Document rxaQZYa5wwG8RzY7jZMN9RbnE
' A4r226- ; Report 2457, June 1990
26 / 6 5 9
AFNARLOYMSITSHEOFCUFRUIMNEGS ORPEESRUALTTIIONNG
.
T\ENFTLHOENM-ACNOUATFEADCTAURRTEICOLFES
(Additional`samplings, March andApril 1990)
pu pontregistered trademark
000152
2
5 Battelle Europe
_ EIDon2116
REPORT ANALYSIS OF FUMES RESULTING FROM THE CURING OPERATION
IN THE MANUFACTURE OF
TEFLON-COATED ARTICLES
(Additional Samplings, March and April 1990)
for DU PONT DE NEMOURS (Belgium)
Mercure Centre Raketstraat 100-rue de la Puse 100
B - 1130 BRUSSELS
June 1990
BATTELLE EUROPE Geneva Research Centres
7, route de Drize 1227 Carouge/Geneva
Switzerland
Du Pont registered trademark
s
000112
EID902117
TAOFBCONLTENETS rage
SINMARY
1. INTRODUCTION
1
2. S2A.M1PLOEUTCLOILNLEECOTFISOANMPLING PROCEDURES
3 3
2.2 2.3
SAMPLING OF PARTICULATES COLLECTION OF HYDROGEN FLUORIDE
AND
HYDROLYSABLE
. 6
FLUOROCOPOUNDS
3. A3N.A1LYPTAIRCTIACLUMLEATTHEODMASTTER (Aerosols)
88
.
3.1.1 GRAVIMETRIC DETERMINATION OF PARTICULATES
'
3.1.2
3.1.3
SDCEATNENRIMNIGNATEILEOCNTROOFNBMIISCPRHOESNCOOLPYA
8
8
:
3.2 DETERMINATION OF HYDROGEN FLUORIDE AND HYDROLYSABLE
FLUOROCOMPOUNDS
10
4.
RESULTS 4.1 PARTICULATE
MATTER
un n
4.2 ANALYSIS OF HYDROGEN FLUORIDE AND KYDROLYSABLE FLUOROCOMPOUNDS
13
S. DISCUOSFSREISUOLTNS
15
BIBLIOGRAPHICREFERENCES
20
EiGURES 1-8
TABLES 1-6
NEXES 1-3
000124
EID902118
STORY
In a previous study (Reference 2: Battelle Report 2329, October
1989), the composition of the fumes resulting from the curing of
different types of coating materials was analysed. Samples were
taken from the fumes released during the curing Of the most
representative Teflon cookware and industrial cooking products,
during the routine fabrication procedures in a Teflon coating
plant, and analysed in the Geneva Laboratories in Battelle-Europe.
The results showed that large variations occurred in the concen
tration of particulate emissions (ranging from less than 0.1 ng/n'
up to 104 mg/n') in the frame of Silverstone and Silverstone Supra
coatings. Large variations also occurred in the concentration of
i
fluorides in the fumes (ranging from 0.11 mg/m' F" up to 1.2 mg/m'
7) resulting from the curing of Silverstone coating materials.
In order to better interpret the data, further analytical study was undertaken. The objective of the present study was to analyse the particulates and fluorides in the fumes resulting from the curing of one SilverStone coating material, by using different sampling procedures. This was needed because the concentrations are dependent upon the sampling conditions.
Samples of funes from the stacks of one conveyor oven were collected during the usual curing operation of SilverStone pewter coating, in a Teflon coating plant.
The following sampling procedures were used:
A. Isokinetic sampling according to Italian Standard. The particulates were collected on glass wool placed in a stainless steel container, or on glass fiber membranes with a nominal pore diameter of 0.45 micrometer. Both types of filters were dried to constant weight at 105C before and after sampling. Gaseous fluorides were collected in impingers containing alkali solution, placed in line after the filter.
000225
RIC000597 EID902119
5. sseanmbpzlainnegs tweicthhniqpuoersesusoefd 0.i4n mtihceropsreetveirousdissmteutdeyr. vFeorleycuasrebdenaftoer wtehree.coclollelcetcitoend ofonparftiiltceurlsatewshi(caherovseorles).conOndeitisoentedof acsamprloeosm TCehmpootrhaetrurseetinofcsoenbtrroalnleesd vheurmeiddirtiyedbteofocroenstanadntawfetiegrhtsaamtpl1i0n5g.C bceoflolreecteadndonaftseerpacroaltleecstaimnpglintghelipnar,tiucsuilnagtessl.kelFtlusoorliudseisonvsertso absorh hydrogen fluoride and hydrolysable fluozocompounds
haned bcyondcietnfterraetnitonproofcepdaurrteisc,ulvaatsesd,etceorlmliencetdedbyongrdaivfifpeerternyt. Sfiolmteerosf
;
Cthoeo1bt1aeirnsinwfeormeaetxiaomninoend tbyhesmcaonrnpihnogloeglyecotfropnarmtiiccruolsactoepsy. iAnLLordtehre
:
cfialrtbeorns,diussueldfifdoer atnhde bcioslplheecntoilonAowfaspadretticeurlmaitneesd, nwerteheexetxrcarcatcetds.by
Te analyses of particulates and fluorides emulting from she curing
of SilverStone coating materials are summarized as follows:
1. Particulates
The average concentration of particulstes collected by isokinetic
sampling according to Italian Standard was 2.35 mg/m' in the entry
Lstraectkionasndwe0r.6e9mfgo/unmd? uisnintghegleaxsist fstiabcekr. mAebmoburtanetheorsagmleascsoncweono-l filters.
hpoelycaavrebroangaetec,on(cFeC)ntrmaetaibornanoefs apanrdtidcruileadtetso ccoonlslteacntetdwbeyigBhattcaetll1e05oCn
was 2.45ng/n' on the entry and 3.87mg/d in the exit stack.
