Interface in Composite Materials [and Discussion]

Author(s): P. Ehrburger, J. B. Donnet, A. R. Ubbelohde, J. W. Johnson, M. O. W. Richardson

and R. A. M. Scott
Source: Philosophical Transactions of the Royal Society of London. Series A, Mathematical and
Physical Sciences, Vol. 294, No. 1411, New Fibres and Their Composites (Jan. 21, 1980), pp.
495-505
Published by: The Royal Society
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Phil. Trans.R. Soc.Lond.A 294, 495-505 (1980) 495
in GreatBritain
Printed

Interfacein compositematerials

BY P. EHRBURGER AND J. B. DONNET

Centrede Recherches
surla Physico-Chimie
desSurfacesSolides,
24, Avenuedu President
Kennedy,68200 Mulhouse,France

[Plate 1]

The mechanical characteristicsof a fibre-resincomposite depend primarilyon the

mechanical propertiesof the combined materials,the surfaceof the fibre,the nature
of the fibre-resinbonding as well as the mode of stresstransferat the interface.
These two last pointsare related to the surfacepropertiesof the fibres.The various
types of bonding that may occur between fibrous materials (carbon, glass and
organic fibres) and organic polymers, including the relevant theories, are briefly
reviewed.
In order to optimize the fibre-resininteractions,it is oftenessential that the inter-
face should be chemicallymodified.The various possible treatmentsmay be classified
under threeheadings: chemical surfacemodificationof the fibre,sizing and polymer
fixation(grafting).
The major factorsthat influencethe interactionsbetween high-performance fibres
and organic resinswill be established and discussed, as illustratedin a few selected
examples.

INTRODUCTION
It is a well known fact that unidirectional composites reinforcedwith high modulus fibres
exhibitexcellentcharacteristicsin thedirectionof the reinforcement.However, theirweak point
lies in theirmoderate shear strength.This may be aggravated by the decrease in strengthof the
composite during weathering,which renders the problem of the coupling between fibre and
matrix even more intricate.
Interfacial stressesin compositesare due to the shrinkingof the resin and the differencein
elasticitymodulus between matrix and reinforcingagent. The stresstransferat the interface
thereforerequires an efficientcoupling between fibreand matrix. It is, however,importantto
optimize the interfacialbonding, since a direct linkage between fibreand matrixgives rise to
rigid, low impact resistancematerial.
Among the many factorsthat govern the characteristicsof composites involving a fibrous
material and a macromolecular matrix,it appears certain that the adhesion between fibreand
matrixplays a predominantpart. Although the differentauthorsdo not always agree as to the
nature, the intensityand the properties of the interfacial bonding (physical or chemical,
reversibleor irreversible)it seems clear that one of the main criteria is the absence of inter-
facial defects,i.e. the existenceof a smooth interfacialadhesion.
Many models have been suggested,but only thosewith a directbearing on compositeswill be
dealt with in the firstpart. As to the influenceof surfacechemical functionsin carbon fibres-
epoxy resin composites, attention will be paid to them in the second part.
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496 P. EHRBURGER AND J. B. DONNET

FIBRE-RESIN INTERFACIAL BONDING

As a rule, in compositematerials,mechanical bonding is distinguishedfromspecificbonding.

Mechanicalbonding
This model consistsof a linkage phenomenon, a mechanical anchoringof the polymerinto
the pores and the unevennessof the fibre,afterhardeningof the polymer.The interpenetration
of two solids is, in fact,a mechanical factorwhich promotesthe adherence between two bodies.
Wake (I959) has shown that the adherence to fabricsbased on continuousbut variouslyshaped
yarns is proportional to the surface area of the fabrics. However, the rugosityis a positive
factoronly in so far as the substrateis perfectlywetted by the liquid. As a matterof fact,if the
liquid cannot penetrateinto the asperitiesof the substrate,the hardeningof the resinis accom-
panied by the formationof interfacialcavities which are liable to initiate the failure of the
interfacialbond.
In this model, the adherence and wettingcriteriaare thereforecloselyrelated. Thus, in the
case of a good wetting,an increase in the specificsurfacearea of graphite fibres,achieved by
nitric oxidation improves the interlaminarstrength(i.l.s.s.) of the correspondingcomposites
(table 1) (Donnet et al. 1974) .

