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OAR Box 1413 

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36) 11-1-33 

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A-94-52 

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TOJ • List 

From: J. H. Kiekhaefer 

Ve have finished evaluation of output of styrene off the O'Hare line. The 

result sheets and calculations are attached. Ve measured emissions by 

determining the difference in weight between materials going into the 

process as compared vith those coming out. Measurements were made on two 

seperate consecutive days. Essentially, we measured a running emission 

rate of 71.1 lb/hr on the first day and 62.6 lb/hr on the next. This was a 

12% difference in the results between the two days in styrene emitted per 

hr fromthe process. #MT \<\. S lb«J)*.. (e.»*V.iW«*-__# yo."7 *^il*u-/h#wi wsedl.) 

I believe the measurement process is reproduceable and that the difference 

between the two days is real. The reason for the difference appears to be 

evaporation of styrene off the two large holding tanks due to venting of 

those tanks to the outside. This resulted in less styrene being in the 

applied resin on the second day. This is supported by a change of 

specific gravity of the resin from 1.12 on the first day to 1.21 on the 

second day. ' t • 

Ve know that the venting of the holding tanks occurs during running and 

that RMT measured it to be responsible for an emission rate of 4.6 lb/hr. 

It will need to be confirmed whether this emission actually goes on during 

all hours or only when the process is running. If it occurs at all hours, 

the amount of emission it is responsible for would be (4.6 lb/hr) (24 

hr/day)(365 dayB/yr)=40,296 lb/yr. 

Besides effecting emissions levels from the process from one day to the 

next and greatly adding to total emissions, the venting of the tank also 

has a great impact on guality. The large change in specific gravity of 

the resin between days resulted in the signs being 5.4% thicker on the 

second day as compared to the first. Besides product guality, I can 

imagine that this type of resin change would greatly effect operating 

parameters on the line. Resin reactivity is bound to be effected as well 

as vetout of the composite and paper materials by the resin. I am sure 

this factor is a significant contributor to scrap and difficulty running 

the line. 

I am not sure what the thinking in design was behind the venting of the 

holding tanks. Whether it is going on only during running, or at all 

hours, the emissions that are occurring are avoidable. There is no reason 

that ve cannot eliminate the stack connections and operate from closed 

vessels which have one way pressure relief valves and fluid level 

monitors. Ve should consider this even if we are going to be running only 

one more year. 

Let's get back, then, to assessing the validity of the reported emission 

levels. For the purposes of the assessment, let's take the first days 

results which essentially represent emissions with the specific gravity of 

the resin at the proper level, as it should be in the future. The 

emissions measured were 71.1 lb/hr. From this we can subtract 1.1 lb/hr 

emissions which is what RMT measured comes from the electric' oven zone and 

4.6 lb/hr which is what they measured due to holding tank venting. This 

will give us 65.4 lb/hr emission from the flow coating zone, obviously the 

bulk of our running emission. Let's look at whether this number is 

realistic. 

To: P Hennessey, J Jackson, J Dyer, S Cantveil, G Gyllstrom, G Jehlik, T 

Carpentier, D Knudtson, K Veber, G Witte. 

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RMT measured stack emissions from the flow coating zone as 13.5 lb/hr 

while running. This then infers, that if the measured total emissions 

from the flow coating zone is correct, we have 51.9 lb/hr fugitive 

emission from the flow coating zone into the work'area; Having been in 

the work area, this is hard for mc to believe. It is also hard for me to 

believe that 79% of our emissions from the flow coating area are not being 

collected to the stack. 

A second check which challenges the validity of the measured emission 

output, is that it represents an emission of 47V of the styrene that vent 

into the process to begin with. It is hard to believe that proper resin 

cure and sufficient wetout of materials could occur with such a loss. 

