Thesis - Gel-L Scott Crump

PROCESS OPTIMIZATION OF PHOTOCURABLE POLYESTER GEL
COAT AND LAMINATE
by
L. SCOTT CRUMP
Submitted in partial fulfillment of the requirements

For the Degree of Master of Science
Thesis Advisor: Professor Alex. M. Jamieson
Department of Macromolecular Science and Engineering

CASE WESTERN RESERVE UNIVERSITY
Cleveland, Ohio
May , 2014
CASE WESTERN RESERVE UNIVERSITY

GRADUATE STUDIES
We hereby approve the thesis of Larry Scott Crump

candidate for the Master of Science-Macromolecular Science & Engineering degree.
(signed) Professor A. Jamieson __________________________________
Professor H. Ishida______________________________________
Professor D. Schiraldi (chair)_____________________________
date
______________________
I grant to Case Western Reserve University the right to use this work irrespective of
any copyright, for the Universitys own purposes without cost to the University or to
its students, agents, and employees. I further agree that the University may reproduce
and provide single copies of the work, in any format other than in or from
microforms, to the public for the cost of reproduction.
_________________________________________
ii
Process Optimization of Photocurable Polyester Gel Coat and Laminate

List of Tables
.
Table of Contents
Table of Contents.....
vi
List of Tables........
xii
List of Figures
xvi
Acknowledgements.....
xviii
Chapter I The Composite Open Molding Process..
Chapter II UV Curing Equipment and Radiometry
16
Chapter III Chemistry of Thermosetting Unsaturated Polyester and

Acrylate Systems..
34
Chapter IV Characterization of Resin / Coating State of Cure...
70
Chapter V Modeling the Degree of Cure of a 2D UV Curing Process
75
Chapter VI Process Optimization - Defining the Process Window
142
Balancing Safety, Throughput, Capital Investment and

Operating Costs
Chapter VII Case Study Flat Construction Panel Laminate..
150
Bibliography..
156
iii

List of Tables
Table of Contents
Chapter I The Composite Open Molding Process.
a. Unsaturated Polyester Resin Based Composite Products

b. Application of the In-Mold Coating (Gel Coat)
i. transfer to the mold
ii. rheology of gel coat
iii. curing the gel coat film on the mold
c. Reinforced Laminate Application
Chapter II UV Curing Equipment and Radiometry.
a. Lighting systems
i. bulb design
ii. reflector design light ray management
iii. temperature management in UV curing applications
-dichroic reflectors
-bulb diameter
iv. metal halide doping to modify the spectral power
distribution
v. lamp motion relative to the target
b. Radiometers and radiometric characterization of a UV
curing process
iv
16

List of Tables
Chapter III Chemistry of Thermosetting Unsaturated Polyester
and Acrylate Systems..
a. Synthesis of thermosetting polyester and acrylate
oligomers (condensation polymerization)
b. Network formation of thermosetting polyester and acrylate
oligomers (free-radical polymerization)
i. Microgel formation and macrogelation
ii. Kinetics of redox initiated polymerization of UPR
styrene
iii. Kinetics of light induced polymerization involving
multifunctional monomers
c. Formulation of conventional gel coat and resins
d. The Case for UV Curable Composite Materials
e. Formulation of UV curable gel coat and UP resins
.
i. Historical work in the area of UV curable composites

ii. Classification of photoinitiators photolysis
mechanisms
iii. Physical Concepts of UV Curing interaction of light
with the photocurable material
iv. Photobleaching and high radical yield-impact of
acylphosphine oxide photoinitiators- curing thick films
containing titanium dioxide pigment
v. Light scattering within a coating or laminate
vi. Commercial applications for UV curable composites
34

List of Tables
Chapter IV Characterization of Resin / Coating State of Cure 70
a. Qualitative methods for estimating cure
i. Probing techniques to assess cure hardness
development, dry-to-touch assessment
ii. Limitation of probing techniques to assess cure
b. Quantitative methods for cure characterization
i. Analytical methods used to study cure during the
product development cycle( DSC, FTIR )
ii. Process quality control methods to measure cure
NIR, dielectric spectroscopy
vi

List of Tables
Chapter V Modeling the Degree of Cure of a 2D UV Curing
Process
75
a. Studies of coatings and laminate resin related variables

i. Experiment 1 Effect of pigmentation-screening
study involving ten different colors
ii. Experiment 2 Effect of TiO2 concentration
iii. Experiment 3 Effect of gel coat film thickness
iv. Experiment 4 Factorial study of photoinitiator
concentration, UV energy, and film
thickness
v. Experiment 5 - Binder / reactive diluent selection
vi. Experiment 6 Light transmission studies in the
laminate resin
b. Studies of UV curing equipment variables
i. Experiment 7 Reciprocal law for UV energy,
independence of irradiance and line
speed
ii. Experiment 8 DSC cure studies in clear and
white
gel coat effect of film thickness and UV
energy
iii. Experiment 9 Temperature-Energy-Irradiance map
for several UV light sources
iii. Experiment 10 Variations in energy and
irradiance of a single 600 W/inch lamp as function
of distance from the lamp centerline
iv. Experiment 11 Measurement of energy and
irradiance from a bank of five 600 W/inch lamps
as a function of lateral position
vi. Experiment 12 Testing the additive law for UV
energy using two 600 W/inch lamps
vii

List of Tables
vii. Experiment 13 Effect of UV energy and irradiance
level on the surface temperature of the coating
viii. Experiment 14 Validation of the cosine law for
non-perpendicular exposure conditions
ix. Experiment 15 Effect of lamp height on UV
energy and irradiance
x. Experiment 16 Evaluation of dichroic reflectors
c. Studies of the reflectivity of the mold surface
Experiment 17 Effect of reflectivity on cure
d. Integrated mathematical model for a UV conveyor line
i. Mathematical model development
ii. Simulation 1 - Validation of the mathematical model
iii. Simulation 2 - The effect of lamp spacing on the
irradiance and energy distribution
iv. Simulation 3 The effect of a lamp failure on the
irradiance and energy distribution
v. Simulation 4 The effect of lamp height on energy
level and uniformity
viii

List of Tables
Chapter VI Process Optimization - Defining the Process 142
Window. Balancing Safety, Throughput,
Environmental Impact,
Capital Investment and Operating Costs.
a. Safety considerations
b. Throughput considerations
c. Environmental benefits of UV curable composites
c. Economic considerations
Chapter VII Case Studies Flat Construction Panel
150
Laminate
Bibliography
156
ix

List of Tables
Table #
Description
Chapter I - The Composite Open Molding Process
Page
U.S. Markets and Applications for Unsaturated Polyester Based

Composites
Cone and plate rheometer programming sequence to simulate the

rheological lifecycle of a commercial gel coat.
Application flow requirements of gel coat and solvent based

paint
Summary of lamination process features and limitations
12
Chapter III - Chemistry of Thermosetting Systems.

1
Gel Point Time data set used to validate the redox cure kinetic
model
46
Commercially available photoinitiators
53
Energy absorbed in the top 1% and bottom 1% of a coating film
59
Chapter IV - Characterization of Resin / Coating State of

Cure
1
Effect of Tg on the surface tackiness of UPR prepolymer
68
Chapter V - Modeling the Degree of Cure of a 2D UV

Process
1
2
Factorial study of photoinitiator concentration, UV energy, and

TiO2 concentration
Binder / reactive diluent selection
80
82
Reciprocal law for UV energy, independence of irradiance and

line speed
86
Variations in energy and irradiance of a single 600 W/inch lamp

as function of distance from the lamp centerline
95-96
Gaussian fit parameters to model light dispersion a 600 W/inch

lamp
x
98

List of Tables
6
Measurement of energy and irradiance from a bank of five 600

W/inch lamps as a function of lateral position
102
Testing the additive law for UV energy using two 600 W/inch
lamps
106
Effect of UV energy and irradiance level on the surface

temperature of the substrate
109
Validation of the cosine law for non-perpendicular exposure

conditions
113
10
UV Energy and irradiance measurements at various lamp heights

static one minute exposure
114
11
The irradiance from a point source of light varies with the square
of the distance from the source
115
12
Evaluation of dichroic reflectors
116
13
White UV curable gel coat results on a reflective and nonreflective mold
120
Chapter VI - Process Optimization - Defining a Process

Window
1
Effect of lamp spacing on UV energy level and uniformity
129
Chapter VII Case Study Flat Construction Panel Laminate

1
Summary of UV Curing Knowledge (from Experiments 1- 18)
xi
143
Process Optimization of Photocurable Polyester Gel Coat and Laminate List of

Figures
Figure #
Page
Controlled stress cone and plate rheometer
Experiment to simulate the shear history of a commercial

polyester gel coat and automotive polyurethane paint
Chapter II - UV Curing Equipment and Radiometry

1
Reflector designs to focus (elliptical), collimate (parabolic), and

disperse (dimpled) light energy
19
21
2
IR absorbing dichroic reflector
3
Relative spectral power distribution of commonly used UV bulbs
25
UV curing lighting systems
26

1
Production of unsaturated polyester resin solutions
33
Polymerization of UPR prepolymer and crosslinking monomer
37
Formation of a UPR-styrene microgel
41
Microgel formation and Macrogelation in UPR-Styrene System
42
Effect of curing temperature on the gel point time redox

initiator system UPR-styrene monomer
46
Effect of initiator concentration on the gel point time redox

initiator system UPR-styrene monomer
47
Effect of cobalt accelerator concentration on the gel point time

redox initiator system UPR-styrene monomer
47
Light induced free radical formation in a coating film
54
UV Transmission characteristics of monomers, oligomers, and

films commonly used for UV cure applications (path length=10
mm UV cell, 100% concentration)
56
xii

Figures
10
Absorption-scattering characteristics of titanium dioxide pigment
57
11
Effect of the absorptivity on light transmission characteristics in

a film
58
12
Fraction of incident energy absorbed in the top 1% and bottom

1% of a film
59
13
Time-lapsed UV absorption spectrum of phosphine oxide

photoinitiator
62
14
Comparison of photobleaching and non-photobleaching

photoinitiators
63
15
UV Composites publications
64
Chapter IV - Characterization of Resin / Coating State of

Cure
1
Evaporative losses of reactive monomers in gel coat film

measured by FTIR (T=25C)
67

Process
1
Screening experiment to evaluate the effect of color

pigmentation on the degree of UV cure
72
Kubelka-Munk prediction of light absorption and scattering in an

opaque pigmented film
73
Reflectance spectra for the ten pigmented gel coats shown in

photograph 1
74
Absorption spectra of the photoinitiator solution
75
Effect of UV energy on cure of a UPR laminate containing 35%

short fiber E-glass reinforcement (0.75% BAPO photoinitiator)
84
Effect of UV energy on surface temperature of a UPR laminate

containing 35% short fiber E-glass reinforcement (0.75% BAPO
photoinitiator)
84
Effect of photoinitiator concentration on the cure of a UPR

laminate containing 35% short fiber E-glass reinforcement
85
xiii

Figures
(BAPO photoinitiator) 5 minute static exposure
8
Energy and irradiance vs. conveyor speed
87
Energy requirements to cure a clear gel coat and white gel coat
89
10
Energy and surface temperature profiles for several

commercially available UV lamps
91
11
UV lighting set-up for experiment 10 a single 600 W/inch

Fusion UV lamp
93
Energy distribution for a Fusion 600 W/in lamp
97
UV lighting set-up for experiment 11 a bank of five 600

W/inch Fusion UV lamps
100
Measured UV Energy Bank of five 600 W/inch Fusion UV

lamps
103
13
UV lighting set-up for experiment 12
104
14
Output from two 600 W/inch UV lamps
107
15
Effect of lamp type, lamp height, line speed, and reflector type
on UV energy, irradiance, and exit temperature
110
16
Correlation of UV energy and irradiance with the surface

temperature of a part being cured with UV lamps
111
17
Validation of the cosine law for non-perpendicular exposure

conditions
112
18
Schematic of lighting set-up for experiment 15
113
19
UV Energy and irradiance measurements at various lamp heights

static one minute exposure
115
20
Inverse square law validation
115
21
Interactions of UV light with the coating and mold surface
117
22
UV-Visible reflection from polyester tooling gel coat various

colors
119
11.5
12
12.5
xiv

Figures
23
UV-Visible reflection from metal molds and aluminum flake

filled polyester tooling gel coat
119
24
Schematic of a conveyor line with the coordinate system

indicated
121
25
Lamp height dependence of the pre-exponential multiplier and

dispersion parameter
123
26
Schematic of an industrial UV curing line
126
27
Ten lamp UV curing conveyor Two rows of five lamps
127
28
Validation of the predictive model to estimate UV energy and

irradiance levels
128
29
The effect of lamp spacing on the level and uniformity of UV

energy
130
30
The impact of a lamp failure on the UV energy and irradiance

distribution
132
31
The effect of lamp height on the level and uniformity of UV

energy
134
Chapter VI - Process Optimization - Defining a Process

Window
1
Process window for UV curable gel coat
xv
138

Figures
Photograph #
Description
Page
Application of white gel coat to a large hull mold
Application of white gel coat to a large hull mold (2)
3
3
Application of barrier skin coat laminate on the white gel

coat
Completed hull after being removed from the mold
Spray pattern test prior to applying the gel coat on a deck

mold
Clear gel coat applied to a mold used to make a synthetic

marble sink.
Black gel coat applied to a cowling mold for a small tractor
Gel coat applied to a tub/shower mold
Severe de-wetting of a clear gel coat
10
De-wetting (crawling) of a white gel coat
11
Hand lay-up process
13
12
Hand lay-up process (2)
13
13
Spray-up process using an external mix chopper gun with

continuous E-glass roving
13
14
Vacuum infusion lamination of a small boat hull
14
15
Hybrid process open mold wet lay-up followed by press

molding to cure electrical panels Wet lay-up compression
molding
14
16
Open molding process automated lamination of roofing

panels
14
17
Closed molding resin transfer molding (RTM) of toy

locomotive
14
xvi

Figures
18
Dry reinforcement charged in to RTM mold prior to mold

closure
14
19
Casting molding of synthetic marble sink ( non-reinforced

part)
15
20
demolding the cured sink bowl

Bottom view of UV lamp housing with the shutter open and 17

the bulb exposed
Top view of UV lamp housing. The red hoses are used for
water cooling during operation
17
Electrode style medium pressure mercury vapor lamp

( the bulb is energized by applying an electric current
across the metal electrodes)
17
Electrodeless style medium pressure mercury vapor lamp

( the bulb is energized with microwave heating)
18
UV lamp with an electrode style bulb and a dimpled

reflector capable of producing diffusely reflected light
18
Modular microwave UV lamp Bottom view note the

metal mesh designed to prevent leakage of the RF waves
produced by the magnetron heating source
18
Modular microwave UV lamp Bottom view electrodeless

style bulb and elliptical reflector - note RF leakage monitor
interlocked to the power supply
18
Modular microwave UV lamp side view - note the 6

diameter air cooling hose
18
Bench scale UV conveyor and 6 modular microwave

electrodeless lamp
27
10
Pilot scale UV conveyor fitted with two 10 modular

microwave electrodeless lamps
27
11
Industrial robotic curing
27
xvii

Figures
12
Industrial robotic curing
27
13
Photodiode radiometer with dry air purge line
31
14
UV lamp housing with a process radiometer mounted on

the lamp housing to monitor the lamp output
31
15
Traveling radiometer top view photodiode array is

visible
31
16
Traveling process radiometer bottom view controls and

readout are visible
31

1
Alligatoring phenomena the top 1-3 mils is cured while

the balance of the film is wet
60
Uncured coating material which remains after the cured

surface film is peeled away
60
Chapter IV - Characterization of Resin / Coating Cure

1
Colored gel coat films before UV curing
71
Colored gel coat films after UV curing
72

Process
1
UV Curing line used to develop the irradiance and energy

process model
94
Chapter VII Case Study Flat Construction Panel

Laminate
Application of the white UV curable gel coat to the
reflective mold
146
UV curing of the white gel coat
146
Cured white gel coat film
147
Hand lay-up of the laminate
147
xviii

Figures
5
UV curing the laminate
148
Cured laminate
148
xix
Acknowledgement
I would like to thank my wife Ruth for giving me the many uninterrupted hours
needed to prepare this paper.
xx
Abstract
by
L. SCOTT CRUMP
It is the purpose of this project to develop the basic process data and approach
needed to produce photocurable gel coated laminates. A review of the composite
open molding process is made describing the application steps used to produce
conventional composite parts prepared from unsaturated polyester resins. A summary
of the current state of the art in ultraviolet (UV) curing equipment and process
radiometers is given to develop the basis for the experimental portion of the report.
The basic chemistry of thermosetting polyester and acrylate oligomers is reviewed
with particular emphasis given to redox and photoinitiation processes. The physical
concepts of UV curing related to the interaction of light(transmission, absorption, and
scattering) within the coating film and photoinitiating molecules is discussed along
with the analytical methods to characterize the degree of cure of the
photopolymerizing system. Material and process design data are generated through
systematic experimentation. The material variables studied include the selection of
pigmentation, photoinitiator type and concentration, and resin / reactive diluents
chemistry. Process variables studied include coating thickness, lamp type and
placement (height, spacing, orientation), and throughput. A rigorous mathematical
model and associated software is developed and used to simulate the UV energy and
xxi

irradiance distribution for a 2D panel conveyor curing station. General considerations
are discussed to optimize the throughput of a production curing station while
maintaining a safe operation. The material and process data and the simulation
software are then tested and validated by constructing a pilot scale UV curing station
and producing large scale UV cured gel coated composite laminates.
xxii

1) The Composite Open Molding Process
a. Unsaturated Polyester Resin Based Composite Products
The leading trade organization for the U.S. Composites Industry, the American
Composites Manufacturers Association (ACMA), classifies unsaturated polyester resin
(UPR) based composite materials within markets Reinforced Market, and NonReinforced Market1. Products within the reinforced market contain some form of
continuous or short fiber reinforcement, normally E-glass. Reinforced composite
materials are used in processes such as sheet molding compound (SMC), resin transfer
molding (RTM), reaction injection molding (RIM), pultrusion, filament winding, vacuum
bagging, and open molding hand lay-up lamination. Non-reinforced products include
casting resins and gel coats. The total U.S. market for gel coat is approximately 100 MM
lbs/year. The market division and end-use application of UPR composites is summarized
in table 1.
Reinforced Market
Construction (664 MM lbs)
Non-Reinforced Market
Transportation / Body Putty (69 MM lbs)
Consumer and Recreational (73 MM lbs)
Construction (0.4 MM lbs)
Electrical / Electronic (61 MM lbs)
Consumer Goods (36 MM lbs)
Marine (314 MM lbs)
Gel Coats (102 MM lbs)
Transportation (160MM lbs)
Other (253 MM lbs)
Other (15MM lbs)

Total ( 1.29 B lbs)
MM=million
Total (0.55 B lbs)

B=billion
Table 1 U.S. Markets and Applications for Unsaturated Polyester Based Composites 1
1
L. Scott Crump May 2014

b. Application of the In-Mold Coating (Gel Coat)
A gel coat is a formulated in-mold coating typically based on unsaturated polyester
resin (UPR). The formulation building blocks of a gel coat consist of:
the polymeric binder ( unsaturated polyester oligomer)
fillers and pigments ( impart color and rheological modification)
additives (impart flow control, curing, storage stability, exterior durability, etc.)
solvent/reactive diluent ( typically styrene monomer)
Transfer to the Mold

The gel coat is spray or brush applied onto a high gloss (85) open mold to a film
thickness of 0.020 0.030 inches (20-30 mils). This film thickness is a 10-20 fold
increase over conventional painting applications such as automotive paints. The mold is
constructed of either fiber reinforced polyester (FRP) tooling materials, epoxy, or
polished metal. The mold surface is treated with a release agent to lower the mold surface
energy to 26-34 dyne/cm prior to coating application to aid in the separation of final
composite article from the mold 2. The gel coat application process is shown for a variety
of applications including marine market, construction market, and the sanitary market in
photographs 1- 8 below.
2

Photograph 1 Application of white gel coat to

a large hull mold
Photograph 2 - Application of white gel coat to a

large hull
Photograph 3 Application of barrier skin coat

laminate on the white gel coat
Photograph 4 Completed hull after being

removed from the mold
Gel coat application 55 foot luxury yacht
3

Photograph 5 Spray pattern test prior to

applying the gel coat on a deck mold
Photograph 6 Clear gel coat applied to

a mold used to make a synthetic marble
sink.
Photograph 7 Black gel coat applied to a

cowling mold for a small tractor
Photograph 8 Gel coat applied to a

tub/shower mold
The reduced surface energy mold represents a significant departure from substrates
encountered in the conventional painting process in which the applied coating is meant to
permanently adhere to the substrate. The surface energy of primed surfaces and surfaces
treated with chemical conversion treatments3 such as phosphates and chromates have
surface energies 50 dynes/cm. High surface energy substrates such as these are easily
wetted by the applied coating due to the high work of adhesion. Not surprisingly a
common problem with in-mold coatings is de-wetting of the low surface energy mold
4

(photograph 9-10). De-wetting is best addressed by modification of the gel coat surface
tension, film thickness, and rheology.
Photograph 9 - Severe de-wetting of a clear gel

coat
Mold surface energy= 20 dynes/cm
Coating surface tension= 41 dynes/cm
Initial film thickness = 20 mils
Photograph 10 De-wetting (crawling) of a

white gel coat
Mold surface energy= 22 dynes/cm
Coating surface tension= 33 dynes/cm
Initial film thickness = 16 mils
Rheology of Gel Coat

Conventional polyester based gel coats have rheological performance requirements that
differ substantially from those of solvent based paints . The gel coat is first pumped from
a container to a high pressure airless spray gun. Typical gel coat fluid delivery rates of 25 pounds per minute are 3-10 times those of solvent based paints. The fluid pressure at
the tip of the spray gun needed to achieve these delivery rates is approximately 1000 psi.
The gel coat should resist sagging at 30 mil film thickness. The rheological lifecycle of a
commercial gel coat and commercial automotive polyurethane paint have been simulated
using a controlled stress cone and plate rheometer (figure 1).
5

M=torque
=angle
r=radius
=rotational speed
=shear stress (Pa)
=shear rate (1/s)
=viscosity
(Pa-s)
shear stress=viscosity x shear rate

= x
Figure 1 Controlled stress cone and plate rheometer
The rheometers applied shear stress has been programmed to simulate pumping,
spraying and post-spray recovery of the viscosity. The programming sequence used to
control the rheometer is provided in table 2 below. The results of the experiment are
shown in figure 2.
Sequence #
Sequence 1
Sequence 2
Sequence 3
Sequence 4
Sequence 5
Function
equilibration
pumping
spraying
recovery (fast)
recovery (slow)
Maximum
Stress Duration
9 Pa
6000 sec
80 Pa
15 sec
324 Pa 15 sec
9 Pa
45 sec
9 Pa
750 sec
Maximum*
Collection
Interval
1 point/60 sec
1 point/30 sec
1 point/30 sec
2 points/sec
1 point/3 sec
# Points
Collected
10
4
4
99
250
Table 2 Cone and plate rheometer programming sequence to simulate the rheological
lifecycle of a commercial gel coat.
6

Rheological
Gel Coat
Solvent Based Paint
Performance
Requirement
No sedimentation of
similar requirement for both types of coatings
fillers and pigments

Ease of pumping from the
similar requirement for both types of coatings
container to a spray gun

Ease of atomization at the
Commonly used equipment:
Commonly used equipment:
spray gun
airless spray gun with a tip
air atomizing pressurized
opening of 0.020 and fluid
pot spray gun with a tip
pressure of 1000 psi. The
opening of 0.060 an a fluid
fluid lines are frequently
pressure of 60-100 psi.
heated to 100F to lower the

viscosity under high shear.
Sag resistant at the applied Typical application thickness: Typical application
film thickness
20-30 mils
thickness: 1-3 mils
Shear stress calculation
Shear stress calculation
gh
gh
10 lb/gal.=1200 kg/m3
10 lb/gal.=1200 kg/m3
g=9.8 m/s2
g=9.8 m/s2
h=30 mils=7.63 x 10 -4m
h=2 mils=5.08 x 10-5m
9.8 kg/m-sec2 = 9.8 Pa
9.8 kg/m-sec2 = 0.6 Pa
Excellent leveling is required for both coatings, but for

different reasons. Proper leveling of the paint improves the
Leveling
gloss and DOI. Proper leveling of the gel coat is required to

prevent a textured appearance on the mold side of the gel
coat due to uneven film thickness.
7