TABLE 1
fibre(typeI) SB.E T. (fibre)
/(mlg-1) composite)
i.l.s.s.(carbonfibre-epoxy /MPa
non-treated 0.4 22
nitricacidtreated 1.4 43

It is also worthnoting that pittingthe surfaceof carbon fibresby oxidation in air at 870 K
significantlyincreases the shear strengthof the resultingthermosettingcomposites (Clark et al.
I 974) -
Physicalcoupling
In this model, the forcesof interfacialbonding are so-called secondary or van der Waals
forces. They include mostly London dispersion forces, dipolar interactions and hydrogen
bonding. Their energyis usually comprised between 8 and 16 kJ/mol.
Generally speaking, these forces are involved in the wetting and adhesion phenomena
(Zisman I963). In the case of composite formation,this model stipulatesthat strongadhesion
may only be achieved ifthe materialsfacingeach other are in close contact. In thisconnection,
it is worth noting that the shear strengthhas been related to the wettingangle between resin
and carbon fibre(Yamamoto et al. 1971).

Chemicalcoupling
In the chemical bonding model, the adsorption of chemical groups and the formationof
true covalent bonds between fibreand matrix are assumed. The forcesof interfacialbonding
are, in this case 'primary forces' of high energy (40-400 kJ/mol)i.e. covalent, ionic or metal
bonds. Chemical groups that give rise to such bonding are seldom available on a surface,and
the aim of surfacetreatmentsis to insertthem at the interface.
For glass fibresthe surfaceis treatedwithcoupling agents,mainlyof the silane type,described
among others by Plueddemann (I 970). The bonding between fibre and resin involves the
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 INTERFACE IN COMPOSITE MATERIALS 497

formationof hydrogenbonds between the silanol groups of the fibreand the partlyhydrolysed
silanes according to the scheme shown in figure 1, where R is a group compatible with the
resin.
An overall interpretationof the characteristicsof the coupling agents according to the theory
of the chemical bond is however not completely satisfactory.Other theorieshave been pro-
posed, more particularlyan enhanced ageing resistanceof the compositein a humid atmosphere
(Outwater & Murphy I970).

R resin

- Si-
0-
-o

Si
glass fibre
FIGURE 1. Schematicdiagramofsilane fixationon a glassfibre.

For carbon fibres,the presenceofcarboxylicand phenolic surfacegroupssuggeststhe creation

of covalent bonds betweenfibreand matrix.This last possibilitywas checked by causing surface
groups to react with model compounds. Thus, by reacting epichlorohydrinwith oxidized type
I fibre,an irreversibleamount of chlorine,close to the number of acidic groups,has been found
(Donnet et al. I974) (figure2).

C-OH + CH2-CH-CHj-C1
_'.~0'

C-O-CH2-CH-CHj-C1
OH

FIGURE 2. Chemicalreactionbetweencarbonfibreand epichlorohydrin.

The model of the chemical bonding, however,is only an extensionof the physical coupling
as suggestedby Kaelble (I97I). Both are dependent on a good contact and hence upon a good
wettingbetween fibreand matrix. Only the bonding energymay vary fromone model to the
other even thoughthe broad scatteredspectrumof the various possible bonds (hydrogen,ionic,
covalent bonds) renderstheiridentificationdiicult.
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498 P. EHRBURGER AND J. B. DONNET

Flexible
interlayer
The insertionof a non-rigidinterlayerbetween the fibreand the matrixconstitutesanother
practical means of ensuringa good stresstransfer.Broutman& Agarwal (I 973) calculated that
although the strengthof the composite varies little with the modulus of the interlayer,the
ruptureenergyofthe compositepasses througha maximumfora modulus lower than thatof the
resin used. It appears, therefore,that coating the fibreswith a polymer provides a means of
increasing the impact strengthof the composite (Fila et al. I972; Hancox & Wells I977).
A simple process to establish such a non-rigidlayer and ensure a good adherence between
fibre and matrix has been employed by Riess et al. (1974). They modifiedcarbon fibresby
graftinga copolymer bearing flexiblesegments (polyisoprene,PI) and segmentscompatible
with the matrix(styrenemaleic anhydridecopolymer,SMA). The bonding between the carbon
fibreand the polyisoprenesequence consistsof dipole-dipole interactionsresultingfromsalified
carboxylic groups, as shown in figure3.