A third crosscheck, which questions the validity, has to do with 

calculating the evaporation rate of styrene off an exposed wet resin 

surface. I estimate the area of exposed wet resin on the flow coating 

zones to be (40ft) (3.5ft)=140 sq ft. Dividing this into our measured 65.4 

lb/hr emission from the flow coating gives us an evaporation rate of 

65.4/140 » 0.47 lb/hr/sq ft. This is large compared to that calculated to 

be coming off the vented holding tanks which is 4.6 lb per hr/19.24 sq ft 

=0.24 lb/hr/sq ft. * • 

i 

In summary, I would say the measured styrene coming off the flow coating 

zone is hard to believe, yet on the outside fringe of the possible* I 

recommend that before we go further, we closely check its validity 

experimentally in the lab. Ve can doe this by putting resin into a 1 sq 

ft pan and measuring weight loss after 15 minutes to give us a Ib/hr/sqft 

rate. Another part of this work should be to actually go out and measure 

the area of exposed wet resin that we have (including dispensing cans, dam 

pools, and wet materials). Multiplying these two outcomes should give us 

expected losses from the flow coating zone which we can compare with that 

which we measured. If there is a marked difference, we will then need to 

decide which figures to use in stating our emission output. 'This 

experimental work will be.done immediately after the Holidays. 

9 o-fyjrk' 

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To: ' List 

From: J. H. Kiekhaefer 

Grant Witte has finished evaluation of output of styrene off Pultruder 2. 

His result sheets and calculations are attached. He measured emissions by 

determining the difference in weight between materials going into the 

process as compared with those coming out. Measurements were made on two 

seperate days (on yellow stake runs). There was little difference in the 

results between the days Indicating experimental reproduceabillty. 

Essentially, Grant found there were 2.85 lb/hr total emissions for each 

stake die in the three die machine when the machine was run at a speed of 

91.25 ft/hr with 3 one minute die cleaning dwells per hr. Ve believe the 

bulk of these emissions come from styrene evaporation off wet resin 

surfaces including the mixing drum, the dispensing pail, the dip tank, and 

the wet composite before it enters the die. Another source is hot 

vaporized styrene coming from the exit side of the die. 

For each pultruder, then, the total calculated emissions are as follows: 

Pultruder 1 - 5.70 lb/hr (olwtufe. W. G«T w** \.y ib/k*. MI* I.S txil/Ko *s C*A./K**I) 

Pultruder 2 - 8.55 lb/hr . ° 

In. order to calculate total daily emissions which are not understated, one 

should multiply these numbers by the total number of hours where wet resin 

ls exposed for evaporation. This would include the time of the following 

activities: 

Time mixing resin. ^._j__*.««-»* 4K*-*. rtrNv* Ovx>*+**»4- *-«* U*»<_ fij-niitt/x-a pc 

Time to initiall y fill di p tanks . »-*-.+• <{ ns*+\>m* . 

Time betwee n di p tank filling and Initiation of continuou s running . 

Time of continuous running. 

Time of takedown activities from end of continuous running to when wet 

resin ls no longer exposed. 

Daily emissions will need to be calculated by time not by number of stakes 

produced or amount of resin used. The reason for this is that the bulk of ' 

our emissions appear to be due to evaporation of styrene from exposed wet 

resin surfaces. Since evaporation is occurring into an open air 

environment, the two determining factors of how much styrene is evaporated 

is the surface area exposed and the time of exposure. Once the machine is 

loaded with wet resin surfaces, we are emitting even when the line is not 

moving. To reduce emissions per stake it is obvious we need to minimize 

dwell times and keep the line moving as fast as possible. To reduce 

emissions overall, it its obvious that we must reduce the surface area of 

exposed wet resin. Following is an estimate of what that is for each 

pultruder. 