Table 3 Application flow requirements of gel coat and solvent based paint
Pump - Spray - Sag Simulation for Gel Coat and Polyurethane Paint
Gel Coat Viscosity
10,000.00
400
Polyurethane Paint Viscosity

Shear Stress
350
1,000.00
300
250
10.00
200
1.00
150
Shear Stress (Pa)
Viscosity (Pa-s)
100.00
0.10
100
0.01
50
0.00
0
30
60
90
120
150
180
210
0
240
Time (sec)
Figure 2 Experiment to simulate the shear history of a commercial polyester gel coat
and automotive polyurethane paint
In the first sequence of the rheological simulation the coating is placed in the gap
between the cone and plate and allowed to recover from any shear induced viscosity
changes resulting from loading the sample by maintaining a shear stress on the gel coat of
9 Pa for a period of ten minutes (0.54 Pa for the automotive coating). The shear stress is
raised to 80 Pa for 15 seconds and then to 324 Pa for 15 seconds to simulate pumping and
spraying during the second and third sequence respectively. The final two sequences are
the viscosity recovery sequences. The shear stress is lowered to a value which represents
the shear stress for a fluid of density and thickness h applied to a vertical surface as
calculated in table 3. The actual shear stress applied to the gel coat during viscosity
recovery was 9 Pa (0.54 Pa for the automotive coating). While both coatings shown in
8

figure 2 exhibit complex pseudoplastic and time-dependent behavior, the initial viscosity
recovery of the gel coat is more rapid than automotive polyurethane paint. The fully
recovered viscosity (plateau viscosity) of the gel coat is more than three hundred times
greater than the automotive paint. While rapid recovery and high plateau viscosity are
essential for the gel coat to resist sagging these conditions increase the likelihood of air
entrapment in the film if excessive fluid atomization is used during the spray process.
Trapped air bubbles which remain in the cured gel coat film are known as surface
porosity and subsurface porosity. Porosity is a very undesirable film defect due to the
reduction in exterior durability and blemished surface quality created by the voids in the
film.
Curing the gel coat film on the mold

Commercial gel coats are cured via addition of 1-3% of a free radical redox initiator
solutions such as methyl ethyl ketone peroxide (MEKP). MEKP is an organic peroxide, a
high explosive similar to acetone peroxide, and is dangerous to synthesize. Unlike
acetone peroxide however, MEKP is a colorless, oily liquid at room temperature. Dilute
solutions of MEKP, typically containing 9-11% active oxygen, are used in industry and
by hobbyists to initiate the polymerization of polyester resins. The initiator decomposes
in the presence of transition metals such as cobalt and tertiary amines such as
dimethylaniline which are added as a component of the gel coat or resin formulation.
These additives are commonly referred to as promoter packages.
9

methyl ethyl ketone peroxide monomer (MEKP)
As a conventional free radical polymerization, the kinetic mechanism of the styreneunsaturated polyester reaction can be expressed by initiation, propagation, and
termination. The subject of free-radical polymerization of polyester and acrylate
oligomers will be discussed in detail in chapter three.
ROOH + Co 2+
RO* + R*
+ OH- + Co 3+
ROOH + Co 3+
RO* + R*
+ H+
+ Co 2+
Redox decomposition of organic peroxide initiator in the presence of cobalt salts4.
The gel coat film cure time is the elapsed time from the addition of the initiator until
sufficient network structure develops to allow removal of an integral film from the mold.
Typical film cure times will depend upon temperature, initiator concentration, promoter
type and concentration and can vary from 10 minutes to 2 hours. Following the initial
film cure the gel coat continues to develop hardness as the reaction proceeds. The
copolymerization of styrene and fumarate polyester unsaturation is diffusion controlled
with typical room temperature conversion level of reactive double bonds5 being 80-90%.
Following the film cure of the gel coat the laminate may be applied.
10

c. Reinforced Laminate Application
Laminate Processes
Following the initial film cure of the gel coat a fiber reinforced laminate or cast laminate
is applied to the back side of the coating. The entire laminate may be applied and cured as
a single layer or the laminate may be built progressively, layer upon layer. The specific
laminate materials and construction sequence are known as the laminate schedule and
will depend on several factors including the choice of lamination process, the desired
surface smoothness, reinforcing glass content, part volume and mechanical property
design requirements such as specific strength, and stiffness which may require the
incorporation of coring materials within the laminate. A summary of laminate process
features and limitations is given in table 4.
Laminate Options for UV Curing

UV curing is a line-of-sight process. An essential requirement is the ability to directly
irradiate the gel coat or laminate being cured. The lamination processes listed in table 4
which satisfy this requirement are the open mold lay-up processes ( hand lay-up, chopped
spray-up laminate process-both manual and robotic), and the closed molding bagging
processes ( vacuum bagging, SCRIMP process, ). SCRIMP, the patented Seeman
Composite Resin Infusion Molding Process, is a variant of classical vacuum bagging6,7.
11

OPEN MOLDING LAMINATE PROCESSES

Part
Are gel coats
Volume
commonly
Glass Content
Low<1000
used with
Low36%
Process
High>10,000 this process?
High50%
Hand lay-up
Low
Yes
Low
Spray-Up
laminate
Low
Yes
Low
Process
Spray-Up
laminate
High
Yes
Low
Process automated
Casting
Medium
Yes
None
Filament
Medium
No
High
winding
Wet lay-up
compression
Medium
No
Medium
molding
Surface
Quality
(gloss,
smoothness)
High
Possible
use of
coring
materials?
Yes
High
Yes
High
Yes
High
No
Low
No
Low
No
CLOSED MOLDING LAMINATE PROCESSES

Are gel
coats
Surface
Part
commonly
Glass
Volume
used with
Content
Quality
Low<1000
this
Low36%
(gloss,
Process
High>10,000
process?
High50% smoothness)
Vacuum bag
/ infusion
Low
Yes
High
High
SCRIMP/ZIP
Pultrusion
High
No
High
Low
Compression
Varies with
molding
High
No
Low
use of LPA
SMC / BMC
Resin
transfer
Medium
Yes
Medium
High
molding
(RTM)
Reinforced
Reaction
injection
High
No
Low
Low
molding
(SRIM)
Table 4 - Summary of lamination process features and limitations
12
Possible use of
coring
materials?
Yes
No
No
Yes
No

Photograph 11 Hand lay-up process
Photograph 12 Hand lay-up process (2)
Photograph 13 Spray-up process using an

external mix chopper gun with continuous Eglass roving
13

Photograph 14 Vacuum infusion lamination of a small boat hull
Photograph 15 Hybrid process open mold

wet lay up followed by press molding to cure
electrical panels Wet lay-up compression
molding
Photograph 16 Open molding process

automated lamination of roofing panels
Photograph 17 Closed molding resin transfer
Photograph 18 Dry reinforcement charged in
14

molding (RTM) of toy locomotive
to RTM mold prior to mold closure
Photograph 19 Casting molding of synthetic

marble sink ( non-reinforced part)
Photograph 20 Demolding the cured sink bowl

(see photo. 6 for the clear gel coat application)
15

a. Lighting systems
Numerous lighting sources have been used to photocure polymeric materials
including sunlight, fluorescent lamps, carbon-arc lamps, xenon lamps, and mercury
vapor lamps1,2,7. Mercury vapor lamps are by far the most commonly used source of
UV light for industrial applications due to the selection of intensity, spectral power
distribution, and stability. Lamps based on the mercury vapor bulb will be the focus
of the remainder of this section.
UV lamp assemblies3-6 consist of a bulb, a reflector, a housing, a cooling source, and

a power supply. A conventional lamp assembly is shown in photographs 1-2. The
bottom view of the lamp provides a clear view of the bulb, reflector, and the shutter
which can be closed to block the light from exiting the lamp. The bulb surface
temperature during operation is approximately 800C and cooling is required8.
i. Bulb Design
UV bulbs consist of an evacuated glass tube containing a small quantity of mercury.
The mercury is heated to produce an emission spectrum containing ultraviolet light.
The bulb shown in photograph 3 is an electrode arc style bulb. This type of bulb has
two electrodes located at each end of the glass tube. An excitation voltage is applied
across the electrodes to produce UV light. A shortcoming of this style of bulb arises
from the glass-metal interface design which can degrade and overheat during lamp
operation resulting in variable light intensity and ultimately bulb failure. Bulb
16

degradation occurs due to oxidation of the electrodes and the metal wiring connectors
on the voltage lines resulting in poor conductivity which can lead to localized
overheating at the electrodes and bulb failure. The electrodeless bulb, shown in
photograph 4, consists of an evacuated glass tube containing a small quantity of
mercury. This type of bulb is heated using microwave energy by placing the bulb
inside a lamp housing fitted with a magnetron and radio frequency (RF) waveguide.
The RF energy is contained within the lamp housing by placing a thin metal mesh
sheet at the base of the lamp housing. A separate RF monitor is electrically
interlocked with the lamp power supply to prevent leakage of microwave energy.
reflector
shutter
arc style bulb
Photograph 1 Bottom view of UV lamp

housing with the shutter open and the bulb
exposed
Photograph 2 Top view of UV lamp

housing. The red hoses are used for
water cooling during operation
Photograph 3 Electrode arc style medium pressure mercury vapor bulb

( the bulb is energized by applying an electric current across the metal electrodes)
17

Photograph 4 Electrodeless style medium pressure mercury vapor bulb

( the bulb is energized with microwave heating)
Photograph 5 UV lamp with an electrode

style bulb and a dimpled reflector capable
of producing diffusely reflected light (ref.
5-6)
Photograph 6 Modular microwave UV

lamp Bottom view note the metal
mesh designed to prevent leakage of the
RF waves produced by the magnetron
heating source
RF Detector
Photograph 7 - Modular microwave UV

lamp Bottom view electrodeless style
bulb and elliptical reflector - note RF
leakage monitor interlocked to the power
Photograph 8 Modular microwave UV

lamp side view - note the 6 diameter
air cooling hose (air flows from top to
bottom through the lamp)
18

supply
ii. Reflector Design Light Ray Management
Several reflector designs may be used with the UV curing lamp. The reflector
partially circumscribes the UV bulb (270 o arc) collecting approximately 75% of the
light emitted by the bulb. The elliptical reflector design produces a reflected ray
pattern that is concentrated at a fixed distance from the base of the lamp housing
known as the focal plane. The curing process is said to be in focus when the
material being polymerized is positioned in or near the focal plane. Maximum photon
flux, or irradiance, occurs within the focal plane of the lamp. When using an elliptical
reflector, the process is out of focus when the target material is located at a distance
beyond the focal plane. The focal plane is generally located at a distance of 3-7 inches
from the bulb. The exact distance can be obtained from the lamp manufacturer or
empirically by taking radiametric measurements.
Ultraviolet Light Reflectors

Elliptical
Parabolic
Dimpled
Focal Plane
Figure 1 Reflector designs to focus (elliptical), collimate (paraboloic), and disperse

(dimpled) light energy
19

Reflector designs are also available to collimate the light (parabolic design) or
provide diffusely reflected light (dimpled design). Light ray management issues such
as the choice of reflector and distance from the lamp to the target will depend on the
specific factors such as the optical density (thickness, light absorption and scattering
characteristics) of the polymerizing material, curing speed requirements, and flash
point. Proper cleaning of the reflector is important to maintain the reflector efficiency.
Reflectors are usually cleaned at pre-set intervals with an alcohol solution to remove
any contamination. Consideration of equipment selection for the specific case of
curing gel coat and laminating resins will be covered in greater detail in Chapter VI.
In general, curing applications utilizing in-focus high intensity lighting are reserved
for cases involving materials with low optical density where high rates of cure are
possible. An example of this would be a graphic arts application of a UV curable ink
for a magazine advertisement. The film thickness of the ink is a fraction of a mil and
cure speeds of 300 feet per minute and greater are possible. As will be discussed in
greater detail in chapters IV and VI, gel coats and laminates are cured with nonfocused lighting to lower the light intensity for a variety of reasons such as substrate
temperature sensitivity, cure speed, safety, and the exposure time dependent
absorption characteristics of the gel coats and laminating resins.
iii. Temperature Management in UV Curing Applications

The optical efficiency of the lamp/reflector system is the ratio of light collected and
reflected versus the total light emitted in any spectral range. UV curing lamps
produce significant levels of infrared and visible radiation. As mentioned previously
20

the surface temperature of the fused quartz UV bulb is approximately 800o C during
operation. It is generally desirable to maximize the ratio of UV band / IR band
radiation to keep the substrate and polymerizing coating or resin temperature as low
as possible while performing the UV curing. The primary source of infrared energy is
the hot quartz bulb itself rather than the plasma inside the bulb. In addition to proper
airflow to remove heat from the target, the following two strategies may be employed
to effectively manage the temperature:
1) Dichroic coatings on the reflector8 Dichroic filters operate using the principle of
interference. Alternating layers of an optical coating are built up on the reflector,
selectively reinforcing certain wavelengths of light and interfering with other
wavelengths. By controlling the thickness and number of the layers, the frequency
(wavelength) of the passband of the filter can be tuned and made as wide or narrow as
desired. A reflector having good reflectance to UV and poor reflectance to IR can
reduce the IR irradiance at the surface while providing UV irradiance. Dichroic
reflectors are sometimes referred to as cold mirrors due to the property of
selectively absorbing IR waves and reflecting UV waves.
UV
Visible
IR
Dielectric Series
Absorbing Layer
Thermally Conductive Substrate
Figure 2 IR absorbing dichroic reflector
21

The thickness of a single layer of a dichroic coating and its refractive index will
determine the reflected and non-reflected (transmitted) wavelengths.
REFLECTED
4nt
;
' odd '
TRANSMITTED
4nt
' even'
Where t is the thickness of the film, n is its refractive index, odd and even are
integers. When the film thickness is a multiple of the quarter-wavelength in the film,
that wavelength will be reflected.
Industrial dichroic reflectors are produced by vacuum deposition coating of a large

number (fifty or more) of thin layers of hard, transparent dielectric materials on the
conventional polished stainless steel reflector. Each layer has a different refractive
index from its adjacent layer. The coatings are formed using various inorganic oxides
such as aluminum oxide and silicon dioxide. The coating thickness of each layer is
very precisely controlled to achieve the cumulative constructive interference over the
UV spectral range of interest. The initial coating has an absorbing (black) coating in
which visible and IR waves are converted into heat (figure 2). The stainless steel
reflector base is thermally conductive and the heat is easily removed by cooling it.
The ratio of UV energy (200-450 nm) to IR energy (700-2500 nm) from an
electrodeless mercury UV bulb is
EUV/EIR= 1.73 where the UV band is 200-450 nm and the IR band is 700-2500 nm.
The radiant energy from the bulb reaching the target, ETARGET, can be determined
from the energy balance below:
EREFLECTED
22
EDIRECT
ETARGET

ETARGET E REFLECTED E DIRECT

E REFLECTED
MAX
MIN
E .R .( )
2
where EREFLECTED is the energy reflected which reaches the target, and EDIRECT is the
energy traveling directly from the bulb to the target without being reflected. E is the
spectral irradiance from the bulb at wavelength , R is the reflectance from the
surface of the lamp reflector, is the angle subtended by the reflector, and is the
sector of the reflector that is obscured by the bulb itself. EREFLECTED represents the
energy that reaches the target after being reflected, and EDIRECT is the energy radiating
directly from the bulb to the target. The reflector of an electrodeless lamp wraps
about the bulb including an angle of approximately 270 o collecting approximately
75% of the light emitted from the bulb. A 90% IR absorbing dichroic reflector can
increase the EUV/EIR ratio by decreasing the reflected IR waves.
EUV
E IR
1.73
5.3
(
1
0
.
75
)
(
0
.
75
)(
1
0
.
9
)
dichroic
direct reflected
2) Bulb diameter Infrared energy is also focused via the reflector as well as being
directly radiated to the target. The primary source of infrared energy is the hot quartz
bulb envelope itself rather than from the plasma inside the bulb. The energy radiated
by the bulb is described by the Stefan-Boltzmann law:
E eAT 4
where e is the emissivity of the surface, A is the surface area of
the bulb, is the Stefan-Boltzmann constant, and T is the temperature of the bulb in
23

o
K. Electrodeless style UV bulbs utilized in the microwave lamps are reported8 to
emit less IR radiation than conventional arc type bulbs due to their smaller surface
area. A comparison of arc-style and electrodeless bulbs is given below. Both lamps
are made of fused quartz and they will have the same emissivity. The only term that
will differ is the bulb surface area.
The ratio of surface area of the bulbs is the same as the ratio of their outer diameter
(25mm and 11 mm respectively):
E IR ARC STYLE
E IR ELECTRODEL ESS
eAIR ARC STYLE T 4

eAIR ELECTRODEL ESS T
AIR ARC STYLE

4
AIR ELECTRODEL ESS
D IR ARC STYLE
D IR ELECTRODEL ESS
25 mm
2 .3
11 mm
Thus the smaller diameter bulb produces less heat. A recent patent application9
reports good temperature management using LED lamps to perform photocuring.
iv.
Metal halide doping to modify the spectral power distribution
Metal halide lamps are mercury vapor bulbs with the addition of metal halogens. The
metal halogens are added to create specific wavelength lines of ultraviolet radiation to
match the sensitivity of the photopolymer and photoinitiators being exposed. Metal
halogens are compounds composed of metal and halogen elements combined within a
curing bulb to form salts. Common metals added to the mercury bulb include galliumindium (known as gallium bulbs or V bulbs) and iron-cobalt (known as iron bulbs
or D bulbs). The electronegative halogens chemically react within the UV curing
bulb to cause a reaction in which the metals take on a positive charge. As the internal
24

temperature of the metal halide lamp increases to the vaporization point of the metals,
the positive ions being produced allow the metals to release their outer electrons
causing ultraviolet radiation output at specific wavelengths.
The relative spectral power distributions of the mercury, iron, and gallium bulbs are
shown in figure 3.
Spectral Output of UV Lamps
Relative Energy
Watts / Inch
Gallium Doped Lamp
Iron Doped Lamp
gy
Mercury Lamp
200
250
300
350
400
450
W avelength (nm)
Figure 3 Relative spectral power distribution of commonly used UV bulbs

(data obtained from Fusion UV Systems)
The mercury lamp provides the greatest output in the far UV (<300 nm). Most
polymers absorb light below 290 nm limiting the mercury bulb to surface cure
and thin film cure applications. Another shortcoming of the mercury lamp is the
25

generation of ozone arising from the peak around 250nm. The iron doped
mercury lamp provides significant energy in the 340-400 nm range. The gallium
doped mercury bulb provides significant energy in the 390 440 nm range. The
interaction of light within a thick film of photocuring material will be discussed in
greater detail in Chapter III. It is critical to match the spectral power distribution
of the light source with the transmission-absorption characteristics of the coating ,
and photoinitiator.
v. Lamp motion relative to the target

UV curing process typically offer several advantages over oxidative, thermal, and
peroxide cure coating systems such as cure speed, energy utilization, and the abilityt
formulate with non-polluting multifunctional acrylate monomers and oligomers. To
realize these benefits however it is usually necessary move the lamp over the coating
or move the coating under the lamp to perform the UV curing step. Conveyors and
industrial robots are used move the lamp relative to the surface of the coating
providing control of the cure speed and energy exposure that is not possible with
fixed lamps (see figures 9-12)
Lighting systems can be designed with linear, rotational, and complex programmed
motion paths to address a wide range of curing requirements.
Rotation
Linear
26 Linear with
Rotation
Complex Motion
Industrial Robot

Figure 4 UV curing lighting systems
UV curing is a line-of-sight curing process. The material to be cured must be

capable of being directly illuminated by the light source or possible to illuminate with
the use of reflectors.
Photograph 9 Bench scale UV conveyor

and 6 modular microwave lamp
Photograph 10 Pilot scale UV

conveyor fitted with two 10 modular
microwave lamps (built by the author)
Photograph 11 Industrial robotic curing
Photograph 12 Industrial robotic curing
b. Radiometers and radiametric characterization of a UV curing process

27

UV curing of coatings and composite laminates requires precise control of the process
variables related to energy exposure to insure safety and full development of
properties resulting from complete cure. Process radiometers are widely used in UV
curing applications to develop the process window, monitor and control levels of
energy exposure. Some of the basic terminology used for ultraviolet curing process
design and measurement is presented below. A more complete listing of terms may be
found in reference 10.
TERMINOLOGY
Absorbance An index of the light absorbed by a medium compared to the

light transmitted through it. Numerically, it is the logarithm of the ratio of
incident spectral irradiance to the transmitted spectral irradiance. It is a
unitless number. Absorbance implies monochromatic radiation, although it is
sometimes used as a average applied over a specific wavelength range.
Additive lamps Medium pressure mercury vapor lamps (arc or microwave)

that have had small amounts of metal halides added to the mercury within the
buld. These materials will emit their characteristic wavelengths in addition to
the mercury emissions. This term is preferred over the term doped lamps.
Cosine response Description of the spatial response to the incident energy

where the response is proportional to the cosine of the incident angle.
Dynamic exposure Exposure to varying irradiance, such as when a lamp

passes over a surface or a surface passes under a lamp or lamps. In the case of
dynamic exposures, energy is the time integral of the irradiance profile.
Effective energy density Radiant energy, within a specified wavelength

range, arriving at a surface per unit area, usually expressed in Joules per
square centimeter or millijoules per square centimeter (J/cm2 or mJ/cm2).
Alternate terms are exposure , or energy.
Irradiance Radiant power, within a specified wavelength range, arriving at a

surface per unit area. It is expressed in watts or milliwatts per square
centimeter (W/cm2, or mW/cm2).
28

Irradiance profile The irradiance pattern of the lamp; or, in the case of
dynamic exposure, the varying irradiance at a point on a surface that passes
through the field of illumination of a lamp or lamps.
Peak irradiance The intense peak of focused power directly under a lamp.
The maximum point of the irradiance profile.
Power The operating power of tubular UV lamps is commonly reported in

watts per inch or watts per centimeter. This is derived simply from the
electrical power input divided by the effective length of the bulb. (It does not
have a direct meaning to the output efficiency of the lamp, to the curing
performance, nor to the irradiance delivered to a work surface).
Radiometer A device that senses irradiance incident on its sensor element.

