Professional Documents
Culture Documents
by
L. SCOTT CRUMP
May , 2014
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
Table of Contents
Table of Contents.....
vi
List of Tables........
xii
List of Figures
xvi
Acknowledgements.....
xviii
16
34
70
75
142
150
Bibliography..
156
iii
Table of Contents
Chapter I The Composite Open Molding Process.
iv
16
34
vi
75
vii
viii
150
Laminate
Bibliography
156
ix
Description
Chapter I - The Composite Open Molding Process
Page
12
Gel Point Time data set used to validate the redox cure kinetic
model
46
53
59
68
80
82
86
95-96
98
102
Testing the additive law for UV energy using two 600 W/inch
lamps
106
109
113
10
114
11
The irradiance from a point source of light varies with the square
of the distance from the source
115
12
116
13
120
129
xi
143
Page
Chapter I - The Composite Open Molding Process
19
21
2
IR absorbing dichroic reflector
3
25
26
33
37
41
42
46
47
47
54
56
xii
57
11
58
12
59
13
62
14
63
15
UV Composites publications
64
67
72
73
74
75
84
84
85
xiii
87
Energy requirements to cure a clear gel coat and white gel coat
89
10
91
11
93
97
100
103
13
104
14
107
15
Effect of lamp type, lamp height, line speed, and reflector type
on UV energy, irradiance, and exit temperature
110
16
111
17
112
18
113
19
115
20
115
21
117
22
119
11.5
12
12.5
xiv
119
24
121
25
123
26
126
27
127
28
128
29
130
30
132
31
134
xv
138
Description
Chapter I - The Composite Open Molding Process
Page
3
3
10
11
13
12
13
13
13
14
14
15
14
16
14
17
14
xvi
14
19
15
20
Top view of UV lamp housing. The red hoses are used for
water cooling during operation
17
17
18
18
18
18
18
27
10
27
11
27
xvii
27
13
31
14
31
15
31
16
31
60
60
71
72
94
146
146
147
147
xviii
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
xxii
Non-Reinforced Market
Transportation / Body Putty (69 MM lbs)
Table 1 U.S. Markets and Applications for Unsaturated Polyester Based Composites 1
1
L. Scott Crump May 2014
additives (impart flow control, curing, storage stability, exterior durability, etc.)
2
L. Scott Crump May 2014
3
L. Scott Crump May 2014
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
L. Scott Crump May 2014
5
L. Scott Crump May 2014
M=torque
=angle
r=radius
=rotational speed
=shear stress (Pa)
=shear rate (1/s)
=viscosity
(Pa-s)
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
L. Scott Crump May 2014
Gel Coat
Performance
Requirement
No sedimentation of
spray gun
20-30 mils
gh
gh
10 lb/gal.=1200 kg/m3
10 lb/gal.=1200 kg/m3
g=9.8 m/s2
g=9.8 m/s2
10,000.00
400
350
1,000.00
300
250
10.00
200
1.00
150
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
L. Scott Crump May 2014
9
L. Scott Crump May 2014
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+
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
L. Scott Crump May 2014
11
L. Scott Crump May 2014
Surface
Quality
(gloss,
smoothness)
High
Possible
use of
coring
materials?
Yes
High
Yes
High
Yes
High
No
Low
No
Low
No
Possible use of
coring
materials?
Yes
No
No
Yes
No
13
L. Scott Crump May 2014
14
L. Scott Crump May 2014
15
L. Scott Crump May 2014
reflector
shutter
RF Detector
Parabolic
Dimpled
Focal Plane
19
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21
L. Scott Crump May 2014
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.
EREFLECTED
22
L. Scott Crump May 2014
EDIRECT
ETARGET
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
the bulb, is the Stefan-Boltzmann constant, and T is the temperature of the bulb in
23
L. Scott Crump May 2014
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
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 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
L. Scott Crump May 2014
Relative Energy
Watts / Inch
gy
Mercury Lamp
200
250
300
350
400
450
W avelength (nm)
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
28
L. Scott Crump May 2014
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.
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
L. Scott Crump May 2014
t1
E(
2 )
I (
2 )
dt
t0
Infrared Radiance the heating effect from infrared energy emitted by the hot
quartz bulb.
