J.M.

HUBERCORPORATION

PTASTICS
ADDITIVES
GROUP

PERFORMANCEE\ALUATION
OF CIIEMICAL FOAMNG
AGENTSBY GASEYOLUTIONAI\D
RATEANALYSIS
BY

CLAUDE R.ANDREWS
GERARDMOONEY

J. M. HUBERCORPORATION
CHEMICALSDTVISION
HAVRE DE GRACE.MD 21078

EXOTIIERMIC CTTBMICAL FOAMING

The performance of Chemical Foaming Agents AGENTS:
(CFAs) is a function of temperature,pressure,gascapacThe most widely used exothermic CFA is
ity, rateof gasrelease,carier,andtheindividualchemical azodicarbonamide.This CFA is a yellow powder that
components.The evolution of gasfrom elevencommer- decomposesat 195oC to 2I6oC, dependingupon the
cial CFAs is evaluatedby a kinetic methodology under methodof preparation. It evolvesapproximately220 ccl
known thermal stressand at constantpressure. This g of gasafterdecomposition.Thedecompositionratecan
method has been titled the Gas Evolution Atd Rate be adjusted by activators, and a wide range of lower
(GEAR) apparatus.The apparatusconsistsof a linear decomposition temperaturescan be attained. Suitable
temperatureprogrammedfurnace, a gas collection sys- activatorsinclude transition metal salts (lead, cadmium
tem, and a computerizedgasvolume measuringsystem. and zinc), polyols, urea, alcohols, amines and some
Provisions are made to samplethe evolved gas for gas organic acids. Unlike many other organic CFAs,
do not supportcombustion.
chromatographicanalysis,if desired. The volume of gas azodicarbonamides
evolved is measuredin real time under known thermal
Azodicarbonamidesarecapableof generatinglarge
conditionsandthedatais loggedeveryeightseconds.Up
quantitiesof gas.TheexothermicreactionsoftheseCFAs
to 240 data points are measuredin a normal test lasting
arediffrcult to control in mostfoaming applications.This
about35minutes.Thed ataareanalyzedviacomputerand
leadsto coarsercell structures,voids, andpoorersurface
the following four datasetsarepreparcd. Thesesetsare:
quality forthe finishedparts.Thethennaldecomposition
of azodicarbonamideis known to generatecyanuric acid
1. Thermalresponseof samplevs time
which contributes to 'plate out' on mold surfacesand
2. Totalvolume andtemperatureof samplevs time extrusionequipment.
ABSTRACT:

3. Decompositionmodality (flow rate) and

temperatureof samplevs time
4. Kinetic responseand temperatureof samplevs
time.

ENDOTIMRMIC
AGENTS:

CIIBMICAL

FOAMING

SODIUM BOROHYDRIDE:

TheseCFAs producegasas a result of a chemical

reaction rather than thermal decomposition. Sodium
This methodallows the comparisonof both endotborohydridefoaming agentsproducecopiousamountsof
hermic andexothermicCFAs gasevolution performance
hydrogengasupon reactionwittt water or when activated
by variousparameters.It alsoallowsa comparisonof the
by a proton source.The decompositionof sodium bororelative speedof the various CFAs.
(i.e.up
temperatures
hydrideis independentofprocessing
pure
sodium
to 5(X)"C,the degradationtemperatureof
INTRODUCTION:
borohydride).
CIfiMICAL FOAMING AGENTS:
Chemicalfoaming agentsproducegasby a chemical reaction. The reactionmay be a thermal decomposition or a reaction between two or more components.
CFAs areselectedfor specific enduseapplicationsbased
on their decompositionor gasgenerationtemperatures.It
is importantto matchthedecompositiontemperaturewith
the processingtemperatureof the polymer to be foamed.
If the polymer is processedat temperaturesbelow that of
the CFA, little or no foaming will occur. Additionally, if
the processing temperature is significantly above the
CFAs decompositontemperature,poor (overblown, ruptured) cell sffucture and surfaceskin quality will likely
result. CFAs may be either organic or inorganic chemicals. The thermodynamics of the gas formation with'
CFAs areclassifiedaseither exothermic(heatreleasing)
or endothermic(heat absorbing).