The construction consists of a photonic diode detector with an instantaneous
signal output that is proportional to the radiant flux over a wavelength range.
Static exposure Exposure to a constant irradiance for a controlled period of

time. Contrast with dynamic exposure.
UV Ultraviolet Radiant energy in the 100 nm to 450 nm range. Radiant

energy in the 100 nm to 200 nm is referred to as vacuum UV (VUV), because
it does not transmit in air
VUV, UVA, UVB, UVC, UVV UVA is commonly referred to as long

wavelength UV. UVC is commonly referred to as short wavelength UV. UVV
is very long wavelength UV.
VUV: 100 - 200 nm
UVC: 200 280 nm
UVB: 280 315 nm
UVA: 315 400 nm
UVV: 400 450 nm
The key optical and physical characteristics of the curing equipment are:
UV Irradiance the radiant power, within a stated wavelength range, arriving at the
surface per unit area. Irradiance varies with lamp output power, efficiency, and focus
of the reflector system. Irradiance is a characteristic of the lamp geometry and power
and does not vary with line speed.
29

UV Energy Density the radiant energy, within a stated wavelength range, arriving
at a surface per unit area. The energy, sometimes referred to as dose, is the total
accumulated photon quantity. Energy is inversely proportional to line speed under
any given light source, and proportional to the number of exposures (for example,
rows of lamps).
t1
E(
2 )
I (
2 )
dt
t0
Spectral Distribution is the radiant energy as a function of wavelength or

wavelength range. It may be expressed in power units or in relative terms
(normalized). The radiant energy from a bulb is presented by grouping the data in 10
nanometer bands in the form of a distribution plot.
Irradiance Profile is the irradiance as a function of distance from the centerline of

the lamp. This profile takes the form of a Gaussian distribution. The peak irradiance
value occurs at the centerline. The irradiance profile is characteristic of the lamp
design. Increasing the power to the lamp does not change the ratio of peak irradiance
to total energy (at any speed). The e profile of a lamp can change if the bulb sags out
of the focused position, or if the reflector has been deformed.
Infrared Radiance the heating effect from infrared energy emitted by the hot
quartz bulb.
30

The radiometer shown in photographs 13-14 is mounted on the side of the UV curing
lamp and measures the instantaneous irradiance (mW/cm2) from the lamp. The fixed
mounted (static) radiometer is used to monitor the output stability of the lamp. The
distance and angle of the radiometer with respect to the lamp must be held constant.
A second type of radiometer, the traveling (dynamic) process radiometer (see
photographs 15-16), is placed on the conveyor belt and used to measure the irradiance
(mW/cm2) arriving at the surface. This instrument also serves as a dosimeter, with the
capability of reporting the energy (mJ/cm2) which is the time integral of the
irradiance.
Photograph 13 Photodiode radiometer

with dry air purge line
Photograph 14 UV lamp housing with a

process radiometer mounted on the lamp
housing to monitor the lamp output
31

Photograph 15 Traveling process
radiometer top view sensor is visible
Photograph 16 Traveling process

radiometer bottom view controls and
readout are visible
Modern instruments measure multiple UV bands (UVC, UVB, UVA, UVV). The
responsivity of a radiometer is the amplitude of the response of a detector to different
wavelengths. Radiometers need to be calibrated periodically due to solarization of the
sensing element which can affect the responsivity of the radiometer. Other important
information that should be known to avoid errors include:
The dynamic range of the radiometer The range of the instrument must be
adequate for the irradiance to which it is exposed. If the light intensity exceeds
the radiometer limit the result will be an under reporting of irradiance
(W/cm2) and radiant energy (J/cm2).
The sampling rate of the radiometer / dosimeter the dosimeter calculates the
accumulated photon count by measuring the irradiance at specific sampling
intervals. The sampling rate should be adequate for the process being
measured. For example, assume the irradiance profile of a lamp was 3 inches
wide. A traveling radiometer with a sampling rate of 10 samples/second
moving at a line speed of 2.5 feet/minute would take a measurement every a
measurement every 1/12 of an inch (i.e. 36 measurements within the
irradiance profile). This would provide a reliable measure of the lamp energy.
On the other hand, if the line speed was 120 feet/minute, the radiometer would
collect one measurement for every four inches of travel. This condition would
produce a reporting serious error for the lamp irradiance and energy.
32

Additional information that should be known about the radiometer includes the
spatial response, the threshold response (minimum irradiance), and temperature
tolerance limits.
Lamp monitoring is a critical process control parameter for a UV cure process in a
production environment. In many cases, however, equipment design does not allow
conventional radiometers11-13 to be used so alternatives must be found. A common
method is to use radiachromic tags14 (a film or paper strip coated with a UV sensitive
dye that undergoes a photochemical color change upon exposure). The extent of the
color change can be correlated with the exposure conditions. Radiachromic tags
function as dosimeters and can be very useful under the right conditions and provide
extremely reliable process control information.
33

Chapter III Chemistry of Thermosetting Unsaturated Polyester and Acrylate
Systems
Systems
a. Synthesis of thermosetting polyester and acrylate oligomers
(condensation polymerization)2-7
Unsaturated Polyesters
The first reported synthesis of polyester resins was carried out by Julian Hill, a
member of Wallace Carothers team, at the Dupont Research Labs in 1933 1. The
unsaturated polyester resin solutions used in the production of gel coats and
laminating resins are low molecular weight condensation oligomers (Mn 1000
5000) which have been diluted in a reactive diluent such as styrene2 or methyl
methacrylate.
SATURATED
DIBASIC ACIDS
UNSATURATED
DIBASIC ACIDS
PHTHALIC ANHYDRIDE
ISOPHTHALIC ACID
ADIPIC ACID
TERPHTHALIC ACID
CHLORENDIC ANHYDRIDE
MALEIC ANHYDRIDE
FUMARIC ACID
GLYCOLS
HYDROCARBON
MODIFIERS
PROPYLENE GLYCOL
DIETHYLENE GLYCOL
ETHYLENE GLYCOL
DIPROPYLENE GLYCOL
NEOPENTYL GLYCOL
OTHER GLYCOLS
DICYCLOPENTADIENE
ESTERIFICATION
UNSATURATED
POLYESTER
CONDENSATE
REACTIVE MONOMERS
PROMOTORS,
INHIBITORS,
ETC.
STYRENE
METHYL METHACRYLATE
VINYL TOLUENE
PARA-METHYL STYRENE
ALPHA-METHYL STYRENE
FREE RADICAL
INITIATOR
CROSSLINKED
UNSATURATED
POLYESTER
34

Systems
Figure 1 Production of unsaturated polyester resin solutions

Reactants are chosen on the basis of the specific properties needed for the application.
Laminating resins based on phthalic anhydride / maleic anhydride/ propylene glycol
(PAn/MA/PG) are in frequent use due to the combination of low cost, good balance
of thermal mechanical properties (Tg, strength, elongation), and the ability to conduct
the condensation with glycol with a short cycle time in a single processing step. In
recent years the use of dicyclopentadiene (DCPD) has been incorporated into
laminating resins to lower volatile organic content (VOC) due to increasing
regulations (NESHAP national Emission Standards for Hazardous Air Pollutants).
The use of dicyclopentadiene allows resin producers to prepare resins with lower
solution viscosities and therefore higher solids content. The primary drawbacks of
DCPD based resins are 20-40% lower thermal-mechanical properties, high resin
color, and poor secondary bonding.
Gel coat resins based on isophthalic acid / maleic anhydride / neopentyl glycol
(IPA/MA/NPG) offer an excellent balance of thermal-mechanical properties needed
to preclude cracking, provide surface hardness, and prevent fiber printing. Neopentyl
glycol (2,2,dimethyl-1,3 propane diol) imparts excellent hydrolytic stability due to
steric hindrance of the ester group by the methyl groups and the absence of alphahydrogen atoms. Condensation reactions carried out with IPA/MA/NPG have the
disadvantage of greater production cycle times than PAn/MA/PG condensation
polymers. The former polymer requires a two step synthesis due to the unequal
35

Systems
reactivity of isophthalic acid and maleic anhydride with alcohol. Resins with high
levels of neopentyl glycol are commonly modified with a non-linear glycol or a
glycol with bulky side groups to improve the solubility in styrene. Common glycols
used for this purpose include 1,2 propane diol, and 2- butyl, 2- ethyl 1,3 propane diol.
Adipic acid may be used as a flexibilizing diacid in gel coat and laminating resins
when water resistance and Tg can be compromised.
Terephthalic acid (TPA), a configurational isomer of isophthalic acid (IPA), offers

slightly improved thermal resistance and favorable costs compared to isophthalic acid
in UPR resin applications. Unfortunately the reactivity of the carboxylic acid groups
on TPA is lower than those of IPA resulting in a 50% increase in cycle time (30 hours
vs. 20 hours). Polyester resins based on TPA can be prepared via alkoxylation by
reacting the terephthalic acid with ethylene oxide or propylene oxide when pressure
reaction vessels are available.
While liquid samples of UPR resins are easily analyzed, the chemical structure of
samples of cured polyester resins are not readily elucidated in solid form by
spectroscopic techniques (H-NMR, FTIR) or chromatography (GPC/HPLC) since the
cured polymer is not soluble in organic solvents. Certain features of the cured
network such as the fraction of maleic anhydride carbon-carbon double bonds
reacting into the network may be analyzed by C-NMR3. The most common method
to analyze cured polyester resins involves hydrolysis of the ester group followed by
condensation with monofunctional reactants such as acetic acid. The low molecular
36

Systems
weight (Mn<300) fragments can be easily quantified by several techniques (GC-MS,
NMR).
The average molecular weight and molecular weight distribution of the unsaturated
polyester greatly affect the properties of the cured styrene-crosslinked network2.
Below the critical molecular weight of entanglement the melt viscosity of the
polyester varies linearly with the molecular weight. Mechanical properties improve
sharply initially with increases in molecular weight. Above a certain molecular
weight, the mechanical properties become relatively insensitive to further increases in
molecular weight. During the synthesis of polyester resins, the diacids and glycols are
charged to the reaction kettle in a non-stoichiometric ratio of COOH:OH to preclude
the gel point. A common charge ratio is 1.05 moles of OH per 1.0 moles of COOH.
The presence of excessive acid or alcohol end groups are known to have a detrimental
effects on the properties of the cured network. The presence of a low molecular
weight tail in the distribution may adversely affect the water resistance and
mechanical properties. The number of end groups may be reduced by charging
monofunctional acids and alcohols to the latter stages of the cook, effectively capping
the polymer chain ends.
In addition to the considerations above, the physiochemical characteristics of the

cured polyester resin depend on the choice of crosslinking monomer, concentration
of maleic anhydride in the UPR, and the ratio of the polyester carbon-carbon double
bonds to monomer carbon-carbon double bonds. A generalized coding approach to
37

Systems
specify the prepolymer composition is :SA:UA:G:M , where SA= moles of saturated
acid, UA=moles of unsaturated diacid, G=moles of glycol, M=moles of crosslinking
monomer C=C. Specific resin compositions used by gel coat and resin suppliers are
confidential and are not disclosed in this paper. Typical resin formulations are
available in the patent and trade literature listed in the references. A commercially
useful gel coat may have the following molar ratio of reactants SA:UA:G:M = 1.0 :
1.0 : 2.1 : 2.0. High temperature molding resins useful for sheet molding compounds
(SMC) may have the approximate molar ratio SA:UA:G:M 0 : 1 : 1: 1.5. Higher
levels of saturated diacid to unsaturated diacid, SA:UA, will result in a lower glass
transition temperature due to a reduction in crosslink density4. The specific ratio of
monomer to unsaturated diacid, M:UA, depends on the reactivity ratios of the
monomers. As shown in figure 2, the disappearance of C=C double bonds was
studied by transmission FTIR for an unsaturated polyester prepolymer diluted with
styrene monomer. A second sample was prepared in which the prepolymer was
diluted a methacrylate monomer, 1,6 hexanediol diacrylate. Peaks centered at 911
cm-1 (styrene C=C), 815cm-1 (methacrylate C=C), and 982 cm-1 (UP C=C) were
used to follow the reaction. The sample was cured at room temperature using a cobalt
octoate promoter and methyl ethyl ketone peroxide initiator.
38

Systems
Reactivity - UPR / monomer C=C by FTIR
100
Fumarate C=C (UPR-Styrene)

STYRENE C=C (UPR-Styrene)
Fumarate C=C (UPR-Acrylate)
Acrylate C=C (UPR-Acrylate)
Double Bond Conversion
90
80
70
60
50
40
30
20
10
0
0
20
40
60
80
100
120
140
Time Since Initiation (minutes)
Figure 2 Polymerization of UPR prepolymer and crosslinking monomer
As predicted from published reactivity ratios the fumarate-ester copolymerizes more

readily with styrene monomer than with methacrylate monomer. The conversion of
double bonds during the formation of the crosslinked network is diffusion controlled
and based on monomer mobility. Using FTIR it is possible to determine the amount
of unreacted double bonds which remain trapped in the polymer due to vitrification of
the system. It has been shown experimentally for styrene monomer:maleate-ester
combinations, where copolymerization is favored over homopolymerization, the
maximum fraction of the maleic anhydride carbon-carbon double bonds in the
polyester is reacted into the network3,5 when M/UA>2. Rapid copolymerization of
styrene with unsaturation present in the prepolymer occurs3 when the maleic acid (cis
isomer) is isomerized to fumaric acid (trans isomer).
39

Systems
HO
HO
O
OH
C
C
C
C
C
C
fumaric acid (trans isomer)
maleic acid (cis isomer)
OH
In practice, the cis-trans isomerization is accomplished by the sequence of addition of

reactants to the reaction vessel as well as proper temperature control during heat-up.
With good synthesis processing controls in place it is possible to achieve >90%
isomerization to the trans isomer. High levels of isomerization are particularly
important for prepolymers used in exterior gel coat formulations where unreacted
double bonds may lower exterior durability. In addition to the degree of
isomerization, it is important to allow for reductions in prepolymer reactivity
associated the double bond saturation reaction, also known as the Ordelt reaction,
which occurs when an alcohol adds directly to the fumarate-ester carbon-carbon
double bond6,7.
HO
HO
O
C
C
C
C
OH
fumaric acid (trans isomer)
CH3
C
C
O
CH2
OH
CH3
CH2
OH
OH
propylene glycol
40
H
C
H
O
Ordelt Reaction - double bond saturation

Systems
Vinyl Ester Resins

A second major class of thermosetting polymers used to produce recreational
composite products is based the acrylation of bisphenol A epoxides, or vinyl ester
resins
(VE). The prepolymer is diluted with styrene monomer to produce the VE resin.
CH3
CH2 CH CH2 O
CH2 CH
CH2
HO
CH3
CH3
CH2
methacrylic acid
bisphenol A epoxy
O
H2C
C
CH3
CH3
CH2 CH CH2 O
OH
O
O
CH2 CH
CH3
CH2 O
OH
CH2
CH3
epoxy diacrylate (vinyl ester resin)
Cured vinyl ester resins exhibit corrosion resistance and thermal-mechanical

properties that are superior to UPR resins. Tensile strength, elongation and Tg values
are 20-50% higher with vinyl ester resins than with UPR resins. Due to the presence
of the bisphenol moiety, the exterior durability of vinyl ester resins is extremely poor
and should not be used for exterior coating applications requiring color or gloss
stability.
41

Systems
b. Network formation of thermosetting polyester and acrylate oligomers
(free-radical polymerization)
i. Microgel formation and macrogelation
For a free radical crosslinking copolymerization of a monovinyl-divinyl system,
cyclization or intramolecular reaction has been reported8. The cyclization was thought
to be a major reason to explain that many experimental gellation results deviated
greatly from the theoretical prediction by classical Flory-Stockmayer theory. It has
been proposed that in the early stages of the reaction, the occurrence of cyclization
leads to the formation of internally crosslinked and rigid structures in the primary
polymer chain called microgels. Many of the vinyl or vinylene groups are buried
within the core of the microgels and show a reduced or completely suppressed
reactivity. Unsaturated polyester resins contain between 2-15 vinylene groups per
polyester molecule depending on the molecular weight and the level of unsaturation.
Low molecular weight DCPD modified polyesters will possess a low number
vinylene groups per molecule. High molecular weight propylene glycol-maleate
polyesters contain a large number of vinylene groups per polyester molecule. The
cyclization effect and the microgel formation is more important for the UPR-styrene
resins than the monovinyl-divinyl system8. Coagulated polyester nodules have been
found in the pre-gel phase of curing UPR resins44. The microgel particles are
composed of densely crosslinked domains46.
42

Systems
Growth of Free Radicals
Microgel Particles
I*
(a)
(b)
Figure 3 Formation of a UPR-styrene microgel

(a) Growth of the free radical - I*: free radical initiator, *:growing free radical,
______
: UPR molecule, ------: styrene chain (b) Schematic drawing of the
microgel
particle
The mechanism of network formation in UPR-styrene systems is reported to occur in
four stages8. During the first stage, the induction stage, the initiators produce free
radicals which trigger the polymerization. At the beginning of the reaction, all the
free radicals formed from the initiators are immediately consumed by the inhibitorretarder additives9,10 in the resin solution. Additives commonly used in include
hydroquinone derivatives and tertiary butyl catechol. At this point, no polymerization
has occurred due to the inhibition effect and the viscosity is relatively constant. The
second stage, microgel formation, follows the induction stage. During the microgel
formation stage the initiator continues to produce free radicals which can react with
styrene and UPR vinylene unsaturations to form polymer chains through
43

Systems
intermolecular and intramolecular reactions. The intramolecular reaction produces
crosslinked coils, i.e. microgels. Given the high degree of crosslinking, free radicals
on the polymer chain which are buried in the interior of the microgel particle are
occluded. This implies that termination among polymeric radicals may not be
important and may be neglected. As shown in figure 4, the crosslinks between
individual microgel particles may also be neglected because of the low concentration
of microgels. Accordingly, the viscosity changes very little during stage II, the
microgel formation stage.
Macrogelation
VISCOSITY,
(or 0)
Transition
Microgel
Formation
Induction
TIME, t
(or t/tgel = R*/Rc)
II
III
IV
Figure 4 Microgel formation and macrogelation in UPR-styrene system
44

Systems
The pendent carbon-carbon double bonds on the unsaturated polyester molecule are
either buried within the microgel particle where they may increase the article
crosslink density, or on the surface of the particle where they may react with
surrounding comonomers and other microgel particles. The third stage, the transition
stage, is characterized by the simultaneous formation of new microgel particles and
the formation of inter-microgel crosslinks. The inter-particle covalent bonding
produces a viscosity rise that is much more pronounced than in the previous stages.
During the final stage, the macrogelation stage, the concentration of microgel
particles is high and the inter-particle microgel crosslinking reaction is favored over
the formation of new particles. The viscosity rises very rapidly during the
macrogelation stage until the gel point.
ii. Kinetics of redox initiated polymerization of UPR-styrene8,43-47
The decomposition of peroxides such as methyl ethyl ketone peroxide in the presence
of a metal salt such as cobalt octoate produces the primary free radicals for the
initiation step. The peroxide may also decompose at higher temperature resulting
from the laminate exotherm.\
(1) Decomposition of Peroxides
(i) Thermal decomposition
k
1 RO OH
ROOH ( I )
(2R)
(1)
(ii) Redox decomposition
k
2 RO ( R) OH Co3
ROOH ( I ) Co2
k
3
2 ROO ( R) H Co2
ROOH ( I ) Co
(I) =peroxides
(R ) =primary free radicals
k1, k2 rate constants of thermal and redox decomposition
45
(2)
(3)

Systems
(2) Inhibition
R Z
P
(4)
(3) Initiation
R S
S
R E
E
(5)
(4)Propagation
then eqns. (5) and (6) become
S S
S
(6)
S E
E
k
E S
S
p
R M
R
(7)
E E
E
where
S stands for styrene monomer
E stands for polyester vinylene groups
where R = all free radicals (i.e. primary, plus S , plus E
and M = all reactive groups (i.e. S and E)
(5) Termination
As previously discussed the termination step among polymeric radicals may
be neglected because of the formation of highly crosslinked microgels
RATE EQUATIONS
Combining eqns. 1,2,3, and 7, we obtain the rate equations for the peroxide
decomposition and the radical formation in eqns. 8 and 9.
d[ I ]
[ I ](k1 k2 [ I a ]) [ I ](k10 k20 [ I a ])e Ea / RT
dt
(8)
d [ R]
f [ I ](2k1 k 2 [ I a ]) f [ I ](2k10 k 20 [ I a ])e Ea / RT
dt
(9)
where the activation energies (Ea) of the two decomposition rate constants are
assumed to be the same
Integrating eqns. (8) and (9) at isothermal conditions one obtains the concentrations
of peroxides and free radicals at time t,
recalling
dv
ln v and ln(a / b) ln(a) ln(b)
v
[ I ] [ I o ] e ( k1 k2 [ I a ])t
(10)
46

Systems
Combine eqn. (9) and (10) and integrate
[ R] f [
2k1 k 2 [ I a ]
] [ I o ][1 e ( k1 k2 [ I a ])t ) ]
k1 k 2 [ I a ]
(11)
Where [Io] is the initial concentration of peroxide, [Ia] is the concentration of

accelerator (cobalt), and f is the initiator efficiency
Rearranging eqn(11)
f [ I ](2k1 k2 [ I a ]) [ R](k1 k2 [ I a ])
(k1 k2 [ I a ])t ln o
f [ I o ](2k1 k2 [ I a ])
(12)
[ R](k1 k 2 [ I a ])
ln 1
f [ I o ](2k1 k 2 [ I a ])
If
[ R] f [ Io] , recalling -ln(1-x/y) ~ x/y as x/y 0
then
(k1 k 2 [ I a ])t
[ R](k1 k2 [ I a ])
f [ I o ](2k1 k 2 [ I a ])
Solving for t
[ R] / f
[ R] f
exp[Ea / RT ]
[ I o ](2k1 k2 [ I a ]) [ I o ](2k10 k2o [ I a ])
At the gel point, t= tgel
(13)
[ R] Rc RI RII RIII RI IV
Where Rc = sum of radicals generated during phases I-IV

Thus
t gel
Rc / f
Rc / f
e Ea / RT
0
o
[I o ](2k1 k2 [I a ]) [I o ](2k1 k2 [I a ])
47
(14)

Systems
By ratio of eqn 13 and 14
t
t gel
[ R]
Rc
(15)
which implies that the pre-gel region may be simply expressed as a function of
[R ]/Rc , independent of polymerization conditions such as T, [Ia], [Io]
The following data set will be used to demonstrate the practical application of eqn.
14 to predict the gel point time by modeling the influence of:
(a) curing temperature
(b) initiator concentration
(c) accelerator concentration
Sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
% Cobalt Temp (C) Temp (K)

0.10
30
303.15
0.10
40
313.15
0.10
50
323.15
0.10
60
333.15
0.10
70
343.15
0.10
30
303.15
0.10
30
303.15
0.10
30
303.15
0.10
30
303.15
0.10
30
303.15
0.02
30
303.15
0.05
30
303.15
0.10
30
303.15
0.15
30
303.15
0.20
30
303.15
% MEKP
0.40
0.40
0.40
0.40
4.00
0.20
0.40
0.60
0.80
1.00
0.40
0.40
0.40
0.40
0.40
Gel Time
(minutes)
26
16
4
2.5
1.5
184
27
17
10
7
55
38
29
17
13
Table 1 Gel Point Time data set used to validate the redox cure kinetic model
Eqn. 14 can be rearranged to study
(a) curing temperature
48

Systems
Ea
Rc / f
1
A1 B1 eqn. 16
ln(t gel ) ln
0
o
T
[ I o ](2k1 k 2 [ I a ]) RT
ln [ gel time (minutes) ]
Effect of Curing Temperature on the Gel Point Time

(0.1% cobalt octoate, 0.4% MEKP)
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
R2 = 0.97
0.0029
0.003
0.0031
0.0032
0.0033
0.0034
-1
(1/T) K
Figure 5 Effect of curing temperature on the gel point time redox initiator system
UPR-styrene monomer
(b) initiator concentration (MEKP)
f (2k10 k 2o [ I a ])
[ I o ] B2 [ I o ]
Rc exp[Ea / RT ]
1
t gel
eqn. 17
[ Gel Time (minute) ]-1
Effect of Initiator Concentration on the Gel Point Time

(0.1% cobalt octoate, 303K)
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
R2 = 0.99
0.2
0.4
0.6
0.8
1.2
% Initiator
Figure 6 Effect of initiator concentration on the gel point time redox initiator
system UPR-styrene monomer
49

Systems
(c) accelerator concentration (cobalt salt)
1
t gel
2 f k10 [ I o ] f k 20 [ I o ]
[ I a ] A3 B3 [ I a ]
Rc e Ea / RT Rc e Ea / RT
eqn. 18
[ Gel Time (minutes) ]
-1
Effect of Accelerator Concentration on the Gel Point Time

( T=303 K, MEKP=0.4%)
0.10
R2 = 0.96
0.08
0.06
0.04
0.02
0.00
0
0.05
0.1
0.15
0.2
0.25
% Cobalt Accelerator
Figure 7 Effect of cobalt accelerator on the gel point time redox initiator system
UPR-styrene monomer
iii. Kinetics of light induced polymerization involving
multifunctional monomers
For the chemist accustomed to working with conventional MEKP cured gel coats and
UPR resins which have cure times of 0.75 1.5 hours at room temperature, the most
surprising features in UV curing is that the polymerization can develop so extensively
in less that 1-2 minutes of UV light exposure. At first glance it would appear that the
only between UV curing and thermal or redox curing is the initiation step.
Re
R
Structure capable
of producing
radicals
do
t io
it ia
x In
n M
M
+,
EK
R*
Thermal Initiation H
Ph
o to
in it
ia t
io n
Free Radica l
R*
50
R*

Systems
We now consider the kinetics of UV curing below.

