r i I: 2

3,34% .e M333“ _
«I!

I

g}.
armada"

4.. :m

. u: .
“Pant!

 

Lkﬁwn . A . . . . . A , . :u
.1 .555“. . . . : .
.icrztwg. . , n . L
‘ . Eta-smug“
- ‘0‘
rain

imam»;
“p.4- \Rnx‘

m L.
3

:3 ‘

A. ,1! .

i . I.) t.

I It: .
. a.

 

a... ~ .,
n2: ..
“‘3‘. ‘
EVA.
luv.

.12.

:33 x .3
a vyﬁ:.hat1.h
£31.15: 7. _.
z 1.2!. S...
32...; z
.3

th‘Vﬁﬂu »:

 

‘ I i
I...» : up“.
2:... y” av?!"

 

. a if...

.5300: .ql
.y 31...)..31.

Inﬂux... 3
.i, , .

 

ﬁt. 1 .V

199‘. i‘ , . , I . .

m. I .....\I....r » i ‘ ‘ . V 4 . r v3. Q... I . . . .A 31...; ....‘ . I-
is. , , .

 
 
 

LIBRARIES
MICHIGAN STATE UNIVERSITY
EAST LANSING, MICH 48824-1048

This is to certify that the
thesis entitled

THE EFFECTS OF ELECTRON BEAM CURED COATINGS
ON POLYMER SUBSTRATES

presented by

NORBISMI NORDIN

has been accepted towards fulﬁllment
of the requirements for the

Master of degree in Packaging

 

 

Science
SAW,“ M

 

Major Professor’s Signature
W 97/ Lava—’97
7 /

Date

MSU is an Afﬁnnative Action/Equal Opportunity Institution

O-------g-----.----u--n-c-----—--o- --—

-.-.-.-.-.-.-.-.-.-.-i—I--

 

PLACE IN RETURN BOX to remove this checkout from your record.
TO AVOID FINES return on or before date due.
MAY BE RECALLED with earlier due date if requested.

 

DATE DUE

DATE DUE

DATE DUE

 

Mm g a 7mm

 

060;)” I

 

 

 

 

 

 

 

 

 

 

 

 

 

2/05 c:/ClRC/DateDue.indd—p.15

 

*-

THE EFFECTS OF ELECTRON BEAM CURED COATINGS ON POLYMER
SUBSTRATES

By

Norbismi Nordin

A THESIS
Submitted to
Michigan State University

in partial fulﬁllment of requirements
for the degree of

MASTER OF SCIENCE
School of Packaging

2005

ABSTRACT
THE EFFECTS OF ELECTRON BEAM CURED COATINGS 0N POLYMER
SUBSTRATES
By

Norbismi Nordin

Like ultraviolet curing, electron beam curing is a growing technology which is now
commercially available. The electron beam curing technology has been proved to offer
numerous beneﬁts and advantages in every aspect of its application. Various industries
have been switching to the technology in order to improve performance, increase
proﬁtability and gain environmental acceptance. However, in the ﬂexible packaging
materials industry, converters and end users currently appear to be fragmented in their
approach to this technology. Because concerns have been expressed about the effect of e-
beam curing on the functionality of ﬂexible packaging materials, this study will provide
converters and end users with information that will facilitate their decision about whether
e-beam cured coatings are appropriate for their applications. Performance of two co-
extruded and two metallized ﬁlms coated with electron beam curable coatings were
studied to determine whether any changes occurred as a result of the electron beam-cured
coatings. Tests of selected mechanical properties and migrational behavior of the
substrates were done on both the base ﬁlms (uncoated and uncured) and the treated ﬁlms

(coated and cured) for comparison.

Copyright by
NORBISMI NORDIN
2005

For my beloved husband and daughter, Azril Haris and Nur Alya Batrisyia

iv

ACKNOWLEDGEMENTS

All praise is due to Allah (SWT) who gave this humble servant the guidance to
ﬁnally complete this thesis as partial requirement of my master’s degree. I would ﬁrst
like to express my great appreciation to my major professor, Dr. Susan Selke for all her
guidance, advice, support, patience and kindness. I also would like to extend my
appreciation to Dr. Laura Bix and Dr. Andre Lee for their valuable comments. I would
also like to thank the Center of Food and Pharmaceutical Packaging Research (CFPPR)

for the ﬁnancial and KRAFT for the material support.

This thesis is also the result of the Du’aas of my husband, Azril Haris, my mother,
Dr. Robiah Hamzah and my daughter, NurAlya Batrisyia, for being my greatest
inspirations, for their love, encouragement and supports for me to pursue my dream.

Without all of you, I would not be able to accomplish this.

I also wish to thank Dr. Gary Burgess, Dr. Maria Rubino and Robert Hurwitz for

their help and advice, also friends at School of Packaging who always be of great help
whenever I ask for. Of course, ﬁrst and last, all praise and thanks are due to Allah (SWT),

may He (AWJ) forgive us for any mistakes and show us the right path.

TABLE OF CONTENTS

LIST OF TABLES ................................................................................ viii

LIST OF FIGURES ................................................................................. x

INTRODUCTION ..................................................................................... 1
CHAPTER 1

LITERATURE REVIEW ......................................................................... 4

1.] Electron beam source and radiation ................................................... 4

1.2 Electron beam curing ................................................................... 6

1.3 Electron beam-curable coatings ....................................................... 9

1.4 Electron beam curable coatings versus ﬁlm lamination .......................... 10

1.5 Effect of electron beam curing on properties of polymer ﬁlms .................. 12
CHAPTER 2

MATERIALS AND METHODS ................................................................ 17

2.1 Materials ................................................................................ 17

2.2 Methodology ........................................................................... 18

2.2.1 Mechanical Properties ...................................................... 18

a) Tensile properties ..................................................... 18

b) Coefﬁcient of Friction (COF) ....................................... 19

c) Tear strength ......................................................... 20

d) Heat-seal Strength ................................................... 21

e) Scuff resistance ...................................................... 23

t) Dart drop impact test ................................................ 24

2.2.2 Chemical Properties ........................................................ 24

a) Migration testing ..................................................... 24
CHAPTER 3

RESULTS AND DISCUSSION ................................. , ............................... 26

3.1 Tensile Properties ...................................................................... 26

3.1.1 Load at peak ................................................................. 27

3.1.2 Elongation at break ......................................................... 29

3.2 Coefﬁcient of Friction (COF) ......................................................... 30

3.3 Tear strength ........................................................................... 31

3.4 Heat-seal Strength ..................................................................... 33

3.5 Scuff resistance ........................................................................ 35

3.6 Dart drop impact test .................................................................. 36

3.7 Total Migration ........................................................................ 37

vi

CHAPTER 4

CONCLUSIONS AND RECOMMENDATIONS ............................................ 42
APPENDICES
A: Tests Data and Results ................................................................. 44
B: Statistical Analysis and Calculation Example ....................................... 57
C: UV/V IS Spectrums ...................................................................... 65
D: FTIR Spectrums ......................................................................... 82
REFERENCES ...................................................................................... 99

vii

LIST OF TABLES

Table 1: Comparison of material cost estimation between EB coatings and bi-layer
ﬁlm lamination .......................................................................................... 10

Table 2: Sealing conditions for all substrates ................................................... 22

Table 3: Tensile strength mean comparison between treatments, separately for each
substrate in MD and CD ................................................................. 27

Table 4: Peak load mean comparison between treatments separately for each substrate
in MD and CD ............................................................................ 28

Table 5: Mean comparison of percent elongation at break between treatments,
separately for each substrate in MD and CD .......................................... 30

Table 6: Mean comparison of the Coefficient of Static and Kinetic Friction for all
substrates .................................................................................... 31

Table 7: Tearing force mean comparison between treatments, separately for each

substrate in MD and CD ................................................................ 32
Table 8: Peak seal strength forces mean comparison between treatments, separately for

each substrate in MD and CD ........................................................... 33
Table 9: Modes of failure .......................................................................... 34

Table 10: Qualitative rub resistance romparison of substrate A and substrate B... . ........35
Table 11: Qualitative rub resistance comparison of substrate C and substrate D ........... 36
Table 12: Summary of the dart drop impact test results ....................................... 37

Table 13: Total migration mean comparison for Substrates A and B in 10% ethanolzwater
simulant .................................................................................. 40

Table 14: Total migration mean comparison for Substrates A and B in 95% ethanolzwater

simulant .................................................................................. 40
Table A.1: Tensile strength data ................................................................... 45
Table A2: Load at peak data ...................................................................... 45

viii

Table A3: Percent elongation at break data ..................................................... 46

Table A.4: Coefﬁcient of Friction data ........................................................... 46
Table A5: Elmendorf tear strength data .......................................................... 47
Table A6. 1: Peak seal strength data .............................................................. 48
Table A.6.2: Average seal strength data .......................................................... 48
Table A.7.1: Dart drop chart Of substrate A ...................................................... 49
Table A.7.2: Dart drop chart of substrate B ...................................................... 50
Table A.7.3: Dart drop chart of substrate C ...................................................... 51
Table A.7.4: Dart drop chart of substrate D ...................................................... 52
Table A8. 1: Total migration for substrate A in 10% ethanol:water simulant .............. 53
Table A.8.2: Total migration for substrate B in 10% ethanol:water simulant .............. 53
Table A.8.3: Total migration for substrate A in 95% ethanol:water simulant .............. 54
Table A.8.4: Total migration for substrate B in 95% ethanol:water simulant .............. 54
Table A.8.5: Total FCS for substrate C in 10% ethanol:water simulant ..................... 55
Table A.8.6: Total FCS for substrate D in 10% ethanol:water simulant ................... .55
Table A.8.7: Total FCS for substrate C in 95% ethanol:water simulant ..................... 56
Table A.8.8: Total FCS for substrate D in 95% ethanol:water simulant ..................... 56

ix

LIST OF FIGURES

Figure 1: Schematic of electron gun ................................................................ 4
Figure 2: EZCure electron EB curing unit by Energy Science, Inc ............................ 8
Figure 3: EZCure electron EB curing unit dimensions .......................................... 9
Figure C. 1 .1: Substrate A in 10% ethanol for 24 hours ........................................ 66
Figure C. l .2: Substrate A in 10% ethanol for 48 hours ........................................ 66
Figure C.1.3: Substrate A in 10% ethanol for 120 hours ....................................... 67
Figure C.1.4: Substrate A in 10% ethanol for 240 hours ....................................... 67
Figure C.1.5: Substrate A in 95% ethanol for 24 hours ........................................ 68
Figure C. 1 .6: Substrate A in 95% ethanol for 48 hours ........................................ 68
Figure C. l .7: Substrate A in 95% ethanol for 120 hours ....................................... 69
Figure C.1.8: Substrate A in 95% ethanol for 240 hours ....................................... 69
Figure C2. 1: Substrate B in 10% ethanol for 24 hours ........................................ 70
Figure C.2.2: Substrate B in 10% ethanol for 48 hours ........................................ 70
Figure C.2.3: Substrate B in 10% ethanol for 120 hours ....................................... 71
Figure C.2.4: Substrate B in 10% ethanol for 240 hours ....................................... 71
Figure C.2.5: Substrate B in 95% ethanol for 24 hours ........................................ 72
Figure C.2.6: Substrate B in 95% ethanol for 48 hours ........................................ 72
Figure C.2.7: Substrate B in 95% ethanol for 120 hours ....................................... 73
Figure C.2.8: Substrate B in 95% ethanol for 240 hours ....................................... 73
Figure C.3.1: Substrate C in 10% ethanol for 24 hours ........................................ 74
Figure C.3.2: Substrate C in 10% ethanol for 48 hours ........................................ 74
Figure C.3.3: Substrate C in 10% ethanol for 120 hours ....................................... 75

Figure C.3.4: Substrate C in 10% ethanol for 240 hours ....................................... 75

Figure C.3.5: Substrate C in 95% ethanol for 24 hours ........................................ 76
Figure C.3.6: Substrate C in 95% ethanol for 48 hours ........................................ 76
Figure C.3.7: Substrate C in 95% ethanol for 120 hours ....................................... 77
Figure C.3.8: Substrate C in 95% ethanol for 240 hours ....................................... 77
Figure C.4.1: Substrate D in 10% ethanol for 24 hours ........................................ 78
Figure C.4.2: Substrate D in 10% ethanol for 48 hours ........................................ 78
Figure C.4.3: Substrate D in 10% ethanol for 120 hours ....................................... 79
Figure C.4.4: Substrate D in 10% ethanol for 240 hours ....................................... 79
Figure C.4.5: Substrate D in 95% ethanol for 24 hours ........................................ 80
Figure C.4.6: Substrate D in 95% ethanol for 48 hours ........................................ 80
Figure C.4.7: Substrate D in 95% ethanol for 120 hours ....................................... 81
Figure 04.8: Substrate D in 95% ethanol for 240 hours ....................................... 81
Figure D.1.1: Substrate A in 10% ethanol for 24 hours ........................................ 83
Figure D.1.2: Substrate A in 10% ethanol for 48 hours ........................................ 83
Figure D. 1 .3: Substrate A in 10% ethanol for 120 hours ....................................... 84
Figure D.1.4: Substrate A in 10% ethanol for 240 hours ....................................... 84
Figure D. 1 .5: Substrate A in 95% ethanol for 24 hours ........................................ 85
Figure D. 1 .6: Substrate A in 95% ethanol for 48 hours ........................................ 85
Figure D.1.7: Substrate A in 95% ethanol for 120 hours ....................................... 86
Figure D.1.8: Substrate A in 95% ethanol for 240 hours ....................................... 86
Figure D2. 1: Substrate B in 10% ethanol for 24 hours ........................................ 87
Figure D.2.2: Substrate B in 10% ethanol for 48 hours ........................................ 87

xi

Figure D.2.3:
Figure D.2.4:
Figure D.2.5:
Figure D.2.6:
Figure D.2.7:
Figure D.2.8:
Figure D.3.1:
Figure D.3.2:
Figure D.3.3:
Figure D.3.4:
Figure D.3.5:
Figure D.3.6:
Figure D.3.7:
Figure D.3.8:
Figure D.4.1:
Figure D.4.2:
Figure D.4.3:
Figure D.4.4:
Figure D.4.5:
Figure D.4.6:
Figure D.4.7:

Figure D.4.8:

Substrate B in 10% ethanol for 120 hours ....................................... 88
Substrate B in 10% ethanol for 240 hours ....................................... 88
Substrate B in 95% ethanol for 24 hours ........................................ 89
Substrate B in 95% ethanol for 48 hours ........................................ 89
Substrate B in 95% ethanol for 120 hours ....................................... 90
Substrate B in 95% ethanol for 240 hours ....................................... 90
Substrate C in 10% ethanol for 24 hours ........................................ 91
Substrate C in 10% ethanol for 48 hours ........................................ 91
Substrate C in 10% ethanol for 120 hours ....................................... 92
Substrate C in 10% ethanol for 240 hours ....................................... 92
Substrate C in 95% ethanol for 24 hours ........................................ 93
Substrate C in 95% ethanol for 48 hours ........................................ 93
Substrate C in 95% ethanol for 120 hours ....................................... 94
Substrate C in 95% ethanol for 240 hours ....................................... 94
Substrate D in 10% ethanol for 24 hours ........................................ 95
Substrate D in 10% ethanol for 48 hours ........................................ 95
Substrate D in 10% ethanol for 120 hours ....................................... 96
Substrate D in 10% ethanol for 240 hours ....................................... 96
Substrate D in 95% ethanol for 24 hours ........................................ 97
Substrate D in 95% ethanol for 48 hours ........................................ 97
Substrate D in 95% ethanol for 120 hours ....................................... 98
Substrate D in 95% ethanol for 240 hours ....................................... 98

xii

INTRODUCTION

The use of electron beam (EB) curable coatings, inks and adhesives has increased
dramatically over the last decade. Energy curing use in packaging decoration and
protection started with the ﬁrst commercial run of UV (ultraviolet light) curing inks and
coatings in 1969.(10‘12) The use of EB products for similar application took another ten
years for commercialization due to economic considerations. These technology are used
in a variety Of applications such as printing inks, overprint varnishes, release coatings,
primers, pigmented paints, clear topcoats, pressure sensitive adhesive and the list of
applications keeps growing within a very wide range of industries“) Flexible ﬁlms used
as packaging materials is one of the industries that are developing the use of EB curing
technology in many applications.

The recent advances in electron beam curing chemistry and curing equipment
encouraged the increased use of this technology, besides offering numerous advantages
over conventional curing systems. RadTech International summarized three compelling
reasons to convert to UV and EB technologym) The ﬁrst, improved productivity, is
based on the speed of curing, which is generally less than a second, compared to
conventional coating methods. Compared to water base coatings web line speeds of 500

feet per minute (15)

, it is not uncommon for BB or UV technology to have web line speeds
of 1,000 feet per minute. The second advantage is suitability for sensitive substrates
because most EB ad UV systems do not contain water or solvent. With total control of

the cure temperature, the process becomes a very practical choice for heat-sensitive

substrates. The third reason is that it is both environmentally and user friendly. Since

typical compositions are solvent-free, emissions and ﬂammability are no longer an issue.
Compatibility with virtually any application technique is a characteristic with light cure
systems and space requirements are minimal. For example, UV lamps can generally be
installed on existing production lines. More advantages of this technology will be
explained in detail in the literature review.

Despite all of these advantages, UV or EB still have not been universally accepted
as technologies of choice for converters. The reasons seem to be most evident in ﬂexible
packaging, particularly for food packaging. The three major reasons are the cost Of
materials, the fear of adopting a relatively new and radical method, and the impression
that that the chemistry is or can be harrnful.('2’24) Actually all these reasons unfounded. A
review of the literature shows that application of this technology will result in signiﬁcant
savings on materials and equipment costs, and that they are safer than conventional
systems. (12. 17, 21.38, 43)

Another concern of converters and end users regards the actual application of EB
curing to ﬂexible packaging materials as the substrate. The impact of the EB curing on
the substrate itself needs to be studied, since the energy can cause changes within the
substrates just as the energy will cause the ink or coating to crosslink. As EB energy can
be used to alter products to achieve desired features, further exposure might result in
degradation of those properties. Based on these concerns, this study investigated the
effect of EB curing on the functionality of several ﬂexible packaging materials. The
effects of EB curing of overprint varnishes on different laminating ﬁlms were quantiﬁed.

Selected mechanical and chemical properties of substrates were evaluated to determine

what changes occurred as a result of the e-beam cured coatings. The results of this study

will provide converters and end users with information that will facilitate their decision

about whether EB cured coatings are appropriate for their applications.