Numerousproductsbasedon sodium borohydride

exist in polyethylene and polystyrene carriers. Some
gradesare activatedby specialchemical additives. The
sodium borohydride concentratesare typically S-lOVo
active and are reportedstableto moisture in the concenffate form. Sincehydrogenis the gasproducedwith this
foaming agent,caremust be taken not exceedthe explosive limit of 4Vo(v/v) of hydrogenin air.
TRADITION AL AC ID / CARB ONAT E
SYSTEMS:
The most well known endothermicCFAs arefrom
the acid/carbonatefamily. These foaming agentstake
advantageof the chemicalreactivity of inorganic carbonateswith acidicspeciesto evolvecarbondioxidegas.The

most widely used acidlcarbonatesystemsare basedon

sodiumbicarbonateandcitric acid derivatives. The acid/
carbonateproductsare available as l00%opowders or as
concenffatesin universal waxy-type carriers. The concentrateproductsareavailablein up to7}Vo activeCFAs.
The gas evolution of these acidlcnbonate products
dependson theleveloftheiractivity andin whichformthe
productis used. The typical lffi%o activeCFA produces
approximately 150 cclg of carbondioxide gas.

(HZO displacement),and a gas volume device. The

temperatureof the furnaceand sample,and the output of
the gasvolume device are collectedby an IBM@ Model
XT computer using a digidlanalog signal converter
boardwith associatedsoftware.

DPERIMENTAL

The results of each evaluation are normally expressed graphically. The graphsgeneratedare:

The reaction time is monitored every two seconds

and the data logged every eight secondsinto a data file.
Thegascollectionsystemallowssamplingofthe evolved
gas for chromatographic analysis using a Hach-Carle
The commercially available acidlcarbonatesys- AGC 400, fitted for refinery gases.
temsareGenerallyRecognizedAs Safe(GRAS) by theU.
This systemallows the useof a 1.00gram sample
S. Food andDrug Adminisffation and approvedfor food
contactapplications.The evolvedcarbondioxide gasis for t00%oactivepowdersand4.00gramsfor21%oconcennonflammable,posesno threatof explosion,anddiffrrses ffates. The sample weight is adjustedso that the tested
powder. It
readily from foamedproductsallowing for shorterform- samplewill contain1.00gratnof lUU%oactive
canbe usedfor either exothermicor endothermicCFAs;
ing cycletimes.
one exceptionis 5-I0Vo borohydridein a carrier due to
The universalwaxy-typecariers havebeenknown spacelimitations of the sampletube. It can also evaluate
to causescrew slippage. High percentageconcentrates carriersin which the CFAs arecompoundedif thecarriers
usedin conjunctionwith manytraditionalmixing systems areknown and available.
often resultin poor dispersion.Poor dispersionleadsto
Thethermalprofile found to afford thebestdatawas
variationsin the foaming processand causesvoids and
thin skins which may lead to mechanicalfailure in fin- a program which rose from room temperature(25'C) to
3 15"C in 17 minutes,andthenwasisothermal at315"Cfor
ishedproducts.
16 minutes. These parameterswere used to allow the
The gas capacityof CFAs has beenevaluatedby evaluationof 1.ff) gram of exothermic
their reaction with water and/or by thermal techniques
CFAs. Thetotaltestlasted35minutesandcollected
either with the use of a gasburet or a mercury displacement technique. The sametype of apparatuscanbe used 240 data points fo_rtime, furnace temperafure,sample
to determinethe gasevolution rate. The water technique temperature,and volume of gasliberated.
is not applicable to the exothermics while the thermal MATERIALS TESTED:
techniqueis applicableto both. Other techniquesarethe
Eleven commercial CFAs and one laboratory preDifferential Scanning Calorimetry (DSC) for thermal
paredCFA were tested and the datarecorded.The data
effectsandThermogravimefricAnalysis(TGA) for weight
sets are analyzed via commercially available spreadloss.Theproblemwith thesetechniques(TGA andDSC)
sheetsandstatisticalregressionprograms.
The CFAs are
is the small sample weight used in the test (10 to
listed under general classificationsas shown in Table I
4Omilligrams).The DSC and TGA testsmust both be
(Page7).
performed to prove that a thermal effect and a chemical
gasreactionhasoccurred.
RBSULTS:
METHODOLOGY :