Initiation:
h
PI
R
Propagation:
p
R M
RM or P
Termination:
kt
Pn Pn
products
Ri I ai I 0 (1 10 A )i I 0 (1 10 b[ PI ] )i
R p k p [ R ][ M ]
(1)
(2)
Rt k t [ P]2 Ri
(3)
combining (1)-(3)
Rp
kp
kt
0.5
( I ai ) 0.5 [ M ]
kp
kt
0.5
( I 0 (1 10 b[ PI ] )i ) 0.5 [ M ]
With conventional addition polymerization of a monofunctional monomer such as

styrene, where termination occurs by bimolecular interaction of radicals to form a
dead polymer, a large in crease in the rate of initiation will result in a decrease in the
polymerization efficiency since the formation of radicals in large concentration will
favor termination over propagation. It is expected that the kinetic chain length and the
quantum yield for polymerization, p, will decrease with increasing light irradiance
levels. While this conclusion is reported54 to be valid for monofunctional monomers,
it no longer holds for multifunctional monomers where a close to first order
relationship between Rp and irradiance level is observed. The explanation for this
effect is the progressive occlusion of polymer radicals in the network under
formation. As soon as one of the pendant double bonds starts to polymerize, the
radical becomes attached to the network and loses its mobility. The radical will
51

Systems
continue to grow as long as monomer molecules can pass close by, but it has little
chance to encounter another crosslinked radical to undergo bimolecular termination.
c.
Formulation of conventional gel coat and resins
Specific commercial gel coat and laminating resin formulations are the property of
material suppliers and will not be disclosed. Disclosures limited to those readily
available in public documents (patents, articles, conference proceedings, etc.) provide
sufficient information for the purpose of this report.
\
d.
The Case for UV Curable Composite Materials
UV curable composite resins and coatings offer the potential for environmental waste
reductions, productivity gains through decreased cycle time and controlled operating
conditions, as well as gains in exterior durability11,15-19. Low temperature UV curable
powder coating provide manufacturers with greatly reduced cycle times and cure
energy demands.12 Low VOC liquid UV curable coatings for plastic substrates
produce less air pollution requirement, outstanding mar resistance, better space
utilization due to rapid cure rates(less curing space required), and less curing energy
when compared to conventional thermally cured coatings13. UV curable pultruded
laminates offer lower air pollution (low VOC), elimination of dimensional change
associated with elevated temperature processing, increased resin storage stability, and
52

Systems
lower energy costs14. Additional benefits of UV curable materials include the
elimination of metering and mixing plural component systems, and the re-use of resin
waste.
e. Formulation of UV curable gel coat and UP resins
.
i. Historical work in the area of UV curable composites20,21,52
Initial work conducted in the mid-1960s discussed the UV and electron beam (EB)
curing of UPR prepolymers diluted in styrene monomer. Deninger reports curing
UPR resins with low pressure mercury vapor fluorescent lamps using a diphenyl
disulphide photoinitiators. Cure was achieved with three minutes of exposure52. Fuhr
reports curing thin unpigmented unsaturated polyester ( phthalic anhydride, propylene
glycol, maleic anhydride) castings under fluorescent lighting using a bezoin ether
photoinitiator. The exposure time was 10-15 minutes.
The spatial and temporal control afforded by photopolymerization make it attractive

for rapid and inexpensive processing of polymeric composites. However,
photopolymerization of thick and fiber-filler polymers is more challenging than
curing of thin-film systems due to the exponential reduction in light intensity through
the sample resulting from absorption and scattering. Therefore, proper selection of
the initiator formulation and illumination wavelength are imperative to ensure that the
samples cure throughout. With the advent of high irradiance (600 W/inch) lamps and
specialized photoinitiators it is now possible to cure gel coats and laminates in a
continuous manner at several feet per minute.
53

Systems
ii. Classification of photoinitiators photolysis mechanisms 11, 22-24

The various photoinitiators in use today can be classified into three major catregories,
depending on the mechanism involved in their photolysis.
Radical formation by photocleavage This class includes aromatic carbonyl
compounds that undergo Norrish type 1 fragmentation when exposed to UV light
O
OCH3
OCH3
Dimethoxybenzil ketal
OCH3
+
C
OCH3
Free Radicals
The benzoyl radical was shown to be the major initiating species while the other
fragments contribute to a lesser extent.
Radical generation by hydrogen abstraction Aromatic ketones like benzophenone or
thioxanthone when promoted to their excited statesby UV radiation do not undergo
fragmentation, but rather a hydrogen abstraction from a proton donor molecule to
generate a ketyl radical and the donor radical. The initiation of polymerization usually
occurs through the donor radical with the ketyl radical disappearing by bimolecular
coupling. Tertiary amines are commonly used as hydrogen donors.
54

Systems
O
R-H
OH
C
*
R*
Cationic Photoinitiators diaryliodonium salts (Ar2I+X-) generate strong Bronsted

acids in the presence of a hydrogen donor which are efficient initiators for the
polymerization of epoxy monomers.
Table 2 below lists some of the common commercially available photoinitiators

which will be referred to in chapter V.
55

Systems
Type
Common
Name
Chemical Name
Hydroxy
Ketone
Hydroxy
Ketone
Dimethyl
Ketal
Irgacure
184
1-Hydroxycyclohexyl
phenyl ketone
Irgacure
2959
2- Hydroxy-1-[4-(2hydroxyethoxy)phenyl]2-methyl -1-propanone
, -dimethoxy- phenylacetophenone
Irgacure
651
Structure
O
OH
O
HO
CH3
OH
CH3
CH3
O
O
H3C
-Amino
Ketone
Irgacure
907
-Amino
Ketone
Irgacure
369
BAPO
Irgacure
819
MAPO
BAPO /
Hydroxy
Ketone
2- Methyl-1-[4(methylthio)phenyl]- 4morpholinyl) -1propanone

2benzyl-2(dimethylamino)-1-[4(4-morpholinyl)
phenyl]-1-butanone
Phenylbis(2,4,6trimethylbenzoyl)phosphine oxide
Lucrin
TPO
Diphenyl(2,4,6trimethylbenzoyl)phoshpine oxide
Irgacure
1800
25% CGI 403 bis(2,6Dimethoxybenzoyl)(2,4

, 4-trimethylpentyl)
phosphine oxide / 75%
Irgacure 184
CH3
CH3
S
H3C
CH3
CH3
CH3
25%
CH3
75%
O
H3C
BAPO /
Hydroxy
Ketone
Irgacure
1850
50% CGI 403 bis(2,6Dimethoxybenzoyl)(2,4

, 4-trimethylpentyl)
phosphine oxide / 50%
Irgacure 184
50%
+
50%
CH3
O
O
H3C
Table 2 Commercially available photoinitiators

56

Systems
iii. Physical Concepts of UV Curing interaction of light

with the coating - curing thick UPR films containing titanium
dioxide pigment
The effective generation of free radicals in a thick film such as a gel coat or
unsaturated polyester laminate requires (1) a light source with sufficient irradiance in
a wavelength band(s) consistent with the absorption characteristics of the
photoinitiator and the transmission characteristics of the remaining components of the
coating, (2) adequate transmission/scattering of the irradiance through the thickness
direction of the film, (3) absorption of photons by the initiating molecule, and (4)
conversion of absorbed energy to radical generation by the photoinitiator. A review of
the physics of the interaction of light with matter provides the following general
Wavelength
I() x
IRRADIANCE
# radicals/sec =
# photons
second
Wavelength
T()
x
TRANSMISSION
()
QUANTUM YIELD
# photons transmitted
through the coating film
# photons absorbed
by the photoinitiator
# radicals formed
# photons
through the coating
# photons absorbed
Figure 8 Light induced free radical formation in a coating film
57
Wavelength
Wavelength
A()
ABSORPTION
Quantum Yield
Absorbance
Transmission
Light Energy
sequence leading to the formation of free radicals from a photoinitiator:

Systems
The quantum yield of a radiation-induced process is the number of times that a
defined event such as a chemical reaction step occurs per photon absorbed by the
system. Thus, the quantum yield, is a measure of the efficiency with which
absorbed light produces some effect. For the successful initiation of the chemical
curing reaction there must be some overlap of the susceptibility of the photoinitiator,
A() x (), and the transmission of energy to the photoinitiator molecule E() x
T() from the light source. Medium pressure mercury lamps (H- bulb) have a spectral
power distribution that is not well suited for thick UPR systems (see figure 3 in
chapter II). The majority of the energy for the H- bulb is below 300 nm and is
therefore absorbed in the surface layers of the film. The UV transmission spectrum
for a large number of UV curable monomers and oligomers is presented in figure 9
below. The majority of these substances are aliphatic in nature and allow complete
light transmission above 350 nm. The styrene monomer (thick red curve) also shown
little absorption above 350 nm. The transmission characteristics of the UPR
prepolymer as well as clear films of UPR prepolymer crosslinked with styrene show a
marked increase in absorption of light between 350-380 nm. This is thought to be due
to conjugation of the carbonyl groups and the aromatic ring present in the diacid
(isophthalic acid) used to prepare the UPR prepolymer. Likewise, the
scattering/absorption characteristics of rutile titanium dioxide do not favor the use of
short wavelength H-bulbs (see figure 10). The excellent visual opacity of films
containing titanium dioxide is due to the ability of the pigment to scatter light in the
visible portion of the electromagnetic spectrum (400- 700 nm). The UV absorption of
58

Systems
titanium dioxide below 370 nm is high. The spectral band of 370 420 nm is window
available to thick cure coatings containing titanium dioxide50,53,54. Metal halide
bulbs are used in many types of applications whose photochemistry requires different
UV wavelengths to initiate the photopolymerization process due to light transmission
barriers associated with mercury bulbs. The gallium doped medium pressure mercury
vapor lamp is a much better choice for UV cure of thick white coating films since the
spectral power distribution of the lamp overlaps the transmission window of the
coating.
1 0 mi l s Cl ear Gel Coat
UV Spectrophotomer Scan Data
30 mi l s Cl ear Gel Coat

Styr ene
MMA
BYK-306
Hel oxy 505
120
EPON 828
SR 230
SR 231
SR 238
100
SR 306
SR 351
SR 502
80
SR 506
%T
Cyr acur e UVR-621 8
60
10 mil film clear gel coat

30 mil film clear gel coat
40
Cyr acur e UVR-61 1 0

Acetoni tr i l e
Ebecr yl 270
Ebecr yl 230
Ebecr yl 3700
Styrene monomer (thick red line)
CN963E80
Ebecr yl 4830
20
5-7 mil UPR prepolymer (uncrosslinked resin

solids) (thin black line)
Ebecr yl 8402
Ebecr yl 8804
Uvacur e 1 500
K-1 26
K-1 26
Resiprepolymer
n Sol i ds B1 91 -1 1 2
UPR
220 245 270 295 320 345 370 395 420 445 470 495 520 545 570 595 620 645 670 695
Ebecr yl 8804
Epi -Cur e 3270
Wave Lengths
Epi -Cur e 9552

Uvacur e 1 500
Ebecr yl 270
M P 30-36
M P 1 0-52
Figure 9 UV Transmission characteristics of monomers, oligomers, and films

commonly used for UV cure applications (pathlength=10 mm UV cell, 100%
concentration)
59

Systems
Reflectance and Absorbance of Rutile Titanium Dioxide

100
% Absorbance , % Reflectance
90
80
70
60
50
40
30
20
Absorbance
Reflectance
10
0
300
350
400
450
500
550
600
650
700
Wavelength (nanometers)
Figure 10 Absorption-scattering characteristics of titanium dioxide pigment
iv. Photobleaching and high radical yield-impact of

acylphosphine oxide photoinitiators
If we imagine an ideal clear, non-pigmented film (i.e. no scattering centers) of unit
thickness, the irradiance at the top surface of the film, I0, from an overhead lamp will
be attenuated through absorption Ia or transmitted It
I0
I0 Ia It
Ia
It
60

Systems
According to the Beer-Lambert law , the transmission, T, is related to the absorbance
T I t / I 0 10 Abs 10 bc , the fraction of light absorbed, fa is
f a 1 T 1 10 Abs , and
I a I 0 (1 10 A ) .
Using a numerical simulation in which the film is divided into 100 layers we can
repeatedly apply the calculation below to each layer to estimate the relative light
intensity within each layer as a function of the absorption characteristics of the film.
I a I 0 (1 10 A /100 ) .
The results of the simulation point out that while the concentration of photoinitiator
may be uniform, the distribution of UV intensity is not uniform. For strongly
absorbing systems the light reaching the bottom of the film is negligible.
Simulation of Light Intensity Transmitted through a Film
Relative Light Intensity
1.2
1
Abs=0.1
0.8
0.6
0.4
Abs=0.5
Abs=1.0
Abs=2.0
0.2
0
0
0.2
0.4
0.6
0.8
1.2
1.4
Fractional Film Depth
Figure 11 Effect of the absorptivity on light transmission characteristics in a film
61

Systems
For most photoinduced free radical polymerizations, the uniformity of double bond
conversion as a function of coating thickness and the overall degree of conversion are
crucial to achieve the performance characteristics of the coating. Further simulation
results to determine the fraction of energy absorbed within the top 1% and bottom 1%
of the coating film are presented in table 2 and figure 12 below. The results obtained
agree with literature results48. The maximum fraction of light absorbed in the bottom
layer occurs when the absorbance is between 0.4-0.5. Even under this best case, the
energy absorbed in the top layer of the film is 2.5 to 3 times greater than the energy
absorbed in the bottom. The film has been defined to be optically dense when the
ratio of
A
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Fraction
Fraction
Absorbed- Absorbedtop 1% bottom 1%
0.230
0.183
0.459
0.291
0.688
0.347
0.917
0.368
1.145
0.366
1.372
0.349
1.599
0.324
1.825
0.295
2.051
0.264
2.276
0.233
Ratio
Top:Bottom
1.3
1.6
2.0
2.5
3.1
3.9
4.9
6.2
7.8
9.8
Table 3 Energy absorbed in the top 1% and bottom 1% of a coating film
62

Systems
% Energy Absorbed in the 1% Layer
% Energy Absorbed in the top and bottom 1% of a coating film

2.5
2
1.5
1
0.5
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Absorbance value
Absorbed-top 1%
Absorbed-bottom 1%
Figure 12 Fraction of incident energy absorbed in the top 1% and bottom 1% of a

film
the light absorbed in the top layer and bottom layer is greater than 10. Consider a
strongly absorbing layer (Abs.=3) in which the ratio is
fraction absorbed in the top 1%

993
fraction absorbed in the bottom 1%
In this case we see poor through-cure of the film. This is illustrated in photographs 12 below where a white gel coat was drawn down to a thickness of 10 mils and
exposed to a medium pressure mercury (H-bulb) vapor lamp. The photoinitiator
used, Irgacure 184, is an -hydroxy ketone which undergoes Norrish type I
fragmentation when exposed to UV light. This combination of lamp and
photoinitiator produced an effect known as alligatoring. The effect is so named
because the coating has a pronounced wrinkled surface appearance. The gel coat
shrinks approximately 7% by volume during cure. The alligatoring effect occurs
63

Systems
when the top surface layer cures with commensurate shrinkage. The bulk of the film
located beneath the surface remains completely uncured.
Photograph 1 Alligatoring phenomena

the top 1-3 mils is cured while the balance
of the film is wet
Photograph 2 Uncured coating

material which remains after the cured
surface film in photograph 1 is peeled
away
Referring back to the review of the physics of the interaction of light with matter
presented in figure 8,
I() x
IRRADIANCE
# radicals/sec =
# photons
second
T()
x
TRANSMISSION
A()
ABSORPTION
()
QUANTUM YIELD
through the coating film
# photons absorbed
# radicals formed
# photons
through the coating
# photons absorbed
we can improve the cure of the gel coat film by switching from the short wavelength
H-bulb to the long wavelength gallium V-bulb. This change provides irradiance in a
wavelength band that is consistent with the transmission characteristics of the film.
Unfortunately, this change alone will not solve the issue of poor through-cure of the
10 mil film since the photoinitiator itself strongly absorbs the UV light. The solution
64

Systems
lies in the use of a photobleaching photoinitiator24-32. These initiators are in the
phosphine oxide family and function mechanistically via photocleavage. Several
commercially available phosphine oxide initiators appear in table 2 above. By
replacement of the -hydroxy ketone photoinitiator with bisacyl phosphine oxide
(Irgacure 819) it is possible to achieve rapid through-cure of the 10 mil gel coat using
a gallium V-bulb. The photochemical reason behind the improved through-cure of the
optically dense white coating lies in the very different photolysis process of the two
photoinitiators. The phosphine oxide types of photoinitiators have extended
absorption into the UV visible region. The primary photolysis at longer wavelength
causes an -cleavage of one of the CO-P bonds. The radical-radical recombination of
the benzoyl and phosphinoyl radical is inefficient due to steric and planarization
restraints 49. The same mechanism is also controlling the second cleavage of the
primary formed acylphosphinoyl radical now attached to a growing chain end. The
photolysis results in a loss of absorption at 350 < < 410 nm. Therefore, increased
photon absorption will occur in the deeper layers of the coating as the irradiation
continues. The time-lapsed UV absorption spectrum of the phosphine oxide51 is
shown in figure 13. The photobleaching effect in the depth direction of the coating
film is presented schematically in figure 14.
65

Systems
0.5
Photobleaching Effect of Phosphine Oxide Photoinitiator

20 sec
40 sec
60 sec
0 sec irradiation tim e
30 sec
10 sec
Absorbance
0.4
0.3
0.2
0.1
concentration=1.02 x 10
-3
m olar in m ethanol
0.0
320
340
360
380
400
420
440
460
W avelength (nanometers)
Photobleaching
Figure 13 Time-lapsed UV absorption spectrum of phosphine oxide photoinitiator
LIGHT
INTENSITY
MOLD
MOLD
Non-Photobleaching
LIGHT
INTENSITY
LIGHT
INTENSITY
LIGHT
INTENSITY
LIGHT
INTENSITY
MOLD
Exposure Time
MOLD
LIGHT
INTENSITY
MOLD
MOLD
Figure 14 Comparison of photobleaching and non-photobleaching photoinitiators
66

Systems
R
R
H3C
H3C
R
O
P
O
C
CH3
O
P
O
C
CH3
H3C
H3C
CH3
H3C
O O O
C P C
H3C
CH3
CH3
H3C
CH3
O
C
H3C
O
P
H3C
O
C
CH3
H3C
CH3
R
bisacylphosphine oxide
CH3
O
C
H3C
R
n
CH3
Reaction 2 Photolysis of BAPO

While UV curing of UPR resins was first reported in the mid-1960s
20,21,52
the
commercial availability of phosphine oxide photoinitiators in the late 1980s led to a

renewed interest in UV technology for UPR based composites applications starting in
the mid-1990s.
67

Systems
Publication of Documents (patents, articles) Related to
Photocuring of UPR Glass-Reinforced Composites
16
# Documents Published
14
12
10
8
6
4
2
0
1965
1970
1975
1980
1985
1990
1995
2000
2005
2010
Publication Year
Figure 15 UV Composites publications

Source - Chemical Abstracts Services SciFinder-keyword: photocure, unsaturated
polyester, composite
v. Light scattering within a coating or laminate 33-35

Several authors report improved cure reaction in UV formulations containing
particles designed to scatter the incident light, effectively lengthening the path of the
UV light within the film. In one study34 a UV curable powder coating containing
light-refractive microbeads was reported to exhibit improved through-cure
properties. In a separate report35 a polyester acrylate coating containing silica
nanoparticles was studied by photo-DSC and UV-visible and FTIR spectroscopy. As
the concentration of silica nanoparticles was increased up to 5%, the exotherm,
ultimate percentage conversion, and cure rate increased gradually, whereas they
decreased above 10%.
68

Systems
vi. Commercial applications for UV curable composites 36-42
UV curable composite applications reported in the literature include:
Simulated marble containing clear urethane acrylate36
Flat UPR-multifunctional acrylate gel coated laminates prepared using a

transparent mold with bidirectional cure37
Roofing panel laminates with good weather resistance38
Gel coated laminates used as wood paneling replacements for spas39, 40
Protective gel coats applied to filament wound high pressure tanks41
Residential doors prepared entirely from composite materials42
69

Chapter IV - Characterization of Resin / Coating State of Cure
a. Qualitative methods for estimating cure

i. Probing techniques to assess cure hardness
development, dry-to-touch assessment
Several probing methods to have been used to determine the state of cure of gel coats
and resin laminates. All of these methods involve touching the surface of the curing
material to assess the level of cure. One pass/fail method involves the use of a small
wooden spatula to test the rigidity of the curing film. In another approach the curing
is assessed by pressing a cotton ball on the coating surface. The coating is said to be
cured when the cotton fibers do not remain stuck on the coating1. In yet another
method known as the circular drying time recorder (ASTM 5895), a small weighted
stylus inscribes the curing film in a circular motion that is approximately three inches
in diameter. Once sufficient cure is developed the moving stylus tears the coating
film. With a basic knowledge of the angular velocity of the stylus and the distance
traveled from the starting point to the point the film is torn it is possible to determine
the curing time of the film. Finally, there is the thumb pressure test. A common
ranking scale used with the thumb test is
1=wet, 2=very tacky, 3=tacky, 4=slight tack, 5=dry.
70

ii. Limitation of probing techniques to assess cure
The first obvious limitation of probing methods to determine the state of cure of a
thermosetting film is that they are not quantitative. Secondly, probing techniques are
biased toward the surface of the film or laminate. As it turns out this is a serious
limitation with gel coat films where it is possible to develop a lacquer dry on the
surface if (a) the solvents/reactive diluents are sufficiently volatile, and (b) the glass
transition temperature of the uncrosslinked polymer melt is sufficiently high. The
evaporative loss of reactive monomer is shown in figure 1 where a UPR prepolymermonomer blend was spray-applied to a small glass mold and allowed to sit for
specific intervals. Samples were collected and analyzed to determine compositional
changes arising from evaporative losses of styrene and methyl methacrylate
monomer.
71

b. Quantitative methods for cure characterization
i. Analytical methods used to study cure during the
product development cycle( DSC, FTIR )
ii. Process quality control methods to measure cure NIR,
dielectric spectroscopy
0.6
Com positional Changes In Conventional Gel Coat Resulting

From Evaporative Losses of HAPS Monom ers
PEAK HT .
% CHANGE
Resin
Styrene
MMA
FTIR Absorbance
0.5
0.4
W EIGHT
CHANGE
Resin (g)
Styrene (g)
M MA (g)
Total (g)
% Loss
Pre
Post
100.0
100.0
100.0
100.0
91.5
66.8
Pre
Post
48.5
39.1
12.4
100.0
0.0
48.5
35.8
8.3
92.6
7.4
Post
+5
100.0
79.1
40.0
Post
+ 10
100.0
73.7
25.3
Post
+ 15
100.0
69.2
21.0
Post
+ 30
100.0
53.9
4.6
Post
+ 5
48.5
30.9
5.0
84.4
15.6
Post
+ 10
48.5
28.8
3.1
80.4
19.6
Post
+ 15
48.5
27.1
2.6
78.2
21.8
Post
+ 30
48.5
21.1
0.6
70.1
29.9
Styrene
0.3
Pre-spray composition
Post-spray composition
Post-spray + 5 minutes
0.2
Resin - isophthalate
ring bending m ode
Methyl Methacrylate
0.1
0.0
950
900
850
800
750
700
-1
wavenum ber (cm )
Figure 1 Evaporative losses of reactive monomers in gel coat film measured by

FTIR (T=25C)
Peaks at 731 cm-1(UPR prepolymer-isophthalate ring bending mode), 815 cm-1
(methyl methacrylate C=C bond), and 911 cm-1 (styrene monomer C=C bond) were
monitored to follow the change in composition. The spectra were normalized using
the prepolymer peak since the resin solids is non-volatile. After thirty minutes on the
glass plate roughly one-half of the styrene monomer and nearly all the methyl
methacrylate evaporated.
72
650

Unsaturated polyester resins are well known to be air-inhibited due to the formation
of stable peroxide radicals at the air-resin interface. A lacquer dry effect in which the
back side of the film appears to be cured is observed if the Tg of the uncured film is
greater than 15C. To better illustrate this point the tack-Tg data for a series of three
UPR prepolymers is given in table 1. The lacquer dry effect may also be seen by
conducting an acetone wipe test. The cured gel coat (mold side) is not dissolved by
the solvent while the back side is easily removed. Attempts9-12 to overcome oxygen
inhibition of UPR resins include the use of:
insoluble paraffin waxes forming a surface barrier to preclude oxygen
modification with oxidative curing moieties such as conjugated fatty acids,

dicyclopentadiene, and allylic ethers
oxygen scavenging additives
inert gas blanketing
Resin Designation
Tg (C ) of the uncured
Surface Tackiness Level
prepolymer
A
14.3
dry no tackiness
11.3
slightly tacky to the touch
-5
very tacky to the touch
Table 1 Effect of Tg on the surface tackiness of UPR prepolymer

b. Quantitative methods for estimating cure
i. Analytical methods used to study cure state during the product
development cycle (DSC, FTIR)
While numerous methods have been used to study cure including touch1, Koenig
pendulum hardness, Sward rocker hardness, radiachromic labels2, differential
73

scanning calorimetry (DSC)3-5, FTIR6, NIR7-8, gel fraction measurements20, and laser
nephelometry 21, the most commonly used methods for development and process
definition are DSC and FTIR.
ii. Process quality control methods to measure cure NIR,

dielectric
spectroscopy
The conversion of double bonds in UV-cured acrylic coatings on various substrates
was followed in-line by near-IR (NIR) reflection spectroscopy7-8. Quantitative data
were obtained directly from the intensity of the acrylic overtone band at 1620 nm,
which allows very easy calibration of the method. The custom-made probe head of
the NIR spectrometer was fitted to several pilot-scale coatings and curing lines, and
the conversion was determined in clear and pigmented coatings. It was shown that
reasonable conversion data can be obtained at line speeds of at least 120 m/min.
Another in-line sensing technique22, dielectric spectroscopy, places the curing resin in
an oscillating electric field. The ionic mobility (ion viscosity) is measured and
correlated with the state of cure. This method is useful until the point of vitrification,
but not sensitive to changes in the later stages of cure.
74