30
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31
L. Scott Crump May 2014
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
L. Scott Crump May 2014
33
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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
L. Scott Crump May 2014
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
L. Scott Crump May 2014
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
L. Scott Crump May 2014
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.
38
L. Scott Crump May 2014
100
90
80
70
60
50
40
30
20
10
0
0
20
40
60
80
100
120
140
OH
C
C
C
C
C
C
OH
C
C
C
C
OH
fumaric acid (trans isomer)
CH3
C
C
O
CH2
OH
CH3
CH2
OH
OH
propylene glycol
40
L. Scott Crump May 2014
H
C
H
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
41
L. Scott Crump May 2014
42
L. Scott Crump May 2014
Microgel Particles
I*
(a)
(b)
VISCOSITY,
(or 0)
Transition
Microgel
Formation
Induction
TIME, t
(or t/tgel = R*/Rc)
II
III
IV
44
L. Scott Crump May 2014
k
1 RO OH
ROOH ( I )
(2R)
(1)
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
L. Scott Crump May 2014
(2)
(3)
(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
[ R] f [
2k1 k 2 [ I a ]
] [ I o ][1 e ( k1 k2 [ I a ])t ) ]
k1 k 2 [ I a ]
(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
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 ])
(13)
[ R] Rc RI RII RIII RI IV
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)
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
% 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
L. Scott Crump May 2014
Ea
Rc / f
1
A1 B1 eqn. 16
ln(t gel ) ln
0
o
T
[ I o ](2k1 k 2 [ I a ]) RT
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
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
L. Scott Crump May 2014
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
-1
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*
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 ]
c.
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.
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
L. Scott Crump May 2014
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.
53
L. Scott Crump May 2014
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
L. Scott Crump May 2014
R-H
OH
C
*
R*
55
L. Scott Crump May 2014
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
Lucrin
TPO
Diphenyl(2,4,6trimethylbenzoyl)phoshpine oxide
Irgacure
1800
CH3
CH3
S
H3C
CH3
CH3
CH3
25%
CH3
75%
O
H3C
BAPO /
Hydroxy
Ketone
Irgacure
1850
50%
+
50%
CH3
O
O
H3C
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
# photons transmitted
through the coating
# photons absorbed
by the photoinitiator
57
L. Scott Crump May 2014
Wavelength
Wavelength
A()
ABSORPTION
Quantum Yield
Absorbance
Transmission
Light Energy
120
EPON 828
SR 230
SR 231
SR 238
100
SR 306
SR 351
SR 502
80
SR 506
%T
60
40
CN963E80
Ebecr yl 4830
20
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
% 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)
I0
I0 Ia It
Ia
It
60
L. Scott Crump May 2014
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
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
61
L. Scott Crump May 2014
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
62
L. Scott Crump May 2014
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%
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
L. Scott Crump May 2014
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
# photons transmitted
through the coating film
# photons absorbed
by the photoinitiator
# radicals formed
# photons
# photons transmitted
through the coating
# photons absorbed
by the photoinitiator
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
L. Scott Crump May 2014
65
L. Scott Crump May 2014
40 sec
60 sec
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
LIGHT
INTENSITY
MOLD
MOLD
Non-Photobleaching
LIGHT
INTENSITY
LIGHT
INTENSITY
LIGHT
INTENSITY
LIGHT
INTENSITY
MOLD
Exposure Time
MOLD
LIGHT
INTENSITY
MOLD
MOLD
66
L. Scott Crump May 2014
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
20,21,52
the
# Documents Published
14
12
10
8
6
4
2
0
1965
1970
1975
1980
1985
1990
1995
2000
2005
2010
Publication Year
68
L. Scott Crump May 2014
69
L. Scott Crump May 2014
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
L. Scott Crump May 2014
71
