Studies on Preparation of Cyclic Olefin Copolymer Blends and Characterization of Their Mechanical, Thermal and Barrier Properties

STUDIES ON PREPARATION OF CYCLIC OLEFIN COPOLYMER BLENDS AND CHARACTERIZATION OF THEIR MECHANICAL, THERMAL AND BARRIER PROPERTIES

Thesis submitted to Gujarat Technological University

For the Award of

Doctor of Philosophy

Chemical Engineering

SHAH HETALBEN CHANDRAVADAN

Enrollment No: 149997105009

Under Supervision of

Dr. Sudhir Kumar Nema

GUJARAT TECHNOLOGICAL UNIVERSITY AHMEDABAD

APRIL– 2021

STUDIES ON PREPARATION OF CYCLIC OLEFIN COPOLYMER BLENDS AND CHARACTERIZATION OF THEIR MECHANICAL, THERMAL AND BARRIER PROPERTIES

Thesis submitted to Gujarat Technological University

For the Award of

Doctor of Philosophy

Chemical Engineering

SHAH HETALBEN CHANDRAVADAN

Enrollment No: 149997105009

Under Supervision of

Dr. Sudhir Kumar Nema

GUJARAT TECHNOLOGICAL UNIVERSITY AHMEDABAD

APRIL– 2021

DECLARATION

I declare that the thesis entitled “Studies on Preparation of Cyclic Olefin Copolymer Blends and Characterization of Their Mechanical, Thermal and Barrier Properties” submitted by me for the degree of Doctor of Philosophy is the record of research work carried out by me during the period from May 2015 to September 2019 under the supervision of Dr. Sudhir Kumar Nema and this has not formed the basis for the award of any degree, diploma, associateship, fellowship, titles in this or any other University or other institution of higher learning.

I further declare that the material obtained from other sources has been duly acknowledged in the thesis. I shall be solely responsible for any plagiarism or other irregularities, if noticed in the thesis.

Signature of the Research Scholar: Date: 12/04/2021

Name of Research Scholar: Shah Hetalben Chandravadan

Place: Ahmedabad

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CERTIFICATE

I certify that the work incorporated in the thesis “Studies on Preparation of Cyclic Olefin Copolymer Blends and Characterization of Their Mechanical, Thermal and Barrier Properties” submitted by Ms. Shah Hetalben Chandravadan was carried out by the candidate under my supervision/guidance. To the best of my knowledge: (i) The candidate has not submitted the same research work to any other institution for any degree/diploma, Associateship, Fellowship or other similar titles (ii) The thesis submitted is a record of original research work done by the Research Scholar during the period of study under my supervision, and (iii) The thesis represents independent research work on the part of the Research Scholar.

Signature of Supervisor: Date: 12/04/2021

Name of Supervisor: Dr. Sudhir Kumar Nema

Place: Ahmedabad

Course-work Completion Certificate

This is to certify that Ms. Shah Hetalben Chandravadan enrolment no. 149997105009 is a PhD scholar enrolled for PhD program in the branch CHEMICAL ENGINEERING of Gujarat Technological University, Ahmedabad.

(Please tick the relevant option(s))

He/She has been exempted from the course-work (successfully completed during M.Phil Course)

He/She has been exempted from Research Methodology Course only (successfully completed during M.Phil Course)

√√√ He/She has successfully completed the PhD course work for the partial requirement for the award of PhD Degree. His/ Her performance in the course work is as follows-

Grade Obtained in Research Methodology Grade Obtained in Self Study Course (Core Subject)

(PH001) (PH002)

BB AB

(Dr. Sudhir Kumar Nema)

PhD Supervisor

Originality Report Certificate

It is certified that PhD Thesis titled “Studies on Preparation of Cyclic Olefin Copolymer Blends and Characterization of Their Mechanical, Thermal and Barrier Properties” by Ms. Shah Hetalben Chandravadan has been examined by us. We undertake the following: a. Thesis has significant new work / knowledge as compared already published or are under consideration to be published elsewhere. No sentence, equation, diagram, table, paragraph or section has been copied verbatim from previous work unless it is placed under quotation marks and duly referenced. b. The work presented is original and own work of the author (i.e. there is no plagiarism). No ideas, processes, results or words of others have been presented as Author own work. c. There is no fabrication of data or results which have been compiled / analyzed.

d. There is no falsification by manipulating research materials, equipment or processes, or changing or omitting data or results such that the research is not accurately represented in the research record. e. The thesis has been checked using URKUND (copy of originality report attached) and found within limits as per GTU Plagiarism Policy and instructions issued from time to time (i.e. Permitted similarity index <10%).

Signature of the Research Scholar: Date: 12/04/2021

Name of Research Scholar: Shah Hetalben Chandravadan

Place: Ahmedabad

Signature of Supervisor: Date: 12/04/2021

Name of Supervisor: Dr. Sudhir Kumar Nema

Place: Ahmedabad

Document Information

Analyzed document Thesis_070421_Check.pdf (D100806156)

Submitted 4/6/2021 9:37:00 PM Submitted by Hetalben Chandravadan Shah

Submitter email [email protected]

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Sources included in the report

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URL: https://www.sciencedirect.com/science/article/pii/S0014305718309819 1 Fetched: 4/6/2021 9:39:00 PM

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URL: https://www.sciencedirect.com/topics/materials-science/polymer-blend 1 Fetched: 4/6/2021 9:39:00 PM

URL: https://juniperpublishers.com/rapsci/RAPSCI.MS.ID.555699.php 1 Fetched: 4/6/2021 9:39:00 PM

URL: https://www.researchgate.net/publication/223032106_Oriented_structure_and_anisotro ... 1 Fetched: 4/26/2020 1:31:32 AM

URL: https://www.researchgate.net/publication/230691119_Thermal_Thermo-Mechanical_and_D ... 2 Fetched: 12/16/2019 5:56:32 PM

URL: https://www.researchgate.net/publication/264261865_Phase_morphology_of_PPCOC_blends 2 Fetched: 12/16/2019 5:57:00 PM

URL: https://www.researchgate.net/publication/324507130_Effect_of_Cyclo-Olefin_Copolyme ... 2 Fetched: 4/6/2021 9:39:00 PM

URL: https://www researchgate net/publication/230462603 High-density polyethylenecycloo 1 Fetched: 12/18/2019 3:26:29 AM

URL: https://www.polyplastics.com/en/product/lines/film/packaging_e.pdf 2 Fetched: 4/6/2020 5:49:28 PM

URL: https://topas.com/sites/default/files/files/Packaging_E_2014-06.pdf 2 Fetched: 9/11/2020 6:46:52 PM

URL: https://core.ac.uk/download/pdf/153515856.pdf 1 Fetched: 4/6/2021 9:39:00 PM

URL: https://1library.net/document/y9d643wq-copolymer-loading-polyethylene-characteriza ... 2 Fetched: 9/11/2020 5:29:09 PM

URL: https://www.researchgate.net/publication/327120715_Effect_of_LLDPE_on_Aging_Resist ... 1 Fetched: 4/6/2021 9:39:00 PM

URL: https://topas.com/tech-center/performance-data/modulus-blends 1 Fetched: 4/6/2021 9:39:00 PM

PhD THESIS Non-Exclusive License to GUJARAT TECHNOLOGICAL UNIVERSITY

In consideration of being a PhD Research Scholar at GTU and in the interests of the facilitation of research at GTU and elsewhere, I, Shah Hetalben Chandravadan having

Enrollment No. 149997105009 hereby grant a non-exclusive, royalty free and perpetual license to GTU on the following terms:

a) GTU is permitted to archive, reproduce and distribute my thesis, in whole or in part,

and/or my abstract, in whole or in part ( referred to collectively as the “Work”)

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mentioned in paragraph (a); c) GTU is authorized to submit the Work at any National / International Library, under

the authority of their “Thesis Non-Exclusive License”; d) The Universal Copyright Notice (©) shall appear on all copies made under the

authority of this license; e) I undertake to submit my thesis, through my University, to any Library and Archives.

Any abstract submitted with the thesis will be considered to form part of the thesis. f) I represent that my thesis is my original work, does not infringe any rights of others,

including privacy rights, and that I have the right to make the grant conferred by this

non-exclusive license. g) If third party copyrighted material was included in my thesis for which, under the terms

of the Copyright Act, written permission from the copyright owners is required, I have

vii

obtained such permission from the copyright owners to do the acts mentioned in

paragraph (a) above for the full term of copyright protection. h) I retain copyright ownership and moral rights in my thesis, and may deal with the

University in this non-exclusive license. i) I further promise to inform any person to whom I may hereafter assign or license my

exclusive license. j) I am aware of and agree to accept the conditions and regulations of PhD including all

policy matters related to authorship and plagiarism.

Signature of the Research Scholar:

Name of Research Scholar: Shah Hetalben Chandravadan

Date: 12/04/2021 Place: Ahmedabad

Signature of Supervisor:

Name of Supervisor: Dr. Sudhir Kumar Nema

Date: 12/04/2021 Place: Ahmedabad

Seal:

viii

Thesis Approval Form

The viva-voce of the PhD Thesis submitted by Ms. Shah Hetalben Chandravadan (Enrollment N o .149997105009) entitled “Studies on Preparation of Cyclic Olefin Copolymer Blends and Characterization of Their Mechanical, Thermal and Barrier Properties” was conducted on Monday, 12 th April 2021 at Gujarat Technological University.

(Please tick any one of the following option)

The performance of the candidate was satisfactory. We recommend that he/she be awarded the PhD degree.

Any further modifications in research work recommended by the panel after 3 months from the date of first viva-voce upon request of the Supervisor or request of Independent Research Scholar after which viva-voce can be re-conducted by the same panel again.

(Briefly specify the modifications suggested by the panel)

The performance of the candidate was unsatisfactory. We recommend that he/she should not be awarded the PhD degree.

(The panel must give justifications for rejecting the research work)

Dr. Sudhir Kumar Nema Dr. D.D.Kale Name and Signature of Supervisor with Seal 1) (External Examiner 1) Name and Signature

Dr. Nishant Pandya 2) (External Examiner 2) Name and Signature

Abstract

In this study, Linear low density polyethylene (LLDPE)/ cyclic olefin copolymer (COC) were melt blended for different compositions (95/05, 90/10, 85/15, 80/20) by using Haake co- rotating twin screw extruder equipped with a blown film unit to make films and sheets using compression molding press. Effects of COC loading in LLDPE on mechanical properties such as tensile strength, elongation, tensile modulus and tear strength in both machine as well as transverse direction were investigated. Thermal properties such as Dynamic Mechanical Analysis (DMA) and Differential Scanning Calorimeter (DSC) were analyzed. Oxygen Transmission Rate (OTR) and Water Vapor Transmission Rate (WVTR) were carried out to study barrier properties of film. Melt Flow Index (MFI) analysis, X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) were analyzed. There was remarkable increase in Tensile strength and modulus was observed. When only 10% COC is added, the modulus increases threefold, and when 20% COC is added, the modulus increases fivefold over that of LLDPE. The addition of stiffened COC accounted for the reduction of elongation in the LLDPE/COC blends film. The effect of COC loading on melting temperature and degree of crystallinity was investigated using a differential scanning calorimetric analysis (DSC) on polymers and their blends. The presence of COC had no effect on the melting (T m) or crystalline temperature (T c) of LLDPE, according to the study. Dynamic mechanical study showed increase in storage modulus for all LLDPE/COC blend ratio. The increase in storage modulus is due to presence of stiffened COC in the LLDPE/COC blends. Tan δ value increases due to the increase in the amorphous content of the system with an increase in the COC content. The reduction in oxygen and water vapor transmission rates was observed because addition of high dense COC domains. Bulky norbornene units of COC forces the gas molecules to follow the longer path. Plasma treatment using Hexamethyl Disiloxane (HMDSO) was carried out to further study the oxygen and water vapor transmission rates of 5 and 10 wt % COC. SiO x was expected to give partially cross linked coating also known as protective barrier coating, which could help in improving the barrier properties. Melt flow index analysis was performed to determine the melt blend's ease of flow. The MFI values of the LLDPE/COC blend increased as the temperature rose, which was due to a decrease in viscosity.

A relatively good adhesion between the COC and the LLDPE matrix was observed by scanning electron microscopy and samples do not show co-continuous or matrix-droplet type morphology , which can be correlated with increase in mechanical and barrier properties. FTIR was used to determine and compare the characteristic absorption peaks of LLDPE, COC, and LLDPE/COC blends. X-ray diffraction was carried out to study the effect of blend composition on crystallinity. There are slight changes observed in the crystalline structure of LLDPE after addition of COC, However, significant changes are not observed. Findings of this work may provide useful insights to prepare better quality blends using commodity polyolefin i.e., LLDPE and engineering polyolefin i.e., COC for various packaging applications.

Acknowledgement

“It gives me immense pleasure to remember the ocean of guidance, support and encouragement from Supreme God.”

I am deeply thankful to my supervisor Dr. Sudhir Kumar Nema , (Scientific Officer –H, FCIPT (IPR)-Gandhinagar) for his unconditional support during each and every stage across the tenure of this research work. The research would not have come to this shape without his deep involvement. I thank him for his critical observations about my capabilities and limitations, which brought a significant change in my development during this research. I am very much thankful to my DPC members, Dr. R. Sengupta (Professor Chemical engineering department) and Dr. Sandeep Rai (GRP limited-Ankleshwar) for their guidance and focused reviews across the tenure of the research, which helped me understand my work in great depths.

I am truly blessed to have encouragement and support from Mr. Pradip Mukherji. I am extremely thankful to Prof. R N Desai , Prof. N.M Patel , Prof. B. G. Basantani , Prof. K. P. Jain , Prof. Stuti Shah , Prof. S. R. Shah and Ms. Jagravi, who stood by me wherever I needed their support. I am very much thankful to all LDCE staff for their motivation and support at all stages of this work.

I also extend my heartful thanks towards Mr.Timothy Kneale , (President, TOPAS Advance Polymers, USA) for his help in supply of COC material free of cost for research purpose and Dr. Pradeep Upadhyay (Principal Director & Head-CIPET Ahmedabad) for his support. I greatly appreciate and acknowledge the support received from institutions and laboratories.

I am also thankful to FCIPT, Gandhinagar, especially to Ms.Purvi Dave for their constant help & all the related facilities. I am thankful to Mr. Purvish Patel (Packaging Solutions), Mr. Parag Parikh and Mr. Harshad (Universal Masterbatch LLP), Mr. Manish Bhai (Deepak Polyplast) for their guidance and ever readiness to help me in this research. I am grateful to the individuals, who contributed directly or indirectly to this report by providing me with the necessary information and valuable suggestions. xii

Finally, I acknowledge the people who mean a lot to me, my parents Mr. Chandravadabhai & Ms. Hansaben and my parents in laws , Mr.Dalpatbhai and Ms.Pinakini , who always supported me with love and their support to manage life along with this research. Besides all this, I am highly thankful to my life partner Mr. Nirav for his unconditional support to overcome difficult stages during the tenure of this research and showing confidence in me and giving me freedom to choose what is best for me, without his support, care, flawless love, patience, and sacrifice, it would not possible to achieve this goal. I love you all for giving shape my life & study. I would never be able to repay the love and warmth showered upon by my loved ones. I will always remain obliged to the wonderful group of friends who always stood by me whenever I needed them.

Hetal Shah

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Dedicated to………. Supreme God Pradip Mukherji Sir and My beloved husband, Nirav

Table of Content

Declaration ………………………………………………………………………………... iii Certificate …………………………………………………………………………………. iv Course-work Completion Certificate ……………………………………………………... v Originality Report Certificate …………………………………………………………….. vi

PhD Thesis Non-Exclusive License ………………………………………………………. vii Thesis Approval Form …………………………………………………………………….. ix Abstract …………………………………………………………………………………… x Acknowledgement ………………………………………………………………………… xii Table of Content ...... xiv

List of Abbreviation ...... xviii

List of Symbols ...... xxi

List of Figures ...... xxiii

List of Tables ...... xxviii

CHAPTER 1 ...... 1

Introduction ...... 1

Polymer blends...... 1

1.1.1 Background ...... 1

1.1.2 Classification of polymer blends ...... 2

Thermodynamic approach to the miscibility of polymer blends ...... 3

Preparation and manufacture of polymer blends ...... 5

Different techniques used in characterization of blends ...... 8

Properties of polymeric blends ...... 16

xiv

Sector wise applications of polymer blends and alloys ...... 17

Polymer blending for packaging Applications ...... 18

Commonly used plastics in flexible packaging ...... 20

Processes for film converting for flexible packaging ...... 24

1.9.1 Comparison of Blown and Cast Film Processes ...... 26

Typical Properties for Flexible Packaging Films...... 27

Importance of various properties on polymer packaging ...... 29

Techniques used in the present study...... 35

Thesis organization ...... 36

CHAPTER 2 ...... 38

Literature Review...... 38

Polymer - Polymer blends ...... 38

Plasma Enhanced chemical vapor deposition (PECVD): SiO x Coating ...... 55

Definition of the problem...... 59

Identified gaps in the literature ...... 60

Objectives and Scope of work ...... 61

CHAPTER 3 ...... 63

Materials and Methodology ...... 63

Materials ...... 63

3.1.1 Cyclic Olefin Copolymer (COC) ...... 63

3.1.2 Linear low density polyethylene (LLDPE) ...... 63

Preparation of blends ...... 64

Sample Preparation ...... 66

3.3.1 Compression molding ...... 66

3.3.2 Blown film ...... 66

3.3.3 Experimental Setup & Plasma Production ...... 67

Sample characterization ...... 69

3.4.1 Melt flow Index (MFI) ...... 69

3.4.2 Differential scanning calorimetry (DSC) ...... 70

3.4.3 Dynamic mechanical analysis ...... 72

3.4.4 Mechanical properties ...... 73

3.4.5 FTIR spectroscopy ...... 74

3.4.6 X-ray diffraction ...... 75

3.4.7 Morphological analysis ...... 77

3.4.8 Barrier properties ...... 77

CHAPTER 4 ...... 81

Blends: Processing and Thermal properties ...... 81

Introduction ...... 81

Compounding of polymer blends...... 82

Melt flow analysis ...... 83

Blown Film Extrusion ...... 86

Study of Thermal Properties ...... 89

4.5.1 Differential Scanning Calorimetric study ...... 89

4.5.2 Dynamic Mechanical Analysis ...... 94

CHAPTER 5 ...... 105

5 Blends: Mechanical, Morphological and Barrier Properties ...... 105

Introduction ...... 105

Study of Mechanical Properties ...... 106

xvi

FTIR spectroscopic study ...... 110

X-ray Diffraction study ...... 116

Study of Barrier Properties ...... 119

5.5.1 Plasma enhanced PECVD for SiO x coating ...... 124

5.5.2 Experimental demonstration to study barrier properties of blend films ...... 127

Outcomes with respect to objectives ...... 132

CHAPTER 6 ...... 135

Conclusion ...... 135

Conclusion and Future Scope of Work ...... 135

References ...... 139

List of Publications ...... 148

Appendix A ...... 149

Appendix B ...... 151

Appendix C ...... 154

Appendix D ...... 159

Appendix E ...... 183

Appendix F...... 184

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List of Abbreviation

AFM Atomic Force Microscopy AlOx Aluminum Oxide ANS Acrylonitrile Styrene ASTM American Society For Testing and Materials BR Blow Ratio BUR Blown-up ratio COC Cyclic Olefin Copolymer CPE Chlorinated Polyethylene CTFE Chlorotrifluoroethylene DSC Differential Scanning Calorimetry DTA Differential Thermal Analysis EAA Ethylene Acrylic Acid ECO Ethylene/Carbon Monoxide EMA Ethylene Methacrylate EOC Ethylene-Octene Copolymer EPDM Ethylene-Propylene-Diene Monomer EVA Ethylene Vinyl Acetate EVOH Ethylene Vinyl Alcohol Copolymers FRR Flow Rate Ratio FTIR Fourier Transform Infrared Spectroscopy FWHM Full Width at Half Maximum HDPE High Density Polyethylene HMDSO Hexamethyldisiloxane IPN Interpenetrating Polymer Networks IR Infrared LCB Long Chain Branching LCST Lower Critical Solution Temperature LDPE Low Density Polyethylene LFW Layflat Width

xviii

LLDPE Linear Low Density Polyethylene MAH Maleic Anhydride MAXS Medium-Angle X-Ray Scattering MD Machine Direction MFI Melt Flow Index MVTR Moisture Vapor Transmission Rate MW Molecular Weight MWD Molecular Weight Distribution NMR Nuclear Magnetic Resonance OPS Oriented Polystyrene OTR Oxygen Transmission Rate PA Polyamide PAB Polymer Alloy and Blends PAN Polyacrylonitrile PA-PVD Plasma Assisted Physical Vapour Deposition PE Polyethylene PECVD Plasma-Enhanced Chemical Vapor Deposition PEN Polyethylene Naphthalate PET Poly Ethylene Terephthalate PEVA Polyethylenevinyl Acetate PGA Polyglycolic Acid PHA Polyhydroxyalkanoates PLA Polylactic Acid PMMA Polymethylmethacrylate POE Polyolefin Elastomer PP Polypropylene PS Polystyrene PVC Polyvinyl Chloride PVDC Polyvinylidene Chloride PVOH Polyvinyl Alcohol RH Relative Humidity SAXS Small-Angle X-Ray Scattering SEM Scanning Electron Microscopy

SiO x Silicone Oxide

xix

TD Transverse Direction TEM Transmission Electron Microscopy TGA Thermo Gravimetric Analysis TMA Thermo Mechanical Analysis UCST Upper Critical Solution Temperature UHMWPE Ultra High Molecular Weight High Density Polyethylene VLDPE Very Low Density Polyethylene VTMOS Vinyl Trimethoxy Silane WAXD Wide-Angle X-Ray Diffraction WAXS Wide-Angle X-Ray Scattering WVTR Water Vapor Transmission Rate XRD X-Ray Diffraction

List of Symbols

∆Gm Gibb’s free energy

∆Hm enthalpy of mixing

∆Sm entropy of mixing ϕ composition T temperature p pressure

Tg glass transition temperature

Tm melting Temperature

Tc crystalline Temperature λ wavelength θ angle d distance n order of diffraction P properties I interaction term

Xv volume fraction

Xm mass fraction ρ density

ρa density of amorphous component

ρc density of crystalline component

Aa areas under the curve corresponding to amorphous contribution

Ac areas under the curve corresponding to crystalline contribution

Do die diameter

Df film diameter H film thickness

Xc crystallinity

Hº f reference value of the fully crystalline polymer

xxi

wss weight fraction E* complex modulus E' storage modulus E'' loss modulus Tan δ loss tangent or loss factor ε strain ∆L change in length

L0 initial length L length of specimen during the tensile test m mass t time V volume R gas constant

xxii

List of Figures

Figure 1.1 Classification of Polymer blends ...... 2

Figure 1.2 Phase diagram showing the UCST and LCST for polymer...... 4

Figure 1.3 Idealized DMA scan ...... 11

Figure 1.4 Schematic of experimental X-ray set-up. (a) In reflection-mode for XRD (b) In transmission-mode for WAXS (or XRD) and SAXS...... 12

Figure 1.5 Diffraction of X-rays from planes of lattice separated by distance d...... 13

Figure 1.6 Mechanism of Fourier transform infrared spectroscopy ...... 14

Figure 1.7 Property-Composition dependence for a miscible polyblend...... 16

Figure 1.8 Worldwide distribution of different plastics used in packaging...... 18

Figure 1.9 India LLDPE market share...... 18

Figure 1.10 Chemical structure of polyethylene...... 21

Figure 1.11 Common Polymers for Packaging Applications...... 21

Figure 1.12 Blown film process...... 25

Figure 1.13 Cast film process...... 26

Figure 1.14 Values of Oxygen Transmission Rate (OTR) of conventional packaging materials...... 32

Figure 1.15 Values of Water Vapor Transmission Rate (WVTR) of conventional ppackaging materials...... 33

Figure 1.16 Applications of polyethylene films...... 34

Figure 2.1 Structure of Norbornene...... 40

Figure 2.2 Synthesis steps of the COC copolymer ...... 40

Figure 2.3 COC market -2018 ...... 41

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Figure 2.4 Molecular structures, properties and general applications of three broad categories of PE resins...... 43

Figure 2.5 Tan δ versus temperature for LDPE/EVA & HDPE/EVA copolymer blends: (a) full temperature range; (b) magnified temperature range...... 45

Figure 2.6 (a) Tensile strength and modulus of PP, COC and PP/COC blends (b) Elongation of PP, COC and PP/COC blends ...... 46

Figure 2.7 (a) Effect of temperature on the storage modulus of PP, COC and PP/COC blends at a frequency of 1 Hz (b) Effect of temperature on the Tan δ of PP, COC and PP/COC blends at a frequency of 1 Hz ...... 47

Figure 2.8 IR spectra of PP/COC blends ...... 48

Figure 2.9 WAXS pattern of the PP, COC and PP/COC blends ...... 48

Figure 2.10 Effect of the composition of HDPE/COC blends on the temperature dependence of the storage modulus and loss modulus. HDPE/COC: 100/0 (full line); 75/25 (dash-dot- dot line); 50/50 (dashed line); 25/75 (dash-and-dot line); 0/100 (dotted line)...... 49

Figure 2.11 SEM micrographs of PE matrix/COC 80/20 pellet (a) and film (b)...... 50

Figure 2.12 DSC results of LLDPE, COC and their blend...... 51

Figure 2.13 X-ray diffraction patterns for some composites samples and neat polymers. .. 52

Figure 2.14 Mechanical properties of COC/EVA blends...... 53

Figure 2.15 Temperature dependence of elastic modulus of COC/POE blends...... 54

Figure 2.16 Temperature dependence of loss modulus of COC/POE blends...... 54

Figure 2.17 Oxygen concentration vs. Oxygen Transmission Rate ...... 57

Figure 2.18 Oxygen transmission rate of untreated PE, single-layer SiO x deposited PE, double-layer SiO x deposited PE and conventional 5-layer (different polymers) structure. . 58

Figure 2.19 Types of SiO x film growth mechanism from HMDSO monomer...... 58

Figure 2.20 Oxygen permeation values detected for PEVA foil with barrier layers of PVDC, plasma polymerized HMDSO and parylene...... 59

Figure 2.21 Effect of oxygen and moisture on sample ...... 60

Figure 3.1 Structural formula of COC ...... 63

Figure 3.2 Representation of LLDPE with short chain branching ...... 64

xxiv

Figure 3.3 Structural formula of LLDPE ...... 64

Figure 3.4 Preparation of blends using Haake twin screw extruder...... 65

Figure 3.5 Compression molded sheets of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 , and L0C100 blends...... 66

Figure 3.6 Preparation of Blown film using Haake tubular blown film extrusion...... 67

Figure 3.7 Experimental schematic diagram for PECVD...... 68

Figure 3.8 PEVCD System ...... 68

Figure 3.9 (a) Schematic representation Melt flow index tester (b) Melt flow index tester...... 69

Figure 3.10 DSC Instrument working Principle...... 70

Figure 3.11 Thermal transitions in (A) amorphous and (B) semicrystalline polymers...... 71

Figure 3.12 Differential scanning calorimetry analyzer...... 72

Figure 3.13 Dynamic mechanical analyzer...... 73

Figure 3.14 Trouser tear test sample configuration...... 74

Figure 3.15 FTIR spectrometer ...... 75

Figure 3.16 Schematic representation of the Bragg equation...... 76

Figure 3.17 X-ray diffractometer (left) and sample holder (right)...... 76

Figure 3.18 SEM analyzer (left) and coated sample (right)...... 77

Figure 3.19 Mechanism of working of WVTR equipment...... 78

Figure 3.20 WVTR Analyzer...... 78

Figure 3.21 (a) OTR testing setup (b) Gas permeation analyzer (c) Sample Preparation. 79

Figure 4.1 Granules of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 ...... 82

Figure 4.2 Graph showing MFI of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 84

Figure 4.3 Blown film samples of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 87

Figure 4.4 Blown film line ...... 88

Figure 4.5 DSC thermograms of L100 C0...... 90

xxv

Figure 4.6 DSC thermograms of L0C100 ...... 90

Figure 4.7 DSC thermograms of L95 C05 ...... 91

Figure 4.8 DSC thermograms of L90 C10 ...... 92

Figure 4.9 DSC thermograms of L85 C15 ...... 92

Figure 4.10 DSC thermograms of L80 C20 ...... 93

Figure 4.11 Effect of temperature on E' , E'' and Tan δ of L 100 C0...... 96

Figure 4.12 Effect of temperature on E' , E'' and Tan δ of L 0C100 ...... 96

Figure 4.13 Effect of temperature on E' , E'' and Tan δ of L 95 C05 ...... 97

Figure 4.14 Effect of temperature on E' , E'' and Tan δ of L 90 C10 ...... 97

Figure 4.15 Effect of temperature on E' , E'' and Tan δ of L 85 C15 ...... 98

Figure 4.16 Effect of temperature on E' , E'' and Tan δ of L 80 C20 ...... 98

Figure 4.17 Storage modulus ( E' ) of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 99

Figure 4.18 Enlarged graph of Storage modulus ( E' ) of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 100

Figure 4.19 Loss modulus (E '') of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 101

Figure 4.20 Enlarged graph of Loss modulus (E '') of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 101

Figure 4.21 Tan δ of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 102

Figure 4.22 Enlarged graph of Tan δ of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 102

Figure 5.1 Tensile strength of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 ...... 106

Figure 5.2 Tensile modulus of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 ...... 107

Figure 5.3 % Elongation of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 ...... 108

Figure 5.4 Tear strength of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 ...... 109

Figure 5.5 IR spectrum of L 100 C0...... 110

Figure 5.6 IR spectrum of L 0C100...... 112

xxvi

Figure 5.7 IR spectrum of L 95 C05...... 113

Figure 5.8 IR spectrum of L 90 C10...... 113

Figure 5.9 IR spectrum of L 85 C15...... 114

Figure 5.10 IR spectrum of L 80 C20...... 114

Figure 5.11 Combined IR spectrum of L95 C05, L90 C10, L85 C15 and L 80 C20...... 115

Figure 5.12 X ray diffraction graph of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 116

Figure 5.13 Merged X ray diffraction graph of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 ...... 117

Figure 5.14 Schematic description of the transport of gas molecules through a polymer film...... 120

Figure 5.15 Illustration of the ‘‘tortuous pathway’’ ...... 121

Figure 5.16 SEM micrographs of granules of (a) L100 C0 (b) L 95 C05 (c) L 90 C10 (d) L85 C15 (e) L80 C20 and (f) L0C100 ...... 122

Figure 5.17 SEM micrographs of films of (a) L100 C0 (b) L 95 C05 (c) L 90 C10 (d) L85 C15 and (e) L80 C20...... 123

Figure 5.18 SiO x film coating on film surface using HMDSO ...... 124

Figure 5.19 SEM micrograph of (a) L 95 C05 (60±5 µm film) (b) L 90 C10 (60±5 µm film) (c) SiO x coated L 95 C05 (40±3 µm film) (d) SiO x coated L 90 C10 (40±3 µm film) (e) SiO x coated L 95 C05 (60±5 µm film) (f) SiO x coated L 90 C10 (60±5 µm film)...... 126

Figure 5.20 Oxidation process in banana without film, with LLDPE and all compositions of LLDPE/COC film (A-without film; B- L100 C0; C- L95 C05 ;D - L90 C10 ; E- L85 C15 ; F- L80 C20 ) ...... 130

th Figure 5.21 Condition on 6 day (a) Banana without film (b) Banana packed in L100 C0 film and (c) Banana packed in L 90 C10 film ...... 131

xxvii

List of Tables

Table 1.1 PAB compounders ...... 6

Table 1.2 Advantages and disadvantages of some PAB mixers ...... 6

Table 1.3 Techniques of analysis of polymer blends...... 15

Table 1.4 Comparison of Blown and Cast Film ...... 27

Table 1.5 Typical Properties for Flexible Packaging Films...... 28

Table 1.6 Common resins used in flexible packaging and their functions...... 29

Table 1.7 Effect of increase in crystallinity on different polymer properties...... 31

Table 1.8 Classification of the current major gas barrier technologies ...... 34

Table 2.1 CVD,PVD and PECVD advantages and disadvantages...... 56

Table 3.1 Weight percentage and total weight of LLDPE and COC in the blends...... 65

Table 3.2 Melt Flow Index (MFI) ranges of typical PE grades by process ...... 70

Table 4.1 MFI and FRR of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 85

Table 4.2 Blown film parameters ...... 88

Table 4.3 Results obtained from the DSC test of L100 C0, L95 C05, L90 C10, L85 C15 and L80 C20...... 94

Table 4.4 Storage modulus (E') at different temperatures and Tan δ and T g of the L 100 C0,

L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 ...... 103

Table 5.1 Main absorptions of LLDPE in the IR region and their assignment...... 111

Table 5.2 Main absorptions of COC in the IR region and their assignment...... 112

Table 5. 3 Main absorptions of L95 C05, L90 C10, L85 C15 and L 80 C20 in the IR region and their assignment ...... 115

xxviii

Table 5.4 FWHM and Crystallites size of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 obtained from XRD data...... 118

Table 5.5 OTR and WVTR of L 100 C0, L95 C05, L90 C10, L85 C15 and L 80 C20...... 121

Table 5.6 Comparison of OTR and WVTR of SiO x coated and uncoated L95 C05 and L 90 C10...... 125

xxix

Polymer blends

CHAPTER 1

Introduction

Polymer blends

1.1.1 Background A polymer blend is a mixture of two or more polymers that have been blended together to create a new material with distinct physical properties. Polymer blending is a quite simple and cost effective technique and has garnered increasing interest for developing polymeric materials that can be useful for commercial applications. Appropriate selection of the constituent polymers can modify the properties of the blends for their end use [1]. Blends provide the necessary flexibility to tailor a specific material for a given application, and in some cases, they provide improved properties as compared to their substituent materials. New polymer development and commercialization takes many years and is also highly expensive. On the other hand, polymer blending process is very cheap to operate and it is often likely to reduce the time for incorporating commercialization [2].

A large number of commercial polymer blends have now become available, and persistent effort to create new materials with improved chemical or mechanical performance is being projected relentlessly [3]. The modification in the performance of polymer systems has been the subject of interest in many newer studies. Blending also produces materials with exceptional combinations of mechanical, chemical, barrier, thermal, and morphological properties [4, 5]. Blending offers an easy and fairly economical method to develop polymeric materials with desirable properties. Blending of polymers also provides an easy and useful means of reuse and recycling of polymer wastes. The benefits of polymer blending can be summarized as follows:

Introduction

• They offer the simplest way for combining exceptional properties of different existing polymers. • They are a cost-effective technique for new materials and products to fill the economic and performance gap. • They generate materials and products with tailor-made properties. • They improve processing ability. • They reduce time for successful development of new polymer blends. • Ready availability of equipment as already existing ones can be used.

1.1.2 Classification of polymer blends Polymer blends can be classified into different classes on the basis of aspects such as: the number of homopolymers used for blending, miscibility of the constituent polymers, biodegradability, nature of constituent polymers, and so on. Fig.1.1 [6] represents a schematic classification of the polymer blends.

