Factors determining the adhesion and barrier properties of PVdC-coated PET beverage containers

355 Pages·2017·8.86 MB·English

Loughborough University
Institutional Repository
Factors determining the
adhesion and barrier
properties of PVdC-coated
PET beverage containers
ThisitemwassubmittedtoLoughboroughUniversity’sInstitutionalRepository
by the/an author.
Additional Information:
• A Doctoral Thesis. Submitted in partial fulfilment of the requirements
for the award of Doctor of Philosophy at Loughborough University.
Metadata Record: https://dspace.lboro.ac.uk/2134/27197
Publisher: (cid:13)c T.M. Robinson
Rights: ThisworkismadeavailableaccordingtotheconditionsoftheCreative
CommonsAttribution-NonCommercial-NoDerivatives2.5Generic(CCBY-NC-
ND2.5)licence. Fulldetailsofthislicenceareavailableat: http://creativecommons.org/licenses/by-
nc-nd/2.5/
Please cite the published version.
This item was submitted to Loughborough University as a PhD thesis by the
author and is made available in the Institutional Repository
(https://dspace.lboro.ac.uk/) under the following Creative Commons Licence
conditions.

For the full text of this licence, please go to:
http://creativecommons.org/licenses/by-nc-nd/2.5/
LOUGHBOROUGH
UNIVERSITY OF TECHNOLOGY
LIBRARY
AUTHOR/FILING TITLE
~O::~~~~_~~_T--I-~-------------
i_ __________
,
i- ---------------------------------------- ---------
ACCESSION/COPY NO.
1---______________ __ _ ~Q_Lf.~ ~~·Q.~~lQ _________ _
i VOL. NO. CLASS MARK
~7
30 APR 1997
- 3 OCT 1997
0401137570
1111111 111111

lFAcrolRS DlB"1!'lBl!W!l!mNG IHlB ADHlBSION
AND 18Al!UU1BlR. JP!RQlplB!RTJ!1BS
OIF JPY4C-QQAIJBD !PlBT 18lBWlMGlB mNTAlNlBlRS
A Doctoral Thesis
Submitted in Partial Fulfilment of the Requirements for the Award of
DOCTOR OF PHILOSOPHY
of the Loughborough University of Technology
01/04/1990
© T.M. Robinson 1990