CHAPTER 1
LITERATURE REVIEW

1.1 Electron beam source and radiation

Electron beams are generated using electron guns in a manner similar to that used
in a TV picture tube. A beam from these guns can be deﬂected and focused magnetically
to create a small spot that moves rapidly. Another way to generate EB is by using linear
ﬁlaments and cathodes, directed by electrostatic electrodes to form their image on a
substrate, as in Figure 1. For higher energy and higher production speed requirements,

multiple ﬁlaments or cathodes can be used.

 

Structure Terminal

 
   
  
  
  
 
 

Electron Gun
Chamber (W)

Filamen (F)
Vacuum
Electron Beam (B)
Shielding
Metallic Foil (F)

Moving product (P)

 

 

 

Figure 1: Schematic of electron gun (50)

On an industrial scale, accelerators are used to generate electrons. When the
generated electron-beam is directed at a target consisting of a high-atomic-number metal,

such as tungsten or gold, X-rays with a broad spectrum of energies will be produced. The

amount of energy absorbed, also known as the dose, is measured in units of kiloGrays
(kGy), where 1 kGy is equal to 1,000 Joules per kilogram, or MegaRads (MR or Mrad),
where 1 MR is equal to 1,000,000 ergs per gram. The accelators are generally described
in terms of their energy and power. The low-energy accelerators range from 150 keV to
2.0 MeV while the medium-energy accelerators have energies between 2.5 and 8.0 MeV.
High-energy or electron linear accelerators have beam energies above 9.0 MeV.
Accelerator power is a product of electron energy and beam current. Available beam
powers range from 5 to about 300 kW, for example a 5.0 MeV accelerator at 30 mA will

have a power of 150 kW.(34)

Ionizing radiation is radiation that can ionize a molecule. The term ionizing
radiation usually refers to the type of radiation that will ionize oxygen in air. Therefore, it
is, radiation with a wavelength shorter than 253 nm, which includes x-rays generated in
EB-curing systems. Unlike UV energy, EB energy ionizes anything in its path until all
electrons are absorbed.(50) In general, EB radiation of materials begins when electrons
with typical energies in the keV and MeV range are absorbed in matter and produce
secondary electrons as a result of the energy degradation process. The fast electrons
results in the formation of radicals, ions, trapped electrons and excited states of molecules
or atoms through a Coulomb interaction of these secondary electrons with the atoms or
molecules of the absorber. As a result, these fast electrons are able to initiate chemical
changes in materials and modify them. Details on the principles and chemistry of
ionizing radiation are well described elsewhere. (10’26’50)

For more than 40 years, such kinds of modiﬁcations have been used to change

polymer structures and propertiesm) Structure and property modiﬁcations such as

grafting, crosslinking and degradation of polymers can be induced by these electrons and
by other ionizing radiation. Modiﬁcation of the surface properties of polymers by
grafting is achieved by graﬁ copolymerization with different monomers. Grafting of
polymers can be accomplished by electron beam irradiation of the polymer backbone to
form radical sites, which then react with monomers present as liquid or vapor. Cross-
linking usually tends to improve mechanical and thermal properties and chemical,
environmental and radiation stabilities of materials. It occurs when two radicals produced
on neighboring polymer units recombine. The relative molecular mass of the
macromolecule increases and the melting point rises. Simultaneously to cross-linking,
polymer degradation may take place by chain scission, which can lead to a decrease of
the molecular mass. However, in some materials only one of these effects may be
predominant during the radiation process. “6) Various applications of BB in achieving ,

desired modiﬁcations mentioned above are presented elsewhere. “4"6‘18'2'32’25’33'47’

1.2 Electron beam curing

EB curing is deﬁned as “the use of electron beams as an energy source to induce a
rapid conversion of especially formulated 100% reactive liquids to solids”.(33) Free radical
or cationic polymerization is initiated by the fast electrons and then followed by intensive
crosslinking. In such way, dense polymer networks with tremendous abrasion, scratch
and chemical resistance are produced.

Cationic polymerization differs from classic radical polymerization in several
ways. The polymerization is not affected by oxygen, therefore curing can be done in air

without a nitrogen blanket. The initiating species can be a stable chemical compound

(including a proton or a carbonium ion) and usually can endure much longer than a free
radicals. A considerable post-cure effect is observed; cationic polymerization results in a
slower curing process than with free radicals. The initiating species can migrate over
macroscopic distances even in opaque materials and in the dark (i.e. after radiant energy
exposure stops). Cationic polymerization is also often supported by thermal activation.
Besides all the applications mentioned above, the most important and growing
application of fast electrons with typical energies between 120 and 300keV (electron
beam) is curing of solvent-free monomer/Oligomer coatings, paints and printing inks.(33)
Although EB curing technology is a long established, 30-year-old technology with solid
advantages, the curing units have traditionally been cost prohibitive. Dump truck sized
curing units were criticized for consuming; additionally, these units commonly cost
around seven ﬁgures, a signiﬁcant capital investment. Modiﬁcation and calibration of the
curing unit to collaborate with an existing process line also has been a huge contribution
in this prohibitive cost. (37)
The recent increased interest in this application is, in part, a result of the recent
availability of lower-voltage, lower-cost EB units“) For ﬂexible packaging material, e-
beam curing offers a number of advantages, especially to the converters. A high speed
curing process that instantly dries up all coatings or ink in-line, producing 100% solid
coatings, results in very high throughput rates. The lack of photoinitiator for curing the
electron beam-based coatings/inks results in lower-cost formulation than UV-based

coatings or inks. The utilization of energy in BB curing is also reported to be more

efﬁcient than the forced-air drying tunnels for water-based or and solvent-based cured

coatingsm) Unlike thermal curing, strict temperature or moisture controls may not be

needed as only a moderate increase of temperature (about 15°C) occurs during the curing.

Other than that, EB curing offers competitive treatment cost per unit of product
compared to more conventional chemical processes and it also produces hard, high gloss,
stain, chemical and abrasion resistant ﬁnishes, especially for coatingsm‘m The use of
volatile or toxic chemicals can be avoided since uses solventless inks and varnishes. This
results in very low to no Odor and extractables, and complies with the environmental and
FDA regulation. In addition, there is no need for oxidizers, incinerators or solvent-waste
disposal as required for solvent-based systems.(27‘35) Less space than for drying ovens
associated with water- and solvent-based systems is now required for a compact e-beam
curing unit, which can easily be ﬁt in any desired place in the production or printing line

(Figure 2 & 3).”“5’

 

 

Figure 2: EZCure electron EB curing unit by Energy Science, Incas)

 

 

 

   
    

 

 

5843 6233’
[1492] [1594]
Lts
[3751

 

l

115i4]

 

 

 

Figure 3: EZCure electron EB curing unit dimensions in inch [mm]. (28)

1.3 EB- curable coatings

EB-curable coatings generally consist of solventless liquids that can be applied to
a substrate and converted into a solid, adherent ﬁlm within a fraction of a second upon
exposure to a beam of electrons. The coatings are combinations of oligomers (polymers
with low molecular weights) and monomers, which control the viscosity before curing.
Typical oligomers are acrylated urethane polyesters, acrylated epoxies and polyesters. A
typical multifunctional monomer is trimethylolpropane triacrylate (TMPTA).“6) Flat
surfaces such as paper sheets or webs, plastic sheets or ﬂexible ﬁlms, plastics, metal and
wood are common materials used as the substrate. Typical application techniques for EB-

cured coatings are spray, roll coating, and curtain coating“)

According to a survey done by RadTech International, one of the most signiﬁcant
applications of EB-curable coatings is in graphic arts coatings.‘l3 ‘17) Accounting for
about 25% of the use of all UV/EB formulated products, this application is the single

biggest end user, with over 19,000 metric tons of product by year 2001. Many survey

respondents indicated that EB overprint coatings applications including ﬂexible ﬁlm, foil
and board offer good potential growth and graphic arts applications (including coatings
and inks) for food packaging represents a big potential growth opportunity.

Issues of health and safety concerns in using electron beam curable coatings for
food packaging applications were explained by Dr. Don Duncan, Director of Research at
Wikoff Color Corporation. According to him, the EB coatings, when properly applied
and cured, are fully suitable for most food packaging applications where three conditions
apply: ﬁrst, there is no intent of direct contact; second, the UV/EB print is separated from
the food by a “functional barrier”; and third, the use of the UV/EB inks or coatings

results in a food package free of Odor or taintm)

1.4 Electron Beam curable coatings versus film lamination

Flexible ﬁlm used as packaging materials in confectionary packaging for instance,
involves the use of reverse-side-printed oriented polypropylene (OPP), which is then
adhesive-laminated to another opaque ﬁlm. A cold-seal adhesive is Often then applied to
the backside of the opaque ﬁlm for subsequent cold sealing after ﬁlling. Replacing this
bi-layer laminate structure with a single ply ﬁlm (e. g. a direct-printed mono-web of
thicker OPP ﬁlm) and an EB ‘top coat’ delivers signiﬁcant savings in material cost to the
converter and the end-user alike. BB is used to cure these overprint coatings with
properties strong enough to replace a layer of that opaque ﬁlm. Additionally, since the
ﬁlm will be wound on itself with the cold-seal adhesive on its backside, the EB-curable

coatings must also have excellent block resistance. (27)

10

Another practical objective in using EB-curable coatings is to replace an outer
ﬁlm in constructions in which the outer ﬁlm functions only for graphics protection. “827)
The EB-curable coatings, when applied over the printing, result in improved scratch and
scuff resistance and provide high gloss, are odor free because they contain no
photoinitiator, and provide a manageable coefﬁcient of friction (COF). In addition to the
material savings realized from replacing a layer of ﬁlm, there are the cost reductions
realized from streamlining the printing and converting process. Many laminated
structures take days to complete while EB cured coatings are processed instantly in-line,

thus allowing the converter to print and ship the product in the same dayfzng)

A cost estimation on the use of EB coating versus lamination was done by Rick
Sanders of Energy Sciences, Inc. to provide information to the converter and end-user on

how EB coating can yield signiﬁcant savings in material cost (Table 1).“)

Table 1: Comparison of material cost estimation between EB coatings and bi-layer
ﬁlm lamination

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

EB COATINGS vs. LAMINATIONS
Replace Two-Ply Laminations with Monoweb and EB Overprint Varnish
Assumptions:
Product Width 36 inch Wide
Production Hours 4,000 hours per year
Line Speed 500 feet per minute
Total Annual Production 51.8 MSI
Current Structure Proposed Structure
SOG BOPP/RP/ADH/I .4 Mils 2.0 mil BOPP/Surface Print/EB
BOPP OPV
$ per 1,000 Square Inches (MSI) $ per 1,000 Square Inches (MSI)
Cost of 500 & 1.4 Mils
OPP $0.1207 -----
Solvent-Based Adhesive $00100 -----
Cost of2.0 Mil OPP ----- $01000
EB OPV @ $4.00/lb
And 1.8 lbs/ream ..... $00160
Total $01307 per MSI $0.1 160 per MSI
Total Cost per Year $6,770,260 $6,008,800
Net Savings per Year $761,460

 

 

 

 

Source: Ink World Magazine, February 2003

11

The economic and toxic reduction assessment for Metallized Products, Inc. (MP1)
in Manchester proved that the use of EB-coatings for their product resulted in a huge
economic advantage when compared to thermal coating.(49) Even though a large capital
investment was required for purchasing and installing the EB-unit, MPI was able to
recover their investment, on their second EB-unit, over the course of two years because
numerous factors affected annual operating costs, such as production speed and energy
cost.

Even though converting from conventional coating systems to electron beam
cured coating systems has proven to offer numerous advantages, development of this
technology is still in the early stages compared to other EB curing applications. Only a
small amount of literature related to EB-cured coatings on polymer substrates is
available. Recent articles and papers on EB curing of coatings mostly emphasized
advantages of converting from the use of conventional coatings to the EB-curable
coatings.

The available studies from late 80$ throughout the 903 on EB curing or
processing of newly-developed polymers mostly provide ideas on correlation of some
parameters such as degree of curing and radiation doses to the mechanical and chemical

properties of the electron beam-cured samples.

1.5 Effect of electron beam curing on properties of polymer films

As EB curing is expected to result in modiﬁcations of at least the polymer

surface, a primary objective of most of the studies was to examine how far EB curing will

12

affect the properties and functionality of the cured polymers. Selected mechanical
properties such as tensile properties, hardness, and ﬁlm structure plus migrational
behavior (total/overall migration) of the EB-cured samples were thoroughly discussed.

In a study on the effects of ionizing treatments (gamma photons & electron beam)
on food simulant-packaging material combinations, Pillettem) proved that the electron
beam treatment (energy of 6 MeV) did not show any statistically signiﬁcant difference in
the structural, physicochemical and mechanical properties of the combinations, control
and treated ﬁlms. No statistically signiﬁcant differences were also found for
combinations in the total migration test in alcoholzwater simulants. Very small total
migration was also found within the limit of the detection level (<1mg/dm2). The
chemical analysis of volatiles showed the formation of hydrogen and methane. For that
reason, some “microscopic” modiﬁcations were expected in the ﬁlms due to the
treatment.

The effect of EB radiation dosage and sensitizer (tri-methylolpropane
trimethacrylate, TMPTMA) level on tensile properties of EVA was investigated by
Datta.“9) The study showed that a higher amount of TMPTMA and higher dosage of
radiation both had an adverse effect on the mechanical properties of EVA. Tensile
strength and elongation at break depend on the degree of strain-induced crystallization
which, in turn, depends on the polymer chain length and degree of crosslinking.
Therefore, when crosslinking increases, the tensile strength may increase up to a certain
level, beyond this level, the tensile strength is expected to decrease. A decrease in tensile

strength might also result from a decrease in chain length due to chain scission. On the

13

other hand, the modulus, which strongly depends on crosslinking density, was found to
increase with increased degree of crosslinking.

Oliver et al (39) studied the mechanical properties of electron beam cured
tripropylene glycol diacrylate (TPGDA) and propoxylated glycerol triacrylate (GPTA)
ﬁlms. The ﬁlms were cured with two radiation doses (7.5 kGy and 105 kGy) and their
tensile properties, including Young’s modulus, were determined. For higher dose samples
(105 kGy) , tensile stress rise was steep at low draw ratios, indicating a larger Young’s
modulus compared to the lower dose samples. As the electron beam curing dose
increased, mechanical rigidity of the polymer network substantially increased, which is
attributed to an increase of crosslinking density.

The acrylic resins used in the electron beam curing applications allow the widest
latitude of formulation, besides representing the fastest curing systems. With proper
formulation, acrylics can cure with doses as low as 1-5 Mrad. Even though the dose-to-
cure is equally important for a variety of acrylic systems, this system is not highly dose-

rate (current in mA) dependent. A study by Schroeter‘46)

on the effect of dose on
properties for silicon resin mixtures consisting of various mixtures of acrylate and
methacrylate monomer/polymer per thousand grams of silicon resin showed that the
MEK-rub resistance obtained at any given dose is independent of dose rate. He also
proved that properties such as solvent resistance and hardness of EB-cured resins
improved as the total dose increases.

A similar study that supports Schroeter was done by Batten et al.(1 I) on electron

beam curing of silicon-containing acrylates as a new surface-coating material.

Performance and ﬁlm-forming properties of a series of synthesized silicon-containing

14

mono-, di-, tri- and tetraacrylates at increased curing doses were reported based on the
results of similar physical tests; solvent rub resistance, pencil hardness and brittleness.
From the results, they found that all tested silicon-containing acrylates cured rapidly at
low doses. With increasing curing dose (2.5, 5, 10, 20, 40 and 60kGy), only tetraacrylates
and triacrylates cured at low doses to give hard ﬁlm with a high degree of ﬂexibility
while possessing good solvent resistance. On the other hand, monoacrylates polymerized
to give highly viscous ﬂuid, whereas diacrylates cured rapidly to give soﬁ ﬁlms.

Lox and Waldenm) did a study using a UV spectrophotometer to assess the effect
Of electron beam radiation upon migrational behavior of plastics. A single-sided
migration test for 10 days at 40°C with ethanol:water was done on shrinkable PVC ﬁlms
radiated with increasing radiation doses from 3, 5, 7.5, 10, 20 and 25 kGy. A detailed
explanation of how to measure migration and migrational behavior can be found in their

(3 1) and in a study by Lox et al.(29) The ﬁnal result for total migration

previous study
clearly demonstrated a drastic rise of migration rates at low-dose rate, probably due to the
formation of small molecules. Conversely, at higher doses (>10 kGy), the migration rate
decreases. The radiation process interferes with the pure migrational process (migration
of un-radiated ﬁlms) as less diffusible molecules were present after the high-dose
exposure of the ﬁlm.

A study on effects of electron beam treatment Of the principal ﬂexible food
packaging materials (LDPE and OPP) by Gante and Pascattm) focused on chemical
structure and mass transfer phenomena with an increasing dose of radiation. NO

signiﬁcant changes were observed in the structure of polymer matrices or in oxygen

permeability after ﬁlms were treated at approved dose levels (<110kGy). However,

15

several structural changes were observed by FTIR analysis at 100kGy and higher. With
regard to total migration in ethanol:water simulants, all total migration data at increased
doses were < 1 mg/dmz, which is within the accepted limits Of European Communities
(EC) Regulations for polyoleﬁns. The chemical analysis of volatiles from these ﬁlms
showed the presence of many different compounds in the treated ﬁlm, which is
comparable to the results from Lox and Walden.

As mentioned before, the EB-curable coating must have an excellent block
resistance. Block resistance is the tendency of a coating not to adhere to another surface.
An example Of poor block resistance is when a part is painted and wrapped with paper,
and the paper sticks to the “dry paint”. If the paint is fully dry and not able to ﬂow, the
block resistance is usually good. Kauffmanm) proved that a commercially available EB
coating for OPP for confectionary applications, termed as a release lacquer, exhibits low
Odor, high gloss, low COF and exceptional block resistance to a widely used cold-seal

adhesive.

16

CHAPTER 2

MATERIALS AND METHODS

2.1 MATERIALS

All ﬁlm samples were provided by Kraft. The tested substrates were 2 coextruded
ﬁlms (Substrates A and B) and 2 metallized polypropylene ﬁlms (Substrates C and D).
One overprint varnish, coded as C1, had been applied to the coextruded polypropylene,
and a different varnish, C2, to the metallized ﬁlms, and the varnishes were e-beam cured
before receipt. Identical base ﬁlms were also provided. The coated ﬁlms were also
printed with blue, white and blue plus white, each color in 50mm stripes at the center area
of the ﬁlms. The base ﬁlms (uncoated and unprinted) were tested as controls, for
comparison with the e-beam cured coated ﬁlms.