Chapter V - Modeling the Degree of Cure of a 2D UV Curing Process
Chapter V Modeling the Degree of Cure of a 2D UV Curing Process
a. Studies of coatings and laminate resin related variables2-11

i. Experiment 1 Effect of pigmentation-screening study
involving ten different colors
Previously, the criteria set forth for effective generation of free radicals in a thick film
of gel coat was stated to be (1) a light source with sufficient irradiance in a
wavelength band(s) consistent with the absorption characteristics of the photoinitiator
and the transmission characteristics1 of the remaining components of the coating, (2)
adequate transmission/scattering of the irradiance through the thickness direction of
the film, (3) absorption of photons by the initiating molecule, and (4) conversion of
absorbed energy to radical generation by the photoinitiator. Photocrosslinking of nonpigmented glass fiber-reinforced composites, based on vinyl ester and unsaturated
polyester has been reported for 2 mm thick laminates, containing 30-40% glass fiber
mats2. As the concentration of photoinitiator increases, the degree of polymerization
reaches a maximum and then decreases. This effect is very marked for film
thicknesses >1 mm. The optimum level of photoinitiator decreases as the sample
depth increases1. Photoinitiators with a high extinction coefficient at the principal
wavelength of the UV source give rise to optimum concentrations at lower initiator
levels. Several studies reported in the literature3,5,6 for white thermosetting coatings
containing rutile TiO2. The degree of cure depended strongly on the film thickness
and concentration of pigment. With the proper selection of lamp and photoinitiator
75

(electrodeless V and D bulbs and 2,4,6-trimethylbenzoyldiphenoylphosphine oxide) it
was possible to properly cure films 12 mils in thickness.
The physical interactions between electromagnetic radiation and color pigments in
pigmented UV coatings complicate the through-cure of such coating films. Certain
pigments7 do not allow adequate transmission/scattering of the irradiance through the
thickness direction of the film and therefore cannot be cured in thick with UV curing.
An experiment was conducted in which a series of different color pigments were
added to a UV curable gel coat base formula and cured. In this screening experiment
the gel coats were drawn down on a white mold at 20 mils thick. All formulas
contained 1% bisacyl phosphine oxide/1-Hydroxycyclohexyl phenyl ketone (Irgacure
819/Irgacure 184, 1:3 ratio), and were irradiated under two rows of Honle Gallium
metal halide lamps at a line speed of 2 feet per minute. None of the samples reached
full cure throughout the entire film thickness of 20 mils. At the conclusion of cure test
the cured portion of the film was peeled off of the uncured coating beneath. The cured
film thickness was measured along with the degree of cure by DSC.
Photograph 1 Colored gel coat films before UV curing

76

Photograph 2 Colored gel coat films after UV curing
The results of the screening experiment are summarized in figure 2. Four of the ten
colored films were cured to a depth greater than 5 mils with 75% or more conversion
of double bonds ( blue, white, almond, and light tan). The curing response of the
remaining six samples were less responsive to the UV exposure.
100
10
80
60
40
20
0
Blue Orange Green
Red
Yellow Black
Grey
Thickness of Cured Film , x (mils)
Degree of Cure % (DSC)
Mils Cured
Degree of Cure (%)
lamp
9 inches
cured gel coat
wet gel coat

mold
2 ft/min
White Lt Tan Almond
Color of the Gel Coat
Figure 1 Screening experiment to evaluate the effect of color pigmentation on the

degree of UV cure
77
20 mils

The results obtained in the screening experiment can be explained in terms of the
scattering and absorption of light within the film. As mentioned in chapter III several
authors report improved cure reaction in UV formulations containing particles
designed to scatter the incident light, effectively lengthening the path of the UV light
within the film.chap III ref. 33-35 The incident incident on an opaque film is either
scattered or absorbed. The relative amount of absorption and scattering can be
determined for a given wavelength by measuring the reflectance spectrum R(). The
Kubelkla-Munk theory states that
K (1 R ) 2
S
2R
equation 1.1
where K= the absorption coefficient, S=scattering coefficient, and R=reflectance.

For a mixture of colorants such as the case for the screening experiment
K
c K c 2 K 2 c3 K 3 ...
K
mixture 1 1
S
c1 S1 c 2 S 2 c3 S 3 ...
mixture S mixture
equation 1.2
Relationship Between Measured Reflectance and the Absorption

(K) and Scattering (S) Coeffcients in an Opaque Film
10
K/S
8
6
4
2
0
0
0.2
absorption dominates
0.4
0.6
Reflectance
0.8
scattering dominates
Figure 2 Kubelka-Munk prediction of light absorption and scattering in an opaque

pigmented film11
The reflectance spectrum were measured for the ten pigmented gel coat samples at 20
nm intervals over the visible portion of the spectrum (400 700 nm) figure 4 .
78

Recall that the gallium doped mercury bulb provides the most significant energy in
the 390 440 nm range. The absorption spectra of the photoinitiator solution that is
presented in figure 5 indicates a maximum in absorption of light at 420 nm. This peak
location is an ideal match for the gallium type metal halide electrodeless UV lamp for
the purposes of maximizing the photons absorbed by the photoinitiator.
The reflectance curves in figure 4 clearly show that the four colors with the best cure
response also have the lowest K/S ratio i.e. greatest scattering in the wavelength
range of interest. Conversely, the colored films with the poorest cure response
(yellow, red, green, orange, black) have the highest light absorption in the wavelength
range of interest. From this experiment we can conclude that UV curing is not a
viable option for curing films containing tinctorial pigments with strong absorbance
in the 390-500 nm range. During the cure of a UPR laminating resin, the resin shrinks
Reflectance Curve for Several Gel Coat Colors

5-8 % by volume.
100
white
almond(off white)
80
% Relectance
orange
red
grey
60
light tan
yellow
40
20
green
blue
black
0
350
400
450
500
550
600
650
700
750
Wavelength (nanometers)
Figure 3 Reflectance spectra for the ten pigmented gel coats shown in photograph 1
79

One consequence of the shrinkage of the matrix resin around the reinforcing fiber is
the appearance of an uneven surface known as fiber prominence or fiber printing at
the surface of the laminate. A major function of a gel coat is to serve as a fiber-print
blocking layer. The maximum cured film thickness is approximately four mils in this
case, which is too thin for gel coat applications requiring good surface smoothness.
Absorbance Calibration Curves - Photoinitiator Solution

0.900
0.800
%PI solids
0.00
0.10
0.20
0.50
0.75
1.00
1.50
2.00
2.50
3.00
Absorbance Units = -log(T)
0.700
0.600
0.500
0.400
0.300
0.200
0.100
0.000
350
400
450
500
550
600
650
Wavelength nm
Figure 4 Absorption spectra of the photoinitiator solution
80
700
750

ii. Experiment 2 Effect of TiO2 concentration
Objective: The objective of the experiment is to determine the correct level of
titanium dioxide to use in a white gel coat formula.
Approach: Gel coat formulas were prepared with increasing levels of pigment and
exposed in a UV curing application. The cured films were evaluated visually for
surface quality and cure.
INPUT FACTORS
1) Type of experimental design or comparative strategy: simple ladder study
FIXED FACTORS these factors
will be held constant
UNITS
LEVEL
A)
Photoinitiator level and type
Irgacure 819 at 0.5%
B)
Line speed
fpm
20
C)
Coating thickness
mils
16
D)
Coating
na
UPR diluted in styrene, rutile TiO2
E)
Lighting
na
600 W/in Fusion lamp, std. reflector, at 4

inches, V bulb
2) How many independent factors are to be studied? 1
How many Tests will be conducted? 2
UNITS
FACTOR Variable these factors will
LEVELS
be systematically varied
A)
concentration of titanium dioxide
10, 15, 20
LIST OF RESPONSE VARIABLES

TEST METHOD TO USE
RESPONSE VARIABLE NAME
A)
visual assessment of cure and

surface quality
UNITS
na
visual
RESULTS
Run #
% TiO2
Visual Assessment of the Film
10
cure: slightly tacky on the surface, wet below the surface

appearance: the surface is smooth no alligatoring texture noted
15
cure: slightly tacky on the surface, wet below the surface

20
sample was not run based on the results of run #2
81

CONCLUSIONS
The level of pigment should be held to a maximum of 10% to prevent the
alligatoring texture which can occur with a cure and shrinkage gradient in the
thickness direction.
iii. Experiment 3 Effect of gel coat film thickness

Objective: The objective of the experiment is to determine the process window for
the gel coat film thickness.
Approach: Gel coat formulas were applied at varying film thickness using a draw
down bar on a mylar film and exposed in a UV curing application. The cured films
were evaluated visually for surface quality and cure.
INPUT FACTORS
1) Type of experimental design or comparative strategy: simple ladder study
UNITS
LEVEL
A)
Photoinitiator level and type
Irgacure 819 at 1.0%
B)
Line speed
fpm
10
C)
Coating type
na
UPR-styrene, rutile TiO2-10%
D)
Lighting
na

inches, V bulb

UNITS
LEVELS
A)
Coating thickness
mils
7, 10, 16

TEST METHOD TO USE
A)

surface quality
UNITS
na
visual
82

RESULTS
Run #
Film
Thickness
mils
1
cure: dry on the surface, good thru cure

10
cure: very slight tack on the surface, good thru good

16
cure: slightly tacky on the surface, good thru good

appearance: the surface is smooth slight alligatoring texture noted
CONCLUSIONS
The wet film thickness should be held to 10 mils to prevent the alligatoring texture
which can occur with a cure and shrinkage gradient in the thickness direction.
83

iv. Experiment 4 Factorial study of photoinitiator

concentration, UV energy, and TiO2
concentration
Objective: The objective of the experiment is to determine the process window for
the gel coat film thickness.
Approach: Gel coat formulas were applied at varying film thickness using a draw
down bar on a mylar film and exposed in a UV curing conveyor application. The
cured films were evaluated visually for surface quality and cure.
INPUT FACTORS
1) Type of experimental design or comparative strategy: full factorial 23 design
UNITS
LEVEL
A)
Coating type
na
UPR-styrene, rutile TiO2-10%
B)
Lighting
na

inches, V bulb


LEVELS
UNITS
A)
Coating thickness
mils
7, 10, 16
B)
Photoinitiator concentration
0.1%, 0.5% Irgacure 819
C)
Line speed
fpm
5,20

TEST METHOD TO USE
A)

surface quality
UNITS
na
visual
84

RESULTS
Run
% PI
#
1
0.1
Line
Film
Speed
Thickness
(fpm)
(mils)
cure: tack free, good thru cure

appearance: no alligatoring texture
0.1
16
cure: tacky surface, incomplete thru cure

appearance: some are smooth, other areas show texture
0.1
20
cure: tacky surface, incomplete thru cure

0.1
20
16
wet film
0.5
cure: well cured

0.5
16
cure: dry on the surface, dry below

appearance: alligatoring texture is present
0.5
20
cure: tacky surface

0.5
20
16
cure: tacky surface, wet below the surface

Table 1 - Factorial study of photoinitiator concentration, UV energy, and film

thickness
CONCLUSIONS
All films at 16 mils were had a textured appearance while the 4 mil film is easily
cured with proper selection of line speed. It is necessary to use 0.5% PI to achieve
good surface cure with this lamp-PI combination.
85

v. Experiment 5 - Binder / reactive diluent selection
Objective: The objective of the experiment is to study the differences in UV cure
response using different binder chemistry (UPR-styrene, thermosetting acrylic)
Approach: Gel coat formulas were using two different binder chemistries and
applied at varying film thickness using a draw down bar on a mylar film and
exposed in a UV curing conveyor application. The cured films were evaluated
visually for surface quality and cure.
INPUT FACTORS
UNITS
LEVEL
A)
1.0% Irgacure 819
B)
TiO2 type and concentration
rutile, 10%
C)
Lighting
na

inches, V bulb
UNITS
LEVELS
A)
Coating thickness
mils
7, 10, 16
B)
Line speed
fpm
5, 10, 20, 40, 80
C)
Binder chemistry
na
UPR-styrene , thermosetting acrylate

diluted with multifunctional acrylate
monomers

TEST METHOD TO USE
A)

surface quality
UNITS
na
visual
86

RESULTS
Run
Binder
Line
Film
chemistry
Speed
Thickness
(fpm)
(mils)
10
UPR

UPR
10
16
cure: tacky surface, complete thru cure

appearance: some areas show texture
UPR
16
cure: slight tacky surface

appearance: alligatoring texture
UPR
12

UPR
10
10
cure: v. slight surface tack , good thru cure

Acrylic
20
10

Acrylic
40
10

Acrylic
80
10

Acrylic
20
16

Table 2 - Binder / reactive diluent selection
CONCLUSIONS
The difference in cure response is dramatic. The thermosetting acrylic is cured at
eight times the line speed of the UPR based gel coat. The film is also observed to cure
without the surface wrinkling issue at a thickness 16 mils.
87

vi. Experiment 6 UV Curing studies of a UPR laminate

Objective: The objective of the experiment is to determine the process conditions
necessary to cure a fiber reinforced UPR laminate
Approach: Photoinitiator was added to a general purpose orthophthalic laminating
resin and exposed in a static UV curing application. The laminate was prepared
using three plies of 1.5 ounce/ft2 chopped strand mat.
INPUT FACTORS
UNITS
LEVEL
A)
Laminate materials
na
UPR-styrene, 35% E-glass , 3 plies of 1.5

oz/ft2 CSM
B)
Lighting
na
100 W/in Honle UVASPOT 400 lamp,

dimpled diffuse reflector, at 14 inches, V
bulb
UNITS
LEVELS
A)
Exposure time
minutes
0-20
B)
0-2% Irgacure 819

TEST METHOD TO USE
UNITS
A)
Barcol hardness
Barcol units
Barber-Coleman stylus hardness tester
B)
Double bond conversion
DSC
C)
Surface temperature
D)
UVV energy
embedded thermocouple
2
J/cm
88
visual

RESULTS
)
40
100
93
92
90
94.5
36
89
34
83
32.4
80
32
30
28
70
60
58
55
50
26
63
60
60
57.5
24
22
20
49
18
16
40
Barcol hardness (exposed surface)
14
30
30
12
Barcol hardness (Mylar film side)

20
0
0
100
200
Conversion by thermal DSC analysis

(%)
4.32
3.24
2.16
1.08
0 0 0
10
10
9.18
21
total received energy
conversion and barcol hardness
38
6
4
total received light energy (J/cm2)
2
0
300
400
500
600
700
800
900
1000
1100
1200
1300
exposure time (s)
Figure 5 Effect of UV energy on cure of a UPR laminate containing 35% short fiber
E-glass reinforcement (0.75% BAPO photoinitiator)
40
180
38
160
160
160
160
36
34
140
32
30
28
120
120
26
24
100
22
20
80
80
18
77
71
67 68
68
12
50
40
maximum reached temperature (C):

Tmax.
9,18
40
exposure time at Tmax (s): tmax

20
4,32
3,24
2,16
1,08
total received light energy (J/cm2)
100
200
10
8
6
4
2
0
0
16
14
60
300
400
500
600
700
800
exposure time (s)
89
900
1000
1100
1200
0
1300
total received energy
maximum reached temperature and

exposure time at Tmax
32,4

Figure 6 Effect of UV energy on surface temperature of a UPR laminate containing
35% short fiber E-glass reinforcement (0.75% BAPO photoinitiator)
100
91
Barcol hardness and conversion
90
93,5
93 92
93
93
93
92
88
80
70
62
60
54
51
50
56,5
55,2
57
57
54
53
52
49
45,5
45
4241
40
37
30
20
BARCOL hardness (exposed side)

BARCOL hardness (Mylar film side)
conversion by thermal DSC analysis (%)
10
7
4
0
0
0
0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9
1,1 1,2 1,3 1,4 1,5 1,6 1,7 1,8 1,9
% of BAPO / formulation
Figure 7 Effect of photoinitiator concentration on the cure of a UPR laminate

containing 35% short fiber E-glass reinforcement (BAPO photoinitiator) 5 minute
static exposure
CONCLUSIONS
From the results presented in figures 5-7 we can conclude that full cure as measured
by hardness development and DSC double bond conversion can be achieved under
these curing conditions in approximately three minutes of exposure (~ 4 J/ cm2 UV
energy). The maximum surface temperature reached is 60 C. The minimum level of
photoinitiator needed to achieve full cure is approximately 0.3%.
90
2,1

b. Studies of UV curing equipment variables
i. Experiment 7 Reciprocal law for UV energy,
independence of irradiance and line speed
Objective: The objective of the experiment is to determine the dependence of UV
energy and irradiance on the line speed in a conveyor curing apparatus.
Approach: An EIT Power Puck radiometer / dosimeter was used to monitor the
UV energy and irradiance levels.
INPUT FACTORS
A)

UNITS
LEVEL
Lighting
na

inches, V bulb
UNITS
LEVELS
A)
Conveyor speed
fpm
0-40

TEST METHOD TO USE
A)
B)
UNITS
W/cm2
Irradiance
EIT Power Puck
UV energy
J/cm
EIT Power Puck
RESULTS
Line
Speed
2
4
5
6
8
10
15
20
25
40
UVA
UVB
UVC
UVV
UVA
UVB
UVC
UVV
W/cm2
0.132
0.132
0.132
0.132
0.132
0.132
0.132
0.132
0.132
0.132
W/cm2
0.066
0.066
0.066
0.066
0.066
0.066
0.066
0.066
0.066
0.066
W/cm2
0.004
0.004
0.004
0.004
0.004
0.004
0.004
0.004
0.004
0.004
W/cm2
0.468
0.468
0.468
0.468
0.468
0.468
0.468
0.468
0.468
0.468
J/cm2
5.478
2.862
2.269
1.896
1.382
1.079
0.689
0.533
0.443
0.269
J/cm2
2.987
1.586
1.223
1.08
0.738
0.544
0.379
0.274
0.253
0.143
J/cm2
0.132
0.078
0.061
0.054
0.032
0.023
0.017
0.011
0.012
0.006
J/cm2
18.46
9.423
7.527
6.192
4.607
3.601
2.269
1.772
1.434
0.893
Table 3 - Reciprocal law for UV energy, independence of irradiance and line speed
91

UV Energy and Irradiance vs. Conveyor Speed

Irradiance (W/cm2)
UVA
Energy(J/cm2)
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
5
4
3
2
1
0
0
20
40
UVA Irradiance
(W/cm2)
Energy (J/cm2)
60
-1
Line Speed (fpm) ~ (Exposure Time)
Figure 8 Energy and Irradiance vs. Conveyor Speed

CONCLUSION
The UV energy varies with the reciprocal of line speed. The irradiance (photon flux)
is fixed for a given lighting configuration.
1
v
(equation 7.1)
92

ii. Experiment 8 DSC cure studies in clear and white gel

coat role of film thickness and UV
energy
Objective: The objective of the experiment is to determine the UV energy
requirements needed to cure a clear gel coat and a white gel coat.
Approach: Photoinitiator was added to a general purpose orthophthalic laminating
resin and exposed in a static UV curing application. The laminate was prepared
using three plies of 1.5 ounce/ft2 chopped strand mat.
INPUT FACTORS
UNITS
LEVEL
A)
Laminate materials
na

oz/ft2 CSM
B)
Lighting
na
400 W/in Fusion lamp, std. reflector, at

19 inches, V bulb
C)
Irradiance level
W/cm2
UVV=0.14
UNITS
LEVELS
A)
UV Energy
J/cm2
0-6
B)
Film thickness
mils
0-20

TEST METHOD TO USE
A)
Double bond conversion
UNITS
%
DSC
93

RESULTS
Dose-Cure Response for White UV Curable, Ultra Low HAPS Weather Resistant Gel Coat,
and Conventional UPR Clear Gel Coat
100
% Cure Measured by DSC
90
80
70
60
50
DoseUVV wht vs cure wht 20
White - 10 mils
White 15 mils
White 20 mils
Clear 10 mils
Clear 15 mils
Clear 20 mils
40
30
20
10
0.0
NCLUSIONS
0
0.5
1.0
2
UVA Dosage (Joules / cm )
1
3
4
UVV Dosage (Joules / cm 2)
1.5
Figure 9 Energy requirements to cure a clear gel coat and white gel coat
CONCLUSIONS
The chemical conversion as measured by DSC is dependent on the film thickness and
pigmentation. All clear gel coats reach 90-95% of double bond conversion with 2
J/cm2 of UVV energy. The thick (20 mil) pigmented film requires ~ 5 J/cm2 to reach
full cure.
94

iii. Experiment 9 Temperature-Energy-Irradiance map

for several UV light sources
Objective: Determine the relationship between lamp height and the UVV and UVA
energy and maximum surface temperature.
Approach: The distance from the lamp to the radiometer is systematically varied in
a static exposure test.
INPUT FACTORS
UNITS
LEVEL
A)
Exposure time
min

oz/ft2 CSM
B)
Lighting
na
400 W/in Fusion lamp, std. reflector, at

19 inches, V bulb
C)
Irradiance level
W/cm2
UVV=0.14
UNITS
FACTOR Variable these factors
LEVELS
will be systematically varied

A)
Lighting source
na
(1) Honle UVASPOT 400 with gallium

metal halide lamp
(2) Honle UVASPOT 400 with iron metal
halide lamp
(3) Fusion 400 W/cm2 lamp with gallium
metal halide lamp
(4) Fusion 400 W/cm2 lamp with iron
metal halide lamp
(5) Phillips VHO fluorescent lamp with
1500 mA ballast
B)
Lamp height
inches
0-34

TEST METHOD TO USE
UNITS
A)
UV Energy
J/cm2
EIT Power Puck radiometer-dosimeter
B)
Surface temperature
Fluke IR thermometer
95

RESULTS
Light (UVV & UVA) Dosage Comparison for Several Illumination Sources
(exposure interval = 1 minute)
100
T@3min>250F
T@3min=137
2
Dosage of Light (J/cm )
T@3min=169F
10
UVV Light from Fusion UV Lamp

400 W/inch with Gallium Doped Bulb
UVV Light from

Honle UV Lamp
Gallium Doped Bulb
120F
106F
T@3min=97F
UVA Light from Fusion UV Lamp
400 W/inch with Gallium Doped Bulb
T@3min=102F
120F
T@3min=82F
T@3min=94F
UVA Light from

Honle UV Lamp
Gallium Doped Bulb
UVA Light from Honle UV Lamp

Iron Doped Bulb
UVV Light from VHO Flourescent

Lamp
uo
T@3min= RT for VHO
UVV Light from Honle UV Lamp

Iron Doped Bulb
T@3min=75
0.1
10
15
20
25
30
Lamp Distance from the Surface of the Mold (Inches)
Figure 10 - Energy and surface temperature profiles for several commercially

available UV lamps
CONCLUSIONS
The irradiance from a point source of light varies with the inverse square of distance.
As shown in figure 10 the UV energy falls sharply as expected with distance from the
lamp. The power of the lamps increases in the following order:
Phillips VHO fluorescent< Honle < Fusion.
96
35

The VHO and Honle lamps have reflectors which produce diffusely reflected light.
The energy increases in a monotonic fashion as the distance from the lamp to the
radiometer decreases. The Fusion lamp utilizes a parabolic lamp with a focal length
of approximately three inches. The measured energy and irradiance actually drops
slightly for the Fusion lamp when the distance from the lamp to the radiometer is less
than the focal length.This trend is not observed for the Honle lamp that has a dimpled
reflector which produces diffusely reflected light. The data in figure 10 may be used
with a dose-conversion plot for the polymerizing material (see figure 9) to select an
equipment set-up (type of lamp, distance, exposure interval). A separate measurement
of surface temperature after three minutes of irradiation provides additional process
information that can be used to ensure safe operation. To achieve proper cure it may
be important to keep the surface temperature below some critical temperature to
minimize the risk of fire due to the flash point of a volatile ingredient in the
polymerizing material. For example, if the energy requirement is 4 J/cm2 UVV and
the maximum temperature requirement is 100 F, the following curing conditions will
provide the required energy and temperature control.
VHO lamp 2 minutes of exposure at a distance of 4 inches

Fusion ( gallium lamp) 40 seconds of exposure at a distance of 22 inches
97

iv. Experiment 10 Variations in energy and irradiance of
a single 600 W/inch lamp as function
Objective: The objective of the experiment is to develop the mathematical model
needed to predict the energy and irradiance emanating from a UV curing lamp
Approach: A systematic collection of radiometric measurements will be collected
from a UV conveyor system built by the author and shown in photograph 1 and
figure 11 fitted with Fusion UV lamps. For this experiment only one of the lamps in
use. The UV irradiance and energy is measured directly below the centerline of
lamp 3. The UV irradiance and energy is also measured at six inch intervals
laterally from the centerline of lamp three. The data collected from this experiment
is then fitted to several distribution models.
Experiment #10 Irradiance and energy distribution
from a single 600 W/ inch UV lamp
Air plenum
600 W/inch Fusion UV lamp
off
off
Lamp 1
Lamp 2
on
off
off
Lamp 3
Lamp 4
Lamp 5
h=height
-36
-30 -24 -18 -12
-6
12
18 24 30 36
Figure 11 Schematic of experiment 10 set-up
98
Radiometric data was collected at 6 inch

lateral intervals

INPUT FACTORS
1) Type of experimental design or comparative strategy:
FIXED FACTORS these UNITS
factors will be held constant
during the experiment
LEVEL
A)
line speed
14
B)
lamp reflector type and bulb na

position within the reflector
fpm
std. reflector, 209 position

FACTOR Variable these
UNITS
How many Tests will be conducted?