Figure 1.1 Classification of Polymer blends

Thermodynamic approach to the miscibility of polymer blends

According to miscibility polymer blends are classified by two types miscible (homogeneous) or immiscible (heterogeneous) blends. Miscible blends are mostly visibly clear and to the segmental level they are homogeneous. By changing the mixture composition, temperature or pressure of the polymer blend, single-phase blends also undergo phase separation. Miscibility and phase behavior of polymer blends have been studied by various researchers [7][8] since, the properties of a polymer blend depends on the final morphology. In general, polymer blends can be immiscible, partially miscible or completely miscible depending on the value of ∆Gm i.e., Gibb’s free energy [9]. It is given by

∆Gm = ∆Hm - T∆Sm (1.1)

∆Hm, and ∆Sm are the enthalpy and entropy of mixing at temperature T, respectively.

For a stable one-phase system, the following two conditions must be satisfied:

∆Gm <0; (1.2) 2 2 (∂ (∆Gm)/ ∂ϕi )T,p > 0 (1.3)

Where ϕ is the composition, it is taken as the volume fraction of one of the components, whereas, T is temperature and p is pressure.

∆Sm is a quantity of disorder or randomness, it is favorable for mixing or miscibility mainly for low molecular- weight solutions and is always positive. In case of polymers, ∆Hm is also a deciding factor for miscibility because polymer solutions have monomers with a high molecular weight. ∆Hm is the heat that is either consumed or generated during mixing i.e, endothermic or exothermic respectively. If the mixing is exothermic then the system shows miscibility due to strong specific interaction between the blend components. Hydrogen bonding, dipole–dipole, and ionic interactions are the most common- interaction observed in polymer blends. There are several methods that can be used to recognize the specific

Introduction

interaction in polymers, such as, nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, small-angle neutron scattering etc.

In Phase diagram, upper critical solution temperature (UCST), lower critical solution temperature (LCST), combined LCST and UCST, or closed-loop-shaped are observed experimentally in polymer blends system as shown in Fig. 1.2. LCST & UCST are the most commonly observed phase diagrams which represent phase separation of a miscible blend during heating and phase separation of a miscible blend during cooling respectively [10],[11]. Phase separation can be followed by a number of experimental techniques that include light scattering, neutron scattering, ellipsometry, and rheology. The generated morphology can be characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), infrared, near-infrared and Raman spectroscopy.

Figure 1.2 Phase diagram showing the UCST and LCST for polymer.

Preparation and manufacture of polymer blends

Polyblends can be of two types based on method of preparation: A) Physical blends and B) Chemical blends. A) Physical Blends This is the most significant class of polymer blends having no primary bonding involving polymer components. These blends are prepared by mechanically mixing of the component polymers. On the basis of nature of mixing, polyblends may be further divided as: i) Melt Blending Melt blending is the simplest method of mixing the polymers mechanically using continuous or batch mixers for the preparation of blend. In melt mixing, two or more polymers plus any desired additive or filler are metered by weight ratio into a shear intensive extruder. The constituents are mixed at elevated temperatures (i.e., above the melting points of the polymer constituents) by extruder screw which exerts mechanical shearing forces and ensures even distribution and thorough blending of alloy and blend elements [8]. In Table 1.1 a list of Polymer alloys and blends (PAB) compounders is given and the advantages and disadvantages of the typical machines are listed in Table 1.2 [12].

The entire process of compounding comprises of four stages: i. Preparation of ingredients (drying, sizing, heating etc.), ii. Premixing (dry blending, breakage of agglomerates, fluxing etc.), iii. Melt mixing with dispersive and distributive field, iv. Chopping e.g. granulating, pelletizing or dicing

Introduction

Table 1.1 PAB compounders No Machine Function

1. Continuous mixers Twin screw extruder Primary PAB compounder

Twin shaft intensive mixers Primary PAB compounder

Disc extruder Adaptable for compounding

Single screw extruder Second choice

Single shaft mixer Second choice

2. Batch mixers Roll mills Laboratory and short run

Internal sigma blade mixers Laboratory and short run

Table 1.2 Advantages and disadvantages of some PAB mixers Machine Advantages Disadvantages 1. Twin screw Uniform high shear stress Capital cost extruder flow, short residence time, self-cleaning, flexibility and ease of change. 2. Single screw Cost, availability, Poor control, low rate of extruder flexibility, for modification shearing, long residence time, of screws and add-ons dead-spaces 3. Internal mixers Uniformity of stress Capital and operational cost, history, control long cycle, batch to batch variation 4. Multi stages system Flexibility, control, Capital cost uniformity

The simplicity in the preparation makes melt blending technique technologically very vital and offer various advantages over the other blending techniques like,

1. The technique of preparation is the simplest one from the technological point of view. 2. The ingredients are readily available and are easily identified.

Preparation and manufacture of polymer blends

3. The blending procedure does not introduce any impurities in the systems. 4. It does not require removal of the extraneous solvent as it is done in solution polyblends. 5. The control and degree of mixing of two polymers can be attained by the balance of equipment design and temperature control which produce rheological properties required for controlling the rate and degree of mixing. 6. The shear action of mechanical blending generates free radicals through polymer degradation reaction. These free radicals cause formation of the true chemical grafting between the two components. The quantity and importance of such grafted materials depend upon the temperature, shear-gradient and duration of the blending. ii) Solvent cast blends These blends are prepared by solution blending technique. In the preparation of the blends, the two polymers are dissolved separately in the same solvent. The two solutions are mixed and are brought to equilibrium [12]. This method is generally used for theoretical studies where behavior of polyblends is to be known at molecular level. It offers an advantage over other methods. This method eliminates or at least minimizes the problems of kinetics, incomplete mixing, chemical change caused by heat and shear-gradient, color degradation and premature curing reaction. But, on the other hand, it has some disadvantages since, this method can only be used for such polymers, which are soluble in a common solvent. Furthermore, isolation of the solid polyblends requires removal of the solvent by either evaporation or coagulation, which may cause heterogeneity in the system. The use of solvent causes the general problems associated with it such as: toxicity, flammability, environmental pollution and most important, economic feasibility at industrial level. This method of blending is commonly used in coating industries. iii) Latex Blends If the two polymers are available in latex form, mixing of these two results into the blending at micron level without any problem of heat and shear. The blending of two aqueous latexes is of an economic advantage because of the absence of solvent in latexes. After coagulation or evaporation, solid polyblends can be obtained. This process of blending thus, offers a major advantage in technological applications due to its industrial applicability and economic feasibility, but scale of dispersion is too coarse for practical use. For further

Introduction

improvement, fusion at molecular level had to be done by heat or shear application. Furthermore, it has a limitation of availability of the two polymers in latex form and high level of impurities present in the latexes.

B) Chemical Blends The method of preparation for these blends involves participation of the chemical reactions. Depending upon the chemical reaction, these blends have been further divided into two sub- blends: i) Graft Polyblends In commercial practice, the graft copolymerization often produces homopolymers, which produce strong interfaces due to grafting reaction, and becomes semi-compatible or compatible with graft copolymers. The separation of these from the bulk product becomes a formidable task. In the solution graft copolymerization, this is a common feature. Such block and graft copolymerization reactions actually produce polyblend systems directly, which are called graft polyblends. The systems sometimes are of industrial and commercial importance. In many cases these graft polyblends are then used for further polyblending with the same or other homopolymers or copolymers by latex or melt blending. Here, the existence of the original graft polyblend undoubtedly facilitates the latter melt blending step. ii) Interpenetrating polymer networks (IPN’s) IPN’s can be classed as polyblends, obtained in such a way that two or more separate polymeric species are present, such that, at least one of them, being in the form of crosslinked network structure and the other interpenetrating network structure as crosslinked or non- crosslinked polymers.

Different techniques used in characterization of blends

The performance of two polymers in a mixture will not essentially match to the behavior of each of the individual polymers. Numerous techniques are adopted for characterization of polymer blends. A brief summary of the techniques is given below.

Different techniques used in characterization of blends

(a) Optical Techniques Optical properties of polymer blends have been used to analyze blends. The film prepared from a miscible blend is found to be optically clear. The film prepared from immiscible blend is opaque even when small amount of second component is present in the film. This method is not reliable as transparent film can be prepared from immiscible blends if very thin film is examined or two polymers have similar or equal refractive index. Opacity is caused by the light scattered from the polymer domains in heterogeneous mixtures. For film to be transparent, critical domain size < 100 nm is required. Similarly the difference in refractive index of the two component should be >0.001 if transparency is to be used as criteria for miscibility. Light scattering techniques have been used to study the compatibility of the polymer mixtures [8]. Heterogeneous blends are always opaque if the dispersed particles in them are large enough to scatter visible light and their films thick enough to make scattering complete.

(b) Microscopy Techniques Microscope is an important technique for studying visually (i) the character of the dispersed phase, (ii) Identification of the predominant phase, and (iii) Phase separation in a polymer blend. This technique is important in predicting the final properties of polymer blends. A variety of microscopy techniques have been used, including: (a) Light microscopy, (b) Scanning electron microscopy (SEM), (c) Transmission electron microscopy (TEM), (d) Atomic force microscopy (AFM), etc.,

(c) Solution Techniques Viscosity determination is a useful technique for characterization of polymer blends. Differential solubility was one of the earliest techniques used for analyzing Polymer blends, block and graft copolymers. If one can find a solvent which only dissolves one component, and leaves the rest of the system undissolved, then the relative amounts and structures of the different components can be known. (i) Solution in common solvent Solubility differences between components of polymer blends have also been utilized in other ways. After blending together, polymer pairs may be qualitatively considered as incompatible, semi-compatible or compatible, depending on whether two distinct or

Introduction

immiscible phases remain. Partial mixing of the two polymers takes place at the molecular level or a single thermodynamically stable phase is formed. The allowable concentration of polymer without phase separation increases slightly if the molecular weights of the polymeric constituents are significantly lowered. Phase separation occurs when solutions of different polymers are mixed. This differs from usual cases of phase separation, wherein the two phases contain different amounts of the dissolved components. Analysis of the phase formed after separation of solutions of different polymers shows that, each phase consists mainly of one polymer. Thus, in solutions that undergo phase separation, the polymers are incompatible and completely separate from each other.

(ii) Film Casting Frequently, films are cast from dilute solution of two polymers. An opaque and crumbly film indicates incompatibility and, a clear self-supporting film suggests better compatibility. Since, there is a continuous change in clarity and opacity and, transition from crumbly state to self-supporting state, it is difficult to judge where compatibility trades off and incompatibility starts. Besides, incompatible blends with same or nearly same refractive index form transparent and clear films. A difficult situation has been observed experimentally for several polymer blends. In such types of observations, it is very difficult to ascertain compatibility of a blend.

(d) Thermo-analytical techniques

(i) Thermal and thermo-mechanical analysis A plethora of Thermo-Analytical techniques have been used to study the fundamental behavior of polymers and their blends. These include (a) Dilatometry, (b) Differential Thermal Analysis (DTA), (c) Differential Scanning Calorimetry (DSC), (d) Dielectric relation etc., Dilatometry and DSC have been used extensively to correlate glass transition temperature (Tg) with chemical structures. DSC is a useful technique for the analysis and quality control of polymers. It determines glass transition, melting and crystallization temperature and, degree of crystallinity.

Different techniques used in characterization of blends

Thermo Mechanical Analysis (TMA) measures the mechanical response of a polymer system as the temperature is changed, e.g. stress-strain behavior and torsion modulus. Thermo Gravimetric Analysis (TGA) and TMA also provide useful information particularly, thermal degradation or other chemical changes such as curing reactions in polymer blends.

(ii) Dynamic-mechanical measurements In order to offer a wide variety of performance conditions, polymer blends must show toughness, rigidity, stiffness and thermal resistance, as well as, flexibility, low cost and environment-friendly production. This is a very sensitive tool and has been used to detect compatibility in a polymer blend. When the damping curves from a torsion pendulum test are obtained for the parent components and for the polyblend and the results are compared, a compatible polyblend will show a damping maximum between those of the parent polymers, whereas, the incompatible polyblend gives two damping maxima at temperatures corresponding to those of the parent components.

Dynamic mechanical measurement can also give information on the (i) modulus of polymers and (ii) Glass Transitions of polymers. Fig. 1.3 depicts idealized DMA scan to determine various transition in polymers with respect to temperature [13].

Figure 1.3 Idealized DMA scan

Introduction

(iii) Glass transition studies

If the glass transition temperatures of the polymeric components are known and the glass transition temperature of the polyblend is determined, one of two things can happen. If the polyblend shows two distinct transitions corresponding to the parent polymers, it is incompatible. If the polyblend shows one transition only, the system is compatible i.e., compatibility of blend is indicated by the shift or disappearance of the single components. This is because Tg is a measure of the segmental mobility of a polymer, it must be sensitive to the environment of the segments. Therefore, if a polyblend shows Tg that is similar to the parent components, the chains of the parent polymers must lie within its own kind.

Tg =W 1 .Tgl + W 2 .Tg 2 (1.4)

Where, W1 and W2 are the weight fractions of the two components of the blend Tgl and Tg 2 are the Tg’s of the two components.

(e) X-ray Techniques This technique gives information regarding the geometry of the scattering structures. Scattering is a process that involves the deviation of a beam of radiation or particles from its initial path by the inhomogeneities in the medium through which it traverses. Thus, scattering experiments are easy to conceptualize and require only a source, a sample, and a detector (see Fig. 1.4)[7].

(a) (b)

Figure 1.4 Schematic of experimental X-ray set-up. (a) In reflection-mode for XRD (b) In transmission-mode for WAXS (or XRD) and SAXS.

Different techniques used in characterization of blends

Both, Small-angle and wide angle X-ray scattering and crystallography involve the scattering/diffraction of a highly collimated beam of X-rays that is scattered/diffracted by the sample and measured at an angle of 2 θ with respect to the direct beam.

For an X-ray of wavelength, λ, diffracted at an angle θ by planes of lattice separated by a distance d apart, it follows from Bragg’s law (Fig. 1.5) that:

nλ= 2d sin θ (1.5)

Where n is the order of diffraction and for a first-order diffraction (n=1),

d sin θ = (1.6)

This imposes the limit of resolution; that is, the minimum distance (d min ) at which two particles/atoms can be distinguished, for an X-ray to be

dmin = (1.7)

In terms of 2 θ, a diffraction experiment involving 2 θ > 1° is generally referred to as WAXS, those with 1° > 2 θ > 0.3° are described as medium-angle X-ray scattering (MAXS), and those with 2 θ < 0.3° fall into the category of SAXS [7][14].

Figure 1.5 Diffraction of X-rays from planes of lattice separated by distance d.

(f) Infrared (IR) Technique FTIR stands for Fourier transform infrared, the preferred method of infrared spectroscopy. As shown in Fig. 1.6, when IR radiation passes through a sample, some radiation is absorbed

Introduction

by the sample and some passes through (is transmitted). The spectrum of absorbed light represents a ‘fingerprint’ of the molecular structure of the sample. The usefulness of infrared spectroscopy arises because different chemical structures (molecules) produce different spectral fingerprints. There should be good intermolecular chemical or physical interactions exist between the polymer blend components, in order to obtain a one-phase system. FTIR- spectroscopy is a simple, rapid and straight forward technique to analyze the interaction between functional groups and chemical composition in a polymer blend. FTIR technique provides precise and reproducible data that are accepted for most industrial and research purposes [7].

Figure 1.6 Mechanism of Fourier transform infrared spectroscopy

(g) Mass Spectroscopy Technique Mass spectroscopy is a rapid method of identifying (a) elastomers in rubber vulcanizate products, (b) Pyrolytic fractionation of polymers and subsequent analysis of the pyrolyzate together with gas chromatography or infrared spectra. Compounding has very little effect upon the results because most of compounding ingredients are nonvolatile under the test. They are volatilized, ionized, and separated according to mass and charge (m/e ratio) by the action of electric and magnetic fields. From the abundance of the various ionic species found, the structures of the low molecular weight species can be inferred.

Different techniques used in characterization of blends

(h) Nuclear Magnetic Resonance (NMR) Spectroscopy For more refined measurement of miscibility based on mixing at molecular level NMR can be a potential answer. In NMR either the spin-lattice (T 1) or spin-spin relaxation times for the blends are measured. When the system is immiscible, the relaxation times corresponding to the individual components are obtained but, when the system is miscible, the relaxation times are intermediate of the two extremes. Hence a single T 1 for the blend is believed to indicate the absence of domains in excess of 3 nm. NMR method is particularly attractive in the study of phase separation, induced by thermal treatment in polymer blends. Brief summary of the techniques of analysis their characterization and properties is listed in below Table 1.3.

Table 1.3 Techniques of analysis of polymer blends. Technique Characteristics and properties XRD/WAXRD Morphology (amorphous/crystalline) Surface roughness and Heterogeneous/ homogeneous SEM morphology TEM Morphology and its development Structural heterogeneities Defect structures AFM Crystallization behavior of polymer blends Surface roughness Morphology and microstructure FTIR Component identification and quantitative analysis Interfacial interactions (hydrogen bonding) Crystallization and orientation of polymer blends NMR Local dynamics of polymer blend chain orientation of polymer blends SAXS Dispersion and morphology Phase behavior and structure evolution Lamellar texture and thickness TGA Thermal stability DSC Melting and crystallization behavior Cone calorimetry Flame retardancy, such as heat release rate and carbon monoxide yield Thermal stability Mechanical test Young’s modulus Tensile strength Elongation at break

Introduction

Properties of polymeric blends

The inspiration for the development of polymer blends is generally some combination of economics and blend performance or properties. Miscible blends will follow the rule of mixtures resulting in property additivity. The properties (P) of miscible blends will be a function of composition ( ϕ) and some interaction between the components (I) as represented by the equation

P = P A ϕ A + P B ϕ B + I ϕ A ϕ B (1.7)

The interaction term (I) can be positive or negative. The properties can be density, refractive index, dielectric constant, thermal conductivity, heat capacity, thermodynamic properties, elastic modules, viscosity of melts and surface tension of liquid mixtures. In immiscible blends the properties depend upon the phase morphology and phase interaction, as well as, composition. At the next stage, the blend formulator looks for synergism in performance properties such that, the properties of blends are superior to those of the components as represented in Fig. 1.7 [8]. Positive deviations from linearity have been observed in the composition dependence of tensile strength, flexural strength and elastic modulus of a miscible mixture of a brittle polymer with a ductive polymer. Negative deviations from the additivity are most common for the rheological functions of molten, immiscible polymer blends. Partially miscible blends contain multiphase each of which contains some portions of the components.

Figure 1.7 Property-Composition dependence for a miscible polyblend.

Sector wise applications of polymer blends and alloys

Special domain morphologies can be produced in these kinds of blends to provide unique property advantage. The current interest in the area of blends is to achieve unique interpenetrating morphological structures in primarily immiscible blends. This is done by introducing a small amount of a third component referred to as the compatibilizer. Such blends are referred to as alloys and they can provide properties which are superior to either component. The compatibilizer for polymers A and B can be graft or block copolymers of A and B such that they can interact with each component thus forming a continuous phase.

Sector wise applications of polymer blends and alloys

Polymer blends are replacing the traditional materials and base polymers in end user application and expected to play a key role in the growth of the market in the next coming years. Sector wise applications of PAB: • Packaging (Flexible and rigid) • Automotive • Electrical & Electronics • Consumer Goods • Agriculture • Healthcare etc.,

Among all other applications of polymer blends, packaging application in various sectors like medical, pharmaceutical, consumer, industrial packaging, etc., are the biggest market for polymers. Polyethylenes are the most commonly used in packaging applications as shown in Fig. 1.8 [15]. Considering the application of and the demand for polyolefins can also be classified by the type of conversion process used to make the final end-use part. India LLDPE market share, by application and by volume is shown in Fig. 1.9 [16] .

Introduction

Figure 1.8 Worldwide distribution of different plastics used in packaging.

Figure 1.9 India LLDPE market share.

Polymer blending for packaging applications

Blending of polymers is becoming increasingly important in packaging applications to enhance properties, improve processing, or lower cost. Tailoring mechanical, thermal, barrier and surface properties etc., are just a few of the attributes that can be achieved by blending. The simplest blends can be made by mixing ingredients in the extruder used to convert the resin into a film or coating.

Polymer blending for packaging applications

The final blend properties will depend not only on the flow and stress history, which is process dependent, but also on the thermodynamics and the polymers’ thermal and rheological properties. Most polymer blends are immiscible, resulting in the minor component forming a separate dispersed phase or domain within the major component. The major component forms a continuous phase or matrix. The phase size and shape is known as the blend morphology. Blend morphology has a profound effect on the final properties and is the subject of extensive study. Morphology is influenced by many factors, which include the following: • interfacial tension (thermodynamics); • dispersed to continuous phase viscosity ratio; • elasticity of each phase; • minor component concentration; • mixing and melting order; • stress and flow history.

Even with the flexibility of controlling properties by introducing specific functional layers within a multilayer film, blending can be critical for meeting package requirements. Blending may be needed to make the polymer stable enough to extrude or have the right surface properties after extrusion. Blending may be used to reduce the resin cost. For example, a metallocene polyethylene plastomer (mPE) may be diluted with standard linear low density polyethylene (LLDPE) or low density polyethylene (LDPE) to lower cost.

Blending may also help improve resin processability. Two grades of the same resin with differing flow properties (such as melt index) may be blended together to achieve the proper flow for a given process. LDPE is typically blended into LLDPE to help increase output by reducing extruder pressure and torque and, improving melt strength and bubble stability [17]. Other examples where blending improves processing include: blending amorphous polyamide (nylon) into polyamide 6 (PA6) to increase extruder output and adding amorphous PA or ionomer to ethylene vinyl alcohol (EVOH) to improve thermoformability [18].

Introduction

A polymer deficient in one property is often blended with another one to enhance that property. Blending in cyclic olefin copolymers (COC), for example, can enhance LLDPE stiffness [19]. Soft polymers are often blended into harder polymers to improve the toughness. Examples include blending ethylene vinyl acetate (EVA) into LLDPE, mPE into LLDPE, and ethylene-propylene-diene monomer (EPDM) rubber or mPE into polypropylene (PP) [20].

Barrier properties may be enhanced by blending. High density polyethylene (HDPE) is blended into LLDPE or LDPE to improve moisture barrier performance. Amorphous polyamide is blended into PA6 to improve the oxygen barrier at high relative humidity. Adhesion may be promoted by blending together several resins. For example, adding EMA or EVA to PE can improve adhesion to certain inks. Anhydride modified polyolefins are blended with PE or EVA to improve adhesion to PA or EVOH in coextrusion.

For determining the suitability of polymer for packaging application, consideration of mechanical, thermal, optical and barrier properties, morphology is extremely critical. These properties depend on the structure and type of the polymer. Several key attributes of the finished packaging material are influenced by these properties such as strength, oxygen and water vapor, transparency and the ability to seal off. The importance of these properties on polymer package is described in brief in the following section.

Commonly used plastics in flexible packaging

The distribution in Fig. 1.11 shows that polyolefins such as LDPE, LLDPE, HDPE and PP, along with PET, PS and PVC, are the most widely used plastics for packaging, accounting for almost 90% of the total plastic consumption in packaging worldwide [15].

Polyolefins Polyethylene Polyethylene is one of the most commonly used resins in flexible packaging due to its low cost, outstanding toughness, and flexibility. Polyethylene homopolymers have one of the

Commonly used plastics in flexible packaging

simplest chemical structures of any polymer; they consist simply of carbon and hydrogen atoms as illustrated in Fig. 1.10. Historically, PE was available in three general classes: LDPE, LLDPE, and HDPE. Free radical polymerization has also yielded a variety of ethylene copolymers that are suitable for packaging applications.

Figure 1.10 Chemical structure of polyethylene.

Polyolefins LDPE, LLDPE, HDPE, PP

Ethylene Co-polymer EVA, EVOH, EAA

Substituted Olefins PS, OPS, PVOH, PVC

Acrylonitriles PAN, ANS

Polymer Polyesters PET, PEN, PET-PEN

Polyamides Nylon, Aramids

Regenrerated Cellulose Cellophane, Rayon

Degradable Polyesters PLA, PGA, PHA

Polycarbonates

Figure 1.11 Common Polymers for Packaging Applications.

Low Density Polyethylene LDPE contains long chain branching (LCB), which provides better processibility. The LCB contributes to greater shear thinning behavior in the melt which results in lower pressure during extrusion. The LCB also contributes to better blown film bubble stability and less

Introduction

neck-in during extrusion coating. LDPE generally has lower ultimate seal strength, dart impact resistance, and transverse direction tear strength than LLDPE. Some of the uses for LDPE in flexible packaging include the following: • sealant or tie resin; • adhesive or sealant in extrusion coating onto foil or paperboard; • blending additive for LLDPE in blown film to improve processing (increase bubble stability to improve output) and reduce haze.

Linear Low Density Polyethylene LLDPE, as its name implies, consists primarily of linear chains with no or little long chain branching. The density of LLDPE typically ranges from 0.90 to 0.94 g/cc and is controlled by introducing a comonomer during polymerization. Short chains disrupt crystallinity and lower the density. Some of the uses for LLDPE in flexible packaging include the following: • sealants; • components of tie resins; • bulking layers; • structural layers.

High Density Polyethylene HDPE is a linear polyethylene with no or little comonomer content and density in the range of 0.95 to 0.96 g/cc. It is made via a coordination catalyst similar to the LLDPE process. HDPE has the highest level of crystallinity of the polyethylenes, typically around 50 to 60%. The high crystallinity provides property benefits and trade-offs: • greater stiffness ; • higher melting temperature (135 °C); • high moisture barrier; • excellent grease and oil resistance; • lower clarity, higher haze. In multilayer flexible packaging HDPE is typically used as a structural layer and for its moisture barrier.

Commonly used plastics in flexible packaging

Polypropylene PP finds wide use in flexible packaging for its strength and high melting point. It comes in a variety of forms, depending on its tacticity, crystallinity, molecular weight (MW), molecular weight distribution (MWD), and through the introduction of comonomers. Homopolymer isotactic PP is one of the most commonly used types of PP in flexible packaging. It has a high melting point (161 °C) that is suitable for retort sterilization and other high temperature end uses. It has high stiffness and strength. It is typically used as a structural layer in rigid packaging (blow molded bottles and injection molded or thermoformed tubs or trays) and oriented or cast film, or as a structural layer in coextrusion blown film.

Specialty Polyolefins Cyclic Olefin Copolymers (COC) COCs are polymers of ethylene and norbornene. These are amorphous polymers available with a variety of glass transition temperatures, ranging from about 30 °C to 180 °C. They are stiff, transparent, and have a low moisture vapor transmission rate (MVTR). They find application in pharmaceutical packaging for their moisture barrier capacity and as blending resins with polyolefins for downgauging and enhancing moisture barrier [19],[21] .

Polystyrene PS is an amorphous polymer with a glass transition temperature of 100 °C. At room temperature it is a stiff polymer that is often used in thermoformed cups and trays. It can also be easily foamed and is often used in clamshells for quick service restaurants and other applications. PS can also be oriented into films for various applications although, the clear film tends to be brittle.

Polyvinyl Chloride It comes in rigid and flexible varieties. Flexible PVC contains plasticizers. Some plasticizers in the phthalate family have become controversial in recent years and the industry has moved to replace them. Flexible PVC can be made into a low cost, transparent flexible film suitable for wraps. It has a high oxygen transmission rate.

Introduction

Polyvinylidene Chloride PVDC is a clear barrier polymer made from vinylidene dichloride monomer. It provides a unique combination of oxygen, moisture, and oil and grease resistance. The homopolymer decomposes near its melting point making melt processing a challenge. The addition of comonomer reduces the crystallinity and melting point, allowing the copolymer to be more easily melts processed. PVDC is difficult to melt process into a film, generally requiring temperature isolation and special materials of construction. PVDC brings a distinctive combination of performance attributes, including • moisture, oxygen and arroma barrier; • good seal performance; • excellent transparency and gloss; • good antifog properties; • excellent printability; • good scratch and abrasion resistance;

Polyester The most commonly used polyester in flexible packaging is PET. The two largest applications for PET in packaging are for injection stretch blow molded bottles and biaxially oriented film. While blow molded bottles lie outside the scope of this work, it should be noted that these bottles have undergone significant downgauging over the last several years. Some bottles have such thin walls they might be considered flexible. It has good oxygen barrier but can be coated with PVDC, PVOH, or metallized with aluminum to provide outstanding barrier. It is also used as a substrate for AlO x and SiO x coatings for transparent barrier applications.

Processes for film converting for flexible packaging

Blown Film The blown film process converts polymer resin into a plastic film. Polymer pellets are fed into an extruder, melted, and pumped out a tubular die (Fig. 1.12). In a traditional air

Processes for film converting for flexible packaging

quenched process, the tube travels up a tower where it is pinched off at the top with a nip roll. Air is forced into the middle of the tube, expanding the tube in the hoop direction as it is accelerated in the machine direction by the nip roll. The expansion occurs while the tube is being cooled by air blown across the outside of the bubble. The result is a film with orientation in both the machine and transverse directions [22].

Figure 1.12 Blown film process.

Cast Film

The cast film process involves extruding the polymer through a flat die, drawing it down to the final thickness by pinning the melt extrudate onto a rotating cold roll and rapidly solidifying it (Figure 1.13). In the cast film process, the polymer is stretched in the molten state in the machine direction and very rapidly quenched. Blown film is stretched near its freezing point in both the machine and transverse directions while being more slowly

Introduction

quenched. As a result, cast film properties may differ from films of a similar composition made on the blown film process [22].

Figure 1.13 Cast film process.

1.9.1 Comparison of Blown and Cast Film Processes

In the blown film process, the melt is simultaneously cooled and stretched in both the machine and transverse directions over a relatively long process time (on the order of 1 s or more). Most of the stretching takes place near the freezing point. In the cast film process, the polymer is stretched primarily in the machine direction before the polymer is quenched but over a much shorter process time (on the order of 0.1 s or less). The result is that blown film typically has more crystallinity and is more balanced in orientation in the machine and transverse directions (Table 1.4) [22]. Greater crystallinity produces a dense film, higher haze, less transparency, and higher barrier properties. Cast film is typically softer and more transparent. It also may thermoform more easily.

Typical Properties for Flexible Packaging Films

Table 1.4 Comparison of Blown and Cast Film Attribute Blown Film Cast Film Film Properties Crystallinity Higher Lower Haze Higher Lower Gloss Lower Higher Barrier Higher Lower Stiffness Higher Lower Thermoformability Lower Better Orientation MD and TD MD Operation Flexibility in width More Less Gauge variability More Less Trim waste Less More Output per film width Lower Higher Flexibility for short runs More Less Initial capital investment Lower Higher

Typical Properties for Flexible Packaging Films

Table 1.5 provides some typical properties and test methods that characterize the functionality of various resins and substrates used in flexible packaging. Most of these properties are material properties. Table 1.6 lists some of the common resins used in flexible packaging and the functions they most often provide. A common problem with comparing material properties from multiple sources is that, the differences in test methods and the method of fabricating the samples may have a significant impact on the measured values. For example, films made on cast and blown film processes will likely have differences in machine and transverse direction physical properties. Even with samples prepared on the same type of fabrication process, differences in processing conditions may impact the properties [22].

Introduction

Table 1.5 Typical Properties for Flexible Packaging Films. Property ASTM Standard Why It is Important

Density D792 Enters into cost (per area), needed for layer control Melt flow rate D1238 Indicates flowability in a polymer process; inversely related to viscosity and molecular weight;

Tensile strength D882 Important for gauging the strength of the package

Tensile modulus D882 Helps determine how stiff the package will be; also related to strength, integrity, impact resistance and puncture resistance

Elongation at break D882 Related to toughness

Tear strength D1922 (Elmendorf) Notched or unnotched tear D1004 (Graves) resistance Melt temperature D3418 Related to seal initiation (Semi crystalline temperature, determines extrusion polymers) temperature

Glass transition E1356 (DSC) Need to be above Tg to melt temperature (Tg) E1640 (DMA) process; material becomes brittle below Tg Impact strength D3420 (Spencer) High speed impact toughness D1709 (Dart Drop)

Clarity,haze,gloss D1746 (clarity) Optical properties D1003 (haze) D2547 (gloss) Oxygen F1927, D3985, Inversely related to oxygen barrier transmission rate F2622, D1434

Moisture vapor F1249, E96 Inversely related to moisture barrier transmission rate

Importance of various properties on polymer packaging

Table 1.6 Common resins used in flexible packaging and their functions. Tie-Layer Structural Resin Sealant Barrier Adhesive Layer LDPE X X X LLDPE X X HDPE X X PP X X X PS X PET X X PVC X EVA X X X Ionomer X X EMA X X Tie resin X PA X X EVOH X PVDC X PLA X

Importance of various properties on polymer packaging

Polymer morphology Thermoplastic usually are crystalline, amorphous or semi-crystalline (combination of crystalline and amorphous region). The properties of thermoplastics are strongly influenced by their morphology. Degree of crystallinity is the one of the most important morphological characteristics of a polymer. Most of the synthetic polymers are semi-crystalline consisting both crystalline and amorphous regions [15],[23].

Crystallinity Polymer crystallinity is characterized by well-ordered regions of parallel, aligned chains. Disordered or misaligned polymer chains give rise to amorphous regions in the polymer matrix. Crystallinity decreases with increased branching because the branch points produce irregularities in molecular packing. Similarly, copolymerization introduces asymmetry in the

Introduction

polymer structure, and consequently limits the extent of crystallinity. Chain properties such as tacticity and presence of pendant groups can also have a strong effect on crystallinity [15].

Degree of Crystallinity The degree of crystallinity of a polymer is a measure of the relative amounts of crystalline and amorphous regions, and is expressed on either volume basis or mass basis. Degree of crystallinity can be determined using various methods such as density measurement, X-ray scattering, and heat of fusion measurement.

(i) Density measurement is based on the two-phase model of polymer behavior [24]. If the densities of the crystalline and amorphous components of the polymer are known, the degree of crystallinity of a polymer sample (on mass or volume basis) can be calculated using the following equations:

( ) Xv = (1.8) ( )

= ∗ (1.9)

Where, Xv and Xm are the volume fraction and mass fraction of crystalline material

in the sampler respectively, whereas, ρ, ρa and ρc are densities of the sample, the amorphous component and the crystalline component respectively.

(ii) X-ray diffraction (XRD) can also be used to determine the degree of crystallinity of polymer samples. A typical XRD curve for a semi-crystalline polymer consists of sharp Bragg peaks corresponding to the crystalline regions and a broad, diffuse halo corresponding to the amorphous regions. The XRD curve can be resolved into crystalline and amorphous contributions, and the areas under the curve

corresponding to amorphous contribution ( Aa) and crystalline peaks ( Ac) can be used to determine the mass fraction of crystalline component as:

Xm= (1.10)

Importance of various properties on polymer packaging

(iii) Measurement of heat of fusion is usually done using a differential scanning calorimeter (DSC). A comparison between the heat of fusion of the polymer sample and that of 100% crystalline polymer can also provide an estimate of the degree of crystallinity.

