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OAR Box 1500 

Prepped by Ollie Stewart 

Document Number: 

54) ll-C-80 

Docket Number: 

A-94-52 

Printed 8/5/2008 1:51:29 PM Sheet 54 of 343 
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From: MADELEINE STRUM 

To: Internet."blacovara@aol.com" 

Date: 11/19/97 4:10pm 

Subject: comments on VSR test outline 

<WP Attachment Enclosed> 

Bob— 

My comments are in bold. Candace Sorrell, the Emission Measurement Center 

lead for this test, has not gotten a chance to look at this yet. She may have 

more comments on the laboratory test procedures, repeatability issues, etc. 

Thanks for this early draft. 

Let me know if you'd rather do a conference call or meet in person on Dec^ji 

2 and your preferred times. 

Madeleine 

CC: RTP6.RTPEML.SORRELL-CANDACE 
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DRAFT - WORK IN PROGRESS 

Proposal 

Date: 11/14/97 

From: Bob Lacovara - CFA 

To: MACT Summit Group 

Madeleine Strum - EPA 

Resin Suppliers 

Suppressant Suppliers 

Re: Development of Standard Styrene Suppressant Effectiveness Test 

I. Background 

Recent testing has documented the effectiveness and benefits of styrene suppressants in reducing 

emissions. However, it has been recognized that suppressant efficiency may be variable over the 

range of possible suppressant and resin system combinations. Because ofthe potential array of 

combinations, a standardized test method must be developed to document the performance of 

suppressants under specific conditions. 

During the course ofthe CFA Open Molding Test Project, attempts were made to correlate the 

California SCAQMD Rule 1162 "Pie Pan" test to the results ofthe large-scale emissions testing 

being conducted. It was found that the 1162 pie pan test exhibited little or no correlation to 

emissions developed in laminate samples. Therefore, it has been determined that a new test 

method is required to accurately determine the effectiveness of suppressant additives. 

This proposed test method incorporates a laminate and mechanical comment by M. Strum: 

maybe the word "manual" should be used instead since the roll-out is done by hand roll-out 

method to more closely approximate the conditions found in actual molding operations. 

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This test is designed to be a direct comparison between a specific resin with and without a 

suppressant additive. It is not designed to determine actual emissions from the molding process. 

It is anticipated that the data generated from this test comment by M. Strum: add the words 

"will be entered into a model to estimate the performance of a particular suppressant/asapplied resin combination which will then be entered...." will be entered into the CFA 

emissions model as a suppressant modifier factor. This factor is part of a more comprehensive 

formula to determine overall process emissions comment by M. Strum delete "overall process 

emissions" and replace with "a MACT point-value system type model which reflects 

accurate emission reduction credits to the various emission reduction techniques which a 

facility could choose to meet MACT". 

II. Points of General Consensus 

1) The effects of suppressants can be variable with specific resin systems and specific 

suppressants. Comment by M. Strum: Add "For example, it has been demonstrated that 

suppressants are less efTective when they are used with filled resins as compared to unfilled 

resins." 

2) The SCAQMD Rule 1162 type "pie pan" test does not correlate well with actual laminate test 

results. 

3) There are distinct stages of emissions generation during the laminating process. 

a. Spray-up or flow chopping: comment by M. Strum: may need to include pressure fed 

rolling and flow (non chopping) here since that is the way the industry proposed the 

process groupings to be. On the other hand, if we want to model flow chopping, versus 

flow non chop versus pressure fed roller differently, it would still be ok within the 

mechanical process grouping since I envision spray chopping would be different from flow 

chopping. May just want to change to "a. Mechanical application" 

Stage 1 - Spray or flow coater comment by M. Strum: "Mechanical" application of resin to 

mold surface. 

Stage 2 - Roll-out or mechanical manipulation of laminate surface. 

Stage 3 - Post roll-out curing stage 

b. Hand Lay-up (manual application):Comment: may not want to distinguish between manual 

(bucket and brush) and other non-spray mechanical means of application (such as flow 

coater, pressure fed roller, etc). 

Stage 1 - Manual transfer of resin from container to mold surface. 

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Stage 2 - Roll-out or mechanical manipulation of laminate surface. 

Stage 3 - Post roll-out curing stage 

Want to address filament winding here as well? 

I suggest this section be re-written to be kept very general, such that the three stages are: 

Stage 1 - Application of resin to mold surface. 

Stage 2 - Roll-out or mechanical manipulation of laminate surface. 

Stage 3 - Post roll-out curing stage 

Would these three stages address filament winding as well (I don't think so since resin is 

applied to filaments which are then applied to resin ~ would we want to combine these in 

defining application of resin to mold surface)? 