The methodologydevelopedmeasuresthe thermal

effectsof the sampleandthe gasevolution volume of the
L THERMAL RESPONSE:
CFA at a constantpressure(4.5"H2O) with reactiontime.
The difference (delta Ts) betweenthe sampletemThe furnaceis linearly programmedandits temperafureis
peratureand the mathematicallymodeledand regressed
alsomonitoredsimultaneously.
baseline is shown on the Y axis versusthe temperature
The Gas Evolution And Bate (GEAR) apparatus programtime. The actualsampletemperature(Y2 [right
consists of a linearly programmable thermal regulator handlaxis)is alsoshown.Theobjectivesof thesedataarc
(0"C to 649'C), atubefurnace,agasfransfersystemwhich to identify aod to quantify the thermal behavior of the
allowsforpressuremeasurement,
a gascollectionsystem

CFAs. Exothermicbehaviorof Celogen AZI30 is shown volumemeasureddividedby thesampleweight. Thetotal

in FigureI. Endothermicbehaviorof IUVoSodiumboro- volumeresponseandgascapacityfor Celogen,4.2130is
shownin FigureIII and for I}Vo SodiumBorohydridein
hydride is shownin Figure [I.
FigureIV.
40

180

300

35

300

160

260

30

zzo S
u
rso H
o

.o 25
8 2 0
o
t'
15

r+oR
t-

.2
100 6

60

10

8 1 0 1 2 1 4 1 6 1 8 2 0 2 2 2 4

-deltaTs

I
fll

fi rzo
5 roo

220 A
t
m

reoB

9 B o

rcoF
(r,
rooE

F 6 0
IF 4 0

60

20

-5
o

260

140
ci

2 6 2 8 3 0 3 2 3 4

o 2 4 6 I

10 12 14 16 18 20 22 24 26 28 30 32 34

20

TIME min.
---TEMP.
-TOTALVOLUME

TIME min.
---TEMP.

cc./g = 31.4

Figure IV: Gear Data Total Volume Response107oNaBHa

Figure I: Gear Data Thermal ResponseCelogenAZ I30.

3. DECOMPOSITION MODALITY
(FLOW RATE RESPONSE):

5
0
-5

260

-10

22ogt

g'ls
E -20
o
E -2s

:g

rso Hl
qt
rao S

-35

tU'
100 E
o

-40

60

-30

-45 I
0

20

810121416182022242628303234
TIME min.
- - -TEMP.
detta Ts

Figure II: Gear Data Thermal ResponseIOVoSodium

Borohydride.

The flow rate response(cclmin) is the first derivative of thetotalvolumeresponsewith respectto time. The
objectivesof thesedataaretoidentify andto quantiSrthe
foaming behavior of the chemical foaming agent with
respectto modaliff (the number of foaming events)and
the temperatures(initial and final) at which they occur.
The flow rateof the sampleis shownon the Y axis versus
the temperatureprogram time. The sampletemperafure
(Y2 axis) is also shown. The flow rate responsefor
Celogen AZI30 is shown in Figure V and for I07o
SodiumBorohydridein FigureVI. A 57odatasmoothing
factor is applied to all flow rate datato reducethe signal
to noiseratio.

2. TOTAL VOLUME RESPONSE:

The total volume generatedby the sampleis shown
on the Y axis versusthe temperatureprogram time. The
actualsampletemperature(Y2 axis) is also shown. The
gascapacityof theCFA is calculatedby subtractingtheair
expansionof the testvessel( s.7cc) from the maximum

300
200

zzofl

o
t
iso H
o
r4o f,

E rso
UJ
ktr

=
o
J
lt

350

260

j
E

1oo

to
100 E
@

50

300

175'Ct

300
260
g 2so
ut

22oEl
v
reo Fl
o

j zoo
J

o
>

150

raoR

tat,

F 100

1ooE

at

50

60

0
o

10
-

12

14

16 18 20 22 24 26
TIME min.
TOTAL VOLUME .-.TEMP.