Importance of polymer morphology in packaging applications Several important properties of polymers depend on their degree of crystallinity. Table 1.7 lists the effect of increase in the degree of crystallinity on various mechanical, optical, and barrier properties of polymers. Crystallinity of polymers affects the tensile strength and transparency of polymer films which are important criteria in some of the packaging applications [25]. As crystallinity and tensile strength of polymer films increases, the transparency decreases [26].

Polymers with a high degree of crystallinity typically exhibit efficient chain packing with low diffusion coefficients and favorable barrier properties. Certain polymers such as PE exhibit high transmission rates for gases despite having considerably high crystallinity. However, even for PE the transport coefficients (diffusivity and permeability) decrease with increasing degree of crystallinity [15].

Table 1.7 Effect of increase in crystallinity on different polymer properties. S/N Properties Effect of crystallinity 1 Density ↑ 2 Tensile strength ↑ 3 Clarity ↓ 4 Permeability ↓ 5 Opacity ↑ 6 Compressive strength ↑ 7 Impact strength ↓ 8 Tear resistance ↓ 9 Toughness ↓ 10 Ductility ↓ 11 Ultimate elongation ↓ [↑ represents increase and ↓ represents decrease (with increasing crystallinity)]

Introduction

Barrier properties In several applications, such as packaging of oxygen sensitive food products, it is desirable for the packaging material to have a high resistance to transmission of gases (such as oxygen and water vapor). Plastics having excellent barrier properties are required to get the desired characteristics in such packaging materials. Barrier property is inversely related to permeability: lower value of permeability implies better barrier property. Permeability of a penetrant in a polymer is dependent on the solubility coefficient and diffusion coefficient [26]. Several factors influence gas permeability of plastics films, such as integrity of the film, crystalline-to-amorphous ratio, mobility of polymeric chains, hydrophobic-hydrophilic ratio.

Oxygen Permeability This is a key factor in food packaging applications as exposure of food products to oxygen can cause oxidation and undesirable changes in food quality. It is necessary to use food packaging films having high resistance to oxygen transmission to ensure quality and maintain long shelf life. The standard method for determining OTR for film is ASTM D3985 [22]. The OTR is directly related to oxygen permeability, and is an important measure of barrier properties of the packaging film. Representative OTR trend for several polymers is shown in Fig. 1.14 [15]:

Figure 1.14 Values of Oxygen Transmission Rate (OTR) of conventional packaging materials.

Importance of various properties on polymer packaging

Water Vapor Permeability Water vapor permeability (WVP) is a critical parameter in food packaging applications as contact with water vapor may cause certain food items to lose texture. Films prepared from hydrophilic polymers are expected to allow a higher transmission rate of moisture than those prepared from hydrophobic polymers [27]. The standard method for determining the WVTR is ASTM F1249 [22]. Fig. 1.15 represents WVTR of conventional plastic packaging materials [15].

Figure 1.15 Values of Water Vapor Transmission Rate (WVTR) of conventional ppackaging materials.

Importance of barrier properties in packaging applications To prevent the packaged goods from oxidative degradation, moisture absorption and contamination, favorable barrier property is a necessary condition for packaging materials. Amongst the conventional plastics using in packaging, polyethylene (LDPE and HDPE) has good moisture barrier property (Fig. 1.15) whereas polyvinyl alcohol (PVA) and polyvinylidene chloride (PVDC) are good oxygen barriers (Fig. 1.14) [26]. Major technologies to enhance the gas barrier property used in today’s industry can be roughly classified as: (i) coating; (ii) multi-layer; and (iii) blending; as illustrated in Table 1.8.

Introduction

Table 1.8 Classification of the current major gas barrier technologies

There are some area of applications where barrier properties plays a major role are packaging in food products as well as packaging of metallic parts and machinery for corrosion protection for metal components as shown in Fig 1.16. They are generally made from polyethylene (PE), which is readily available, cost effective, and usually recyclable.

Figure 1.16 Applications of polyethylene films.

Techniques used in the present study

Importance of thermal properties in packaging applications Polymer thermal properties, such as glass transition temperature and heat deflection/ distortion temperature, affect the mechanical behavior of polymers and hence, are instrumental in deciding suitability of polymers for certain packaging applications. Glass transition temperature is very important when the packed material is to be stored in a frozen environment. In such cases, one must ensure that the glass transition temperature of packaging material is lower than the freezer temperature. Otherwise, the packaging material will become brittle, and may crack. Heat of fusion is another thermal property that plays an important role in deciding the packaging material. If the heat received from external environment or source is larger than the heat of fusion, the structure of polymer may change and the packaging may fail.

Importance of mechanical properties in packaging applications Packages are continually subjected to variable mechanical loads from handling, loading and transportation, to storage. The packaging material should be able to withstand these mechanical loads, external abrasion and any other changing environmental conditions, such as temperature and pressure, to ensure damage-free product supply. Ideally, the packaging material should undergo a wide variety of mechanical tests such as tensile test, impact test, bursting test, tear strength test, flexural test, compression test, and other product specific tests.

Techniques used in the present study

Considering the importance of blends with improved mechanical, thermal and barrier properties, in the present study two different polymeric material have been selected via COC and LLDPE. Their blends are prepared with different COC loading on LLDPE using melt mixing technique using twin screw extruder. Conversion of polymer blends into film is done by using blown film extruder and sheet by using compression molding.

Further in this study thermal properties of polymer blends are determined using various sophisticated instruments such as by differential scanning microscopy and dynamic mechanical analysis; morphology studies by Scanning electron microscopy, X-ray

Introduction

diffraction and Fourier transform infrared spectroscopy. In order to study mechanical performance of the film, tensile strength, elongation, tensile modulus, tear strength; and to study barrier properties of the films, oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) are being utilized in the present study. With this in mind, the author has taken up to study the preparation of cyclic olefin copolymer loading on LLDPE and characterization of mechanical, thermal and barrier properties and the results are presented in this thesis.

Thesis organization

The thesis consists of six chapters which delivers a series of experiments and theoretical studies are conducted. Chapter 1 is of introductory nature which gives glimpse of the work embodied in the thesis and its aim is to provide fundamental components of research in the present work.

The Chapter 2 briefly presents the work done by various researchers on various aspects needed to develop COC blends and effect of their loading on various polymers and their properties. Thus, based on the conclusions derived from the literature, problem definition, and research gap are discussed and in order to develop the LLDPE/COC blends the objectives of present work were decided accordingly.

The Chapter 3 describes the materials, experimental setup and characterization techniques used in the study. It includes the melt compounder used for preparation of blends, blown film extruder and compression molding machine for preparation of samples, experimental setup used for PECVD technique and instrumentation and analysis techniques used for the samples.

The Chapter 4 of the thesis describes the blend preparation, blown film parameters as well as the effect of temperature and load on MFI of blends. This chapter discusses the thermal analysis of LLDPE, COC and LLDPE/COC blends and their experimental results are reported.

Thesis organization

The Chapter 5 discusses the mechanical, barrier and morphological properties along with FTIR and XRD analysis of the blends and compared with pure materials. This chapter discusses the effect of thin SiO x films deposition on blend film samples using the PECVD method. Achievements with respect to objectives are discussed in this chapter.

In the final, Chapter 6 discusses the conclusion of the thesis. The chapter also presents possible scope of work for the future.

Literature Review

CHAPTER 2

Literature Review

The commercialization of new polymers appears to be indefinite. However, preparing polymer blends from existing polymers will be more cost-effective. In recent years, there has been a surge of scientific and technological interest in the possibility of combining two or more polymers with properties that differ from the base polymer to create new materials via simple mechanical mixing [8][12].

Polymer - Polymer blends

The polymer blends can be divided into two groups:

(i) Commodity polymer blends (ii) Engineering blends –in which at least one component of the blend is an engineering resin. In last few years, the progress in engineering blends has been particularly impressive. About 20% of engineering resins are sold as blends [28]. The required advantageous features are impact resistance, stiffness, barrier properties, flame retardancy, thermal stability, chemical resistance, easy processability etc.

Polyolefins are synthetic polymers of olefinic monomers. They are the largest polymer family by volume of production and consumption. Polyolefin blends are a subset of polymer blends and may be classified into two groups. The first group contains polyolefins only, which are formulated to broaden the range of structures, properties, and applications offered by polyolefins. The second group contains polyolefins and nonpolyolefins, which are formulated to mitigate some of the property drawbacks of the polyolefin or the

Polymer - Polymer blends nonpolyolefin. For a blend to be classified as a polyolefin blend, it is presumed that the polyolefin component holds significant composition in the blend [29].

Nonolefinic thermoplastic polymers that in principle may be blended with polyolefins include polyamides (nylons) such as polyamide 6, polyamide 66, polyphenylene sulfide (PPS), polyphenylene ether (PPE), and polyphenylene oxide (PPO); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polycarbonates, polyethers, and polyurethanes; vinyl polymers such as polystyrene (PS), polyvinyl chloride (PVC), polymethylmethacrylate (PMMA), and ethylene vinyl acetate copolymer (EVA); block and graft copolymers (styrene–acrylonitrile copolymer, styrene–butadiene copolymer, styrene–ethylene–butadiene–styrene terpolymer, etc.); and liquid crystalline polymers (LCPs).

The properties that polyolefins normally contribute in blends with other polymers include high melt strength and elasticity, toughness, low viscosity for processability, low polarity, dielectric constant and loss and, chemical resistance and moisture absorption resistance. Nonpolyolefins contribute to high modulus, heat resistance, and oxygen or solvent barrier properties. For example, barrier properties of polyolefins can be improved by blending with polymers such as ethylene vinyl alcohol and polyvinylidene chloride. Blends of polyolefins with nylons and polycarbonate (PC) allow balanced control of permeability and water retention. Polystyrene (PS) is an interesting candidate for blending with polyolefins for mechanical reasons as, well as, for paintability and printability [29][30].

Since the late 1990s, another group of polyolefins, cyclopolyolefins, were developed [31][32]. They are homo- or copolymers formed by the polymerization of norbornene shown in Fig. 2.1. The bridged ring structure of norbornene does not readily fit into crystalline lattices, which together with comonomers make the resins completely amorphous with high transparency and high glass transition temperature.

Literature Review

Figure 2.1 Structure of Norbornene.

Cyclic olefin copolymer is a copolymer mainly produced by using metallocene catalysts during polymerization of norbornene and ethylene chain copolymerization. COC is a new member from polyolefin family. The scheme of the synthesis of COC from ethylene and norbonene in two steps is given in Fig. 2.2 [33].

Figure 2.2 Synthesis steps of the COC copolymer

Various forms of COCs are used as engineering thermoplastics having properties like: • High glass transition temperatures in combination with excellent transparency, • Low density, • Very low moisture absorption, • Outstanding moisture barrier effect, • High stiffness and strength, • Very good electrical insulation properties, low dielectric loss, • Very good melt processability / flowability

Polymer - Polymer blends

• Good chemical resistance to acids and alkalis and polar organic solvents, • Excellent biocompatibility , • Halogen-free, environmental friendly and recyclability.

COC exhibit an outstanding combination of properties, which makes it suitable for the range of applications [31][34][35]. The key end-use industries of COC include packaging, healthcare, optics, electronics etc. The packaging segment holds a prominent share in the global COC market [36]. The use of conventional plastic for packaging applications has been banned in many countries [36]. Governments across the world are striving to shift to sustainable alternatives for conventional plastic resins for packaging. Therefore, growth in the packaging segment is expected to drive the global COC market (Fig. 2.3) [36]. Several researches [37][38][39] have been carried out on COC and its blends.

Figure 2.3 COC market -2018

Among polyolefin, polyethylene (PE) has a long and rich history of product, process and fabrication innovations to meet growing market needs over the last 75 years. Many different types of ethylene homopolymers and copolymer resins have been developed with

Literature Review

a broad range of performance to meet the requirements of a variety of applications, and as a result PE is consumed in the highest volume today.

Polyethylene is composed of only carbon and hydrogen (with some notable exceptions) which can be combined in a number of ways to make different types of PEs. There are various molecular architectures that have been commercialized over the last 70 years to make different types of ethylene homopolymers and copolymers. These can be generally grouped into major types: • Low density PE (LDPE); • Ethylene vinyl acetate copolymer (EVA); • Acrylate copolymers such as ethylene methyl acrylate (EMA), ethylene ethyl acrylate (EEA) and ethylene n-butyl acrylate (EnBA); • Ionomers; • High density PE (HDPE); • Ultra high molecular weight high density PE (UHMWPE); • Linear low density PE (LLDPE); • Very low density PE (VLDPE); • Homogeneous PE produced via single-site catalysts (including metallocene) (polyolefin plastomers, polyolefin elastomers, mLLDPE, mVLDPE); • Olefin block copolymer.

There are still other minor types of ethylene copolymers including:

• Chlorinated PE (CPE) made via chlorination of HDPE powder; • Cyclic olefin copolymers (COC), made from ethylene and norbornene comonomer using a single-site catalyst; • Ethylene/carbon monoxide (ECO) copolymers, which are photodegradable and made using a high pressure free-radical polymerization process, and are used to make six-pack loop carriers for beverage; • Ethylene/vinyl trimethoxy silane (VTMOS) copolymers, used in the wire and cable Industry for moisture curing; • Ethylene/maleic anhydride (MAH) copolymers made using the high pressure

Polymer - Polymer blends

process and used mainly as a compatiblizer; • Specialty ter-polymers made in a high pressure process such as ethylene/ acrylic acid/acrylate; ethylene/butyl acrylate/carbon monoxide; ethylene/ vinyl acetate/carbon monoxide; ethylene/butyl acrylate/glycidyl methacrylate, etc.; • MAH-grafted-PE resins, used in tie-layers, tying ethylene vinyl alcohol (EVOH) or polyamide to a PE layer in multilayer co-extruded barrier films.

Even though these are major types of ethylene homopolymers and copolymers, generally PE resins are classified into three broad categories; LDPE, LLDPE and HDPE. Molecular structures, properties, and general applications of these three broad categories of PE resins are shown in Fig. 2.4 [30],[40].

Figure 2.4 Molecular structures, properties and general applications of three broad categories of PE resins.

LLDPE is an excellent choice for a variety of packaging applications due to its wide range of properties, including a low cost and an excellent set of mechanical/physical/chemical properties such as tensile and tear strength, modulus, puncture resistance, elongation at break, and so on.

Literature Review

Globally LLDPE has a huge market and is used in many different industries for different applications. LLDPE have been attracting major attention as packaging materials because of its outstanding light weight, flexibility, strength, toughness, sealability, transparency and very good processability. However, there is an expected basic disadvantage, which is their lower thermal properties, high permeability, which is an important concern to provide long shelf life for specific types of aplications [29]. Therefore, improvements in properties of LLDPE will be beneficial for the many applications.

More than 60% of linear low-density polyethylenes (LLDPE), for example, have been blended with other polyolefins: polypropylene (PP), polyethylene (PE) and copolymers such as ethylene-vinyl acetate (EVA). It has been well demonstrated that a number of physical properties and the processability of polyolefins can be improved by blending [41]. The properties of LLDPE blends frequently depend on its interfacial adhesion, phase structure, compatibilizer used etc., because of the limited compatibility of the polymers [42]. Polyolefins, such as LLDPE, provide a diverse range of structures, properties, and processing capabilities, making them popular in industrial film applications. The morphology of polymer blends has long been recognized as influencing their physical and mechanical properties.

F. Al-Attar et al. [43] investigated mechanical, thermal and rheological properties for different blend ratios of LLDPE and LDPE and reported that at high concentration of LLDPE, phase separation was evident in the DSC results for all blend ratios. J.V. Gulmine et al. [44] investigated the FTIR characterization of three major polyethylene grades, LDPE, HDPE, and LLDPE, and discovered the optimum conditions for the analyses, allowing them to be clearly identified.

H. A. Khonakdar et al [45] studied miscibility and various transitions using morphology and DMA, respectively of binary blends of EVA with HDPE and LDPE. There was reduction in all the transition temperatures after addition of EVA. This was attributed to the decreased crystallinity of the system, which enhances the molecular motions in the amorphous phase, leading to a lowering of all transition temperatures. Tan δ peak broadens with increasing EVA content in the blends was observed as shown in Fig. 2.5.

Polymer - Polymer blends

Figure 2.5 Tan δ versus temperature for LDPE/EVA & HDPE/EVA copolymer blends: (a) full temperature range; (b) magnified temperature range.

Huijun Su et al. [46] investigated structure and oxygen-barrier properties of LLDPE /EVOH copolymer/LLDPE composite films prepared by microlayer coextrusion. The gas- barrier properties and phase morphology of the alternating-layered (EVOH/LLDPE/LLDPE-g-MAH)/LLDPE composites were studied by oxygen permeation coefficient measurement and scanning electron microscopy observation. The thickness of the EVOH/LLDPE layer decided the quality of the barrier to the gas.

Yi Ren et al. [47] found a different relationship between tear strength and film orientation in LLDPE made with different co-monomers. The tie-chain concentration or the connected degree of the crystals at chain level is an important governing factor for intrinsic tear strength of polyethylene films. For a given film orientation, films made of 1-hexene and 1-octene-based LLDPE resins have significantly higher intrinsic tear strength and less decrease in machine direction (MD) tear strength. That is, for a given orientation in MD,

Literature Review

the MD tear drops significantly for films made with butene-based resin, but not nearly as much for films made with hexene and octene-based resins.

Aravinthan Gopanna et al. [48] studied PP /COC blends and their dynamic mechanical, mechanical, rheological and morphological properties. In order to improve dimensional stability and other properties, COC is blended with different commodity plastics to improve properties. Immiscibility of PP and COC in the blend system was reported from DMA results, where, individual glass transition temperature (T g) for PP and COC blends. There was increased tensile, flexural strength and modulus increased and decreased impact strength and elongation at break after addition of COC as reported in Fig. 2.6 & 2.7 (a) and (b).

(a)

(b)

Figure 2.6 (a) Tensile strength and modulus of PP, COC and PP/COC blends (b) Elongation of PP, COC and PP/COC blends

Polymer - Polymer blends

(a)

(b) Figure 2.7 (a) Effect of temperature on the storage modulus of PP, COC and PP/COC blends at a frequency of 1 Hz (b) Effect of temperature on the Tan δδδ of PP, COC and PP/COC blends at a frequency of 1 Hz

Aravinthan Gopanna et al. [37] studied FTIR, Raman spectra and wide-angle X-ray scattering (WAXS) patterns of PP, COC and its blends. They found that PP/COC blends did not produce new chemical reactions because the strength of fundamental vibration peaks in the spectra varies as the constituent content of the blends changes. Addition of COC to PP causes notable changes to the IR peaks and Raman bands of the PP/COC blends as indicated in Fig. 2.8 and Fig. 2.9. The addition of COC to PP altered the crystal structure of the material, as demonstrated by the WAXS pattern.

Literature Review

Figure 2.8 IR spectra of PP/COC blends

Figure 2.9 WAXS pattern of the PP, COC and PP/COC blends

Luca Fambri et al. [49] investigated that viscosity ratio decreases with temperature and increases with shear rate, in rheological study by means of melt flow analysis and capillary rheometry on PP/COC blends. At high shear rate, melt viscosity of blends showed a negative deviation form log linearity at all measured temperatures for shear rate of 100 and 1000 s -1.

Polymer - Polymer blends

M. Ebrahimi et al [50] used a combination of rheological measurements, X-ray diffraction (XRD), and scanning electron microscopy (SEM) to investigate the effects of shear rate and organoclay on the morphology of PP/COC (80/20 wt. %) blends. The COC phase was discovered to be converted to finely dispersed fibrils in the PP matrix. The SEM micrographs of cryo-fractured surfaces of PP/COC blend at three different shear rates show that droplet size decreases as shear rate increases.

Pegoretti A. et al. [51] studied tensile mechanical properties of PP/COC blends. Forming under designated conditions of mixing, PP and COC were found to be compatible polymers. The data reported that the adhesion between components was good without any compatibiliser used. With increasing fraction of COC component in the blends resulted in an increase in the tensile strength and modulus, whereas, decrease in the yield strain, and strain at break.

J. Kolarik et al. [52] studied the effect of COC on HDPE to produce polyolefin materials with increased stiffness and tensile strength. There is strong interfacial adhesion in the HDPE/COC blends is reported. Dynamic mechanical patterns (Fig. 2.10) of the HDPE/COC blends taken in the interval from -140 °C to 120 °C display three loss modulus peaks.

Figure 2.10 Effect of the composition of HDPE/COC blends on the temperature dependence of the storage modulus and loss modulus. HDPE/COC: 100/0 (full line); 75/25 (dash-dot-dot line); 50/50 (dashed line); 25/75 (dash-and-dot line); 0/100 (dotted line).

Literature Review

In HDPE/COC blends creep resistance is relative to the COC fraction whereas HDPE and HDPE-rich blends show very nonlinear creep behavior [53].

S. Taglialatela Scafati et al. [54] prepared cast films of PE matrix/COC blend containing from 5 to 20 wt % COC. Good distribution and dispersion of the COC in the PE matrix was achieved although incompatibility of the blend components reported in SEM analysis (Fig. 2.11). The elastic modulus showed an increase of about five times than that of the PE matrix by adding only 5 wt % of COC.

Figure 2.11 SEM micrographs of PE matrix/COC 80/20 pellet (a) and film (b).

I.M. Alwaan et al. [55] studied the behavior of thermodynamic and kinetic characteristics of LLDPE/COC blend compression molded sheet crystallinity by means of DSC (Fig. 2.12). The COC obstructs the crystal growth and nucleation geometries of LLDPE blends. Increase in loading of COC increases (A0-100% LLDPE to A100-100% COC) the disorder of LLDPE chains and in the presence of amorphous COC crystallinity is not easy to form.

Polymer - Polymer blends

Figure 2.12 DSC results of LLDPE, COC and their blend.

A. Dorigato et al [42] prepared polyethylene and COC sheet samples using hot pressing and studied morphological behavior, calorimetric and dynamic mechanical characteristics, tensile and creep properties. They reported an increase in in impact strength, but decrease in the blend ductility due to increasing fraction of COC. Enhancement in thermo-oxidative degradation and interfacial adhesion is observed. More than 20 % COC reduces creep compliance.

S. Sanchez-Valdes et al . [56] reported the influence of compatibilizer on flammability and filler dispersion characteristics of PE/COC blends. X- ray diffraction pattern of PE shows the distinguishing diffraction peaks of a semi-crystalline structure (Fig. 2.13 (a)) while the PE/COC blend (Fig. 2.13 (b)) shows a more amorphous structure with a noticeable reduction in the intensity of the PE crystalline diffraction peaks. This is attributed to the influence of the more amorphous COC in the blend.

Literature Review

Figure 2.13 X-ray diffraction patterns for some composites samples and neat polymers.

Aleksandra Ostafinska et al. [57] studied HDPE/COC blend using melt mixing followed by injection molding and observed an increase in the mechanical performance after addition of stiff oriented COC into HDPE. It was reported that the interfacial adhesion was unusually high, which could be due to the excellent compatibility or even partial miscibility of the blend components observed from the combined results from SEM, mechanical properties measurements and theoretical calculations based on predictive models. Also the yield strength, the elastic modulus and the micro hardness were very high, higher than the theoretical values expected by the equivalent box model.

Ali Durmus [58] prepared COC/EVA blends with ratios 90/10, 80/20, and 70/30 by melt mixing in a twin screw extruder, followed by cast film, and investigated microstructural, rheological, mechanical, and viscoelastic properties of film blends. The films exhibited distinct immiscible “matrix–droplet” or “co-continuous” blend morphology, as well as reductions in the young's modulus and yield stress, as well as increased strain at break, as shown in Fig. 2.14.

Polymer - Polymer blends

Figure 2.14 Mechanical properties of COC/EVA blends.

H. A. Khonakdar et al. [39] investigated the dynamic mechanical properties, morphology, and rheology of COC, Polyolefin Elastomer (POE), and their blends. Immiscibility between blends was visible in the SEM image. Melt viscosity, storage modulus, and Han diagrams were used to analyze the blends' rheological behavior. The storage modulus of neat COC was greater than that of neat POE, while the modulus of the blends was in between the modulus of the neat polymers, according to the findings (Fig. 2.15). DMA demonstrated that COC/POE blends were immiscible, which was supported by morphological and rheological findings. Figure 2.16 depicts the loss modulus of COC/POE blends.

Literature Review

Figure 2.15 Temperature dependence of elastic modulus of COC/POE blends.

Figure 2.16 Temperature dependence of loss modulus of COC/POE blends.

P. Doshev et al . [59] investigated COC/ethylene-octane copolymer (EOC) blends which showed phase separation forming matrix-droplet type morphology. Co-continuous morphology was found in the composition range of 70-25 wt. % COC in dependence on the method of blending.

Plasma Enhanced chemical vapor deposition (PECVD): SiOx Coating

A thermoplastic urethane and a cyclo olefin copolymer such as norbornene-ethylene were also used to create transparent thermoplastic blends. Norbornene-ethylene copolymers usually have a T g of less than 150° C and contain at least 50 mole % ethylene. Because the indices of refraction of both components are similar, a transparent blend is formed that can be used in a variety of applications requiring transparency, such as electronic and semi- conductor packaging, hard disc drive constituents and packaging, optical devices and films, and so on.[60].

PMMA and COC blend properties such as glass transition temperature (T g), the melt flow index, and the viscosity as a function of shear stress were determined by M. Sahli et al.[38].

Plasma Enhanced chemical vapor deposition (PECVD): SiO x Coating

Chemical vapor deposition (CVD) is a technique used for the deposition of thin films on the surface occurs due to the chemical reaction in vapor phase. Other common deposition procedures include physical vapor deposition technique (PVD), which uses evaporation, sputtering, and other physical processes to produce vapors of materials instead of chemical processes [61]. Whereas Plasma-enhanced CVD (PECVD) uses electrical energy for producing a plasma, and the produced plasma activates the reaction by transferring the energy of its species to the precursors and induces free radical formation followed by radical polymerization [62]. Among CVD and PVD, PECVD can extend applicability of the vapor deposition process to various precursors, including reactive organic, inorganic, and inert materials. The by-products of the CVD process maybe toxic and their neutralization can make the process expensive. However, PECVD, which has seen a rapid development in the last few years, has eliminated these problems to a great extent as discussed in Table 2.1 [61].

Literature Review

Table 2.1 CVD,PVD and PECVD advantages and disadvantages. CVD PVD PECVD ADVANTAGES ADVANTAGES ADVANTAGES • Avoids the line-of • Atomic level control of • Avoids the line-of sight sight chemical composition issue to certain extent • High deposition rate • Not requiring the usage • High deposition rate • Production of thick of special precursors • Low temperatures coating layers • Safer than CVD due to • Both organic and • Co-deposition of the absence of toxic inorganic materials as material at the same precursors or by- precursors time products • Unique chemical properties of the DISADVANTAGES DISADVANTAGES deposited films • Requirement of high • Line-of-sight • Thermal and chemical temperatures deposition stability • Possibility of toxicity • Low deposition rate • High solvent and of precursors • Production of thin corrosion resistance • Mostly inorganic coating layers • No limitation on materials have been • Requirement of substances: complicated used annealing time geometries and composition

DISADVANTAGES • Existence of compressive and residual stresses in the films • Time consuming specially for super- lattice structure • High cost of equipment

Gas diffusion barrier on polymeric substrate is an essential part of modern packaging for protection of food and non-food products against outside environment. Molecular structure of thin polymer film is found in the form of chains oriented like networks. This structure possesses certain porosity as well as gaps through which gas molecules can easily pass through and reach the packed product. Plasma surface modification such as crosslinking, coating etc. on top of it reduces such pores and gaps by forming an even, smooth and almost impermeable layer and thus prevent gas molecules reaching the packed product. Plasma deposited inorganic coating on polymer surface have been used in recent years as an alternative to metallized polymers for packaging applications due to their transparency,

Plasma Enhanced chemical vapor deposition (PECVD): SiOx Coating recyclability, microwave use and excellent barrier properties [63]. According to the review article [64], gas transport properties of cold plasma treated films are still being investigated and these properties are essential for design of packages suitable for food product and also the assessment of product safety.

P. Kikani et al. [65] studied deposition of nano-scale SiO x films on LDPE and Silicon surface by radio frequency (13.56 MHz) capacitively coupled Oxygen/HMDSO plasma at low pressure. Film properties such as surface chemistry, wettability and gas diffusion barrier were studied as a function of oxygen concentration in oxygen/ HMDSO gas mixture . They observed that, increase in oxygen concentration in gas mixture improves the wettability of the deposited film and improves gas barrier property of LDPE surface as shown in Fig. 2.17.

It was observed that deposition rate of SiO x film decreased with increase in oxygen concentration.

Figure 2.17 Oxygen concentration vs. Oxygen Transmission Rate

Purvi Dave et al. [66] studied SiO x coated single layer of LDPE packaging film. The surface of LDPE film was modified with the help of SiO x coating deposited by plasma-enhanced chemical vapor deposition (PECVD). It has been observed that the OTR values reduces for film deposited with higher oxygen concentration in SiO x coating (Fig. 2.18). It was observed that film structure changes from linear type to network type as oxygen concentration increases in the oxygen- Hexamethyldisiloxane (HMDSO) gas mixture. Network-type film structure exhibited better oxygen diffusion barrier property (Fig. 2.19) [67]. OTR of polyethylene film was reduced up to 350 cc/m 2*day from 3500 cc/m 2*day.

Literature Review

Figure 2.18 Oxygen transmission rate of untreated PE, single-layer SiO x deposited PE, double-layer SiO x deposited PE and conventional 5-layer (different polymers) structure.

Figure 2.19 Types of SiO x film growth mechanism from HMDSO monomer.

Radek Prikryl et al. [68] prepared the SiO x barrier nano coatings on selected polymer matrices such as polyethylenevinyl acetate (PEVA) and Polyvinylidenchlorid (PVDC) to increase their resistance against permeation of toxic substances. The SEM microstructure of

SiO x nano coatings prepared by thermal deposition from SiO in vacuum by the Plasma Assisted Physical Vapour Deposition (PA-PVD) method or vacuum deposition of hexamethyldisiloxane (HMDSO) by the Plasma-enhanced chemical vapor deposition (PECVD) method have been studied. It has been concluded that the HMDSO method, which makes it possible to influence the SiO x nano coating thickness and better quality, is more appropriate as shown in Fig. 2.20.

Definition of the problem

Figure 2.20 Oxygen permeation values detected for PEVA foil with barrier layers of PVDC, plasma polymerized HMDSO and parylene.

Dynamic mechanical analysis, mechanical properties such as tensile strength, modulus and tear strength, as well as, barrier properties of polymer blends are very important to estimate their suitability in the particular field of application in packaging. Because of a high fraction of ethylene units, COC is likely to be compatible with polyethylene and other polyolefins without addition of special compatibilizers [42]. As per best of our knowledge, not enough data is available on miscibility behavior in COC based blends, mainly on LLDPE and COC blends and its relation with mechanical, thermal and barrier properties.

There is no work is reported on SiO x coating on LLDPE/COC blend film.

Definition of the problem

For more than 50 years, polyolefins such as LLDPE have been attracting major attention as packaging materials because of its outstanding light weight, flexibility, strength, toughness, sealability, transparency and very good processability. LLDPE has lower thermal and high permeability properties. These properties are important concern for specific packaging applications where long shelf life of the product is required (Fig. 2.21). Because LLDPE has

Literature Review

poor barrier properties, therefore it has restriction for some packaging applications. There are some engineering plastics like PVDC and PCTFE, which require compatibilizer for better mixing. These plastics uses advanced and expensive processing equipment and they also reduce the potential for recycling. At present multilayer high barrier polymer films are used in market for packaging. Multiple polymer materials are used in multilayer film structures for producing package, which increases its cost multi-fold and also makes it difficult to recycle. The equipment cost for producing multilayer films is also of high value. Hence, the development of surface modification technologies to improve barrier properties PE films would be of great help to packaging industries in producing low cost environment friendly packages.

Development of polymeric materials with good thermal, optical, and barrier to oxygen or water vapor with improved mechanical properties, processability and recyclability considering the environmental concern has attracted much attention during the recent years. Therefore, improvements in properties of LLDPE will be beneficial for the many applications, in particular packaging of food products, non-food products, pharmaceutical, medical etc. Like other glassy amorphous polymers, COC has low elongation at break. For this reason, it is rarely used as a pure monolayer structure, unless exceptional optics are needed.

Figure 2.21 Effect of oxygen and moisture on sample

Identified gaps in the literature

After a complete investigation of the existing literature, a number of gaps have been seen in the COC and LLDPE blends.

• The majority of the researchers have prepared COC blends using melt compounding followed by either cast film or compression molding process. From the literature

Objectives and Scope of work

survey, it has been observed that little research work on LLDPE/COC blending has been done using blown film extrusion.

• MFI testing to check processability of COC and LLDPE blend was not carried out at different temperatures to process in blown film extrusion.

• There is a need to optimize process parameters to achieve optimum performance of LLDPE/COC blend.

• Systematic study on effect of COC loading on LLDPE blend’s thermal properties, XRD pattern, FTIR has not been done.

• Mechanical properties such as tensile strength, elongation, tensile modulus and tear strength of COC and LLDPE blend film is another thrust area that has not been explored fully in the previous studies.

• Also, the effect of COC loading on LLDPE blend film on barrier properties has not been completely investigated especially using Plasma enhanced chemical vapor

deposition (PECVD) technique for SiO x coating.

• In order to investigate the barrier performance of COC and LLDPE blend film, practically barrier properties need to be measured.

Objectives and Scope of work

The aim of the project was to prepare polymer blends and study their thermal, mechanical and barrier properties. Thermoplastic polymer blend of a selected commodity polymer to provide low cost and processability with an engineering polymer for high stiffness, thermal stability, oxygen barrier properties was selected for economic and recyclability reasons, instead of using a laminated/co-extruded structure. COC has significantly superior barrier properties than LLDPE and can be used in blends to modify oxygen and water vapor transmission rates. Compared to LLDPE, COC has higher thermal stability and higher Tg. COC has good compatibility with LLDPE without addition of compatibilizer, it forms uniform blend due to high fraction of ethylene units.

Literature Review

Following are the objectives of the research work-

• Preparation of COC and LLDPE blends containing 5, 10, 15 and 20 wt% COC in LLDPE.

• Measure Melt Flow Index (MFI) of LLDPE/COC blends with varying content of COC. Evaluation of effectiveness of MFI data to prepare blown film from LLDPE/COC blend.

• Analysis of thermal properties of blends by Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA) and study of surface morphology using Scanning Electron Microscopy (SEM).

• Investigation of mechanical properties such as tensile strength, tensile modulus, % elongation and tear strength.

• Investigation of barrier properties such as Oxygen Transmission Rate (OTR) and Water Vapor Transmission Rate (WVTR) of blends.

• Evaluation of barrier properties of polymer blend films after Plasma Enhanced

Chemical Vapor Deposition (PECVD) SiO x surface coating.

