sessi n tuopi otetrapeD rapeD rapeD tnemt fo iBfotnemt iBfotnemt cudorpo stcudorpoiB cudorpo t t dna iBdnas iBdnas syso syso smetsysoiB smet smet - o t- o l t- o aA l t aA l aA DD DD DD 65 65 65 MMultifunctionalMultifunctionalultifunctional coatings coatings coatings for for for / / / 0202 0202 0202 as oFaninamsr N oFaninamsr N oFaninamsr N pplant-basedplant-basedlant-based textiles textiles textiles and and and ootherotherther cellulosic cellulosic cellulosic substrates substrate substratess NNinainaNina Forsman Forsman Forsman setartsbuscisolullecrehtodnaselitxetdesab-tnalprofsgnitaoclanoitcnufitluM setartsbuscisolullecrehtodnaselitxetdesab-tnalprofsgnitaoclanoitcnufitluM setartsbuscisolullecrehtodnaselitxetdesab-tnalprofsgnitaoclanoitcnufitluM BUSINESSBUSINESSBUSINESS + + + ECONOMECONOMECONOMYYY B I I I NBS NBS NBS 879 - 879 - 879 259 - - 259 - 06 259 - - 06 - 06 - 8283 - 8283 5 - 8283 5 ( p - 5 ( r p i n ( r p i t n r i t de n ) t de ) de ) ARTARTART + + + B I I I NBS NBS NBS 879 - 879 - 879 259 - - 259 - 06 259 - 06 - 06 - 9283 - 9283 2 - 9283 2 ( - 2 ( dp f ( dp ) f dp ) f ) DESIGNDESIGNDESIGN + + + S I I I NSS NSS NSS 9971 - 9971 - 9971 - 4394 4394 ( p 4394 ( r p i n ( r p i t n r i t de n ) t de ) de ) ARCHITECTURARCHITECTURARCHITECTUREEE S I I I NSS NSS NSS 9971 - 9971 - 9971 - 2494 2494 ( 2494 ( dp f ( dp ) f dp ) f ) SCIENCESCIENCESCIENCE + + + TECHNOLOGTECHNOLOGTECHNOLOGYYY tirvno laA laA laA ot isrevinUot yt isrevinUot yt isrevinU yt CROSSOVECROSSOVECROSSOVERRR nirenigE cieC loohcS oohcS ol oohcS ol l o f imehCf imehCf ac imehC ac ac l gnEl i gnEl i gnE een i r een i r een i gn r i gn gn DOCTORALDOCTORALDOCTORAL mtss BnstcdroiftetrapeD rapeD rapeD tnemt iBfotnemt fo iBfotnemt cudorpo t cudorpo t stcudorpoiB dna iBdnas iBdnas syso syso smet smet smetsysoiB +ficida*GMFTSH9 +ficida*GMFTSH9 +ficida*GMFTSH9 DOCTORALDOCTORALDOCTORAL DISSERTATIONSDISSERTATIONDISSERTATION SS www . www a . a www a l . a t a o l a t . o fi l t . o fi . fi DISSERTATIONDISSERTATIONDISSERTATIONSSS laA laA yt isrevinUot laA yt isrevinUot yt isrevinUot 0202 0202 0202 Aalto University publication series DOCTORAL DISSERTATIONS 56/2020 Multifunctional coatings for plant- based textiles and other cellulosic substrates Nina Forsman The public defense on 24th April 2020 at 12:00 will be organized via remote technology. Link: https://aalto.zoom.us/j/6093297778 Zoom Quick Guide: https://www.aalto.fi/en/services/zoom- quick-guide A doctoral dissertation completed for the degree of Doctor of Science (Technology) to be defended, with the permission of the Aalto University School of Chemical Engineering, at a public examination held at the lecture hall Ke2 of the school on the 24th of April 2020 at 12 noon. Aalto University School of Chemical Engineering Department of Bioproducts and Biosystems Bioproduct Chemistry Supervising professor Professor Monika Österberg, Aalto Univeristy, Finland Thesis advisor Dr. Vânia M. Moreira, University of Coimbra, Portugal and University of Helsinki, Finland Preliminary examiners Professor Martti Toivakka, Åbo Akademi, Finland Professor Vincent Nierstatz, University of Borås, Sweden Opponent Prodessor Aji Mathew, Stockholm University, Sweden Aalto University publication series DOCTORAL DISSERTATIONS 56/2020 © 2020 Nina Forsman ISBN 978-952-60-3828-5 (printed) ISBN 978-952-60-3829-2 (pdf) ISSN 1799-4934 (printed) ISSN 1799-4942 (pdf) http://urn.fi/URN:ISBN:978-952-60-3829-2 Images: Cover photo by Valeria Azovskaya Unigrafia Oy Helsinki 2020 WAN E S CO IC L D A B R E O L Finland N PrintedPrinted matter 1234 5678 4041-0619 Abstract Aalto University, P.O. Box 11000, FI-00076 Aalto www.aalto.fi Author Nina Forsman Name of the doctoral dissertation Multifunctional coatings for plant-based textiles and other cellulosic substrates Publisher School of Chemical Engineering Unit Department of Bioproducts and Biosystems Series Aalto University publication series DOCTORAL DISSERTATIONS 56/2020 Field of research Bioproduct Technology Manuscript submitted 10 January 2020 Date of the defence 24 April 2020 Permission for public defence granted (date) 18 March 2020 Language English Monograph Article dissertation Essay dissertation Abstract Many materials and surface treatments used today are based on unsustainable fossil-fuel derived synthetic polymers. Cellulose, a raw material from nature, has the potential to be used in many applications, but its widespread application is hampered by its inherent hydrophilic properties. In this work, wax particles are used together with polycations to render cellulosic surfaces hydrophobic yet breathable using the layer-by-layer method. Already two bilayers gave good hydrophobicity, which could be enhanced by optimizing the polycation adsorption, the curing temperature and surface roughness of the