Exposed Vet Resin Surfaces 

Pultruder 1 Pultruder 2 

Mixing drum 3.2 sg ft 3.2 sg ft 

Dispensing pail 1.4 sq ft 1.4 sg ft 

Dip tank 4.0 sg ft 6.0 sq ft 

Composite 5.0 so ft 7,5 Sfl ft 

Total 13.6 sq ft 18.1 sq ft 

To: P Hennessey, J Jackson, J Dyer, S Cantwell, G Gyllstrom, G Jehlik, T 

Carpentier, D Knudtson, C McElfresh, K Veber, G witte. 

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11/17/95 10:51 ®91 9 541 7155 RTI- CEA Lgjuua 

• • » . 

• • • : 

i said above that the results we got were reproduceable. A second 

question is "Are they realstic?". If we are to believe RMT's measurement 

of stack emissions(1.3 lb/hr on Pultruder 1 and 2.0 lb/hr on Pultruder 2), 

then we must conclude that we have a very large amount of fugitive 

emission in the work area. Having been in the work area, this seems 

intuitively hard for me to believe. Another point, though, which does 

seem to support these emission results, is that they represent emissions 

of only about 13% of the styrene that went into the process which ls not 

unrealistic conceptually. There is one way that we could get a better 

idea of validity, and that is to experimentally determine the expected 

evaporation rate of styrene from our exposed wet resin surfaces. Ve can 

doe this by putting resin into a 1 sq ft pan and measuring weight loss 

after 15 minutes to give us a lb/hr/sqft rate. Another part of this work 

should be to actually go out and measure the area of exposed wet resin 

that we have. Multiplying these two outcomes should give us expected" 

losses from the wet resin surfaces and this will give us an additional 

judgement on the validity of our stated emission rates. This work will be 

done immediately after the Holidays. 

9/ *$# 

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11/17/95 10:54 ©919 541 7155 RTI- CEA ignu4 

1. INTRODUCTION. 

1,1 Background 

V.M. Brady Company (V.H. Brady), Signmark Division, operates a 

facilit y at 3328 Vest Cameron Avenue, Milwaukee, Visconsin, at vhich the 

company manufactures fiberglass signboards. Operations performed at this 

facilit y include dip and flow coating of fiberglass substrates with 

styrene-based resins. Styrene polymerizes on these substrates to. form the 

finished products. The coating activities are performed on tvo process 

line s (flow coating of paper and fiberglass webs on the O'Hare line , and 

dip coating of roving on the Pultrusion line), and result in the emission 

of styrene at the facility to the ambient air. Styrene is stack-vented 

to the ambient air from storage tanks, the flow coating zone, and an 

electri c oven zone on the O'Hare line; and from the dip coating zone on 

tha Pultrusion line . 

fljj RMT, Inc., (BMI) performed stack testing at the Signmark Division 

„t for styrene emissions from the O'Hare and Pultrusion lines, and prepared 

pJ' this report presenting and discussing the results of the staek testing. 

The tests vere conducted on September 19,' 1989. The following personnel 

were involved' in coordinating the field portion of che stack testing: 

tf V.H. Brady Chuck Koehler 

^ John Kiekhaefer 

0

RKT, Inc. David Seitz 

Martin Scromberger 

M 

1 

1 

1.2 P\HTpo«e 

The purpose of this project vas to quantify che staek emission rates 

of styrene from the O'Hare and Pultrusion lines, and to present the test 

results. 

1003.09 101:RTF:bradl010 1-1 

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11/17/95 10:54 ©91 9 541 7155 RTI- CEA Igiuio 

3. TEST RESULTS AND REGULATORY IMPUCATION S 

T he results of the stack emission testing for styrene from che 

O'Hare and Pultrusion lines are summarized in Table 3-1. Emission rate 

calculations are presented in Appendix A . Production data observed and 

collected during the testing, along with associated calculations and 

Material Safety Daca Sheets (MSDSs), are presented in Appendix B. 

According to V.H . Brady production staff, production levels run o n bot h 

•..;"] the O'Hare and Pultrusion lines vere at or near maximum levels. Resi n 

usage rates averaged 50.7 gallons per hour en the O'Hare line and 7.5 

•y-\i gallons per hour on the Pultrusion line. 