2x3x11=66
LEVELS
factors will be systematically

varied during the experiment
A)
Lamp type
na
iron and gallium doped metal

halide medium pressure mercury
lamps
B)
Lamp height, h
inches
5, 9, 14
C)
Lateral position of the radiometer inches

relative to the centerline of lamp 3
-30, -24, -18, -12, -6, 0, 6, 12, 18,

24, 30

TEST METHOD TO USE
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
PowerPuck process radiometerdosimeter UVA, UVB, UVC, UVV
B)
Irradiance
W/ cm2
99

Photograph 1 - UV Curing line used to develop the irradiance and energy process
model Two rows of five lamps each lamp is rated at 6000W (built by the author)
100

RESULTS
Experiment #10 - Variation in Dose and Intensity as a Function of Distance from Centerline - Single 600 W/inch Lamp
UVA
UVB
UVC
UVV
UVA
UVB
UVC
UVV
Reflector
W/cm2
W/cm2
W/cm2
W/cm2
J/cm2
J/cm2
J/cm2
J/cm2
STD 209
0
0
0.013
0.053
0.172
0.223
0.169
0.061
0.023
0
0
0
0
0.009
0.042
0.147
0.2
0.159
0.05
0.014
0
0
0
0
0
0.002
0.007
0.011
0.008
0.002
0
0
0
0
0.012
0.045
0.189
0.588
0.84
0.61
0.197
0.058
0.015
0
0
0
0.023
0.123
0.382
0.516
0.436
0.156
0.053
0
0
0
0
0.008
0.092
0.308
0.438
0.379
0.113
0.021
0
0
0
0
0
0.002
0.013
0.02
0.017
0.003
0
0
0
0
0.029
0.126
0.458
1.343
1.934
1.578
0.555
0.146
0.035
0
UVA
UVB
UVC
UVV
UVA
UVB
UVC
UVV
Reflector
W/cm2
W/cm2
W/cm2
W/cm2
J/cm2
J/cm2
J/cm2
J/cm2
STD 209
0
0
0.078
0.625
0.786
0.181
0.017
0
0
0
0
0.058
0.464
0.798
0.195
0.009
0
0
0
0
0.003
0.024
0.049
0.012
0
0
0
0
0.014
0.245
1.963
2.663
0.579
0.048
0.007
0
0
0
0.096
0.713
0.869
0.216
0.016
0
0
0
0
0.058
0.514
0.852
0.227
0
0
0
0
0
0.001
0.025
0.049
0.011
0
0
0
0
0.014
0.299
2.196
2.793
0.699
0.076
0.005
0
UVA
UVB
UVC
UVV
UVA
UVB
UVC
UVV
W/cm2
0
0
0.01
0.022
0.057
0.106
0.117
0.091
0.042
0.019
0.008
0
0
W/cm2
0
0
0.009
0.021
0.51
0.099
0.114
0.091
0.039
0.014
0
0
0
W/cm2
0
0
0
0.001
0.003
0.006
0.007
0.005
0.002
0
0
0
0
W/cm2
0.006
0.013
0.03
0.074
0.186
0.362
0.41
0.307
0.128
0.057
0.022
0.012
0.005
J/cm2
0
0
0.016
0.066
0.199
0.369
0.409
0.329
0.139
0.056
0.009
0
0
J/cm2
0
0
0.008
0.058
0.16
0.299
0.368
0.282
0.113
0.029
0
0
0
J/cm2
0
0
0
0
0.006
0.014
0.019
0.0014
0.003
0
0
0
0
J/cm2
0.011
0.041
0.102
0.282
0.687
1.246
1.416
1.111
0.49
0.214
0.073
0.038
0
SET 1
Position (inches)
-36
-30
-24
-18
-12
-6
0
6
12
18
24
30
36
Line
Speed
Lamp
Height
Bulb
Type
14
9"
Line
Speed
Lamp
Height
Bulb
Type
SET 2
Position (inches)
-36
-30
-24
-18
-12
-6
0
6
12
18
24
30
36
14
5"
Line
Speed
Lamp
Height
Bulb
Type
Reflector
14
15"
STD 209
SET 3
Position (inches)
-36
-30
-24
-18
-12
-6
0
6
12
18
24
30
36
101

Results of experiment 10 (continued)
Experiment #10 - Variation in Dose and Intensity as a Function of Distance from Centerline - Single 600 W/inch Lamp
SET 4
Position (inches)
-36
-30
-24
-18
-12
-6
0
6
12
18
24
30
36
Line
Speed
Lamp
Height
Bulb
Type
14
9"
Line
Speed
Lamp
Height
Bulb
Type
UVA
UVB
UVC
UVV
UVA
UVB
UVC
UVV
Reflector
W/cm2
W/cm2
W/cm2
W/cm2
J/cm2
J/cm2
J/cm2
J/cm2
STD 209
0
0.011
0.043
0.191
0.822
1.026
0.686
0.143
0.028
0.007
0
0
0
0.012
0.049
0.236
0.31
0.155
0.03
0.008
0
0
0
0
0
0.003
0.017
0.022
0.01
0.001
0
0
0
0
0.009
0.029
0.118
0.501
0.615
0.382
0.083
0.013
0.005
0
0
0.019
0.109
0.469
1.782
2.232
1.342
0.359
0.089
0.006
0
0
0
0.012
0.117
0.514
0.683
0.362
0.058
0
0
0
0
0
0
0.005
0.037
0.05
0.022
0.002
0
0
0
0
0.014
0.067
0.293
1.055
1.322
0.973
0.244
0.039
0.008
0
UVA
UVB
UVC
UVV
UVA
UVB
UVC
UVV
W/cm2
W/cm2
W/cm2
W/cm2
J/cm2
J/cm2
J/cm2
J/cm2
0
0.014
0.143
1.63
2.35
0.832
0.008
0
0
0
0.032
0.448
0.713
0.289
0
0
0
0
0.001
0.031
0.05
0.019
0
0
0
0.01
0.094
0.979
1.402
0.487
0.006
0
0
0.016
0.209
2.055
2.885
1.116
0.003
0
0
0
0.037
0.578
0.89
0.379
0
0
0
0
0.001
0.042
0.065
0.025
0
0
0
0.008
0.141
1.258
1.696
1.23
0.14
0
UVA
UVB
UVC
UVV
UVA
UVB
UVC
UVV
W/cm2
0
0.009
0.024
0.072
0.234
0.535
0.567
0.39
0.136
0.046
0.017
0.008
0
W/cm2
0
0
0
0.019
0.065
0.154
0.175
0.121
0.042
0.013
0
0
0
W/cm2
0
0
0
0
0.004
0.011
0.015
0.009
0.002
0
0
0
0
W/cm2
0
0.007
0.016
0.045
0.14
0.316
0.325
0.229
0.082
0.028
0.012
0.006
0
J/cm2
0.006
0.016
0.066
0.246
0.769
1.586
1.799
1.236
0.486
0.163
0.053
0.013
0.004
J/cm2
0
0
0
0.05
0.202
0.459
0.573
0.375
0.13
0.025
0
0
0
J/cm2
0
0
0
0
0.011
0.03
0.5
0.024
0.006
0
0
0
0
J/cm2
0
0.008
0.043
0.155
0.458
0.929
1.02
0.72
0.291
0.096
0.032
0.002
0
SET 5
Position (inches)
-36
-30
-24
-18
-12
-6
0
6
12
18
24
30
36
Reflector
14
5"
STD 209
Line
Speed
Lamp
Height
Bulb
Type
Reflector
14
15"
STD 209
SET 6
Position (inches)
-36
-30
-24
-18
-12
-6
0
6
12
18
24
30
36
Table 4 - Variations in energy and irradiance of a single 600 W/inch lamp as function
CONCLUSIONS
The UV energy, E, and irradiance, I, at a given height can be modeled using a
Gaussian distribution as shown in the plots below. The plots show measured and
102

predicted values. This simple model can be used to predict the energy and irradiance
at any point in a lateral direction, x, from the centerline, for a given light source
see figure 11.
E ( x) e
( x ) 2 / 2 2
equation 10.1
The variance in the UV energy for a given lamp height is determined experimentally
and given the symbol 2 in the above equation. Finally, the energy (or irradiance) can
be predicted for a given lamp height by adding the pre-exponential factor,
E ( x) e ( x )
/ 2 2
equation 10.2
Light Dose as a Function of Lateral Distance

from Lamp Centerline (1 F600 V Bulb), h=5"

from Lamp Centerline (1 F600 D Bulb), h=5"
-40
-20
3.5
UVA
2.5
UVB
UVC
1.5
UVV
Pred UVV
0.5
Pred UVA
Pred UVB
-0.5 0
20
40
Light Dosage (J/cm^2)
3.5
-20
UVA
UVB
1.5
UVC
UVV
Pred UVV
0.5
Pred UVA
0
0
20
40
Pred UVB
-40
-20
Pred UVC
20
Pred UVB
40
Pred UVC
UVA
2.5
2
UVB
1.5
1
UVV
UVC
Pred UVV
Pred UVA
-0.5 0
20
40
Pred UVB
Pred UVC
Light Dose as a Function of Lateral Distance from

Lamp Centerline (1 F600 D Bulb), h=15"
1.5
2
UVA
Pred UVA
0
-0.5 0
Postion from Lam p Center (inches)

Lamp Centerline (1 F600 V Bulb) , h=15"
UVB
UVC
0.5
UVV
Pred UVV
0
-20
Pred UVV
0.5
0
Postion from Lamp Center (inches)
-40
UVV

from Lamp Centerline (1 F600 D Bulb), h=9 "
2.5
-0.5
UVC
1.5

Lamp Centerline (1 F600 V Bulb), h=9"
-20
UVB
0.5
Postion from Lamp Center (inches)
-40
UVA
-40
Pred UVC
3
2.5
20
40
-0.5
Postion from Lam p Center
(inches)
Pred UVA
Pred UVB
UVA
1.5
UVB
UVC
UVV
0.5
Pred UVV
Pred UVA
0
-40
-20
0
-0.5
Pred UVC
Figure 11.5 - Energy distribution for a Fusion 600 W/in lamp
103
20
40
Pred UVB
Pred UVC

Lamp
Type
Lamp
Height
(inches)
UVA
mean ()
multiplier ()
deviation ()
mean ()
multiplier ()
deviation ()
15
mean ()
multiplier ()
deviation ()
mean ()
multiplier ()
deviation ()
mean ()
multiplier ()
deviation ()
15
mean ()
multiplier ()
deviation ()
UVB
Gaussian Fit Parameters

0.00000 0.00000
11.57073 9.92356
5.28289 4.64510
0.00000 0.00000
10.17411 8.27409
7.59037 7.18900
0.00000 0.00000
9.57635 7.93098
9.07173 8.56618
0.00000 0.00000
38.56027 11.65706
5.24585 5.13373
0.00000 0.00000
38.17928 10.57973
6.71062 6.08503
0.00000 0.00000
38.06210 10.91138
8.41678 7.62644
UVC
UVV
0.00000
0.51988
4.22922
0.00000
36.54624
5.21233
0.00000
0.34061
6.38360
0.00000
36.88191
7.47998
0.00000
0.24079
5.52495
0.00000
33.47463
9.39456
0.00000
0.82608
4.98923
0.00000
27.80929
6.12651
0.00000
0.70966
5.56374
0.00000
24.17421
6.97518
0.00000
3.11249
2.48341
0.00000
22.30008
8.61793
Table 5 - Gaussian fit model parameters to predict UV energy for each illuminant and
lamp height from experiment 10
104

Lamp
Type
Lamp
Height
(inches)
15
15
mean ()
multiplier ()
deviation ()
mean ()
multiplier ()
deviation ()
mean ()
multiplier ()
deviation ()
mean ()
multiplier ()
deviation ()
mean ()
multiplier ()
deviation ()
mean ()
multiplier ()
deviation ()
UVA
UVB
UVC
UVV
0.00000
10.82014
5.41602
0.00000
4.27172
7.47303
0.00000
2.79495
9.38288
0.00000
30.45388
5.10805
0.00000
17.76406
6.62695
0.00000
11.99079
8.20430
0.00000
9.05737
4.53771
0.00000
3.73605
7.20369
0.00000
2.61999
9.00296
0.00000
9.12884
5.04142
0.00000
4.76346
6.07212
0.00000
3.54498
7.92036
0.00000
0.52208
4.25630
0.00000
0.18101
6.38799
0.00000
0.15389
8.16852
0.00000
0.62493
4.92265
0.00000
0.32375
5.76366
0.00000
0.24967
6.62035
0.00000
32.97452
4.94404
0.00000
15.08903
7.12584
0.00000
9.30460
8.97439
0.00000
18.17575
5.11560
0.00000
10.49976
6.58698
0.00000
7.07839
8.38082
Table 5 cont. - Gaussian fit model parameters to predict irradiance for each illuminant
and lamp height from experiment 10
105

v. Experiment 11 Measurement of energy and irradiance
from a bank of five 600 W/inch lamps
Objective: The objective of the experiment is to study the energy and irradiance
pattern in the lateral direction (i.e. perpendicular to the direction of conveyor travel)
from a bank of UV lamps
Approach: A systematic collection of radiometric measurements will be collected
from a UV conveyor system built by the author and shown in photograph 1 and
figure 12 fitted with Fusion UV lamps. One row of five 600W/inch lamps are used
in this experiment. All five lamps are energized during the data collection period.
The UV irradiance and energy is measured directly below the centerline of lamp 3.
The UV irradiance and energy is also measured at six inch intervals laterally from
the centerline of lamp three.
Experiment #11 Irradiance and energy distribution from a bank of five 600 W/ inch UV lamps
Air plenum
on
on
on
on
on
Lamp
1
Lamp
2
Lamp
3
Lamp
4
Lamp
5
Radiometric data was collected at 6 inch

lateral intervals
h=height
-60 -54 -48 -42 -36
-30 -24 -18 -12
-6
12
18 24 30 36
42 48
54 60
Figure 12 UV lighting set-up for experiment 11 a bank of five 600 W/inch Fusion
UV lamps
106

INPUT FACTORS
LEVEL
A)
line speed
14
B)
lamp reflector type and bulb na

position within the reflector
std. reflector, 209 position
C)
lamp type
na
gallium doped metal halide
D)
lamp height
inches
11
fpm

\
UNITS
How many Tests

conducted? 17
LEVELS
will
be

A)
Lateral position of the radiometer inches

relative to the centerline of lamp 3
-54, -48, -42, -30, -24, -18, -12, -6,

0, 6, 12, 18, 24, 30, 36, 42, 48, 54

TEST METHOD TO USE
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
107

RESULTS
Position (inches)
-54
-48
-42
-36
-30
-24
-18
-12
-6
0
6
12
18
24
30
36
42
48
54
UVA
W/cm2
0
0
0.011
0.036
0.122
0.273
0.365
0.404
0.425
0.438
0.456
0.449
0.408
0.331
0.158
0.037
0.009
0
0
UVB
W/cm2
0
0
0
0.019
0.089
0.217
0.296
0.327
0.353
0.384
0.376
0.381
0.386
0.296
0.126
0.029
0
0
0
UVC
W/cm2
0
0
0
0
0.004
0.011
0.014
0.016
0.017
0.019
0.019
0.02
0.02
0.015
0.006
0.001
0
0
0
UVV
W/cm2
0
0.006
0.03
0.114
0.425
1.029
1.374
1.531
1.604
1.677
1.659
1.614
1.54
1.264
0.556
0.12
0.032
0.006
0
UVA
J/cm2
0
0
0.016
0.086
0.313
0.649
0.879
0.986
1.026
1.062
1.086
1.026
0.946
0.752
0.399
0.079
0.016
0
0
UVB
J/cm2
0
0
0
0.037
0.231
0.51
0.708
0.797
0.843
0.877
0.856
0.865
0.835
0.654
0.312
0.046
0
0
0
UVC
J/cm2
0
0
0
0
0.009
0.022
0.033
0.038
0.041
0.044
0.042
0.044
0.042
0.031
0.012
0
0
0
0
Table 6 - Measurement of energy and irradiance from a bank of five 600 W/inch
lamps as a function of lateral position
CONCLUSIONS
The first observation, one that is not unsurprising, is that the UV energy distribution
is symmetric about the centerline of the center lamp (#3). Secondly, we can see that
the distribution is no longer Gaussian as was the case for a single lamp. The final
observation requires a basic knowledge of the lamp dimensions. The lamp housing of
the Fusion Systems I600M UV lamps used in this experiment is 10.5 inches. The
lamps were placed side-by-side with no space between the housings. This implies the
distance from the centerline of lamp #3 to the outer edge of lamp #1 (or #5) is (2.5) x
(10.5)=26.25. At the lamp height of 11 the UV energy decreases rapidly beyond
the edge of the bank of lamps as shown in figure 13.
108
UVV
J/cm2
0
0.005
0.093
0.341
1.125
2.454
3.301
3.731
3.898
4.031
3.939
3.736
3.557
2.872
1.428
0.323
0.096
0.011
0

Lateral UVV Dose Uniformity for a Row of F600

Lamps
1 row - V Bulb
lamp lamp lamp lamp lamp

1
3
5
2
4
4.5
4
UVV Dose (J/ cm^2)
3.5
3
2.5
2
1.5
1
0.5
0
-80
-60
-40
-20
-0.5 0
20
40
60
Position from the Centerline of the Middle Lam p (Inches)
Figure 12.5 Measured UV Energy Bank of five 600 W/inch Fusion UV lamps
109

vi. Experiment 12 Testing the additive law for UV energy using
two 600W/inch lamps
Objective: The objective of the experiment is to test the hypothesis that the total
UV energy at any point from multiple light sources can be calculated as the sum of
the energy form each contribution light source.
Approach: Two lamps will be used for this experiment. The distance between
lamps will be progressively increased and the irradiance and energy will be
measured in the lateral direction (perpendicular to the direction of travel).
Experiment #12 Testing the additive nature of UV energy from multiple light sources using two
600 W/ inch UV lamps
y
on
Radiometric data was collected at 10.5 inch
lateral intervals
on
Lamp 3
Fixed
position
Lamp 1
Variable
position
Lamp width = 10.5 inches

h=height
-31.5
-21
-10.5
centerline position of the stationary lamp

x=location of the radiometer-dosimeter measurement
y=lamp separation (centerline to centerline)
h=height of the lamp from the surface
Figure 13 UV lighting set-up for experiment 12
110
10.5
21
31.5
42
51.5
62
Values
0 inches (fixed)
-31.5, -21, -10.5, 0, 10.5, 21, 31.5, 42, 51.5, 62 inches
10.5, 21, 31.5, 42 inches
11 inches (fixed)

INPUT FACTORS
1) Type of experimental design or comparative strategy: ladder study with 2 variables
LEVEL
A)
lamp height from surface
inches
11
B)
conveyor speed
fpm
14
C)
lamp type
na
1 row, gallium metal halide V

bulb, std reflector

UNITS

34
LEVELS

A)
x location (lateral position) of

the radiometer-dosimeter
measurement
inches
In intervals of 10.5 from -31.5 to

52.5
B)
y- separation distance between the

lamps (centerline-to-centerline)
inches
10.5, 21, 31.5, 42

TEST METHOD TO USE
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
111

RESULTS
The position of the spacing between the stationary and adjustable position lamp (y)
and the position (x) of the radiometer-dosimeter are noted in table 7 below. The width
of each lamp is 10.5 inches. A lamp (center-to-center) distance of 10.5 inches implies
the two lamps are side-by side with no space between the lamps.
UVA
Run #
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
Position (x) of of
the RadiometerDosimeter
Lamp Separation
(relative to the
(y) Center to
Center (inches) stationary lamp) W/cm2
10.5
-31.5
0
10.5
-21
0.009
10.5
-10.5
0.078
10.5
0
0.367
10.5
10.5
0.365
10.5
21
0.096
10.5
31.5
0.011
10.5
42
0
10.5
52.5
0
21
-21
0.007
21
-10.5
0.069
21
0
0.314
21
10.5
0.164
21
21
0.273
21
31.5
0.126
21
42
0.012
21
52.5
0
31.5
-21
0
31.5
-10.5
0.057
31.5
0
0.291
31.5
10.5
0.11
31.5
21
0.065
31.5
31.5
0.257
31.5
42
0.099
31.5
52.5
0.01
42
-21
0.007
42
-10.5
0.065
42
0
0.28
42
10.5
0.13
42
21
0.015
42
31.5
0.041
42
42
0.237
42
52.5
0.09
42
63
0.014
UVB
UVC
UVV
UVA
UVB
UVC
UVV
W/cm2
0
0
0.074
0.342
0.315
0.068
0
0
0
0
0.061
0.299
0.141
0.245
0.101
0
0
0
0.052
0.282
0.092
0.052
0.221
0.07
0
0
0.06
0.276
0.108
0.011
0.0322
0.203
0.066
0
W/cm2
0
0
0.004
0.021
0.016
0.003
0
0
0
0
0.003
0.019
0.007
0.013
0.005
0
0
0
0.003
0.018
0.005
0.002
0.011
0.003
0
0
0.003
0.017
0.006
0
0.001
0.01
0.003
0
W/cm2
0
0.027
0.248
1.254
1.374
0.326
0.032
0
0
0.019
0.204
1.089
0.556
1.071
0.461
0.036
0
0.015
0.173
1.002
0.354
0.218
1.015
0.347
0.028
0.018
0.197
0.946
0.418
0.048
0.136
0.9
0.309
0.041
J/cm2
0
0.013
0.189
0.843
0.796
0.236
0.016
0
0
0.006
0.146
0.683
0.409
0.586
0.296
0.016
0
0
0.123
0.622
0.263
0.163
0.586
0.243
0.013
0.006
0.139
0.586
0.303
0.033
0.089
0.543
0.155
0.026
J/cm2
0
0
0.155
0.729
0.675
0.168
0
0
0
0
0.113
0.599
0.333
0.501
0.227
0
0
0
0.088
0.556
0.214
0.113
0.497
0.176
0
0
0.109
0.531
0.24
0.016
0.063
0.455
0.226
0
J/cm2
0
0
0.006
0.041
0.031
0.004
0
0
0
0
0.004
0.035
0.014
0.023
0.009
0
0
0
0.003
0.032
0.008
0.003
0.022
0.006
0
0
0.004
0.03
0.1
0
0
0.02
0.005
0
J/cm2
0
0.067
0.611
2.843
2.916
0.82
0.088
0
0
0.046
0.473
2.3
1.364
2.26
1.09
0.093
0
0.032
0.408
2.081
0.852
0.576
2.313
0.879
0.073
0.041
0.458
1.958
0.961
0.146
0.361
2.049
0.79
0.117
Table 7 - Testing the additive law for UV energy using two 600 W/inch lamp
112