Materials

CHAPTER 3

Materials and Methodology

Materials

3.1.1 Cyclic Olefin Copolymer (COC) Cyclic olefin copolymer (COC) is copolymer of ethylene and norbornene groups as shown in Fig. 3.1. Cyclic olefin copolymer (COC), TOPAS 8007 (density = 1.02 g/cc, MFI=1.8 g/10 min at 190 °C and 2.16 kg), was donated by TOPAS Advanced Polymers. The norbornene content in this COC grade is around 35% with a glass transition temperature of 78 °C.

[The norbornene (fraction Y) and ethylene (fraction X) copolymer].

Figure 3.1 Structural formula of COC

3.1.2 Linear low density polyethylene (LLDPE) LLDPE are produced by copolymerization between ethylene and α-olefin comonomer such as 1-butene, 1-hexene or 1-octene. It results in an ethylene/ α-olefin copolymer with many short chain branches along the polymer backbone as shown in Fig. 3.2. The side chains are known as pendant groups, or short chain branching.

Materials and Methodology

Figure 3.2 Representation of LLDPE with short chain branching

The structure is essentially linear but because of the short chain branching it has a low density. The structure gives the material much better resilience, tear strength and flexibility. This makes LLDPE an ideal material for the manufacture of film products.

LLDPE F19010 (Butene comonomer based), density = 0.918 g/cc, MFI=0.90 g/10 min at 190°C and 2.16 kg, was obtained from Reliance Industries limited. With but-1-ene,

CH 3CH 2CH=CH 2, the structure of the polymer is as shown in Fig. 3.3:

Figure 3.3 Structural formula of LLDPE

Preparation of blends

LLDPE/COC blends are prepared by melt blending techniques using co-rotating intermeshing twin screw extruder (Haake Rheomix TW100) at Central Institute of Plastics Engineering & Technology (CIPET), Ahmedabad as shown in Fig. 3.4, in the compositions of 100:0, 95:05, 90:10, 85:15, 80:20, and 0:100 where, the numbers represent the weight percentages of LLDPE and COC, respectively. The coding system and compositions of the investigated samples are referred as L 100 C0, L95 C05 , L 90 C10 , L 85 C15 , L80 C20 , and L0C100 respectively where, the subscripts indicate the weight percentage of LLDPE and COC in the blend (Table 3.1). Processing parameters for preparation of blends through twin screw extruder were: Screw speed: 50 rpm; Cylinder temperature profile: 210, 220, and 230 ºC;

Preparation of blends

Die exit temperature 230 ºC. Each batch of LLDPE/COC blend was prepared of 02 kg with weight percent of LLDPE/COC as shown in Table 3.1. After the melt blending, extrudate were quenched in a cold water bath and granulated. Granules were pre-dried for 24 hrs at 60 ºC in a vacuum oven.

Table 3.1 Weight percentage and total weight of LLDPE and COC in the blends. Sr. No Blend LLDPE COC LLDPE COC (wt %) (wt %) kg kg

1 L100 C0 100 00 2.0 00

2 L95 C05 95 05 1.9 0.1

3 L90 C10 90 10 1.8 0.2

4 L85 C15 85 15 1.7 0.3

5 L80 C20 80 20 1.6 0.4

6 L0C100 00 100 00 2.0

Figure 3.4 Preparation of blends using Haake twin screw extruder.

Materials and Methodology

Sample Preparation

3.3.1 Compression molding Pre-dried granules of LLDPE, COC and LLDPE/COC blends were compression molded at the temperature of 250 ºC under a pressure of 200 psi (1.38 MPa) for the time period of 10 min into sheets, with a thickness between 2.5-3 mm (Fig. 3.5). Sheets were prepared using square mold with length=180 mm, width=180 mm and thickness =3 mm. The thickness of sheets was measured using Vernier caliper. Compression molded sheets were prepared at CIPET-Ahmedabad.

Figure 3.5 Compression molded sheets of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 , and L0C100 blends.

3.3.2 Blown film Films of LLDPE/COC blends were prepared using Haake tubular blown film equipment facility available at CIPET-Ahmedabad as shown in Fig. 3.6. The film thickness was approximately 40±3 µm and it was measured using plastic film digital thickness gauge meter. The processing

Sample Preparation

temperature was kept at 210–240 ºC. Prepared samples were used to determine mechanical properties, barrier properties, XRD pattern and morphological study.

Figure 3.6 Preparation of Blown film using Haake tubular blown film extrusion.

3.3.3 Experimental Setup & Plasma Production

In this study, thin SiO x films were deposited using the PECVD method. Fig. 3.7 shows experimental setup used for present PECVD experiments. This set up contains stainless steel process chamber with 60 cm diameter and 30 cm height. Hexamethyldisiloxane (HMDSO) along

with oxygen (O2) were used as plasma forming gas and were introduced into the process zone via multipoint gas feeding shower head. Plasma was generated at 50 Watt power between two

parallel plate electrodes (35 cm diameter) using radio frequency (13.56 MHz) O2/HMDSO power source. The gap between electrodes was kept 3.5 cm. Samples were placed on the bottom electrode. Fig. 3.8 represents actual plasma enhanced chemical vapor deposition (PECVD) equipment setup at Facilitation Centre for Industrial Plasma Technologies (FCIPT),

Gandhinagar. SiO x was carried out under condition of 10 min cleaning and 20 min coating

time, 0.07 Mbar pressure in O2/HMDSO gas mixture followed by cooling for 30 min. The coated films were further evaluated for OTR and WVTR. Thickness of the deposited films was measured using a NanoMap-500ES contact mode stylus profilometer. In our experiments, we aimed at preventing an ingress of oxygen/water molecules from film

surface by deposition of thin (100–500 nm) SiO x coating using PECVD method.

Materials and Methodology

Figure 3.7 Experimental schematic diagram for PECVD

Figure 3.8 PEVCD System

Sample characterization

3.4.1 Melt flow Index (MFI) The most commonly used rheological measurement for polyolefins is the melt flow index (MFI). It is a measure of the mass of polymer that flows from an orifice under a given weight at a prescribed temperature. The melt indexer consists of a heated tube, a piston for pushing the melted polymer, a weight that lies on top of the piston, and an orifice at the end of the tube as shown in Fig. 3.9 (a). The dimensions of the orifice are specified in ASTM D1238 and fixed by the design of the instrument. The polymer pellets are introduced into the tube, and the piston is inserted to remove air from above the melting resin. After a prescribed amount of time to allow the polymer to melt and come to temperature, the weight is placed on top of the piston. The polymer that flows from the orifice in 10 min is weighed. The result is reported in grams per 10 min. The weight and temperature are also reported.

For polyethylene, the standard temperature and weight is 190 °C and 2.16 kg, and the measurement is often called the melt flow index or MFI. Higher temperatures are used for resins with higher melting points. Table 3.2 gives the typical MFI range for various processes [22]. Melt flow index (MFI) of the LLDPE, COC and LLDPE/COC blends were carried out as per ASTM D1238 at 190 ºC, 230 ºC and 260 ºC for 2.16 kg and 5 kg load. Five samples were used for each test and the average value was taken. MFI was measured using Melt flow tester (Deepak Poly Plast Pvt. Ltd.) available at L.D College of Engineering-Ahmedabad.

Figure 3.9 (a) Schematic representation Melt flow index tester (b) Melt flow index tester.

Materials and Methodology

Table 3.2 Melt Flow Index (MFI) ranges of typical PE grades by process Typical MFI range for Process PE, g/10 min (190 ºC /2.16 kg) Blown film 1-5 Blown film (high stock UMW- 0.01-1 high –density polyethylene) Cast film 2-7 Extrusion coating 4-15

3.4.2 Differential scanning calorimetry (DSC) Differential scanning calorimetry (DSC) is a technique used to investigate the response of polymers to heating. DSC can be used to study the melting of a crystalline polymer or the glass transition. The DSC set-up is composed of a measurement chamber and a computer. Two pans are heated in the measurement chamber. The sample pan contains the material being investigated. A second pan, which is typically empty, is used as a reference. The computer is used to monitor the temperature and regulate the rate at which the temperature of the pans changes (Fig. 3.10). A typical heating rate is around 10 °C/min. The rate of temperature change for a given amount of heat will differ between the two pans. The difference in heat output of the two heaters is recorded. The result is a plot of the difference in heat flow versus temperature (Fig. 3.11) [69].

Figure 3.10 DSC Instrument working Principle.

Sample characterization

Figure 3.11 Thermal transitions in (A) amorphous and (B) semicrystalline polymers.

As the temperature increases, both amorphous and semicrystalline polymers go through the glass transition (T g). Amorphous polymers (A) do not exhibit other phase transitions. However, semicrystalline polymers (B) undergo crystallization and melting (at temperatures

Tc and T m, respectively).

The differential scanning calorimetry (DSC) [Model: (PERKIN ELMER, Diamond DSC)] analysis was carried out at CIPET- Ahmedabad. DSC analysis was done under nitrogen purging rate at 50 ml/min (Fig. 3.12). The samples were heated at a rate of 10 °C/min from 0 to 200 °C and then cooled at the same rate back to 0 °C. A 2nd heating cycle of up to 200°C was then performed under the same conditions as the 1st heating cycle. The melting temperature of LLDPE in the blends could thus be evaluated, and it’s percent crystallinity

(XC) was calculated as the ratio of the melting enthalpy ( ∆Hf) to the weight fraction of

LLDPE in the blends ( wss ), and the reference value of fully crystalline polyethylene ( ∆Hºf), which was taken as 293.6 J/g. The percent crystallinity was calculated using Equation (3.1).

% = ∗ 100 (3.1) ∗ º

Materials and Methodology

Figure 3.12 Differential scanning calorimetry analyzer.

3.4.3 Dynamic mechanical analysis

The dynamic mechanical analysis are widely used to characterize the viscoelastic properties, transition and relaxation behavior of polymers (As shown in Fig. 1.3). DMA measures stiffness and damping, these are reported as modulus and tan delta respectively. The viscoelastic parameter are defined as follows:

E*=E'+E'' (3.2)

Tan δ=E''/E' (3.3) where E*, E' and E'' are complex, storage, and loss modulus, respectively, Tan δ is loss tangent or loss factor. The storage modulus is the measure of the sample’s elastic behavior. The ratio of the loss to the storage is the Tan δ and is often called damping. It is a measure of the energy dissipation of a material [7]. DMA was conducted by Inkarp Instruments (Model: EXSTAR DMS 6100) dynamic mechanical analyzer equipment available at CIPET-Ahmedabad (Fig. 3.13) using three point bending at a constant frequency of 1 Hz. The temperature range was from –120 to +120 °C at a heating rate of 2 °C/min. The dimension of the test specimen was approximately 54 mm × 13 mm × 3 mm.

Sample characterization

Figure 3.13 Dynamic mechanical analyzer

3.4.4 Mechanical properties Tensile properties are measured using tensile testing machine that provides for a constant slow rate of deformation and uses a load cell to measure and record the force required to produce that deformation. ASTM D882 [70] provides a standard method for measuring the tensile properties of film. Strips are cut from the sample and placed in the gripping jaws of a tensile testing machine. The load is measured as the gripping jaws are pulled apart at a constant speed.

Strain or elongation: The change in length as the specimen is stretched between the moving grips of the tensile tester is known as strain or elongation:

ε = ∆L / L 0 (3.4)

Where ε = Strain, ∆L =change in length ( L-L0), L0= initial length of the specimen, L= length of specimen during the tensile test. When ε is expressed as a percentage, it is known as the % elongation.

Materials and Methodology

Tensile modulus.: The slope of a tangent drawn parallel to the initial linear portion (before the yield point) of the stress vs strain curve is known as the tensile modulus, elastic modulus or Young’s modulus. The modulus is related to the stiffness of the material.

Tear strength: The trouser tear method is a slow speed tear resistance test and is described in ASTM D1938 [71]. A standard tensile tester is used with a crosshead speed of 250 mm/min. The rectangular tear specimen is precut on one end in what resembles a pair of trousers (Fig. 3.14). The two sides of the precut region are placed in the grips of the tensile tester and the force needed to propagate the tear is measured. The tear resistance is the force divided by the specimen thickness.

Figure 3.14 Trouser tear test sample configuration.

The tensile properties and trouser tear strength in Machine direction (MD) as well as Transverse direction (TD) were determined using Universal testing machine (Deepak Polyplast Pvt. Ltd.) according to ASTM D882 and ASTM D1938 respectively for prepared film samples. Total three samples for each blend were tested and average of the three samples is reported in Table 5.5. Mechanical testing was carried out at testing equipment manufacturing unit of Deepak Poly Plast Pvt. Ltd.

3.4.5 FTIR spectroscopy The chemical composition and interactions between functional groups in a polymer blend can be studied using FTIR spectroscopy. In FTIR, infrared radiation is passed through a sample, some of which is absorbed by the sample and some of which is transmitted. The resulting spectrum demonstrates molecular absorption and transmission, resulting in a molecular fingerprint of the sample. The energy of these IR rays can be related to the

Sample characterization vibrational energy of various bonds found within different functional groups in a compound [72]. FTIR spectra of the raw materials and blends were recorded by ASTM E1252 using Cary 630 Agilent FTIR spectrometer instrument available at CIPET-Ahmedabad (Fig. 3.15). For LLDPE, COC, and their blends, spectra in the range of 4000–400 cm -1 were recorded. The compression molded samples were cut and mounted on the sample holder for data collection.

Figure 3.15 FTIR spectrometer

3.4.6 X-ray diffraction X-ray diffraction (XRD) is used to determine the phase of a crystalline substance and can provide information on crystal structure and percent crystallinity. X-rays are produced in a cathode ray tube by heating a filament to generate electrons, then applying a voltage to accelerate the electrons in the direction of a sample and bombarding it with electrons. When electrons have enough energy to transfer the sample's inner shell electrons, characteristic X-ray spectra form. As the detector and sample rotate, the strength of the reflected X-rays is measured. Constructive interference occurs and a peak in intensity occurs when the geometry of the incident X-rays impinging the sample satisfies the Bragg's Equation (n.λ=2d sin θ) * where d is the spacing between the diffracting planes, is the incident angle, n is an integer (usually 1), and λ is the wavelength of the incident radiation (Fig. 3.16) [73]. The XRD pattern of a polymer sample includes both sharp and large peaks, depending on the percentage of crystalline and amorphous portions in the substance. Peaks in crystalline regions are sharp and narrow, whereas peaks in amorphous regions are diffused and wide [7].

Materials and Methodology

Figure 3.16 Schematic representation of the Bragg equation.

X-ray diffraction (XRD) is a method mainly used for phase identification of a crystalline material and can provide details on percent crystallinity and crystal structure. X-ray scattering patterns of the LLDPE and COC blends prepared as film samples are collected using Cu-Kα radiation ( λ = 1.54 nm) produced by X-ray diffractometer (Bruker D8 Discover) instrument facility available at Indian Institute of Technology (IIT), Gandhinagar as shown in Fig. 3.17 controlled at 40 kV and 30 mA. XRD pattern in 2 Theta (2 θ) range of 10 º- 80º was analyzed.

Figure 3.17 X-ray diffractometer (left) and sample holder (right).

Sample characterization

3.4.7 Morphological analysis The morphology of the samples were determined by scanning electron microscopy (SEM) using a JOEL FESEM (JSM-7600F) (Fig. 3.18). The surfaces were gold-coated by a sputtering coating unit model JOEL JFC-1600 instrument facility available at IIT, Gandhinagar.

Figure 3.18 SEM analyzer (left) and coated sample (right).

3.4.8 Barrier properties

Water vapor transmission rate (WVTR) WVTR is the steady state rate at which water vapor permeates through a film at specified conditions of temperature and relative humidity. Dry nitrogen gas is swept through a chamber where the test film acts as the membrane separating this dry gas stream from a "wet" nitrogen stream on the other side as shown in Fig. 3.19. The partial pressure difference creates a driving force for the water vapor to permeate through the film to the low pressure side. The barrier of the film determines how much water vapor can transfer, and this is continuously measured in the outgoing stream of the dry side. WVTR was evaluated using

Extra solution (PermeH 2O) as per ASTM F1249 (38°C and 90% RH) at CIPET, Ahmedabad (Fig. 3.20).

Materials and Methodology

Figure 3.19 Mechanism of working of WVTR equipment.

Figure 3.20 WVTR Analyzer.

Oxygen Transmission Rate (OTR)

OTR is the steady state rate at which oxygen gas permeates through a film at specified conditions of temperature and relative humidity. In this test, gas (normally at 1 atm) is introduced on one side of the flat film which is supported with a filter paper and a sealed ‘O’ ring. The pressure in receiving chamber is measured with a mercury manometer. Provided that the pressure on the higher pressure side remains much larger than that on the lower pressure side, the pressure difference essentially remains constant. The test setup is shown in Fig. 3.21 (a).

Sample characterization

(a)

(b)

(c)

Figure 3.21 (a) OTR testing setup (b) Gas permeation analyzer (c) Sample Preparation.

Materials and Methodology

OTR is calculated using Equation (3.5).

= [cc / (m2 * day * 1bar)] (3.5) ∗ ∗∗

Where is the volume of the chamber; R is gas constant; T is temperature; P is applied pressure of test gas on higher pressure side; A is the test area; and is differential pressure.

This rate is the sample OTR and is recorded in units of cc/ (m2 * day). The oxygen transmission rate (OTR) was evaluated using Gas permeation analyzer (GBPI, Model: N500), instrument facility available at FCIPT, Gandhinagar showed in Fig. 3.21 (b) as per ASTM D1434.

Introduction

CHAPTER 4

Blends: Processing and Thermal properties

Introduction

LLDPE is a semi crystalline polymer that is used extensively due to its unique combination of properties, cost and ease of fabrication. It can be processed by a variety of fabrication techniques. One of the most widely techniques to convert polymer resin into a plastic film is the blown film extrusion process. Also twin screw extruders are more efficient in preparation of polymer blends in continuous manner and the compound will perform as required and achieve the desired properties.

Thermal properties of polymers govern their behavior during heating from solid amorphous or crystalline state to molten state. Polymer materials can undergo several phase transitions upon heating, and each transition determines a specific thermal property. Such thermal properties associated with phase transitions include glass transition temperature, crystallization temperature, and melting temperature. Thermal stability of plastics defines the temperature up to which they are able to maintain their mechanical properties without degrading. Design of polymer packaging materials generally requires knowledge of the above thermal properties [15].

Polymer thermal properties, such as glass transition temperature and heat deflection/ distortion temperature, affect the mechanical behavior of polymers and hence, are instrumental in deciding suitability of polymers for certain packaging applications. Glass transition temperature is very important when the packed material is to be stored in a frozen environment.

Blends: Processing and Thermal properties

Thermal analysis of polymers provides information about their thermal transitions, to determine suitability of material for intended usage. Considering the importance of processability and thermal properties in plastic packaging applications the results obtained from these characterizations are discussed and processing parameters used to prepare blends are reported in this section.

Compounding of polymer blends

As mentioned in chapter 3, blending of LLDPE and COC in specified composition is carried out using lab scale Haake twin screw extruder. Fig. 4.1 shows the granules prepared after blending various ratios of LLDPE and COC as well as pure material. It can be seen from the figure below that the granules of all blend components are of uniform size which is a very important parameter in processing. After visual analysis it was observed that granules were of uniform size.

Figure 4.1 Granules of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

Melt flow analysis

To check the processability of the LLDPE/COC blends to make film samples using blown film extrusion, Melt flow index (MFI) test is carried out and the results obtained are discussed in the next section. Molded samples are also prepared using compression molding process and are also used for characterization purposes.

Melt flow analysis

Melt flow testing is simply a measure of the flow of a polymer when melted. Melt flow testing is very common in quality control and process control laboratories. It is mostly seen in compounding or manufacturing/converting facilities. Melt flow data are used for estimation of flow properties for simple extrusion processes and predictions of how a polymer will behave in a number of processing techniques.

The weight of material extruded in grams through a small orifice in 10 minutes is known as the Melt Flow Index (MFI). MFI and viscosity are inversely proportional, and viscosity for polymer materials is affected by the applied force. The MFI is calculated using the following equation:

∗ MFI = (4.1)

Where, m - The average mass of the cut-offs, in grams; t - The cut-off time-interval, in seconds. 600- The factor used to convert grams per second into grams per 10 min (600 s);

Table 4.1 shows the MFI value measured at three different temperatures of 190 ºC, 230 ºC and 260 ºC at 2.16 kg and 5 kg load for L100 C0, L95 C05 , L90 C10 , L85 C15 , L80 C20 and L0C100 . Mass of the material extruded from die is determined and detail results of 05 different mass for each blend extruded in 10 sec are reported in Appendix A for all samples and average of the mass is used to calculate MFI. The MFI of L0C100 at 260 ºC and 5 kg load is much higher than that for both 230 ºC and 190 ºC. L0C100 becomes less viscous than L100 C0 at higher temperatures, specifically at 260 ºC for 2.16 kg and 5 kg load. These data reveal that

Blends: Processing and Thermal properties

viscosity of L0C100 is more sensitive to temperature than that of L100 C0. The MFI value seems to be closely linked with the compositions. Thus as the compositions of L0C100 has increased in L100 C0, the MFI values increased gradually for all loads and temperatures. While performing MFI test on L0C100 at temperature 230 ºC and 260 ºC and 5 kg load, fibrous behavior of L0C100 was observed.

When the minor component's viscosity is greater than that of the major component, the minor component is coarsely dispersed. When the minor component has a lower viscosity than the major component, it is finely dispersed [74]. Here L0C100 acts as a minor component and it has lower viscosity than L100 C0. Due to its amorphous structure, the temperature dependence of MFI is higher for L0C100 than L100 C0. MFI increases for L95 C05 , L90 C10 , L85 C15 and L80 C20 for all three temperatures of 190 ºC, 230 ºC and 260 ºC at 2.16 kg and 5 kg loads as shown in Fig. 4.2. MFI ranges of typical PE grades by process reported in Table 3.2. As the preferable range for MFI to process under blown film extrusion is 1-5 g/10 min. After finding the MFI values of LLDPE/COC blend, it is investigated that the MFI comes under acceptable range to be processed using blown film extrusion.

70 2.16kg,190°C 2.16kg,230°C 60 2.16kg,260°C 5kg,190°C 50 5kg,230°C 5kg,260°C

30 MFI (g/10 min) (g/10 MFI 20

0 L100C0 L95C05 L90C10 L85C15 L80C20 L0C100

Figure 4.2 Graph showing MFI of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 .

Melt flow analysis

Flow Rate Ratio (FRR) is obtained in case two conditions are employed, by dividing the MFI at one condition by the MFI at the other condition. FRR is calculated by taking ratio of MFI at 5 kg load to MFI at 2.16 kg load at three different temperatures and reported in Table 4.1. All the blend compositions show a very comparable ratio of MFI values at 5 kg and 2.16 kg loads.

Table 4.1 MFI and FRR of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 . At 190 °C Blend MFI g/10min FRR (Ratio of MFI Composition at 5 kg and MFI at Sr. No 2.16 kg 5 kg 2.16 kg) 1 0.93 2.79 3.00 L100 C0 2 1.06 2.80 2.64 L95 C05 3 1.11 2.97 2.68 L90 C10 4 1.13 3.09 2.73 L85 C15 5 1.15 3.20 2.78 L80 C20 6 1.80 5.12 2.84 L0C100

At 230 °C MFI g/10min FRR (Ratio of MFI Blend at 5 kg and MFI at Composition Sr. No 2.16 kg 5 kg 2.16 kg) 1 1.54 4.99 3.24 L100 C0 2 1.92 5.59 2.91 L95 C05 3 2.01 5.98 2.98 L90 C10 4 2.06 6.28 3.05 L85 C15 5 2.14 6.85 3.20 L80 C20 6 11.06 29.84 2.70 L0C100

At 260 °C MFI g/10min FRR (Ratio of MFI Blend at 5 kg and MFI at Composition Sr. No 2.16 kg 5 kg 2.16 kg) 1 2.37 7.27 3.07 L100 C0 2 2.62 8.26 3.15 L95 C05 3 2.91 8.82 3.03 L90 C10 4 3.23 10.19 3.15 L85 C15 5 3.65 11.09 3.04 L80 C20 6 29.41 62.42 2.12 L0C100

Blends: Processing and Thermal properties

This indicates that the molecular weight distribution shows a similar pattern for all the L100 C0,

L95 C05, L90 C10, L85 C15 and L80 C20 , except for L0C100 material, which shows slightly different

FRR at 230 ºC and 260 ºC. This is because at higher temperature and load, viscosity of L0C100 decreases drastically and hence increases MFI as compared to L100 C0.

As discussed above, the MFI and FRR values provide correlations to the molecular weight and molecular weight distribution. FRR is better applied in the extrusion process or in applications requiring high melt viscosity materials of similar or other reasons, such as needs regarding product consistency, dimension stability and requirements on mechanical properties. The lower MFI value indicates a higher material viscosity, which corresponds to a higher molecular weight. The higher molecular weight correspond to higher flow rate ratio (FRR) and it represents the broadening of molecular weight distribution. Results obtained from MFI reveals that, all the blends can be used to process using blown film extrusion.

Blown Film Extrusion

Results obtained from the MFI test revealed that the prepared LLDPE/COC blends can be processed in blown film extrusion. A lab scale Haake blown film extrusion equipment is used to make film samples. Films prepared from L100 C0, L95 C05 , L90 C10 , L85 C15 , L80 C20 and

L0C100 blends are shown in Fig. 4.3.

Due to the higher compositions of LLDPE in LLDPE/COC blend it is easy to prepare films from blends. However, film with higher L0C100 content i.e., above 20 wt%, is difficult to extrude the blend as well as L0C100 film using lab scale extruder. While processing the blends to make film, the problem that occurs is that the melt starts to form fibrous behavior as observed while performing in MFI test and also poor bubble stability. This is because of higher stiffness of L0C100 . Therefore, considering the processability and cost for preparation of blends, LLDPE/COC blends are prepared up to L80 C20 . In DMA analysis, L0C100 test specimens are required which are not possible to prepare using blown film, are prepared using compression molding technique as mentioned in section 3.3.1.

Blown Film Extrusion

Figure 4.3 Blown film samples of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 .

The parameters of the blown film process are illustrated in Fig. 4.4. Some useful calculations such as Blown-Up Ratio (BUR) and Blow Ratio (BR) for this process are calculated as per the following equations and results of the same are reported in Table 4.2. To produce best physical properties in extruded film, the proper balance of film orientation in the machine and transverse direction of a film must be achieved. This relationship is achieved by adjusting the blow up ratio of the film. The blow up ratio (BUR) is the ratio of bubble diameter to the die diameter; it indicates the amount of stretching the polymer is undergoing during the shaping of the film.

Blow-Up Ratio (BUR) = Bubble diameter (Df)/ Die diameter (Do)

= 2 LFW / π Do = (0.637 x LFW / Do) (4.2)

Blow Ratio (BR) = LFW / Do (4.3)

Where, Lay flat is the width of the collapsed film and Die diameter is the fixed diameter of a given die. Blown film equipment used has a die diameter (D o) 25 mm and die gap 0.8 mm. Since it is not

Blends: Processing and Thermal properties

easy to measure the bubble diameter directly, the bubble diameter is calculated from the lay-flat width. The bubble diameter is 0.63 times the film lay-flat width (LFW). For LLDPE, standard BURs are between 2:1 and 3.5:1. BUR affects the orientation of the polymer molecules. In blown film extrusion, by pulling the film in two directions, the molecules become oriented in both directions. This gives a better balance in properties from MD to TD. Bubble instability problem is typically observed if the BUR is too high; excessively high MD/TD oriented film is produced when the BUR is too low.

Figure 4.4 Blown film line Table 4.2 Blown film parameters Layflat Bubble Film Blow Ratio Blown-up Sr. Blend Width Diameter Thickness (BR) ratio No Compositions (LFW), (D f), mm ( H), µm (BR = (BUR = mm LFW/D o) Df/D o) Average Blown Film 85 56 40 3.40 2.24 Parameters

1 L100 C0 85 56 39-42 3.40 2.24

2 L95 C05 89 59 38-40 3.56 2.36

3 L90 C10 84 55 40-42 3.36 2.20

4 L85 C15 90 58 37-40 3.60 2.32

5 L80 C20 76 51 40-43 3.04 2.04

Study of Thermal Properties

As noticed from the blown film processing, for L95 C05, L90 C10, and L85 C15 , bubble stability is observed. For L80 C20 , the change in bubble shape is not consistent. This is because of the higher stiffness of the L0C100 . It can be seen from Table 4.2 that the BUR for L100 C0, L95 C05 ,

L90 C10, and L85 C15 is around 2.2-2.4. From the results obtained, it is observed that L90 C10 has similar bubble properties as L100 C0, whereas L80 C20 has low LFW about 76 mm and less bubble diameter about 51 mm. In case of L80 C20 , it has low BUR of 2.04, which is low as compared to L100 C0 and L95 C05, L90 C10, and L85 C15 . Low BUR has higher properties in the MD, less TD shrinkage and low MD tear strength.

Study of Thermal Properties

4.5.1 Differential Scanning Calorimetric study

Melting and crystallization behavior of the L100 C0, L95 C05 , L90 C10 , L85 C15 , L80 C20 and L0C100 are obtained by DSC analysis. Fig. 4.5 to Fig. 4.10 represents the DSC curves for the L100 C0,

st L95 C05 , L90 C10 , L85 C15 , L80 C20 and L0C100 , these figures show the 1 heating cycle (top), cooling cycle (middle) and 2nd heating cycle (bottom). Heat/Cool/Heat is designed to erase previous thermal history by 1st heating the material, where relaxation or molecular rearrangement can occur, then cooling at a known rate before heating again [75].

Enthalpy, H, is the ‘‘heat content’’ of a material. The absolute enthalpy of a material cannot be measured directly; however, a change in enthalpy, ∆H, can be measured directly by DSC. The change in enthalpy of a material is either endothermic, such as melting or exothermic, such as curing or recrystallization. The ∆H or change in enthalpy is expressed in normalized terms of joules per gram (J/g). The ∆H obtained from DSC for L100 C0, L95 C05,

L90 C10, L85 C15 and L 80 C20 are reported in Appendix B. The specific enthalpy of fusion of a sample determined from the peak area is proportional to its degree of crystallinity. The proportionality factor, ∆Hc, is equal to the enthalpy of fusion of a 100% crystalline material. The melting peak area of a semicrystalline material was compared to the melting peak area of a 100% crystalline structure [76]. % Crystallinity ( Xc) is determined from enthalpy using equation 3.1 mentioned in section 3.4.2.

Blends: Processing and Thermal properties

The most relevant thermal properties are mentioned in Table 4.3. For L100 C0, melting temperature (Tm) and crystallization temperature (T c) are reported at 124 °C and 110 °C, respectively.

40 L C 30 100 0 20 1st heating cycle 10 0 -10 40 0 20 40 60 80 100 120 140 160 180 200 30 20 10 Cooling cycle 0 -10 40 0 20 40 60 80 100 120 140 160 180 200 30 Heat Flow Endo(mW) Up 20 2nd Heating cycle 10 0 -10 0 20 40 60 80 100 120 140 160 180 200 Temperature (°C)

Figure 4.5 DSC thermograms of L100 C0.

10 L0C100 0

-10 1st Heating cycle

50 0 20 40 60 80 100 120 140 160 180 200 40 30 20 Cooling cycle 10 0 0 20 40 60 80 100 120 140 160 180 200 5 Tg Heat FlowEndo Up (mW) 2nd Heating cycle

-5 0 20 40 60 80 100 120 140 160 180 200 Temperature (°C)

Figure 4.6 DSC thermograms of L0C100 .

Study of Thermal Properties

st DSC thermogram for L0C100 is presented in Fig. 4.6, the 1 heating cycle shows a change in slope at around 85°C due to stresses introduced into the material as a result of handling, thermal history, or processing; these stresses are removed when the material is heated through its glass transition. During the quench cooling from temperature 200 °C to below

Tg, the thermogram does not show a crystallization phenomenon because L0C100 is amorphous. The graph shows the presence of the glass transition at about 83.62 °C, as the molecules go from a rigid to a fluid structure, in the 2nd heating cycle after the internal stresses were relieved. [77] .

DSC thermogram for L95 C05 blend is presented in Fig. 4.7. It can be seen that the Tm of st nd L95 C05 blend for 1 and 2 heating cycle are 122.79 °C and 123.88 °C, respectively

(Appendix B). There is negligible difference in Tm of L100 C0 and L95 C05, whereas Tc is

110 °C for both L100 C0 and L95 C05.

40 L95 C05 30 1st Heating Cycle 20 10 0 40 0 20 40 60 80 100 120 140 160 180 200 30 20 Cooling cycle 10 0

40 0 20 40 60 80 100 120 140 160 180 200

Heat Flow Endo Up (mW) Up Flow Endo Heat 30 20 2nd Heating Cycle 10 0

0 20 40 60 80 100 120 140 160 180 200 Temperature (°C)

Figure 4.7 DSC thermograms of L95 C05 .

Similarly, DSC thermogram for L90 C10 blend is presented in Fig. 4.8. It can be seen that st nd the Tm of L90 C10 blend for 1 and 2 heating cycle are 121.71 °C and 123.95 °C, respectively (Appendix B). Tc is similar as L100 C00 and L95 C05 , which is 110 °C .

Blends: Processing and Thermal properties

40 L90 C10 30 1st Heating cycle 20 10 0

30 0 20 40 60 80 100 120 140 160 180 200 20 10 0 Cooling cycle -10

40 0 20 40 60 80 100 120 140 160 180 200 30 Heat Flow Endo Up (mW) Endo Flow Heat Up 20 2nd Heating cycle 10 0 -10 0 20 40 60 80 100 120 140 160 180 200 Temperature (°C)

Figure 4.8 DSC thermograms of L90 C10 .

50 40 L85 C15 30 1st Heating cycle 20 10 0

50 0 20 40 60 80 100 120 140 160 180 200 40 30 Cooling cycle 20 10 0

50 0 20 40 60 80 100 120 140 160 180 200 40 Heat Flow Endo Up (mW) Flow Endo Heat 30 2nd Heating cycle 20 10 0 0 20 40 60 80 100 120 140 160 180 200 Temperature (°C)

Figure 4.9 DSC thermograms of L85 C15 .

Study of Thermal Properties

10 0 L80 C20 -10 1st Heating cycle -20 -30 -40 10 0 20 40 60 80 100 120 140 160 180 200 0 -10 -20 Cooling cycle -30 -40 10 0 20 40 60 80 100 120 140 160 180 200 0 Heat Flow Endo Up Up (mW) Endo Flow Heat -10 2nd Heating cycle -20 -30 -40 0 20 40 60 80 100 120 140 160 180 200 Temperature (°C)

Figure 4.10 DSC thermograms of L80 C20 .

DSC thermogram for L85 C15 and L80 C20 blend are presented in Fig. 4.9 and Fig. 4.10, respectively. It can be seen that, there is 2-3 °C increase in Tm of L85 C15 and L80 C20 blend st nd for both 1 and 2 heating cycle (Appendix B), also 1-2 °C increase in Tc of L85 C15 and

L80 C20 blend .