Substrate A was a ﬁve-layer ethylene vinyl alcohol (EVOH) co-extruded ﬁlm
with a plastomer sealant consisting of co-polymer polypropylene (COPP) / tie / EVOH /
tie / linear low density polyethylene (LLDPE)-Metallocene sealant. Substrate B was a
ﬁve-layer EVOH ﬁlm coextruded with ethylene vinyl acetate (EVA) and cyclic oleﬁn
copolymer-LLDPE (COC-LLDPE) consisting of COC-LLDPE / tie / EVOH / tie / EVA.
Both substrates had a gauge of 3.0 mils and were coated with C1 coating.

Both substrates C and D were metallized OPP with C2 coating. The differences
between the two substrates were that substrate C was a vacuum-metallized, high barrier
OPP ﬁlm with proprietary sealant with 0.7 mil gauge, while Substrate D was an
asymmetrical opaque barrier PP ﬁlm metallized on one side and heat sealable on the

other side, with 1.0 mil gauge.

17

2.2 METHODOLOGY

The mechanical properties tested included tensile properties, Elmendorf tear
strength, dart drop impact strength, coefﬁcient of friction, scuff resistance and heat seal
behavior. The tests were performed according to standard ASTM methods, with
appropriate modiﬁcation.

The chemical properties testing involved 95% ethanol and 10:90 ethanol/water,
the FDA-recommended simulants for fatty foods and for aqueous, acidic and low-
alcohol-containing foods, respectively, for migration testing. The extracted liquid was
tested by spectrometry techniques, and the pattern of peaks from the cured coated

materials compared to that from the base ﬁlms.

2.2.1 MECHANICAL PROPERTIES TESTS

A) Tensile Properties

The test for tensile properties of the substrates was performed according to
standard ASTM method D882-01 “Standard Test Method for Tensile Properties of Thin
Plastic Sheeting?“ This test method covers determination of tensile properties of plastics
in the form of thin sheeting, including ﬁlm less than 1.0 mm or 0.04 inch in thickness. In
this test, tensile properties of the control ﬁlms were compared to the treated ﬁlms. For the
treated ﬁlms, there were three treated areas of interest in the ﬁlm structure where the
tensile strength was measured: coated, uncoated and printed. Printed samples were taken

from the printed center area of the ﬁlms. Uncoated samples were taken from the ﬁlm

18

edges. Coated samples were taken from the coated but unprinted area between the
uncoated edge and the printed center.

Since the substrates were anisotropic materials, a total of ten specimens were
tested from each substrate, ﬁve replicates each for the machine and cross directions. The
thickness of each substrate (control, uncoated, coated and printed) was measured with an
auto micrometer by Testing Machines, Inc. (model 549M) according to ASTM D 6988-
03 “Standard Guide for Determination of Thickness of Plastic Film Specimens.”(8) Based
on ASTM D 6287-98 “Standard Practice for Cutting Film and Sheeting Test Specimens,”
(7) the JDC Precision Sample Cutter (Model 1-10) was used to cut the ﬁlms into strips of
uniform 25 mm (1.0 in) width and length at least 50 mm (2.0 in.) longer than the grip
separation. The INSTRON 4201 machine with initial grip separation of 2 inch and
crosshead speed of 20 in/min was used to obtain the specimens’ break/peak load and

elongation. Detailed procedures and apparatus used are described in the ASTM standard.

B) Coefﬁcient of Friction (COF)

The static and kinetic coefﬁcients of friction (COF) of the plastic ﬁlms were
determined according to the standard ASTM method D1894 “Static and Kinetic
Coefﬁcients of Friction of Plastic Film and Sheeting?“ The method covers
determination of coefficients of starting and sliding friction of plastic ﬁlm and sheeting
when sliding over itself or other substances at speciﬁed test conditions.

The Monitor/Slip Friction machine (model 32-06) by Testing Machines Inc.
which is equipped with a moving sled with a stationary plane similar to Method A of

assembly of apparatus in the ASTM standard was used in this test. This equipment has

19

the ability to calculate and display both static and average kinetic COF during one test
cycle. A square metal block sled of 200 grams weight, measuring 2.5 inch by 2.5 inch
was used for testing both the control and the treated ﬁlms. For the treated ﬁlms, both
unprinted and printed areas were randomly tested. Five specimens of 3 inch by 18 inch
from each substrate were tested for both static and kinetic coefﬁcient of friction. As the
ﬁlms may exhibit different frictional properties in their respective principal directions
due to anisotropy or extrusion effects, the common practice of testing the specimens was
employed, that is by testing with the ﬁlm’s machine direction on machine direction (MD

on MD).

C) Tear Strength

The substrates’ tear strength was measured using an Elmendorf tear tester using a
similar method as for paper. The test for tear strength was performed according to the
standard ASTM method D1922-03a “Propagation Tear Resistance of Plastic Film and
Thin Sheeting by Pendulum Method” to determine the average force to propagate tearing
through a speciﬁed length of plastic ﬁlm or nonrigid sheeting after the tear has been
started, using an Elrnendorf-type tearing tester. Rectangular specimens were cut using an
Elmendorf standard cutter.(4) The tearing force of both the EB-cured ﬁlms and control
ﬁlms was measured in the machine direction (MD) and cross direction (CD). For the
treated ﬁlms, there were two treated areas of interest in the ﬁlms’ structure where the
tearing force was measured: unprinted and printed. Printed samples were taken from the
printed center area of the ﬁlms while the unprinted samples were taken randomly from

the unprinted area of the ﬁlms.

20

The Elmendorf tearing tester (Model 60-100) by Thwing-Albert Instrument
Company was used in this test. Determination of number of plies to be used in testing for
each substrate differs based on several factors such as the tearing behavior and the
average scale reading obtained from the test. Based on the standard, the maximum
accuracy of the apparatus lies in the scale range from 20 to 60. Therefore, enough
sandwiched specimens should be tested to produce a scale reading between 20 and 60.

The number of plies for Substrate A was based on the scale reading produced by
its CD specimens since the MD did not produce a scale reading within the required range
(20 — 60). A single ply was used for Substrate B based on its tear behavior (oblique tear
in opposite direction). For both metallized ﬁlms (Substrates C and D), the appropriate
numbers of plies were selected to produce scale readings of 10 or 20 only, since both
substrates are relatively weak. The maximum number of plies that ﬁt into the

instrument’s clamp was not sufﬁcient to produce the desired scale readings (2O -60).

D) Heat— Seal Strength

The heat-seal strength of both cured and control ﬁlms was measured in the MD
and CD according to the ASTM F88-OO “Standard Test Method for Seal Strength of
Flexible Barrier Materials?“ For the treated ﬁlms, only printed and unprinted areas were
evaluated. The unprinted specimens were randomly cut from the unprinted coated or
unprinted uncoated areas on the ﬁlms. The ﬁlms were cut into l-inch wide strips using a
JDC Precision Sample Cutter (model JDC 1—10) and ﬁn-sealed with seal width of 1.0

inch, under speciﬁed conditions of temperature, pressure and dwell time. Both sealers

21

used are from SENCORP Systems, Inc., the hot jaw heat sealer (Model 12ASL) and the
thermal impulse sealer (Model 16TP).

Samples of all substrates were sealed initially with sealing conditions provided by
the manufacturers. However, due to different sealers used for sealing, the ﬁnal sealing
conditions were based on the strongest seal that could be achieved. The sealing

conditions for all substrates are summarized in Table 2 below:

Table 2: Sealing conditions for all substrates

 

FILMS SEALER TYPE SEALING CONDITIONS
Temperature: 24OF
Substrate A Hot J aw Heat Sealer Dwell time : 0.5 second
Pressure : 25 psi
Temperature: 250F
Substrate B Hot Jaw Heat Sealer Dwell time : 1.4 second
Pressure : 25 psi
Temperature: 230F
Substrate C Hot Jaw Heat Sealer Dwell time : 1.0 second
Pressure : 25 psi

Dwell time : 0.6 second
Pressure : 30 psi

 

 

 

 

Substrate D Thermal Impulse Sealer

 

 

 

 

 

Seven sealed replicates were prepared for each substrate ﬁlm: control, unprinted
and printed. The IN STRON 5565 machine with grip separation rate of 12 inch per minute
and initial grip separation distance of 1 inch was used to obtain the average and peak load
from the seal proﬁle (plot of force versus grip separation). The method used to hold the

ﬁlm specimens during the test was the unsupported tail method.

22

E) Scuff resistance

The Sutherland dry rub test was performed according to ASTM D 5264-98
“Standard Practice for Abrasion Resistance of Printed Materials by the Sutherland Rub
Tester”(6) to determine the durability and abrasion resistance Of only the printed surface
of all substrates. Test ﬁlms with dimensions of 2 x 7 inches were cut from the printed
area of the substrate and attached to the device. Similar ﬁlm samples were attached to a 4
lb test block used to rub the test specimen. This standard 4 lb test block produced a
contact pressure of 1 lb per square inch. Then, both test ﬁlms were rubbed against one
another at controlled speed and controlled cycles in increment of 5 strokes up to 25
strokes. Once the rubbing stopped, the test ﬁlm was examined to see any type of failure
such as ink transfer, wearing or scratching of the printed surface.

Rubbing the same ﬁlms against one another did not result in any difference in rub
resistance, even with 25 strokes. Therefore, in order to allow much more in-depth
abrasion testing, a material with a more abrasive surface was used and attached to the test
block instead of the ﬁlm samples.

A GA—CAT (Comprehensive Abrasion Tester (CAT) by Gavarti Associates Ltd.
of Milwaukee, WI.) standard receptor A-4 was used and attached to the test block. The
test ﬁlm and the standard receptor were rubbed against one another under the same test
conditions and the test ﬁlm was observed for the type of failure. With the standard
receptor, adequate differences in rub resistance of the printed ﬁlms were established and

comparison between the printed ﬁlms with similar coatings was made.

23

F) Dart Drop Impact Test

This test was performed according to standard ASTM method D1709-01 “Impact
Resistance of Plastic Film by the Free-Falling Dart Method?“ The test determines the
energy that causes different plastic ﬁlms to fail under speciﬁed conditions of impact of a
free-falling dart. This energy is expressed in terms of the weight (mass) of the missile
falling from a speciﬁed height which would result in 50% failure of specimens tested.

The Test Method A with standard staircase testing technique was used in this
study. Test Method A employs a dart with a 38 mm (1.5 in) diameter hemispherical head
dropped from a height of 0.66 m (26 in). In the staircase testing technique, a uniform
missile weight is employed during the test and the missile weight is decreased or
increased by the uniform increment after the test of each specimen, depending upon the
result (fail or not fail) observed for the specimen. The control ﬁlms and the printed area
of the treated ﬁlms were cut into 6—inch square ﬁlms with at least 20 replicates and tested
using a dart missile weighing 48 grams and 15 gram rings as increments. The apparatus,

testing procedure and calculation used are described in the ASTM standard.

2.2.2 CHEMICAL PROPERTIES

A) Migration testing

The polyoleﬁn migration test involved the FDA-recommended simulants for fatty
foods (95/100% ethanol) and for aqueous, acidic and low-alcohol-containing food (10:90
ethanol/water). The test was performed according to the USFDA Guidance for Industry

of Chemistry Recommendations for Preparation of Food Contact Notiﬁcations and Food

24

Additive Petitions for Food Contact Substances (F CS)‘5 ') and ASTM D 4754 “Standard
Test Method for Two-Sided Liquid Extraction of Plastic Materials Using FDA Migration
Cell.”(5) TO determine the total migration, substrates were stored at 40°C for 10 days in
contact with the food simulants as recommended by the FDA. For each substrate, a single
sample was prepared initially to examine the result using sampling periods of 24, 48, 120
and 240 hours. Based on the results of that single sample, triplicate samples were then
prepared for the actual data. The amount of FCS that migrated from the samples was
determined by weighing the samples before and after exposure to the simulants.

The remaining simulants were then tested using the Perkin Elmer (Lambda25)
UV/V IS Spectrometer and Fourier Transform Infrared Spectroscopy (FT-IR)
Spectrometer; model Spectrum 1000 also by Perkin Elmer. The absorbance of the
remaining simulants was scanned from the whole region of the visible light wave length
to the UV light wavelength (190 nm — 1100nm) to detect any appearance of peaks of the
migrants in the simulants. In the F T-IR testing, the simulants were scanned from infrared
light frequency of 515 cm'l to 4000 cm'1 to observe the percent transmittance Of the
migrants. For both UVN IS and FTIR, the pattern of peaks from the cured coated
(treated) materials was compared to that from the base (control) ﬁlms to possibly see

indication of any new migrants from the cured coated ﬁlm.

25

CHAPTER 3

RESULTS AND DISCUSSION

3.1 TENSILE PROPERTIES

In order to compare and verify any differences in tensile properties between the
EB-cured ﬁlms and the control ﬁlms, three-way analysis of variance (ANOVA) was
employed to analyze the results. The experiment has a three-way factorial design (4 x 4 x
2) with 5 replicates. Residual diagnostics was done to check the normality and
distributional assumptions of this dataset.(43) The residuals plot showed no pattern
indicating any violation of normal distributional assumptions that are required for
statistical inference in this model.

The result from the ANOVA table with the lack-Of-ﬁt test in Type III fully
adjusted sums of squares table shows that the 3-way interaction among all factors is
signiﬁcant (P-value of <0.0001) . That means the tensile strength measurement does
depend on these three important factors. Therefore, inferences involving any particular
factor were done within the combination of levels of the other two factors using the F-test
with Type I error rate of 5% (see Appendix B).

Since the point of interest is to verify any differences in tensile strength between
treatment levels, the summary of tensile strength mean differences between levels of
treatment for each substrate and direction combination is presented in Table 3. All values
were obtained at break except for substrate A in the CD, where the maximum value was

obtained at yield.

26

Table 3: Tensile strength mean comparison between treatments, separately for each

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

substrate in MD and CD.
SUBSTRATE TREATMENT Tensile Strength (Ib/inchz)
MD CD
SUBSTRATE A Control 17,223a 3,665a
Coated 13,768b 3,043a
Uncoated 15,872a 3,246"
Printed 13,369b 3,0693
SUBSTRATE B Control 3,107a 3,054a
Coated 2,873a 2,965a
Uncoated 3,028a 2,352a
Printed 2,8143 2,836a
SUBSTRATE C Control 13,245a 35,011a
Coated 16,377b 34,1 1 1a
Uncoated 16,081b 38,470b
Printed 14,167a 30,177c
SUBSTRATE D Control 18,290a 48,046a
Coated 16,149b 42,016b
Uncoated 16,396b 42,710bc
Printed 16,510b 43,727c

 

 

 

 

 

 

For each substrate and direction, different letters aﬁer TS indicate a
signiﬁcant difference (P<0.05) between treatments.

In general, signiﬁcant differences in tensile strength as a function of treatment were

found for substrate A, C and D ﬁlms, but not for substrate B.

3.1.1 Load at Peak:

Since coating and printing slightly increases the thickness of the ﬁlm, it will
slightly decrease the calculated tensile strength if the coating or printing does not
contribute any strength and the strength of the base ﬁlm is unchanged. Therefore, as an
alternative to analyzing tensile strength, the analysis can be done on the peak load. The

same statistical method, three-way analysis of variance (ANOVA) and Type 1 error rate

27

of 5%, was used. The summary of peak load mean differences between levels of

treatment for each substrate and direction combination is presented in Table 4.

Table 4: Peak load mean comparison between treatments separately for each substrate in
MD and CD.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

SUBSTRATE SAMPLE Ave. Thickness Peak Load MD (lbs) Peak Load CD (lbs)
(mil) Average Average
Control 2.4 41.34a 8.80a
SUBSTRATE Coated 3.0 41.30“ 9.13“
A Uncoated 2.9 46.03b 9428
Printed 3.1 41.44“ 9.51“
Control 3 .0 9.3 28 9.16a
SUBSTRATE Coated 3.0 8.62“ 8.90“
B Uncoated 3.0 9.09“ 8.56“
Printed 3.1 8.72“ 8.79“
Control 0.7 9.27“ 24.51“
SUBSTRATE Coated 0.7 l 1.46b 23.88“
C Uncoated 0.6 9.65“ 23.08“
Printed 0.8 l 1.33b 24.14“
Control 1.0 18.29“ 48.05“
SUBSTRATE Coated 1.1 17.76“b 46.21C
D Uncoated 1 .0 16.40b 42.71 b
Printed 1.1 18.16“ 48.1“
For each substrate and direction, different letters after Peak Load indicate a signiﬁcant difference (P<0.05)
between treatments.

The statistical analysis shows that there are signiﬁcant differences in peak load
between MD and CD of all substrates except substrate B. While some statistically
signiﬁcant differences were found between the control and one or more of the
subcategories of treated ﬁlms in all substrates except substrate B (see Appendix B), in the
base comparison of whether there was a difference between the printed ﬁlm and the
control, a signiﬁcant difference was found only for substrate C, as its peak load actually

increased by more than 20%. Therefore, much of the difference found in the tensile

28

strength comparison does, in fact, seem to be due to the increase in thickness attributable

to the coating, rather than to any effect of the e-beam curing.

3.1.2 Elongation at break

Percent elongation at break for all substrates was also measured by dividing the
change of the specimen’s length by it’s the initial jaw separation, which was 2.0 inches.
The data were transformed to natural log in order to satisfy the normality and
distributional assumptions required for statistical inference using this data. The same
statistical method (three-way ANOVA) using Type 1 error rate of 5% conﬁrmed that
percent elongation at break between MD and CD for all substrates was signiﬁcantly
different except for substrate B. No signiﬁcant difference of percent elongation between
control and treated ﬁlms was found for substrates B and D. The summary of percent
elongation at break mean differences between levels of treatment for each substrate and

direction combination is presented in Table 5.