"Thhiecahvevreargeeccoonndcietnitornaetdioinn 6of34praerltaitciuvleatheusRciodlilceycsttedzooonmXtCemspeesrbartaunrees
was 18.6mg/m3 in the entry stack and 5.68ng/n' in the exit stack.
.
E2120
Z
00012
Thess results, together with the electron microscopic examinations of filters, seem to indicate that a big part of the substances retained on the membrane filters consists of liquid material. The proportion of non volatile to slightly volatile substances of the funes seems to be higher in the exit than in the entry of the conveyor oven, and these particulates seem to be retained in a different manner by different types of filters.
The bisphenol A concentration of all samples vas lover than 0.003
ng/n3.
2. Fluorides
The total fluoride concentration in the samples collected in the
frame of the previous study during the curing. of silverstone
coating products varied between 0.11 and 1.2 ng/n', `the average
concentration was 0.5ng/n'.
sampling procedures, similer
In the present
results were
study, using
obtained. The
the same
concen-
tration varied between 0.07 ng/n and 1.7 mg/m? and the average
concentration was 0.4mg/m.
The average concentration of gaseous fluorides, collected according
to the Italian Standard procedure, was only 0.06 mg/n3. The
concentration ranged from 0.01 mg/m' up to 0.19 mg/m'. The con-
centration of particulated fluorides which are retained by the filters is not included in these values.
000127
EID902121
ANALYSIS OF FUMES RESULTING FROM THE CURING OPERATION
IN THE MANUFACTURE OF
TEFLON-COATED ARTICLES
(Additional Samplings, March and April 1990)
1
INTRODUCTION
A previous study (Reference 2: designed to cover the analysis
Battelle Report 2329, October 1989) of emissions which results from the
curing
showed
of the most
that large
representative Du Pont
variations occurred
TEFLON
in the
coating products
concentration of
particulate emissions ng/n?) in the frame of
(ranging from less than 0.1 Silverstone and Silverstone
mg/m' Supra
up to 104 coatings.
eThtehsoexylpaatretdicaullkaytlepshencoolnttayipneedsumrfaaicntlayntsdecaonmdpoBsiistpihoennolprAo,duacstswelofl
as fatty acids in the case of Silverstone Supra coatings.
some ilters cenperature
used for the collection of particulates, and reveighed after nine months, showed
stored at roo a considerable
weight loss days after
(up to sample
37% of the weight of particulates measured sone collection). This weight loss indicated the
presence of slowly evaporating material.
Large variations also occurred in the the fumes (ranging from 0.11 ng/n' B"
concentration of fluorides in up to 1.2 mg/m' ) resulting
from the curing of Silverstone' coating materials.
hu Pont registered trademark
=
000128
EID902122
--2-
In on
oparrdteircutloatienscearnpdretfeluobreitdteesr
vtehrossenedeadtead,.
furcher
snalysical
date
Tphaerticcounlcaetnetsratniaoyndeofpenfdluoornidtehse asnadmpelvienng mcoornedittihoensc,onacsentlrianteiaorngeosf
Vteolnopceirtayturiens
fporrobceondaintdionstiancgk,of
ntehteurfeiltoefr,
the etc.
filter
material,
aInhderetfhoerefltuhoeripdreessenitn
study the
fvuassesderseisgunletdintgo
afnraolmyztehethecuprairntgicuoflatoense
Silverstone coating product under different sampling conditions.
000514
EID902123
Sse
2.
SAMPLECOLLECTION
he sampling of funes has been performed at an industrial plant dwuirtihngfotlhleowciunrgintghroefe DcuodPeontsysStielmv:ers4t5o3-n5e16,pew4t5e6r-23c6o,ati4n5g6-m3a0t0e.rials,
Iofhe acpopnrvoexyiomratoevleyn
CTH2 16 m
was used for long hested
the curing. tunnel, in
This which
oven the
consists articles
prayed slowly
twhirtohugdhistpheershieoantewderezonienstroatducceodntornotlolead
mtoevmipnegragtruirdesa.nd
roved
.
The schematic conveyor oven
darreawignigvenandin a thteypiacnanlexetsemNpoesr.atu1reandpro2f. ilTehe fomraxitmhuiss
ture ached in the oven during the sample collection was
"empers re
around 430C
hcreosfsu-nseesctoifontsheofovaebnouatre28recmmovxed30thcrao.ugShmavlelrti(caabloutst5a0ckmsmof) sqhuoalrees
woveernes;cutthein stahmeplsitnagckpsroabtesabvoeurts
2 m height above introduced into
the the
upper level of stacks through
"hese entry
ahnodlese.xitFusmteacskasm,pluessinwgerdeiffceorlelnetctesdampsliimnugltparnoecoeudsulryesf.rom
the
hopeeraitdieonntiafnidcatthieonsamopflitnhge cosnadmiptlieosnscoalrleecptreedsendtuerdinign
the curing Table 1.
2.1 QUTLINE OF SAMPLING PROCEDURES
To types of sampling procedures were used:
A.
Isokinetic (Referance
s1)ampfloirngt,heacmceoarsduirnegmentto
oIftalgiaasneousstanedmairsdssionUsN.ICHTIhXe
samples were collected by AMBIO S.C.n.1.