28

30

32

34

20

cclg = 303

Figure III: Gear Data Total Volume ResponseCelogen AZ I30

| 233"C

60
20

8 1 0 1 2 1 41 6 1 8 2 0 2 2 2 4 2 6 2 8 3 0 3 2 3 4
-

TIME min.
FLOW RATE ---TEMP.

Figure V: Gear Data Flow Rate ResponseCelogen AZ 130

35
300

300
30

260

260

25

22o R
o

o
(t

lso il
m

LrJ
F

o
140 o
m
t100 I
c
o
60

o
J
l!

8 1 0 1 2 1 4 1 6 1 A 2 0 2 2 2 4 2 6 2 8

3 0 3 2 3 4

E i 5

raoR
t-

U'

10

100 6

5
0

20

zzoS
t
teo fll
U'

.d 20
E

60
0

TIME min.
---TEMP.

Figure VI: Gear Data Flow Rate ResponseIUVoNaBHa

Vt = maximum volume of gasgenerated

Vx = volume of gasgeneratedat time t.
The purpose is to determine "foam time" of the
CFA. The foam time is definedasthetime in minutesthat
is necessaryfor the CFA to generate63Voof its gas
capacity.This is accomplishedby plotting thetime of the
temperatureprogram(Y axis) versusthe kinetic response
(X axis). Regressionanalysisofthe linearportionsresults
in straightline equation(s).The slopeof the regression
equation is the foam time. Longer foam times denote
slowerkineticsof gasreleasefromthe CFA. Thetemperature of the sample (Y2 axis) is shown. The kinetic
responsefor Celogen AZl30 is shownin FigureVII and
for IOToSodiumBorohydridein FigureVItr. The performance results for all twelve CFAs from the described
testingare shownin Table II (Page8).
35
30
260
25

10
5
0

220 m
o

F
m
o
o
m
tI
c
o

180 m

140
100
60
20

0.5
-

I
T|ME

3.5
2
2.5
3
ln VY(Vt-Vx)
---TEMP. -0.282*X+14.607
1.5

20

--- TEMP.
- 6.105*X+6.46

DISCUSSION OF RESULTS:

A first orderreactionkinetics equationis appliedto

the total volumedata. This kinetic responseis ln[Vt/(Vr
Vx)l where:

E t s
tr

2.186*X+12.848

Figure VIII: Gear Data Kinetic ResponseIUVoNaBHa

4. KINETIC RESPONSE:

E20

5 2 2
ln VU(Vt-Vx)

-T|ME

FLOW RATE

Figure VII: Gear Data Kinetic ResponseCelogenAZ I30

BXOTIIERMIC
AGENTS

CITEMICAL FOAMING

POWDERS:
The CFAs (AZL30, AZNP130 and OT) exhibit
large gas capacities, sharp exothermic thermal events
with relatively small temperatureintervals (i.e. initial to
final), andfoaming eventswith very shortfoam times and
equivalentspeeds. The foaming eventsclearly follow
first order gasreleasekinetics and occur simultaneously
with the thermalevents.
ENDOTIIBRMIC
AGENTS

CIIEMICAL

FOAMING

POWDERS:
HydrocerolandActivex@331exhibit small,broad
endothermicthermaleventswith largetemperatureintervals and a broad single foaming event with long foam
timesandslow speeds.The foamingeventsoccursimultaneouslywith the thermal eventsand follow first order
gasreleasekinetics. Activex 331 is the slowestfoaming
agent. Activex 131 has a dual foaming mode with two
temperature intervals, but both events exhibit similar
foam times, and occur at different temperatures. The
foaming eventsfollow first order gasreleasekinetics and
occur simultaneouslywith thermalevents. Activex 131
and Hydrocerolhave similar foam times.
CONCENTRATES:
70VoConcentrates:
CLM 70 hasa lower gascapacitythanHydrocerol
but similar thermal and foaming characteristics. The
foam time of the CLM 70 is essentiallythe same as
Hydrocerol.The presenceof thecarrierdoesnot appearto
impact the CLM 70 foamingperformance. BIH 70 and

