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Designation: D 7029 04

Standard Test Method for

Determination of Reactivity of Unsaturated Polyesters and

1
Vinyl Esters at 180.0F [82.2C]
ThisstandardisissuedunderthexeddesignationD7029;thenumberimmediatelyfollowingthedesignationindicatestheyearof
originaladoptionor,inthecaseofrevision,theyearoflastrevision.Anumberinparenthesesindicatestheyearoflastreapproval.A
superscriptepsilon(e)indicatesaneditorialchangesincethelastrevisionorreapproval.

1. Scope
1.1 Thisstandardprovidesastandardizedtestmethod
for determining the gelation and exotherm curve of
unsaturatedpolyesterandvinylesterresins.Thismethod
provides guidance for measurement of the Standard
180F[82.2C]ExothermCurvealongwithinformation
onvariancesofthemeasurementwhichmayberequired
forspecialresins.Thistestmethodprovidesinformation
concerning the reactivity of unsaturated polyester and
vinylesterresinsastheygothroughpolymerizationafter
mixingwiththeinitiator.
NOTE1ThereisnoknownISOEquivalenttothisstandard,
althoughISO584issimilar.

1.2 ThevaluesstatedineitherSIunitsorinchpound
unitsaretoberegardedseparatelyasstandard.Thevalues
stated in each system may not be exact equivalents;
therefore,eachsystemshallbeusedindependentlyofthe
other.Combiningvaluesfromthetwosystemsmayresult
innonconformancewiththestandard.
1.3 Thisstandarddoesnotpurporttoaddressallofthe
safetyconcerns,ifany,associatedwithitsuse.Itisthe
responsibility of the user of this standard to establish
appropriatesafetyandhealthpracticesanddeterminethe
applicabilityofregulatorylimitationspriortouse.
2. ReferencedDocuments
2.1 SocietyofPlasticsIndustry,Inc.:
HandbookofReinforcedPlasticsProcedurefor
RunningExothermCurvesUsingtheBlockTest
Method
2.2 ISOStandard:
ISO584ReinforcedPlasticsBasedonUnsaturated
PolyesterResinsDeterminationofReactivityat
80C2
3. Terminology
3.1 Denitions:
1
ThistestmethodisunderthejurisdictionofASTMCommitteeD20on
Plastics and is the direct responsibility of Subcommittee D20.18 on
ReinforcedThermosettingPlastics.
CurrenteditionapprovedMay1,2004.PublishedJune2004.
2
Available from American National Standards Institute (ANSI), 25 W.
43rdSt.,4thFloor,NewYork,NY10036.

3.1.1 geltimetheperiodoftimeinminutesand
secondsrequiredfortherecordingpyrometertogofroma
temperaturebelow(usually10to30For5.5to16C)bath
temperatureto10F[5.55C]abovethebathtemperature,
typically150F[65.5C]to190F[78.8C]forabathat
180F[82.2C].
3.1.2 cure timethe period of time in minutes and
secondsrequiredfortherecordingpyrometertogofroma
temperaturebelow(usually10to30For5.5to16C)bath
temperature to the maximum temperature reading,
typically150F[65.5C]tothemaximumtemperaturefor
abathat180F[82.2C].
3.1.3 intervaltimetheperiodoftimeinminutesand
secondsrequiredfortherecordingpyrometertogofrom
10F[5.5C]abovethebathtemperaturetothemaximum
temperature reading, typically 190F [78.8C] to the
maximumtemperature.Thus,intervaltimeiscuretime
minusgeltime.
3.1.4 peak exothermthe maximum temperature
reachedduringthetesting.
3.1.5 recordingpyrometerabroadclassoftemperature
measuring devices including thermocouples with the
abilityforcontinuoustemperaturerecording.
3.1.6 initiatoracompoundthatgeneratesfreeradicals
to startthefreeradicalpolymerizationoftheunsaturated
polyesterandvinylesterresins.Itistypicallyaperoxide.
4. SummaryofTestMethod
4.1 Polyester or vinyl ester resin is mixed with the
initiatorinabeakercausingapolymerizationoftheresin
tooccur.Heatwillacceleratethepolymerizationreaction.
The exotherm generated by the resin as it cures is
measuredusingathermocouple.Thecurveisplottedand
thetimetoreachvarioustemperaturesalongwiththepeak
temperatureobtained(peakexotherm)isdetermined.The
initiatornormallyemployedtogeneratethetestresultsis
benzoylperoxide,althoughthemethodmaybeusedwith
otherinitiatorsystems.
4.2 Thetestmethodisusefulinprovidinginformation
abouttheheatgeneratedduringcureoftheresinandthe
lengthoftimetheresinremainsintheliquidstatepriorto
polymerizationintosolidform.