'•iJ Detailed stack test data, including air sampling data forms, styrene 

sample results, and gas flow computation sheets are presented in 

;:fij Appendix C. 

F or the O'Hare line, the total styrene emission rate was measured i 

^ B to average 19.2 pounds per hour from the three stacks venting this line. « Acetone, 1,1,1-trichloroethane,- methylene chloride, and xylene wer e also 

deceeced in the samples. See Table 3-2. The maximum emission rate of 

jj9J| these compounds totaled approximately 0.6 pounds per hour, based o n the 

maximum concentrations measured for each compound. Therefore, the total 

a 

_:-jg emission rate of organic compounds vas measured to be approximately 19.8 

•uk pounds per hour. 

, The O'Hare line appears to fall within che "fabric coating" RACT 

category in NR 622.08, Visconsin Administrative Code. This section limits 

the VOC content of the coating to 2.9 pounds per gallon, excluding vater. 

T he VO C eontent of the coating applied at the O'Hare line vas calculated 

to be 2.88 pounds per gallon from data supplied b y V.H. Brady. 

i 

i 

• 

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For the Pultrusion line, the styrene emission race vas measured to 

average 1.2 pounds per hour from the single stack venting this line . 

Other organic compounds vere found co be emitted at 0.072 pounds per hour, 

t 

or less, based on the maximum concentrations measured. See Table 3-2. 

Therefore, the total emission rate of organic compounds vas measured to 

be approximately 1.3 pounds per hour, or less. 

I 

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TABLB 3-1 

STACK TESTIHC SESULTS FOX STYHENE 

Uns/Swk 

i 

i 

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0'Hare/Storage Tanks 

0'Har«/Flov Coating Zone 

O'Hare/Electric Oven Zone 

Puicrusion/Dip Coacing Zone 

Run 

Number 

• 1 

2 

3 

Avarage 

1 

2 

3 

Average 

1 

'. 2 

3 

Average 

1 

2 

3 

Average 

Emission Race 

rTc-untis uar Hour) 

S.O 

6.9 

3.9 

6.6 

12.7 

13.8 

U.O 

13.5 

1.1 

0.9 

1.2 

1.1 

1.2 

1.2 

1.1 

1.2 

1 

ft 

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TABLE 2-1 

AVERAGE MEASURED STACK EMISSION RATES FOR STYRENE 

O'HARE UN E 

Average 

Emission Rate 

Staek rPounde per Hour) 

Storage Tanks &•& 

Flow Coating Zone 13.5 

Electric Oven Zone 1-1 

Total 19.2 

FtJLTRDSION LIH2 

Average 

Eaission Rate 

Stack rPounds per Hour) 

Dip Coacing Zone 1.2 

Coacing Application RaCe: 7.5 gallons per hour (average) 

«j Coacing Application Rate: '50.7 gallons per hour (average) 

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4. TEST METHODS 

RNT employed NIOSH Method 1501 to collect gas samples In che exhaust 

stacks serving ehe O'Hare and Pultrusion lines. This taeehod. contained 

iii Appendix E. uses cvo, tvo-stage charcoal sarbenC Cubes connected In 

series via flexible tubing for sample collection. SKC Model 226 PCXR7 

battery-operated personal sampling pumps vers ussd to dtav gas samples 

chrough tbe sorbent tubes ac rates of approximately 0.2 liCers per minute. 

The personal sampling pumps were calibrated befora and afcer each test run 

chrough che use of a rotooeter. The ro Come cer vas calibrated prior Co che 

testing chrough Che use of a soap bubble me cer. In general, the gas 

samples vere drawn from stack centers located immediately belov the 

. velocity pressure sampling ports. Individual test runs vere approximately 

45 minutes in duration. Analysis of che gas samples vas performed by che 

Wisconsin Occupational Health LaboraCory in Madison, Visconsin, by 

des orb ing the samples vith carbon disulfide and 'Injection into a gas 

chromatograph equipped vith a flame lonizsclon detector for Identification 

and quantification. For each test run, only one of the cvo sorbent cubes 

vas analyzed since no breakthrough of styrene in the primary sorbent cube 

vas noted. 