COONa
NaOOC
A - B C :| D

FIGURE A, fibre;B, elastomer;

3. Fixationofblockpolymeron carbonfibrethroughdipole-dipoleinteraction.
C, SMA; D, matrixofcomposite(Riess etal. 1974).

of thusobtainedepoxycompositesare shownin table 2. It

The mechanicalcharacteristics
improved.
appears that the impact strengthhas been significantly

TABLE 2t
carbonfibre-epoxy
composites

carbon fibre(typeII) i.s.s./MPa resilience/(J

cm-2)
non-treated 71 4.0
PI-SMA treated 80 6.3
t Riess et al. 1974.

The 'Kevlar type' organic fibreshave likewise been polymer treated with positive results.
According to Wake (1972), the fibresurfacemay react with an isocyanate linked polymeras
indicated in figure4.
Using polyurethane treatment,Riess & Reeb (1977) significantlyimproved the torsion
of Kevlar-epoxy composites.
stiffness
Beforeconcluding thissection,it is worthnotingthat the model of the flexibleinterlayerhas
also been suggestedto account forthe behaviour of silane coupling agents in glass-fibrebased
composites.In fact,Bascom (1972) reportsthat afterhydrolysis,the silanes may have an effect
on resin polymerizationand hence on its physico-chemicalpropertiesin the vicinityof the
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 INTERFACE IN COMPOSITE MATERIALS 499

\\ \-C-NH\ \ \ + NCO

11
C=O
I
NH

FIGURE 4. Reaction of isocyanatelinkedpolymerwithKevlar fibre(Wake I972).

interface.Unfortunately,the extentof thismodificationand the thicknessof the interlayerthat

is affectedare not well known. The thicknessis estimated to lie between 5 nm and 1 jum,
depending on the composites. However, the theoryof the deformable layer (Kenyon I968)
appears to be general and to apply to various typesof fibreand organic resin composites.

INTERFACIAL PROPERTIES OF CARBON FIBRE-BASED COMPOSITES

It is well known that the interlaminarshear strength(i.l.s.s.) of carbon fibre-basedcom-
posites may be increased significantlyby oxidation. Generally, the oxidation reactions bring
about a simultaneous increase of the fibre surface and the number of surface groups. Both
factorsmay have beneficial effectson the fibre-resinbonding. A thirdpossible reason for the
improvementof the i.l.s.s. is the removal of surface defectson the carbon fibres(McKee &
Mimeault I973).

Anodic
oxidation
ofthefibres
In order to investigatethe effectof surfacegroups on the fibre-resinbonding, we developed
surfacetreatmentsthat alter the nature and the number of surfacegroups withoutaffectingthe
surface area. Previous studies showed that shorttime anodic oxidations in various electrolytes
(diluted nitricacid, alkaline medium) permit the achievement of such conditions (Ehrburger
et al. I 974, I 975) .
Experimentshave been carried out with carbon fibre,ex-PAN fibre (AC fibre,type II). The
acidic groups were of two types: the strongerones (carboxylic and some phenolic groups) were
estimated with sodium hydroxide,whereas sodium ethanolate was used for the weaker ones
(hydroxylicgroups). In the latter case, all the acidic functionson the carbon surface were
neutralized (Scholz & Boehm I970). The data in table 3 reveal that the number of functions

TABLE 3
acidic surfacegroupsneutralizedwith

carbonfibre SB.E.T./(m2 g-1) NaOH/(giequivg-1) NaOC2H,5/(jiequivg 1)

AC non-treated 0.3 7 10
A_-HNO3 0.3 14 20
AC-NaOH 0.3 16 17
II91]