5. sampling techniques described in Battelle Report (Reference 2);
Teflon FEP tubes (6 mm 0.D., 4 mm I.D.), bent at the end to
RIC000602
000120
EID902124
Se
5s0amplweisthveareracdoilulsecotfed50by=nBavtetreellues.ed as sampling probes. The
CFioglulreecti1ngshtohwes futmhee sdaimapglreasm. oIft ctohnesiesqtueidpmoefnttwousseadmpblyingMMBlIinOesf:or iLinnea Qstfaoirnltehsescosltleeecltiocnonotfainpearrti(ccuelsatteelsloo)n agnldassofwooglasekoeupst
fsolluuotriiodness; in two Drechsel type impinges containing alkell = mleimnberaAnesforandthoef gcaosleloeucstiofnluoorfidepsartiincuallakteelsi soonlutgiloansss. fiber
mIFheietstboerrna,lnyewdihinifcftheheriescnacgseleabsoesftwwieoneonel tAih.neTtthhweeoIsctaaemlspielainonfgStlalinindneeasrQdLaNsnedtthhgeoldasnsascUunrifecibheoifrn
No. the
5c8o5ll(eRcetfieornenocfe
a1e)roTseoclosmmeanbdosveth1e00usCe
aonfdglaatsshiogfh
qcuoanrctesntwroaotliofnosr
(above 10 mg/m') and the use of filter membranes below 100C and at
low concentrations (below 10 mg/m').
Foilgluerceti2osnhoowfs ftuhseedsieamgpelaens.of ItthecoenqsuiisptmeedntofustewdobysaBmaptltienlglelifnoers:the mleimnebra1ne ffoirltetrhse, collection of particulates (serosols) on
Li1nueor2ocfoonrpotuhnedscolilnecatlikoanliofsohlyudtrioogne.n fluoride and hydrolysable
2.2 SAMOPFPLARTIICUNLATGES
z
ProcedureA
g
AisitBaIim0nmlecdsoislalmseettceeterel,d cwpoiantrthtaiicnauelrnaot(meLisinnaeleiQtp)ho.erreoFdooinnamgeglltaaessrss offwiobo0el.r43pmleammcbiercdarnoemisenteorfa
000121
Eonzs
5.
(Line A). Both types of filters were dried to constant weight at 105C before use. During sampling the flow rate on both lines was regulated in order to obtain a linear velocity of gas in the probe identical to the linear velocity of gas in the stack. The volume, temperature and pressure of the gas was measured and the normalized sample volume was calculated for 0C and 1013 mbar. The sample volume ranged from 0.0235 to 0.0687 Nn'.
ProcedurBe Battelle used polycarbonate membranes of 47 mm diameter and 0.01 mm thickness with pores of 0.4 micrometer diameter (Nuclepore Corporation, Pleasanton, Ca, U.S.A., Ref. No. SN 111 130), for the collection of particulates (aerosols). One set of these filters were dried to constant weight at 105C; another set was conditioned at 25C and 65% relative humidity during 96 hours before weighing. The filters were then placed in Gelman Stainless Steel filter holders of 47 mn diameter. The flow-rate in the sampling line 1, measured by the rotameter, was 4 to 8 L/min during the collection of particulates. This corresponds to a linear velocity of about 1.4 to 2.8 m/s in the probe. This was lower than the calculated linear gas velocity in the stacks, which was 5.3 m/s in the entry and 6.1 m/s in the exit stack. The pressure-drop across the filter was about 100 mbar at the start of sampling and increased with time. The sample volume for the particulates ranged from 0.067 to 0.228 nnd (refer to Table 2). The following parameters were measured during the sampling operations: flow rate, gas volume, atmospheric pressure, pressure drop across the sampling device, ambient temperature. These are needed
000122
EID902126
i
S-
in order to (273K, 760
calculate the sample mag), according to
volunes for normalised the equation:
VouVX m>mx i2mT
v, = sample volume in Nm' (normalized cubic meters)
v
2
=
=
saammbpileentintemm3permaetausrueredK,in atnhde
gas
meter
= atmospheric pressure - pressure drop in m
Kg.
conditions
2.3 COLLECTION OFHYDROGEN FLUORIDE ANDHYDROLYSAPLE
'ELUOROCOMPOUNDS.
ProcedurAe
GtansetowuosDfrleucohrsiedle-sim(pHiFngaenrdshyidnrosleyrsiaebsl,e ffilluloerdocwoimtphou2n5d0s)mlweranedsa1m5p0lemdl
0.05% aqueous cho inpingess
potassium was of the
hoyrddreorxiodfe 6 stoolu8tiLo/nm.inT,hecofrlroewsproantdeisngthtrooutghhe
ieokinetic content of
gas each
velocity impinges
through the probe. was transferred into
After sampling, the separate polyethylene
bottles.
ProcedurBe
FhleuosridMeisdge(tKF Iamnpdingheyrdsroliynsssbelreiesf,luoeraocchomfpiolulnedds)wivvteehrree1c0soaommllpelde0d.i1nino
"aqueous bath of
sodium hydsoxide ice-uater during
solution. The the sampling,
impingess in order to
prevent
evapo
"tion hem.
oTfhethfeloNwaOrHatseolutthiroonusghdutehetoimbpuibnbgleirnsg
the was
warm fumes through of the order of 2
L/min, and the sampling lasted in most cases 100 to 120 minutes,
which resulted in fume samples of about 0.2 wn.
000123
EID902127
=
7s
Aifntteor asa5m0plmiin-gpotlhyeetchoynlteennet
of the bottle.
three impingers was The impingers were
transferred washed with
mall portions (2-3 ml) of distilled water and the washings were
collected in the same bottle.
the Teflon Jo ml 0.1 N
NFEaPOHtuabnidngsmlaelaldipnogrttioontshe(3i-n5pimnlg)erosf
was also rinsed with distilled water and
`hese washings were collected in a separate polyethylene bottle:
000124
EID902128
e-
3.
BALYTICAL METHODS
The gravimetric determination of procedure A was done in the laboratory
particulstes of AMBIO. The
collected by other analyt-
ical determinations were made in the Battelle-Europe laboratories,
Geneva.