29

Table 5: Mean comparison of percent elongation at break between treatments, separately
for each substrate in MD and CD.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

SUBSTRATE TREATMENT —-i° ° i? “i” “‘ 2”"

D

SUBSTRATE A Control 68.4“ 594“

Coated 86a 332‘“c

Uncoated 96a 338'“c

Printed 93 .4a 92*b

SUBSTRATE B Control 549a 624a
Coated 486“ 590“

Uncoated 466iI 566a

Printed 477“ 552“
SUBSTRATE C Control 109“ 44“
Coated 208b 61a

Uncoated 148“ 54.6a
Printed 181b 50“
SUBSTRATE 1) Control 217“ 56“
Coated 239“ 67“
Uncoated 222“ 60a
Printed 23 5a 64a

For each substrate and direction, different letters aﬁer % elongation indicate a signiﬁcant difference
(P<0.05) between treatments.

* There was considerable variation in elongation at break for these samples. For coated and uncoated, one
sample of each broke prematurely and results were excluded ﬁ'om the calculation. For the printed samples,
3 of the 5 samples broke at very low elongations, and are included in the average. The main reason for this
is because substrate A is a machine direction oriented ﬁlm; therefore when the strips were stretched in the
CD, premature breakage was likely, resulting in variation in the results.

3.2 COEFFICIENT OF FRICTION (COF)

An unusual result was obtained from the control ﬁlms of substrates B, C and D
where their kinetic COF was found higher than their static COF. Repeated tests were
performed on the substrates to verify these values, and resulted in consistent COF values.
Therefore, these unusual results appeared to be the true COF values for these substrates.

The differences in the static and kinetic coefﬁcient for both control and treated ﬁlms were

30

statistically compared. Using the two population t-test with Type 1 error rate of 5%, we
found that that only Substrate C showed signiﬁcant difference between control and
treated ﬁlms in both its static and kinetic COF. The static COF of control and treated ﬁlms
of Substrates B and D were found not signiﬁcantly different, but both substrates showed
signiﬁcant differences in their kinetic COF. For Substrate A, only its static COF showed
signiﬁcant differences between the control and treated ﬁlms. Where signiﬁcant
differences were found, the treated ﬁlms had lower coefﬁcients of friction than the
control ﬁlms. The summary of COF mean comparison of the ﬁlms is presented in Table 6

below:

Table 6: Mean comparison of the Coefﬁcient of Static and Kinetic Friction for all

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

substrates
SUBSTRATES FILM STATIC COF KINETIC COF
a a
SUBSTRATE A Control 0.1690b 0.1 158al
Treated 0.1 120 0.1088
a a
SUBSTRATE B Control 0.1958a 0.3268b
Treated 0.2110 0.1616
a a
SUBSTRATE C Control 0.2584b 0.3652B
Treated 0.1278 0.1238
a a
SUBSTRATE D Control 0.2970a 0.3950b
Treated 0.2092 0.1 830
For each substrate and direction, different letters alter COF indicate a signiﬁcant difference (P<0.05)
between treatments.

3.3 TEAR STRENGTH

The tearing force of each substrate was determined using this equation:

16 x Average Scale Reading
Number Of Plies

 

Tearing Force, grams =

31

The same statistical technique used in the tensile properties was employed to analyze the
tearing force data, except that the experimental design for this dataset was a three-way
factorial design (4 x 3 x 2) with 10 readings. These data were also transformed to natural
log in order to satisfy the normality and distributional assumptions required for statistical
inference with this data. The test results for each substrate are summarized in Table 7

below:

Table 7: Tearing force mean comparison between treatments, separately for each

 

 

 

 

 

 

 

 

 

 

 

 

 

 

substrate in MD and CD.
SUBSTRATE FILM TEARING FORCE (g9_
MD CD
SUBSTRATE A Control 53.07“ 127.73“
(3 PLIES) Ugrinted 50.67““ 117.33“
Printed 48.27“ 121.87“
SUBSTRATE 3 Control 554.40“ 154.40“
(1 PLY) Unprinted 743.30“ 152.80“
Printed 722.40“ 1 17.60“
SUBSTRATE C Control 6.91“ 4.05“
(30 PLIES) Unprinted 5.92“ 4.27“
Printed 5.65“ 4.24“
SUBSTRATE 1) Control 11.09“ 7.12b
(30 PLIES) Unprinted 9.04“ 555“
Printed 9.23“ 5.68“

 

 

 

 

 

 

For each substrate and direction, different letters after Tearing Force indicate a signiﬁcant difference
(P<0.05) between treatments.

From the analysis, we found that all substrates showed signiﬁcant differences in tear
strength between the control and treated (printed & unprinted) ﬁlms as well as between
MD and CD. However, there was no pattern to the behavior. Tear strength increased with
treatment for substrate B in the MD and C in the CD, while it decreased for substrates A

and D, and for substrate B in the CD and substrate C in the MD.

32

3.4 HEAT-SEAL STRENGTH

The peak seal strength and average seal strength data are presented in Appendix
A, Table A6] and Table A.6.2. Since the peak strength data shows a lot more variation
than the average strength, the peak strengths were statistically analyzed using three-way
analysis of variance (ANOVA) with Type 1 error rate of 5%. In order to assure the
normality and distributional assumptions required for statistical inference of this data, the
peak strength data were transformed to natural log before further analysis. From the
analysis, we found that only substrate B showed no difference in peak seal strength
between its MD and CD ﬁlms, while the other substrate’s MD and CD peak seal
strengths were signiﬁcantly different from each other. Signiﬁcant differences were found
between control and printed ﬁlms for substrates A, C, and D in the MD (see Appendix).
For A, seal strength increased, while for C and D it decreased. All other differences were
not signiﬁcant. The summary of peak seal strength mean differences between treated and
control ﬁlms for each substrates with MD and CD combination is presented in Table 8.

Table 8: Peak seal strength force mean comparison between treatments, separately for

 

 

 

 

 

 

 

 

 

 

each substrate in MD and CD.
SUBSTRATE DIRECTIONS PEAK SEAL STRENGTH (lbs/inch)
CONTROL UNPRINTED PRINTED
SUBSTRATE A MD 13.8386: 15.6271: 23.4301;“
CD 8.6171 10.6086 9.6671
SUBSTRATE B MD 9.6314: 9.7043: 10.5701;“
CD 8.9600 9.5914 9.1729
SUBSTRATE C MD 0.8729: 0.7629: 05929:
CD 0.6543 0.5286 0.5257
SUBSTRATE D MD 2.0657: 1.6314“: 1.4100:l
CD 2.1357 2.2129 2.1114

 

 

 

 

 

 

 

For each substrate and direction, different letters after Peak Seal Strength indicate a signiﬁcant difference
(P<0.05) between treatments

33

The test strip failure modes were also identiﬁed in this test. Based on the ASTM
standard, seven modes of failure were illustrated and categorized into failure and types.

The modes were numbered (Table 9) to make it easier for reference.

Table 9: Modes of Failure

 

 

 

 

 

 

 

 

 

 

Number Failure Type
1 Seal Adhesive (peel)
2 Material Cohesive
3 Material Delamination
4 Material Break
5 Material Break/Tear (remote)
6 Material Elongation
7 Seal + Material Peel + Elongation

 

 

 

Most of the MD ﬁlms of control substrate A experienced Modes land 3, while the
CD ﬁlms experienced a combination of Modes 1, 2 and 6. All MD ﬁlms of unprinted
substrate A failed in Mode 1 while the printed ﬁlms failed in both Modes 1 and 3. All
treated CD ﬁlms failed in Mode 4. For substrate B, all ﬁlms, control, unprinted and
printed, in both MD and CD failed in a combination of Modes 1 and 6. All substrate C
control MD ﬁlms failed in a combination of Modes 1 and 2, while most of its CD ﬁlms
failed in a combination of Modes 1 and 3. For most of treated substrate C, both MD and
CD ﬁlms failed in a combination of Modes 1 and 4. Substrate D control ﬁlms, both MD
and CD, experienced a combination of Modes 1, 3 and 4. As for its treated ﬁlms
(unprinted and printed), both MD and CD ﬁlms mostly experienced failure in Modes 1

and 4.

34

3.5 SCUFF RESISTANCE

Comparison was made between two substrates with similar coatings which had
undergone identical test conditions. This means that the abrasion resistance of printed
Substrate A was compared to printed Substrate B and the abrasion resistance of printed
Substrate C was compared to printed Substrate D. For every 5 stroke increment, adequate
differences of rub resistance between the two different tested substrates were identiﬁed
and compared.

According to the Packaging Institute“)

, ink transfer may be deﬁned as the
presence of ink residue on a portion of the test strip other than where it was printed.
Wearing may be deﬁned as abrasion of a printed ink ﬁlm. Scratching occurs where a
relatively deep, sharply deﬁned cut is made in the ink ﬁlm. Based on these deﬁnitions,

qualitative evaluations of each pair of substrates at 5 strokes and 25 strokes are presented

in Tables 10 and 11.

Table 10: Qualitative Rub Resistance Comparison of Substrate A and Substrate B

 

 

Number of Strokes Substrate A Substrate B
Appearance of wearing and Appearance of wearing and
5 deep scratching on one third only light scratching on
of ﬁlm surface. ﬁlm surface.

 

. . Increased wearing and light
Extenswe wearmg and deep . _
. scratchmg in 2/3 of the
2 5 scratching on the overall

surface.

surface but no obvious

deep scratching.

 

 

 

 

 

35

Table l 1: Qualitative Rub Resistance Comparison of Substrate C and Substrate D

 

 

Number of Strokes Substrate C Substrate D
Appearance of extensive Appearance of wearing and
5 wearing and light scratching light scratching only on 2/3
on overall ﬁlm’s surface. of ﬁlm’s surface.

 

Increased extensive wearing Increased wearing and light

and appearance of deep scratching on 2/3 of the
25 scratching on the overall surface but no obvious
surface. deep scratching.

 

 

 

 

 

From the qualitative results above, it can be concluded that Substrate B has higher rub

resistance than Substrate A and Substrate D has higher rub resistance than Substrate C.

3.6 DART DROP IMPACT

Complete data for each dart drop test for all substrates are listed in Table A.7.1 to
Table A.7.4 in Appendix A. These tables illustrate failure and non failure results at each
tested weight along with the calculated dart impact failure weight for all substrates. The

impact failure weight for each substrate was determined using the following equation:

A 1
W, =W + AW —-——

where : Wp = impact failure weight, (g)
W0 = missile weight to which an i value of zero is assigned.
AW = missile weight increment (15 gram)
A = total of in,- 's

N = total number of failures

36

A sample of a chart and dart impact failure weight determination of one of the ﬁlms is

presented in Appendix B. The summary of the dart drop impact test results is presented in

Table 12 below:

Table 12: Summary of the Dart Drop Impact test results.

 

 

 

 

 

 

 

 

 

SUBSTRATE FILM N A W0 AW W1: (g)
mm 5.22:: :3 3 2: 1: 2:
mm. :22: :3 :: 1:: 1: :2::
suns—me $222: 1: : 2: 1: 2:
SUBSTRATE 1) $2223 :3 194 1:: 1: 1155105

 

 

 

 

 

 

 

 

 

From the results, the printed ﬁlms of Substrate A and D Showed slightly higher
impact strength than the control ﬁlms, whereas for Substrate B and C, the control ﬁlms
showed higher impact strength than the printed ﬁlms. Nevertheless, impact strengths
between the control and printed ﬁlms of all substrates showed only very small differences

from each other.

3.7 TOTAL MIGRATION

The amount of F CS that migrates from the substrates to the simulants was
determined by weighing the samples, before and after exposure to the simulants. The

total migration for the substrates was calculated and expressed in milligrams of

37

migrant(s) per square decirneter of sample exposed, B using the equation from ASTM

 

Standard D 4754 as below:
E = (W - B)
[(27: R2 + CT)N]
where: W = initial weight of plastic ﬁlm disk (before exposure), mg.

B = ﬁnal weight of plastics ﬁlm disks (after exposure), mg.

= Radius of the disk, m
C = Circumference of disk, m.
T = Thickness of disk, m.

= Number of disks per cell

Complete results of the substrates weight difference and the total migration are
presented in Table A8] to A.8.8 in Appendix A. Table A81 to A.8.4 shows the results
for substrates A and B exposed to 10% and 95% ethanol:water simulant and Table A85
to A.8.8 are the results for substrates C and D.

The results of both metallized ﬁlms (Substrates C and D) clearly showed no
pattern of behavior in their weight differences when exposed to both 10% and 95%
ethanol. Some of the samples showed both decrement and increment of weight over time.
For instance, the metallized coatings of the control ﬁlms of Substrate C were observed to
be ﬂaking off when exposed to 10% ethanol for 120 and 240 hours, which probably
explains the increase in weight difference for these samples. On the other hand, the
metallized coating of all samples were still intact when exposed to 95% ethanol. While
increased weight loss over time was found in treated C samples exposed to 10% ethanol,

the reverse result was found for samples exposed to 95% ethanol.

38

Two of the control ﬁlms of substrate D exposed to 10% ethanol: water showed no
difference in weight while a consistent decrease in weight over time was found when
exposed to 95% ethanol. The treated ﬁlms of substrate D exposed to 10% ethanol showed
high decrement in the 24 hours samples, followed by constant weight difference over
time for 48 and 120 hour samples. However an unexpected weight gain was found in the
240 hour sample. When exposed to 95% ethanol, both control and treated samples
Showed inconsistent weight loss over time.

Due to the metallized coating ﬂaking-off the substrates and the inconsistencies of
the data, it is not possible to use the samples’ weight difference as FCS amount to further
calculate the total migration of the substrates. Results showed that migration was in both
directions (from substrate to simulant and from simulant to substrate). For that reason, no
further investigation of the total migration of Substrate C and D were done Since this was
beyond of the scope of this study. Hence, the rest of the discussion on migration behavior
will only focus on total migration of the co-extruded ﬁlms: substrate A and substrate B.

The results for all ﬁlms from both substrates A and B showed a decrease in
weight after being exposed to the both simulants. Thus, the ﬁlms’ weight differences,
which depict the amount of FCS that migrates from the ﬁlms, were used to calculate the
total migration. The total migration data for both substrates were statistically analyzed
using the three-way analysis of variance (ANOVA) with Type 1 error rate of 5%. To
simplify the interpretation of the data, total migration in 10% and 95% ethanol:water
simulant were analyzed separately. Only the data for total migration in 95%
ethanol:water simulant were transformed to natural log in order to satisfy the normality

and distributional assumption requirements. The main interest of this analysis is to verify

39

any differences in total migration between the control and treated ﬁlms of each substrate
at each time of exposure (24, 48, 120 and 240 hours). The summary of total migration
mean differences of each substrate in 10% and 95% ethanol:water simulants are

presented in Table 13 and Table 14, respectively.

Table 13: Total migration mean comparison for substrates A and B in 10% ethanol:water

 

 

 

 

 

 

 

 

simulant.
SUBSTRATES EXPOSURE AVERAGE TOTAL MIGRATION (mg/dmzL
(hours) Control film Treated film
24 0.9347,l 0.6301,
SUBSTRATE 48 0.4440, 0.5134,
A 120 0.3505, 0.4434,
240 0.5842, 0.6301,,
24 1.2835, 1.4702,
SUBSTRATE 48 0.9801, 0.7468f
B 120 1.0735g 0.9335g
240 1.4235,1 1.7269,,

" '5’.’ ‘— m—v- -2I\.I .'.

 

 

 

 

 

 

 

 

 

For each substrate, different subscripted letters after Total Migration indicate a signiﬁcant

diﬁ’erence (P<0.05) between ﬁlms within hours.

Table 14: Total migration mean comparison for substrates A and B in 95% ethanol:water

 

 

 

 

 

 

 

 

 

 

 

simulant.
2
SUBSTRATES ET??? AVE‘éiﬁ'finliA" ”GRAE‘Siédmﬁim’
24 1.5189,l 0.7234,
SUBSTRATE 48 0.8880, 0.9568,
A 120 0.9814, 1.1201,
240 1.0749, 1.2368,
24 3.2204f 2.3570,
SUBSTRATE 48 1.7036, 1.5402g
B 120 1.9836,, 1.4935,,
240 2.3103; 2.4503,

 

 

 

 

 

For each substrate, different subscripted letters after the Total Migration indicate a signiﬁcant
difference (P<0.05) between ﬁlms within hours.

From the analysis, no signiﬁcant difference was found between the control and

treated ﬁlms of both substrates A and B exposed in 10% ethanol: water simulant, within

40

each time of exposure. AS for substrates exposed in 95% ethanol: water simulant, the
control and treated ﬁlms of both substrates also showed no signiﬁcant difference from
each other except for ﬁlms from substrate A exposed for 24 hours.

The analysis also indicated some Signiﬁcant differences in total migration
between time of exposure for control and treated ﬁlms of each substrate. However, with
the inconsistent pattern of the data, it is not possible to draw any concrete conclusions.

The UV/V IS and the FTIR Spectrums of the remaining simulants from the
migration test for control versus treated ﬁlms of all substrates are illustrated in Appendix
C and Appendix D, respectively. Figure C.1.1 to Figure C.4.8 are the WW IS Spectrums
while Figure D1.1 to Figure D.4.8 are the FTIR Spectrums. When comparing the
simulants from the substrates’ control ﬁlms with treated ﬁlms, the patterns of both
UV/V IS and F TIR Spectrums noticeably illustrated differences between the ﬁlms. This
difference also means that there are indications of new migrants from the treated ﬁlms
compared to that control ﬁlms. These indications can be veriﬁed by further identifying all

the migrants; however this is beyond the scope of this study.

41

CHAPTER 4

CONCLUSION AND RECOMMENDATIONS

The difference in selected mechanical and chemical properties between the
control and treated ﬁlm of all substrates was demonstrated and discussed in detail in the
previous chapter. Even though most of the tests showed signiﬁcant differences in the
mechanical properties between control and treated ﬁlms, these differences are relatively
small and will not result in major changes in performance. As for the chemical properties,
the total migration of the control and treated ﬁlms of both substrates A and B were found
to not signiﬁcantly differ from each other even though the pattern of the total migration
data was found inconsistent over time. For that reason, it can be said that e-beam curing
does not have much impact on the migrational behavior of these substrates. With these
results, it can be concluded that the e-beam cured ﬁlms should be suitable for many
ﬂexible packaging applications.

In the case of substrates C and D, the chemical properties could not be described
by only total migration determination. A single-Sided migration test where only the
sealant or heat-sealable side of the substrates is exposed to the food simulants is highly
recommended for substrate C and D to avoid the problem of the metallized coating
ﬂaking off the substrate during the migration period. In addition, Speciﬁc migration tests
would be useﬁIl to further investigate substances that migrate from the substrates to the
food stimulant. An indication of new migrants was found in the treated ﬁlms when

comparing their UV/V IS and F TIR Spectrums with the control ﬁlms. Testing the

42

remaining simulants through the GC-mass Spectrometry is recommended in order identify

peaks of signiﬁcant size that differ between the control and the treated ﬁlms.