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500 P. EHRBURGER AND J. B. DONNET

that may be measured with sodium ethanolate is similar whateverthe type of electrolyteused
forthe anodic etching (HNO3 or NaOH). Yet, the treatmentof the fibresin alkaline medium,
AC-NaOH, yields comparativelystrongeracidic groups since theymay all be neutralizedwith
sodium hydroxide.The uncertaintyof the measurementsis of + 2 jiequiv/g forAC-HNO3 and
AC-NaOH fibres.
of modified
Bondingproperties carbon
fibres
Unidirectional composites have been formedby using treated carbon fibresand an epoxy
resin (Ehrburger et al. 1974). The interlaminar shear strengthof the composites has been
measured with the cantilever test as previouslydescribed (Donnet et al. I974). The mode of
failure of the composite in this test has been determined by analysing the load-deflexion
diagram. In fact, the shape of this diagram reveals the nature of the bonding between the
componentsof the material (Hanna & SteinsigerI969). Two extremecases may occur.
The interfacialbonding is weak; in that case 'pull out' is responsibleforthe rupture.As the
fibresare not matrixbound, theyslide in theirbeddings and load transfercan no longer take
place (shear failure).
The interfacialbondingis strong;thenthe matrixtransfers the load to the fibresuntilreaching
of the breakingpoint. In thiscase, the failureis sudden and catastrophic (tensile failure).
Most cases of failurelie between theseextremes,the relativeimportanceofwhich depends on
the interfacialbonding.
The load-deflexiondiagram of compositescomprisingAC fibresare shownin figure5.

1.5

1.0

0 o.4 0.$
I/mm
deflexion,
FIGURE 5. Load-deflexiondiagramsforcarbonfibres-epoxy
composites:curve 1, non-treatedAC fibres;
2, AC-HNO3; 3, AC-NaOH.

The compositescontaininguntreatedfibresdisplaysa shear failuremode. On the otherhand,

AC-NaOH fibresinduce a tensilefailuremode. In the case ofAC-HNO3 fibres,the failuremode
is intermediate.The values of the i.l.s.s. as well as the mode of the failureof the compositesare
given in table 4.
It appears that anodic treatmentresultsin similar improvementsof the shear strength,
whereas the failure modes observed are definitivelydifferent.The aspects of the fractureof
the samples observed by scanning electron microscopyconfirmthe mode of failure (figures6
and 7). For AC-HNO3 fibres,'pull out' of the carbon fibresis still observed, whereas with
AC-N aOH fibres,the fracturesurfaceof the compositeis clean and smooth.
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Phil. Trans.R. Soc. Lond. A, volume294 & Donnet,plate 1
Ehrburger

tD- s~~~~~~~~~~~~~~~~~~~~~.A

FIGURE 6. Scanningelectronmicrographofthe fractureofAC-HNO2-epoxycomposite.

FIGURE 7. Scanningelectronmicrographof the fractureofAC-NaOH-epoxy composite.

(;Facing p. 500)

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 INTERFACE IN COMPOSITE MATERIALS 501

TABLE 4
carbonfibre-epoxycomposites

carbonfibre i.1.s.s./MPa failuremode

AC non-treated 55 shear
AG-HN03 85 intermediate
AC-NaOH 92 tensile

In order to relate the propertiesof the compositesto thoseof the carbon fibres,the number of
acidic groups was varied at the carbon surfacethroughpyrolysisat 1273 K for 3 hours, in an
inert atmosphere.The data are included in table 5.

TABLE 5
acidic surfacegroupsneutralizedwith carbonfibre-epoxy
composite

carbonfibre NaOH/(pteq g1) NaOC2H5/(geq g-1) i.d.s.s./MPa failuremode

AC-HNO3 14 20 85 intermediate
AC-HN03 1273 K 0 15 77 intermediate
AC-NaOH 16 16 92 tensile
AC-NaOH 1273 K 0 13 77 intermediate

It is seen that, afterpyrolysis,the strongacidic groups that may be neutralized with sodium
hydroxide are destroyed,whereas the weak acidic groups are only partlyremoved. Moreover,
the nature of the acidic functionsdetermineslargely the failuremode of the composite in the
Rsheartest. The presence of strongacidic groups resultsin a tensilefailure mode, i.e. a strong
interfacialbonding. On the other hand, the failurein shear would rathercorrespondto weak
acidic groups.
In figure8, the i.l.s.s. of the material has been plotted against the total amount of acidic
groups. A clear correlation indeed appears between the content of acidic functionsand the
ultimate value of the shear strength.

10

C1 FW I
/
_6 - /
.{/
4/

10 20
acidic groups/(jiequivg-1)
FIGURE 8. Interlaminarshear strengthof the compositeplottedagainstthe amountof acidic group
neutralizedby sodiumethanolate.