L. Scott Crump May 2014
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
Post-spray + 10 minutes
Post-spray + 15 minutes
Post-spray + 30 minutes
Post-spray + 60 minutes
Post-spray + 120 minutes
0.2
Resin - isophthalate
ring bending m ode
Methyl Methacrylate
0.1
0.0
950
900
850
800
750
700
-1
650
Resin Designation
Tg (C ) of the uncured
prepolymer
A
14.3
dry no tackiness
11.3
-5
74
L. Scott Crump May 2014
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
Mils Cured
Degree of Cure (%)
lamp
9 inches
cured gel coat
2 ft/min
20 mils
K (1 R ) 2
S
2R
equation 1.1
equation 1.2
K/S
8
6
4
2
0
0
0.2
absorption dominates
0.4
0.6
Reflectance
0.8
scattering dominates
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
L. Scott Crump May 2014
0.800
%PI solids
0.00
0.10
0.20
0.50
0.75
1.00
1.50
2.00
2.50
3.00
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
80
L. Scott Crump May 2014
700
750
UNITS
LEVEL
A)
B)
Line speed
fpm
20
C)
Coating thickness
mils
16
D)
Coating
na
E)
Lighting
na
UNITS
LEVELS
be systematically varied
A)
10, 15, 20
UNITS
na
visual
RESULTS
Run #
% TiO2
10
15
20
81
L. Scott Crump May 2014
UNITS
LEVEL
A)
B)
Line speed
fpm
10
C)
Coating type
na
D)
Lighting
na
LEVELS
be systematically varied
A)
Coating thickness
mils
7, 10, 16
UNITS
na
visual
82
L. Scott Crump May 2014
Film
Thickness
mils
1
10
16
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
L. Scott Crump May 2014
UNITS
LEVEL
A)
Coating type
na
B)
Lighting
na
UNITS
be systematically varied
A)
Coating thickness
mils
7, 10, 16
B)
Photoinitiator concentration
C)
Line speed
fpm
5,20
UNITS
na
visual
84
L. Scott Crump May 2014
RESULTS
Run
% PI
#
1
0.1
Line
Film
Speed
Thickness
(fpm)
(mils)
0.1
16
0.1
20
0.1
20
16
wet film
0.5
0.5
16
0.5
20
0.5
20
16
85
L. Scott Crump May 2014
UNITS
LEVEL
A)
Photoinitiator concentration
B)
rutile, 10%
C)
Lighting
na
UNITS
LEVELS
be systematically varied
A)
Coating thickness
mils
7, 10, 16
B)
Line speed
fpm
C)
Binder chemistry
na
UNITS
na
visual
86
L. Scott Crump May 2014
Binder
Line
Film
chemistry
Speed
Thickness
(fpm)
(mils)
10
UPR
UPR
10
16
UPR
16
UPR
12
UPR
10
10
Acrylic
20
10
Acrylic
40
10
Acrylic
80
10
Acrylic
20
16
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
L. Scott Crump May 2014
UNITS
LEVEL
A)
Laminate materials
na
B)
Lighting
na
UNITS
LEVELS
be systematically varied
A)
Exposure time
minutes
0-20
B)
Photoinitiator concentration
UNITS
A)
Barcol hardness
Barcol units
B)
DSC
C)
Surface temperature
D)
UVV energy
embedded thermocouple
2
J/cm
88
L. Scott Crump May 2014
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
14
30
30
12
0
0
100
200
4.32
3.24
2.16
1.08
0 0 0
10
10
9.18
21
38
6
4
2
0
300
400
500
600
700
800
900
1000
1100
1200
1300
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
9,18
40
4,32
3,24
2,16
1,08
100
200
10
8
6
4
2
0
0
16
14
60
300
400
500
600
700
800
89
L. Scott Crump May 2014
900
1000
1100
1200
0
1300
32,4
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
10
7
4
0
0
0
% of BAPO / formulation
90
L. Scott Crump May 2014
2,1
A)
UNITS
LEVEL
Lighting
na
UNITS
LEVELS
be systematically varied
A)
Conveyor speed
fpm
0-40
UNITS
W/cm2
Irradiance
UV energy
J/cm
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
L. Scott Crump May 2014
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
1
v
(equation 7.1)
92
L. Scott Crump May 2014
UNITS
LEVEL
A)
Laminate materials
na
B)
Lighting
na
C)
Irradiance level
W/cm2
UVV=0.14
UNITS
LEVELS
be systematically varied
A)
UV Energy
J/cm2
0-6
B)
Film thickness
mils
0-20
UNITS
%
DSC
93
L. Scott Crump May 2014
RESULTS
Dose-Cure Response for White UV Curable, Ultra Low HAPS Weather Resistant Gel Coat,
and Conventional UPR Clear Gel Coat
100
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
L. Scott Crump May 2014
INPUT FACTORS
FIXED FACTORS these factors
will be held constant
UNITS
LEVEL
A)
Exposure time
min
B)
Lighting
na
C)
Irradiance level
W/cm2
UVV=0.14
UNITS
LEVELS
Lighting source
na
B)
Lamp height
inches
0-34
UNITS
A)
UV Energy
J/cm2
B)
Surface temperature
Fluke IR thermometer
95
L. Scott Crump May 2014
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
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
T@3min=75
0.1
10
15
20
25
30
96
L. Scott Crump May 2014
35
97
L. Scott Crump May 2014
off
off
Lamp 1
Lamp 2
on
off
off
Lamp 3
Lamp 4
Lamp 5
h=height