3.1 PARTIMACTTEUR(LAeArosTolEs)
3.1.1 GRAVINETRICDETERMINATIONOFPARTICULATES
4
Atfrtaenrsposratmepdliinng,cltohseedfpiolltyecrasrbwoenraeterceomnotvaeidnefrrsominthtehe flialbtoerrathoorlydearn,d
rfeiwletiegrshewdasunddreiredthteo scaomnestcaonntdiwteiiognhst aast b1e0f5orCe asnadmptlhiengo.thOenresestetweosf
conditioned at 25C and 65% relative humidity before weighing.
3.1.2 SCANNINGELECTRONMICROSCOPY
A piece with a
of about thin gold
10 mn diameter was cut from the filters, layer under vacuum and examined by a
covered scanning
electron microscope JEOL JSH-840. Photographs of representative
areas were made using magnification x 1000 and x 5000.
3.1.3 DETERMIOFNBAISTPHIENOOLNA
The filter membranes were placed in 15 ml screw-capped glass vials
and extracted with 2.0 grade) in an ultrasonic
ml carbon bath, for
disulfide 15 minutes
(Merck, at 25C.
Spectroscopic 3.0 ml carbon
disulfide was used for the extraction of glass wool filters. An
aliquot of the extract was analyzed by GC-MS.
he following instruments were used: - Hewlett-packard model 5935C Gas Chromatograph/Mass Spectrometer - HP7673 Automatic Liquid Sampler
600125
EID902129
z
fr
_ Hewlett Packard Series 300 computer based workstation, with
.
#P9153C Disc HP Think Jet
PDrriivneterandand40 HPMegCaoblyotre PDrioscPlotter.
We used the following instrumental conditions:
Gas chromatography : column
15 m x coated
0.25 with
mm I.d. fused silica capillary, 1.0 um SPB-1 (chemically bonded,
polydinethylsiloxane, Supelco Cat. No. &-
7300)
carrier gas
helium; column head pressure: 7 psi; flow
Injector
.
rate: 1 ml/min split/plitless;
splitiess
mode
during
0.75
nin
Go/MS interface: direct capillary interface
Ionization
+ electron impact
Electron energy Temperatures
: .
70 eV oven: initial:
60C
initial time: 1.5 min
final: 250C final time: 5.0 min
rate: 5C/min
Injector port: 220C
Transfer line: 280C
Ton source: 200C
Acquisition mode
:
Mass Analyzer: 180C Scan; 40 to 550 A/Z;
0.84
scans/second
Ton source pressure :
Sample volume
1-2.107 torr 1 ul, with HP7673 ALS.
The low resolution (M/ = 1000) mass spectra obtained by each GC/MS run were stored on magnetic disc.
TihdeentpiefaikedofbybitshpeherneotlentAioinn ttihmee
total (35.2
ion chromatogram (TIC) wes minutes) and by the charact-
eristic mass spectrum, shown in annex 3.
000126
EID902130
2
-10-
External standard calibration method, by peak area measurements in the TIC, was used for the quantitation of bisphenol A. Calibration curve was prepared with standard solutions, containing 0, 10, 50 and 100 mg/ul bisphenol A in carbon disulfide.
3.2 DETERMINATIONOFHYDROGENFLUORIDEANDHYDROLYSABLEFLUOROconpounDs
We performed the determination of total F" according to the NIOSH P & CAM 117 method (Reference 3), using a fluoride specific electrode and TISAB buffer solution.
Following instruments were used:
:
- Model 407A Specific Ion Meter (Orion Research AG, Kisnacht,
Switzerland)
- Model 96-09 Fluoride Combination Electrode (Orion)
- Model E536 Potentiograph (Metzohm AG, Herisau, Switzerland)
- Model 6.0216.000 Conbined pH Glass Electrode (Netrohm).
The sample solutions were transferred with small volumes of distilled water into a 150 ml beaker. The pH of the alkaline solution was adjusted with some drops of concentrated acetic acid (Merck, analytical grade) to 7.0 and the solution was evaporated on a hot plate to a residual volume of 3 to 5 ml. 1.0 ml of TISAS III buffer concentrate was added and the solution was transferred into 2 10 ml volumetric flask. The voluse was adjusted with distilled water to 10 ml and the solution was mixed. The pH of the solution after mixing was about 5.5.
Calibration of the instrunent was performed with two concentrations of Fstandard solutions (e.g. 107 M and 107%M) which covered the range of the sample concentration.
000127
EID902131
Su
"
RESULTS
The samples of fumes enalysed in the frame of this study resulted
from the curing of SilverStone, which is one of the most represent
waittihvepDeuwtPeorntcoTleofrlohnas ktihtechfeonlwlaorweincgoarteifnegr.enTcheiss: three code system,
PRIMER
469-516
INTERMEDIATE COAT 456-236
ToPCOAT
156-300
AuLnLdersamfpalbersicawteiroen
collected during conditions. The
routine maximum
tceumrpienrgatoufre
the coating during the
sceuerninbgy otpheeratteimopneriantutrheeprcoofnivleeyor(Anonveexn 2w)asthearwoournkdin4g30coCn.diAtsiocnasnabree
typical of those used by the Teflon coating industry.
tThaeblesam1 pplreesveonltusm,es,in thaeddiwteiiognht toaptphleiedidecnotaitfeidcawteitondisofperssaimopnlescuraendd sintactkhse owvheenrepetrhehosuarmpl(egs/howuerr)e, caonldletchteed.flow rates (m3/hour) in the
4.1 PARTICULATEMATTER
pThaertirceuslualttesmaotfterth(esegrroasvoilsm)etcroilcledcetteedrmoinnfaitlitoenrs oufndetrhedifafirebroernnt sampling conditions are presented in Table 2.
he average concentration of particulates collected by isokinetic esxaimtplsitnagckw.asAb2o.u3t5ntgh/eNms3ameincotnhceenetntrraytisotnasckwsereandfo0u.n6d9 bnyg/unsminginglatshse fiber membrane or glass wool filters.
pThoelyacvaerrbaogneatecon(c2eC)ntrmaetmibornaneofs
particulates and dried to
collected by Battelle on constant weight at 105C
RICO00610
000125
EID902132
-12-
was 2.45 mg/Nm' in the entry and 3.87 mg/Mm' in the exit stack.