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502 P. EHRBURGER AND J. B. DONNET

DISCUSSION

The data obtained with anodically treatedcarbon fibresclarifythe predominantrole played

by the surface acidic groups. The presence of weak acidic functions (mainly OH groups)
enhances the interlaminarshear strengthwithoutaffectingsignificantly the mode of failure,i.e.
the nature of the interfacialbonding. This would be consistentwith an increase in interfacial
coupling, as a resultof betterfibrewettingby the resin.
The presence of strongeracidic groups (COOH and OH) resultsin an increased adhesion
between fibre and matrix. In fact, both the shear strengthand the mode of failure of the
composite are affected.The adhesion between fibre and matrix is thus enhanced when the
surfaceof the reinforcingagent has the abilityto formchemical bonds with the resin.A similar
observation has been made with glass-epoxy composites which suggeststhis to be a general
phenomenon (Kenyon i968). It must be stressed,however,that the theoryof the flexiblelayer
previouslyexposed also permitsan interpretationof these results.As a matter of fact, it has
been observed that the surfaceof the reinforcingagent could alter the polymerizationreaction
of the resinswith the resultantchanges in theirrheological and mechanical propertiesat the
interface(Cuthrell I967; Kenyon I968; Bessel et al. I972; Beaumont I974). This means that
chemical functionsmay induce polymeralterationsat the time of gelation in the vicinityof the
fibre,thus creatinga layer with differentmechanical properties.The extentof such a layer at
the interfacewould then be dependent on the nature and the amount of surfacegroups. How-
ever, it is difficultto state preciselythe exact nature of the alterationsin the resin.
The example of the carbon fibresis a good illustrationof the intricatephenomena occurring
at the interfaceof a composite material. In this particular case it was possible to demonstrate
that the nature and the amount of acidic groups play a definitepart in the interfacialstress
transfer.Althoughtheirmechanismof action has so farnot been fullyelucidated,it appears that
if properly inserted on the surface, they will provide a means for optimizing the bonding
between fibreand matrix.

REFERENCES (Ehrburger& Donnet)

Bascom,W. D. 1972 Macromolecules 5, 792-798.
Beaumont,P. W. R. 1974 J. Adhesion 6, 107-137.
Bessel,T., Hull, D. & Shorthall,J. B. I972 FaradaySpec.chem.Soc. 2, 137-143.
Broutman,L. J. & Agarwal,B. D. I974 Polym.EngngSci. 14, 581-588.
Cuthrell,R. E. I967 J. appl.Polym.11, 1495-1507.
Clark,D., Wadsworth,N. J. & Watt,W. I974 Proc.2ndCarbon FibresConference, pp. 44-5 1. London: The Plastics
Institute.
Donnet,J. B., Papirer,E. & Dauksch,H. I974 Proc.2ndCarbon FibresConference,pp. 58 64. London:The Plastics
Institute.
Ehrburger,P., Herque,J. J. & Donnet,J. B. I974 Proc.4thConf.Ind.CarbonandGraphite, pp. 201-208. London:
Societyof Chemical Industry.
Ehrburger,P., Herque, J.J. & Donnet,J. B. I975 Petroleum derived carbons.A.C.S. SymposiumSeries,vol. 21
pp. 324-334. The AmericanChemicalSociety.
Fila, M., Bredin,C. & Piggott,M. R. 1972 J. Mater.Sci. 7, 983-988.
Hancox, N. L. & Wells,H. I977 FibreSci. Technol. 10, 9-22.
Hanna, G. L. & Steinsiger,S. I969 Composite materials, anddesign,vol. 460,pp. 182-191. ASTM Special
testing
TechnicalPublication.
Kaelble, D. H. I97I Physicalchemistry ofadhesion, pp. 45-83. New York: Wiley-Interscience.
Kenyon,A. S. I968 J. ColloidInterface Sci. 27, 761-771.
MacKee, D. & Mimeault,V. 1973 Chemistry andPhysicsofCarbon, vol. 8, pp. 151-241.New York: M. DekkerInc.
Outwater,J. 0. & Murphy,M. C. 1970 J. Adhesion 2, 242-253.
[ 94 ]