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D 7029 04
5. SignicanceandUse
5.1 This test method is used to
measurethereactivityofdifferentlots
ofunsaturatedpolyesterandvinylester
resins. The information provided by
thistestcanbeusedforassessingthe
predictedperformanceofaresinwhen
usedinelevatedtemperatureaspartof
the process used to convert the resin
intoanishedproduct.
5.2 The method is used in research
and development by companies that
manufacture resins and for incoming
quality control companies using these
polymers as raw materials for
production.Themethodisbasedonthe
methodswhichwerepreviouslyoutlined
inthe HandbookofReinforcedPlastics,
Procedure for Running Exotherm
Curves Using the Block Test Method
publishedbytheSocietyofthePlastics
Industry.

6. Interferences
6.1 The results obtained can be
inuencedbythetypeofresinused,the
ageoftheresin,theageoftheinitiator
and the type of initiator used. Care
shall be taken to assure that the
chemicalsusedarestoredandusedin
accordance with the manufacturers'
guidelines.
6.2 Controlofthebathtemperature
andthecirculationwithinthebathcan
affecttheresultsofthetest.Careshall
be taken to control the bath
temperature and agitation to comply
withthemethodinstructions.
7. Apparatus
7.1 Recording Pyrometer, Iron
Constantan, 60 in. [1.5 m] per hour
chartsspeedorequivalent.
7.2 Thermometer, with divisions
every 0.1F [0.05C] capable of
readingaminimumof18061F[82.2
60.5C]orequivalent.
7.3 Constant Temperature Water
Bath,oralternatemedia bathcapableof
beingcontrolledto180 6 0.5F[82.2 6
0.2C] with an agitation rate of 1 to 2
timesthebathcapacityperminute.The
bathshallhaveaminimumcapacityof
2.5gal[8.8

L]anshallbettedwithacoverwith
access holes for the bath heater,
thermometer,andtesttubesinorderto
minimizeevaporationofwater.
7.4 Borosilicate Glass Test Tubes,
of19mmdiameterand150mmlength
withplainendandlip.
7.5 Type J Thermocouple Needle,
made from 304 stainless steel, 6 in.
[152 mm] in length, with an outside
diameterof18in.[3.2mm]connected
toaTypeJJackAssemblyor
equivalent.
7.6 Type J Double Conductor,
B&SGaugewirewith polyinsulation
and color coding (white for
positive/red for negative) to connect
Type J thermocouple needle to
recordingpyrometerorequivalent.
7.7 ElectronicBalance,suitablefor
accurateweighingto
0.1 gandaminimumcapacityof200
g.
7.8 MachinedCenteringDevice,for
centeringthermocoupleneedlewithin
theresinsample.Thisdevicemaybe
madefromreinforcedplastics,micarta,
or other suitable material. See Fig. 1
forthesetupofthedevice.
7.9 Beaker(150mL),madeofglass
orplastic.
8. ReagentsandMaterials
8.1 Styrene Monomer,with15 6 5
ppmofTertiaryButylCatechol(TBC)
Inhibitor.
8.2 InitiatorType:
8.2.1 Type I98 % Benzoyl
Peroxidecrystals.
8.2.2 Type IIBenzoyl Peroxide
paste/emulsion with a tolerance of 6
1.5 % of the specied concentration
with a maximum of 18 % water.
Example:40%benzoylperoxidewith
arangeofconcentrationfrom38.5to
41.5%.
8.2.3 Type IIIInitiator(s) mutually
agreed upon by laboratories running
thetest.
8.3 Unsaturated Polyester and
VinylEsterResin.
8.4 SiliconeGrease.