43

APPENDIX A

TEST DATA AND RESULTS

44

Table A1: Tensile Strength Data

 

AVERAGE &

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

TENSILE STRENGTH asi)
SUBSTRATES DIRECTIONS STANDARD
DEVIATION Control Coated Uncoated Printed
MD Average 17,223 13,768 15,872 13,369
SUBSTRATE Std Deviation 1,579 256 591 889
A CD Average 3,666 3,043 3,247 3,069
Std Deviation 178 32 39 66
MD Average 3,108 2,874 3,028 2,814
SUBSTRATE B Std Deviation 102 56 157 66
CD Average 3,054 2,965 2,853 2,836
Std Deviation 117 70 90 95
MD Average 13,245 16,377 16,081 14,168
SUBSTRATE C Std Deviation 4,145 1,222 3,120 1,285
CD Average 35,011 34,111 38,470 30,178
Std Deviation 3,149 833 1,429 1,712
MD Average 18,290 16,149 16,396 16,51 1
SUBSTRATE Std Deviation 1,287 725 891 452
D CD Ame 48,046 42,016 42,710 43,727
Std Deviation 1,023 479 1,291 1,287
Table A2: Load at Peak Data
AVERAGE & LOAD AT PEAK (psi)
STANDARD _
SUBSTRATES DIRECTIONS DEVI ATION COHU'OI Coated Uncoated Prmted
MD Average 41.336 41.304 46.03 41.444
SUBSTRATE Std Deviation 3.7904 0.7671 1.7140 2.7547
A CD Average 8.7974 9.1296 9.4162 9.5152
Std Deviation 0.4271 0.0948 0.1 123 0.2048
MD Average 9.3228 8.6206 9.0854 8.7248
SUBSTRATE Std Deviation 0.3051 0.1692 0.4700 0.2032
3 CD Average 9.162 8.8954 8.5582 8.7922
Std Deviation 0.3505 0.2109 0.2707 0.2946
MD Average 9.2716 1 1.464 9.6486 1 1.334
SUBSTRATE Std Deviation 2.9016 0.8552 1.8722 1.0280
C CD Average 24.508 23.878 23.082 24.142
Std Deviation 2.2046 0.5829 0.8572 1.3699
MD Average 18.29 17.764 16.396 18.162
SUBSTRATE Std Deviation 1.2871 0.7971 0.8913 0.4973
D CD Averaﬂ 48.046 46.218 42.71 48.1
Std Deviation 1.0235 0.5268 1.2908 1.4154

 

 

 

 

 

 

 

 

45

 

 

Table A.3: Percent Elongation at Break Data

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

% Elongation at Break
SUBSTRATES
TREATMENT MD CD
Control 68.4 594
SUBSTRATE A Coated 86 332
Uncoated 96 338
Printed 93. 92
Control 549 624
SUBSTRATE B Coated 486 590
Uncoated 466 566
Printed 477 552
, Control 109 44
SUBSTRATE C Coated 208 61
Uncoated 1 48 54.6
Printed 1 8 1 50
Control 217 56
SUBSTRATE D Coated 239 67
Uncoated 222 60
Printed 235 64
Table A.4: Coefﬁcient of Friction Data
AVERAGE
SUBSTRATES & STATIC COF KINETIC COF
STD.DEV. CONTROL PRINTED CONTROL PRINTED
Average 0.169 0.112 0.1158 0.1088
SUBSTRATE A Std.Deviation 0.0509 0.0074 0.0696 0.0722
Average 0.1958 0.211 0.3268 0.1616
SUBSTRATE B Std.Deviation 0.0665 0.0718 0.0348 0.0929
TR 1 Average 0.2584 0.1278 0.3652 0.1238
SUBS TE C Std.Deviation 0.0241 0.0233 0.0455 0.1007
Average 0.297 0.2092 0.395 0.183
SUBSTRATE D Std.Deviation 0.0635 0.1060 0.0180 0.1365

 

 

 

 

 

 

 

46

 

Table A5: Elmendorf Tear Strength Data

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

SUBSTRATES DIRECTIONS AVERAGE TEARING FBRCE (g0,
& STD.DEV Control Unprmted Prmted
MD Average 53.07 50.67 48.27
SUBSTRATE A Std Deviation 7.69 1 1.86 7.59
(3 PLIES) CD Average 127.73 117.33 121.87
Std Deviation 3.43 8.62 13.77
MD Average 554.40 743.36 722.40
SUBSTRATE B Std Deviation 22.33 29.23 37.72
(1 PLY) CD Average 554.40 152.80 117.60
Std Deviation 22.33 27.83 9.28
MD Average 6.91 5.92 5.65
SUBSTRATE C Std Deviation 0.32 0.33 0.25
(30 PLIES) CD Average 4.05 4.27 4.24
Std Deviation 0.30 0.44 0.27
MD Average 1 1.09 9.04 9.23
SUBSTRATE D Std Deviation 0.36 0.53 0.31
(30 PLIES) CD Average 7.12 5.55 5.68
Std Deviation 0.22 0.33 0.31

 

 

 

 

 

 

47

 

Table A.6.l: Peak Seal Strength Data

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Devnation CONTROL UNPRINTED PRINTED

MD Avergge 13.8386 15.6271 23.4300

SUBSTRATE A Std Deviation 3.8860 5.3354 1.5041
CD Average 8.6171 10.6086 9.6671

Std Deviation 1.9215 1.3752 2.3547
MD Averge. . 9.6314 9.7043 10.5700

SUBSTRATE B Std Dev1at10n 0.2061 0.2178 0.2605
CD Average 8.9600 9.5914 9.1729

Std Deviation 0.3525 0.2785 0.3138

MD Average 0.8729 0.7629 0.5929

SUBSTRATE C Std Dev1at10n 0.0256 0.2179 0.1643
CD Average 0.6543 0.5286 0.5257

Std Deviation 0.1373 0.0717 0.1091

MD Averag; . 2.0657 1.6314 1.4100

SUBSTRATE D Std Dev1at10n 0.4605 0.3360 0.5996
CD Average 2.1357 2.2129 2.1114

Std Deviation 0.7790 0.6515 0.4418

 

 

 

Table A.6.2: Average Seal Strength Data

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

SUBSTRATES DIRECTIONS Average & AVERAGE SEAL STRENGTH (lbs/Inch)
Std Dev1at10n CONTROL UNPRINTED PRINTED

MD Average 5.4143 6.2829 5.9486

SUBSTRATE A Std Dev1at10n 2.2301 2.4390 5.9486

CD Average 5.1900 5.2857 6.2957

Std Deviation 2.3925 2.7141 3.1553

MD Average 8.9700 9.0571 9.4886

SUBSTRATE B Std Deviatlon 0.3158 0.1762 0.1833

CD Average 7.9971 8.1614 8.3186

Std Deviation 0.1292 0.1767 0.1129

MD Average 0.5000 0.5643 0.3600

SUBSTRATE C Std Dev1at10n 0.1519 0.1433 0.1274

CD Average 0.3414 0.3771 0.3243

Std Deviation 0.0703 0.0298 0.1 186

MD Average 0.6400 0.5929 0.4157

SUBSTRATE D Std Dev1at10n 0.3749 0.3477 0.1539

CD Average ' 0.8343 0.8286 0.8829

Std Deviation 0.3090 0.2024 0.2684

 

 

 

 

 

 

 

 

 

48

 

 

:33 jg": jg"... I i

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

O 0 av
o o m x x x o o o o o o 8
n _ n x x x x x x x o M:
N N _ x .8
a. _ a 8 2 M: t S a E 2 S : 2 a w a o m 4 m m _ av
. . . m 833E038 . “>2 ram
685...
_ amen; _ _ “£35. _ _ «Qua? _ a E
o o o o o o a.
o o m o x o x x o o x x o S
m _ m x x x x x M:
a. _ a a 8 2 i t 2 2 E 2 2 : S o w R e m w m N _ av
. . . . 30.6 Esau—zoom “>2 tan
”—95.50

4 2.2.3.5 .8 :26 3.5 :5 "Ed «33

49

 

1321.3 _ _u£u3<_ _umm_u.§_ E E

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

O 0 mm—
o o _ o o x m:
_ N _ o o o x as
c N m x O O X 0 O x O m:
2 N m x x x x x we
.s_aNN_NoNEN_:£2:N_N_:2aNNemva_ @
. m Re Ezcozwom :5 two
6855
3N3"; _ _ ”21544 _ awe—us: _ E E
0 mm.
o o m:
o o _ o x as
c _ o o o o m:
v N N o x o o o x o «2
N. m e o x x o x x 0 SN
2 v N x x x ”MN
§ _ a N ”N N NN _N 8 2 N. t 2 2 E 2 N_ : 2 a N N o m w m N _ 3
. . macho Buses—Vow :5 ED
".93an

m 3.535 a. :26 35 :5 “24.. 2.3

50

_ ”8nt _ _ ”£354 _ mans: _mu<_

 

 

 

O

O

O O

O

0 av

 

X

X

0 X

X

X X 0 0 mo

 

 

NMO

Nr—O

ma

 

 

E

 

 

E

om

 

2

 

M:

 

C

 

m:

 

 

3

 

 

 

 

 

2 Q 2 S

o

 

 

 

 

 

 

 

 

 

 

m 9v 3:5:me

H3 Ema

 

 

 

_ as 1.3 _

_ “£354 _

_w@n§:

"BET—m

HE

 

O

O

0

av

 

0 mo

 

X

X

X X 0 O as

 

tho

Nv—O

NWM

 

 

 

 

on

3

 

 

M:

 

C

 

E

 

f

 

3

 

Q S I o—

 

 

 

 

a

 

xx 8
4NN_ A3

 

 

 

 

 

 

 

 

 

m 06 Essen—wow

 

 

5’ E9

 

"—95.80

9 3.2.35 2 :26 as: :3 5.3. 2...?

51

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

_ 9N2"; _ _ N235. _ _ NNNNuoB _ E E
o NN_
o o o 0 N2
N o N x x x x o 0 N2
N _ N x o x 0 N2
4 N N x x 0 N2
N N _ x N2
E _ a _N NN 2 2 N2 2 2 E 2 N_ : 2 N N N N N N N _ ANN
88v 328: um :5 tan—
"BEF—
_|wm.§u.§ _ _ N23,: _ _ $21.3 _ E E
o o NN_
N o N o x o x o 0 N2
N _ N o o x o x x o 0 N2
N N N x x x x 0 N2
N N 2 x N2
E _ E NN _N ON 2 2 N2 2 2 3 2 N_ : 2 N N N N N N N N ANN
H 3on Etcoswom :5 tan
"—95.30

a 32.2% B 55 9.5 :5 3.2 2.3

52

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Naosaozmou m mo $826 2: 0.8 Sat =< _._
NNN 2 .o $NN2 NNNSNNN NNNNN N 2N2 NNNNN 28: ON I was;
E: .o NNNNN NNNNNSN NNNN._ N52 Nana 28: oNN I N28;
N8 _ .o NNNNN NNNNNSN No2: NNNNN NNNN.N 28: N4 I BEEN
885 NONE NNNNNSN SEN 3N2 NNNNN :8: N I was;
336 NNNI NNNNSNN NNNNN N _ NNN NNNN.N 28: 9N I .938
N8; NNNE NNNSNNN NNNN._ N83 NNNNN 28: NNN I .2250
NNNNN SNNN NNNSNNN 832 N$NN 2de 2:2. N4 I .225
N2; .o NNNN._ NNNSNNN NNNN2 2N2 NNNNN 28: NN - 3E8
Jams: EN 9 Na: :5 3:: ANN E m gamma
N. 395 5:392 3.; 8:95.25 5E .. NON .33. L315..— :3 REE

 

«EN—BEN Bantu—052:0 .33 E m Batman—m he nets—um: .331 ”N.w.< 939—.

 

 

 

 

 

 

 

 

2858:qu m «o 03.6th 05 93 Saw =< _._

m3 2 .o 83.: $8806 ooood wmmmd Smmd N50: ovm I BEEP
Std vmvvd $880.0 mmmod :mmd vmmmd N50: o2 I BN8;
cmmmd v: We Nonooood mmmhd o2 m6 commd N50: wv I 330:.
waMd Smod Nomooocd ooomd 92 We wommd N50: cm I v88;
22 .o and 3298.0 223 336 mmmmd 28; own I .2250
836 336 3-5.8.0 gemd E _ m6 NNGd NSo: o3 I .8280
2.2 .o ovvvd moHnGooé mmmod coomd mnemd NSon xv I 3550

owd N50: vm - .9950

 

 

 

 

 

 

 

 

         

 

wcmmd $86 woumvaod mmmm._ m2 m6

.5:—:5... SEE—cuss: $3 E < oNaNNNN—am L8 .532»: .85. "~.w.< 03:.

53

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

mﬂOﬁMOSQUH m MO owaao>w 05 0.5 Saw =< *
ee_N.e memvd Neneeeee eeem.m- eneme menme £00: own I 033:...
ememe mmev; Neneeeee mmﬂd mmnme emnme v.50: em_ I 088:...
mmmee Nevmg Neneeeee eeeNm mime Esme 200: a: I 882,—.
Nmﬂ ._ enmmd Neneeeee Send eeeme mmeee 200; vm I 0800:.
wewme me_ md Neneeeee eeem.m _ :wme vvwme 2:0: own I 35:00
_NeN.e awe; meneeeee mmmwd Knme eenme N50: em_ I 3.5000
wewee omen; Neneeeee emee; Some geme 8:0: w: I 35:00
econ; vemmﬁ Neneeeee eeee;V wewme Some 2:0: vm - 30:00

  

ans—=8: sonata—0:050 $3 5 m 8053.5 .8.— Eﬁauuﬁz 130,—. "v.e.< 030,—.

28:00:02 m .00 owSoBN 05 2: 800 :< .._

 

 

 

 

 

 

 

 

_Nem.e mama; Neneeeee 32... we _ me memme v.50: evm I 028:.
83 .e 33 ._ meneeeee eeee; Emme some 2:0; em. I 02:05.
eeeﬁe wowed Neheeeee been; wwmme Nemme N50: av I 023;.
_NeN.e vane Neneeeee mmme._ \Immme nvmme N50: vm I 028:.
KN: .e age; meﬂeeee mmmm._ .mmme evmme N50: evm I 30:00
maze Ewee me-meee.e eeev; efme meNme 230: em_ I 35:00
@320 owned meIm—eeee seem; Gmme mane N50: «v I 35:00

 

 

 

 

 

 

 

 

 

 

e on _ m._ meIMeeee beeﬁm memme vmmme 2:0: vm - _0b:00

 

«SN—=87. haiku—0:230 {ewe 5 < 8953.5 .30 stung—z 130,—. "mdé 030,—.

54

Table A.8.5: Total FCS for Substrate C in 10% ethanol:water simulant

 

 

 

 

 

 

 

 

 

 

SUSBTRATE C Initial Wt* (g) Final Wt* (g) Total F CS (mg)
Control - 24 hours 0.0669 0.0668 -0.10
Control — 48 hours 0.0655 0.0654 -0.10

Control — 120 hours 0.0660 0.0667 0.70
Control — 240 hours 0.0654 0.0657 0.30
Treated — 24 hours 0.0799 0.0794 -0.50
Treated - 48 hours 0.0803 0.0798 -0.50
Treated — 120 hours 0.0822 0.0816 -0.60
Treated — 240 hours 0.0809 0.0801 -0.80

 

 

 

 

 

Table A.8.6: Total FCS for Substrate D in 10% ethanol:water simulant

 

 

 

 

 

 

 

 

 

 

SUSBTRATE C Initial Wt* (g) Final Wt* (g) “:25“
Control - 24 hours 0.0954 0.0954 0.00
Control - 48 hours 0.0925 0.0922 ~0.30

Control — 120 hours 0.0952 0.0952 0.00
Control — 240 hours 0.0944 0.0941 -0.30
Treated - 24 hours 0.1088 0.1082 -0.60
Treated — 48 hours 0.1077 0.1072 -0.50
Treated - 120 hours 0.1085 0.1080 -0.50
Treated — 240 hours 0.1078 0.1083 0.50

 

 

 

 

55

 

Table A.8.7: Total FCS for Substrate C in 95% ethanol:water simulant

 

 

 

 

 

 

 

 

 

 

SUSBTRATE C Initial Wt (g) Final Wt (g) Total FCS (mg)
Control - 24 hours 0.0652 0.0653 0.10
Control — 48 hours 0.0669 0.0671 0.20
Control — 120 hours 0.0667 0.0663 -0.40
Control — 240 hours 0.0683 0.0751 6.80
Treated — 24 hours 0.0845 0.0807 -3.80
Treated — 48 hours 0.0851 0.0841 -1 .00
Treated — 120 hours 0.0813 0.0805 -0.80
Treated — 240 hours 0.0848 0.0840 -0.80

 

 

 

 

Table A.8.8: Total FCS for Substrate D in 95% ethanol:water simulant

 

 

 

 

 

 

 

 

 

 

SUSBTRATE C Initial Wt (g) Final Wt (g) Total FCS (mg)
Control - 24 hours 0.0951 0.0949 -0.20
Control — 48 hours 0.0931 0.0929 -0.20
Control — 120 hours 0.0902 0.0899 030
Control — 240 hours 0.0955 0.0951 -0.40
Treated — 24 hours 0.1032 0.1029 -0.30
Treated — 48 hours 0.1092 0.1084 -0.80
Treated — 120 hours 0.1096 0.1089 -0.70
Treated — 240 hours 0.1067 0.1056 -1 .10

 

 

 

 

56

 

 

APPENDIX B

STATISTICAL ANALYSIS AND CALCULATION EXAMPLE

57

STATISTICAL ANALYSIS OF TENSILE STRENGTH:

The GLM Procedure
Least Squares Means
materi*treat*directi Effect Sliced by material for ts

material DF Sum of Squares Mean Square F Value Pr > F

1 7 1443432026 206204575 1 15.28 <.0001

2 7 440485 62926 0.04 0.9999

3 7 4001103311 571586187 319.54 <.0001

4 7 7570903924 1081557703 604.63 <.0001

materi*treat*directi Effect Sliced by material*treat for ts
material treat DF Sum of Squares Mean Square F Value Pr > F
1 ctrl 1 459531463 459531463 256.89 <.0001
1 uncoat 1 398504860 398504860 222.78 <.0001
1 coat 1 287553338 287553338 160.75 <.0001
I printed 1 265205065 265205065 148.26 <.0001
2 ctrl 1 7182400054 7182.400054 0.00 0.9496
2 uncoat 1 77206 77206 0.04 0.8358
2 coat 1 20976 20976 0.01 0.9139
2 printed 1 1181 .779409 1181.779409 0.00 0.9795
3 ctrl 1 1 184427985 1 184427985 662.14 <.0001
3 uncoat 1 1253168303 1253168303 700.57 <.0001
3 coat 1 786262225 786262225 439.55 » <.0001
3 printed 1 640800250 3 640800250 358.23 <.0001
4 ctrl 1 2213548840 2213548840 1237.45 <.0001
4 uncoat 1 1731066490 1731066490 967.73 <.0001
4 coat 1 1672789496 1672789496 935.15 <.0001
4 printed 1 1851826123 1851826123 1035.24 <.0001
materi*treat*directi Effect Sliced by material*direction for ts

material direction DF Sum of Squares Mean Square F Value Pr > F
1 m 3 49343251 16447750 9.19 <.0001
1 c 3 1239680 413227 0.23 0.8747
2 m 3 275353 91784 0.05 0.9846
2 c 3 156722 52241 0.03 0.9932
3 m 3 34167446 1 1389149 6.37 0.0005
3 c 3 174221346 58073782 32.47 <.0001
4 m 3 14426216 4808739 2.69 0.0492
4 c 3 109905001 36635000 20.48 <.0001

58

STATISTICAL ANALYSIS OF THE PEAK LOAD:

The GLM Procedure
Least Squares Means
Source DF Type 111 SS Mean Square F Value Pr > F
material 3 12203.73428 4067.91143 2312.53 <.0001
direction 1 188.70770 188.70770 107.28 <.0001
material*direction 3 20913.19858 6971 .06619 3962.92 <.0001
treat 3 9.52146 3.17382 1.80 0.1497
material*treat 9 137.94372 15.32708 8.71 <.0001
direction*treat 3 34.30347 11.43449 6.50 0.0004
materi*directi*treat 9 35.96887 3.99654 2.27 0.0214
material*direction Effect Sliced by material for tspeak
material DF Sum of Squares Mean Square F Value Pr > F
A 1 11098 11098 6309.10 <.0001
B 1 0.074736 0.074736 0.04 0.8370
C 1 1815.203817 1815.203817 1031.91 <.0001
D 1 8188.468402 8188.468402 4654.99 <.0001

material*treat Effect Sliced by material for tspeak

material

UOw>

DF

3
3
3
3

Sum of

Squares

46.583433
1.634461
12.996159
86.251 127

Mean Square F Value Pr > F

15.52781 1
0.544820
4.332053
28.750376

59

8.83
0.31
2.46
16.34

<.0001
0.8183
0.0655
<.0001

STATISTICAL ANALYSIS OF ELMENDORF TEAR STRENGTH:

full model
The GLM Procedure
Dependent Variable: lntear
Source DF Sum of Squares Mean Square F Value Pr > F
Model 23 766.1460056 33.3106959 3751.81 <.0001
Error 216 1.9177698 0.0088786
Corrected Total 239 768.0637755
R-Square Coeff Var Root MSE lntear Mean
0.997503 2.778681 0.094226 3.391038
Source DF Type III SS Mean Square F Value Pr > F
material 3 708.8706144 236.2902048 26613.6 <.0001
direction 1 9.1312243 9.1312243 1028.46 <.0001
material*direction 3 45.616498] 15.2054994 1712.61 <.0001
treat 2 0.2303226 0.1151613 12.97 <.0001
material*treat 6 1.3903245 0.2317207 26.10 <.0001
direction*treat 2 0.0234593 0.01 17296 1.32 0.2690
materi*directi*treat 6 0.8835626 0.1472604 16.59 <.0001
material*treat Effect Sliced by material for lntear
material DF Sum of Squares Mean Square F Value Pr > F

A 2 0.072989 0.036494 4.11 0.0177

B 2 0.256844 0.128422 14.46 <.0001

C 2 0.062267 0.031133 3.51 0.0317

D 2 1.228548 0.614274 69.19 <.0001

material*direction Effect Sliced by material for lntear
material DF Sum of Squares Mean Square F Value Pr > F

A 1 11.956741 11.956741 1346.70 <.0001

B 1 36.779929 36.779929 4142.55 <.0001

C 1 2.216968 2.216968 249.70 <.0001

D 1 3.794084 3.794084 427.33 <.0001

60

STATISTICAL ANALYSIS OF PEAK SEAL STRENGTH:

full model
The GLM Procedure
Dependent Variable: peak

Source DF Sum of Squares Mean Square F Value Pr > F
Model 23 259.308451 1 11.2742805 190.80 <.0001
Error 144 8.5087974 0.0590889
Corrected Total 167 267.8172485
R-Square Coeff Var Root MSE peak Mean
0.968229 19.74518 0.243082 1.231095
Source DF Type 111 SS Mean Square F Value Pr > F
material 3 251 .4488633 83.8162878 1418.48 <.0001
direction 1 1.0867481 1.0867481 18.39 <.0001
material*direction 3 3.6829840 1.2276613 20.78 <.0001
treat 2 0.0309656 0.0154828 0.26 0.7699
material*treat 6 1.8283756 0.3047293 5.16 <.0001
direction*treat 2 0.0960317 0.0480159 0.81 0.4457
materi*directi*treat 6 1.1344827 0.1890805 3 .20 0.0056
material*direction Effect Sliced by material for peak
material DF Sum of Squares Mean Square F Value Pr > F
A 1 3.386124 3.386124 57.31 <.0001
B 1 0.059890 0.059890 1.01 0.3157
C 1 0.661921 0.661921 11.20 0.0010
D 1 0.661796 0.661796 11.20 0.0010
material*treat Effect Sliced by material for peak
material DF Sum of Squares Mean Square F Value Pr > F
A 2 0.794424 0.397212 6.72 0.0016
B 2 0.024503 0.012252 0.21 0.8130
C 2 0.748228 0.374114 6.33 0.0023
D 2 0.292186 0.146093 2.47 0.0880

61

m8 LB

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

WaughﬁaTr s a: u >2
_ m wmonoa
$33? a... n s. m m...
2 w 3.2
O O O O O 0 3
o o m 0 X 0 X X 0 O X X 0 mo
m _ m X X X X X mm
a om 2 f S 2 2 3 2 Q I S a w n o m w m m ~ g
E LE macho .mucoaoom .5? tan

 

 

 

 

 

SSE AOMHZOU n< mhéhmmbm

"Han—SAV‘XH ZO—P<ADUA<U kGy—G Ega—

62

STATISTICAL ANALYSIS OF TOTAL MIGRATION :.

Total Migration in 10% ethanol:water simulant

full model
The GLM Procedure
Dependent Variable: mig
Source DF Sum of Squares Mean Square F Value Pr > F
Model 15 7.80693490 0.52046233 12.98 <.0001
Error 32 1.28279827 0.04008745
Corrected Total 47 9.08973317
R-Square Coeff Var Root MSE mig Mean
0.858874 22.61036 0.200218 0.885517
Source DF Type 111 SS Mean Square F Value Pr > F
material 1 4.89142083 4.89142083 122.02 <.0001
ﬁlms 1 0.00007752 0.00007752 0.00 0.9652
material*ﬁlms 1 0.00850669 0.00850669 0.21 0.6482
hours 3 1.92365358 0.64121786 16.00 <.0001
material*hours 3 0.52791051 0.17597017 4.39 0.0107
ﬁlms*hours 3 0.12367742 0.04122581 1.03 0.3931
material*ﬁlms*hours 3 0.33168835 0.11056278 2.76 0.0583
material*ﬁlms Effect Sliced by material for mig

material DF Sum of Squares Mean Square F Value Pr > F

A10 1 0.003480 0.003480 0.09 0.7702

BIO 1 0.005104 0.005104 0.13 0.7236

ﬁlms*hours Effect Sliced by hours for mig
hours DF Sum of Squares Mean Square F Value Pr > F
24 1 0.010425 0.010425 0.26 0.6136
48 1 0.020156 0.020156 0.50 0.4834
120 1 0.001666 0.001666 0.04 0.8397
240 1 0.091508 0.091508 2.28 0.1406
material*hours Effect Sliced by material for mig

material DF Sum of Squares Mean Square F Value Pr > F

A10 3 0.508336 0.169445 4.23 0.0126

B10 3 1.943228 0.647743 16.16 <.0001

63

Total Migration in 95% ethanol:water simulant

full model
The GLM Procedure
Dependent Variable: lnmig
Source DF Sum of Squares Mean Square F Value Pr > F
Model 15 7.87143470 0.52476231 6.97 <.0001
Error 32 2.40966036 0.07530189
Corrected Total 47 10.28109506
R-Square Coeff Var Root MSE lnmig Mean
0.765622 76.70448 0.274412 0.357752
Source DF Type 111 SS Mean Square F Value Pr > F
material 1 5.56806069 5.56806069 73.94 <.0001
ﬁlms 1 0.20040213 0.20040213 2.66 0.1 126
material*ﬁlms 1 0.0298851 1 0.0298851 1 0.40 0.5332
hours 3 0.81408388 0.27136129 3.60 0.0238
material*hours 3 0.41745037 0.13915012 1.85 0.1584
ﬁlms*hours 3 0.59419769 0.19806590 2.63 0.0670
material*ﬁlms*hours 3 0.2473 5484 0.08245 161 1 .09 0.3655
material*ﬁlms Effect Sliced by material for lnmig
material DF Sum of Squares Mean Square F Value Pr > F
A95 1 0.037755 0.037755 0.50 0.4840
B95 1 0.192533 0.192533 2.56 0.1196
material*hours Effect Sliced by material for lnmig
material DF Sum of Squares Mean Square F Value Pr > F
A95 3 0.162592 0.054197 0.72 0.5476
B95 3 1.068943 0.356314 4.73 0.0076
ﬁlms*hours Effect Sliced by ﬁlms for lnmig
ﬁlms DF Sum of Squares Mean Square F Value Pr > F
control 3 0.859254 0.286418 3 .80 0.0194
treated 3 0.549028 0.183009 2.43 0.0833

64

APPENDIX C

UV/VIS SPECTRUMS

65

 

 

Control A — Solid Line
Treated A — Dots

 

 

 

 

: i T . l
g . 569.72
'1.
'1‘.
185.0 250 300 350 400 450 500 550 600.0

Figure C.1.1: Substrate A in 10% Ethanol for 24 hours

Control A — Solid Line
Treated A — Dots

380.0

'
"1...".

 

185.0

200 220 240 260 280 300 320 340 360 380 400.0
nm

Figure C. 1 .2: Substrate A in 10% Ethanol for 48 hours

66

. Control A — Solid Line
Treated A - Dots

 

 

 

 

 

: a _ r
380.0
1
-r at:
185.0 200 220 240 260 280 300 320 340 360 380 400.0
nm

Figure C. 1 .3: Substrate A in 10% Ethanol for 120 hours

Control A - Solid Line
Treated A - Dots

 

 

1
549.0

1
, . .‘.‘.'.'.$\w

571.5

 

 

185.0 250 300 350 400 450 500 550 600.0
nm

Figure C. 1 .4: Substrate A in 10% Ethanol for 240 hours

67

Control A - Solid Line
Treated A —- Dots

 

 

 

    

 

    

 

 

. "x.
185.0 200 220 240 260 280 300 320 340 360 380 400.0
nm
Figure C. 1 .5: Substrate A in 95% Ethanol for 24 hours
' Control A — Solid Line
Treated A — Dots
193.0
194.9 198.8
‘ 3 2m .7
\ "-.
2001:,
. 394.0
I960
. . . .................... .r. ....................... ; ____________ I . . ‘
155. 200 220 240 260 230 300 320 340 350.

Figure C.1.6: Substrate A in 95% Ethanol for 48 hours

68

Control A — Solid Line
Treated A — Dots

 

 

 

 

185.0 200 220 240 260 280 300 320 340 350.0

nm
Figure C.1.7: Substrate A in 95% Ethanol for 120 hours

 

 

 

 

 

 

1
Control A — Solid Line
Treated A — Dots
1
4 ‘5 1979 201 2
185.0 200 220 240 260 280 300 320 340 350.0

Figure C. 1 .8: Substrate A in 95% Ethanol for 240 hours

69

Control 8 - Solid Line
. Treated B - Dots

194.09

 

 

T
382.98

 

......
.............................................

 

T I V l l Tr r I I I 1
181 .0 200 220 240 260 280 30 320 34 360 380 397.2

nm
Figure C.2.1: Substrate B in 10% Ethanol for 24 hours

' Control 8 — Solid Line
Treated B — Dots

194.01

 

 

 

 

- at—
337.06
4
. ' ’35
xx".-
‘ I I ..... .....‘. ........ . ...' ........ I ‘ ‘ 1 Y '
185.0 200 220 240 260 280 300 320 340 360 380 400.0

Figure C.2.2: Substrate B in 10% Ethanol for 48 hours

70

 

 

Control 8 - Solid Line
Treated B - Dots

 

 

 

 

 

 

 

 

 

. .1. ' '— A T
383.00
4 "a
.1 ....°o..
J ...........
185.0 200 220 240 260 280 300 320 340 360 380 400.0
nm
Figure C.2.3: Substrate B in 10% Ethanol for 120 hours
. Control 8 - Solid Line
Treated B — Dots
‘ 192.97
_ l 195 or
. l 1" u 1
5! 381 52
1 Egg:
185.0 200 220 240 260 280 300 320 340 360 380 400.0
nm

Figure C.2.4: Substrate B in 10% Ethanol for 240 hours

71

   

 

 

 

 

3 262.87
Control B — Solid Line
Treated B — Dots
193.09
193.96 199.06
207.87
193.
\
195.05
I I I I l h. I l I I r I
185.0 200 220 240 260 280 300 320 340 360 380 400.0

nm

Figure C.2.5: Substrate B in 95% Ethanol for 24 hours

Control 13 — Solid Line
Treated B - Dots

‘

 

 

 

 

l I

I I I I I I I I I
185.0 200 220 240 260 280 300 320 340 360 380 400.0

Figure C.2.6: Substrate B in 95% Ethanol for 48 hours

72

Treated B - Dots

1

Control B — Solid Line

 

 

 

 

 

 

 

 

196.1

105.0 200 220 240 260 280 300 320 340 360 380 400.0
1'"
Figure C.2.7: Substrate B in 95% Ethanol for 120 hours
‘ Control 8 - Solid Line
Treated B — Dots
20 0

196 0

185.0 200 220 240 260 280 nm 300 320 340 360 380 400.0

Figure C.2.8: Substrate B in 95% Ethanol for 240 hours

73

Control C - Solid Line
Treated C - Dots

 

 

 

 

 

T
.2 380.83
185.0 200 220 240 260 280 300 320 340 360 380 400.0

nm

Figure C.3.1: Substrate C in 10% Ethanol for 24 hours

 

 

 

 

 

Control C — Solid Line
Treated C - Dots
.1
_ _ L g T
g . 381 .00
.. 31.";
185.0 200 220 240 260 280 300 320 340 360 380 400.0

nm

Figure C.3.2: Substrate C in 10% Ethanol for 48 hours

74

 

 

Control C - Solid Line
Treated C - Dots

 

 

 

 

 

 

 

 

 

—l_.
= 333.02
" "..'-‘:
.1
185.0 200 220 240 260 280 300 320 340 360 380 400.0
nm
Figure C.3.3: Substrate C in 10% Ethanol for 120 hours
‘ Control C - Solid Line
‘ Treated C 4 Dots .
. , ' T T
E 380 92
. 2'. 197 25
'1
.. 190.013...
185.0 200 220 240 260 280 300 320 340 360 380 400.0

nm

Figure C.3.4: Substrate C in 10% Ethanol for 240 hours

75

 

185.0

.

 

192.99

200

 

Control C — Solid Line
Treated C — Dots

 

220 240 260 280 300 320 340 350.0

nm
Figure C.3.5: Substrate C in 95% Ethanol for 24 hours

Control C - Solid Line
Treated C — Dots

 

.....
.................................................

 

 

185.0

200

220 240 280 280 300 320 340 350.0
nm

Figure C.3.6: Substrate C in 95% Ethanol for 48 hours

76

Control C — Solid Line
Treated C — Dots

 

 

 

 

 

185.0 200 220 240 260 280 300 320 340 350.0

nm
Figure C.3.7: Substrate C in 95% Ethanol for 120 hours

1 197.34
194.99 / Control c — Solid Line
Treated C — Dots

    
 

196.07

  

198.09

 

 

 

185.0 200 220 240 260 280 300 320 340 350.0

Figure C.3.8: Substrate C in 95% Ethanol for 240 hours

77

 

 

 

 

 

 

 

 

1 ' Control D - Solid Line
'1 Treated. D -‘ Dots
193 9
.4
1 "° 329 00
185.0 200 220 240 260 280 300 320 340 360 380 400.0
nm
Figure C .4. l: Substrate D in 10% Ethanol for 24 hours
1
Control D - Solid Line
Treated D - Dots
.1
192.96
‘ _' '— T
5 379.89
. '-'.
" i 1 1 ..... 1 - 1 1 "“ “1 ‘ 1 r ‘i I
185.0 200 220 240 260 280 300 320 340 360 380 400.0

nm

Figure C.4.2: Substrate D in 10% Ethanol for 48 hours

78

. . Control D - Solid Line
Treated D —- Dots

 

 

 

 

 

 

 

194.60
. is 381.01

193.074.
.1
185.0 200 220 240 260 280 300 320 340 360 380 400.0

nm
Figure C.4.3: Substrate D in 10% Ethanol for 120 hours
. Control D — Solid Line
Treated D - Dots
‘ ' ‘ T
- ! 381.92
1 {394.98
1 '7‘:
15.
l

‘ 194.04
185.0 200 220 240 260 280 300 320 340 360 380 400.0

nm

Figure C.4.4: Substrate D in 10% Ethanol for 240 hours

79

 

Control D — Solid Line
Treated D — Dots

 

‘ 196 03
194.00/ 19830
/

 

 

 

.....