The average concentration of particulate matter (aerosols) collected on BC membranes which were conditioned in 65% relative humidity at room temperature was 18.6 ng/Nn' in the entry stack and 5.68 ng/nn' in the exit stack.
Isokinetic sampling according to Italian standards and Battelle's
procedure using PC imately the same
membranes result on
dried at 105C, the gravimetric
both gave approxdetermination of
particulates in the entry stack. In the case of exit stack, the
result obtained by Battelle's procedure was higher.
.
The results obtained by
thfeorBatttheellger-apvriomceetdruirec,
determination of particulates using PC membranes conditioned
in 65% hunidity, were considerably higher, than the corresponding
results obtained according to the Italian standard procedure.
The morphology of particulates, collected by different sampling procedures is shown in Figures 3 to 7. Figure 3 shows the photographs obtained by scanning electron microscopy of one glass fiber membrane filter used for the collection of particulates according to the Italian standard procedure. Only very few irregular shaped dust particles were found on this type of filter. The diameter of particles ranged from to 10 microns. Liguid films at the crossing of some glass fibres can also be observed on the photograph with 5000 fold magnification.
The photographs of polycarbonate membranes used for the sampling of particulates can be seen in Figures 4 and 5.
These filters were dried to constant weight at 105C. The irregular shaped particles of 0.5-10 un dianeter are included in an amorphous iln, resulting from the drying of liquid droplets.
Yo
000129
EID902133
=
S13
Figures 6 and 7 show polycarbonate membranes used for the collection of particulates and conditioned in 65% relative humidity at room temperature. Some areas on both membranes are covered by liquid films. Irregular shaped particles and on sample No. SO (entry stack, Figure 6) also some big conglomerates of 10 to 25 un diameter can bo seen.
Figure shows the electron microscopie photograph of a blank polycarbonate membrane, in which regular, round pores can be observed.
The results obtained by scanning electron microscopy of the filter
t
membranes are summarized in Table 3. These results show that much
of the particulate matter consisted of a liquid material. The
surface of the polycarbonate membranes used for particulates
collection had mostly an oily appearance.
The results on the determination of bisphenol A in the carbon disulfide extract of particulated matter are presented in Table 4. The concentrations of bisphenolA are expressed in micrograms per cubic meter of fumes as well as nanograms per microliter of CS,extract. The concentration of bisphenol A was very low in all samples. The concentration in the fumes of the entry stack were higher than in the exit stack. Very low amounts of bisphenol A (05-2 nanograns) were found in blank Nuclepore membranes, these values would correspond to 0.003-0.01 micrograms per cubic meter as blank values, using for the calculation 0.15 Nn' sample volumes.
4.2 ANALYSISOFHYDROGENFLUORIDEANDHYDROLYSABLE PLUOROCOMPOUNDS
The results are presented in Table 5. The fluoride concentration is expressed in terms of mg fluoride fon (F") per cubic meter. The sample solutions were analysed separately and the F~ concentrations of a pair of solutions belonging to the same sample wre summarised to obtain the Total F~ concentration.
EID902134
2
Sue
he values obtained with the isokinetic sempling method are
generally obtained
lover by the
(vith the Battelle
exception of sample sampling procedure,
3) then based on
the the
values NIOSH
method.
It must through
be the
considered glass fiber
that only membranes
the gaseous fluorides, passing of glass wool, weze enalysed in
the case of fluorides,
the samples collected deposited in the FEP
by AMBIo, sampling
While tubing
thleeapdairntgictuolattehde
impingors, vere also analysed in the case of samples collected by
Bactelle.
It is also possible that the gassous hydrogen fluoride Teacted with
:
tfhleuorgolsaislsicaftiebsersweroer rgeltaasisnedwoobly tahned ftihleterrsesuulsteidngby pAaKrBtIiOc.ulaTtheisd
also may be an explication for the low values obtained with the
Ssokinetic senpling method.
000101
E9135
Ss
Zz
gg
s
`DISCUSSIONOF RESULTS
g
particulates
Particulate matter was collected under different sampling procedures cinosttihneg mfautmeersialr.esuTlhteinfgollforwoimng tfhieltceurrminagtriocfesSainldveprrsotcoendeurepsewwteerre used in the frame of the present study:
Filter material
Procedure
e-- Gelases -- fiber m-- embrane---- Teol-- ation s-- amplinge ,-- ecce or-- dine g to
Italian standard; filters dried at
-
Glass wool
105C
dried at 105C
filters dried at 105C
Polycarbonate membranes with 0.4 um pores
filters conditioned at room tenperature/contzolled humidity
- The concentration of the particulate matter on the fumes resulting
from the curing of SilverStone pewter (samples 13 and 15) and of
sdeitlevremrisnteodnein btlhaeckfrcaomaetiOnfgsa
(samples
previous
s2t8udyand(Re2f9e)renwceere2).alrTehaedsye
samples were collected on polycarbonate room temperature and controlled hunidity
membranes, conditioned at before weighing. Membranes
with pore diameter of 0.4 un were used for the collection of samples
13 and 0.2 um
15, while samples 28 pore diameter. ALL
and 29 these
vere collected on membranes with samples of the present and the
previous study were collected in the entry or exit stacks of same coveyer oven, during the curing of the same or practically
the the
same coating material. However, pieces per hour, the flo rates
the quantity of wet products on the on the stacks, sample volunes, etc.
were not always the same during the sample collection, as can be
seen in Tables 1 and 2 of the reports of the previous and present
studies.