H VSEPA Reference Methods 1 and 2 vere employed by RMT using a 

standard pitot tube and inclined manometer co obtain pertinent daca for 

. determination of seack gas volumetric flov races. Vet bulb/dry bulb 

measurements vere made using a mercury thermometer for determination of 

stack gas moisture contents. 

H Sketches of che stack sampling locations are concalned in 

Appendix F. 

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P.21 

Date: 4-18-94 

; To: Mark Bahner 

Research Triangle Institute 

Piroe: Janeen Jackson 

Brady USA, Inc. - Signmark Div. 

Page 1 of 6 

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W.H. Brady Company (W.H. Brady), Slgnaerk Division, operaeas a 

facility at 3328 Vast Cameron Avenue, Milwaukee, Visconsin, at which the 

coapany manufactures fiberglass signboards. Operations perfonned ac this 

facility Include dip and flov coating of fiberglass substrates with 

styrene-based resins. Styrene polyaerlzes on these substrates Co form the 

finished products. The coating activities are performed on two process 

lines (flov coating of paper and fiberglass webs on the O'Hare line, and 

dip coating of roving on the Pultrusion line), and result In the emission 

of styrene at the facility to the ambient air. Styrene is ateck-ventad 

to the ambient air from storage tanks, the flov coating cone, and an 

elactrle oven zone on the O'Hare line; and from the dip coating zone on 

the Pultrusion line. 

RMT, Inc., (KMT) performed stack testing at the Slgnaark Division 

for styrene emissions from the O'Hare and Pultrusion lines, and prepared 

this report presenting and discussing tha results of the stack testing. 

The tests vere conducted on September 19, 1989. The following personnel 

ware Involved ln coordinating the field portion of che stack testing: 

V.H. Brady 

RMT. Inc. 

Chuck Koehler 

John Klekhaefer 

David Seitz 

Martin Stromberger 

D 

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1.2 Eymjift 

The purpose of this project vas to quantify the stack emission rates 

of styrene from the O'Hare and Pultrusion lines, and to present the test 

results. 

1003.09 lOl.RTP.bradlOlO 1-1 

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3. TEST RESULTS AHD REGULATORT IWLICATIOHS 

The results of the stack emission testing for styrene froa the 

O'Hare and Pultrusion lines are summarized ln Tabie 3*1. Emission rate 

calculations are presented in Appendix A. Production data observed and 

collected during the testing, along vith associated calculations and 

Material Safety Data Sheets (HSDSs). ara presented in Appendix B. 

According to V.H. Brady production staff, production levels run on both 

the O'Hare and Pultrusion lines vere at or near maximum levels. Resin 

usage rates avaragad SO.7 gallons per hour on the O'Hare line and 7,5 

gallons per hour on the Pultrusion line. 

Detailed stack test data, including air sampling data forms, styrene 

sample resulta, and gas flov computation sheets are presented In 

Appendix C. 

For the O'Hare line, che total styrene emission rate vas measured 

to average 19.2 pounds per hour froa the chree stacks venting chis line. 

Acetone, l.i, I-trichloroethane, methylene chloride, and xylene vere also 

detected in che samples. See Table 3-2. Tha maximum eaission race of 

j : . 1 

these compounds totaled approximately 0.6 pounds per hour, based on the 

maximum concentrations measured for each compound. Therefore, che total 

emission rate of organle compounds vas measured to be approxlaately 19.8 j 

pounds per hour. 

