 Department of Communication Design, Yıldız Technical University Turkey

Abstract There has been increasing curiosity for the use of paints that can provide some important features in decoration and art. The additives in paints have importance for production of decorative paints. This paints are used in building, art, automotive sectors. In this study, decorative paints were produced by using rusting method. The most effective parameters in production (amount of additives, concentration of solvents etc.) were determined using the Taguchi optimization method. As a result, the optimum process parameters were investigated by using Taguchi method for 4 parameters and 4 levels. Taguchi method, an alternative to classical optimization methods, was used to achieve low cost-high quality. Then, the results were examined comparatively. After the production of decorative paints containing rust, the paints were applied on canvas and wall. Consequently, visual, physical and chemical tests showed positive results and the paints containing rust will provide for use in variety of paint industries and art.

Key words: Rust, paint, Taguchi, art, decorativeproperties.

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217 Poster Presentations

Prof. Dr. Sevgi Ulutan Ege University Turkey

Sevgi Ulutan graduated from Department of Engineering in Ankara University. After completing her dissertation on poly(vinyl chloride)-silica composites she received her Ph.D degree from Department of Chemical Engineering, Ege University, in 1994. Thereafter she continued her studies on Polymer Technology at the same department where she was promoted to the positions of associate professor and full professor by the years 1998 and 2004, respectively. Her research interests cover the field of polymers mainly used in paint and coating applications and packaging area as well as in composite structures. She is interested in transport and plasticizer migration behaviors and recycling issues. She carried out a study on pervaporation of PTMSP silica composite at Meiji University, Japan. She performed a study on a polyethylene composite at Loughborough University, IPTME, UK, with an award of TÜBİTAK and Royal Society scholarship. She has refereed to several industrial projects and taken parts at scientific and organization committees of several polymer related congresses held in Turkey. She has memberships of UCTEA Chamber of Chemical Engineers (Turkey), Turkish Chemical Society, and, Turkish Society of Polymer Science and Technology.

218 DETERMINATION OF DRYING AGENTS FOR THE RESINS USED IN THE COATING FILM

Göksenin Kurt Çömlekçi, Prof. Dr. Sevgi Ulutan, Mustafa Serhan Aşçıeli, Onur Davuç Ege University Turkey Corrosion prevention endeavors are of industrial importance. Rapid dry film production is the most important step in dye and coating applications. Most preferred resins for metal surface coating are alkyd and epoxy resins. The variety of hardeners and dryers for these resins and insufficient empirical data makes their application difficult.

In this project, epoxy resin DGEBA has been mixed with various ratio of phenalkamine and polyamine hardeners while Tung and Linseed Oil alkyd resins have been mixed with various ratio of octoate dryers.

The performances of the coatings have been taken under investigation in terms of their drying period, adhesion and corrosion resistance. Durable coatings were successfully produced as confirmed with Corrosion and Drying test images of resin formulations. The best type of dryers and hardeners under the present conditions were determined utilizing the Cross-Cut tests results which assess the adhesion of dye. The corrosion behaviors of the coatings were investigated by salt spray test method. Optimization of Parameters as the amounts of Epoxy and Alkyd resins, Dryers and Hardeners was achieved, as well.

Thus the coating films of Epoxy and Alkyd resins have been produced applying the most convenient parameters in accordance with the desired properties.

Key Words: Epoxy, DGEBA, tung oil, linseed oil, alkyd, dryer, hardener

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221 Poster Presentations

Katia Padoan

THOR Specialties Italy

222 AMMETM TECHNOLOGY FOR DRY FILM PRESERVATION -ADVANCED MICRO MATRIX EMBEDDING-

Katia Padoan THOR Specialties Italy

In the field of material protection by industrial biocides such as the paint film protection from fungal and algal deterioration, conventional biocide preparations are increasingly replaced by innovative technologies. Thor Group succeeded to develop and introduce to the market new dry film biocides with new enhanced properties, based on a special formulation technology: AMMETM-Technology (Advanced Micro Matrix Embedding). There are wide range of different dry-film preservative formulations available on the market which are successfully used in many coatings, with the following enhanced properties: • Stability: improved in-can, thermal and UV stability, reduced discoloration risks. • Toxicology: reduced environmental and human toxicity, readily biologically degradability. • Emissions and release: slow release, reduced leaching and air emissions. • Efficacy: high fungicidal and algicidal efficacy, global approval.