000122
EID902136
Cas -
The results of the determination of particulates in the fumes resulting from the curing of Silverstone coating materials obtained in the present study, as well as the variables of sampling, are compared to thoss from the previous study in Table 6.
In the case of samples collected by the isokinetic sampling
procedure, the ratio of the linear velocities in the probe and in
the stack are assumed to be 1. In the other cases, the average
Linear velocity (cn/s) in the probe wes calculated fxom the measured
gas volume (Lj, the duration of sampling (minutes) and the internal
Cross-section of the tubing used as probe. The linear velocity in
the stacks was calculated from the flow rate in stack (see Table 1
.
of the previous and present reports) end the cross-section of the
:
stacks (28 cn x 30 cm).
In the case of sample 29 (entry stack), the C membrane with 0.2 um diameter pores, used for sampling, wes rapidly clogged by an oily deposit, the flow rate and linear velocity on the probe diminished rapidly and the pressure drop across the filter increased. Therefore onlya small sample volume wes collected, which explains that this result is not representative (concentration of particulates (65.6 nara).
In the case of samples 15 and 28, both collected in the exit stack, the average linear gas velocity in the probe was about three times higher, then the calculated linear velocity of gases in the chimney. The concentration of particulates in these samples was very lov, less than 0.1 and 0.15 mg/m' respectively. The reason for these low values is, that the flow rate on the exit stack was ten times smaller than in the entry stack and the biggest part of funes vas extracted through the entry stack.
discarding these extreme cases and analysing the remaining data, following conclusions can be made:
000122
EID902137
:
-
- No correlation was found between the ratio of linear gas veloci-
ties in probe/stack and the concentration of particulates.
- The concentration of `wet' particulate matter, collected on PC
membranes and conditioned humidity before weighing,
at room temperature in controlled was considerably higher, than the
concentration of *dry" particulates, collected either on PC
membrane or on glass fiber filters and dried to constant weight
at 105C. from 3.9
The concentration to 20.7 mg/m} with
of an
"wet' particulate average of 10.5
matter ranged mg/m' and che
concentration of "dry" particulate matter ranged from 0.48 to 4.66
ng/n with an average of 2.35 mg/m'.
. 3
- The concentration of particulates depends on the nature of filter material used for collection, Using PC membranes, the concen-
.
tration range was between 0.48 3.0 mg/m', while in the case of
and 4.66 mg/m' with glass fiber filters
an average of the range was
between 0.58 and 2.77 ng/n}, with an average of 1.7 mg/m'
The concentration of stack was only about
wet' particulates in the fumes Of the exit the half of the concentration found in the
fumes of the entry stack of the same conveyor oven. The collection
of particulate samples 46 and 47, as well as 49 and 50 in the two
stacks of the conveyor oven were done simultaneously.
The concentration of "dry" particulates, collected on glass fider
membranes or glass wool filters was also lower in the fumes of the
exit stack (average 0.69 mg/m'), than in the fumes of the entry
stack (average: 2.35 mg/m'). The concentration of dry' particu-
Jates, of the
collected on exit stack
polycarbonate (average: 3.87
membranes, wes higher mg/m'), than in the
in the fumes fumes of the
entry stack (average: 2.48 mg/m').
our explanation for the difference in particulate concentration found in the fumes of the exit and entry stacks, using different filter materials is that the composition of fumes resulting from the curing of Silverstone' coating materials is not the same in the
RIC000616
000124
EID902138
C-
entry and exit conveyor oven,
stacks. the most
From the wet costing volatile constituents
entering into the are released first;
"hile the costed articles are approaching the substances are released and the fumes contain
exit, less volatile a higher proportion
of non-volatile particles. Thess non volatile substances vere
retained on the polycarbonate membranes having 0.4 um pores with &
higher efficiency than on the glass fibers.
The filter holders of glass fiber membranes or glass wool were heated in the stack in order to prevent condensation of vapors, while the filter holders of the polycarbonate membranes were not heated and permitted thus the condensation of slightly volstile substances. This also makes a difference in the nature and amount
:
ocfedupraerst.iculated matter retained by the different sampling pro-
The Italian standard procedure, using isokinetic sampling and glass fiber membranes below 100C or glass wool above 100C, is designed to measure the concentration of dust in the stack gases, in other words only non-volatile particulsted matter. The procedure used by Battelle was aimed at the collection of all the aerosols, both Liquids and solids dispersed in the stack gases, in order to get information on their composition. Therefore the concentration of particulates measured by the Battelle procedure is higher than the dust concentration measured according to the Italian standard.
The scanning electzon microscopy of filter membranes, used for sampling of particulates, showed that a considerable proportion of pcaorattiicngulatcoendsimsattsteorf rleisquulitdingmatferroimal.theThceursionlgidof pSairltvieclresstonhead irregular shapes and their size varied from 0.5 um to 10 km in the case of samples collected in the entry stack and from about 0.5 to 6 um in the case of samples collected in the exit stack. Some big (10-25 um) conglomerates, consisting of small solid particles cemented together by a liquid mass, have also been chserved in samples from the encry stack
000125
EID902139
H
:
-19-
The bisphenol A concentration, determined in the carbon disulfide extract of particulates, was lower than 0.003 mg/m' in all of the samples of the present study. In the frame of the previous study relatively high concentration of bisphenol A (4.2 ng/n') was found in sample 29 (see Table 9, cont.) of the previous report).
Hydrogen fluorideandhydrolysable fluorocompounds
The total fluoride concentration in samples 13, 14, 28 and 29,
collected in the fumes resulting from the curing of Silverstone
coatings in the frame of the previous study, varied between 0.11 and
1.2 mg/n3, with an average of 0.5 mg/m' (refer to Table 5 of the
previous report). The present study, using the same sampling
'
procedures, gave similar results: the concentration varied between
0.07 and 1.7 ng/n and the average concentration was 0.4 mg/m'.