In case of blends, it can be seen from Fig. 4.7 to 4.10 that T m and Tc of LLDPE are not much affected by the presence of COC in LLDPE/COC blends. The results obtained such as melting temperature, enthalpy and crystallization temperature are reported in Table 4.3, refer Appendix B. The intensity of the endothermic peak related to the melting of the crystalline regions of LLDPE is higher than blend with amorphous COC because of cyclic structure of norbornene. It can be seen from the results that about 1 ºC difference in Tm of

L100 C00, L95 C05 and L90 C10 , whereas about 2-3 °C difference in Tm of L85 C15 and L80 C20 blend as compared to L100 C00, L95 C05 and L90 C10. Increase in T m and T c is due to the increasing composition of COC in LLDPE.

Blends: Processing and Thermal properties

Table 4.3 Results obtained from the DSC test of L100 C0, L95 C05, L90 C10, L85 C15 and L80 C20.

Sample Melting Enthalpy Crystallization PE % Crystallinity Temperature T m [°C] Temperature [% X c ] ∆H [J/g] Tc [°C]

1st 2nd 1st 2nd 1st 2nd Heating Heating Heating Heating Heating Heating cycle cycle cycle cycle cycle cycle

L100 C0 122.49 124.45 59.19 44.34 110.20 20.20 15.13

L95 C05 122.79 123.88 53.85 43.19 110.68 19.34 15.51

L90 C10 121.71 123.95 47.84 41.26 110.48 18.14 15.64

L85 C15 125.82 126.70 48.74 37.84 112.55 19.57 15.19

L80 C20 125.16 125.70 44.99 38.95 111.58 19.19 16.36

In the above Table 4.3, % Crystallinity ( Xc) is determined from enthalpy (Please refer appendix B for enthalpy values) using equation 3.1 mentioned in section 3.4.2. Addition of COC in LLDPE results in the slight change in the crystallinity of the blend compared to

L100 C0 [42]. Addition of COC hindered the nucleation process and crystal growth geometries of LLDPE/COC blend. Similar results were found by Kolarik et al. [52] where HDPE crystallinity decreases with addition of COC, because lower compositions of COC accounts for very less change in crystallinity.

In DSC study, T m of the blend shows no major shift as compared to LLDPE after addition COC in the blend. Even though COC is highly amorphous, addition of lower content of COC

(20 wt% and less), crystallinity of the blends is not much affected.

4.5.2 Dynamic Mechanical Analysis

Another thermal properties to analyze thermal transition and viscoelastic behavior of the material are studied by dynamic mechanical analysis. The dynamic mechanical properties, that is, storage modulus (E '), loss modulus (E '' ) and damping (Tan δ) v/s temperature graph for L100 C0, L95 C05 , L90 C10 , L85 C15 , L80 C20 and L0C100 are shown in Fig. 4.11 to Fig. 4.16.

Study of Thermal Properties

The temperature of -120 to +120°C was selected for the DMA analysis, because phase transitions of LLDPE and COC occurs in this temperature range.

Storage modulus indicates the capacity of material to store the input mechanical energy. Higher the G' means higher strength or mechanical rigidity. At very low temperature, molecules are tightly compressed. As increase in temperature warming and expansion of molecules occurs, which increases the free volume. This is the gamma transition, T γ. As the temperature and free volume increase continuously, the entire side chains and localized groups of atoms begin to have enough space to move and the material starts developing some toughness. This transition, called the beta transition (T β). As heating continues, the T g, or glass transition, appears when the chains in the amorphous regions begin to coordinate large scale motions. Since the T g only occurs in amorphous material, in a 100% crystalline material there would not be a T g. Continuous heating induces a crystal-crystal slip in crystalline or semi-crystalline polymer, Tα* occurs, which is known as the alpha star transition (Tα*), and there is slippage of the crystallites past each other. Finally, the melt is reached where large- scale chain slippage occurs and the material flows. This is the melting temperature, Tm. Various transition in polymers with respect to temperature are reported in Fig. 1.3 for idealized DMA scan reported in Chapter 1 (section 1.4) [13].

A trend similar to semi crystalline polymer is shown in case of L100 C0 where a continuous decrease in the storage modulus with increasing temperature is observed, because of its semi crystalline nature, the modulus drop is at a slower rate (Fig. 4.11), whereas in case of L0C100 as shown in Fig. 4.12, E' does not decrease continuously with the entire temperature range rather shows a drastic fall around T g (~78 °C) [45].

The value of E ' of L0C100 is higher than that of L100 C0 due to the rigid chain structure of

L0C100 . The storage modulus of L100 C0 is lower than that of L0C100 for temperature above -100 °C and over the whole temperature range, and the difference becomes more significant at higher temperatures due to the rigid chain structure of L0C100 . Fig. 4.13 to Fig. 4.16 represents the individual graph showing thermal transition and viscoelastic behavior by E',

E'' and Tan δ of L95 C05 , L90 C10 , L85 C15 and L80 C20 . All the blend shows similar behavior as

L100 C0 because of high content of LLDPE in the blend as well as COC also contains the ethylene units in its molecular structure.

Blends: Processing and Thermal properties

E' MPa E'' MPa Tan δ L100 C0 7000 600 0.8

Storage Modulus (MPa) 6000 500 Loss Modulus (MPa) 5000 Tan D 0.6 400 4000 300 3000 0.4 200 2000 Storage Modulus (MPa) Modulus Storage 100 1000 0.2

0 0

-1000 -100 0.0 -100 -50 0 50 100 Temp (°C)

Figure 4.11 Effect of temperature on E' , E'' and Tan δ of L100 C0.

E' MPa E'' MPa Tan δ L0C100 7000 1200 2.5 Storage Modulus (MPa) 6000 Loss Modulus (MPa) 1000 Tan D 2.0 5000 800 4000 1.5 600 3000 1.0 2000 400 Storage Modulus (MPa) Modulus Storage 0.5 1000 200

0 0 0.0 -1000 -100 -50 0 50 100 Temp (°C)

Figure 4.12 Effect of temperature on E' , E'' and Tan δ of L0C100 .

Study of Thermal Properties

δ E' MPa L95 C05 E'' MPa Tan 600 0.8 Storage Modulus (MPa) 5000 Loss Modulus (MPa) 500 Tan D 4000 0.6 400 3000 300 0.4 2000 200 Storage Modulus Storage (MPa) 1000 100 0.2

0 0

-1000 -100 0.0 -100 -50 0 50 100 Temp (°C)

Figure 4.13 Effect of temperature on E' , E'' and Tan δ of L95 C05 .

E' MPa E'' MPa Tan δ L90 C10 14000 1200 1.2

12000 Storage Modulus (MPa) Loss Modulus (MPa) 1000 1.0 Tan D 10000 800 0.8 8000 600 0.6 6000 400 4000 0.4 Storage Modulus (MPa) 200 2000 0.2

0 0 0.0 -100 -50 0 50 100 Temp (°C)

Figure 4.14 Effect of temperature on E' , E'' and Tan δ of L90C10 .

Blends: Processing and Thermal properties

δ E' MPa L85 C15 E'' MPa Tan 10000 800 1.5 Storage Modulus (MPa) 8000 Loss Modulus (MPa) Tan D 600 1.0 6000 400 4000 0.5

StorageModulus(MPa) 200 2000

0.0 0 0

-100 -50 0 50 100 Temp (°C)

Figure 4.15 Effect of temperature on E' , E'' and Tan δ of L85 C15.

E' MPa E'' MPa Tan δ L80 C20 1000 1.5 12000 Storage Modulus (MPa) Loss Modulus (MPa) 800 10000 Tan D 1.0 8000 600

6000 400 0.5 4000 Storage Modulus (MPa) Modulus Storage 200 2000 0.0 0 0

-100 -50 0 50 100 Temp (°C)

Figure 4.16 Effect of temperature on E' , E'' and Tan δ of L80 C20 .

Study of Thermal Properties

For better comparison, graphs of E', E '' and Tan δ are shown separately for L100 C0, L95 C05 ,

L90 C10 , L85 C15 , L80 C20 and L0C100 in Fig. 4.17 to Fig. 4.22. In case of blends, the E' for all compositions except L95 C05 , are higher than those of L100 C0 at below 0°C (Fig. 4.17). Above

0°C, the E' is higher for all blends and at all temperatures compared to L100 C0. Remarkable enhancement around 25°C is noticed, where E' of L90 C10 is 2179 MPa as compared to

794 MPa of L100 C0, this is because of a fraction of the stiffer COC component. For L90 C10 ,

L85 C15 and L80 C20 samples, they have almost the same E' at temperature above 0 °C, higher than L100 C0 but lower than L0C100 . Even at 90 °C, E' of L90 C10 is 362 MPa as compared to

20 MPa of L0C100 . Below -100 °C (except for L95 C05 ) and above 80 °C, E' of all blends are higher than that of L0C100 . The storage modulus results of the different samples are in line with the tensile modulus results. Only selective data of E' obtained from the test results are reported in Table 4.4. Data for the temperature range is reported in Appendix C. E' at -120 °C, -25 °C, 0 °C, 25 °C, 50 °C and 90 °C for all blend compositions is mentioned in

Table 4.4 [42]. These temperatures were selected because, T g of LLDPE in the range of

-120 °C and COC has T g close to 80 °C and few points in between have been taken, where some shift has been observed.

14000 L 100 C0 12000 L 95 C05 L 90 C10 10000 L 85 C15 L C 8000 80 20 L 0C100 6000

4000

Storage Modulus (MPa) Storage Modulus 2000

-100 -50 0 50 100 Temp (°C)

Figure 4.17 Storage modulus ( E' ) of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

Blends: Processing and Thermal properties

Enlarged Storage Modulus Graph 8000 L 100 C0

L 95 C05 7000 L 90 C10 L C 6000 85 15 L 80 C20

5000 L 0C100

4000

3000

StorageModulus (MPa) 2000

1000

0 -75 -50 -25 0 25 Temp (°C)

Figure 4.18 Enlarged graph of Storage modulus ( E' ) of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

Loss modulus (E '' ) is a measure of the viscous behavior of the polymeric materials. The peak of E '' corresponds to the commencement of significant segmental movement of the polymeric chain. Fig. 4.19 shows the variation of loss modulus as a function of temperature for all blend compositions. The loss modulus peak at about -120, -25 and 40°C corresponds to γ-transition, β-transition, and α-transition, respectively for LLDPE. The γ- peak at about -120°C corresponds to local molecular mobility in the non-crystalline regions of LLDPE. The β-transition at around -25 °C can be seen as glass transition temperature for LLDPE (Fig 4.20). The α-relaxation peak of LLDPE at about 40°C is associated with some type of molecular motions in crystals and interfacial regions of lamellae.

Due to presence of ethylene units in COC, similar transition peaks can be seen in

LLDPE/COC blends. The 87°C peak corresponds to glass transition (α-transition) of L0C100 , which is also observed by a sharp drop in the storage modulus graph as shown in Fig. 4.17. E'' dependences show regular changes with increasing fraction of COC in blends. The higher loss modulus for L90 C10 and above means lower elastic recovering, which can be attributed to the higher polymer rigidity. As shown in Fig. 4.20, LLDPE/COC blends show elastic response as compared to viscous response of COC.

100

Study of Thermal Properties

1200 L 100 C0

L 95 C05

1000 L 90 C10

L 85 C15 L C 800 80 20 L 0C100 600

400

Loss Modulus (MPa) 200

-100 -75 -50 -25 0 25 50 75 100 Temp. (°C)

Figure 4.19 Loss modulus (E '') of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

Enlarged Loss Modulus Graph 400 L 100 C0

L 95 C05

L 90 C10

L 85 C15

L 80 C20 L C 200 0 100 Loss (MPa) Modulus

0 -50 -25 0 25 50 75 100 Temp. (°C)

Figure 4.20 Enlarged graph of Loss modulus (E '') of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

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Blends: Processing and Thermal properties

2.5 L 100 C0

L 95 C05 2.0 L 90 C10

L 85 C15

1.5 L 80 C20 δ L 0C100

Tan 1.0

0.5

0.0

-100 -50 0 50 100 Temp(°C)

Figure 4.21 Tan δ of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

Enlarged Tan δ Graph 1.0 L 100 C0

L 95 C05

L 90 C10

L 85 C15

L 80 C20 δ L 0C100 0.5 Tan

0.0 25 50 75 100 Temp(°C)

Figure 4.22 Enlarged graph of Tan δ of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

102

Study of Thermal Properties

Fig. 4.21 shows the variation of Tan δ with the temperature for L100 C0, L95 C05, L90 C10, L85 C15,

L80 C20 and L 0C100 . Predictions of the miscibility of polymeric systems using dynamic mechanical investigation have been carried out by various researchers [42] [48]. In blends of any two polymers, the presence of a single T g, which is intermediate between those of the pure polymers confirms the miscibility of the systems. Whereas, if the Tan δ vs. temperature curve shows two peaks corresponding to the T g’s of individual polymers confirms the incompatible system. A highly compatible blend shows only a single peak between the transition temperatures of the component polymers; whereas broadening of the transition occurs in the case of partially compatible systems. Shifted Tg’s are also indicative of partial miscibility [78].

L0C100 shows a sharp peak at about 87°C (Fig. 4.21) which represents the glass transition temperature and is attributed to the micro-brownian motion of amorphous polymer chains.

The peak intensity of the L0C100 varies with respect to their weight fraction in the blend system as shown in Fig. 4.22. Because of the interaction between LLDPE and COC, we get a broad peak for the L0C100 phase in the blends. The broadness of the peaks is an indication of an interaction between the components. There is some interaction between the two polymers on account of the similarity of the structures between LLDPE and COC. COC contains polyethylene segments. Therefore, these segments are compatible with the LLDPE phase. As a result, T g is shifted. In the case of blends, Tan δ shows a single broad peak which represents partial compatibility of the blend components.

Table 4.4 Storage modulus (E') at different temperatures and Tan δ and T g of the L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

Tg E' [MPa] COC Sample Tan δ [ ºC] at -120 ºC -25 ºC 0 ºC 25 ºC 50 ºC 90 ºC Tan δ

L100 C0 6,361 2,115 1,237 794 393 79 0.25 -

L95 C05 4,825 1,955 1,402 1,031 717 163 0.31 80.19

L90 C10 12,375 4,760 3,215 2,179 1,333 362 0.27 88.75

L95 C15 9,418 4,390 3,154 2,277 1,463 275 0.47 87.15

L80 C20 11,712 4,812 3,215 2,229 1,429 365 0.43 85.96

L0C100 5,691 4,864 4,574 4,320 3,895 20 2.34 87.93

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Blends: Processing and Thermal properties

As the compositions of COC in blend is only 5 to 20 wt %, LLDPE/COC blend shows transition behavior similar to the LLDPE material.

After studying thermal properties of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 , DMA study concludes that at lower compositions of COC the LLDPE/COC blend shows partial miscibility the same is confirmed by SEM analysis in Chapter 5, Fig. 5.16. From Table 4.4, it is observed that E' of L 90 C10 is highest amongst all blends at -120 ºC. Also remarkable increase in the storage modulus at room temperature with addition of COC, which will be useful for packaging applications. Overall results reveals that, L90 C10 blend gives good results compared to other blends in lower COC content.

104

Introduction

CHAPTER 5

5 Blends: Mechanical, Morphological and Barrier Properties

Introduction

A goal of the packaging industry has been to provide cost effective means for preserving the materials from aging/oxidation. The plastics are emerging as a rising star of packaging and will play a major role in packaging. Apart from cost and other factors, selection of a polymer for packaging applications requires good barrier properties against water vapor and oxygen. Further, it also requires good mechanical performance and transparency; therefore, polymers are being dominated the packaging industry.

Tensile strength is a measure of a film's resistance to stretching and therefore is an important property to correlate with end-use performance. Tensile modulus gives stiffness of the polymer, which is an important characteristic for packages that need to maintain their shape. The data obtained from mechanical testing will help to identify product quality and quality control checks for materials. Tear strength is one of the important mechanical properties of the material and it measures the force needed to rip a material and to make the crack continue until it fails.

The shelf life of products can be increased by using packaging materials that could control or minimize the permeation of O 2/H 2O towards the internal atmosphere. Barrier properties are mainly correlated with the intrinsic structure of the polymer such as the degree of crystallinity, nature of the polymer, crystalline/amorphous phase ratio, etc. [79]. Measure of barrier properties of plastics plays a vital role for maintaining the quality of the package.

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Blends: Mechanical, Morphological and Barrier Properties

Morphological study of polymers provides information about phase behavior, dispersion of blends and defects on the surface.

Considering the importance of mechanical, barrier and morphological properties in plastic packaging applications the results obtained from these characterizations are discussed and results obtained are reported in this section.

Study of Mechanical Properties

The mechanical properties of film are affected to a greater or lesser extent by all processing variables, through the influence of processing on the molecular orientation in the film and the crystallinity. Because of orientation in the film, the tear and tensile properties are directional and values are quoted for both the Machine Direction (MD) and the Transverse Direction (TD). The tensile strength, tensile modulus, elongation and tear strength for

L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 are shown in Fig. 5.1, 5.2, 5.3 and 5.4, respectively.

35 MD 30 TD

10 Tensile Strength (MPa) Strength Tensile 5

0 L100C0 L95C05 L90C10 L85C15 L80C20

Figure 5.1 Tensile strength of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 .

106

Study of Mechanical Properties

The tensile strength gives information about serviceability for most applications. It can be seen from Fig. 5.1 that the tensile strength of the blend film increases for MD and TD. The tensile strength of the L100 C0 films is higher in the MD than TD, which is attributed to the presence of the long fibril structure [80]. Increase in tensile strength from 15 MPa to

24 MPa for MD and 12 MPa to 19 MPa for TD is observed for L90 C10 blend film. For

L90 C10 , tensile strength increases 60 % in MD & 58 % in TD as compared to L100 C0. Similarly, an increase in tensile strength is observed for other blend compositions also. The results obtained for tensile strength are reported in Table 5.5.

The Tensile modulus of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 film is represented in Fig. 5.2. The tensile modulus of the blend films increases with increasing COC content.

In MD and TD, the tensile modulus for L100 C0 film are 82 MPa and 108 MPa, respectively, while in MD and TD, the tensile modulus for L80 C20 film are 399 MPa and 284 MPa, respectively, as shown in Fig. 5.2. For L90 C10 , tensile modulus increases 194 % in MD and

30 % in TD than L100 C0. A tensile modulus increase is also an agreement with the results obtained for storage modulus as shown in Table. 4.4, where 174 % increase in storage modulus (at 25 °C) is reported after addition of COC for L90 C10 compared to L100 C0. The results obtained for tensile modulus for film samples are reported in Table 5.5.

450 MD 400 TD

350

300

250

200

150

Tensile Modulus (MPa) Modulus Tensile 100

0 L100C0 L95C05 L90C10 L85C15 L80C20

Figure 5.2 Tensile modulus of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 .

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Blends: Mechanical, Morphological and Barrier Properties

The % elongation of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 film is represented in Fig. 5.3.

The addition of stiffened COC accounted for the reduction of % elongation in the L90 C10 blend film approximately 49 % in MD and 18 % in TD as shown in Fig 5.3. After addition of COC in LLDPE, MD elongation shows drastic reduction as compared to TD elongation.

The elongation of the L95 C05, L90 C10, L85 C15, and L80 C20 film lies between the range of L100 C0 and L0C100 and value varies with respect to the COC fraction in the blend [54]. From these results, it is implied that gauge reduction is possible without property loss.

700 MD 600 TD

500

400

300 % Elongation %

200

100

0 L100C0 L95C05 L90C10 L85C15 L80C20

Figure 5.3 % Elongation of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 .

Tear strength, or the ability of the film to withstand any extension of a hole or a slit in the film, is an important property in many film applications. Because of orientation effects, poorly-made films can have the undesirable tendency to split readily once a hole or slit is initiated in the film.

108

Study of Mechanical Properties

700

MD 600 TD

500

400

300

Tear Strength (gm) 200

100

0 L100C0 L95C05 L90C10 L85C15 L80C20

Figure 5.4 Tear strength of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 .

Tear strength of L100 C0, L95 C05, L90 C10, L85 C15, and L80 C20 film in MD and TD is illustrated in Fig. 5.4. As LLDPE showed spherulitic structures with local orientation, L100 C0 has greater tear strength in TD than in MD [22][47]. After addition of COC, MD tear strength is higher than L100 C0 film for all compositions of LLDPE/COC blend film except L80 C20 , whereas tear strength in TD decreases for all compositions of LLDPE/COC blend film as compared to L100 C0 film. As L100 C0 has higher tear strength in the TD than the MD, this makes it difficult to use these materials for applications, where tear in TD is required. After addition of COC into LLDPE, TD tear decreases, which can be used to facilitate easy tear in TD [81].

The results obtained from tear strength reveals that maximum increase (52 %) in MD tear strength is observed for L90 C10 film compared to L100 C0 than all other blends. Depending on the end use application, plastic film is selected as per properties required. Amongst the prepared blends,

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Blends: Mechanical, Morphological and Barrier Properties

Amongst all blends, highest tensile strength and tensile modulus is observed for L80 C20 in both MD and TD , whereas, tear strength is highest for L90 C10 film in MD and for L95 C05 in

TD. L95 C05, L90 C10, L85 C15, and L80 C20 can be used as per strength and stiffness required in end use applications.

FTIR spectroscopic study

FTIR spectroscopy has been applied for blend studies because the physical properties of polymer blends are affected by the structures of the molecular chains. Depending on the nature of the blending, different polymer blends are able to exhibit different types of interactions and configurations [72]. The infrared spectra of L100 C0, L95 C05 , L90 C10 , L85 C15 ,

L80 C20 and L0C100 are shown in Fig. 5.5 to 5.10.

Infrared spectrum of L100 C0:

−1 The infrared spectrum of L100 C0 in the range of 400-4000 cm is shown in Fig. 5.5. The −1 −1 - CH 2 – asymmetric stretching at 2916 cm , symmetric stretching at 2849 cm , bending vibration at 1466 cm −1, and the wagging vibration of C-H at 717 cm −1 were observed [44].

Figure 5.5 IR spectrum of L 100 C0.

110

FTIR spectroscopic study

Table 5.1 Main absorptions of LLDPE in the IR region and their assignment.

Band (cm −1 ) Assignment

2916 CH 2 asymmetric stretching

2849 CH 2 symmetric stretching

1466 Bending deformation

1379 CH 3 symmetric deformation

1304 Twisting deformation

1019 C==C bending

717 Rocking deformation

Infrared spectrum of L0C100 :

-1 The infrared spectrum of L0C100 in the range of 400-4000 cm is shown in Fig. 5.6. COC is copolymerized from ethylene and norbornene, the absorption bands at 2924 cm -1 and 2868 cm -1 are assigned to asymmetric and symmetric stretching vibrations, respectively. IR -1 peak exhibited at 1459 cm corresponds to bending vibrations mode of - CH 2 – group. IR peak at 930 cm -1 and 1254 cm -1 regions are attributed to C-H bending vibration. The absorption peak displayed at 1294 cm -1 region is related to stretching vibration mode of C-C backbone [37][82][83]. The peak around 700-900 cm -1, which can be assigned to the presence of 4 or more CH 2 units of norbornene copolymer in COC, are in good agreement with previous reports. The peak at 1664 cm -1 in the monomer corresponds to the unsaturated C=C bond [84].

111

Blends: Mechanical, Morphological and Barrier Properties

Figure 5.6 IR spectrum of L 0C100.

Table 5.2 Main absorptions of COC in the IR region and their assignment

Band (cm −1 ) Assignment

2924.1 CH 2 asymmetric stretching

2868.2 CH 2 symmetric stretching

1654.9 C=C stretching

1459.3 Bending deformation

1364.2 CH 3 symmetric deformation

1155.5 Wagging deformation

1039.9 C=C bending

930.0 C-H bending

717.5 Rocking deformation

Infrared spectrum of L95 C05, L90 C10, L85 C15 and L 80 C20 :

The infrared spectra of L95 C05, L90 C10, L85 C15 and L80 C20 are shown in Fig. 5.7 to 5.10.

IR spectra of L95 C05, L90 C10, L85 C15 and L80 C20 show the characteristic bands of both L100 C0 −1 and L0C100 . All blends show peaks ranging from 2940–2868 cm , which correspond to

112

FTIR spectroscopic study the -CH stretching mode and a peak at 1466 cm −1 , which correspond to the -CH bending mode. It is also observed that the intensity of absorption peak at 1019 cm −1 (Shown as arrow in Fig. 5.11), which is related to norbornene units ring deformation vibration increases as COC content rises in the LLDPE/COC blends; these are in good conformity with formerly reported results [37].

Figure 5.7 IR spectrum of L 95 C05.

Figure 5.8 IR spectrum of L 90 C10.

113

Blends: Mechanical, Morphological and Barrier Properties

Figure 5.9 IR spectrum of L 85 C15.

Figure 5.10 IR spectrum of L 80 C20.

114

FTIR spectroscopic study

Figure 5.11 Combined IR spectrum of L95 C05, L90 C10, L85 C15 and L80 C20.

Table 5. 3 Main absorptions of L95 C05, L90 C10, L85 C15 and L80 C20 in the IR region and their assignment Band (cm −1 ) Assignment

L95 C05 L90 C10 L85 C15 L80 C20

2918.5 2916.4 2918.5 2918.5 CH 2 asymmetric stretching

2851.4 2849.5 2854.4 2851.4 CH 2 symmetric stretching

1466.7 1466.7 1466.7 1466.7 Bending deformation

1366.1 1379.1 1364.2 1364.2 CH 3 symmetric deformation

1304.6 1304.6 1306.4 1304.6 Twisting deformation

1019.4 1019.4 1019.4 1041.3 C=C bending

719.4 719.4 719.4 719.4 Rocking deformation

COC is copolymer of ethylene and norbornene and due to presence of large ethylene units in it, there is not much change observed after addition of COC in LLDPE.

115

Blends: Mechanical, Morphological and Barrier Properties

X-ray Diffraction study

The XRD patterns of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 are shown in Fig. 5.12.

Data of XRD of all samples are reported in Appendix D.

3000 L100C0 2000

1000 0 3000 L95C05 2000

1000 0 3000 L90C10 2000

1000 0 3000 L85C15

Intensity (a.u.) 2000

1000 0 3000 L80C20 2000

1000 0 3000 L0C100 2000

1000 0 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 2 Theta

Figure 5.12 X ray diffraction graph of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

116

X-ray Diffraction study

L100 C0 and L0C100 show the characteristic diffraction peaks of a semi-crystalline and amorphous structure, respectively. L100 C0 is characterized by 2 θ peaks at 21.52° and 23.86°. COC is characterized by a broad peak at 17.54°, similar results are reported by other researchers[37][56][85]. The XRD pattern of L100 C0 reveals high intensity peaks, which corresponds to the crystalline regions and the low intensity peaks, corresponds to the amorphous regions.

While the LLDPE/COC blends show reduction in the high intensity peaks. This means that the crystallinity of the LLDPE was slightly decreased by addition of COC, due to the presence of the more amorphous COC in the blend [84]. As the composition of COC increases in LLDPE from 5-20 wt % the intensity of the broad peak at 17.5° increases and it is visible in L95 C05, L90 C10, L85 C15 and L80 C20, which is shown by arrow in Fig 5.13. This reveals that the slight change in the crystalline structure of LLDPE is observed after addition of COC, however, drastic changes are not observed, which is confirmed by the % crystallinity results obtained for blends, reported in Table 4.3 in DSC analysis.

4000 1500 L C 3500 0 100 L 80 C20 L C 3000 1000 85 15 L C Intensity 90 10

2500 500 L 95 C05

L 100 C0 2000 10 15 20 2 Theta 1500 Intensity 1000 500 0 -500 0 10 20 30 40 50 60 70 80 90 2 Theta

Figure 5.13 Merged X ray diffraction graph of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 .

117

Blends: Mechanical, Morphological and Barrier Properties

The values of Full Width at Half Maximum (FWHM) for each peak is calculated using Origin Pro software and the crystallite sizes of the film samples are also measured from their XRD peaks using the Scherrer equation (eq. 5.1). The results obtained are reported in Table 5.4.

= (5.1)

Where, β is the half-width of the diffraction peak in radians, K is equal to 0.9, θ is the Bragg angle and λ is the wavelength of the X-rays, λ= 1.54 Å.

Table 5.4 FWHM and Crystal lites size of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 obtained from XRD data. Blend Crystal size (D) 2 Theta Intensity FWHM Compositions in Å 18.53 421.00 8.52 9.44 21.48 2946.00 0.48 167.52 L100 C0 23.79 375.00 0.38 216.44 36.34 109.00 0.48 173.27 18.65 446.00 7.88 10.22 21.48 3155.00 0.47 171.10 L95 C05 23.77 396.00 0.43 187.28 36.33 163.00 0.70 118.72 18.36 537.00 7.53 10.68 21.47 3537.00 0.46 174.15 L90 C10 23.76 470.00 0.44 186.35 36.30 162.00 0.51 162.50 18.46 669.00 7.22 11.15 21.47 3187.00 0.49 165.86 L85 C15 23.77 627.00 0.53 153.67 36.35 149.00 0.82 102.18 18.39 645.00 7.26 11.09 21.45 2729.00 0.49 164.69 L80 C20 23.76 674.00 0.54 150.57 36.27 119.00 0.77 108.86

L0C100 17.54 1553.00 5.08 14.35

118

Study of Barrier Properties

In the case of semicrystalline polymers, the presence of crystallites in the amorphous matrix leads to the different transport properties of gas/vapor molecules compared to amorphous polymers [86][87]. Crystallites are considered to be impenetrable. Penetrant molecules generally enter through the free volume available in the amorphous interlayer separating two crystallites due to segmental mobilities in the amorphous region. There are two processes by which gases and vapors may pass through polymeric materials: a) A pore effect, in which the gases and vapors flow through microscopic pores, pinholes and cracks in the materials. b) A solubility-diffusion effect, in which gases and vapors dissolve in the polymer at one surface, diffuse through the polymer by virtue of a concentration gradient and evaporate at the other surface of the polymer. This solution-diffusion process is also known as “activated diffusion,” and “permeability” [88] .

As reported by Kofinas et al. [87], gas molecules are unable to permeate through the polymer crystallites due to the availability of less volume in that region and a large tortuous path between the crystallites. Thus, the gas permeation into semicrystalline polymers is then confined to the amorphous regions. The reduction in permeability value is proportional to the volume fraction of the crystalline phase [89].

Barrier to the permeation of gas and water vapor is a very important aspect from packaging viewpoint. The mechanism for permeation through a polymer film is that the permeant is absorbed onto the film surface, diffuses through the film, and desorbs on the other side. Fig. 5.14 shows the transport of gas molecules through a polymer film. Melt blending of a COC, which has a high barrier properties should mainly affect the diffusion step, while minor effects are expected on the adsorption and desorption processes [22][90].

119

Blends: Mechanical, Morphological and Barrier Properties

Figure 5.14 Schematic description of the transport of gas molecules through a polymer film .

To study barrier properties of L100 C0, L95 C05, L90 C10, L85 C15 and L 80 C20 films, OTR and

WVTR were measured and the results are reported in Table 5.5. OTR and WVTR of L0C100 was not carried out because L 0C100 film was difficult to prepare, because of its higher stiffness lack of bubble stability is observed. For OTR and WVTR data for L0C100, please refer Appendix D. The pressure on one side of OTR chamber is 1013 mbar (1 bar) above atmospheric pressure and the other side of the chamber is 5x10 -2 mbar. The LLDPE/COC blend film separate these compartments. Similarly for WVTR, the pressure of wet and dry sides are regulated by two independent pressure gauge of 10 5 Pa (1 bar) on both sides and automatic carrier gas supply to the dry side.

It can be seen from the result obtained that there is reduction in OTR and WVTR of all blend compositions after addition of COC. OTR falls to about 33 % and 41 % for L95 C05 and L 90 C10 film, respectively. Similarly, WVTR falls to about 25 % and 31 % for L95 C05 and L 90 C10 film, respectively. We are only discussing about L 95 C05 and L 90 C10 . We are not going to discuss

L85 C15 and L 80 C20 even though we have done analysis on L 85 C15 and L 80 C20 . It is reported by many authors [91][92] that, the reduction in transmission rate after addition of high dense

120

Study of Barrier Properties

COC domains force the gas molecules to follow the longer path as shown in Fig. 5.15 [22] as a tortuous pathway.

Table 5.5 OTR and WVTR of L100 C0, L95 C05, L90 C10, L85 C15 and L80 C20. Thickness Blend Oxygen transmission Water vapor of the rate (OTR), transmission rate film, µm cc/ (m2 * day) (WVTR), gm/ (m2 * 24 hr) L100 C0 7164 16.4

L95 C05 4821 12.3 40±3 L90 C10 4250 11.2

L85 C15 3760 9.3

L80 C20 3575 8.5

Figure 5.15 Illustration of the ‘‘tortuous pathway’’

Morphological study for granules of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L 0C100 was carried out are SEM micrograph for the same are reported in Fig.5.16. Also, SEM micrograph for L 100 C0, L95 C05, L90 C10, L85 C15, and L 80 C20 blend films are reported in Fig. 5.17. LLDPE/COC blend granules and films do not show co-continuous or matrix-droplet type morphology as reported by other researchers [54][93] rather, it shows a relatively good interfacial adhesion between the COC and the LLDPE matrix. However, LLDPE/COC blend films have shown a few cracks on the film surface as observed in Fig. 5.17. Some manufacturing defects having random scratches of a few micrometers can also affect the

121

Blends: Mechanical, Morphological and Barrier Properties

barrier properties of the film. Because of micro cracks, which are formed in the film, they allow oxygen and water vapor to pass through it, so there was a requirement to study the deposit of coating for further improvement in the barrier properties.

(a) (b)

(e) (f)

Figure 5.16 SEM micrographs of granules of (a) L100 C0 (b) L 95 C05 (c) L 90 C10 (d) L85 C15 (e) L80 C20 and (f) L0C100 .

122

Study of Barrier Properties

Methods for achieving high barrier properties of monolayer polymers include deposition of thin metal coating, deposition of oxide films such as silicon oxide (SiO x). So, we have adopted the PECVD process to deposit SiO x coating to improve barrier properties.

(a) (b)

(e)

Figure 5.17 SEM micrographs of films of (a) L100 C0 (b) L 95 C05 (c) L 90 C10 (d) L85 C15 and (e) L80 C20.

123

Blends: Mechanical, Morphological and Barrier Properties

5.5.1 Plasma enhanced PECVD for SiO x coating

The molecular structure of polymer film is found in the form of chains oriented like networks. This structure possesses certain porosity as well as gaps through which gas molecules can easily pass through and reach the packed product. Plasma surface modification, such as cross-linking, coating, etc., also reduces such pores and gaps by forming an even, smooth and almost impermeable layer, thus preventing gas molecules from reaching the packed product. Plasma deposited inorganic coating on polymer substrates has been exploited in recent years as an alternative to metalized polymer for packing applications due to its transparency, recyclability, microwavability and excellent barrier properties[63][94].