-36
-6
12
18 24 30 36
98
L. Scott Crump May 2014
LEVEL
A)
line speed
14
B)
fpm
UNITS
Lamp type
na
B)
Lamp height, h
inches
5, 9, 14
C)
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
99
L. Scott Crump May 2014
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
L. Scott Crump May 2014
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
L. Scott Crump May 2014
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
of distance from the lamp centerline
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
L. Scott Crump May 2014
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
-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
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
1.5
2
UVA
Pred UVA
0
-0.5 0
UVB
UVC
0.5
UVV
Pred UVV
0
-20
Pred UVV
0.5
0
-40
UVV
2.5
-0.5
UVC
1.5
-20
UVB
0.5
-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
103
L. Scott Crump May 2014
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
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
L. Scott Crump May 2014
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
L. Scott Crump May 2014
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
h=height
-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
L. Scott Crump May 2014
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)
C)
lamp type
na
D)
lamp height
inches
11
fpm
UNITS
will
be
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
107
L. Scott Crump May 2014
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
L. Scott Crump May 2014
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
1 row - V Bulb
3.5
3
2.5
2
1.5
1
0.5
0
-80
-60
-40
-20
-0.5 0
20
40
60
Figure 12.5 Measured UV Energy Bank of five 600 W/inch Fusion UV lamps
109
L. Scott Crump May 2014
Experiment #12 Testing the additive nature of UV energy from multiple light sources using two
600 W/ inch UV lamps
y
600 W/inch Fusion UV lamp
on
Radiometric data was collected at 10.5 inch
lateral intervals
on
Lamp 3
Fixed
position
Lamp 1
Variable
position
-31.5
-21
-10.5
110
L. Scott Crump May 2014
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)
LEVEL
A)
inches
11
B)
conveyor speed
fpm
14
C)
lamp type
na
UNITS
inches
B)
inches
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
111
L. Scott Crump May 2014
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
L. Scott Crump May 2014
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)
113
L. Scott Crump May 2014
LEVEL
A)
lamp type
B)
three rows
C)
substrate
steel Q-panel
na
will
be
fpm
5, 10 , 20, 40
B)
bulb type
na
C)
na
D)
inches
6, 15
114
L. Scott Crump May 2014
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
C)
Fluke IR thermometer
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
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
115
L. Scott Crump May 2014
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
Energy (J/cm2)
12
3V,15",Std Reflector
10
2V+1D,6",Std Reflector
2V+1D,15",Std Reflector
3V,6",209 Reflector
3V,15",209 Reflector
2V+1D,6",209 Reflector
4
2V+1D,15",209 Reflector
2
0
0
10
20
30
40
50
Line Speed
25
3V,15",Std Reflector
2V+1D,6",Std Reflector
20
2V+1D,15",Std Reflector
3V,6",209 Reflector
15
3V,15",209 Reflector
2V+1D,6",209 Reflector
10
2V+1D,15",209 Reflector
5
0
0
10
20
30
40
50
Line Speed
190
180
170
3V,6",Std Reflector
160
3V,15",Std Reflector
150
2V+1D,6",Std Reflector
140
2V+1D,15",Std Reflector
130
3V,6",209 Reflector
120
3V,15",209 Reflector
2V+1D,6",209 Reflector
110
2V+1D,15",209 Reflector
100
90
80
0
10
20
30
Line Speed
116
L. Scott Crump May 2014
40
50
20 0
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
200
180
R 2 = 0.16
160
140
120
100
80
60
40
20
0
0
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
angle of incidence
degrees
0, 60
A)
RESPONSE VARIABLE
NAME
Energy
UNITS
J/ cm2
B)
Irradiance
W/ cm2
118
L. Scott Crump May 2014
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
=E x cos()
eqn 14.1
2 inches
4 inches
FOCAL PLANE
8 inches
21 inches
33 inches
LEVEL
A)
lamp type
na
B)
exposure time
minutes
inches
2, 4, 8, 21, 33.5
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
120
L. Scott Crump May 2014
120
Energy (J/cm2)
100
Irradiance (W/cm2)
80
1.5
60
40
0.5
20
0
Irradiance (W/cm2)
140
10
20
30
40
Distance (inches)
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)
-2.32051E-08