The average concentration of gaseous fluorides, collected in alkali solutions, according to the Italian standard procedure, was lower (0.06 mg/m'). The concentrations ranged between 0.01 and 0.15 ng/a'. The particulated fluorides, retained by the glass fiber filters or glass wool were not determined.
000476
EID902140
S20
`BIBLIOGRAPHICREFERENCES
1. vMoegtloidaotiU.nicDheitnerNn.i5n8a9zi(oEndeizdieoinefl1u9o82r)uriMisguarsesoaslilee edmeiissfilounorucroin particellari. Metodo potenziometrico (EM/14).
2.
Battelle Analysis
RoefpoFrutses232z9e,suOlcttionbgerfr1o9m89t.he
. Curing
Operation
in
the
Manufacture of Teflon-coated Articles.
:
3. UN.ISO.SH DMeapnauratlmeonft AonfalHyetailctahl, MEedtuhcoadtsi,onSeachodndWeEldfiatriso,n, CiVnocliunmaeti1,.
Ohio (1977). Pluoride and Hydrogen Fluoride in Air, Method No.
Pecan 117.
000127
EID902141
-2-
LI OFFS IGUT RES FIGURE 1 - Diagram of sampling equipment, according to Italian
Standards, for the measurement of gaseous emissions. FIGURE 2 - Diagram of sampling equipment used by Battelle. FIGURE 3 - Photographs of glass fiber membrane 1/1 No. 18. FIGURE 4 - Photographs of polycarbonate membrane filter No. 43. FIGURE 5 - Photographs of polycarbonate membrane filter No. 44. FIGURE 6 - Photographs of polycarbonate membrane filter No. 49. FIGURE 7 - Photographs of polycarbonate membrane filter No. 50. FIGURE 8 _ Photographs of a blank polycarbonate membrane filter.
000138
EID902142
22
LI OFS TABT LES
Table 1 - Samples collected in Smaltiriva-plant, Monte Marenzo, 22/390 - 4/4/90.
Table 2 - Particulate matter collected under different sampling conditions.
Table 3 - Scanning electron microscopy of filter membranes.
Table 4 - Determination of bisphenol A in CS,-extract of partic-
:
lates.
Table 5 - Determination. of hydrogen fluoride and hydrolysable luorocompounds .
Table 6 - Particulate concentration in function of sampling conditions.
0001. 09
EID902143
ile
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000150
EID902144
;
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000441
EID902145
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HE ER RT
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SNM &
,
[| UNE '
2697 '25KV
X5,000
po &
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FIGURE 3 - Photographs of glass fiber membrane 1/1 No. 18
000122
EID%02146
Fagin as a
= Ee L A SoER N SEpe a
RR 5
ae
PR
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Ea
MR vi
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Agdre SAY 3 LT
BNCLo wa JU ny
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[RFE]EES CRECHL IT--T 1
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FIGURE 4 - Photogaphs of polycarbonate membrane filter No. &3
000323)
E9147
SR
Soe ih IP
Seger NI
Bast 1UNE
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2781 25KV X5,008 16m WD4g
FIGURE 5 = Photographs of polycarbonate membrane filter o. 45
000124
EID902148
BABIES as RTs
Bay aXge Hate oh Sh SNE SR RRREIE Ex 85 iae{T5T ReR LT SS a AA S BE.C oa ae
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PALER
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FIGURE 7 = Bhotogzaphs of polycarbonate membrane filter No. 50
000426
E9150
HREEIES ASRA
pr as Ra
Py AR ERA ON NERDSAIRE
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HT SIRE
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FIGURE 8 _ Photographs of a blank polycarbonate membrane filter
000714
EID902151
.
TABLE 1 SAMPLES COLLETED I SHALTANASLANTAONTE MARERED 2350-4450
fGrte aa Nets wy
E(iAN Gp aceon Ey R oruoR nmENy vite Em amuak Gi meeon tu DsoRmuAommEn Mem Em Wsueess tm
&&a ew 0 Ew a"5"@ ew iaooe wen "awo tm ey
Q mfoa rs AiwllF(lyowWs Diao
Cobenity wo
d Vaou e 1E00
emo se 1690 23Es0 pemmmersaw 002s 85
a0 se 0 T vimR sooEmNONwn oom: es
aso sh 1600 280 pew
cours 3s
we Sa 190 TVEiHsoRomOEwm:en outs 95
emo se 0 vEusoowen 00308 81
ame se wo fviEtr zsomd Own ootos 1
aw0 se aso 33Es0 games
comer ar
we Sa 1080 JYEAIRsSoSomENNOSHumen oot 41
m0 se 10 uae gummwmesws oc ss
awe Se tee yemRssoSomEwiNvwSe cos os
armas
ee tooo P L42E9S0Ecaa E rneRmewoniloso AS01TH7s1 7780
ee 1000 43180 umemensicsos o07an 70