Output of Two Fusion F600 UV Lamps as a Function of Lamp-toLamp Centerline Distance

Distance Between
Lamp Centerlines
3.5
U V V E n e r g y (J / c m ^ 2 )
10.5
21
2.5
31.5
42
2
1.5
1
0.5
0
-42.0 -31.5 -21.0 -10.5 0.0 10.5 21.0 31.5 42.0 52.5 63.0 73.5
-0.5
Radiometer-Dosimeter Position (relative to the staionary lamp)
Figure 14 Output from two 600 W/inch UV lamps

CONCLUSIONS
The total UVV energy from two parallel Fusion 600 W/in lamps is shown in figure
14. Since the light rays are highly collimated, changes in the spacing of the lamps
have a pronounced effect on the distribution of energy. The area under the energy
curve remains constant for all lamp configurations.
113

vii. Experiment 13 Effect of UV energy and irradiance level on the surface
temperature of the coating
Objective: The objective of the experiment is to understand the effect of UV
energy and irradiance levels on the surface heating effect which occurs during UV
irradiation with high power UV curing lamps.
Approach: It is important to control the surface temperature of liquid coatings and
resins containing flammable components for process safety reasons. The maximum
temperature reached during the cure process should be maintained below the lowest
flash point of the components in the mixture. In this experiment, the lighting
conditions were systematically varied to provide a broad range of UV energy ( 2
46 J/cm2 ) and UV irradiance ( 0.7 4.6 W / cm2 ). Three rows of lamps were
employed within the UV conveyor to create a large heating effect. A metal Q-panel
was used as the substrate.
INPUT FACTORS
1) Type of experimental design or comparative strategy: full factorial
LEVEL
A)
lamp type
Fusion 600 W/inch lamp
B)
# rows of lamps within the

conveyor
three rows
C)
substrate
steel Q-panel
na
2) How many independent factors are to be studied? 4 How many Tests

conducted? 32
UNITS
LEVELS
will
be

A)
line speed of the conveyor
fpm
5, 10 , 20, 40
B)
bulb type
na
three rows of gallium (V bulbs),

two row of gallium (V bulb) plus
one row of iron (D bulb)
C)
bulb position within the reflector
na
standard position, 209 position
D)
lamp height from the substrate
inches
6, 15
114

TEST METHOD TO USE
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
C)
Surface Temperature of the

Q-panel exiting the UV
conveyor
RESULTS
UVA
Run #
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Line
Speed
5
10
20
40
5
10
20
40
5
10
20
40
5
10
20
40
5
10
20
40
5
10
20
40
5
10
20
40
5
10
20
40
Lamp
Height
6
6
6
6
15
15
15
15
6
6
6
6
15
15
15
15
6
6
6
6
15
15
15
15
6
6
6
6
15
15
15
15
Bulb Type Reflector W/cm2

3V
STD
0.499
3V
STD
0.478
3V
STD
0.478
3V
STD
0.499
3V
STD
0.174
3V
STD
0.138
3V
STD
0.171
3V
STD
0.171
2V, 1D
STD
1.316
2V, 1D
STD
1.221
2V, 1D
STD
1.221
2V, 1D
STD
1.316
2V, 1D
STD
0.311
2V, 1D
STD
0.261
2V, 1D
STD
0.256
2V, 1D
STD
0.248
3V
209
0.683
3V
209
0.67
3V
209
0.67
3V
209
0.683
3V
209
0.235
3V
209
0.18
3V
209
0.18
3V
209
0.235
2V, 1D
209
1.85
2V, 1D
209
1.856
2V, 1D
209
1.856
2V, 1D
209
1.85
2V, 1D
209
0.527
2V, 1D
209
0.501
2V, 1D
209
0.501
2V, 1D
209
0.424
UVB
W/cm2
0.483
0.397
0.397
0.483
0.189
0.137
0.195
0.195
0.426
0.402
0.402
0.426
0.207
0.195
0.136
0.127
0.596
0.558
0.558
0.596
0.268
0.178
0.178
0.268
0.505
0.517
0.517
0.505
0.252
0.235
0.225
0.183
UVC
W/cm2
0.037
0.023
0.023
0.037
0.022
0.011
0.022
0.022
0.028
0.024
0.024
0.028
0.024
0.024
0.011
0.012
0.034
0.038
0.038
0.034
0.027
0.013
0.013
0.027
0.037
0.04
0.04
0.037
0.029
0.026
0.027
0.023
UVV
W/cm2
1.839
1.771
1.771
1.839
0.432
0.414
0.414
0.414
1.891
1.784
1.784
1.891
0.386
0.412
0.38
0.375
2.396
2.29
2.29
2.396
0.629
0.582
0.582
0.629
2.215
2.159
2.159
2.215
0.611
0.563
0.579
0.561
UVA
J/cm2
8.004
3.712
1.966
0.983
4.305
2.166
1.119
0.556
12.33
5.855
3.155
1.526
6.884
3.378
1.662
0.826
8.821
4.795
2.199
1.162
5.362
2.389
1.216
0.606
13.34
6.911
3.529
1.739
8.097
3.635
1.926
0.976
UVB
J/cm2
6.871
3.123
1.696
0.826
4.203
2.072
1.067
0.548
6.892
3.021
1.696
0.801
4.486
2.148
1.029
0.501
8.508
4.541
2.05
1.101
5.735
2.443
1.24
0.62
8.352
4.199
2.131
1.08
5.984
2.477
1.316
0.654
UVC
J/cm2
0.493
0.201
0.111
0.058
0.357
0.167
0.089
0.045
0.512
0.213
0.117
0.055
0.394
0.184
0.085
0.039
0.575
0.303
0.138
0.076
0.485
0.182
0.094
0.047
0.656
0.315
0.161
0.084
0.55
0.201
0.114
0.057
UVV
J/cm2
26.96
12.61
6.559
3.254
13.21
6.812
3.495
1.713
21.99
10.42
5.553
2.731
11.74
5.703
2.875
1.44
28.95
15.38
7.003
3.657
16.25
7.694
3.886
1.928
23.87
12.08
6.277
3.128
13.64
6.212
3.206
1.655
TOTAL
W/cm2
2.858
2.669
2.669
2.858
0.817
0.7
0.802
0.802
3.661
3.431
3.431
3.661
0.928
0.892
0.783
0.762
3.709
3.556
3.556
3.709
1.159
0.953
0.953
1.159
4.607
4.572
4.572
4.607
1.419
1.325
1.332
1.191
Table 8 Effect of lighting configuration and line speed on UV energy, irradiance,

and surface temperature
115
TOTAL
J/cm2
42.328
19.646
10.332
5.121
22.075
11.217
5.77
2.862
41.724
19.509
10.521
5.113
23.504
11.413
5.651
2.806
46.854
25.019
11.39
5.996
27.832
12.708
6.436
3.201
46.218
23.505
12.098
6.031
28.271
12.525
6.562
3.342
T Exit (F)
171.8
134.6
105.5
91.2
126.8
108.5
93.2
86.8
172.2
134.4
113.1
94.2
132.9
108
99.4
95.6
183
146
118
103
138
115
104
90
160.4
138.3
112.5
98.5
138
112
97
97

UVA Dose Data
16
14
3V,6",Std Reflector
Energy (J/cm2)
12
3V,15",Std Reflector
10
2V+1D,6",Std Reflector
3V,6",209 Reflector
3V,15",209 Reflector
2V+1D,6",209 Reflector
4
2
0
0
10
20
30
40
50
Line Speed
UVV Dose Data

35
30
3V,6",Std Reflector
Energy (J/cm2)
25
20
3V,6",209 Reflector
15
10
5
0
0
10
20
30
40
50
Line Speed
Exit Temperture (degrees F)
Conveyor Exit Temperature (degrees F)
190
180
170
3V,6",Std Reflector
160
150
140
130
3V,6",209 Reflector
120
110
100
90
80
0
10
20
30
Line Speed
116
40
50

Figure 15 Effect of lamp type, lamp height, line speed, and reflector type on UV
energy, irradiance, and exit temperature
20 0
Exit Temperature (F)
18 0
R 2 = 0.96
16 0
14 0
12 0
10 0
80
60
40
20
0
0
10
20
30
40
50
Total Energy (J/cm2)
200
Exit Temperature (F)
180
R 2 = 0.16
160
140
120
100
80
60
40
20
0
0
Irradiance Level (W/cm2)
Figure 16 Correlation of UV energy and irradiance with the surface temperature of

a part being cured with UV lamps
CONCLUSIONS
Under the test conditions used in experiment 13 the substrate temperature heating
effect is well correlated with the total UV energy. The exit temperature of the
substrate is not well correlated with UV irradiance levels.
117

viii. Experiment 14 Validation of the cosine law for
non-perpendicular exposure conditions
Objective: The objective of the experiment is to measure changes in UV energy
and irradiance levels due to the angle of incidence of the light rays.
Approach: A radiometer-dosimeter was placed under a UV lamp at two angles of
incidence ( = 0 flat, and = 60 angled) as shown below in figure 17.
Experiment #14 Validation of the cosine law for non-perpendicular exposure conditions
PowerPuck
=60
Figure 17 Validation of the cosine law for non-perpendicular exposure conditions
UNITS
LEVELS

A)
angle of incidence
degrees
0, 60

TEST METHOD TO USE
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
118

RESULTS
Angle
=0
=60
ratio
arc cosine
UVA
0.642
0.334
ENERGY (J / CM2)
UVB
UVV
0.256
1.283
0.102
0.651
0.5202
58.7
0.3984
66.5
0.5074
59.5
INTENSITY (W/CM2)
UVA
UVB
UVV
0.06
0.028
0.122
0.038
0.016
0.066
0.6333
50.7
0.5714
55.2
0.5410
57.2
Table 9 - Validation of the cosine law for non-perpendicular exposure conditions

CONCLUSIONS
The UV energy and irradiance on a surface that is not perpendicular to the light
source varies according to the cosine law.
=E x cos()
eqn 14.1
ix. Experiment 15 Effect of lamp height on UV energy

and irradiance
Objective: The objective of the experiment is to understand the effect of lamp
distance from the curing material on the UV energy and irradiance received at the
surface.
Approach: A single Fusion F450 lamp is energized for one minute above a
radiometer-dosimeter. The distance between the lamp and the radiometer-dosimeter
is systematically varied.
2 inches
4 inches
FOCAL PLANE
8 inches
21 inches
33 inches
Figure 18 Schematic of lighting set-up for experiment 15

119

INPUT FACTORS
LEVEL
A)
lamp type
na
Fusion F450 lamp, V bulb
B)
exposure time
minutes
2) How many independent factors are to be studied?

UNITS

LEVELS

A)
lamp height (h)
inches
2, 4, 8, 21, 33.5

TEST METHOD TO USE
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
RESULTS
Height (inches)
2
4
8
21
33.5
Irradiance
UVA
0.179
0.598
0.183
0.028
0.023
UVB
0.066
0.335
0.078
0.013
0.025
UVC
0.006
0.021
0.006
0.001
0.030
UVV
0.903
2.177
0.764
0.113
0.060
Energy
UVA
11.440
34.920
10.002
1.578
1.104
UVB
3.780
14.690
4.310
0.726
0.768
UVC
0.240
0.670
0.290
0.000
0.105
UVV
58.340
130.700
42.620
6.534
3.210
Table 10 UV Energy and irradiance measurements at various lamp heights static

one minute exposure
120

UV Irradiance and Energy as a Function of Distance from
the Light Source
2.5
120
Energy (J/cm2)
100
Irradiance (W/cm2)
80
1.5
60
40
0.5
20
0
Irradiance (W/cm2)
UVV Energy (J/cm2)
140
10
20
30
40
Distance (inches)
Figure 19 - UV Energy and irradiance measurements at various lamp heights static

one minute exposure
Distance Irradiance Energy
2
2
(h)
(W/cm ) (J/cm )
2
0.903
58.34
4
2.177
130.7
8
0.764
42.62
21
0.113
6.534
33.5
0.06
3.21
1/h2
0.25
0.0625
0.015625
0.002268
0.000891
Table 11 The irradiance from a point source of light varies with the square of the
distance from the source
UV Irradiance (W/cm2)
Inverse Square Law for Irradiance

2.5
-2.32051E-08
in focus
2
1.5
1
inside the focal plane
0.5
0
0
0.05
0.1
0.15
0.2
1 / (lamp height)
0.25
0.3
Figure 20 Inverse square law validation

CONCLUSIONS
As noted in figures 19 and 20 the inverse square law is validated for the UV lamps at
distances greater the focal length of the UV reflector.
121

x. Experiment 16 Evaluation of dichroic reflectors
Objective: The objective of the experiment is to evaluate the use of dichroic
reflectors to lower the surface temperature of the substrate.
Approach: Direct comparison of a standard reflector and a dichroic reflector using
a Q-panel steel substrate.
INPUT FACTORS
LEVEL
A)
conveyor speed
fpm
15
B)
lamp type
na
two rows of gallium lamps, plus

one row of iron lamps 600
W/inch Fusion
C)
lamp height
inches
2) How many independent factors are to be studied?

UNITS

LEVELS

A)
reflector type
na
standard reflector, dichoric

reflector

TEST METHOD TO USE
RESPONSE VARIABLE
NAME
A)
surface temperature
RESULTS
Run #
33
35
Line
Speed
15
15
Lamp
Height
4
4
UNITS
F
STD
dichroic
T Exit (F)
142
140
Table 12 Evaluation of dichroic reflectors

CONCLUSIONS
The dichroic cold mirror reflector did not appear to reduce the surface temperature.
122

c. Studies of the reflectivity of the mold surface
Experiment 17 Effect of reflectivity on cure
Objective: The objective of the experiment is to evaluate the effect of the mold
reflectivity on the degree of cure of a photocurable white gel coat.
Approach: Direct comparison of the extent of cure on a polished stainless steel
mold and a composite mold with an orange polyester tooling gel coat. As noted in
figure 21 below there are several possibilities for the interaction of UV light with
the coating and mold surface. Case 1 the light is completely absorbed within the
coating film. This case is unacceptable since it would result in incomplete thru-cure
of the coating. Case 2 the light is partially absorbed in the coating film. Some of
the light passes through the coating film and is absorbed within the mold surface.
Case 3 - the light is partially absorbed in the coating film. A portion of the light
passes through the coating film and is absorbed within the mold surface. A portion
of the light reaching the mold surface is reflected back into the coating film further
promoting UV curing of the coating.
Case 1
The incident light
is absorbed
within the
coating film
I0
I0
IA
Coating
Case 2
The incident light is
partially absorbed
within the coating
film. The light that is
transmitted through
the film is absorbed
by the mold
IT
Case 3
The incident light is
partially absorbed
within the coating
film. The light that is
transmitted through
the film is reflected by
the mold back into the
coating film
I0
IA
IA
IT
IR
Mold
I0
IA
IT
IR
= incident light
= absorbed light
= transmitted light
=reflected light
Figure 21 Interactions of UV light with the coating and mold surface

123
IA
IA

INPUT FACTORS
UNITS
How many tests will be conducted? 7

LEVELS

A)
mold type-color
na
polyester molds
(1) orange
(2) green
(3) black
(4) white
(5) silver-reflective Al flake pigment
other molds
(6) polished aluminum
(7) polished stainless steel

TEST METHOD TO USE
A)
RESPONSE VARIABLE
NAME
Mold reflectance
UNITS
%
124
Perkin-Elmer Lambda 6 UV
spectrophotometer with an integrating
sphere accessory

RESULTS
Multi-colored composite
Total %R (specular reflectance included)
Figure 22 UV-Visible reflection from polyester tooling gel coat various colors
Stainless Steel, Aluminum, and

Reflective Composite
Total %R (specular reflectance included)
Figure 23 UV-Visible reflection from metal molds and aluminum flake filled
polyester tooling gel coat.
125

Run #
1
2
Lamps
1 row V, 1
row D
1 row V, 1
row D
Lamp
Height
(inches)
Coating
Thickness
(mils)
Line
Speed
(fpm)
5-6
8-12
7.5
Coating
white,
UPR
white,
UPR
20
7.5
3 rows V
white,
UPR
3 rows V
white,
UPR
12
4 rows V
white,
UPR
12
3 rows V,
1 row D
white,
UPR
7
8
3 rows V,
1 row D
1 row V, 1
row D
5
9
white,
UPR
white,
UPR
12
12
12
Mold
polished
stainless steel
polished
stainless steel
composite mold
with orange
tooling gel coat
composite mold
with orange
tooling gel coat
composite mold
with orange
tooling gel coat
composite mold
with orange
tooling gel coat
composite mold
with orange
tooling gel coat
polished
stainless steel
UVV
(J/cm2)
UVA
(J/cm2)
Result
17.8
13.1
coating is well cured
17.8
13.1
7.4
2.2
12.1
3.9
16.1
5.2
22.4
12.1
15.5

coating is dry on the top surface but
there is some slight haze on the mold
following de-mold indcating
incomplete thru-cure
12.8
9.6
coating is dry on the top surface but

wet against the mold
the coating film is rubbery, not
completely cured, marginal surface
gloss
the coating film is rubbery, not
completely cured, marginal surface
gloss - better than run 4
Table 13 White UV curable gel coat results on a reflective and non-reflective mold
( V lamp=gallium metal halide,
D lamp=iron metal halide)
CONCLUSIONS
The reflectance characteristics of various pigmented polyester tooling gel coats is
presented in figure 22. Only the white tooling gel coat has any reflectance below 400
nm. As noted in figure 23 the polished stainless steel, polished aluminum, and
aluminum flake filled polyester mold exhibit significant reflection in the wavelength
range of interest for BAPO photoinitiators (370 420 nm). The data in table 13
provides a practical energy requirement to cure the film. The extent of cure is highly
dependent upon the film thickness as might be expected. A direct comparison of the
non-reflective orange composite mold and the reflective polished stainless steel mold
is given in runs #7 and #8. The coating cured on the stainless steel mold is better
cured than the coating on the orange composite mold when the UV energy is
approximately equal. Separate tests with the white composite mold resulted in slightly
better coating cure than the orange mold, but not as well as the stainless steel mold.
126

d. Integrated mathematical model for a UV conveyor line (experiment
18)
i. Mathematical model development
The results provided in the preceding experiments have provided the components of
a mathematical model to predict UV energy and irradiance levels. An integrated
model capable predicting UV exposure levels for a conveyor system with multiple
banks (rows) of UV curing lamps will now be developed. Several simulations will be
conducted using a software version of the model prepared by the author. The model
will be validated using with actual process data from an industrial scale UV conveyor
system discussed in Chapter 7.
Consider a line with conveyor
Y-direction
Direction of travel
h-direction
Lamp height
X-direction
Perpendicular to travel
Figure 24 Schematic of a conveyor line with the coordinate system indicated
The distribution of UV energy, E (J/cm2) and irradiance (W/cm2) from a high

powered industrial UV lamp (Fusion UV Systems 6000 watt lamp) were shown from
experiment 10 to be approximated in the x-direction according to a Gaussian
distribution:
127

E ( x) E e
( x ) 2 / 2 E 2
I ( x) I e ( x )
Where E,
eqn. 18.1
/ 2 I 2
eqn. 18.2
I, E, and I are the pre-exponential and dispersion parameters
developed in experiment 10. An additional finding of experiment 10 is that the preexponential and dispersion parameters are dependent on the lamp height, h.
(h)
( h)
eqns. 18.3, 18.4
Combining eqns. 18.1-18.4 we obtain
E ( x, h) E (h) e[ ( x )
I ( x, h) I (h) e[ ( x )
/ 2 E ( h ) 2 ]
/ 2 I ( h ) 2 ]
eqn. 18.5
eqn. 18.6
The functional form of the lamp height (h) dependence on the pre-exponential
multiplier, , and the dispersion term, in equations 18.3 18.6 was chosen to be a
simple quadratic model.
128

(h) 0 1h 2h 2
(h) 0 1h 2h 2
To illustrate the technique to model the height dependence of
(h) and (h), an
example is provided below using the UVV band irradiance level as the response
variable. The irradiance level for each UV band (UVV, UVA, UVB, UVC) was
collected at three lamp height settings (5, 9, 15). The data was fitted to the model
shown in equation 18.2 and summarized in the table below.
Model Parameters for the UVV band to predict irradiance levels
from a single 600W/inch Fusion UV lamp
Dispersion parameter
Lamp
Pre-exponential term
Height h
5
5.1156
18.17575
9
6.58698
10.49976
15
8.38082
7.07839
(h) 33.84 3.8073h 0.1349h 2

(h) 2.9665 0.4643h 0.0069h 2
The pre-exponential multiplier decreases with increasing lamp height and the
dispersion term increases with increasing lamp height as expected see figure 25.
129

20
h) = 0.134h2 - 3.807h + 33.84
18
Parameter Value
16
14
12
10
8
6
4
(h) = -0.006h2 + 0.464h + 2.966
2
0
0
5
10
15
h = Lamp Height (inches)
20
Figure 25 Lamp height dependence of the pre-exponential multiplier and dispersion

parameter
Next, we will add a term to the model to account for the line speed of the conveyor
system
v(fpm).
A finding of experiment 7 is that the energy, E (J/cm2) varies with
the inverse of the line speed. The irradiance, I (W/cm2) is independent of the line
speed.
1
v
I v
The reference line speed, vref, used to produce the results for experiment 10 was 14
fpm.
A term will now be added to equation 18.5 to allow computation of UV energy for
any line speed, V. The instantaneous photon flux (i.e. irradiance) does not depend on
line speed.
130

v
[ ( x ) 2 / 2 E ( h ) 2 ]
E ( x, h, v) E (h) e
vref
eqn. 18.7
Based on the findings of experiment 14 a term will now be added to equation 18.7 to
adjust the predicted UV energy and irradiance level at non-normal angles of
incidence.
v
[ ( x ) 2 / 2 E ( h ) 2 ]
E ( x, h, v) cos() E (h) e
vref
eqn. 18.8
[ ( x ) 2 / 2 I ( h ) 2 ]
I ( x, h) cos() I (h) e
eqn. 18.9
The UV energy and irrandiance at a point in the x direction (see fig. 24) from a
conveyor with multiple lighting sources is the sum of the energy from each source
ETOT E1 E2 ...
I TOT I1 I 2 ...
Ei
eqn. 18.10
i 1
Ii
i 1
eqn. 18.11
The UV irradiance at a point in the x-direction is not cumulative.
The UV energy for a bank of two lamps then may be determined from
131

ETOT ( x, h, v, )
v
vref
[ ( 1 x ) 2 / 2 E 1 ( h ) 2 ]
[ ( 2 x ) 2 / 2 E 2 ( h ) 2 ]
cos(
)
[
(
h
)
e
(
h
)
e
]
E1
E2
eqn. 18.12
A common equipment configuration for an industrial curing line includes multiple

rows of UV lighting (figure 26) . High levels of UV energy are often needed to
achieve satisfactory cure of optically thick materials such as pigmented gel coats.
Multiple rows of lighting may be needed for one of two reasons:
1)
to meet the energy requirements needed to complete the

photopolymerization while maintaining acceptable conveyor line speed,
and/or
2)
to allow for different spectral power distributions required to activate

multiple photoinitiators such as a surface cure photoinitiator (shorter
wavelength required) and a through-cure photoinitiator (longer wavelength
required).
The generalized form of the model for n rows of m lamps within each row is
given below:
v
ETOT ( x, h, v, ) nrows
vref
m
[ ( i x ) 2 / 2 Ei ( h ) 2 ]
cos(
(
h
)
e
i
Ei
i 1
eqn. 18.13
I TOT ( x, h, ) cos() i I i (h) e[ ( i x )

i 1
where i is the centerline position of lamp i .