4) The effect of suppression is negligible during the resin application portion ofthe process (i.e. 

during the spray transfer or manual transfer of resin to the mold surface). 

5) Suppressing action is effected by the roll-out, or mechanical manipulation, portion ofthe 

laminating process, when the laminate surface is being disturbed by FRP rollers, brushing, etc. 

Comment: It is believed that there will be some effectiveness of the suppressant at this 

stage, but it may not be as great as the effectiveness in the curing stage. Note: the reason 

for assuming some effectiveness at the stage when the resin is being worked is that previous 

testing has shown a maximum overall suppressant efTectiveness of 40% while only 25% of 

the total emissions were released during curing as indicated by emission profiles. Thus 

some ofthe emission reduction must also come from the other two stages. 

6) Once the roll-out (mechanical manipulation) ofthe laminate is concluded the effects of 

suppressants become significant. 

III. Current Premise for Test Development 

1) Only emissions stages 2 and 3 need to be encompassed by the test method. 

Comment: Only emissions stages 2 and 3 will be encompassed by the laboratory part of the 

test method. A VSR effectiveness model will then use the laboratory test method results to 

provide the input; for the MACT model. 

2) Fiber reinforcement should be incorporated into the test sample to provide laminate surface 

effects. 

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3) Mechanical roll-out is needed to encompass the stage 2 effects. 

4) Test method should be as simple as possible. 

5) Testing should be able to be duplicated and used on a broad scale. 

Comment by M. Strum: Add: "If possible, the test method should be able to be conducted 

by resin manufacturers or suppressant manufacturers on the "as-applied" resins (may need 

definitionfof as-applied) so that these material suppliers (if asked by the composites 

manufacturer) could supply the data to the composite manufacturers. However, it is the 

composite manufacturers that are ultimately responsible for the result ofthe test. Would 

resin manufacturers be willing to do this on a gel time specific basis, since gel time is a very 

composite-manufacturer specific parameter? Would test method gel time be the cup gel 

time at a specific temperature or the actual gel time? It appears part of this test would 

require determination of the gel time of the resin so that the test would be specific for a 

specific gel time and results could only be used for that specific gel time tested. 

IV. Test Development Issues 

1) Determining weight loss by a gravimetric method is simple. 

* The use offa lab balance as the primary measurement method would be appropriate, if 

repeatability can be established. 

2) Appropriate glass fiber reinforcement and resin to glass ratio must be selected. 

* 11/2 oz./ft2 Chopped Strand Mat (CSM) Fiberglass Reinforcement @ a ratio of 25% glass to 

75% resin by weight will be selected for initial trials. Comment by M. Strum : could a few 

ratios be looked at and compared with this selection so that the effect of this parameter is 

known? 

3) Test laminate size must be determined. 

* The test laminate size will be 12" x 12" for the initial trials. This size provides a convenient 

enclosure size and sample resin quantity. 

Comment by M. Strum: The thickness ofthe laminate needs to be determined (the surface 

area ofthe laminate should not effect the effectiveness ofthe suppressant, but would it 

affect the repeatibility/accuracy?). 

4) A method of distributing the resin across glass fiber reinforcement must be devised. 

* Initial trials will be carried out by manually pouring resin across the CSM surface. This method 

will be evaluated fbr repeatability.iWe need to better define how the laminate sample is 

prepared. Are these following steps to prepare the laminate sample correct? (1) The 

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reinforcement is placed in the test pan, (2) a specified amount of resin is poured over the 

reinforcement, and (3) the resin is rolled out for a specified amount of time. 

5) A method of controlling the action ofthe FRP roller may be required. 

* Initial trials will be carried out using manual rolling for a specified period of time. This method 

will be evaluated for repeatability. If repeatability cannot be established using this method, a 

mechanical rolling device will be devised. 

6) Length of test must be established. 

* Because this test is focused on stage 2 & 3 emissions, it is important that the test run be of 

duration that there is a reasonable certainty that styrene emissions have reached a baseline level. 

In the absence ofthe more complex requirements to establish a baseline, the following is 

proposed: 

- There is a relationship between gel time and overall cure time with a vast majority of resin and 

initiator systems. Therefore, using gel time multiplied by a factor can establish a period in which 

the laminate can be expected to have achieved baseline emissions. 

- It is proposed that the initial testing use the formula of gel time (min.) x 6 to establish the test 

duration. 

- Using the examples of two common gel times of 15 and 30 minutes, the total test time would be 

90 minutes and 180 minutes respectively. Previous testing has shown these times adequate for 

emissions to decline to baseline levels. Comment by M. Strum: what about waiting for weight 

loss to achieve a constant value. Does a time need to be specified. 

7) Test procedure must be developed. 