HK 70 are 707o concentratesof different commercial

CFAs and haveslightly different foamingperformance,
foam times, and speeds.HK 70 is the slowestchemical
foaming agentof the 70Voconcenfrates.
25VoConcentrates:

F. Lewis, ffid JohnV. Ofndani for their assistance

in the
preparationof this work. Finally, the authorswould like
to expresstheir appreciationto Dr. SatishK. Wason and
Dr. SushilK. Bhalla for their supportandencouragement.
RBFERENCES:

1. "IJsersGuide - Activex Products",ChemicalsDiviActivex 535 and235havetheexpectedgascapacity

sion,J, M. HuberCorporation,Havrede Grace,MD,
and foaming characteristicsof the parentpowders. The
1992 (in print)
foam time for Activ ex 235 is slightly longer than the
parentCFA. The foam time for Activex 535 is signifi- 2. "Testing Procedures",Ficel, North America, March
18,1980
cantly longerthanthe Activex 33I (6.22minutesto 8.10
minutes).This shift strongly suggestsan impact of the 3. Semerdjiev,Stefan,Inffoduction To StructuralFoam,
carrier on the gasreleasekinetics of the parentpowder.
Societyof PlasticEngineers,BroolcfieldCenter,CT
Activex 535is the slowestchemicalfoamingagentof the
1982
group tested.
4. "IndusfitrrTrends And PerformanceCharacteristics
l07o Concentrate:
Of VariousBlowing Agents",PradeepDamle,Quantum-USI Division, presentedat 19thAnnual StrucThe lU%oconcentrateof sodium borohydride in
turalPlasticsConference,SPI,Atlanta,Georgia,April
polystyrenewaslaboratoryprepared.The GEAR, DSC,
L4-17
, I99l p.116
andTGA dataconfirm that no foaming or thermalevents
occuredfor pure sodium borohydride under the thermal 5. "Basic Principles: POLYMERIC FOAMS - Prepasffessstudied.The IUVoconcenffateof SodiumBorohyration, Processesand Properties"J. L. Throne predride showsendothermicthermalbehavior,aswell astwo
sentedat Atlanta, Georgia,November I4-I5,1990
sequential foaming events with significantly different
initial and final temperaturesand foam times. A proton BIOGRAPTIY:
donor was usedto initiate the gasrelease.
Claude R. Andrews
CONCLUSIONS:
The methodologyasdescribedmeasuresthe CFAs
performancewith a precisionof * 5Vo(one sigma).
The performanceof exothermic and endothermic
CFAs are measuredby thermal, flow tate, volume, and
kinetic response,aswell asgascapacity.

ClaudeR. Andrewsis a SeniorResearchScientist

and headsappliedresearchat J. M. Huber Corporation,
ChemicalsDivision. Mr. Andrewshas30yearsof diverse
experiencein analytical chemisfiy, inorganic synthesis,
and plasticstechnology. He holds severalU. S. patents
andhasauthorednumerouspublications. Mr. Andrews is
well known in industry by his work in the developmentof
new techniques to understandthe basic technological
phenomemarelatedto ttre plasticsindustry.