All these properties are due to the far better stability of the biocide in the film. Active molecules based on AMMETM Technology require overall concentrations that are in many applications lower than those of standard actives, because there is no overdosing necessary in order to compensate a quick decrease in concentration.

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225 Poster Presentations

Yrd. Doç. Dr. Selcan Karakuş Istanbul University Turkey

Universities and Colleges Attended: 2006-2011 Doctorate ((Physical Chemistry), Istanbul University, Istanbul, Turkey. 2003-2006 Master of Science (Physical Chemistry), Istanbul University, Istanbul, Turkey. 1999-2003 Chemistry, Istanbul University, Istanbul, Turkey.

Universities and Colleges attended: 2006-2011 Doctorate ((Physical Chemistry), Istanbul University, Istanbul, Turkey. 2003-2006 Master of Science (Physical Chemistry), Istanbul University, Istanbul, Turkey. 1999-2003 Chemistry, Istanbul University, Istanbul, Turkey.

Patent: • Karakuş S., Kilislioğlu A,Tuba Şişmanoğlu,Selcan Karakuş, "ANTİBAKTERİYEL KİTOSAN/ Fe- SİLİKA NANOBIYOMALZEMESİ", TÜRKİYE, Patent, 2014/07284 , Haziran 2014. • Karakuş S., Kilislioğlu A., Kişmir Y., "ANTİBAKTERİYEL KİTOSAN/ Cu-SİLİKA NANOBİYOKOMPOZİTİ", TÜRKİYE, Patent, 2014/00711, Ocak 2014. • Karakuş S., Kilislioğlu A, Selcan Karakuş, Ezgi Tan, Öykü Ürk, "ANTİBAKTERİYEL GÜNEŞ KORUMA ETKİLİ TOKSİK OLMAYAN NANO YAPILI KATKI MADDESİ", TÜRKİYE, Patent, 2014/07134, Haziran 2014.

226 REMOVAL OF ACID RED 336 DYE USING GREEN TEA ADSORBENT

Yrd. Doç. Dr. Selcan Karakuş Istanbul University Turkey Colored wastewater produced by the textile industry makes it one of the biggest polluters in the world. Many research studies have been conducted to determine the most efficient way to reduce this colored wastewater. The techniques looked at include: membrane filtration, biological processes, coagulation–flocculation, oxidation and adsorption. Among these, the most effective and economical technique found is the adsorption process.

In this study, the kinetic, isotherm and thermodynamic models of Acid Red 336 (textile dye) on modified green tea was investigated. The result of adsorption kinetic data showed that the adsorption equilibrium of acid red dye on green tea could be reached in 24 hours and was fitted well by the pseudo first order model. The different adsorption isotherm models (Langmuir, Freundlich and Temkin) were calculated. The adsorption process can be best simulated by the Langmuir monolayer isotherm equation (R2 >0.999). From the thermodynamic study, a negative ΔH0 (6800 Jmol−1) shows that the Acid Red 336 adsorption process is exothermic in nature at 298-318 Kelvin. Moreover, the positive ΔS0 explains that the adsorption system is random. The low Ea confirms the adsorption process is a physical process. The results of the adsorption experiments suggest that the adsorption of Acid Red 336 on green tea is an effective, economic and random process.