FIG. 1 Machine Centering Device for Thermocouple Assembly

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D 7029 04
9. Hazards
9.1 Initiators such as benzoyl
peroxidemustbestoredinaccordance
withmanufacturers'guidelines.Failure
to do so can result in the materials
becoming unstable causing re or
explosions.
9.2 Directly mixing metals like
cobalt and other chemical with the
initiators can create explosive
conditions.
10. TestResults
10.1 Asinglemeasurementofeach
propertytobeevaluatedisconsidered
onetestresult.
11. PreparationofApparatus
11.1 Adjustthewaterbathto1806
0.5F [82.2 6 0.25C] using a
calibratedthermometer.
11.2 Allowthewaterinthebathto
equilibrate in temperature while
circulatingforaminimumof60min.
12. CalibrationandStandardization
12.1 The thermometer and
pyrometer utilized during the testing
shall be calibrated against a known
standardorbetraceabletoacertied
source.
13. Conditioning
13.1 No special atmospheric
conditioning is required for this test
procedure.
13.2 A means must be provided,
eitherbyairtemperatureorhotplate,
etc. to condition the resin to
temperature prior to addition of
initiator.
14. Procedure
14.1 Weigh1.00 6 0.02gofactive
benzoylperoxideintoa
150 mL beaker. Add 1.00 g of the
styrene monomer to the initiator and
mixthoroughly.
NOTE 2The above may be obtained by
weighing1gofTypeIbenzoylperoxideor
by using 2 g of a 50 % Type II benzoyl
peroxide or by adding an amount of an
alternative concentration of paste/emulsion
initiatorthatfulllsthenecessary1%active
initiator.

14.2 Place resin to be used in a

suitablecontainerandadjusttheresin

temperature to 77.0 6 0.5F [25 6

0.25C].
14.3 Add 100 6 0.02 g of the
temperatureadjustedresinintothe150
mLbeakercontainingtheinitiatorand
styrenemonomer,ifused(forTypeI
andTypeIIinitiators,TypeIIImaynot
require any styrene), and mix
thoroughly,beingcarefultoentrapas
littleairaspossibleintothemixture.
14.4 Let beaker stand for 15 6 5
min at approximately 77F [25C]
priortorunningthetest.
14.5 Pour the initiated resin from
the beaker into the test tube so that
3.0060.05in.[7661mm]oftheresin
isinthetesttube.
14.6 Grease the thermocouple
needlewithathincoatofsiliconeand
insert the needle into the centering
device.Inserttheneedleandcentering
device into the test tube so that it is
centered side to side and so that the
probeis1.50 6 0.05in.[38 6 1mm]
inchesfromthebottomofthetesttube.
Seeattached drawingofthecentering
deviceinFig.1.

14.7 Immerse the test tube in the

180F [82.2C] constant temperature
bathsothelevel ofliquidinthetest
tubeisbelowthesurfaceoftheliquid
in the bath and start the recording
pyrometer.
14.8 When the peak exotherm
temperature is reached, let the
temperaturebegintodropandremove
thetesttubefromthebath.Removethe
testprobefromtheresinandtesttube.
15. CalculationorInterpretationof
Results
15.1 Unlessotherwisespeciedthe
following values shall be measured
fromtherecordingpyrometer:
15.1.1 GelTime150F[65.5C]to
190F[78.8C].
15.1.2 Cure Time150F [65.5C]
tothemaximumtem
perature).
15.1.3 Interval Time190F
[78.8C]tothemaximumtemperature
(Optional).
15.1.4 PeakExothermTemperature.
16. Report
16.1Thefollowingshallbe
includedinthereport:
16.1.1Equipmentused:
16.1.1.1 Thermocoupletypeaswell
as whether it was grounded or
ungrounded,and
16.1.1.2 Initiator type, brand, and
amountused.
16.2Usingtherecordingpyrometer
chart,measureandreportthe
following:
16.2.1 GelTime,
16.2.2 CureTime,