in focus
2
1.5
1
0.5
0
0
0.05
0.1
0.15
0.2
1 / (lamp height)
0.25
0.3
LEVEL
A)
conveyor speed
fpm
15
B)
lamp type
na
C)
lamp height
inches
reflector type
na
Line
Speed
15
15
Lamp
Height
4
4
UNITS
F
STD
dichroic
Fluke IR thermometer
T Exit (F)
142
140
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
IA
IA
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
A)
RESPONSE VARIABLE
NAME
Mold reflectance
UNITS
%
124
L. Scott Crump May 2014
Perkin-Elmer Lambda 6 UV
spectrophotometer with an integrating
sphere accessory
Multi-colored composite
Total %R (specular reflectance included)
Figure 22 UV-Visible reflection from polyester tooling gel coat various colors
Figure 23 UV-Visible reflection from metal molds and aluminum flake filled
polyester tooling gel coat.
125
L. Scott Crump May 2014
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
17.8
13.1
7.4
2.2
12.1
3.9
16.1
5.2
22.4
12.1
15.5
12.8
9.6
Table 13 White UV curable gel coat results on a reflective and non-reflective mold
( V lamp=gallium 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
L. Scott Crump May 2014
Y-direction
Direction of travel
h-direction
Lamp height
X-direction
Perpendicular to travel
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
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)
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
L. Scott Crump May 2014
(h) 0 1h 2h 2
(h) 0 1h 2h 2
To illustrate the technique to model the height dependence of
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
129
L. Scott Crump May 2014
18
Parameter Value
16
14
12
10
8
6
4
2
0
0
5
10
15
h = Lamp Height (inches)
20
v(fpm).
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
L. Scott Crump May 2014
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 energy for a bank of two lamps then may be determined from
131
L. Scott Crump May 2014
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
2)
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
/ 2 Ii ( h ) 2 ]
eqn. 18.14
Y-direction
Direction of travel
h-direction
Lamp height
X-direction
Perpendicular to travel
UV Energy Distribution
18.0
Energy (J/cm2 )
16.0
14.0
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
L. Scott Crump May 2014
204
192
180
168
156
144
132
120
108
96
84
72
60
48
36
24
12
Irradiance Profile
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
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
L. Scott Crump May 2014
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%
136
L. Scott Crump May 2014
UV Energy Distribution
14.0
Energy (J/cm2)
12.0
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
UV Energy Distribution
Energy (J/cm2 )
12.0
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
UV Energy Distribution
Energy (J/cm2 )
12.0
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
L. Scott Crump May 2014
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
L. Scott Crump May 2014
UV Energy Distribution
18.0
Energy (J/cm2 )
16.0
14.0
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 Profile
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
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
Perpendicular to travel
Figure 30 - The impact of a lamp failure on the UV energy and irradiance distribution
139
L. Scott Crump May 2014
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
L. Scott Crump May 2014
UV Energy Distribution
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
UV Energy Distribution
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
L. Scott Crump May 2014
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)
3)
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
Low Energy=
Incomplete
cure
Excessive
Heating
= Fire hazard
Poor wetting
of the mold
146
L. Scott Crump May 2014
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
L. Scott Crump May 2014
ISSUE
Speed of Cure is greater
PROS
CAPEX: fewer molds are
148
CONS
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
CAPEX: allows
fabricators to drop below
the NESHAP 10 ton/year
limit thereby eliminating
the need for capture and
control technology
149
L. Scott Crump May 2014
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
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
10%
23%
4062 g
111 g
915 g
57 g
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