227 Poster Presentations

Yrd. Doç. Dr. Ömer Edip Kuzugüdenli Erciyes University Turkey

Ömer Edip Kuzugüdenli received a mining engineering degree at Istanbul Technical University Mining Faculty. Later on he gained his M.S. and doctoral degrees in applied chemistry at Columbia University’s School of Engineering and Applied Science, New York. Worked as a researcher and an engineer in the areas of mineral processing, chemistry and environmental protection for several years in the USA. Presently, he is a faculty member and is the head of the Division of Industrial Chemistry at the School of Sciences in Erciyes University, Kayseri. His areas of interest include industrial chemistry, surface and colloid chemistry, paint formulation, corrosion, environmental protection, mineral processing and ceramics.

228 THE POTENTIAL USE OF PUMICE POWDER AS PAINT FILLER

Yrd. Doç. Dr. Ömer Edip Kuzugüdenli Erciyes University Turkey Abstract Fillers are among the basic components of most paints. They consist of fine particles of natural minerals or synthetic solids, such as clay, calcite, quarts or ceramics. This presentation covers an experimental study to investigate the potential use of pumice powders as paint filler. Pumice is a silicate mineral of volcanic origin. Acidic types of pumice minerals are usually in the form of light colored, hard, brittle, and porous nature. The pumice samples used in this investigation were hand-picked from ore deposits in Kayseri Region. They were hand crushed, ground in an agate mortar, screened and each fraction was stored in glass bottles separately. Their suspension stabilities were studied as a function of time, size fractions and solvent type. It was observed that fine fractions of pumice produced highly stable suspensions especially in water. This can be explained with interfacial chemistry principles; the hydrophilic characteristic of the mineral surface created increased attraction between the particles and water. The sizes of particles were also found to be very important, i.e., finer particles produced more stable suspensions, as expected. Based on the experimental results, it can be concluded that pumice powders can offer advantageous applications as paint fillers. The ease of grinding, chemical stability, light color and low cost are examples to mentioned favorable features. The porous structure can also be considered another advantage for the particle can absorb the solvent and dissolved components to form more homogenous composition. The experimental results were presented and their significance in paint formulation was discussed.

Key Words: suspension stability, paint fillers, pumice.

229 34 EFFECT OF SOLVENT-FILLER SURFACE COMPATIBILITY ON PAINT DRYING SPEED

Yrd. Doç. Dr. Ömer Edip Kuzugüdenli Erciyes University Turkey Abstract The required drying period is an essential issue on most paint applications. It can be influenced by a number of factors varying from the properties of paint components to the environmental conditions. Sometimes limitations on the length of that period can be imposed by the application area or the type of the surface to be covered. One important factor related to paint components on the speed of drying is the interfacial relationship between the solvent and filler particles. In this investigation, several types of solids with different levels of hydrophobicity, particle shapes and size fractions were tested to determine their drying speeds. Pumice, calcite, sand and coal were the natural minerals used in the study. Two kinds of synthetic organic grains made of polystyrene foam and Teflon were also tested. In the experiments, equal volumes of test materials wetted with water were left to dry in open air under similar temperature and humidity conditions. The reductions in water contents for each type of material having selected size fractions were measured as a function of time. Base on the experimental results, it was found that the drying speeds were significantly influenced by surface hydrophobicity and particle size fractions: Any reductions in both hydrophobicity and size fractions increased the drying time. The findings were presented, and an attempt was made to correlate them with expected influences from other types of paint components were discussed.

Key Words: paint fillers, drying speed, water retention, surface hydrophobicity.

231 34 MEMBERS OF BOSAD BOSAD ÜYELERİ

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SG-Weber Yapı Kimyasalları Soditaş Solvent Sun Chemical Matbaa Şimşek Ambalaj San. Tic. A.Ş Thor-Specialties Srl Türkiye Üçel Boya Paz. San. Tic. San. Tic. A.Ş. Distribütörlüğü AŞ Mürekkepleri ve Gereçleri Ltd. Şti. San.Tic.AŞ 35