132
/ 2 Ii ( h ) 2 ]
eqn. 18.14

Y-direction
Direction of travel
h-direction
Lamp height
X-direction
Figure 26 Schematic of an industrial UV curing line

The complete mathematical model to predict the UV energy and irradiance
levels is given in equations 18.13, and 18.14 respectively. The model will now
be used in the following four simulations.
ii. Simulation 1 - Validation of the mathematical model

The purpose of the first simulation is to validate the predictive capability of
the model. The lighting configuration will be designed to support a four foot
wide conveyor with two rows of lamps. Each row will contain five lamps. The
first row will consist of iron doped metal halide (D-bulb) 600 W/inch Fusion
UV lamps. The second row will consist of gallium doped metal halide (V133

bulb) 600 W/inch Fusion UV lamps. Each lamp is 10.5 inches in width. The
lighting system used to validate the predictive model is shown in figure 27.
Figure 27 - Ten lamp UV curing conveyor Two rows of five lamps

Energy (J/cm2) - UVA
Energy (J/cm2) - UVB
Energy (J/cm2) - UVC
Energy (J/cm2) - UVV
UV Energy Distribution
18.0
Energy (J/cm2 )
16.0
14.0
Line Speed: 5 fpm

Angle : 0 degrees
Lamp Height: 7.5
inches
Lamp Spacing: 0
inches
12.0
V Lamps: 1 row
D Lamps: 1 row
10.0
8.0
6.0
4.0
2.0
0.0
300
288
276
264
252
240
228
216
134
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12
Position from the left edge (inches)

Irradiance (W/cm2) - UVA
Irradiance Profile
Irradiance (W/cm2) - UVB

Irradiance (W/cm2) - UVC
Irradiance (W/cm2) - UVV
Irradiance (W/cm2)
2.50
2.00
1.50
1.00
0.50
0.00
300
288
276
264
252
240
228
216
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12
Position from the left edge(inches)
Figure 28 - Validation of the predictive model to estimate UV energy and irradiance

levels (predicted values shown)
Energy
(J/ cm2)
Irradiance
(W/cm2)
PREDICTED VALUES
UVV UVA UVB UVC
16.6
13.0
5.2
0.26
MEASURED VALUES
UVV UVA UVB UVC
17.8
13.0
5.6
0.38
2.1
2.2
1.9
0.57
0.039
1.8
0.52
0.032
The predicted values the key UV bands (UVV, UVA, UVB) are within 10%
of the measured values.
iii. Simulation 2 - The effect of lamp spacing on the UV energy and irradiance
level
The purpose of the simulation is to study the effect of lamp spacing on the level and
uniformity of the UV light energy delivered to the surface. The lighting configuration
will be designed to support a ten foot wide conveyor with up to three rows of lamps.
Each row will contain eleven lamps. The first row will consist of iron doped metal
halide (D-bulb) 600 W/inch Fusion UV lamps. Subsequent rows will consist of
gallium doped metal halide (V-bulb) 600 W/inch Fusion UV lamps. Each lamp is
135

10.5 inches in width. The lamp spacing for simulation 1 (figure 28) was zero inches.
This is the optimum condition to maximize energy delivery if equipment costs are not
considered. By incorporating space between the lamps within a row it should be
possible to cover more area with a limited number of lamps. The spacing between the
lamps is gradually increased in figure 29 from 3 inches to 6 inches, and finally 12
inches. The result of the increasing spacing between the lamps is a commensurate
increase in coverage area, decrease in energy and decrease in the uniformity of UV
energy and irradiance levels. The results are summarized below:
Spacing Between
Relative Area
Relative Energy
Lateral Variation in
Lamps
Illuminated
Level
Energy
0 inches
100%
100%
0%
3 inches
137%
78%
3.1%
6 inches
181%
50%
24.6%
12 inches
244%
47%
105%
Table 1 Effect of lamp spacing on UV energy level and uniformity

Based on the dispersion pattern of these lamps at the height of 7.5 inches the spacing
between lamps should be limited to less than 3-4 inches to maintain adequate
uniformity.
136

14.0
Energy (J/cm2)
12.0
10.0
Line Speed: 5 fpm

Angle : 0 degrees
Lamp Height: 7.5 inches
Lamp Spacing: 3 inches
V Lamps: 1 row
D Lamps: 1 row
8.0
6.0
4.0
2.0
0.0
300
288
276
264
252
240
228
216
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12

Energy (J/cm2 )
12.0
Line Speed: 5 fpm

Angle : 0 degrees
10.0
V Lamps: 1 row
D Lamps: 1 row
8.0
6.0
4.0
2.0
0.0
300
288
276
264
252
240
228
216
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12

Energy (J/cm2 )
12.0
Line Speed: 5 fpm

Angle : 0 degrees
10.0
V Lamps: 1 row
D Lamps: 1 row
8.0
6.0
4.0
2.0
0.0
300
288
276
264
252
240
228
216
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12
Figure 29 - The effect of lamp spacing on the level and uniformity of UV energy
137

iv. Simulation 3 The effect of a lamp failure on the irradiance and energy
distribution
The modular microwave UV lamps with electrodless bulbs used here are reported to
be highly reliable according to the manufacturer. The mean time to failure is greater
than 2000 hours. The purpose of the simulation is to study the effect of a lamp failure
on the level and uniformity of the UV light energy delivered to the surface. of the
model. The lighting configuration will be designed to support a ten foot wide
conveyor with up to two rows of lamps. Each row will contain eleven lamps. The first
row will consist of iron doped metal halide (D-bulb) 600 W/inch Fusion UV lamps.
The second row will consist of gallium doped metal halide (V-bulb) 600 W/inch
Fusion UV lamps. For the purposes of the simulation, lamp #8 on the second row is
switched off within the predictive model software to simulate a gallium lamp failure
as indicated in figure 30.
The results of the simulation indicate a dramatic localized decrease in energy and
irradiance level near the position of the lamp failure. The UVV energy and the
irradiance level have decreased by 35%. If this were an actual production curing
station it would be important to detect lamp failure immediately. Failure to correct the
situation could result significant quality problems arising from poorly cured coating
or laminate.
138

18.0
Energy (J/cm2 )
16.0
14.0
Line Speed: 5 fpm

Angle : 0 degrees
Lamp Height: 7.5
inches
Lamp Spacing: 0
inches
12.0
V Lamps: 1 row
D Lamps: 1 row
10.0
8.0
6.0
4.0
2.0
0.0
300
288
276
264
252
240
228
216
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12
Irradiance (W/cm2) - UVA
Irradiance Profile
Irradiance (W/cm2) - UVB

Irradiance (W/cm2) - UVC
Irradiance (W/cm2) - UVV
Irradiance (W/cm2)
2.50
2.00
1.50
1.00
0.50
0.00
300
288
276
264
252
240
228
216
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12
Position from the left edge(inches)
Row of V lamps
(iron-metal halide)
Y-direction
Direction of travel
Row of D lamps
(iron-metal halide)
h-direction
Lamp height
Lamp #8 has failed
in the simulation
X-direction
Figure 30 - The impact of a lamp failure on the UV energy and irradiance distribution
139

v.
Simulation 4 Effect of lamp height in energy level and uniformity
The purpose of the simulation is to study the effect of a lamp height on the level and
uniformity of the UV light energy delivered to the surface. of the model. The lighting
configuration will be designed to support a ten foot wide conveyor with up to two
rows of lamps. Each row will contain eleven lamps. The first row will consist of iron
doped metal halide (D-bulb) 600 W/inch Fusion UV lamps. The second row will
consist of gallium doped metal halide (V-bulb) 600 W/inch Fusion UV lamps.
The results presented in figure 31 show two simulations for the UV energy levels at a
lamp height of 3 inches and at 20 inches. The lamps are spaced 10.5 inches apart in
both simulations. Clearly the lamp height and dispersion pattern must be considered
to provide adequate uniformity of the UV lighting conditions.
140


8.0
Energy (J/cm2 )
7.0
6.0
5.0
Line Speed 5
Ref. Line Speed
angle of incidence
lamp height
lamp spacing
lamp width
4.0
14
0
20
10.5
10.5
3.0
V Lamps
#Rows
1
2.0
D Lamps
1.0
0.0
300
288
276
264
252
240
228
216
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12

18.0
Energy (J/cm2)
16.0
14.0
Line Speed 5
Ref. Line Speed
angle of incidence
lamp height
lamp spacing
lamp width
V
V
h
ls
lw
14
0
3
10.5
10.5
12.0
10.0
8.0
V Lamps
#Rows
1
D Lamps
6.0
4.0
2.0
0.0
300
288
276
264
252
240
228
216
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12
Figure 31 - The effect of lamp height on the level and uniformity of UV energy
141

Chapter VI Process Optimization Defining the Process Window
Chapter VI Process Optimization - Defining the Process Window
Balancing Safety, Throughput, Environmental Impact,
Capital Investment and Operating Costs
a. Safety considerations
There are four safety related considerations which must be properly managed when
working with UV curing equipment.
1)
Eye and skin exposure The light energy from high powered UV
curing lamps can burn the cornea and skin. Proper shielding through
equipment design, the use of UV screens, UV blocking safety glasses and UV
blocking creams is necessary.
2)
Fire hazard Some UV lamps emit IR radiation at levels sufficient to

raise the surface temperature of the substrate or coating well above the flash
point of the volatile components that are present ( see Chapter V, Experiment
9 and 13). In the case of static exposures ( i.e. no motion of the lamp relative
to the part) the lamp height and exposure time should be selected to avoid
overheating. Under dynamic exposure conditions a safety interlock should be
used which turns off the lamps if the conveyor motion drops below a specified
setting.
3)
Microwave energy Lamps using the electrodeless bulb design are

heated within an open sided microwave chamber. The RF energy is contained
using a metal mesh screen. Potential RF leaks are detected using an
interlocked RF detector (see Chapter II, photograph 7). It is important to
142

perform periodic inspections to insure the integrity of the mesh screen and
follow the manufacturers placement guidelines for the RF detector.
4)
Breathing air There are several special conditions which may give
rise to compromised breathing air quality. Each of these conditions may be
remedied with proper air make-up systems. These conditions are described
briefly below:
a. Ozone lamps containing mercury may produce ozone due to the
short wavelength UV peak near 250 nm. Fabricators should check with
the equipment manufacturer to determine if this is an issue.
b. Nitrogen blanketing some UV curing applications utilize localized
removal of air within the curing zone through the use of a nitrogen
curtain to cure oxygen inhibited systems. The equipment used to
produce the oxygen free environment (< 200 ppm) consists of a fully
enclosed inerting chamber. Proper air make-up systems may be needed
to maintain breathing air within safe limits depending on the flow rate
of nitrogen, room size, and air flow replenishment.
c. Solvent vapors The air flow within high powered UV curing lamps
and onto the surface of a partially cured coating can create a condition
of forced convection resulting in rapid evaporation of solvent and
monomer. Proper air make-up systems may be needed to maintain
organic levels below the LEL (lower explosive limits) depending upon
the room size, and air flow replenishment.
143

b. Throughput considerations 1-3
UV curing offers tremendous curing speed advantages when compared to
conventional room temperature curing using redox initiators. As noted in Chapter II
the curing time for a conventional gel coat can be reduced from 45 minutes to a few
seconds using UV curing. There are however trade-offs with UV curing which must
be factored into consideration UV curing is a line-of-sight process UV curing has
thickness limitation based on the ability to transmit light through the coating or
laminate. In practice, there are numerous material and process variables which must
be controlled to safely produce a consistently cured part. The foundational work to
define the process window is developed by conducting experiments to study the
influence of pigmentation, film thickness, photoinitiator concentration, energy and
irradiance levels, lamp position, and mold reflectivity on the film formation, degree
of cure, and surface temperature (see chapter V , Experiments 1-4,8,9,15, and 17).
Once these results are obtained, material specifications and equipment configuration
details can be established to meet the design expectations. Once these controls are
implemented the daily operational throughput is managed by careful control of the
line speed and film thickness (figure 1). Unlike most coatings and inks which are
designed to adhere to the substrate, the gel coat must release from substrate (mold). If
the coating is applied too thin, the gel coat will crawl (dewetting) on the low surface
energy surface of the mold (see Chapter I, photograph 10). If the gel coat is too thick
the gel coat will not completely cure in the thickness direction. The resulting cure
gradient will produce the alligatoring texture created by a differential shrinkage in
the thickness direction (see Chapter III, photograph 1). The throughput (line speed) of
144

each coating chemistry will depend upon the desired thickness and reactivity. For
example, as noted in Chapter V, Experiment 5, thermosetting acrylic polymers can be
cured more easily (i.e. thicker, faster) than unsaturated polyester polymers. The
operating line speed should chosen to allow for complete cure while simultaneously
avoiding overheating. Once the process parameters are defined, periodic spot checks
should be made using a process radiometer-dosimeter to assure the process is
operating within the design requirements.
Low Energy=
Incomplete
cure
Valid Process Window
Conveyor Speed (fpm)
Excessive
Heating
= Fire hazard
Coating Film Thickness

Low
Transmission=
Incomplete
cure, alligatoring
texture on the
surface
Poor wetting
of the mold
Figure 1 - Process window for UV curable gel coat
c. Environmental benefits of UV curable composites

Conventional gel coats and laminating resins contain between 30% - 45% reactive
diluents (typically styrene and methyl methacrylate). Presently there are two driving
forces to reduce the use of styrene monomer containing products:
145

1) NESHAP MACT Standard (40 CFR Part 63)

(ref. www.epa.gov/EPA-AIR/2001/August/Day-22/a20895.htm)
Under the Clean Air Act Amendments of 1990, Congress greatly expanded the Air
Toxics program, creating a list of 189 substances to be regulated as hazardous air
pollutants. Rather than regulating individual pollutants by establishing health-based
standards, the new Air Toxics program granted EPA the authority to regulate
specific industrial major source categories with National Emission Standards For
Hazardous Air Pollutants (NESHAP) based on maximum achievable control
technology (MACT) for each source category. Thus, a number of NESHAP
standards have been established to regulate specific categories of stationary sources
that emit (or have the potential to emit) one or more hazardous air pollutants.
NESHAP statndards may cover both major sources and area sources in a given
source category. Major sources are defined as those facilities emitting, or having
the potential to emit, 10 tons per year or more of one HAP or 25 tons per year or
more of multiple HAPs. Major sources are required to comply with MACT
standards. Most composite operations which use conventional gel coats and
laminating resins emit more than 10 tons per year of styrene monomer based on the
EPAs current formulas to compute HAPS emissions. Acceptable remedies to the
styrene emission dilemma include capture and control (i.e. thermal oxidation) or
reduction in source usage (i.e. alternate technologies). Either of these options
present technical and financial challenges for composite fabricators.
146

2) EPA IRIS (Integrated Risk Information System) Carcinogenic

Classification of Styrene Monomer ref. www.epa.gov/iris
The Integrated Risk Information System (IRIS), prepared and maintained by the U.S.
Environmental Protection Agency (U.S. EPA), is an electronic database containing
information on human health effects that may result from exposure to various
chemicals in the environment. IRIS was initially developed for EPA staff in response
to a growing demand for consistent information on chemical substances for use in
risk assessments, decision-making and regulatory activities.
IRIS is closed to the public

Scientific Process rather than a regulatory development process
Viewed as a Uniquely governmental function by the EPA
IRIS has no appeal process to challenge IRIS rulings
The IRIS website is widely used 10,000 hits per day
There is no requirement for the IRIS agency to consider downstream
business impact
IRIS is currently reviewing 79 chemicals
The average time IRIS waits before review a prior IRIS ruling is 15 years
In order to provide some measure of clarity and consistency in an otherwise freeform,

narrative characterization, standard descriptors are used as part of the hazard narrative
to express the conclusion regarding the weight of evidence for carcinogenic hazard
potential. There are five recommended standard hazard descriptors:
1)
2)
3)
4)
5)
Carcinogenic to Human,
Likely to Be Carcinogenic to Humans
Suggestive Evidence of Carcinogenic Potentia,
Inadequate Information to Assess Carcinogenic Potential and
Not Likely to Be Carcinogenic to Humans.
147

Styrene monomer is currently under review by EPA-IRIS. If the EPA classifies
styrene as Likely to Be Carcinogenic to Humans, the implications will create
additional motivation to reduce or eliminate the use of styrene monomer in many
products including gel coats and laminating resins.
UV curable gel coat and resin formulas can be design to combine styrene with
multifunctional acrylate monomers (hybrid approach), or with complete substitution
for the styrene monomer.
c. Economic considerations4
The financial consequences of converting from conventional room temperature curing
with redox initiators to UV curing are expressed qualitatively in terms of capital and
operational expenses. The actual financial impact of UV curing must be made on a
case-by-case basis.
ISSUE
Speed of Cure is greater
PROS
CAPEX: fewer molds are
148
CONS

with UV curing
Energy Usage
required to maintain
production volume
OPEX: less inventory
make to order
OPEX: UV curing requires
less energy than heating
the entire shop
Capital Equipment
Styrene monomer partial

replacement or substitution
with non-regulated
multifunctional acrylates
CAPEX: allows
fabricators to drop below
the NESHAP 10 ton/year
limit thereby eliminating
the need for capture and
control technology
CAPEX: High power UV

Curing lamps cost $500010000 each.
OPEX: Increase in raw
material costs
Chapter VII - Case Study Flat Construction Panel Laminate

Commercially successful applications of UV curable composites include residential
doors1, and paneling for spa sidings2. In this chapter a summary of the knowledge
developed through experimentation (Chapter V) is presented in tabular form below.
This knowledge is then applied in a case study to produce a large flat gel coated
laminate.
149

Chapter VII Case Study Construction of a UV Curable Gel Coated FRP Panel
Expt. Theme
Main Points
1
Pigmentation Gel coat film cure is possible using V bulb in combination with
pigments showing strong scattering ( 390-440nm) , BAPO PI
2
TiO2 conc.
Keep TiO2 concentration at or below 10% to prevent alligatoring
texture
3
Film
Wet film thickness should be 10-12 mils maximum (UPR systems)
thickness
4
PI
Use 0.5% BAPO to cure white gel coat with V bulb
5
Binder
The reactivity of acrylics >> UPR
6
Laminate
3 plies of 1.5 oz. CSM laminate, 0.2% PI, 4-5 J/cm2
thickness
7
Energy vs.
E 1/v
speed
8
DSC cure
White UPR-acrylic system 4J/cm2, UPR clear 4J/cm2 to reach high
study
level of double bond conversion via DSC
9
Lamp type
Lamp power : Fusion> Honle>VHO fluorescent
10
Light
Energy and irradiance dispersion pattern of Fusion UV lamps may be
dispersion
adequately modeled using a Gaussian distribution model
pattern
11
Additive
Energy and irradiance of a bank of shown to be additive at each
nature of UV point in the direction perpendicular to the conveyor travel
Energy
12
Lamp
The energy and irradiance levels drop sharply as the Fusion lamps are
spacing
separated
13
Surface
Surface temperature correlates well with UV energy; does not
temperature correlate with irradiance level
14
Cosine law
E=E cos() , I=I cos()
15
16
17
18
Inverse
square law
Dichroics
Mold
reflectivity
Simulations
E 1/h2
No significant temperature control observed with dichroics
Degree of cure is superior with reflective mold due to internal
reflection
1) Predictive model is validated using measured data
2) Lamp spacing has a pronounced effect on uniformity
3) A single lamp failure within a bank of lamps can result in a
large localized drop in energy and irradiance
4) Lamp height has a pronounced effect on uniformity
150

Table 1 - Summary of UV Curing Knowledge (from Experiments 1- 18)
Case Study Flat Panel Production
The objective of this study is to provide a feasibility demonstration for the production
of a series of large (4 x 8) gel coated FRP panels. Typical applications for this part
include roofing panels, transportation panels use on large transport trucks, siding
panels for recreational vehicles, etc. A UV curable polyester gel coat formulation and
a dual cure laminating resin formulation (proprietary) was prepared. The curing
system consisted of ten Fusion UV System 600 W/inch high output UV lamps. The
lamps were arranged in two rows of five lamps with a separate air plenum to support
the cooling requirements for each row. One row of lamps was fitted with the V bulb
gallium doped metal halide, while the second row was fitted with the D bulb
iron doped metal halide. Standard reflectors were used with the bulb placed in the 209
position to maximize the reflected energy. The lamps were placed a distance of 7.5
inches above the mold surface. The gel coat was applied manually at a thickness of 812 mils using a Binks spray gun (photograph 1). The gel coat was cured at a speed of
5 fpm (photograph 2). The laminate was applied via the hand lay-up process
(photograph 4) . The laminate schedule consisted of an one layer of surfacing veil to
improve the surface cosmetics and one ply of 1 oz./ft2 CSM chopped strand mat (Eglass).
Resin : Glass Ratio (veil)
Resin : Glass Ratio (CSM)
Weight -Resin
Weight - Veil
Weight - CSM
Weight - MEKP
10%
23%
4062 g
111 g
915 g
57 g
151

The laminate was cured using a line speed of 7 fpm. The line speed, lamp spacing,
and lamp height were selected to provide the energy required to achieve proper cure
based on DSC measurements of residual cure energy. The part was allowed to remain
on the mold for 90 seconds prior to demolding. The exit temperature on the surface of
the cured laminate was measured at 168F using an infrared thermometer. A total of
six successful parts were produced in series, demonstrating the feasibility of the
process.
152

Photograph 1 Application of the gel coat on reflective mold surface
Photograph 2 UV Cure of the white gel coat
153

Photograph 3 Cured white gel coat film
Photograph 4 Hand lay-up of the laminate

154

Photograph 5 UV Curing the laminate
Photograph 6 Cured laminate
155

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Thesis - Gel-L Scott Crump

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PROCESS OPTIMIZATION OF PHOTOCURABLE POLYESTER GEL

COAT AND LAMINATE

Submitted in partial fulfillment of the requirements

Thesis Advisor: Professor Alex. M. Jamieson

Department of Macromolecular Science and Engineering

CASE WESTERN RESERVE UNIVERSITY

We hereby approve the thesis of Larry Scott Crump

Process Optimization of Photocurable Polyester Gel Coat and Laminate

Chapter I The Composite Open Molding Process..

Chapter II UV Curing Equipment and Radiometry

Chapter III Chemistry of Thermosetting Unsaturated Polyester and

Chapter IV Characterization of Resin / Coating State of Cure...

Chapter V Modeling the Degree of Cure of a 2D UV Curing Process

Chapter VI Process Optimization - Defining the Process Window

Balancing Safety, Throughput, Capital Investment and

Chapter VII Case Study Flat Construction Panel Laminate..

Process Optimization of Photocurable Polyester Gel Coat and Laminate

a. Unsaturated Polyester Resin Based Composite Products

Process Optimization of Photocurable Polyester Gel Coat and Laminate

i. Historical work in the area of UV curable composites

vi. Commercial applications for UV curable composites

Process Optimization of Photocurable Polyester Gel Coat and Laminate

Process Optimization of Photocurable Polyester Gel Coat and Laminate

a. Studies of coatings and laminate resin related variables

Process Optimization of Photocurable Polyester Gel Coat and Laminate

Process Optimization of Photocurable Polyester Gel Coat and Laminate

Process Optimization of Photocurable Polyester Gel Coat and Laminate

U.S. Markets and Applications for Unsaturated Polyester Based

Cone and plate rheometer programming sequence to simulate the

Application flow requirements of gel coat and solvent based

Summary of lamination process features and limitations

Chapter III - Chemistry of Thermosetting Systems.

Commercially available photoinitiators

Energy absorbed in the top 1% and bottom 1% of a coating film

Chapter IV - Characterization of Resin / Coating State of

Effect of Tg on the surface tackiness of UPR prepolymer

Chapter V - Modeling the Degree of Cure of a 2D UV

Factorial study of photoinitiator concentration, UV energy, and

Reciprocal law for UV energy, independence of irradiance and

Variations in energy and irradiance of a single 600 W/inch lamp

Gaussian fit parameters to model light dispersion a 600 W/inch

Process Optimization of Photocurable Polyester Gel Coat and Laminate

Measurement of energy and irradiance from a bank of five 600

Effect of UV energy and irradiance level on the surface

Validation of the cosine law for non-perpendicular exposure

UV Energy and irradiance measurements at various lamp heights

Evaluation of dichroic reflectors

White UV curable gel coat results on a reflective and nonreflective mold

Chapter VI - Process Optimization - Defining a Process

Effect of lamp spacing on UV energy level and uniformity

Chapter VII Case Study Flat Construction Panel Laminate

Summary of UV Curing Knowledge (from Experiments 1- 18)

Process Optimization of Photocurable Polyester Gel Coat and Laminate List of

Controlled stress cone and plate rheometer

Experiment to simulate the shear history of a commercial

Chapter II - UV Curing Equipment and Radiometry

Reflector designs to focus (elliptical), collimate (parabolic), and

Relative spectral power distribution of commonly used UV bulbs

UV curing lighting systems

Chapter III - Chemistry of Thermosetting Systems.

Production of unsaturated polyester resin solutions

Polymerization of UPR prepolymer and crosslinking monomer

Formation of a UPR-styrene microgel