 

185.0 200 220 240 260 280 300 320 340 350.0
nm

Figure C.4.5: Substrate D in 95% Ethanol for 24 hours

Control D - Solid Line
Treated D - Dots

 

 

 

185.0 200 220 240 260 280 300 320 340 350.0

Figure C.4.6: Substrate D in 95% Ethanol for 48 hours

80

Control D — Solid Line
Treated D — Dots

|94y9605

 
     

 

 

...--1.......-

1 1 1 1 1
185 O 200 220 240 260 280 300 320 340 350.0
nm

Figure C.4.7: Substrate D in 95% Ethanol for 120 hours

Control D - Solid Line
Treated D — Dots

200 98

1970 204 37

 

 

:1
,,-'-;12037t
$119801 ‘

ﬁ
192 9B

 

1 1 1 1 1 1 1
185.0 200 220 240 260 280 300 320 340 350.0
nm

Figure C.4.8: Substrate D in 95% Ethanol for 240 hours

81

APPENDIX D

FTIR SPECTRUMS

82

 

 

  
   
   

Control A — Solid line
Treated A - Dots

1047 87

 

 

1
Foo-II- .
‘1. 14111171) \. ..................
21119.25 " . ...........
.f. «.
1 ' as
1046 28 .

F .'O 0"

[646(1) 'Ooo~oooo.. .30.. .0

618.01
.‘u'.
4000 0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 300 600 515 0

cm-l

 

Figure D. 1 . 1: Percent Transmittance of Substrate A in 10% Ethanol for 24 hours

 

 

Control A - Solid line
Treated A - Dots

  
    
   
 
     

2190 .13

104(- 51

1646 76

GINO“

 

 

341K) ()7
'o-Mv. N’. ..........................
4 .0 ’1‘. ..‘o.

11 2151 25 -. ; ' .......

21.1111 2 .- 1

2140117 5 1040 .19

1646 10 ........... ’ .., .0’u'...-'
61X 48
4000 0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 5150

cm-1

 

Figure D.1.2: Percent Transmittance of Substrate A in 10% Ethanol for 48 hours

83

 

 

 

 

  
  
   
 
   

Control A — Solid line
Treated A - Dots

2521 25

1046 56

 

 

"AT
pgom.‘ ‘4‘”)n5 . .................. - ..
‘ '. .- r .
.-’ 21591.11 .2 3"” ...........
1046.61
‘1 .oen".~.o to 0‘.
1047.03 "1‘: '1' t.
(113 04
570 16
1 'o... f.
‘0‘“...
4000 0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 515 0

cm- I

 

Figure D.1.3: Percent Transmittance of Substrate A in 10% Ethanol for 120 hours

 

 

  
 
 
   
    
 
   

Control A - Solid line
Treated A - Dots

2135 7S

1645 97

(118.21

 

 

9/ T
O 4'..0~“~. I‘ll) TI .'.‘no...‘. . .-
o :a'. 2‘39} '0'. ..’..Caou.”.... .
4
.1 1018.72
10471111 '1 T. '.
617.52 _
577 55
.‘.u". v I
4000 0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 515.0

cm]

 

Figure D. 1 .4: Percent Transmittance of Substrate A in 10% Ethanol for 240 hours

84

 

 

 

 

 

 

 

 

 

ControlA-Solidlino
TreetedA-Dots
323.1-
2118500 1275.01
1852.00 1455. 1 95141
1311255
2 57
. 93.40
3111.02
616. -
1089. 576.03
2976.13
I009” 0.
961‘ , _. .5...“ . we... - ’00.“: '-
.‘~‘o 3369 "I .I.'a‘o I....'...."'. o 3. I .~.
"-. 21.12.00 1925.112 _, 1 1 g .‘
_ :,.. §953.0o 5 3
,3 1654.40 3; 1 '
O .' .'-. 5". .3 80.1.97 "a,
-' : _: ': 5 11274.92 :
a .- J : .0
' . : .. . . 2‘231“, : ”a o". O...
1 : F g g o o.
1 = - 1 a : 1 =
5. 5 1455.. 5 3 617.6 g
55: 5 1418.015 ' 5 576.88':
1 250‘ 1381 15 5 8111.30 '
{harm :
3.25
29 .63
331“ 1090.:
4
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 515.0
cm-l

 

Figure D. 1 .5: Percent Transmittance of Substrate A in 95% Ethanol for 24 hours

 

 

. 1052 37
201111.25

2 47
.1 .15

2974.69
.gﬂ‘oho. 3368.” ...'...llo~oe'

°/11T
p..?‘..oe uI-Cmgn..

:. 5 1925 02 ’-.,-'

4 g 5 1052 411

 

 

4000.0 3600 3200 2800 2400 2000 1800 1600
cm-1

74.76
29.39
1455. '
1419. '
1381.20

71274.73

1:33. :
1 $1330.15
1455.

1419.5
1381.47

1400

1200

loo-on.
111'.“-
. I . l . .

u. . c

:. ::
=E
1090.19:
‘0

1

Control A - Solid line
Treated A - Data

953.25
1118.
574.70
881 78
1.:
’0‘.
'1'".
952.118: -
.~.

1000

6175 .
575.85:

.1...""‘
g—«Iill'Fgooo-aouo-oee-

:4
V0

800 600 515.0

 

Figure D. 1 .6: Percent Transmittance of Substrate A in 95% Ethanol for 48 hours

85

 

 

 

 

 

%T

 

2 65
‘ .73

274.76
1651..) 432.25

1455. 5
1418.1

1380.99

 

 

 

and

L 2974.77
.1161 51 ................
.‘I u .0.'~ log)3l
’4’“. K .
”0 “ J. ' Q.“
"V 1654, 14
4 '0’...‘ 1 ‘ . g“... 0'. .3: T .. .5 f h
5' E :- '1' ""5 [1275.15 95.1.66
5 _: 1456.00 $329.05 , 5 ' ' 1"- .-..
4 £ E 1381.67 E E '1
35"? ,3: 617.0 E
55 T 3555 575.475
g195 57 552: 1111.39 3
'1 293.99 5 E5
Eula fa
5. 3 1091.“
L as
1
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 515.0

 

Figure D. 1 .7: Percent Transmittance of Substrate A in 95% Ethanol for 120 hours

 

 

°/oT

 

2.13192

1651!!

30.51
1455. 1274.73
1419 '

Control A — Solid line
Treated A - Dots

 

 

. 1311140
1‘ 616.‘1
2 , 36 574.75
94.13 141.111
1090.
1
3'15," 9.; 2974.93
.... .n o u .00 I....".. T .‘I..“-. 105038.... .05.
216021 192510 .-"°"‘- .-‘ '1' '-. .-
‘1’ . 1. 5953.12§§ '1,“
1653.91 : ‘6‘.- 1‘. . . .
:2 s a ELHN” a 2.16
E E =“ﬁnnm 2 "Ta
. 5 E :' f z: 5 . 1174.242
,1' E 5 1455, E; 5 617.64 =
5 gé 5 14111.
: £5 .5 13111.12
ggf' 55%! 3111.22
. . min 5515
‘ s nﬁ. =5
3‘35"“; 1.00 1 ES
‘ 1090.1!
.’ :1
40000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 515.0
cm-l

 

86

Figure D.1.8: Percent Transmittance of Substrate A in 95% Ethanol for 240 hours

 

 

 

 

 

  
 

Control 8 - Solid line
Treated B - Dots

  
  

177 42
(118 53

 
    

 

 

4
.‘T t... | .... -‘.
4 5‘". 3441079 g... .................
‘. .. .. .....
'o """"" e ........... . 6666
E 2 '2‘) (.1 0.. ......... or. E...
e ‘~.~ ooooooo ,5 :z
u
111811 a
1451 .10 1
~ 1045.72
1
1 .
I647 34 .....I|.I..II 0"...“
'1. ,5 6111 19
4 o '
..'O.. .0
4111!“) Hill 321!) 23011 241111 2(Il1 181” 16‘” 14“) 121‘1 [000 “('1 “X1 515 (1

cm-l

 

Figure D.2.1: Percent Transmittance of Substrate B in 10% Ethanol for 24 hours

 

 

 
  
   
 
   

 

 

.
Control 8 — Solid line
1 Treated B - Dots
1360 113
4
104.6 ()4
4
%T ....................
yen .................. .
‘ “RN. 344” 5'6 .............. Y '3.
'-. ,r' 2.160 12 1° ,......
1'
4 104676 ..
16411 20 “T I
(118 5
574 55
4000 0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 (300 515 0

cm]

 

 

 

Figure D.2.2: Percent Transmittance of Substrate B in 10% Ethanol for 48 hours

87

 

 

  
 
 
   
 
   
 
   

Control 8 - Solid line
Treated B - Dots

2152.25

1046 48

1644.11)

oooooooo
.......

 

 

./ T 1.0-M I
0 ‘5'. 14‘”; 73 ...I ....................... ~-
‘ ‘- ~' '- ..... ......
2111 94 .1" " ............
1046.32
J :0. I... 1644 g) .’.."‘o..-II-§. $.60}...
(1111.94
r "M‘" Y Y Y ‘ v ‘ T v j, 1 I ‘
4000 0 3600 3200 2300 2400 2000 1800 1000 1400 1200 1000 800 600 515.0

cm- I

 

Figure D.2.3 : Percent Transmittance of Substrate B in 10% Ethanol for 120 hours

 

 

  
 
 
   
     

Control 8 - Solid line
Treated B — Dots

2377.82

617 (13

 

 

J
.I/oT ‘.... .m“.0‘..‘........IIUII...~~..
.’--._ 34011.75 ".1' l
‘1‘ 2131.75 2..
‘e‘. . ._-' .3. ’xv~._~~~
"T" 1046.65 ,. .

1 '1' ".

1649.41 (117 411 '.

574.73 1
4

I ..‘.A‘.-' ‘7 ﬁr V V V 1' V V V Y I I

40000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 5150

cm-1

 

Figure D.2.4 : Percent Transmittance of Substrate B in 10% Ethanol for 240 hours

88

 

 

 

 

Control 8 - Solid line

 

Q/eT

 

2360.11 1924.82

  

 

 

 

 

Treated B - Dots

 

 

1652.34
‘ 274.37
30.65
.1
1455. 1
.1
1413..
1331.35
331.23
2 79
5.60
. 1090. 1
J 2974.97
.00 I‘m... 1‘6““ .-. Q 'I ' ..u......
4 z. . . ..... ... ...-(. 1‘ ‘ 0“. .* ‘ 1009”,“. e.
‘1 0 23a.“ '92" 1” \.. ‘5'. '~.. . a O: .f ...O
‘ ‘- -" "1' . 3"; '1‘ 5953.072
16521111 '2. :‘o 1274.30 3 5 5 2‘
: '3' 9.15.1157 ' ..
.1 11 1 1455. E: . :'.. :3.
5 5 1419 i " T ':
4 5 ' _: 1311120 5 617. E
:' .. 5 574.923:
5 2 ”I“ 5 331.61 '
5 194.91 5
_ : 291 .34 E
7236350.:
°.. ; 1090.5
:LJ
1600 1400 1200 1000 800 600 515.0

4000.0

3600 3200

2800

l 800
cm-1

2400 2000

 

 

Figure D.2.5: Percent Transmittance of Substrate B in 95% Ethanol for 24 hours

 

 

°/oT

 

 

 

Control 3 - Solid line

  

 

 

1924.33 Treated B - Dots
11.25
2341.32 _
1652.57
4.85
1130.43
1455.
1 I41! '1
1331.21
2 54 331.03
9392
1090.
2974.76 ‘ 'Q..~
4. 3...... 3168-72 ........... . '1. 1049.32 ,.
'- '1‘". -. . .- '- '.
-‘ - ”.1 .- 9.. : '3' : 3.,
'. ‘; .\. 5951.‘7E : .
' 2133.25 - ' :- 1 5 -.
00" a : “Io.
165402 E. .-.:' ‘g 5 -.
:‘E . E 0". .0: I E :- e.
:' '-._, ’ 11274.93 5 "2..
: 5 11330.30 3 : ‘1 ..
i 5 ll” 2%! if.
. 3 E . 1455. =E§5 (170 ‘-,
535$; Substrate 81n9596 Ethanol -48hrs 141311 55:; ' 575119':
2913134 0001““ 3 " 3130“ 13111.32 §§ 31111.99
‘ 5 595,61 Treated 8 - Green :: 55
.- 297310 1 5;
3363 53 E 10393::
e .0. :5
I ‘5'. g
2400 2000 1800 1600 1400 1200 1000 800 600 515.0

4000.0 3600 3200

2800
c1114

 

 

Figure D.2.6: Percent Transmittance of Substrate B in 95% Ethanol for 48 hours

89

 

 

 

%T . "

3368.51

3"

w I... I
' £000....

0..

.....&'...'.'leleeeeeeee

S

 

4000.0

3600 3200 2800

     

1925.11)
1652.23 4.85

330.75
19. 1
1455.74

1381.23

 

1653.21

953 15"; :‘o.

"-.. 5330-16 '1
1455 E
1419. = :
1331.03

881.78

 

1800 1600 1400 1200
cm-1

2400 2000

Control 8 - Solid line
Treated B — Dots

600 515.0

 

 

Figure D.2.7: Percent Transmittance of Substrate B in 95% Ethanol for 120 hours

 

°/oT

 

 

 

 

 

Control 8 - Solid line

 

 

4
2533.75 1924. 15
. 2360.75 _
1652.69
274.39
323.113
1455.
1419.1
1331.51
1
2
94.37
-1 10'9.‘
’II' 297‘” 0'.
”s... 3163.59 - ,. 1.1.— ... , °°°° -.. 1049.69
‘ o" 9". eeeee 0. .~‘9 :- ‘e 0"... .‘ '....e
........... 7’" '1' . ,.-° 1 . f":
1 192625 1653115 {1311113472 952.993 5'
..0 :f. ...I: E : O
1455.711 " \c.
'. E E 1‘19.‘ E as 0. fo- :0.
'1 _. 3.3. _: 1311121 5 3' 5 T g.
z 5 if '5 55' z 617 '2
1 . 5 ES 55 1 574.34:
1 23 33 55 311171 ',
p94 25 :25
72163.32; |
'- : 1090.11
0 .;
1600 1400 1200 1000 800 600 515.0

4000.0 3600 3200 2800

1800
cm-1

2400 2000

 

 

Figure D.2.8: Percent Transmittance of Substrate B in 95% Ethanol for 240 hours.

90

 

 

 

°/oT

 

4000.0

 

341K) ('8

.~M...

3600 3200 2800

Control C - Solid line
Treated C — Dots

1645 W)

.....
oooooo " e...
n' e
O C

10") .
1455 14
1045.33

1646 (15

(719 98

2400 2000 1800 1600 1400 1200 1000 800 600 5150

cm-1

 

Figure D.3.1: Percent Transmittance of Substrate C in 10% Ethanol for 24 hours

 

 

°/oT

 

 

Control C - Solid line
Treated C - Dots

214111!)

 

34111.8]
‘
1....
.‘u. u. e". ooooooooo
1040 M ""5
T l '.
4 16471!) 616 ”J '4.-
575 85 '-
1 .-
.. .’
T ..J' Y ' V T 1 Y T Y 1 Y Y '
4000.0 3600 3200 2800 2400 2000 1800 1000 1400 1200 1000 800 600 515 0

cm-l

 

Figure D.3.2: Percent Transmittance of Substrate C in 10% Ethanol for 48 hours

91

 

 

  
   
   
   

 

Control C - Solid line
Treated C - Dots

1047 110

./eT

 

 

 

 

 

D “‘4‘ 4' ..'°‘\ """""""""""""""""
. 3400.011 '5‘":- ...............
4 i 2115 00 3""..145; 4.1. ..................
1 1046.41
l .....
1041» a) .............. ..
(11') 1‘
571. 5.1
J
40000 36700 3200 ZSOO 2400 2000 18100 1200 1400 1200 1000 800 600 515.0
cm]
Figure D.3.3: Percent Transmittance of Substrate C in 10% Ethanol for 120 hours

  
 
 

 

   
 
 
 
   

 

 

 

 

 

 

1 Control C — Solid line
Treated C - Dots
J 2‘01““
1 1046.69
1047 07
°/eT ‘ 5. .7 ' .
"m 34011 (,7 7, ...__ u.-.....-_-—’. __ ,/ \
‘\ ”1’ \f/ \ vﬂwxﬂ
‘1 ’ 236010 " vx _
ll 1,] \ [I iiiiiii ‘ a
l 1 1 V ' “x
J l I ' i \\
‘1‘ / \l! 104172 ”\ \ \
\1 / 1047 00 \“1’] Al
1‘ / 011101 1
1 57695
1
\ 1’
\
\ ,/
4000 o 3000 3200 21100 2400 2000 11100 1000 14100 1200 1000 800 000 5115 0
cm-l
Figure D.3.4: Percent Transmittance of Substrate C in 10% Ethanol for 240 hours

92

 

 

 

 

1926 10

1274.94

ControlC-Solldline
TreetedC-Dote

 

 

 

 

 

 

 

 

 

951.92
1652.06 1455. -
4 I419. -‘
1332.09
2 “*3 616.5
- .70 551.22 577.64
1090.
2975.1!)
an ”.0... -., . W959
‘5‘ 3369. .7 1 ~.
1 " I”
5 .5“ "..
O .‘.
I"
1. I635 (I) ....... .~ 0...
~ ' ". : -"~
' '- ~_:' ’3. 953.40 3 5 '-.
' 3307 ‘3 35 .3.‘
E 145555 127504 ': E '2
5:3“: 1311206 5 ~ ‘ 617.6 '-.
35.1. :4 5.: l 57“72:'.
3.39736 is 112177 3
4 2 26 5;: :
°-. .-' l
.\}68,6L‘° 10907
4 '- _;'
40000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 515.0
cm—l
. _ - ' o
F1gure D.3.5. Percent Transmlttance of Substrate C 1n 95 /o Ethanol for 24 hours
Control C - Solld line
Treated C — Dot:
4 2173 91 32:
1653.64 1455. 1274.57
1419.
1382.61
2 5:
.46
618.1
551 I0 515.64
1059.
2976.211
1
1049.42
9/1' 1" "~ ,4... ............
° 4 3369 39 .... .. ~" ----
-' l‘ l
2537.137 1925.011 "'9... z. ..
165416 "- 5427157 E95236§E -
* :f': l l E E 35 1 "-.
. .E 5 if“ 9.3;)”.15 :: E: “I” ....|....r..~.e.....
4 g :3 ”5‘4; 2 5 5.: 618.28
54 5 14111.. g 53 E
Ems 13111.59 35; :
”is 253 1
293.1 :_: 5 11110.91
. 5 95.69 - 5.
3.33““; 1059.111
\iﬂ.’ i
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 $15 0

cm— I

 

 

Figure D.3.6: Percent Transmittance of Substrate C in 95% Ethanol for 48 hours

93

 

 

    

Control C - Solid line
Treated C — Dots

     
 

 

I925 41

 

111171

    

2519 91

  

'wT 1168 15 - ~'""""" ' - - -.
p--.._‘.' V -'l . 5' . {I ~
4

 

 

 

4000 0 3600 3200 2800 2400 2000 1800 1000 1400 1200 1000 :00 600 5150
cm-1

 

 

 

Figure D.3.7: Percent Transmittance of Substrate C in 95% Ethanol for 120 hours

 

Control c - Solid line
Treated C - Dots

 

 

 

.r/eT -----
1 ‘~|..._.
4
11140 93 574 (.4.
“I.”

l E;

luring!