rID
TIOO~~j]~
rPrIDm
j]~ ~ TI~
'TO ll:Ea'LN .....
or
IJST CONTENTS
. Section Number and Title Page Number
Acknowledgements
List or Figores ii
List or Tables v
Abstract 1
Chapter 1 Introduction 2
1.1. Objectives 3
References 5
Chapter 2 Surface Thermodynamics and Adhesion 6
2.1. Introduction 6
2.2. Thermodynamic Surface Analysis 8
2.2.1. Thermodynamic Treatment of Interfaces 10
2.2.1.1. Work of Adhesion 10
2.2.1.2. Surface Tension and Surface Energy 11
2.2.1.3. Liquid/Solid Contact Angles 11
2.2.2. Wetting 14
2.2.3. Other Methods for the Assessment of Wetting 16
2.2.4. Polar/Non Polar Character of Surfaces 16
22.5. Acid-Base Interactions 20
2.2.5.1. Implications for PVdC Copolymer Coatings 21
2.2.6. ExternallEnvironmental Effects 22
2.2.7. Sessile Drop 23
2.2.8. Surface Energy of Solids 25
2.3. Fracture Mechanics 25
2.3.1. Kinetic Methods of Adhesion Measurement 26
2.3.1.1. Blister Geometry 26
2.4. Experimental Procedure 28
2.4.1. Surfactant Solution Preparation 28
24.2. Surface Energy and Work of Adhesion 29
2.4.2.1. Test Surfaces 32
2.4.3. Peel Tests 33
2.4.4. Axial Pull-Adhesion Tests 33
2.4.4.1. Testing 34
2.5. Results and Discussion 35
25.1. Surface Energy Data 35
25.2. Wetting 50
UST of CONTENTS
2.5.3. Blister Geometty Peel Data 50
2.5.4. Pull Adhesion 51
2.6. Conclusions 53
References 55
Chapter 3 Surrace AIIalysis orpVdC Coatings and PET 58
3.1. Introduction 58
3.1.1. Identification of Surface Chemical Groups 58
3.2. Surface Analysis Techniques 60
3.2.1. Secondary Ion Mass Spectrometry (SIMS) 60
3.2.1.1. Input and Output Species 60
3.2.1.2. Data Analysis 60
3.2.2. Attenuated Total Reflectance (ATR) 61
3.2.3. Augez Electron Spectroscopy (AES) 61
3.2.4. Laser Induced Ion Mass Analysis (LIMA) 61
3.2.5. Chemical Reaction 61
3.2.6. Light Microscopy 62
3.2.7. Electron Microscopy 62
3.3. Introduction to X-Ray Photoelectron Spectroscopy (XPS) 63
3.3.1. Principle ofOperntion 64
3.3.2. Chemical Shift Data 66
3.3.3. Peak Data Analysis 67
3.3.3.1. Deconvolution and Smoothing 67
3.3.3.2. Function Minimization 6S
3.3.3.3. The Simplex Minimization Method 69
3.3.3.4. Use of the Curve Fitting Programmes 70
3.3.4. Notes on Specific Plastics 72
3.3.4.1. The PET Surface 72
3.3.4.2. PVdC Copolymers 73
3.3.4.3. Surface Composition ofPVdC Copolym= 74
3.3.4.4. Coincident Peaks 75
3.3.4.5. Deconvolution: A Summary 75
3.4. Experimental 76
3.4.1. Exposure of the Coating/Substrate Interface 76
3.4.2. XPS Analysis 77
3.4.2.1. Sample Preparation 78
3.4.2.2. Spectra Manipu1ation 78
3.5. Results and Discussion 87
3.5.1. Surface Analysis: Semi-Quantitative and Resolved Peak Data 87
liST of CONTENTS
3.5.1.1. The PET Substrate 89
3.5.1.2. PVdC Copolymer Coatings 105
3.5.1.3. Other Samples 110
3.5.1.4. Specific Points of Interest 111
3.6 Conclusions 112
References 113
Chapter 4 Polymerisation Properties and Structure of PV dC 116
4.1 Introduction 116
4.2 Polymerization Routes for Vinylidene Chloride 119
4.2.1. Homopolymerization 119
4.2.2. Copolymerization 120
4.2.2.1. Reaction Ratios of Comonomers and the ......... .
•••.••... .Effect on Copolymer Composition 120
4.2.2.2. The Q-e Scheme 122
4.2.2.3. Application of the Q-e Scheme to Multi Monomer Copolymerization 123
4.2.2.4. Statistical Treatment (Probabilities) of Copolymer Composition 124
4.2.3. Free Radical Emulsion Polymerization 125
4.2.3.1. Free Radical Generaticn 127
4.2.3.2. Monomer Addition 128
4.2.3.3. The Number of Polymer Particles 129
4.2.3.4. Colloidal Stability 129
4.3 Crystallinity Development and its Measurement 131
4.3.1. Emulsion Dialysis 132
4.3.2. Measurement Techniques 132
4.3.2.1. Infrnred Spectroscopy 132
4.3.2.2. Differential Scanning Calorimetry 133
4.3.2.3. Other Techniques 134
4.4 Glass Transition Temperature (J'g ) 134
4.4.1. Measurement of Glass Transition (Tg ) 135
4.5. Experimental 136
4.5.1. Laboratory Polymerization 136
4.5.1.1. Procedure 136
4.5.1.2. Emulsion Seed Stage 139
4.5.1.3. Monomer Feed Control 140
4.5.1.4. Latex Surface Tension and Solids Content 140
4.5.1.5. Yield 142
4.5.1.6. Emulsion Particle Size 142