* An initial test procedure is proposed in this draft. 

Comment by M. Strum. Should Suppressed and nonsuppressed resins be done at same 

time in same enclosure? If the samples are tested side by side, it needs to be assured that 

both samples are exposed to the same air flow in the enclosure. However, it would needs to 

be assured that one sample does not affect the emissions, released by the other sample. 

Should test include 3 sets of suppressed and non suppressed resins? 

V. Initial Experimental Proposal 

1) Test Set-up: 

a. Test to be conducted in a temperature stable environment, at 770F (40F (250C (1.20C) 

Comment by M. Strum (need to delete degree sign since the translation of the email 

message made it impossible to read the temperature(s?) that are being proposed. 

Should a few temperatures be initially tried to see if there is an effect? If no effect we 

might be able to give a range of temperatures. If big effect we might need to work harder 

to come up with a realistic/representative/ best or worst case temperature. Is the 

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temperature ofthe water bath in which the resin sample temperature is stabilized the same 

as the air temperature? 

b. The test is conducted in an enclosure of ( )" x ( )" x ( )", which incorporates airflow of 

( ) fpm through the enclosure. Comment by M. Strum: when enclosure is open, air flow is 

no longer a constant ( ) fpm through the enclosure. 

c. A shallow test pan (__)" x ( )" is positioned on a digital balance. Comment by M. Strum: 

do we need to specify depth of test pan as well as length and width? Do we need to specify 

the materials ofthe test pan as well (a too heavy a pan will give a large error due to small 

weight differences)? 

d. Balance will be accurate within (( )g 

2) Required Equipment: 

a. Test enclosure w/ fan, baffles, NDO's, and doors 

b. Laboratory balance(s) 

c. Test Pan (dimensions to be specified) 

d. Constant temperature water bath 

e. Gel timer 

f. FRP roller, disposable (size & type to be specified) 

g. Plastic beakers - 200ml 

h. Glass stirring rods 

3) Required Materials 

a. 11/2 oz./ft2 Chopped Strand Mat (CSM) Fiberglass Reinforcement (12" x 12") 

b. Resin 

c. Initiator 

d. Suppressant additive 

4) Test Procedure: 

a. Stabilize resin sample temperature in water bath at 770F ( 40F (250C (1.20C) [Tolerance 

TBD] 

b. Measure resin gel time with identical initiator percentage to be used in pan test [Use standard 

GT procedure] 

c. Establish length of pan test - Gel Time (min.) x 6 = Test Time Span [*appropriate multiplier 

TBD] 

d. Prepare test pan with release agent if required (Which release agent is proposed for this 

test? Unless this release agent is typically used by all facilities during actual production, it 

should not be used during testing because it could affect emissions.) 

e. Place test pan on balance in enclosure 

f. Prepare CSM sample. 

1. Cut to 12" x 12" square 

2. Weigh sample (Target weight 42.5g (4.2g) [*acceptable tolerance TBD] comment by M. 

Strum: don't understand parenthetical remark — must be an email transmission error. 

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g. Place CSM sample in test pan 

h. Place FRP roller on test pan 

I. Tare balance 

j . Measure 130g ( 2g resin into 200ml plastic beaker [*exact quantity & acceptable tolerance 

TBD] Please explain this in more detail. Does this mean you measure 130g of resin with an 

acceptable measurement tolerance of 2 g? 

k. Measure appropriate quantity of initiator (and suppressant additive) into resin sample 

1. Mix resin sample for 1 minute with glass stirring rod 

m. Remove stirring rod and set aside 

n. Start time 

o. Pour resin mixture into pan, distributing uniformly across CSM - set plastic beaker aside 

p. Record initial weight (Iw) - resin applied to laminate in pan (sample weight) 

q. Using the FRP roller, roll the laminate surface for 1 minute, using uniform strokes and speed 

[*time TBD] 

r. Place FRP roller in pan 

s. Close enclosure doors comment by M. Strum: where are enclosure doors open? How to 

make sure air flow is at constant/identical rate during rolling for different tests? 

t. Stop time - Test Time Span (GT x 6 = TTS) 

u. Record final weight (Fw). 

v. Calculate weight loss and emissions percent 

a. Initial weight - Final weight = Styrene loss 

Iw - Fw = SI 

Styrene loss / Initial weight x 100 = % Styrene emissions per resin weight 

SI / Iw x 100 = % Styrene Emissions (RW) 

Comment by M. Strum: results should be % reduction from non suppressed resin: 

{% Styrene Emissions (RW) of nonsuppressed - % Styrene Emissions (RW) of suppressed } 

divided by % Styrene Emissions (RW) of nonsuppressed 

DRAFT - Development of Suppressant Effectiveness Test... 

i