16.2.3 IntervalTime(Optional),and
16.2.4 PeakExothermtemperature.
16.3ReportanyVariancefromthe
standardprocedure.Thesevariances
mayinclude:
16.3.1 Initiator, as designated by
thelaboratoriesrunning
thetests,
16.3.2 BathMedia,asdesignatedby
thelaboratoriesrunningthetests,and
16.3.3 Bath Temperature, as
designatedbythelaboratories running
thetests.
17. PrecisionandBias
17.1 Table 1 is based on a round
robinconductedonfourmaterials(two
resins with a short gel time and two
resins with a long gel time) by six
laboratories.Sampleswerepreparedin
accordancewiththeinstructionsinthis
method usingthe same type initiator.
Evaluationsofgeltime,curetime,and
peak exotherm were made. Each
laboratory generated two test results
for each material.WarningThe
explanation of Sr, SR, Vr and VR are
onlyintendedtopresentameaningful
way of considering the approximate
precisionofthistestmethod.Thedata
in Table 1 shall not be applied to
acceptanceorrejectionofmaterials,as
thesedataapplyonlytothematerials
tested in the round robin and are
unlikelytoberigorouslyrepresentative
ofotherlots,formulations,conditions,
material,orlaboratories.Usersofthis
test method are encouraged to apply
the principles outlined in Practice E
691togeneratedataspecictotheir
materials and laboratory (or between
speciclaboratories).

3
Resin 3 (Long Gel Time)

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Resin 4 (Long Gel Time)

7029 04

Resin 1

TABLE 1 Resin 2
Resin 3
Resin 4
A

Resin 1 (Short Gel Time)

Resin 2 (Short Gel Time)
Resin 3 (Long Gel Time)

Sr = within laboratory standard

deviation for the indicated material. It is
obtained by pooling the within-laboratory
standard deviations of the test results
from all of the participating laboratories:

Resin 4 (Long Gel Time)

Sr 5 @
2

~S2! .
2

Resin 1 (Short Gel Time)

Resin 2 (Short Gel Time)

SR = between-laboratories reproducibility,
expressed as standard deviation:

#/n#

SR
where:
SL

= standard deviation of laboratory means.

Vr = within-laboratory coefficient of
variation for the indicated material. It is
obtained by rst pooling the withinlaboratory standard deviations of the test
results from all of the participating
laboratories:
Sr 5
~S2
2 n

# %

then:
V

Ir

18. Keywords

VR = between-laboratories reproducibility,
expressed as coefficient of variation:
SR
where:
SL
then:
VR
IR

17.2ConceptofrandRinTable
1:IfrandRhavebeencalculatedfrom
a large enough body of data and for
test results that were averages from
testing of 2 specimens for each test
resultthen:
17.2.1 RepeatabilityTwo results
obtainedwithinonelaboratoryshallbe
judgednotequivalentiftheydifferby
more thanthe Sr value orbythe Ir
percentageforthatmaterial. Sr isthe
critical value representing the critical
differencebetweentwotestresultsfor
the same material, obtained by the
same operator using the same
equipmentonthesamedayinthesame
laboratory.
17.2.2 ReproducibilityTwo test
results obtained by different
laboratories shall be judged not
equivalentiftheydifferby

more than the SR value for that

material. SR is the interval
representing the critical difference
betweentwotestresultsforthesame
material, obtained by different
operatorsusingdifferentequipmentin
differentlaboratories.
17.2.3Anyjudgmentinaccordance
with 17.2.1 or 17.2.2 would have an
approximate95%probabilityofbeing
correct.
17.3 There are no recognized
standards by which to estimate the
biasofthismethod.
18.1 cure time; gel time; initiator;
interval time; peak exotherm; resin;
resin reactivity; SPI gel time;
thermoset;unsaturatedpolyester;vinyl
ester

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D 7029 04
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