.E.

=

4000 0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 (>00 515 0

cm-l

 

 

Figure D.3.8: Percent Transmittance of Substrate C in 95% Ethanol for 240 hours

94

 

 

  
  
   
     

Control D - Solid line
Treated D - Date

1651 73

(111115

 

 

 

'E/T .. ' .
e ‘1 ‘3'. 14“!) 75 ..... _n° ‘~.\
31154 51“ ‘ .................. '1’ 3.
' ,3. 2360 14 3.. 1M»...m_'
4 . = : ...............
3.55947 1 ....I.... ran,
’ 1457 10 l
1046 59
1651 09 ”"TI'
617 (9 .0.
577 20
3400 50
..‘.Le....
4000 0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 515 0
cm-l

 

 

Figure DA. 1: Percent Transmittance of Substrate D in 10% Ethanol for 24 hours

 

 

 

 

‘ Control D - SOlld line
N“, M Treated D - Dots
1086. 1
1046 14
1646.27
6111 40
./.T 0.. .“. ’ .§
'4 3400 711 '7.
4 385‘ 2% .".e.e'0 a"
e a".' ‘.
......I. :0. .'?I.ﬁ'~o- N...
0.“. :0. :5 I‘S7(m ...d'.e IO...
"4. 1046 69 "'.

r ....‘Ouou-O"e. ., ‘4'.
1652 8‘) 'r' '6:
6111 21 °.

575 119
1 ...~".. 1 V Y Y 'Y Y Y Y Y T— V I

4000.0 3600 3200 2800 2400 2000 1800 1600 I400 1200 1000 800 600 515.0
cm-l

 

 

Figure D.4.2: Percent Transmittance of Substrate D in 10% Ethanol for 48 hours

95

 

 

'l/eT

 

  
 
 
   
 
   
 
   

1652 99

1457.03

Control D - Solid line
Treated D - Dots

1046.63

 

l
3400.63
“A .3 .'e.
" 'g .3 236032
GP». .359". q, ........................
O..- I: ‘ e‘. .

". $1558.36 1046 95 .-'. .~._

'- .-' 1456.47 1
T 617,2 :-
1652 21 575 15 3
«5’0. 1 Y I v r v y ‘ ‘ v Y 1

4000.0 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 5150
cm-1

 

Figure D.4.3: Percent Transmittance of Substrate D in 10% Ethanol for 120 hours

 

 

'/eT

 

 

1 Control 0 — Solid line
Treated D — Dots
19.43
21311.25 59 34
1457.31
1046.45
.1
1649.25
(317.71
.4
3400.57
1. ’0' 's.
0" .I.
.j '9'?..~.“l“.g.~.~090005.0... Ia.... ....
“W, n eon-0.“.eoeen.... ’. ....

r 1 I °-.

1652 52 617.4 3

576.46;

e.~ .."
V v V 1 V Y 1 V Y 1 Y ' 1 ‘
4000 0 3600 3200 2300 2400 2000 1800 1600 1400 1200 1000 800 600 515.0
cm-l

 

96

Figure D.4.4: Percent Transmittance of Substrate D in 10% Ethanol for 240 hours

 

 

 

 

‘/oT

 

3350 70

2.165.515.

' .I'

2359.91

2 “94

‘ .41
2975.03

’ ..‘eea
v
r"

-'-.

”6.91
297 .87

 

1634.20

275.10

1455. I 329.81

953.59

1419. .~
1351.55
6174
551.511 574.63
1091. .
1050.49
.I... .-
O~.. ‘ 5 O r '0‘.
‘8 .f..-a. :00: ‘0.
.-'“ .6, ': 505.64 ._
‘. .. .°"- '-.'
1607 33 ... : e... g I zia.
.‘u\.~ : ‘-
" 1 617. 3
1455.52 1 “: 551.75 574.51!

1382.33

 

40000

3600

3200

2800 2400

l800
cm-l

2000

1600 1400

800

 

Figure D.4.5: Percent Transmittance of Substrate D in 95% Ethanol for 24 hours

 

 

‘/oT

 

1654.12

Control D - Solid line
Treated D - Dote

 

2360.27
329.51
1455.54 1274.57
1351.44
6174
574.2
2 52
.1 .25 551.97
1091. .
3350.60 2974.119
rune-ea...“- 4"- I0” 5 a"'..
no. a '0..I\..\ ...“~.-. . ~. ' g a...
. .- ‘. .s- -. : -,
. ’9," ° .-‘ 3. 5 953.12; 5%..
_... 5 1652.12 5 '1‘27455 E = - ' :5
' "$35,730.75 E ii ....
e a = :: 'a~.
1455.45 ,4 15 we
it 5 1419. 5 5; 1‘ -._
5?,5 1351.16 555 615.2 a
551 355 575.652
25972 is: 551.70 1
3.75 '-= E
.. : 29".” § 5
£465.32." t 1090i:
'4 2 2,;

 

4000.0

3600

3200

2800 2400

l 800
cm- I

2000

1600 1400 1200

1000

800 600 5150

 

97

Figure D.4.6: Percent Transmittance of Substrate D in 95% Ethanol for 48 hours

 

 

 

 

 

 

 

 

 

 

Carmelo-Soliciting
TmtedD-Dots

  

 

2136.75 1925.47
1651 90
274.83
30.48
1455. ~
1419. :
1381 03
2 {'8 7 881.12
. ‘ 1.87
10”. 5
1 .
297‘.62 ath-lo
3351.05 ,w '
"71.". . 1050111.";
“ﬂux. ." .1 .9 ....... .....
-, . ....... 2361.00 ..... '1. 51.953 13:;
o... .‘..‘.T IOU”, .... z = : E: ’2'. o
r. ~. 1: ' .
’, 5 "'[1'274 79 55 1 '
': S g; 804.24 ‘
1 5 :315 42 a E: ., ..,. ﬂ
'5; 1455. § 17579:
33‘ E 1418 -2 § 617.12
:jf‘ 1.130.110 E 11111.02
29: a E
4 '. .3 ' 5
3350.66 2 .73 3'
1. .g' 1093§
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1000 800 600 515.0

cm- I

 

 

Figure D.4.7: Percent Transmittance of Substrate D in 95% Ethanol for 120 hours

 

 

 

 

 

 

3
1925.11
4 1654.2
11
74.9
110.1
1455.
4 14111.
11 . . 3 1331.3
2 2 ControlD-Soludlme 3 551.1
8 .915 Treated D - 0013 7
J
1090.
4
O " .4‘
T ’M‘\ 0 5 a”... £0499
. 1“ ..... a.
2. "~.
2.1000 ""4' . f“ -. ..
,. , o .., "" g as " ”9.,
.-' -' 5' . 5 if '--*-....
3 5 531.7 5;: f ' '-.
5 1455.9 12751 g 5 § 017.31
:5 E 8 15111.11 8 a. : 7 7 574.0:
out. . - I 9
SE 1' 1 2.":5 11819 0 '..
. 395.5 5555 1
'2 291.8 :3 s5
9"“: 4 '7' EE
3"; 1091.£§
'. ,1 9 E:
1
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1000 800 600 $15
‘1‘"

 

 

Figure D.4.8: Percent Transmittance of Substrate D in 95% Ethanol for 240 hours.

98

 

10.

REFERENCES

ASTM D 882-01 , Standard Test Method for Tensile Properties of Thin Plastic
Sheeting. 2003, Pennsylvania: ASTM International.

ASTM D 1709-01, Standard Test Method for Impact Resistance of Plastic Film
by Free-Falling Dart Method. 2003, Pennsylvania: ASTM International.

ASTM D 1894-01, Standard T est Method for Static and Kinetic Coeﬂicient of
Friction of Plastic Film and Sheeting. 2003, Pennsylvania: ASTM International.

ASTM D 1922-O3a, Standard Test Method for Propagation Tear Resistance of
Plastic Film and Thin Sheeting by Pendulum Method. 2004, Pennsylvania: ASTM
International.

ASTM D 4754-98, Standard Test Method for T wo-Sided Liquid Extraction of
Plastic Materials Using FDA Migration Cell. 2003, Pennsylvania: ASTM
International.

ASTM D 5264-98, Standard Practice for Abrasion Resistance of Printed
Materials by the Sutherland Rub Tester. 2003, Pennsylvania: ASTM
International.

ASTM D 6287-98, Standard Practice for Cutting Film and Sheeting Test
Specimens. 2003, Pennsylvania: ASTM International.

ASTM D 6988-03, Standard Guide for Determination of Thickness of Plastic
Film Test Specimens. 2003, Pennsylvania: ASTM International.

ASTM F88-00, Standard T est Method for Seal Strength of Flexible Barrier
Materials. 2003, Pennsylvania: ASTM International.

Bakish, R., Introduction to Electron Beam Technology. 1962: John Wiley & Sons,
Inc.

99

 

11.

12.

13.

14.

15.

16.

17.

18.

19.

Batten, R.J., Davidson, R.S., Ellis, R.J., Wilkinson, S.A., New surface-coating

materials: electron beam curing of some silicon-containing acrylates. Polymer,
1992.33(14): p.3037-3043.

Beam, A.J., Electron Beam Curing in Flexible Packaging, in Paper, Film & Foil
Converter. 2001. From http://advertiserspﬁ‘c-
online.com/ar/paper_electron_beam_curing/

Biro, D. and R. Sanders, The State of U V/EB in Graphic Arts, in Radtech Report.
2004, Radtech North America. p. 53-56. from

http://www.radtech.org/MarApr04RR_StateUVEBGARTS.pdf#search=‘state%20
of°/o20UV/EB

Burke, J .J . and V. Weiss, Surface Treatment for Improving Performance and
Properties. 1982, New York: Plenum Press.

Casso-Solar Corporation, High Eﬁ‘iciency Drying of Waterbase Coatings and
Adhesive on Paper, Film & Foil, October 2004. Retrieved from
http://www.cassosolar.com/download/Al01 _paper_ﬁlm_&_foil.pdf

Cleland, M.R., L.A. Parks, and S. Cheng, Applications for radiation processing of
materials. Nuclear Instruments and Methods in Physics: Research B, 2003. 208:
p. 66-73.

Cohen, G., Why switch to U V/EB curing?, in PFonline. 2001. Retrieved from
http://www.pfon1ine.com/articles/0701supp04.html

Cohen, G., North America Market Update on U V/EB Technology, in Radtech
2002 International Market Overview Session. Retrieved from
http://www.radtech.org/Market%20Data%20ReportRT%202002.pdf.

Datta, S.K., T.K. Chaki, and D. Khastgir, Effect of electron beam radiation on
mechanical and electrical properties of poly(ethylene-co-vinyl acetate). Die
Angewandte Makromolekulare Chemie, 1996. 238: p. 105-117.

100

 

20.

21.

22.

23.

24.

25.

26.

27.

28.

Duncan, D., U V/EB for Food Packaging - The Invisible Elephant, in Ink World.
2002. Retrieved from
http://www.radtech.org/uveb%20corner%20july.pdf#search='UV/EB%20the%20i
nvisible%20elephant'

Electron Beam C urable Adhesive May Soon Outshine Ultra Violet, in power @
work. 2002. p. 7-9. Retrieved from
http://www.rohmhaas.com/AdhesivesSealants/pdf/power@work_Summer2003.pd
f

Energy Science, Inc., Electron Beam Fundamentals. Retrieved from
http://www.radtech-europe.com/download/chruscielpaperdecemberpdf

Gante, C.R.D. and B. Pascat, Effects of B-ionizing Radiation on Properties of
Flexible Packaging Materials. Packaging Technology and Science, 1990. 3: p.
97-115.

Goldberg, A.G., UV/EB Curing for Laminating Adhesive, in Flexible Packaging.
2004.6(10): p. 36-37.

Griese, E.W., UV, EB, and Aqueous Coatings: Technical Basics. 1998,
GATFWorld. Retrieved from http://www.pneac.org/compliance/Ink-
Paper/coatings.pdf '

Joy T, K., Radiation Chemistry in EB-and U V- Light-Cured Inks. 2000. Retrieved
from
http://www.pcimag.com/CDA/ArticleInformation/features/BNP_Features_ltem
/O,1 846,1 1435,00.html

Kauffman, T., Advances in EB-Curable Adhesive and Coatings for Flexible
Packaging. 2003, Adhesive and Sealants Industry. Retrieved from
http://www.adhesivesmag.com/CDA/ArticleInformation/coverstory/BNPCoverSt
oryItem/O,2103,97289,00.html

Lauppi, U.V., Low voltage, low cost electron beam system - An alternative to UV
curing. Surface Coatings International Part B: Coatings Transactions, 2001.
84(B4): p. 243-336.

101

 

29.

30.

31.

32.

33.

34.

35.

36.

37.

38.

Lox, F., M.S. Choudhry, M.S., Buekens, A. and Decrolyet, P., Evaluation of
Migrational Behavior of Plastic F ood-contact Materials: A Comparison of
Methods. Packaging Technology and Science, 1998. 11: p. 275-283.

Lox, F., de Smet, R., and Walden, A., UV Specrophotometry to Assess the Eﬂect
of Ionizing Radiation upon Migrational Behavior of Plastics. Packaging
Technology and Science, 1991. 4(3): p. 167-170.

F. Lox, F., de Smet, R., Walden, A. and Machiels, V., The Evaluation of Global
Migration and the Assessment of Related Parameters by a Spectrophotometric ,
Methodology. Packaging Technology and Science, 1988. l: p. 11-16. F

Menhert, R., Electron beams in research and technology. Nuclear Instrtunents
and Methods in Physics :Research B, 1995. 105: p. 348-358.

 

Menhert, R., Review of Industrial Applications of Electron Accelerators. Nuclear I!
Instruments and Methods in Physics :Research B, 1996. 113: p. 81-87.

Messick, J., Electron beam processing of plastics: An alternative to chemical
adhesive. 2000, E-BEAM Services, Inc. Retrieved from
http://www.ebeamservices.com/ebeam_spe_antec.htm

Miller, A., Converting for Flexible Packaging. 1994, Lancaster, Pennsylvania:
Technomic Publishing Co, Inc.

Mondelaers, W., Low-energy accelerators in industry and applied research.
Nuclear Instruments and Methods in Physics :Research B, 1998. 139: p. 43-50.

Nablo, S.V., J. Chrusciel, J ., Cleghom, and D.A., Rangwalla. 1., Developments in
low energy electron beam machinery and processes. Nuclear Instruments and
Methods in Physics:Research B, 2003. 208: p. 90-97.

Nielsen, CR. and G.G. Misko, Establishing a Regulatory Status for UV/EB-
Cured Inks and Coatings in Food Packaging. J uly/August 2001 , RadTech Report.
Retrieved from http://www.radtech.org/ju1_aug01 _p_12.pdf

102

39.

40.

41.

42.

43.

44.

45.

46.

47.

48.

Oliver, A., Pakula, T., Ewen, B., Coqueret, X., Benmouna, M., and Maschke, U.,
Mechanical Properties of Electron Beam Cured Monomer and Monomer/Liquid

Crystal Films. Macromolecular Materials and Engineering, 2002. 287: p. 656-
659.

Packaging Institute, Tentative Procedure F or Testing the Dry Resistance of A
Printed Ink Film on Packaging Materials. Undated, Packaging Institute: New
York.

Pillette, L., Effects of Ionizing Treatments on Packaging- Food Simulants
Combinations. Packaging Technology and Science, 1990. 3: p. 17-20.

RadTech International, The UV & EB curing process. 2001. Retrieved from
http://www.radtech.org/uv_eb/curing.html

RadTech Health and Safety Committee, UV/EB Health and Safety -Answers to
Frequently Asked Questions. September/October 1999. Retrieved from
http://www.radtech.org/health_safety/hsfaq.pdf

RTI Technology and EPA, Electron Beam C urable Coatings - Summary. 2003.
Retrieved from http://cage.rti.org/altern_data.cfm?id=oebc&cat=summary

Sanders, R., EB, a bright new ﬁtture for 2003 and beyond, in Ink World. 2003. p.
16-17. Retrieved from http://www.radtech.org/uveb%20comer%20feb%2003.pdf

Schroeter, S.H., Radiation Curing of Coatings. Annual Review of Materials
Science, 1975. 5: p. 115-133. Retrieved from
http://a1joumals.annualreviews.org/doi/pdf710. 1 146/annurev.ms.05.0801 75 .0005 5
5?cookieSet=l

Taniguchi, N., Ikeda, M., Miyamoto, 1., and Miyazak, T., Energy-beam
Processing of Materials - Advance Manufacturing Using Various Energy Sources.
1989, New York: Oxford University Press.

Tempelman, R.J., Statistics for Biologist I and II Lecture Notes. 2004. Michigan
State University.

103

 

49.

50.

51.

Toxic Use Reduction Institute (TURI), Electron Beam Curing of Polymers in
Coating Processes in Metallized Products Inc. 1996.Retrieved from
http://www.turi.org/content/content/view/full/ 1 009

Ultraviolet and Electron Beam (UV/EB) Cured Coatings, Inks and Adhesives.
2001, Environmental Protection Agency (EPA): United States. Retrieved from
http://www.sartomer.com/wpapers/ 1065.pdf

(USFDA) and C.f.F.S.A. Nutrition, USF DA Final Guidance for Industry -
Preparation of Food Contact Notiﬁcations and Food Additive Petitions for Food
Contact Substances: Chemistry Recommendations. 2002, USF DA & CFSAN.
Retrieved from http://www.cfsan.fda.gov/~dms/opa2pmnc.html

104

l -"|..u“p I

‘ ‘ ‘I .-
-' ‘I'l- - ‘

LEAN 37A V1:3“ 11 LIBRAHIL

1293 02736 0522