Although endothermic CFAs have lower gas capacitiesthanexothermicCFAs,thisis nottheonly considerationwhenmeasuringperformance.EndothermicCFAs

Gerard Mooney
may give shorter injection molding cycles, or faster
extrusionrates. Field observationshave shownuniforGerard "Gerr1r" Mooney is the Manager, Plastics
mity in weight reduction and foam structure.Additionally, the foam structure was finer resulting in superior TechnologyatJ.M. HuberCorporation,ChemicalsDivision. He has20 yearsof diverseexperiencein the areas
physicalproperties.
of injection molding, exffusion,and new productdevelA non-commercialversionof this paperwas pre- opment. Mr. Mooney holds severalU. S. patentsand is
sentedat the zhhAnnual SffucturalPlasticsConference. well recognizedin the plasticindustry. Beforejoining J.
SPI,Dallas,Texas,April 5-8,1992.
M. Huber Corporation,Mr. Mooney was a consultantto
Fortune500companiesin thefield ofplasticstechnology.
ACKNOWLEDGBMENTS:
The authorswish to thank the ChemicalsDivision
of the J.M. Huber Corporationfor permissionto publish
this work. The authorsalsothankJudithA. Shenk.Robin

TABLE I. CIIEMICAL FOAMNG AGENTS

EXOTIIBRMIC
1007oACTM POWDERS
AZISO
UR AZODICARBONAMIDE
AZNP130

UR MODIFIED AZODTCARB
ONAMIDE

OT

HYDRAZIDE
UR 4,4'OXYBISBENZENESULFONYL

ENDOTIIERMIC
1007oACTM POWDERS
HYDROCEROL
BIKG CITRIC ACID SALT/SODIUMBICARBONATE
ACTIVEX 331 -JMH

CITRICACIDANORGANICCARBONATE
JMH CITRIC ACID/INORGANICCARBONATES

ACTIVEX T3T
70VoCONCENTRATES
CLM 70

BIKG 70VoCONCENTRATEof HYDROCEROL

BIH 70

BIKG CITRICACID SALT/SODIUMBICARBONATE*

HK 70

BIKG CITRIC ACID SALTIINORGANICCARBONATE

25VoCONCENTRATES
ACTIVEX 535-JMH
ACTIVEX 235-

257oCONCENTRATEof ACTIVEX 331

JMH 25VoCONCENTRATEof ACTIVEX 131

10VoCONCENTRATES
*
l07oNaBH4IN POLYSTYRENE*

XDIFFERENT RATIO

*XT ABORATORY PREPARED

UR= UNIROYAL CORPORATION

JMH = J. M. HUBER CORPORATION

BIKG = BOEHRTNGER INGELHEIM KG

TABLE II
GEAR PERFORMANCE PARAMETERS
CHEMICAL FOAMING AGENTS
CFA
AZI30

BIH 70
f'IK...7'0.'....i...
..,..i.'
.....
.I
Activex535
fietiv

:.,2tr

0.282

1.00

145

,2*15

0r:342

116

195

0.406
...*tffi..

105

.24s
285

l/it,',,It'J,

,t5.;,2

303

175

.ix.

:T

..N
N

.T
1

..'N

t,

100

Aetivex..:,.1,3.,I 14CI

frfi...
...
...
....u
..'.

233

MODE

Hy r.OCeibX,.. u,42i

cl

SPEED

CFATYPE

r44

Activex331

FOAM
TIME
(min.)

CC/G

ffiNF.I.SCI..,....:.r:84
OT

'C
PEAK
TEMP.
i
f

.8$
88
6.9

.N.
N
.N.

I',fi.1t

..t..6.las
22.06

...4r*#7..i
4.20

.t.s.'.8s

27.7'

..ais+..

270

2.19

.t.6.i..$o
1.17

rr..5,,,

:t:8r$0
28.13

l,,i,: '
,ii.:.

:':',','::

152

266

t.

fi:44

t19

t.

6.22

....i..t..'al..
r.44

256

u.fr'.6,...
..
8.10*

14.90

29

:7:4
103

$.6.

t..

il$iil

,15.5

...4:8.3'li'.

*:+1i
,*

165

244

4.48

15.89

.N.

.n..

:l::5:$:.

..Is.8.

.,6ut*-

A.t..ffi$i

158

298

2.19

I.s .iNaHffiS....,.
f
:.3
...;

X=EXOTHERMIC N=ENDOTHERMIC i=INITIAL f=FINAL

SPEED=FOAM TIME/0.282 (SLOWNESS OF REACTION COMPARED TO AZI3O)
* = AVERAGE(4 DETERMINATIONS)+ O.40

7.76