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 INTERFACE IN COMPOSITE MATERIALS 503

Plueddemann, E. P. 1970 J. Adhesion2, 184-201.

pp. 52-56. London:
Riess, G., Bourdeaux,M., Brie,M. & Jouquet,G. 1974 Proc.2ndCarbonFibresConference,
The PlasticsInstitute.
Riess, G. & Reeb, R. I977 D.G.R.S.T. report74.7.1021, Paris.
Scholz, W. & Boehm, H. P. I969 Z. anorg.allg. Chem.369, 327-340.
Yamamoto, M., Yamada, S., Sakatani, Y., Taguchi, M. & Yamaguchi, Y. 1971 Proc. 1stCarbonFibresConference,
pp. 179-184. London: The PlasticsInstitute.
Wake, W. C. I959 Trans Inst. RubberInd. 35, 145-159.
Wake, W. C. I972 J. Adhesion3, 315-324.
Zisman, W. A. I963 Ind. Engng Chem.55, 19-36.

Discussion
A. R. UBBELOHDE, F.R.S. (Department of ChemicalEngineeringand ChemicalTechnology, Imperial
College,London,SW7, U.K.). When certainsurfacetreatmentsare used to 'improve' the contact
between carbon fibresand various matrices,it must be rememberedthat such fibresare often
quite well graphitized. Various formsof anodic treatmentin aqueous electrolytescontaining
(say) OH' or NO' may actually promote formationof intercalation compounds of graphite.
Even if mostof the intrudinganions are subsequentlyremoved,e.g. by hydrolysis,intercalation
would probably involve penetrationof layersin some depth, and leave a fluffier interfaceafter
subsequent treatmentbeforecontact with the resin,than if surfaceimpuritieshad been merely
removed by high temperatureoxidation, or ion bombardment. Titration of the foreignanions
with Boehm's methods may not reveal all thosepresentin the formofintercalationcompounds,
near the surfaceof the carbon fibre,because 'residue compounds' are formed.
Fibres treated anodically should thus be considered rathercritically,since some anions may
actually produce a fluffy interfaceextendinginwards to some depth. Since a great variety of
anions can be used foranodic intercalation,thisprocedure can be varied to check how far the
interfacehas been modifiedin depth, by varyingthe anion.

P. EHRBURGER. We have indeed observed that intercalationoccurs when graphitized carbon

fibresare anodically treated. In fact, there is a tremendousdecrease in the tensile strengthof
those treated fibres (Ehrburger, P., Herque, J. J. & Donnet, J. B. (I975). Petroleum Derived
Carbons,A.C.S. Symposium, 21, 324-334).
However, forfibresheat-treatedat 1100?C, we found no evidence of intercalation.

J. W. JOHNSON(Rolls-Royce
Limited,AeroDivision,Non-MetallicsLaboratories,
PlasticsandComposite
Materials Department, AlfretonRoad, Derby, U.K.). ProfessorUbbelohde's observations on the
electrolyticformationof intercalationcompounds in carbon fibresare very relevant and have
great significanceforcarbon fibrecompositetechnology.Mild anodic electrolysisof carbon fibre
in a varietyof aqueous electrolytesoftenproduces thin film interferencecolours on the fibre
surface; extended electrolysiswill ultimatelyrender the fibre completely transparentso that
it can be examined in the light microscope. The electrolysisis most easily accomplished with
type A or type III fibres,although the swelling accompanying the intercalation bursts the
fibresalong theirlengthsand the propertiesare irretrievablyruined.
Types I and II fibres,ratheroddly, are more resistantto the process but are still susceptible
to a large extent.Orientationis mantained in the swollen state as shown by birefringence,and
details of fibremorphologyare preserved (see figure9).
[ 95 ]
32 Vol. 294. A

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504 P. EHRBURGER AND J. B. DONNET

! FM

FIGURE 9. Fibresof CourtauldsGrafilA anodicailyelectrolysedin dilutesulphuricacid. Note the internalflaw

renderedvisibleand thegeneraltransparency oftheresidues.The sampleis immersedin theelectrolyte and
viewedby Nomarskidifferentialinterferencecontrastin transmission.