The O'Hare line appears to fall within Che "fabric coacing' RACT 

category! in HR 422.08, Visconsin Administrative Coda. This section limits 

Che VOC content of the coating to 2.9 pounds per gallon, excluding vater. 

The VOC content of the coating applied aC Che O'Hare line vas calculaced 

co be 2.88 pounds per gallon from data supplied by V.H. Brady. 

1003.09 101:RTF:bradl010 3-1 

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For tha Pultrusion line, the styrene emission race vas measured to 

average 1.2 pounds per hour from che single stack venting this Una. 

Other organle compounds vere found to be ealcced at 0.072 pounds per hour, 

or lass, based on the maximum concentrations measured. Sea Table 3-2. 

Therefore, the total emission rate of organic compounds vas measured to 

be approxlaately 1.3 pounds per hour, or less. 

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TABLE 3-1 

STACK TESTING RESOLTS FOR STTREME 

UM/StfC» 

0'Hare/Storage Tanks 

0'Hare/Flow Coating Zone 

O'Hare/Eleccrlc Oven Zone 

PuicrusIon/Dip Coating Zone 

1003.09 101:RTF:bradl010.t 

Average 

Run 

Muabey 

1 

2 

3 

Average 

1 

2 

3 

Average 

1 

2 

3 

Average 

1 

2 

3 

Emission Race 

(Pounds oer Hour) 

S.O 

4.9 

3.9 

4.6 

12.7 

13.8 

14.0 

13.S 

1.1 

0.9 

1.2 

1.1 

1.2 

1.2 

l.l 

1.2 

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TABLE 2-1 

AVERAGE MEASURED STACK EMISSIOM RATES FOR STTREME 

O'HARE LINE 

Stack 

Storage Tanks 

Flow Coating Zone 

Electric Oven Zone 

Averege 

Emission Rate 

(Pounds oyr Hftqi-) 

4.6 

13.5 

Total 19.2 

Coating Application Rate: 50.7 gallons per hour (average). 

PULTRU8ION LINE 

Stack 

Dip Coaelng Zone 

Average 

Emission Race 

(Pounds oer Hour", 

1.2 

a 

Coating Application Race: 7.S gallons per hour (average), 

1003.09 101:RTF:bradl010.t 

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i 

jB 4. TEST METH0D8 

RMT employed NIOSH Method 1501 to collect gas samples in the exhaust j 

I ] stacks serving the O'Hare and Pultrusion lines. This method, contained 

in Appendix E, uses tvo, tvo-stage charcoal sorbent tubes connected in 

• series via flexible Cubing for sample collection. SKC Model 224 PCXR7 

^ battery-operaced personal sampling pumps vere used to drav gas samples 

through che sorbenc tubes at rates ef approximately 0.2 liters per minute. . 

0 | 

The personal sampling pumps vere calibrated before snd efter each test run * 

i 

through the use of a rotomecer. The rotometer was calibrated prior to the ! 

testing through the use of a soap bubble meter. In general, the gas 

im samples vere drawn from stack centers located Immediately belov the 

velocity.pressure sampling ports. Individual test runs vere approximately 

45 minutes ln duration. Analysis of the gas samples vas performed by the 

Visconsin Occupational Health Laboratory In Madison, Visconsin, by 

H desorblng the samples vith carbon disulfide and Injection Into a gas 

chromatograph equipped vith a flame Ionization detector for Identification 

i 

and quantification. For each test run, only one of che two sorbent tubes 

was analyzed since no breakthrough of styrene ln the primary sorbent tube 

vas noted. 

USEPA Reference Methods 1 and 2 ware employed by RMT using a 

standard pito t cube and inclined manometer to obtain pertinent data for 

determination of stack gas volumetric flow rates. Vet bulb/dry bulb 

measuremencs were made using a mercury thermometer for determination of 

stack gas moisture contents. 

Sketches of che stack sampling locations are contained ln 

Appendix F. 

i 

1003.09 101:RTF:bradl010 4-1 

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