In our experiments, we aimed to prevent an ingress of oxygen molecules from

LLDPE/COC blend film surface by deposition of thin SiO x films by PECVD method. Considering the cost of COC (approximately 8-9 times higher than LLDPE), we have attempted to keep COC content smaller to deposit SiO x coating. We have mainly focused on L95 C05 and L 90 C10 . Hence, the OTR and WVTR were measured for SiO x deposited

L95 C05 and L 90 C10 films only. Fig. 5.18 shows the SiO x coating on film surfaces using Hexamethyldisiloxane (HMDSO).

Figure 5.18 SiO x film coating on film surface using HMDSO

Thickness of the film is one of the factors which affect the barrier properties. So, we prepared

60±5 µm thickness film from L95 C05 and L90 C10 blends. OTR and WVTR were also studied

124

Study of Barrier Properties

with film prepared with 60±5 µm thickness. SiO x coating was done on 40±3 µm and

60±5 µm film of L95 C05 and L90 C10 . Table 5.6 represents OTR and WVTR of uncoated and

SiO x coated film with thickness 40±3 µm and 60±5 µm and the data obtained are compared.

As shown in Table 5.6, from the after SiO x coating in L95 C05 film (40±3 µm) about 31 % and

39 % decrease in OTR and WVTR, respectively as compared to uncoated L 95 C05 film.

Whereas for the same film thickness SiO x coated L90 C10 film shows about 34 % and 43 % reduction in OTR and WVTR, respectively as compared to uncoated L 95 C05 film.

Table 5.6 Comparison of OTR and WVTR of SiO x coated and uncoated L95 C05 and L90 C10. Thickness Blend Composition Oxygen Water vapor of the transmission rate transmission rate film, µm (OTR), (WVTR), cc/(m2 * day) gm/(m2 * 24 hr)

40±3 Uncoated L95 C05 4821 12.3

SiO x coating L 95 C05 3340 7.5

Uncoated L 90 C10 4250 11.2

SiO x coating L 90 C10 2811 6.4

60±5 Uncoated L 95 C05 3600 6.0

SiO x coating L 95 C05 2600 3.9

Uncoated L 90 C10 2000 5.0

SiO x coating L 90 C10 1100 3.1

There is remarkable reduction in OTR and WVTR for SiO x coated L95 C05 and L 90 C10 film with 60±5 µm thickness is observed and it is reported in Table 5.6. The OTR value of L95 C05 film reduces 28 % after SiO x coating compared to uncoated L95 C05, whereas, OTR value of

L90 C10 film reduces 45 % after SiO x coating compared to uncoated L 90 C10 . Similarly, WVTR decreases 35 % and 38 % after SiO x coating on L 95 C05 and L 90 C10 film, respectively.

SEM analysis is also carried out to study the deposition of SiO x coating on film surfaces. In comparison to 40±3 µm film (Fig. 5.17), less defects and cracks were observed for 60±5 µm

125

Blends: Mechanical, Morphological and Barrier Properties

films (Fig. 5.19 (a) and (b)). This is responsible for the further improvement in barrier properties for uncoated 60±5 µm thickness films than 40±3 µm thickness film.

Also, SiO x coating deposited on the surface has filled the cracks (as seen from Fig. 5.19) causing substantial improvement in OTR and WVTR.

(a) (b)

(e) (f)

Figure 5.19 SEM micrograph of (a) L95 C05 (60±5 µm film) (b) L90 C10 (60±5 µm film) (c) SiO x coated

L95 C05 (40±3 µm film) (d) SiO x coated L90 C10 (40±3 µm film) (e) SiO x coated L95 C05 (60±5 µm film)

(f) SiO x coated L90 C10 (60±5 µm film).

126

Study of Barrier Properties

The obtained results are of great importance due to the possibility of getting better barrier properties of a monolayer polyolefinic film by varying the COC content within 5–10 wt% using already established processing equipment and conditions, while moderately affecting the cost of the product and facilitating end-use recycle. This improvement in barrier properties is attributed to highly cross-linked, pinhole free/ dense, hydrophobic coating of

SiO x on LLDPE/COC blend film samples. Overall barrier studies reveals that, L90 C10 film gives higher reduction in OTR and WVTR after SiO x coating as compared to L95 C05 and

L100 C0.

5.5.2 Experimental demonstration to study barrier properties of blend films

Controlling the permeability to oxygen and moisture are major challenges to preserve the quality of food products because the presence of oxygen facilitates microbial growth, increases oxidative reactions, and induces the development of off-flavor and color changes. For example, the variation in color produced during the storage of fruit juices can be related to the deterioration of the nutritional and organoleptic properties of the food product.

To investigate the barrier properties of plastic film prepared from LLDPE/COC blends, an oxidation process in bananas was manually examined for six days and results obtained are illustrated in Fig. 5.20. All the bananas taken for examination were from the same bunch. Single banana was packed in L100 C0, L95 C05 , L90 C10 , L85 C15 and L80 C20 films using plastic film bag sealing machine available at the grocery shop. The plastic wrap helps contain ethylene gas, which bananas produce naturally while they ripen. Without the plastic wrap, the ethylene gas spreads to other parts of the fruit, helping it ripen faster. So basically, you're trapping the gas in order to prevent it from speeding up the ripening process. This method will not completely stop bananas from ripening, but it will slow the process down.

According to the findings, when COC is added in LLDPE, the barrier properties of the LLDPE/COC film increase steadily as compared to LLDPE. This results states that after the addition of COC, progressive improvement in the barrier properties of LLDPE film has been observed as compared to LLDPE. It can be seen from Fig. 5.22 that on the

127

Blends: Mechanical, Morphological and Barrier Properties

6th day, the ripening rate of bananas is reduced as compared to LLDPE, even for small amounts of COC added in LLDPE such as L90 C10 .

DAY 0DAY

AFTER DAY 1 AFTER DAY

128

Study of Barrier Properties

AFTER DAY 2 AFTER DAY

AFTER DAY 3 AFTER DAY

129

Blends: Mechanical, Morphological and Barrier Properties

AFTER DAY 4 AFTER DAY

AFTER DAY 5 AFTER DAY

Figure 5.20 Oxidation process in banana without film, with LLDPE and all compositions of LLDPE/COC film (A-without film; B- L100 C0; C- L95 C05 ;D - L90 C10 ; E- L85 C15 ; F- L80 C20 )

130

Study of Barrier Properties

(a) Without Film (b) L100 C0 Film (c) L90 C10 Film

CONDITION ON DAY 6

th Figure 5.21 Condition on 6 day (a) Banana without film (b) Banana packed in L100 C0 film and (c) Banana packed in L90 C10 film

131

Blends: Mechanical, Morphological and Barrier Properties

Outcomes with respect to objectives

The aim of the project was to prepare polymer blends from LLDPE and COC and study their thermal, mechanical and barrier properties.

Overall objectives of the presented studies were as followed,

• Preparation of COC and LLDPE blends containing 5, 10, 15 and 20 wt % COC in LLDPE. • Measure Melt Flow Index (MFI) of LLDPE/COC blends with varying content of COC. Evaluation of effectiveness of MFI data to prepare blown film from LLDPE/COC blend. • Analysis of thermal properties of blends by DSC, DMA and study of surface morphology using SEM. • Investigation of mechanical properties such as tensile strength, tensile modulus, % elongation and tear strength etc. • Study of barrier properties of prepared LLDPE/COC blend films using Oxygen Transmission Rate (OTR) and Water Vapor Transmission Rate (WVTR).

• Study of barrier properties of blend films after deposition of SiO x surface coating using Plasma Enhanced Chemical Vapor Deposition (PECVD) method.

With respect to the above mentioned points, we have fulfilled following objectives,

• LLDPE/COC blends were prepared using 5, 10, 15 and 20 wt % COC in LLDPE. • Melt flow index increases slightly with the addition of COC in LLDPE for 190 ºC, 230 ºC and 260 ºC at 2.16 kg and 5 kg load. • Because of the cyclic structure of norbornene, the intensity of the endothermic peak related to the melting of the crystalline regions of LLDPE is higher than that of a

blend with amorphous COC. In comparison to L100 C0, adding COC to LLDPE slightly reduces the crystallinity of the blend. • Enhancement of the storage modulus for all compositions was observed and about

40 % increased for L90 C10 because of a fraction of the stiffer COC component.

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Outcomes with respect to objectives

• Increase in tensile strength and tensile modulus for LLDPE/COC blend film was

observed compared to L100 C0. For L90 C10 , tensile strength increases 60 % in MD &

58% in TD as compared to L100 C0. For L90 C10 , tensile modulus increases 194 % in

MD and 29.63 % in TD than L100 C0. Similarly, for L80 C20, tensile modulus increases

387 % in MD and 163 % in TD than L100 C0. • There is remarkable reduction in OTR and WVTR of LLDPE/COC blend films. Oxygen permeability falls to about 33 % and 41 % by addition of COC composition

as L95 C05 and L 90 C10, respectively. • Water vapor permeability falls to about 25 % and 31 % by addition of COC content

as L95 C05 and L 90 C10, respectively.

• It has been observed that plasma polymerized SiO x coated blend film exhibit superior Oxygen and water vapor barrier properties in comparison to uncoated LLDPE/COC blend film. There is 31 % & 34 % reduction in OTR was observed, when plasma

polymerized HMDSO coating is deposited on L95 C05 and L90 C10 film, respectively as

compared to uncoated L95 C05 and L90 C10 film. Furthermore, It has been observed that

after SiO x coating on 60±5 µm film, the OTR value of L 95 C05 film reduces 28 %

after SiO x coating compared to uncoated L 95 C05, whereas, OTR value of L 90 C10 film

reduces 45 % after SiO x coating compared to uncoated L 90 C10 . Similarly, WVTR

decreases 35 % and 38 % after SiO x coating on L 95 C05 and L 90 C10 film, respectively.

• At has been observed that lower content of COC (10 wt %), i.e., L90 C10 blend has shown optimum barrier, mechanical and thermal properties.

Table 5.5 shows the summary of the results obtained from the characterization of the

L100 C0, L95 C05, L90 C10, L85 C15 and L 80 C20.

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Blends: Mechanical, Morphological and Barrier Properties

8.47 1.15 2.14 3.65 20 3575 0.938 C 125.70 28 / 23 80 399 / 284 236 / 261 233 / 214 L

15 9.37 1.13 2.06 3.23 3760 C 0.933 126.70 26 / 20 85 L 365 / 211 296 / 375 324 / 210

1.11 2.01 2.91 10 4321 11.33 0.927 C 123.95 24 / 19 90 241 / 140 331 / 504 382 / 276 L

1.06 1.92 2.62 05 4821 12.35 0.920 C 123.88 20 / 16 95 134 / 123 466 / 557 L 303 / 331

0 0.93 1.54 2.37

7164 16.41 0.913 C 20 124.45 15 / 12 C 82 / 108 100 80 650 / 616 251 / 471 L and L 15, C 85 .day) .day)

.24 hr) L 2 g 2 % %

°C 10, g/cc MPa MPa C g/10 min g/10 min 90 g/(m cc/(m L Units 05, C 95 L 0, C 100

DSC ASTM D792 ASTM D882 ASTM D882 ASTM D882 ASTM F1249 ASTM F1249 ASTM D1434 ASTM D1238 ASTM D1938 Method

Modulus

5 Typical PropertyValues of L

Table 5. Property Density kg) (2.16 MFI 190 °C 230 °C 260 °C Tensile Strength (MD/TD) Tensile (MD/TD) Elongation break at (MD/TD) Strength Tear (MD/TD) Point Melting MVTR 90%RH) °C, (38 OTR RH) (23°C,50%

*Please refer Appendix E for Data of COC.

134

Conclusion and Future Scope of Work

CHAPTER 6

Conclusion

Conclusion and Future Scope of Work

Cyclic olefin copolymer (COC) has high modulus, thermal stability and superior barrier properties, whereas, LLDPE is one of the widely used plastic material due to its low-cost and good processability. So in the present work, efforts have been made to take the advantage of both the materials, different blends of LLDPE/COC were prepared using blown film extrusion process.

In the present work, a systematic study to prepare Cyclic Olefin Copolymer (COC) and Linear Low Density Polyethylene (LLDPE) blend by varying COC content and using blown film extrusion method is carried out. The prepared blend films are analyzed for surface morphology, change in crystalline and amorphous phases in the blends. Further, how the mechanical and thermal properties of these blends get affected in comparison to the films prepared using 100 % LLDPE. The important point we have considered that mechanical and thermal properties of the blend films should be in appropriate range so that packaging films do not get teared off or elongated. The blend films have been studied for their barrier properties particularly their oxygen transmission rate (OTR) and water vapor transmission rate (WVTR). The focus was to prepare appropriate blends so that barrier films of minimum OTR and WVTR can be obtained for food, pharma and many non-food packaging industries. Therefore, the surface of the blends is coated with plasma polymerized HMDSO (SiO x coating) for further improving the barrier properties of the blended films.

135

Conclusion

The important findings of the present study are mentioned below:

• The first step is to check the processability of the LLDPE/COC blend by MFI. After addition of COC, MFI of LLDPE/COC blends comes under acceptable range (1-5 MFI) for processing using blown film extrusion. Further it has been confirmed experimentally that the LLDPE/COC blend get processed using blown film extrusion.

• DSC results show that melting temperature (T m) and % crystallinity of LLDPE is not much affected by the presence of COC in all the blends prepared in this study. There is

only 1-3 ºC increase in T m and 1-2 % reduction in % crystallinity is observed after addition of COC in LLDPE. This confirms that LLDPE/COC blend can be processed at

the same temperature as LLDPE as T m is not much affected by addition of COC.

• It has been found that above 0°C, the E' (storage modulus) has higher value for all the

blends prepared in comparison to L100 C0. Significant enhancement in E’ value of blend

is observed at around 25 °C where E' of L90 C10 is 2179 MPa as compared to 794 MPa of

L100 C0. This is because of a fraction of the stiffer COC component present in the blend.

Even at 90 °C, E' of L90 C10 is 362 MPa in comparison to 20 MPa of L0C100 . Below

-100 °C (except for L95 C05 ) and above 80 °C, E' of all the blends are higher than that of

L0C100 . For L90 C10 and for higher than 10 % COC content blended films shows stiffness

higher than L100 C0, at low temperature (-120 °C to 0 °C), at room temperature (25 °C) and at higher temperature (above 50 °C).

• In Tan δ graph, a large area under the curve for L0C100 compared to L100 C0 indicates a great degree of molecular mobility, which translates into better damping properties. It means that the material can better absorb and dissipate energy. Presence of a single peak in a Tan δ graph suggests good compatibility of LLDPE and COC polymers in LLDPE/COC blends.

• Addition of COC increases tensile strength in MD and TD and reduction in elongation for MD and TD, which is due to the presence of norbornene in COC that restrict the

136

Conclusion and Future Scope of Work

polymer chain to elongate. For L90 C10 , tensile strength increases 60 % in MD & 58% in

TD as compared to L100 C0.

• For L90 C10 , tensile modulus increases 194 % in MD and 29.63 % in TD than L100 C0.

Similarly, for L80 C20, tensile modulus increases 387 % in MD and 163 % in TD than

L100 C0. Tensile modulus increases as the COC content increases in LLDPE, similar results are seen in case of storage modulus determined using DMA, which is due to presence of stiffened COC components.

• As we know that, tensile strength is an indication of how much stress a plastic can withstand without breaking when it is stretched or pulled. On the other hand, the stiffness of plastic is the ability of the material to distribute a load and resist deformation or deflection. These properties are often needed in conjunction with one another in demanding applications. COC significantly enhances the stiffness of LLDPE film when used as a blend component, which greatly improves the performance of LLDPE/COC blend bags, pouches and other packaging. This occurs even at low addition of COC content in the blend. The added stiffness allows down gauging to thinner and less costly

film structures. These means that L100 C0 having low tensile modulus compared to LLDPE/COC blends and therefore, a relatively thick film must be used to obtain a higher strength bags. After addition of COC in LLDPE, the opposite is true. LLDPE/COC blend has better mechanical strength so a thinner films can be used.

• OTR reduces to about 33 % and 41 % by addition of COC in blends having composition

as L95 C05 and L 90 C10, respectively. WVTR reduces to about 25 % and 31 % by addition

of COC in blends having composition as L95 C05 and L 90 C10, respectively. Therefore, the study reveals that by increasing the content of COC (wt %) results in a progressive decrease of OTR and WVTR with respect to LLDPE.

• LLDPE /COC blend films have a few cracks on their surface. By depositing SiO x coating using PECVD method we made an attempt to fill these cracks and get better barrier

properties. SiO x coating has crosslinked structure and the modified blend films have shown substantial improvement in barrier properties.

137

Conclusion

• The results reveal that in comparison to uncoated L95 C05 blend film, after the deposition

of SiO x coating on L 95 C05 film (thickness 40±3 µm), about 31% and 39% reduction in

OTR and WVTR takes place respectively. Whereas for the same film thickness L 90 C10 film shows about 34 % and 43% reduction in OTR and WVTR respectively.

• Further, it has been observed that the OTR value reduces 28% in the case of SiO x coated

L95 C05 blend film of higher thickness (60±5 µm) in comparison to uncoated L 95 C05,

whereas, OTR value of L 90 C10 film reduces 45% after SiO x coating compared to uncoated

L90 C10 . Similarly, WVTR decreases 35% and 38% after SiO x coating on L 95 C05 and

L90 C10 film, respectively as compare to uncoated blend films. Therefore, it is very clear

that plasma polymer coating of HMDSO (SiO x coating) on blends substantially improves barrier properties.

• In summary, addition of a minor quantity of COC to LLDPE matrix results in the significant improvement of thermal, mechanical and barrier properties of the LLDPE/COC blended films. Considering processing and cost, which significantly important along with all the properties studied, addition of 10 % COC in LLDPE is adequate in getting superior properties.

• In future, attempts can be made to further reduce the compositions of COC in LLDPE

blend and the blend will be coated with SiO x coating to make the packaging film cost effective. Further, the addition of nano-filler for improving barrier properties without drastically affecting mechanical and thermal properties can be studied in future. In addition, performance of LLDPE/COC film on non-food application can also be studied in future to explore other possible applications of these blends.

138

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147

List of Publications

8 List of Publications

1. H. C. Shah , S. K. Nema , “Investigation of Thermal and Melt rheological properties of Linear Low Density Polyethylene/Cyclic olefin copolymer blends”, International Journal for Research in Engineering Application & Management, Vol-04, Issue-11, Feb 2019. ISSN : 2454-9150 (UGC Approved Journal)

2. H. C. Shah , S. K. Nema , “The Effect of Cyclic Olefin Copolymer Loading on Linear Low Density Polyethylene Blends: Characterization by Fourier-Transform Infrared Spectroscopy and X-Ray Diffraction”, International Journal of Scientific & Technology Research Volume 8, Issue 08, August 2019. ISSN 2277-8616 (UGC Care list Journal)

3. H. C. Shah and S.K Nema , “An alternative to PVC in Medical and Pharmaceutical Packaging Applications,” International conference on Advancement in Polymeric Materials (APM) 2016, Ahmedabad.

4. Hetal Shah, Purvi Dave, Sudhir Kumar Nema , “ Mechanical, dynamic mechanical, barrier and morphological properties of LLDPE/COC blends”, (To be submitted in UGC Care list Journal)

148

Appendix A

9 Appendix A

MFI Values of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100 (05 sample of each blend extruded is weighted and average of the mass extruded is used to calculate MFI)

Temperature mass of the material extruded (g) Average (°C), Blend MFI= Load (kg) mass, m and Time t Compositions (600 * m)/t w1 w2 w3 w4 w5 (g) (sec)

L100 C0 0.0157 0.0154 0.0151 0.0158 0.0158 0.0156 0.93

L95 C05 0.0175 0.0172 0.0178 0.0182 0.0177 0.0177 1.06 190 °C & 2.16 kg L90 C10 0.0189 0.0181 0.0190 0.0184 0.0183 0.0185 1.11

For L85 C15 0.0192 0.0186 0.0193 0.0185 0.0185 0.0188 1.13 t=10 sec L80 C20 0.0192 0.0189 0.0195 0.0194 0.0189 0.0192 1.15

L0C100 0.0305 0.0299 0.0302 0.0296 0.0298 0.0300 1.80

Temperature mass of the material extruded (g) Average (°C), Blend MFI= Load (kg) mass, m Compositions and Time t w1 w2 w3 w4 w5 (g) (600 * m)/t (sec) L100 C0 0.0465 0.0454 0.0467 0.0465 0.0471 0.0464 2.79

L95 C05 0.0473 0.0459 0.0466 0.0469 0.0469 0.0467 2.80 190 °C & 5.00 kg L90 C10 0.0485 0.0497 0.0486 0.0504 0.0502 0.0495 2.97

For L85 C15 0.0508 0.0520 0.0511 0.0517 0.0522 0.0516 3.09 t=10 sec L80 C20 0.0533 0.0531 0.0537 0.0540 0.0529 0.0534 3.20

L0C100 0.0859 0.0855 0.0857 0.0846 0.0851 0.0854 5.12

Temperature mass of the material extruded (g) (°C), Blend MFI= Load (kg) Average and Time t Compositions w1 w2 w3 w4 w5 mass, m (600 * m)/t (sec) (g)

L100 C0 0.0250 0.0263 0.0261 0.0257 0.0254 0.0257 1.54

230 °C & L95 C05 0.0316 0.0313 0.0326 0.0320 0.0322 0.0319 1.92 2.16 kg L90 C10 0.0337 0.0339 0.0329 0.0332 0.0341 0.0336 2.01 For t=10 sec L85 C15 0.0352 0.0348 0.0352 0.0332 0.0335 0.0344 2.06 L80 C20 0.0359 0.0371 0.0340 0.0365 0.0352 0.0357 2.14

L0C100 0.1832 0.1858 0.1823 0.1862 0.1843 0.1844 11.06

149

Appendix A

Temperature mass of the material extruded (g) Average (°C), Blend MFI= Load (kg) mass, m Compositions and Time t w1 w2 w3 w4 w5 (g) (600 * m)/t (sec) L100 C0 0.0831 0.0837 0.0830 0.0833 0.0826 0.0831 4.99

L95 C05 0.0929 0.0916 0.0936 0.0928 0.0953 0.0932 5.59 230 °C & 5.00 kg L90 C10 0.0976 0.0991 0.1018 0.0989 0.1011 0.0997 5.98

For L85 C15 0.1062 0.1038 0.1045 0.1034 0.1054 0.1047 6.28 t=10 sec L80 C20 0.1129 0.1139 0.1144 0.1157 0.1137 0.1141 6.85

L0C100 0.4962 0.5021 0.4897 0.5005 0.4978 0.4973 29.84

Temperature mass of the material extruded (g) Average (°C), Blend MFI= Load (kg) mass, m Compositions and Time t w1 w2 w3 w4 w5 (g) (600 * m)/t (sec)

L100 C0 0.0396 0.0384 0.0378 0.0406 0.0414 0.0396 2.37

260 °C & L95 C05 0.0433 0.0445 0.0438 0.0431 0.0440 0.0437 2.62 2.16 kg L90 C10 0.0499 0.0480 0.0485 0.0476 0.0485 0.0485 2.91 For t=10 sec L85 C15 0.0537 0.0529 0.0546 0.0532 0.0544 0.0538 3.23 L80 C20 0.0604 0.0613 0.0599 0.0611 0.0617 0.0609 3.65

L0C100 0.4880 0.4912 0.4919 0.4892 0.4908 0.4902 29.41

Temperature mass of the material extruded (g) Average (°C), Blend MFI= Load (kg) mass, m Compositions and Time t w1 w2 w3 w4 w5 (g) (600 * m)/t (sec) L100 C0 0.1228 0.1192 0.1207 0.1212 0.1218 0.1211 7.27

L95 C05 0.1380 0.1375 0.1368 0.1387 0.1377 0.1377 8.26 260 °C & 5.00 kg L90 C10 0.1458 0.1466 0.1471 0.1482 0.1469 0.1469 8.82

For L85 C15 0.1705 0.1715 0.1696 0.1678 0.1694 0.1698 10.19 t=10 sec L80 C20 0.1830 0.1856 0.1848 0.1843 0.1865 0.1848 11.09

L0C100 0.9979 1.1039 0.9988 1.1042 0.9966 1.0403 62.42

150

Appendix B

10 Appendix B

Data of Tm, Tg and ∆H obtained from DSC Graph of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100.

DSC Graph of L100 C0

DSC Graph of L95 C05

151

Appendix B

DSC Graph of L90 C10

DSC Graph of L85 C15

152

Appendix B

DSC Graph of L80 C20

DSC Graph of L0C100

153

Appendix C

11 Appendix C

Data of Storage Modulus from -120 ºC to +120 ºC of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100

Temp Storage modulus (MPa) (°C) L100 C0 L95 C05 L90 C10 L85 C15 L80 C20 L0C100 -122.094 4938.76 4881.31 12820.2 9697 11971.7 5774.48 -121.845 6399.16 4875.39 12560.9 9562.9 11886.1 5703.72 -120.748 6361.19 4824.89 12374.9 9418.12 11712.1 5691.49 -119.706 6309.24 4773.98 12205.5 9363.83 11601.4 5669.94 -118.937 6253.67 4705.6 12115 9235.52 11484.5 5617.23 -117.683 6175.93 4656.66 11951.4 9103.36 11383.2 5535.74 -116.835 6109.61 4579.8 11777.1 8973.56 11187.2 5522.81 -115.923 6029.69 4493.25 11622 8910.87 11062 5498.54 -114.98 5955.98 4439.68 11466.6 8776.03 10972.3 5447.49 -113.63 5841.28 4369.76 11386.4 8655.76 10857.6 5424.25 -112.69 5765.7 4318.58 11195.4 8514.19 10733.2 5368.83 -111.808 5676.93 4226.18 11060.3 8391.09 10538.2 5353.71 -110.86 5579.89 4156.53 10801.4 8293.62 10404.7 5276.27 -109.86 5505.65 4098.76 10651 8184.13 10300.9 5237.76 -108.945 5426.65 4028.06 10509.8 8074.95 10194.3 5189.09 -107.999 5345.79 3965.66 10366.6 7975.23 10105.5 5154.57 -106.538 5225.13 3918.57 10218.5 7867.96 9790.53 5122.91 -105.601 5150.1 3853.79 10097.4 7776.8 9713.87 5096.35 -104.606 5082.37 3808.9 9958.09 7686.7 9560.57 5050.06 -103.641 4999.1 3775.26 9864.88 7610.72 9456.14 5027.74 -102.673 4935.07 3716.68 9767.02 7530.05 9283.85 5002.8 -101.65 4857.14 3683.06 9615.31 7435.5 9245.01 5003.07 -100.648 4801.5 3628.3 9476.9 7331.99 8937.88 4954.58 -99.6391 4726.29 3591.15 9463.75 7292 8824.89 4938.56 -98.6407 4670.79 3550.75 9342.25 7181.78 8665.44 4919.96 -97.6471 4595.38 3512.92 9262.04 7118.03 8570.34 4882.85 -96.6117 4553.07 3481.2 9177.88 7055.93 8484.8 4878.28 -95.5874 4483.63 3451.27 9138.5 7012.73 8405.95 4848.91 -94.575 4432.72 3429.98 8995.41 6883.94 8303.46 4811.69 -93.5473 4392.13 3395.05 8920.61 6834.55 8230.67 4812.89 -92.5831 4336.03 3358.12 8814.17 6762.42 8161.21 4770.37 -91.5764 4295.1 3342.29 8767.89 6672.97 8054.2 4785.67 -90.5451 4256.59 3313.36 8648.07 6671.13 7993.83 4767.13 -89.4849 4199.6 3305.86 8582.98 6628.21 7965.62 4771.91 -88.9561 4170.78 3280.38 8476.7 6536.49 7912.41 4744.58 -87.9068 4113.48 3251.35 8466.58 6425.51 7821.88 4751.18 -86.8511 4092.19 3220.64 8363.87 6405.9 7795.18 4733.97 -85.7995 4044.39 3207.22 8277.01 6331.92 7773.87 4711.32 -84.7537 4001.96 3184.85 8170.5 6331.65 7722.17 4709.96 -83.6629 3968.14 3156.57 8098.02 6247.46 7666.99 4688.86 -82.5736 3922.79 3145.52 8047.99 6200 7644.76 4699.76 -81.512 3879.28 3118.45 7972.64 6135.7 7542.27 4698.43 -80.9594 3870.44 3083.23 7927.86 6119.93 7472.9 4708.3

154

Appendix C

-79.839 3826.17 3072 7876.15 6038.58 7440.58 4685.42 -78.7677 3788.33 3042.2 7767.24 6021.07 7377.84 4668.71 -77.6717 3757.96 3022.09 7682.76 5964.87 7348.75 4661.59 -76.6001 3708.28 3013.81 7614.49 5916.83 7268.77 4669.72 -75.5324 3675.58 2990.03 7584.03 5909.44 7208.22 4674.98 -74.4722 3644.9 2954.52 7522.95 5863.86 7173.06 4655.07 -73.9452 3633.66 2940.9 7465.27 5842.14 7135.46 4651.37 -72.9117 3582.55 2914.4 7387.03 5806.25 7066.1 4636.46 -71.8674 3546.78 2890.14 7357.02 5797.22 7030.7 4629.96 -70.8564 3534.23 2877.52 7289.1 5822.99 6983.05 4635.91 -69.776 3485.77 2858.42 7272.46 5788.63 6972.8 4643.71 -68.7701 3460.72 2832.79 7227.76 5773.06 6866.56 4636.39 -67.7153 3421.48 2810.41 7141 5773.17 6834.61 4613.95 -66.6647 3394.6 2786.01 7099.51 5749.18 6804.52 4626.89 -65.637 3356.98 2794.13 7065.26 5758.19 6740.3 4634.88 -64.615 3339.01 2769.44 7027.73 5726.76 6740.3 4633.88 -63.5236 3317.8 2755.13 6926.28 5698.42 6723.36 4626.26 -62.9825 3292.38 2728.7 6916.41 5697.94 6699.26 4630.42 -61.9323 3262.32 2712.09 6837.14 5682.54 6627.84 4620 -60.8573 3248.17 2690.46 6804.87 5672.65 6575.95 4613.6 -59.7582 3215.42 2681.71 6748.54 5632.53 6537.15 4609.03 -58.654 3170.72 2654.63 6723.74 5624.4 6506.71 4594.4 -57.4907 3143.75 2646.24 6650.06 5604.24 6474.37 4611.12 -56.9038 3139.3 2605.52 6630.37 5580.65 6457.9 4611.55 -55.7528 3104.41 2598.72 6568.59 5565.44 6431.48 4602.11 -54.5187 3075.79 2575.05 6510.78 5547.61 6394.25 4584.23 -53.9091 3042.19 2566.68 6486.83 5524.75 6347.87 4589.6 -52.6515 3007.61 2541.47 6412.88 5489.18 6331.78 4568.77 -51.3675 2977.6 2532.47 6387.71 5469.31 6226.38 4580.38 -50.683 2943.34 2513.3 6324.45 5437.14 6164.64 4586.47 -49.3767 2925.21 2502.65 6268.45 5422.42 6127.38 4561.64 -48.716 2899.65 2470.59 6253.25 5403.8 6079.16 4574.18 -47.4193 2867.47 2468.01 6193.7 5374.98 6030.73 4572.16 -46.762 2843.57 2441.02 6138.73 5362.16 5970.87 4569.24 -45.4727 2813.95 2421.08 6109.46 5322.38 5940.65 4575.45 -44.8456 2791.43 2415.61 6029.64 5263.91 5885.22 4613.39 -43.5893 2759.22 2390.18 6005.27 5248.2 5855.47 4632.42 -42.9858 2732.16 2362.31 5914.02 5203.76 5790.83 4680.1 -41.7558 2686.69 2345.11 5875.59 5155.63 5742.13 4671.66 -40.5364 2643.8 2328.11 5817.5 5142.9 5692.68 4718.16 -39.9237 2627.13 2292.43 5759.23 5078.66 5632.95 4745.43 -38.7333 2581.05 2288.21 5706.99 5039.11 5566.33 4739.37 -37.5596 2539.1 2255.5 5636.08 5000.93 5509.87 4773.95 -36.9556 2526.11 2224.66 5563.79 4963.47 5452.14 4807.56 -35.7401 2486.3 2206.67 5482.87 4927.57 5399.02 4849.85 -34.5452 2447.8 2184.24 5420.78 4853.82 5350.35 4871.91 -33.9501 2417.69 2157.28 5328.65 4831.78 5290.89 4889.62 -32.7515 2380.85 2133.72 5263.98 4792.09 5270.01 4898.59 -31.6025 2336.86 2110.83 5191.17 4737.43 5227.46 4916.18 -30.4414 2294.68 2072.38 5109.85 4678.53 5171.13 4903.91 -29.8682 2268.92 2058.71 5047.25 4622.83 5083.64 4900.13 -28.7588 2224.77 2026.9 4946 4563.56 5006.81 4892.72 -27.6309 2179.45 2002.95 4907.85 4493.7 4951.23 4880.06