A. R. UBBELOHDE, F.R.S. (Imperial London,

College, U.K.). Two phenomenain thebehaviourof
compositeswarrantsome discussionin termsof solid statechemistry and solid statethermo-
dynamics:
(1) Because of their
reese.Reetd bondfstrs
yle ol the thermal
structure, rv expansion
arl of mostof the
eesbesse fibresunderoa
o ir-lee dis-
cussionat thismeetingis extremely\ _anisotropic.
- K~[6 Parallel to the fibrespine,it will be zero or
evenslightly negative,butin directions
perpendicular tothespinethermalexpansioncoefficients
willtendtobe exceptionally large,becauseofthekindsofforcesholdinga bundletogether in any
fibre.When thecompositeis preparedand used undermoreor lessisothermal conditions,the
verylargeforcesresulting fromnon-uniform thermalexpansionmaynotbe a sourceofinternal
stressand local weakness.However,when it is intendedforuse at high temperatures, very
different fromthoseusedin thefabrication, someintenselocal stresses mustdeveloparoundeach
fibreduringuse. It maybe possibleto buildin someofthesestresses duringfabrication, so as to
compensatepartoftheexternalshockstresses thematerialwillhave toencounter. The shrinking
of chilledmetalintocontainersof different thermalexpansionis a simpleexampleof stresses
builtin duringfabrication.
It would be helpful,and informative to moleculartheory,to have data on the anisotropic
thermalexpansionsoftheprincipalfibres, overthewidestpossiblerangeoftemperatures.
(2) Fromremarks made by one ofthe speakers,one modeofeffective protection ofcomposites
duringuse maybe whentheinterlacelayerbetweenfibreand matrixactsas a shockabsorber,
crackingawayso as to forma kindofshockabsorbingsleevearoundthestrongspinewithinit.
If thisview is correct,the questionarisesas to whathappensto the thinlayerof interface
betweeneach fibrespine,and thematrixin bulk,whenthesystemis exposedto cyclicstresses.
Solid statechemistry and thermodynamics suggestthatthe structure of someinterface layers
may be at least partlyreversible,reverting to the originalstate,or near it, when the stressis

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 INTERFACE IN COMPOSITE MATERIALS 505

asymptoticstate,which should be detectable in the various mechanical stresses.However, some

interfacestructuresmay be brokenwhollyirreversibly in a singlestresssituation.Alternatively,
interfacematerial could probably be found whose structurewould be substantiallyreversible
in each cycle. Possibilitiesof exploringthesealternativemodes of responseto stressof interfaces
between fibresand their matrixpresentsome interestingopportunitiesin solid state thermo-
dynamics.
M. 0. W. RICHARDSON (Department ofMaterials Technology,Loughborough University,
Leicestershire,
U.K.). Regarding the helpful comments of ProfessorUbbelohde, on the need for reversible
energy absorption or modifiedstresstransfermechanismsat the interfaceof the various com-
ponents of composite materials, I should like to point out that Dr E. P. Plueddemann in the
U.S.A. has published some interestingtheorieson 'dynamic equilibriumadhesion mechanisms'.
He claims that these can operate at the interfacebetween a hydrophilicmineral fillerand a
polymermatrix.
P. EHRBURGER.In fact, 'reversible bonds' at the interfaceconstitutea kind of optimization of
the bonding between fibreand matrix. Thus, a covalent bond at the interface,when broken,
cannot be rebuilt again. On the contrary,'secondary forces', i.e. hydrogenbonds, can be re-
built readily at the interface.
R. A. M. SCOTT (ThamesPolytechnic, London,SE 18 6PF, U.K.). We have performedmeasure-
mentson glass-reinforced polystyreneand have found that the usual siloxane keyingagent used
on the surface of the glass fibre produced composites of substantiallyincreased strengthas
compared with those containing uncoated fibres.Bearing in mind the fact that polystyreneis
normally considered as having saturated bonding, could Dr Ehrburgersuggestany reason for
thisbehaviour?
P. EHRBURGER. As already said, the role of the keyingagent is complex and not yet completely
understood. Generally speaking, the coupling agent affectsthe surface energeticsof the fibre
and plays the role of a water scavenger. In Dr Scott's case, the observed increase of strength
of the composite may resultfromthe water removal by the siloxane agent.

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