substrate. The adsorption and layer properties were studied by quartz crystal microbalance with dissipation and atomic force microscopy, the effect of curing temperature was evaluated by scanning electron microscopy, water contact angle and X-ray photoelectron spectroscopy, and the surface roughness was studied by white light interferometer. The coatings were studied on thin films, free-standing cellulose nanofibril films, textiles and all- cellulosic composites. Large-scale fabrics could also be coated. Cooling properties could be added by functional pigments, and dehydroabietanes were studied as contact-active, biocompatibile antimicrobial agents. The results showed that only a small amount of the dehydroabietanes needed to be on the surface to introduce good antimicrobial properties, and the hydrophobicity was increased at the same time. The various surface modifications could enhance the properties of cellulosic materials consequently increasing the use of natural and non-toxic materials in various applications. Keywords surface modification, cellulose, textile, hydrophobic, breathable, antimicrobial ISBN (printed) 978-952-60-3828-5 ISBN (pdf) 978-952-60-3829-2 ISSN (printed) 1799-4934 ISSN (pdf) 1799-4942 Location of publisher Helsinki Location of printing Helsinki Year 2020 Pages 234 urn http://urn.fi/URN:ISBN:978-952-60-3829-2 Sammandrag Aalto-universitetet, PB 11000, 00076 Aalto www.aalto.fi Författare Nina Forsman Doktorsavhandlingens titel Multifunktionella ytbeläggningar för växtbaserade textiler och andra cellulosiska substrat Utgivare Högskolan för kemiteknik Enhet Institutionen för bioproduckter och bioteknik Seriens namn Aalto University publication series DOCTORAL DISSERTATIONS 56/2020 Forskningsområde Bioproduktteknik Inlämningsdatum för manuskript 10.01.2020 Datum för disputation 24.04.2020 Beviljande av disputationstillstånd (datum) 18.03.2020 Språk Engelska Monografi Artikelavhandling Essäavhandling Sammandrag Många material och ytbehandlingar som används idag är baserade på ekologiskt ohållbara syntetiska polymerer från fossila bränslen. Cellulosa, en råvara från naturen, har potential att användas i många tillämpningar, men dess utbredda användning är hindrad av dess inneboende hydrofila egenskaper. I detta arbete används vaxpartiklar tillsammans med polykatjoner för att framställa hydrofoba men andande cellulosaytor genom att använda multiskiktmetoden. Redan två dubbellager gav bra hydrofobitet, som kunde förstärkas genom att optimera adsorbtionen av polykatjonen, härdningstemperaturen och substratets ytråhet. Adsorptionen och skikt- egenskaperna studerades med kvartskristall-mikrovåg med dissipation och atomkraftsmikroskopi, härdningstemperaturens effekt utvärderades med svepelektronmikroskop, vattenkontaktvinkel och röntgenfotoelektronspektroskopi, och ytråheten studerades med vit-ljusinterferometer. Ytbeläggningarna studerades på tunna filmer, fristående filmer av nanocellulosa, textiler och kompositer bestående av cellulosafibrer och upplöst cellulosa. Tyger i större skala kunde också ytbeläggas. Kylande egenskaper kunde inkluderas med funktionella pigment, och dehydroabietaner studerades som kontaktaktiva, biokompatibla antimikrobiella substanser. Resultaten visade att endast en liten mängd dehydroabietaner behövdes på ytan för att ge den goda antimikrobiella egenskaper, och samtidigt ökade hydrofobiteten. De olika ytmodifikationerna kan förbättra cellulosamaterials egenskaper och samtidigt öka använd-ningen av naturliga och ogiftiga material i olika tillämpningar. Nyckelord ytmodifiering, cellulose, textiler, hydrofob, andande, antimikrobiell ISBN (tryckt) 978-952-60-3828-5 ISBN (pdf) 978-952-60-3829-2 ISSN (tryckt) 1799-4934 ISSN (pdf) 1799-4942 Utgivningsort Helsingfors Tryckort Helsingfors År 2020 Sidantal 234 urn http://urn.fi/URN:ISBN:978-952-60-3829-2 Preface This work was carried out at the Department of Bioproducts and Biosystems at Aalto Univeristy. Part of the work for Publications IV and V was also carried out at University of Helsinki. The work with the pigments was carried out at Na- tional Institute of Chemistry in Ljubljana, Slovenia. The research was funded by Aalto Univeristy and Business Finland, and I am grateful for their support mak- ing this research possible. Traveling and getting international experience was made possible thanks to Walter Ahlström Foundation and Climate-KIC: Pio- neers into Practice, and I would like to thank them for the useful experiences they enabled. Monika, thank you so much! Thank you for accepting me as a student, helping (and pushing) me whenever I needed. Your door is always open and I have grown both as a scientist and as a person during this time. I enjoy having you as my supervisor and am proud to graduate in your group. Plus att få tala