155

Appendix C

-26.5243 2136.42 1986.87 4802.67 4433.32 4901.07 4883.26 -25.9724 2114.77 1955.23 4760.03 4389.68 4812.42 4863.53 -24.8917 2080.18 1931.29 4654.8 4337.75 4747.59 4836.42 -23.8264 2029.15 1898.51 4568.42 4265.39 4701.64 4815.82 -22.7506 1990.25 1885.45 4474.05 4210.17 4580.74 4803.18 -21.6922 1946.41 1857.24 4386.35 4178.54 4488.07 4776.86 -20.6293 1906.3 1835.92 4344.49 4114.05 4431.1 4750.07 -19.5677 1865.33 1810.12 4259.76 4043.6 4431.1 4722.42 -18.5475 1835.61 1795.25 4165.16 4016.46 4373.38 4715.74 -17.5304 1794.41 1773.57 4125.82 3945.33 4305.47 4688.36 -16.5135 1754.93 1743.15 4039.2 3924.4 4258.04 4679.54 -15.5032 1723.41 1722.17 4006.51 3847.16 4198.55 4679.84 -14.9848 1708.32 1697.29 3918.37 3830.92 4129.12 4688.26 -13.9233 1672.57 1675.49 3874.72 3780.07 4083.85 4677.61 -12.8497 1636.63 1651.32 3801.44 3706.66 4030.03 4669.51 -11.7274 1600.09 1626.17 3778.42 3688.83 3973.64 4662.62 -10.625 1567.76 1620.54 3728.96 3633.02 3956.6 4648.27 -9.49329 1536.25 1590.45 3690.55 3599.72 3920.09 4650.78 -8.92062 1516.6 1568.03 3669 3547.27 3873.14 4643.13 -7.79837 1480.02 1544.67 3642 3521.72 3831.97 4629.46 -6.65567 1448.93 1532.33 3573.93 3462.5 3775.09 4629.55 -5.46869 1412.42 1513.14 3545.9 3438.41 3718.02 4621.21 -4.89073 1394.53 1499.28 3469.92 3391.16 3646.07 4609.66 -3.65997 1366.11 1489.55 3439.92 3361.03 3582.93 4603.12 -2.45457 1329.03 1469.9 3378.82 3304.49 3510.85 4594.22 -1.86205 1314.76 1460.04 3322.7 3251.01 3439.04 4580.12 -0.62479 1279.22 1441.17 3298.97 3191 3297.93 4579.59 1.23435 1236.7 1402.38 3215.16 3153.59 3214.92 4573.65 2.49182 1208.08 1387.27 3161.68 3132.75 3139.43 4571.53 3.12446 1191.15 1362.78 3126.76 3092.29 3083.58 4567.85 4.78766 1148.72 1343.51 3067.15 3049.05 2988.16 4558.27 5.42025 1144.83 1324.57 3016.78 3004.1 2927.6 4553.64 6.05833 1129.74 1304.26 2991.08 2984.69 2901.35 4542.74 7.3064 1105.9 1284.96 2946.82 2936.87 2853.13 4529.27 8.58793 1079.35 1277.25 2919.5 2887.71 2822.13 4512.79 9.21362 1069.48 1257.72 2874.51 2865.1 2804.79 4499.39 10.45018 1043.06 1237.95 2822.69 2821.76 2804.79 4486.73 11.0733 1031.9 1218.99 2776.49 2776.33 2766.79 4483.31 12.33112 1010.16 1210.32 2754.18 2736.82 2709.31 4466.98 13.57606 983.678 1192.18 2707.04 2716.85 2649.89 4462.24 14.20433 972.834 1177.21 2659.2 2674.45 2586.68 4451.01 15.457 950.964 1165.09 2611.79 2624.27 2520.3 4439.79 16.08656 939.159 1149.13 2566.14 2602.42 2497.72 4422.46 17.35101 916.851 1139.04 2536.52 2559.16 2459.76 4425.1 18.15435 903.951 1124 2487.26 2525.26 2422.35 4406.11 19.42335 882.324 1104.82 2438.84 2486.8 2378.68 4391.69 20.05418 869.988 1095.55 2412.36 2451.98 2356.74 4386.46 21.36392 850.65 1078.89 2363.45 2434.64 2336.59 4373.3 22.02404 840.293 1069.12 2319.01 2393.19 2309.99 4359.54 23.38565 822.202 1050.69 2270.03 2353.88 2295.66 4342.51 24.048 812.192 1043.5 2223.21 2317.14 2252.83 4336.5 25.35666 794.459 1031.47 2178.62 2276.82 2228.81 4320.17 26.00546 785.161 1014.71 2134.68 2234.65 2198.02 4293.59

156

Appendix C

27.26413 767.138 1005.34 2091.19 2218.56 2164.39 4285.3 28.46483 750.395 986.675 2068.57 2185.32 2140.36 4274.99 29.06304 740.418 979.448 2024.56 2150.66 2105.83 4255.89 30.21807 724.765 967.436 1979.2 2118.8 2084.71 4241.07 31.32889 708.198 963.63 1936.49 2086.24 2049.01 4225.07 32.41065 693.97 949.994 1914.77 2071.05 2024.69 4208.64 33.47075 676.671 942.723 1873.86 2035.33 1983.7 4196.48 34.01549 667.62 929.071 1832.76 2005.19 1959.16 4163.26 35.06221 651.25 920.51 1812.93 1973.12 1927 4143.91 36.08756 635.808 907.149 1775.77 1955.13 1915.83 4123.43 37.12746 620.207 893.33 1735.22 1921.33 1895.19 4108.71 38.13816 604.245 881.336 1715.62 1886.87 1877.57 4079.72 39.14917 587.404 863.344 1678.85 1849.94 1850.56 4056.56 40.16518 569.82 855.24 1660.23 1829.59 1813.77 4031.84 41.19993 552.009 842.766 1621.2 1789.63 1775.58 4002.32 42.22968 533.781 828.746 1581.54 1749.67 1740.69 3988.83 43.24819 512.016 816.559 1562.3 1729.55 1704.68 3967.58 44.34387 494.896 802.257 1525.02 1688.54 1627.16 3949.19 45.49078 468.712 788.108 1504.95 1647.53 1588.2 3941.8 46.06408 464.862 770.34 1466.3 1605.44 1557.68 3930.97 47.15101 441.685 756.255 1425.13 1584.08 1535.78 3920.01 48.27387 431.756 749.474 1405.42 1543.56 1517.24 3908.93 49.32492 410.149 733.075 1367.63 1503.36 1462.63 3904.62 50.44549 393.127 717.01 1333.4 1463.38 1428.66 3895.13 51.47087 369.534 700.318 1308.04 1441.58 1395.03 3888.09 52.52174 347.666 682.701 1291.7 1405.18 1358.37 3878.71 53.06045 334.396 666.203 1279.6 1372.81 1284.76 3869.61 54.09831 312.765 649.19 1262.6 1339.38 1245.24 3857.49 55.18067 301.678 635.999 1239.71 1303.5 1212.08 3844.81 56.24573 291.905 622.948 1214.21 1269.46 1171.15 3837.26 57.26004 281.758 613.303 1183.83 1235.23 1106.55 3821.39 58.29915 272.253 597.673 1151.63 1204.07 1076.67 3806.87 59.34072 262.964 583.704 1117.64 1173.67 1049.91 3791.46 60.41594 253.861 569.944 1083.82 1158.54 1024.39 3777.48 61.42448 244.951 554.685 1050.77 1129.15 985.435 3765.87 62.42162 235.767 540.487 1018.86 1099.37 970.078 3757.63 63.48294 227.862 526.109 988.389 1069.73 954.12 3747.64 64.00327 223.504 512.835 958.014 1040.32 942.399 3739.96 65.03971 215.619 499.547 929.299 1012.78 881.031 3733.02 66.02855 206.617 485.49 900.383 983.371 833.928 3718.94 67.02757 198.329 471.471 870.39 955.384 817.902 3703.78 68.0272 190.055 458.241 842.462 927.105 811.729 3671.71 69.01752 184.527 443.656 815.341 899.277 796.354 3633.21 70.03485 180.327 437.604 788.2 870.137 779.645 3582.38 71.05249 175.843 424.527 775.608 842.632 763.222 3503 72.07105 169.79 411.231 749.417 815.797 736.219 3403.08 73.08563 166.171 398.528 724.314 788.15 720.498 3254.85 73.60337 163.319 385.284 698.535 761.87 705.855 3057.49 74.11835 161.247 372.855 676.369 734.687 684.143 2805.92 75.18636 155.106 359.806 644.706 721.848 668.475 2507.92 76.23471 149.048 347.681 619.489 694.154 656.536 2357.75 77.28382 142.419 334.572 599.865 665.455 646.789 2044.41 78.3363 136.827 322.235 582.248 634.358 637.651 1759.31

157

Appendix C

79.41241 130.562 309.35 572.968 601.759 623.191 1547.65 80.48669 124.643 296.64 552.603 567.276 624.969 1096.56 81.01263 121.699 283.739 530.122 527.014 630.7 726.322 82.04424 116.247 270.478 509.941 494.156 619.825 509.406 83.0912 110.745 257.188 489.133 461.593 594.972 265.938 84.13596 105.555 243.073 468.01 428.284 564.079 156.756 85.18729 100.677 229.291 457.604 397.506 527.811 97.4482 86.23985 96.1098 215.747 435.571 367.568 498.434 79.1823 87.27831 91.7046 202.66 416.362 337.896 470.331 53.6247 88.33588 87.3162 190.247 396.574 312.594 441.23 37.1219 89.40599 83.2609 167.833 378.599 291.064 413.097 26.1527 90.46567 79.2534 162.698 361.696 274.743 365.266 19.6462 91.52351 75.4732 149.315 350.263 258.615 346.089 16.8131 92.05289 73.6237 141.041 346.046 244.685 327.441 15.2349 93.10337 70.0812 136.962 331.173 231.625 309.754 12.6563 94.12778 66.6507 129.979 319.375 220.979 293.745 11.222 95.16599 63.0416 123.458 308.457 210.523 279.331 10.0299 96.21248 59.7804 120.665 294.03 206.728 266.371 11.7329 97.24026 56.7356 114.934 281.25 199.707 253.321 11.6103 98.27694 53.6553 109.81 267.247 192.375 242.309 11.057 99.34214 50.7104 107.25 254.575 183.561 231.829 10.5214 100.3736 47.84 103.499 243.289 175.359 221.016 11.5281 101.4094 44.999 101.951 231.151 165.92 201.889 12.6291 102.4457 42.222 100.868 217.911 155.913 191.875 15.5904 103.5125 39.5126 102.818 208.313 146.794 183.26 32.0518 104.0453 38.2789 101.529 202.647 138.013 175.268 36.5352 105.1612 35.6 99.3291 189.716 128.671 167.013 42.4567 106.2272 32.9642 95.3667 177.328 123.763 160.209 49.5404 107.2633 30.4499 92.3742 166.146 114.401 153.727 52.1705 108.3248 27.9312 86.3672 154.569 104.569 146.295 56.4437 109.3792 25.3874 83.4629 142.503 94.4463 138.681 61.2536 110.3761 22.8875 81.1473 129.803 84.0984 124.236 64.1109 111.4047 20.3232 81.0199 116.673 73.1079 115.493 66.0135 112.4566 17.6465 83.1054 102.647 61.5588 106.714 68.2793 113.4877 15.3004 86.245 88.3674 50.9428 97.2594 69.6296 114.0061 14.0764 90.7848 74.0271 45.6899 87.8603 70.6618 115.0449 11.4413 103.646 66.6823 34.7236 79.1768 71.7737 116.0664 8.8937 111.451 52.056 23.3777 69.3008 72.3365 117.0886 6.92698 117.054 37.3603 15.463 58.1576 72.9668 118.1579 5.49221 234.734 24.3679 17.2747 46.6775 73.3957 119.2421 5.89539 267.264 18.6201 55.9976 35.9439 73.4282 120.6728 28.1174 295.218 14.4614 60.832 25.3088 73.0096 121.2212 28.5139 300.856 12.8043 60.832 11.4498 0

158

Appendix D

12 Appendix D

Data obtained from XRD of L100 C0, L95 C05, L90 C10, L85 C15, L80 C20 and L0C100. XRD pattern in 2 Theta (2 θ) range of 10 º- 80º was analyzed. As major peaks were obtained in the 2 Theta range of 10 º- 40º, so data presented below are in the 2 Theta range of 10 º- 40º.

Angle L100 C0 L95 C05 L90 C10 L85 C15 L80 C20 L0C100 Intensity Intensity Intensity Intensity Intensity Intensity (a.u) (a.u) (a.u) (a.u) (a.u) (a.u) 10 209 151 198 196 211 295 10.02 203 161 213 185 201 284 10.04 215 166 205 190 185 319 10.06 230 174 209 180 197 321 10.08 221 187 195 184 193 293 10.1 255 150 226 176 194 339 10.12 238 155 218 202 172 329 10.14 218 198 180 194 184 303 10.16 235 186 210 185 189 322 10.18 225 145 207 196 172 321 10.2 214 147 198 185 167 314 10.22 223 159 187 194 187 321 10.24 217 141 225 163 204 321 10.26 213 159 199 192 194 339 10.28 219 147 191 185 177 288 10.3 233 169 213 171 201 302 10.32 204 167 225 183 174 326 10.34 214 153 186 187 186 325 10.36 218 150 205 185 178 320 10.38 225 143 192 184 208 323 10.4 206 161 211 165 194 322 10.42 202 155 194 199 178 324 10.44 229 136 181 175 183 369 10.46 213 149 179 197 177 330 10.48 212 174 187 212 170 335 10.5 192 148 196 208 183 316 10.52 205 159 200 169 201 310 10.54 210 171 206 197 194 333 10.56 231 170 212 192 217 320 10.58 236 151 184 194 203 315 10.6 221 193 210 176 196 331 10.62 185 162 211 181 175 322 10.64 204 166 224 192 201 323 10.66 214 158 193 212 205 322 10.68 236 155 222 217 189 334 10.7 229 157 171 179 203 338 10.72 216 162 170 170 216 344 10.74 215 168 204 212 203 327 10.76 210 164 173 207 193 302 10.78 232 140 194 184 184 372 10.8 221 172 192 202 202 357 10.82 196 188 204 199 196 338 10.84 214 159 197 203 202 345 10.86 219 179 195 185 189 348 10.88 206 153 220 179 191 357 10.9 206 162 227 204 221 351 10.92 198 147 231 198 216 351 10.94 213 183 195 180 198 345 10.96 234 168 222 198 181 364 10.98 213 140 213 215 213 330

159

Appendix D

11 246 165 211 177 233 338 11.02 187 166 188 209 201 364 11.04 214 163 206 211 233 358 11.06 234 154 236 216 218 351 11.08 204 184 201 205 198 361 11.1 233 178 234 202 241 404 11.12 210 152 213 184 203 370 11.14 199 157 210 203 216 353 11.16 222 154 226 215 199 345 11.18 194 170 217 179 211 343 11.2 221 154 188 186 223 345 11.22 248 181 209 207 194 371 11.24 201 159 211 230 197 378 11.26 192 181 215 178 207 336 11.28 199 161 231 203 203 392 11.3 202 171 185 226 197 368 11.32 222 171 208 228 209 385 11.34 208 166 218 200 217 361 11.36 229 169 214 196 199 404 11.38 196 168 234 197 224 384 11.4 184 172 228 203 195 390 11.42 212 181 192 212 199 414 11.44 200 161 203 220 196 345 11.46 189 191 204 219 202 385 11.48 205 170 219 223 230 405 11.5 191 169 203 198 195 359 11.52 204 168 224 214 249 374 11.54 228 151 221 237 208 362 11.56 188 175 213 219 203 409 11.58 225 163 222 212 206 397 11.6 225 174 210 220 203 408 11.62 192 163 189 196 209 426 11.64 213 161 217 215 234 388 11.66 222 179 235 223 209 400 11.68 195 200 211 195 218 390 11.7 191 161 168 173 204 379 11.72 197 167 219 212 222 388 11.74 196 181 206 202 201 390 11.76 187 185 225 217 220 408 11.78 192 192 202 214 219 388 11.8 204 170 240 218 201 402 11.82 183 182 231 205 231 405 11.84 179 180 190 201 233 455 11.86 196 162 187 220 204 392 11.88 219 164 204 213 239 425 11.9 186 156 221 184 218 399 11.92 209 175 213 214 237 408 11.94 193 180 225 205 226 406 11.96 215 173 230 232 222 422 11.98 206 166 238 188 207 400 12 189 154 222 224 208 413 12.02 201 183 228 238 216 423 12.04 180 179 217 222 220 416 12.06 207 190 256 223 223 427 12.08 190 185 229 249 211 416 12.1 194 167 243 220 213 421 12.12 199 178 216 219 211 422 12.14 187 176 215 247 229 392 12.16 198 163 225 199 229 393 12.18 186 199 216 231 199 430 12.2 191 177 236 238 208 419 12.22 192 157 222 228 218 435 12.24 201 183 237 224 210 401 12.26 198 181 207 221 248 421

160

Appendix D

12.28 174 188 253 193 215 372 12.3 196 207 244 229 238 462 12.32 200 178 230 238 219 407 12.34 212 208 230 234 227 406 12.36 194 193 218 232 213 435 12.38 189 192 233 232 247 423 12.4 178 187 234 229 219 444 12.42 209 170 224 205 225 419 12.44 174 163 223 226 234 425 12.46 182 208 218 219 217 448 12.48 204 179 250 237 218 426 12.5 201 194 220 215 235 441 12.52 190 207 220 231 211 465 12.54 168 156 209 223 238 441 12.56 209 172 239 205 244 474 12.58 201 181 224 209 228 433 12.6 156 177 223 254 239 476 12.62 186 181 215 204 222 474 12.64 206 187 259 217 221 447 12.66 196 193 203 260 246 457 12.68 192 171 233 214 261 490 12.7 186 198 227 234 245 481 12.72 205 187 219 234 223 474 12.74 209 180 219 254 216 495 12.76 195 189 237 239 248 480 12.78 199 197 240 228 208 500 12.8 206 209 260 210 238 450 12.82 181 196 240 224 238 478 12.84 202 163 219 233 210 494 12.86 174 160 263 212 247 475 12.88 184 202 205 259 231 470 12.9 186 179 234 238 245 493 12.92 179 164 255 196 263 539 12.94 190 167 238 237 217 495 12.96 182 181 255 234 259 508 12.98 204 181 221 255 224 498 13 197 203 224 250 208 519 13.02 189 189 233 264 243 473 13.04 187 203 248 230 257 542 13.06 222 171 244 246 271 542 13.08 193 182 239 222 246 502 13.1 191 185 208 239 252 522 13.12 203 192 258 256 273 521 13.14 232 174 233 237 273 519 13.16 224 193 264 251 234 514 13.18 197 181 251 235 256 524 13.2 200 185 263 261 265 529 13.22 196 199 250 255 244 544 13.24 220 190 253 257 242 538 13.26 169 213 234 236 277 562 13.28 223 189 250 240 296 538 13.3 203 198 243 265 270 525 13.32 205 202 246 254 242 590 13.34 225 196 221 237 262 560 13.36 211 193 233 239 269 518 13.38 206 198 241 255 226 523 13.4 185 205 240 276 275 555 13.42 214 212 243 251 287 550 13.44 215 182 238 244 251 538 13.46 180 200 224 283 273 571 13.48 239 190 255 250 242 566 13.5 201 181 273 275 254 589 13.52 203 183 266 252 247 523 13.54 177 186 266 246 263 588

161

Appendix D

13.56 184 195 230 240 252 605 13.58 188 212 241 247 268 566 13.6 182 156 286 234 266 583 13.62 195 189 253 314 281 591 13.64 201 194 262 277 287 579 13.66 185 187 227 247 253 536 13.68 179 171 241 241 240 559 13.7 186 188 264 254 271 598 13.72 218 210 236 237 253 573 13.74 202 205 289 250 309 572 13.76 197 208 267 248 252 616 13.78 212 199 243 262 264 589 13.8 187 178 238 260 290 616 13.82 204 202 262 261 277 598 13.84 205 190 263 249 273 639 13.86 185 196 252 256 265 613 13.88 213 173 243 268 262 576 13.9 207 231 244 260 253 649 13.92 178 203 259 256 294 612 13.94 209 210 230 240 278 659 13.96 184 205 262 251 249 647 13.98 182 183 257 277 282 663 14 170 185 275 258 272 652 14.02 186 237 268 274 266 630 14.04 182 182 266 261 283 604 14.06 200 201 248 279 252 687 14.08 184 196 261 254 292 681 14.1 183 179 250 247 315 696 14.12 173 197 253 294 242 697 14.14 193 216 269 266 263 685 14.16 187 195 264 285 288 717 14.18 187 206 256 283 285 703 14.2 192 198 250 302 273 679 14.22 205 193 230 252 258 662 14.24 178 184 256 288 244 669 14.26 200 206 237 266 278 659 14.28 205 236 253 306 291 708 14.3 194 187 238 277 292 716 14.32 194 196 284 288 263 716 14.34 222 207 238 290 281 713 14.36 201 197 249 265 276 666 14.38 187 207 242 280 276 720 14.4 173 204 242 281 302 751 14.42 172 208 250 302 315 747 14.44 211 191 264 292 312 730 14.46 166 196 256 277 313 741 14.48 200 212 268 302 308 722 14.5 214 178 248 281 273 744 14.52 162 217 267 285 297 758 14.54 207 219 274 292 292 768 14.56 201 189 266 293 311 747 14.58 163 228 278 315 294 762 14.6 175 212 262 271 301 734 14.62 191 227 283 295 315 771 14.64 214 200 309 298 291 744 14.66 210 225 300 314 288 756 14.68 191 205 292 293 340 786 14.7 178 208 288 315 314 865 14.72 210 225 262 301 351 790 14.74 214 176 301 319 296 811 14.76 191 196 257 281 341 786 14.78 203 201 273 318 282 819 14.8 208 201 303 323 331 812 14.82 183 212 286 319 337 809

162

Appendix D

14.84 204 200 287 313 319 781 14.86 183 213 284 279 310 866 14.88 219 206 270 325 331 875 14.9 221 231 259 296 301 875 14.92 176 220 267 308 340 836 14.94 197 210 290 325 348 809 14.96 206 181 284 305 363 904 14.98 191 234 292 290 332 887 15 209 215 297 285 320 842 15.02 200 211 296 335 375 870 15.04 199 246 293 336 294 892 15.06 166 248 284 362 325 860 15.08 223 185 280 296 299 910 15.1 201 212 268 287 319 879 15.12 191 207 277 331 310 893 15.14 239 211 287 368 348 936 15.16 226 219 291 318 329 876 15.18 216 197 279 322 324 942 15.2 195 210 282 329 325 939 15.22 217 204 323 339 338 875 15.24 229 245 313 306 341 962 15.26 188 205 296 359 336 888 15.28 187 200 286 349 341 943 15.3 218 215 304 299 325 1011 15.32 222 208 306 368 359 948 15.34 178 219 334 332 350 1002 15.36 228 223 321 326 365 949 15.38 198 246 340 343 362 986 15.4 181 219 339 315 368 1016 15.42 200 232 319 342 364 1059 15.44 230 199 308 357 367 975 15.46 201 217 318 351 345 1013 15.48 192 216 341 337 357 979 15.5 214 219 333 339 329 1069 15.52 213 255 320 382 379 1065 15.54 223 272 322 354 383 1064 15.56 220 212 312 347 395 1074 15.58 212 226 343 343 377 1083 15.6 217 217 304 336 387 1072 15.62 195 251 336 367 396 1112 15.64 219 216 348 361 354 1097 15.66 201 222 303 347 329 1140 15.68 198 233 365 335 380 1090 15.7 235 231 338 343 369 1092 15.72 234 262 353 384 373 1090 15.74 256 223 357 388 425 1129 15.76 229 243 349 374 417 1156 15.78 247 280 329 403 379 1104 15.8 225 243 353 393 397 1150 15.82 228 236 350 363 401 1210 15.84 270 242 314 394 405 1139 15.86 237 235 344 365 396 1198 15.88 245 222 321 395 389 1157 15.9 200 244 366 383 397 1188 15.92 227 257 335 398 403 1144 15.94 209 249 369 381 427 1196 15.96 197 249 325 359 393 1280 15.98 200 210 338 387 412 1234 16 253 250 341 400 413 1235 16.02 228 240 362 424 439 1268 16.04 245 262 339 429 397 1233 16.06 222 248 355 376 409 1228 16.08 227 263 359 386 388 1267 16.1 229 255 364 397 402 1259

163

Appendix D

16.12 231 267 398 374 377 1252 16.14 234 230 374 389 425 1287 16.16 239 297 395 445 413 1252 16.18 216 252 369 409 436 1305 16.2 256 269 360 362 469 1376 16.22 221 250 388 457 424 1366 16.24 258 254 363 426 425 1338 16.26 227 272 343 409 455 1328 16.28 241 252 411 389 444 1322 16.3 234 268 363 408 471 1357 16.32 218 283 385 465 445 1412 16.34 249 274 395 397 430 1370 16.36 258 289 394 416 437 1392 16.38 235 299 394 421 465 1380 16.4 260 241 398 417 440 1355 16.42 262 283 388 437 462 1381 16.44 238 265 389 433 462 1464 16.46 259 262 389 468 477 1412 16.48 240 274 395 422 494 1363 16.5 264 304 419 426 480 1413 16.52 242 294 402 440 446 1414 16.54 275 274 432 439 461 1398 16.56 258 291 391 471 479 1408 16.58 295 277 388 421 509 1473 16.6 297 260 401 516 448 1420 16.62 257 291 372 458 483 1493 16.64 262 252 433 498 493 1400 16.66 303 280 427 478 504 1444 16.68 253 348 402 473 486 1459 16.7 261 300 429 468 463 1422 16.72 248 300 414 460 482 1511 16.74 256 307 442 480 511 1438 16.76 281 267 396 434 513 1497 16.78 257 272 448 468 521 1484 16.8 303 305 428 485 544 1418 16.82 289 305 432 487 472 1538 16.84 307 278 419 539 495 1518 16.86 262 285 455 471 515 1529 16.88 283 323 445 474 509 1504 16.9 268 298 470 518 489 1452 16.92 264 300 392 494 521 1479 16.94 309 307 425 509 517 1466 16.96 273 325 404 491 533 1584 16.98 274 271 444 503 530 1486 17 284 329 418 501 486 1478 17.02 287 320 483 519 522 1461 17.04 276 310 460 525 487 1502 17.06 279 344 447 523 540 1550 17.08 304 282 427 485 507 1590 17.1 302 308 463 499 519 1507 17.12 295 322 469 501 550 1491 17.14 298 348 457 502 573 1419 17.16 266 351 448 514 548 1574 17.18 297 305 462 537 527 1504 17.2 328 357 461 523 560 1474 17.22 327 339 420 482 535 1469 17.24 296 335 433 500 532 1529 17.26 336 307 456 496 574 1549 17.28 360 321 483 534 537 1490 17.3 313 313 450 530 601 1549 17.32 309 332 466 579 584 1493 17.34 306 315 465 554 544 1509 17.36 308 336 467 600 554 1492 17.38 324 341 415 546 543 1481

164

Appendix D

17.4 307 325 499 531 550 1554 17.42 311 335 470 509 591 1512 17.44 312 333 495 543 527 1492 17.46 311 325 458 517 540 1533 17.48 321 350 524 524 565 1507 17.5 305 337 487 536 547 1513 17.52 340 376 446 518 556 1543 17.54 339 353 453 542 586 1553 17.56 324 362 477 522 534 1464 17.58 344 349 511 609 555 1513 17.6 347 348 510 556 594 1512 17.62 315 355 466 527 589 1500 17.64 315 372 537 539 574 1464 17.66 334 370 496 560 576 1462 17.68 324 381 490 597 579 1530 17.7 332 342 510 580 588 1407 17.72 372 377 492 568 572 1459 17.74 368 376 523 540 582 1511 17.76 344 350 498 615 614 1478 17.78 335 363 518 559 577 1510 17.8 348 381 511 547 574 1410 17.82 343 388 528 587 549 1457 17.84 350 382 485 566 599 1416 17.86 373 410 495 634 614 1435 17.88 348 406 470 589 613 1450 17.9 361 368 566 532 591 1470 17.92 337 371 535 544 599 1408 17.94 367 339 493 597 580 1402 17.96 345 375 467 646 575 1426 17.98 372 349 495 607 617 1422 18 361 382 502 567 566 1431 18.02 350 399 529 613 626 1391 18.04 341 421 534 591 598 1395 18.06 359 369 519 604 588 1379 18.08 358 393 529 615 612 1341 18.1 359 428 512 600 610 1354 18.12 362 430 513 587 597 1313 18.14 367 418 507 575 586 1310 18.16 367 401 509 577 572 1358 18.18 360 367 505 569 636 1359 18.2 376 388 560 595 612 1258 18.22 395 379 514 583 601 1352 18.24 364 397 527 620 580 1291 18.26 336 394 589 623 634 1316 18.28 403 391 542 595 618 1306 18.3 420 386 544 660 618 1276 18.32 402 413 505 647 635 1268 18.34 389 396 525 559 634 1260 18.36 384 430 537 578 588 1249 18.38 391 420 529 653 601 1215 18.4 347 411 553 609 645 1203 18.42 384 398 561 593 622 1227 18.44 396 433 515 629 564 1267 18.46 421 422 550 669 626 1141 18.48 422 399 551 613 617 1147 18.5 374 418 577 625 600 1183 18.52 421 447 558 617 613 1228 18.54 387 412 550 622 607 1149 18.56 372 404 536 612 601 1127 18.58 443 424 547 602 622 1121 18.6 399 433 566 638 621 1156 18.62 448 447 534 645 617 1190 18.64 422 428 547 653 665 1143 18.66 414 446 581 643 649 1159

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Appendix D

18.68 411 430 573 586 667 1088 18.7 435 411 537 579 627 1103 18.72 404 444 512 639 648 1143 18.74 433 428 505 640 587 1094 18.76 419 429 582 618 672 1056 18.78 404 421 553 634 641 1075 18.8 432 451 579 600 637 1058 18.82 455 422 569 630 689 1045 18.84 440 435 576 663 635 1102 18.86 460 440 550 615 603 1016 18.88 422 426 581 598 627 1013 18.9 429 486 577 655 624 1008 18.92 430 465 585 656 641 1003 18.94 458 419 559 633 658 1067 18.96 442 456 642 583 630 1046 18.98 428 477 583 655 639 1017 19 435 477 577 634 590 1019 19.02 420 453 576 623 604 1030 19.04 462 418 557 677 624 1042 19.06 446 445 548 630 649 952 19.08 455 407 588 636 644 958 19.1 436 469 593 558 644 910 19.12 433 434 577 631 602 910 19.14 430 488 599 627 631 938 19.16 421 492 630 632 660 918 19.18 446 480 579 630 630 925 19.2 426 438 525 651 656 929 19.22 435 469 586 586 645 895 19.24 427 470 572 630 609 870 19.26 466 445 598 618 631 803 19.28 412 429 557 612 632 885 19.3 438 466 578 588 664 927 19.32 476 464 575 645 658 865 19.34 457 454 558 608 663 858 19.36 425 463 608 635 694 862 19.38 457 488 558 638 631 868 19.4 461 443 623 640 599 851 19.42 449 452 572 609 607 842 19.44 487 432 563 663 631 817 19.46 470 474 528 612 616 824 19.48 460 450 614 632 643 779 19.5 445 511 616 600 639 801 19.52 493 458 581 627 623 769 19.54 491 460 591 586 640 822 19.56 493 466 541 597 568 836 19.58 490 453 533 654 627 801 19.6 458 467 597 649 606 755 19.62 463 475 608 614 646 803 19.64 480 471 626 656 653 731 19.66 423 460 579 642 617 731 19.68 445 455 567 625 626 764 19.7 443 479 554 619 651 724 19.72 481 454 560 595 620 741 19.74 476 487 541 636 597 731 19.76 470 464 568 570 585 761 19.78 453 463 520 618 607 735 19.8 440 475 565 633 578 714 19.82 470 425 535 628 606 670 19.84 489 449 612 601 627 717 19.86 467 431 567 622 603 711 19.88 454 472 541 603 665 700 19.9 451 470 577 603 615 691 19.92 445 469 613 626 620 664 19.94 481 442 588 619 564 739

166

Appendix D

19.96 413 441 554 617 622 764 19.98 487 471 556 607 611 669 20 425 487 561 630 588 652 20.02 497 460 526 668 609 692 20.04 456 501 577 628 582 659 20.06 521 466 573 584 603 651 20.08 446 509 630 628 613 611 20.1 443 457 586 585 588 660 20.12 482 466 581 615 625 644 20.14 482 455 561 623 624 636 20.16 470 458 547 622 587 591 20.18 471 440 554 598 658 666 20.2 485 457 549 608 634 658 20.22 479 450 609 653 633 600 20.24 492 507 602 621 648 615 20.26 459 520 580 642 655 603 20.28 437 477 565 673 607 555 20.3 486 501 594 570 586 575 20.32 521 481 593 615 626 561 20.34 463 465 590 652 588 588 20.36 499 484 587 638 604 606 20.38 459 499 602 636 667 568 20.4 478 486 588 624 672 563 20.42 497 508 587 613 630 578 20.44 501 568 593 678 664 531 20.46 471 523 666 623 618 576 20.48 485 485 569 669 653 520 20.5 515 523 606 613 625 542 20.52 485 532 652 605 632 538 20.54 498 544 638 601 606 539 20.56 526 549 657 706 646 526 20.58 496 555 657 668 649 542 20.6 503 558 604 683 663 492 20.62 529 562 673 696 690 489 20.64 557 572 648 746 654 526 20.66 527 534 690 686 670 531 20.68 543 586 682 705 679 474 20.7 602 597 688 749 707 529 20.72 574 572 675 711 696 499 20.74 585 612 723 754 715 504 20.76 573 625 711 784 686 454 20.78 610 614 723 754 773 496 20.8 647 623 825 798 819 475 20.82 634 656 823 773 745 450 20.84 664 684 807 783 794 480 20.86 709 696 874 873 827 468 20.88 713 757 871 878 875 521 20.9 750 698 872 929 861 493 20.92 759 822 872 968 881 507 20.94 775 817 967 940 905 474 20.96 839 848 1033 1015 934 433 20.98 928 888 1052 995 951 444 21 937 894 1100 1059 971 486 21.02 980 993 1114 1110 1090 466 21.04 943 994 1244 1214 1101 440 21.06 1063 1033 1231 1246 1135 466 21.08 1079 1124 1269 1340 1151 447 21.1 1181 1264 1381 1386 1230 458 21.12 1212 1263 1514 1461 1284 447 21.14 1307 1379 1608 1478 1384 427 21.16 1316 1450 1742 1547 1447 441 21.18 1501 1537 1787 1607 1529 453 21.2 1625 1606 1910 1897 1684 484 21.22 1605 1708 2045 1856 1716 412

167

Appendix D

21.24 1863 1908 2169 1965 1759 428 21.26 1885 1952 2302 2059 1904 449 21.28 2076 2063 2479 2198 1930 419 21.3 2174 2303 2663 2380 2143 423 21.32 2287 2271 2772 2470 2224 440 21.34 2333 2546 2892 2526 2263 438 21.36 2542 2630 3163 2683 2383 424 21.38 2691 2683 3202 2867 2496 405 21.4 2724 2911 3446 2980 2628 445 21.42 2895 3038 3537 3013 2639 433 21.44 2915 3112 3466 3121 2626 417 21.46 2974 3062 3537 3092 2652 413 21.48 2946 3155 3583 3187 2649 410 21.5 3025 3143 3572 3070 2729 398 21.52 3086 3182 3478 3168 2692 397 21.54 2934 3123 3519 3006 2637 367 21.56 3030 2979 3386 2915 2507 402 21.58 2881 2907 3300 2948 2336 397 21.6 2748 2826 3120 2795 2271 373 21.62 2706 2541 2795 2491 2197 383 21.64 2419 2391 2681 2408 2055 376 21.66 2258 2308 2544 2241 1886 391 21.68 2026 2147 2275 2116 1766 389 21.7 1988 1958 2097 1917 1577 371 21.72 1779 1854 1930 1769 1516 378 21.74 1673 1650 1808 1634 1392 401 21.76 1439 1456 1516 1446 1265 364 21.78 1291 1324 1336 1324 1091 304 21.8 1234 1240 1259 1311 1006 345 21.82 1125 1142 1188 1164 960 360 21.84 986 996 1098 1078 875 337 21.86 910 941 906 964 822 350 21.88 823 854 838 873 792 338 21.9 786 765 853 854 724 315 21.92 740 727 722 830 759 338 21.94 644 675 742 734 657 336 21.96 608 609 683 722 631 315 21.98 580 586 624 637 630 316 22 586 623 652 642 599 323 22.02 541 564 556 706 524 329 22.04 500 514 574 648 575 306 22.06 513 517 547 619 539 288 22.08 468 483 536 636 579 325 22.1 453 473 531 555 527 309 22.12 495 447 487 548 512 296 22.14 469 436 506 509 515 324 22.16 440 456 511 560 528 322 22.18 446 414 502 531 474 300 22.2 424 430 498 509 492 289 22.22 411 417 495 499 465 287 22.24 359 416 475 524 456 313 22.26 416 420 480 437 421 301 22.28 384 424 470 485 434 308 22.3 372 395 448 470 442 304 22.32 355 400 407 493 454 317 22.34 378 381 431 485 439 291 22.36 385 356 390 503 457 272 22.38 352 377 418 444 420 277 22.4 340 376 409 448 412 273 22.42 339 368 401 425 395 299 22.44 342 356 365 406 406 248 22.46 333 337 395 410 420 286 22.48 276 331 404 437 441 278 22.5 333 305 359 419 366 284