ew 100 LL04R800 e acarirr0 ommanosr3 ience 390331230 86633
ew 180 4HF7E21HR3R0 r S 04Pt Gs muicme oWseeeHI 113230
ew 1950 43190 ouimpomses 00670 120
eno 1000 UL413RR/80 CS04imSapCaeetnesncn SS0i.ho1e7e8s 84433 ee to00 40 0am peer asin 0102 82m
5100F Enuy 6360
1600 4/4/90 0S.1 eNNaaOHmimepinrgers ** 0.161 8 62 gs
a547 Exit 6360 en emo
1850 P44/3E31/E88R00 0014 Nhat umPCmambr. 65% rh. 0S.2146233 113277 = 1450 43180044m rams aon 0.143
News Ow Img kN aly a 7 mes "No sl Ging 22 No ws 6 374
000128
EID902152
:
TABLE 2 - PARTICULATE MATTER calcd under ferent samping conditions
sume
FuTeR
Vi Note
gassfowrmembane
V2CESTELLOB gasswool
2iNo 19 gassfoermembane
22CESTELLON gasswool
iNo2 gassfoermemane
STACK ofVsOLaWmMEe oWfEpIaGrHcT. CONCofENpTaRnAicTIONREMARKS tm} mg mgNm
Envy 0.025 0.07 277 iAsGoOnet Envy 0.0425 O11 259 sampling Ext 00506 004 0.79 Ext 00887 00s 058 Emry 00235 0.04 1.70
42 o4umPCmemoracSeC Emy 0471 038 221 fBiAeTrsIEoLrEes 43 04unPCmenbi0SeC Enry 00708 033 486 aioseC 45 04umPCmemori0seC Emry 0.228 041 048 a 04umPCmenori0soC Ext 0.0961 033 3.43 4s O4umPCmemoriGSeC Ext 0.0673 028 431
46 oeumPCmem eswin Ey 0178 295 1657 tBeArTsTELE 4570 o0aauummpPCCmmeemmbbrreesswwrinn EExntvy 001.044223 028924 2507780 caornoeisoneisn 45 oeumPCmemeswrn Ext 0.143 080 559
000129
EID902153
TABLE 5. SCANNING ELECTRON MICROFOFISLTECRMEONBPRANYES
seis
FureR
oOsFscPaARrTTIICLOENS
Fapusre
11 Note 45 44 50 45
glass ber membrane ow ueguiSroshaupmed panics 3 04umPCmembi0scC 10uurmeplas sshoalpeeddpalruiciiesSo0p5ets 4 04unPCmembiioosC uTnnrceigaudieadr isnhaspoeiditpeadrcIlaesu 0cr5o8pleursm
04 um PC mem. 8% rh. uied05f:i1m0s.uumnecgounigalromsehraapteeds p1a0r.c25: 04 um PC mambr. 65% rh. lid fims.uneguTMiar shaped paric- 7
65 1:6 um ow)
:
BLANK 0.4 um PC membr. 65% rh. round pores in fim
e
000150
EID02154
.
TABLE d- DETERMINATIOFN BISPHENOL AN CS2 EXTRACT OF PARTICULATE MATTER
savpLe
FuTER
1 Noss glass fiber membrane 12CESTELLOB glasswool 21No19 glass fiber membrane 22CESTELLON glasswool WINo20 glass fer membrane
STACK BispAhenol cVoolleucmees BispAhenol oul Nma ugnma
Enry 6.08 0.0253 0.48 Enry 1677 0.0425 1.18
Ext 000 00508 0.00 Ext 197 00s 0.08
Emy 026 00235 0.02
42 04umPCmembei0SeC Enuy 98.40 0471 1.15
43 04umPCmemiSoC Envy 83.71 0.0708 2.36
:
4s 04um PC membri0SoC Emry 22.07 0228 0.18
" 04m PC membLI0SOC Exit 4.47 0.0881 0.08
a 04umPCmemb10SoC Exit 4.04 0.0873 0.12
46 50 47 45 -- sn
BLA BLANK
04umPCmemores% ch Enuy 3481 0.178 0.39
04umPCmembreSwrn Envy 35.34 0.142 0.50
O4umPCmembrS%rn. Exit 647 0.1423 0.09
O4umPCmembr.eS%cn Et 5.82 0.143 0.08
g(lGaeslsmafinb)er membrane 0(.o4tumB1PACTCm1e3m)brane 0o.t4 u8m1P8C60m3e)mbrane
0.00
m0.e00m
0.23
0.45
1.08
2.10
000154
EID9N2155
.
`TABLE 5 - DETERMINATION OF HYDROGENFLUORIDE ANDHYDROLYSABLE FLUIORCCOMPOUNDS
Sample Sack
121A HE
Entry
11211 A HE
141/111Q F11LQ UFLOUROURRURII Entry
22221IAA HHEF
Exit
22111101QFLFLUUOORRUURRII Exit
331iHHE2020
Entry
MoFl-/L mg/sF-amp VSoalmupmlee mg/FN-m3 mTogt/alNmF3- Note Nm3
4E-06 1-06
00..00000038
00..00225533
00..00131115
0.04
2E-06 1E-06
0.0004 0.0002
0.0425 0.0425
0.0092 0.0043
0.01
62EE--0066 00..00001014 00..00550066 00..00200789 0.03
22E--0066 00..00000045 00..00668877 00..0000666 0.01
2E-05 SE-06
0.0033 0.001
0.0235 0.0235
0.1415 0.0437
0.19
42F Entry 0.0012 0.2185 0.1715 1.2741 1.70
421
0.0004 0.0732 0.1715 0.4265
44ssFT
Entry 0.0001 0.0238 0.213 0.1115 0.15 SE-05 0.0087 0.213 0.041
4457F Entry 0S.E0-00052 00..00140035 00..33005533 00..01333266 0.17
100F Entry 9E-05 0.0163 0.161 0.1015 0.12
1007
2.05 0.0034 0.161 0.021
4"17F Exit 47EE--005500..00017367 00..226666 00..00521864 0.08
47F a
Exit
4E-05 0.0074 SE-05 0.0102
00..226633
00..00328872
0.07
1
Note:t) one impinger broken
000152
EID902156
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3
{ cTaTmSeIoT eOSnSoIoB Cooiail; 2s2s8s 8338,
2
555 % 2
000153
EID902157
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000154
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EID902158
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EID902159
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MASS SPECTRUM OF BISSaHENOxL A REFERENCE SUBSTANCE
000156
E1Dsn21en