168

Appendix D

22.52 293 305 400 410 414 255 22.54 302 320 372 429 382 259 22.56 296 282 376 380 382 279 22.58 281 319 346 404 397 263 22.6 320 328 357 402 417 291 22.62 328 322 350 366 357 289 22.64 254 293 365 398 362 271 22.66 305 298 349 356 376 281 22.68 264 297 336 381 404 251 22.7 285 305 341 396 325 267 22.72 255 262 327 392 341 244 22.74 260 289 353 362 369 275 22.76 259 267 321 359 342 255 22.78 267 263 321 363 342 294 22.8 271 280 313 364 338 275 22.82 275 287 308 382 360 248 22.84 247 288 319 367 358 280 22.86 270 244 284 356 356 252 22.88 276 261 342 370 351 241 22.9 225 251 278 409 381 262 22.92 255 228 306 343 318 251 22.94 267 241 296 323 321 265 22.96 266 226 309 345 362 259 22.98 238 272 320 350 325 260 23 234 227 291 351 346 255 23.02 249 260 298 332 352 220 23.04 261 227 253 343 370 235 23.06 231 263 300 342 371 252 23.08 208 260 302 341 343 248 23.1 244 252 287 377 355 242 23.12 220 257 329 392 340 251 23.14 247 283 289 351 348 225 23.16 258 232 308 363 346 255 23.18 222 285 303 362 387 241 23.2 232 253 284 371 356 207 23.22 255 238 351 396 370 236 23.24 245 263 312 414 369 228 23.26 243 226 259 375 393 248 23.28 236 253 289 393 387 247 23.3 245 289 297 433 369 220 23.32 255 290 298 439 407 249 23.34 272 267 340 389 433 223 23.36 303 282 342 416 454 213 23.38 277 303 358 384 439 251 23.4 274 277 366 474 487 201 23.42 261 286 346 459 470 221 23.44 279 303 360 482 499 233 23.46 295 287 382 490 545 223 23.48 273 316 380 499 531 213 23.5 285 312 384 550 568 229 23.52 291 314 379 497 564 229 23.54 308 329 405 532 579 205 23.56 349 319 417 569 578 216 23.58 296 342 413 553 585 207 23.6 302 333 419 601 635 219 23.62 368 350 466 616 597 243 23.64 343 334 435 599 678 201 23.66 385 344 464 604 662 228 23.68 327 385 475 628 613 188 23.7 353 396 437 621 663 235 23.72 356 367 406 647 681 221 23.74 395 344 466 653 674 232 23.76 354 353 470 621 664 229 23.78 375 337 427 627 640 211

169

Appendix D

23.8 365 372 422 626 626 205 23.82 384 338 441 657 670 212 23.84 355 346 423 636 642 205 23.86 401 338 448 622 619 211 23.88 313 312 456 617 643 223 23.9 326 352 415 645 617 205 23.92 338 341 430 609 579 176 23.94 320 334 401 537 521 215 23.96 328 299 400 561 584 191 23.98 313 299 370 525 551 195 24 310 315 354 492 567 159 24.02 302 297 343 517 520 180 24.04 270 277 344 513 471 210 24.06 244 281 333 444 443 174 24.08 269 261 308 431 452 206 24.1 244 239 333 431 429 204 24.12 219 216 301 397 395 196 24.14 268 248 271 396 411 198 24.16 219 240 252 384 343 195 24.18 219 226 251 310 337 188 24.2 201 216 261 319 373 155 24.22 226 215 287 360 328 207 24.24 192 197 249 301 302 178 24.26 188 210 212 304 308 197 24.28 189 200 217 275 294 168 24.3 193 206 217 296 287 162 24.32 169 170 192 275 280 163 24.34 148 166 214 271 304 212 24.36 177 209 180 294 268 167 24.38 170 201 178 268 257 192 24.4 175 170 182 239 290 200 24.42 190 145 208 249 234 196 24.44 168 177 193 229 221 171 24.46 142 154 183 236 222 160 24.48 156 175 191 232 250 195 24.5 127 156 209 249 219 170 24.52 134 151 180 239 225 166 24.54 134 144 171 213 207 160 24.56 130 155 181 213 210 168 24.58 127 139 169 199 221 178 24.6 128 131 160 199 186 166 24.62 137 157 165 235 205 165 24.64 142 153 173 175 195 170 24.66 124 144 149 181 190 194 24.68 129 148 160 197 189 175 24.7 140 155 144 205 184 161 24.72 122 154 164 200 209 178 24.74 131 155 146 200 166 156 24.76 113 133 146 206 162 170 24.78 114 140 163 186 194 170 24.8 142 131 141 167 177 179 24.82 135 139 149 171 174 159 24.84 119 134 132 190 178 150 24.86 141 129 185 167 207 160 24.88 114 151 160 171 183 153 24.9 110 132 165 179 159 165 24.92 137 147 142 171 143 169 24.94 108 126 141 171 185 178 24.96 122 108 140 178 164 165 24.98 143 106 154 154 169 164 25 128 134 150 177 141 153 25.02 106 117 131 178 169 159 25.04 111 113 162 181 169 152 25.06 104 135 143 165 157 162

170

Appendix D

25.08 100 110 136 150 154 158 25.1 95 138 141 144 139 149 25.12 113 130 120 160 150 162 25.14 114 133 163 148 167 136 25.16 107 119 130 130 166 129 25.18 107 123 146 129 179 151 25.2 93 106 163 145 168 163 25.22 113 109 137 136 144 149 25.24 89 108 134 169 146 175 25.26 107 120 134 134 153 141 25.28 99 131 156 135 141 136 25.3 113 115 131 155 130 141 25.32 93 100 134 149 166 159 25.34 100 101 131 136 136 128 25.36 100 125 143 134 126 134 25.38 97 112 134 127 134 138 25.4 108 122 124 126 139 156 25.42 109 110 123 125 127 167 25.44 99 112 115 167 136 143 25.46 103 92 99 144 122 146 25.48 98 103 111 144 139 144 25.5 99 105 120 150 140 124 25.52 91 106 136 156 137 149 25.54 91 120 109 120 127 145 25.56 76 94 135 116 147 175 25.58 96 104 107 111 111 153 25.6 98 108 109 146 110 143 25.62 106 103 122 126 150 160 25.64 116 99 115 149 130 141 25.66 92 102 124 131 132 127 25.68 94 89 110 132 118 139 25.7 94 112 118 120 122 138 25.72 80 96 128 135 111 150 25.74 94 100 104 128 99 131 25.76 84 104 113 145 114 145 25.78 81 92 110 138 125 139 25.8 92 114 106 113 115 148 25.82 100 83 99 127 97 138 25.84 79 105 116 130 132 128 25.86 79 97 102 131 105 165 25.88 88 111 116 130 124 139 25.9 92 84 97 144 146 137 25.92 90 105 129 114 110 135 25.94 62 93 95 140 123 124 25.96 70 96 82 132 117 116 25.98 79 95 101 129 124 128 26 80 93 124 119 107 132 26.02 80 88 116 125 114 133 26.04 80 84 86 113 117 135 26.06 91 88 120 120 109 133 26.08 70 94 87 134 118 143 26.1 92 107 77 119 109 141 26.12 82 85 102 114 112 138 26.14 71 80 90 129 113 157 26.16 79 105 88 107 99 128 26.18 83 84 109 98 104 124 26.2 96 92 100 146 113 140 26.22 68 98 89 123 96 122 26.24 79 101 115 107 98 116 26.26 72 105 100 105 107 146 26.28 77 94 92 110 103 110 26.3 69 93 101 114 99 135 26.32 64 103 98 102 103 138 26.34 89 80 82 125 104 133

171

Appendix D

26.36 74 100 94 104 83 131 26.38 84 99 81 105 106 143 26.4 81 88 101 114 93 121 26.42 84 99 111 107 103 125 26.44 78 78 93 108 82 113 26.46 69 85 94 102 119 104 26.48 78 92 88 104 109 119 26.5 66 88 87 117 113 118 26.52 69 92 90 113 112 110 26.54 71 91 80 96 97 133 26.56 76 76 106 113 101 97 26.58 77 85 91 124 103 132 26.6 90 79 93 103 106 123 26.62 68 94 97 104 92 127 26.64 75 74 89 94 106 117 26.66 78 59 81 114 89 128 26.68 75 65 90 101 99 133 26.7 67 104 80 90 94 115 26.72 84 74 97 105 88 132 26.74 77 85 94 92 120 117 26.76 70 96 102 109 114 117 26.78 81 92 87 96 98 130 26.8 58 79 102 106 87 120 26.82 56 82 115 100 94 121 26.84 70 92 100 102 107 124 26.86 79 92 94 90 90 127 26.88 75 88 108 100 102 107 26.9 70 68 71 98 87 128 26.92 63 66 93 110 86 106 26.94 72 101 74 108 98 95 26.96 56 101 93 97 100 122 26.98 66 89 92 105 106 110 27 76 71 98 95 89 121 27.02 85 80 74 108 86 131 27.04 66 80 82 105 107 113 27.06 64 85 105 99 126 122 27.08 72 80 81 92 97 132 27.1 68 78 82 112 87 102 27.12 72 77 82 108 87 119 27.14 73 60 89 86 90 117 27.16 63 88 87 103 81 123 27.18 54 60 81 106 93 126 27.2 84 85 80 89 77 116 27.22 57 75 101 97 86 129 27.24 71 76 86 107 86 114 27.26 62 63 91 94 92 127 27.28 67 81 93 103 91 106 27.3 68 67 85 100 89 115 27.32 65 82 87 98 109 117 27.34 64 85 85 108 96 108 27.36 70 65 82 96 110 133 27.38 65 67 81 102 89 119 27.4 64 83 82 88 93 108 27.42 54 71 82 83 85 106 27.44 65 96 83 89 94 107 27.46 56 85 79 90 83 121 27.48 60 78 69 82 71 131 27.5 57 84 94 98 81 127 27.52 70 71 73 107 94 115 27.54 66 85 72 89 89 96 27.56 58 73 67 87 96 119 27.58 49 93 92 77 81 93 27.6 49 55 85 88 91 107 27.62 66 72 90 79 109 126

172

Appendix D

27.64 55 74 77 102 79 106 27.66 60 75 88 93 68 126 27.68 68 80 87 82 80 118 27.7 67 65 91 83 94 123 27.72 66 67 72 91 72 117 27.74 56 66 81 82 93 108 27.76 75 64 91 71 86 120 27.78 71 85 78 98 81 93 27.8 61 61 78 89 76 111 27.82 55 66 74 89 82 134 27.84 65 79 70 104 103 128 27.86 56 70 63 79 77 115 27.88 59 72 76 99 89 120 27.9 56 74 67 86 78 105 27.92 66 89 81 92 86 110 27.94 58 57 79 96 85 116 27.96 64 61 83 89 70 103 27.98 70 60 82 85 80 102 28 54 74 79 71 73 112 28.02 64 66 61 78 79 118 28.04 62 66 82 90 65 96 28.06 54 65 73 88 110 115 28.08 56 68 52 60 92 110 28.1 70 71 57 79 83 110 28.12 57 69 72 87 61 109 28.14 59 82 77 76 89 108 28.16 55 73 71 95 82 110 28.18 63 70 89 74 92 94 28.2 73 71 74 103 84 119 28.22 64 70 67 81 62 123 28.24 55 74 75 93 72 100 28.26 57 81 70 75 83 111 28.28 67 69 72 80 66 103 28.3 56 66 90 74 79 127 28.32 51 72 73 82 84 119 28.34 52 74 72 75 67 116 28.36 64 60 71 94 76 87 28.38 60 83 94 81 78 114 28.4 51 58 71 74 89 115 28.42 42 71 81 75 72 115 28.44 53 80 80 78 75 102 28.46 59 72 76 97 55 112 28.48 57 77 84 82 69 98 28.5 64 86 74 70 71 96 28.52 80 69 76 90 90 119 28.54 50 78 90 92 84 98 28.56 62 74 69 78 79 102 28.58 56 82 81 82 79 118 28.6 70 59 85 112 91 95 28.62 39 72 98 106 86 111 28.64 70 84 82 82 77 110 28.66 55 80 95 85 77 79 28.68 67 73 80 89 82 105 28.7 62 63 79 94 93 114 28.72 47 66 85 96 89 99 28.74 58 85 84 79 80 109 28.76 52 69 64 58 80 114 28.78 45 73 68 91 68 101 28.8 56 68 82 79 80 86 28.82 51 67 81 64 70 114 28.84 60 78 76 76 76 100 28.86 58 56 86 82 70 112 28.88 58 70 72 65 83 113 28.9 65 68 80 73 68 130

173

Appendix D

28.92 60 78 72 61 74 110 28.94 52 65 64 94 69 102 28.96 56 67 85 69 51 114 28.98 50 64 87 87 69 107 29 50 67 69 95 68 116 29.02 48 63 77 77 62 95 29.04 65 74 83 65 64 117 29.06 40 60 63 70 81 108 29.08 63 57 71 91 74 107 29.1 46 61 68 78 79 101 29.12 46 66 62 69 79 83 29.14 44 64 82 75 66 104 29.16 60 67 71 74 84 102 29.18 45 72 67 66 76 98 29.2 39 68 65 72 74 124 29.22 48 65 65 86 79 108 29.24 66 83 74 68 77 104 29.26 59 70 65 91 82 88 29.28 62 66 89 64 71 92 29.3 44 74 68 76 74 113 29.32 56 61 96 74 81 97 29.34 55 59 63 74 59 90 29.36 51 56 78 76 70 98 29.38 50 67 73 81 73 99 29.4 42 48 69 82 74 111 29.42 54 76 75 83 70 101 29.44 51 72 62 82 75 83 29.46 79 61 74 77 74 90 29.48 58 83 66 79 78 104 29.5 52 66 76 69 66 95 29.52 56 66 74 86 77 100 29.54 52 59 71 71 80 105 29.56 66 74 65 84 79 98 29.58 61 71 68 89 78 103 29.6 51 72 73 97 64 108 29.62 48 83 73 84 94 107 29.64 64 61 72 77 73 113 29.66 49 67 64 88 85 90 29.68 46 76 71 88 73 100 29.7 55 81 68 92 80 109 29.72 73 67 84 71 72 98 29.74 57 84 72 96 77 116 29.76 76 60 66 70 80 103 29.78 70 70 85 106 93 102 29.8 51 90 93 74 69 83 29.82 78 74 91 87 87 100 29.84 52 86 78 101 86 111 29.86 80 75 72 71 75 92 29.88 69 83 87 103 76 95 29.9 60 71 84 84 80 108 29.92 68 71 89 90 86 94 29.94 50 74 70 105 87 106 29.96 62 74 77 98 82 104 29.98 78 80 93 100 95 96 30 52 79 73 81 92 111 30.02 67 66 91 87 94 98 30.04 63 81 94 88 76 86 30.06 69 64 77 77 107 105 30.08 66 92 76 100 73 77 30.1 53 90 99 80 73 83 30.12 63 76 88 96 63 109 30.14 63 70 74 77 76 94 30.16 81 73 69 81 55 121 30.18 58 61 79 66 77 123

174

Appendix D

30.2 58 80 80 77 78 88 30.22 66 64 84 76 73 111 30.24 45 56 73 76 77 107 30.26 62 58 72 83 74 85 30.28 60 75 63 69 71 100 30.3 34 67 74 66 56 86 30.32 69 73 70 72 68 95 30.34 50 75 72 75 73 106 30.36 36 68 68 81 81 104 30.38 42 61 68 75 47 97 30.4 38 50 62 70 67 85 30.42 43 68 67 81 71 100 30.44 60 64 74 77 57 86 30.46 48 44 67 60 73 97 30.48 47 45 65 83 71 93 30.5 59 62 64 79 67 104 30.52 58 60 53 67 62 92 30.54 54 58 70 84 62 92 30.56 47 67 59 67 69 103 30.58 43 58 59 79 58 94 30.6 44 71 63 71 59 89 30.62 54 50 58 73 60 99 30.64 52 59 70 76 71 101 30.66 60 47 70 57 75 105 30.68 36 69 60 76 75 98 30.7 46 53 76 80 63 92 30.72 42 48 49 72 59 87 30.74 59 59 45 73 79 83 30.76 51 60 76 58 67 97 30.78 44 58 55 64 53 98 30.8 61 50 59 74 68 86 30.82 48 58 61 56 67 104 30.84 44 63 69 56 63 79 30.86 49 57 67 58 74 112 30.88 51 55 58 72 64 90 30.9 66 48 77 70 66 104 30.92 33 51 64 73 60 103 30.94 40 63 60 77 55 108 30.96 41 51 69 82 77 92 30.98 52 46 56 61 65 103 31 44 54 45 64 61 103 31.02 60 66 69 71 64 108 31.04 35 60 61 73 66 107 31.06 43 43 59 70 72 88 31.08 54 47 57 67 68 90 31.1 45 50 67 79 52 117 31.12 46 64 72 60 74 102 31.14 48 50 63 77 69 98 31.16 43 48 58 59 66 101 31.18 49 56 61 82 67 89 31.2 34 55 61 63 60 101 31.22 36 58 62 73 54 99 31.24 43 48 52 68 61 97 31.26 33 49 64 74 63 94 31.28 50 67 75 64 51 95 31.3 49 42 63 69 84 90 31.32 43 50 44 80 57 94 31.34 47 54 57 75 53 96 31.36 50 68 66 55 45 95 31.38 37 49 66 74 71 90 31.4 66 65 56 53 64 102 31.42 49 43 47 71 66 109 31.44 47 61 62 52 61 78 31.46 40 60 59 62 70 85

175

Appendix D

31.48 41 45 73 59 49 91 31.5 38 51 61 49 76 95 31.52 50 48 61 69 60 104 31.54 41 50 57 63 61 85 31.56 32 48 66 58 49 107 31.58 45 71 64 70 52 102 31.6 40 54 62 57 61 87 31.62 36 49 49 53 68 97 31.64 39 60 53 75 70 87 31.66 49 40 54 79 60 84 31.68 32 58 55 58 69 105 31.7 49 52 61 52 60 93 31.72 51 55 53 64 60 85 31.74 52 50 57 60 55 85 31.76 37 56 60 60 66 104 31.78 43 65 50 58 52 101 31.8 42 53 49 75 51 111 31.82 41 63 56 52 63 93 31.84 46 61 60 56 58 96 31.86 31 54 66 62 76 94 31.88 35 59 68 63 56 92 31.9 41 48 65 55 67 80 31.92 46 41 65 73 61 97 31.94 48 53 57 57 73 82 31.96 38 46 54 50 53 110 31.98 41 59 51 60 55 97 32 38 49 54 55 57 94 32.02 45 51 55 67 48 99 32.04 42 60 45 71 54 92 32.06 54 51 47 66 67 100 32.08 49 53 42 65 57 87 32.1 51 56 44 73 47 100 32.12 31 53 58 61 65 107 32.14 44 47 69 59 59 90 32.16 51 53 67 54 45 112 32.18 31 42 61 69 53 71 32.2 48 68 63 80 60 100 32.22 47 57 54 65 67 91 32.24 36 60 46 60 46 98 32.26 37 40 50 51 55 95 32.28 37 48 61 51 59 78 32.3 37 54 74 64 67 89 32.32 46 67 53 59 76 105 32.34 55 52 55 60 54 108 32.36 50 58 49 70 61 97 32.38 53 42 59 81 72 92 32.4 43 54 47 69 57 97 32.42 38 42 53 71 58 83 32.44 40 41 53 67 53 94 32.46 33 51 68 60 67 97 32.48 42 65 54 59 44 95 32.5 45 50 52 56 63 103 32.52 40 50 50 71 60 99 32.54 46 45 56 69 65 89 32.56 41 44 45 53 69 95 32.58 42 61 48 71 64 94 32.6 46 52 55 50 61 102 32.62 43 50 58 65 55 105 32.64 30 55 52 44 66 100 32.66 41 61 56 63 55 87 32.68 40 47 57 58 70 95 32.7 39 52 67 67 58 90 32.72 42 43 57 58 63 81 32.74 44 67 61 71 55 107

176

Appendix D

32.76 43 56 51 69 67 83 32.78 43 53 50 59 49 99 32.8 39 64 60 45 64 103 32.82 48 54 48 75 58 82 32.84 25 53 50 64 58 91 32.86 40 40 61 68 59 96 32.88 44 53 58 63 68 91 32.9 41 51 69 46 58 90 32.92 48 57 55 55 48 95 32.94 47 64 47 62 61 93 32.96 54 59 47 60 48 80 32.98 51 53 52 49 53 98 33 47 46 50 49 59 100 33.02 47 49 52 71 60 108 33.04 27 41 72 69 62 97 33.06 45 58 66 45 47 98 33.08 38 49 67 69 64 104 33.1 43 43 42 61 56 88 33.12 55 46 48 62 49 107 33.14 41 53 55 61 61 90 33.16 35 54 62 40 66 101 33.18 44 64 62 68 53 114 33.2 45 52 55 62 54 112 33.22 44 58 47 58 66 85 33.24 39 74 43 55 60 91 33.26 42 58 46 64 61 91 33.28 37 54 61 67 54 88 33.3 35 45 68 74 60 107 33.32 41 42 33 70 52 109 33.34 42 49 55 49 51 94 33.36 40 55 61 67 60 84 33.38 42 61 52 60 51 103 33.4 32 44 66 51 69 89 33.42 49 45 57 53 54 99 33.44 43 42 54 52 52 96 33.46 41 49 60 56 75 99 33.48 37 39 64 70 69 92 33.5 46 59 54 64 63 91 33.52 43 59 61 76 57 86 33.54 37 53 63 50 53 98 33.56 50 46 52 58 74 81 33.58 38 45 60 52 60 96 33.6 37 52 65 64 65 94 33.62 39 53 47 64 47 83 33.64 40 53 53 61 46 94 33.66 35 52 58 60 52 86 33.68 40 44 55 66 74 103 33.7 45 53 46 62 55 100 33.72 39 65 35 62 52 103 33.74 38 59 63 62 41 81 33.76 42 46 56 62 57 102 33.78 41 42 47 73 59 91 33.8 48 59 60 58 54 97 33.82 38 47 59 60 56 90 33.84 59 42 47 45 54 87 33.86 38 54 71 64 70 92 33.88 44 63 59 48 67 107 33.9 30 52 57 47 46 94 33.92 53 49 58 66 58 93 33.94 43 48 64 82 62 93 33.96 45 57 47 50 55 88 33.98 29 50 61 60 58 109 34 47 48 68 47 58 104 34.02 42 47 58 60 58 87

177

Appendix D

34.04 37 48 54 56 58 101 34.06 47 56 72 59 53 86 34.08 39 39 51 52 54 106 34.1 46 56 54 51 39 102 34.12 31 66 62 76 54 117 34.14 35 57 60 49 41 82 34.16 45 51 56 54 50 103 34.18 41 46 43 56 64 90 34.2 42 64 53 62 59 79 34.22 45 35 65 52 41 80 34.24 41 60 53 57 56 88 34.26 42 44 56 54 53 109 34.28 41 53 61 54 54 70 34.3 44 57 46 64 61 98 34.32 47 58 56 66 64 107 34.34 40 53 57 45 50 93 34.36 32 46 68 61 51 104 34.38 40 56 50 58 55 95 34.4 48 54 57 58 72 101 34.42 42 66 56 61 47 101 34.44 35 48 61 66 46 94 34.46 53 57 53 61 54 92 34.48 37 55 64 71 67 105 34.5 45 53 62 52 60 106 34.52 43 65 52 61 71 78 34.54 31 44 48 68 51 100 34.56 32 56 61 53 64 99 34.58 39 57 62 62 51 115 34.6 57 48 57 60 59 108 34.62 37 48 46 72 54 105 34.64 48 51 59 63 55 89 34.66 38 62 67 56 48 105 34.68 41 50 69 70 55 95 34.7 42 66 49 58 57 111 34.72 38 49 60 57 56 99 34.74 41 62 53 56 60 84 34.76 27 49 68 73 46 91 34.78 35 65 42 67 72 83 34.8 38 47 62 64 62 120 34.82 36 65 67 41 67 92 34.84 48 48 47 57 73 99 34.86 39 55 46 55 48 100 34.88 39 50 48 55 73 83 34.9 36 49 55 56 57 87 34.92 31 55 63 45 53 105 34.94 45 47 67 57 50 103 34.96 31 49 61 57 61 93 34.98 38 60 51 51 46 93 35 43 52 52 65 44 106 35.02 34 61 56 59 65 106 35.04 43 50 65 61 62 103 35.06 48 43 60 69 57 71 35.08 36 52 47 61 46 95 35.1 34 45 51 60 48 110 35.12 34 67 45 71 47 99 35.14 37 60 60 63 55 93 35.16 38 65 61 52 55 98 35.18 43 48 56 62 47 105 35.2 39 58 66 48 57 116 35.22 49 49 67 64 69 99 35.24 37 58 36 47 58 100 35.26 39 45 45 75 65 108 35.28 43 61 67 40 71 97 35.3 37 52 63 57 52 108

178

Appendix D

35.32 39 49 51 64 52 103 35.34 58 66 54 59 57 85 35.36 54 52 54 60 56 104 35.38 47 68 54 65 46 96 35.4 54 47 54 54 59 115 35.42 44 54 55 67 66 77 35.44 45 57 71 65 61 108 35.46 46 60 55 61 49 101 35.48 52 65 60 64 60 90 35.5 45 63 55 57 69 100 35.52 50 55 69 69 64 91 35.54 42 54 59 70 60 89 35.56 43 54 50 61 63 108 35.58 44 56 65 57 64 100 35.6 45 56 79 62 68 107 35.62 53 77 56 67 60 98 35.64 38 63 77 68 62 114 35.66 52 64 70 58 60 92 35.68 50 66 63 66 78 88 35.7 52 63 70 98 69 98 35.72 58 69 66 73 58 102 35.74 50 61 64 79 63 114 35.76 39 61 71 72 60 114 35.78 48 68 76 81 73 81 35.8 57 64 68 73 90 117 35.82 62 68 82 64 58 74 35.84 52 73 71 70 82 77 35.86 50 74 84 70 79 83 35.88 58 80 93 81 77 96 35.9 56 81 66 74 77 106 35.92 62 88 71 71 85 110 35.94 74 64 103 83 86 111 35.96 63 84 102 90 89 97 35.98 68 100 110 83 90 111 36 73 96 106 87 78 106 36.02 70 99 114 109 89 114 36.04 74 103 100 83 91 110 36.06 81 114 117 79 93 107 36.08 91 116 131 111 119 111 36.1 82 119 119 113 103 84 36.12 78 116 122 131 114 87 36.14 84 125 130 108 114 83 36.16 126 120 151 104 101 91 36.18 94 153 143 121 130 89 36.2 104 153 155 129 119 109 36.22 106 125 157 122 109 99 36.24 116 130 146 105 111 98 36.26 120 161 162 113 105 114 36.28 108 138 160 123 105 100 36.3 127 156 156 114 112 103 36.32 110 139 162 120 112 84 36.34 109 148 157 115 104 87 36.36 119 153 184 111 105 96 36.38 109 163 137 118 92 115 36.4 122 139 153 149 101 88 36.42 123 147 170 126 98 115 36.44 120 130 129 114 100 95 36.46 107 131 128 113 104 120 36.48 98 147 134 111 93 86 36.5 103 117 114 111 83 112 36.52 92 137 133 122 93 118 36.54 92 113 108 99 86 111 36.56 101 95 100 103 87 109 36.58 80 104 107 91 83 91

179

Appendix D

36.6 92 102 86 101 82 85 36.62 81 100 85 84 86 107 36.64 84 91 77 91 68 94 36.66 64 95 92 77 78 110 36.68 62 87 83 93 74 108 36.7 63 77 68 97 70 105 36.72 59 84 73 80 75 83 36.74 48 87 85 81 62 112 36.76 53 80 69 80 56 98 36.78 37 76 76 75 60 93 36.8 55 80 74 76 51 77 36.82 48 56 61 64 40 88 36.84 48 66 72 78 65 100 36.86 49 58 64 71 67 117 36.88 68 68 56 71 76 114 36.9 56 87 61 75 65 107 36.92 36 63 56 59 70 99 36.94 38 69 56 71 75 101 36.96 58 51 55 59 73 93 36.98 47 70 64 69 53 99 37 58 51 71 65 53 98 37.02 53 64 67 64 62 96 37.04 39 61 69 66 59 109 37.06 49 59 68 57 61 101 37.08 53 52 66 59 54 116 37.1 59 54 62 67 67 106 37.12 42 70 66 63 71 101 37.14 42 56 78 67 65 101 37.16 45 63 68 57 67 103 37.18 52 54 57 53 69 121 37.2 41 56 73 68 65 107 37.22 66 63 59 74 60 91 37.24 44 53 53 60 54 90 37.26 49 59 73 74 73 108 37.28 52 44 56 64 60 112 37.3 46 55 72 62 66 92 37.32 53 61 68 64 58 113 37.34 38 65 60 60 55 107 37.36 48 58 72 76 55 123 37.38 46 55 66 66 63 89 37.4 39 50 71 65 69 92 37.42 42 62 54 68 60 109 37.44 36 74 62 89 62 111 37.46 45 51 56 81 56 110 37.48 48 54 57 78 57 102 37.5 39 57 59 61 55 122 37.52 45 47 48 69 56 115 37.54 40 64 61 63 70 126 37.56 54 38 65 69 58 106 37.58 42 54 80 57 56 105 37.6 42 63 67 63 64 96 37.62 35 67 58 53 59 100 37.64 48 59 63 66 72 109 37.66 46 59 61 44 72 106 37.68 43 59 58 70 73 115 37.7 46 58 46 66 73 127 37.72 48 64 63 74 61 108 37.74 39 56 58 58 58 117 37.76 51 55 53 52 54 102 37.78 34 59 70 59 61 105 37.8 52 55 51 79 49 103 37.82 56 62 67 63 66 100 37.84 46 70 65 52 66 114 37.86 49 45 74 56 68 98

180

Appendix D

37.88 45 59 68 82 50 115 37.9 50 55 60 63 52 107 37.92 55 72 86 67 66 108 37.94 52 62 66 58 87 81 37.96 34 51 78 66 52 107 37.98 41 52 61 75 68 104 38 43 56 71 59 67 117 38.02 47 56 63 62 62 86 38.04 56 62 69 67 63 101 38.06 41 52 50 71 60 104 38.08 53 66 80 74 77 90 38.1 46 65 71 56 54 102 38.12 41 62 66 67 75 122 38.14 45 64 78 67 62 108 38.16 57 60 58 50 64 111 38.18 53 78 70 61 65 108 38.2 54 60 68 65 52 102 38.22 56 57 68 74 72 98 38.24 52 68 65 78 70 88 38.26 31 55 71 56 61 100 38.28 51 64 78 65 56 76 38.3 53 69 84 75 62 107 38.32 43 61 69 89 65 121 38.34 58 62 67 75 61 101 38.36 61 59 79 80 62 115 38.38 40 72 62 65 78 106 38.4 41 71 71 57 53 97 38.42 50 60 70 77 71 111 38.44 45 68 66 79 71 100 38.46 48 84 69 69 69 109 38.48 48 58 59 69 54 120 38.5 48 57 66 75 48 110 38.52 50 55 62 70 55 100 38.54 56 67 66 65 64 89 38.56 30 61 57 72 64 115 38.58 49 63 65 68 61 111 38.6 38 67 55 62 62 107 38.62 51 79 70 60 45 107 38.64 45 62 65 83 67 87 38.66 46 56 68 73 55 93 38.68 35 68 58 64 52 114 38.7 42 57 62 61 64 99 38.72 43 56 70 64 59 92 38.74 48 63 68 76 44 101 38.76 37 42 56 80 60 107 38.78 42 64 51 65 54 108 38.8 45 47 53 79 65 104 38.82 58 61 62 64 68 105 38.84 41 65 66 76 51 109 38.86 45 61 62 57 61 114 38.88 42 59 75 72 79 126 38.9 43 48 63 58 62 103 38.92 40 65 60 60 56 130 38.94 41 65 54 61 75 97 38.96 44 63 59 71 66 124 38.98 46 74 60 60 60 109 39 38 55 60 70 54 120 39.02 41 49 78 77 70 116 39.04 43 63 80 60 48 125 39.06 47 60 64 65 68 104 39.08 50 55 76 65 56 125 39.1 42 63 78 73 65 114 39.12 41 62 65 54 79 107 39.14 32 58 70 66 70 105

181

Appendix D

39.16 42 76 74 69 55 111 39.18 40 50 66 73 61 125 39.2 46 61 66 71 72 126 39.22 49 50 64 81 67 137 39.24 49 64 64 69 70 102 39.26 39 71 58 70 57 111 39.28 49 59 72 69 71 114 39.3 52 62 53 59 62 100 39.32 60 63 58 77 72 132 39.34 63 56 70 83 65 116 39.36 40 62 72 64 63 110 39.38 53 64 63 72 60 93 39.4 52 57 67 64 75 111 39.42 50 69 66 70 64 111 39.44 56 77 77 79 81 111 39.46 62 76 71 75 65 113 39.48 43 63 68 70 76 94 39.5 57 78 68 93 63 121 39.52 46 79 70 76 74 125 39.54 55 87 80 83 84 117 39.56 56 75 78 82 71 110 39.58 52 73 97 95 66 123 39.6 52 81 76 79 91 113 39.62 52 60 74 96 81 111 39.64 49 74 96 62 69 113 39.66 49 79 89 82 76 105 39.68 58 78 106 71 94 114 39.7 52 86 79 68 85 119 39.72 76 84 74 85 79 104 39.74 66 79 80 94 75 113 39.76 71 65 75 96 76 101 39.78 94 85 79 102 63 104 39.8 60 91 86 92 94 98 39.82 76 70 77 82 77 110 39.84 55 87 77 102 92 102 39.86 56 73 80 82 82 99 39.88 58 73 86 95 88 103 39.9 57 78 97 93 85 108 39.92 64 99 91 88 108 113 39.94 51 66 82 93 76 105 39.96 61 83 80 96 76 106 39.98 61 75 83 87 77 102 40 66 71 94 108 81 105

182

Appendix E

13 Appendix E

183

Appendix F

14 Appendix F

184