PII: $1359-835X(98)00019-0 Composites Part A294 (1998) 939-946 1359-835X/985- se front mater © 1998 Published by Elsevier Science Li All rights reserved Flexural and interlaminar shear properties of glass-reinforced phenolic composites Nigel A. St John* and James R. Brown DSTO Aeronautical and Maritime Research Laboratory, P.O. Box 4331, Melbourne, Victoria 3001, Australia (Received 17 December 1996; revised 18 December 1997; accepted 15 January 1998) Low-temperature acid-cured resole phenolic resins and glass-fibre-reinforced polymer (GRP) composites Containing resole matrices are inherently fire-retardant materials that evolve low levels of smoke and combustion products ina fire, The mechanical properties. particularly interlaminar shear strength (ILSS), of glass/phenolic composites are low compared with those of glass/polyester composites, and this is discussed in terms of the compatibility between the reinforcing fibres and resin matrix, the influence of the phase-separated water ‘microdomains which result in voids inthe pheno ic matrix, and the resin strength. An epoxy silane coupling agent 1 the glass fibre ina glass/phenolic composite resulted in a significantly higher ILSS and flexural strength than an aminosilane, which is recommended for use with thermally cured glass/phenolic composites, or a methacryly- functional silane, which is preferred for use with glass/polyester and glasvinyl ester composites, The ILSS of the slassiphenolic composites decreased after expusure to water at elevated temperature: this is attributed 10 a deterioration of the interfacial region and is independent of the silane coupling agent used on the glass reinforcement. © 1998 Elsevier Science Ltd. All rights served, (Keywor INTRODUCTION Glass-flbre-reinforced polymer (GRP) composites are find- ing increasing use in many applications as high-strength, lightweight structures and components in transport, building and maritime industries. A number of applications, how- ever, demand that these composite materials have ire- retardant properties. Phenolic resins and glass/phenolic composites are inherently fire-retardant and have superior flammability properties to polyester. vinyl ester and epoxy resins and composites! *. In addition, phenolics yield very low levels of smoke and combustion produets under both flaming and smouldering fire conditions. However, tradi- tional phenolic resins i.e. those that are cured at elevated temperatures (>160°C), have long been regarded as brittle, intractable materials with limited applications. Because of this, and also because more stringent fire regulations have recently imposed limits on the types of composite that can be used in high fire risk applications, there has been resurgence of interest in the development of improved phenolic resins suitable for use in GRP composites* Recently, new resole phenolic resins have emerged” that are less brittle than traditional high-temperature-cured phenolic resins and maintain their inherent fire retardancy and low smoke emission properties. These resoles are * Corresponding ator enolic resin; glass/phenolic composite: coupling agent; void: interlaminar shear strength) curable at low (<60°C) or ambient temperatures and pressure by the addition of acid catalysts, and are available as. Water-based, controlled-viscosity resins which are suitable for fabrication of GRP composites by hand lay- up, resin transfer or resin infusion moulding, pultrusion and filament winding Although they have an inherent advantage of superior fire-hazard properties, resole phenolic resins also have some disadvantages. Sorathia ef al. have concluded that compo- sites from acid-cured phenolics provide the optimum combination of fire retardance and affordability, but their mechanical properties and durability are currently inade- quate for critical primary structures*®, These properties need to be improved to enable glass/phenolic composites to be competitive with glass/polyester, glass/vinyl ester or slassfepoxy composites in many applications. Tavakoli et al.’ found significant variabilly in the interlaminar shear strengths (ILSS) of phenolic composites prepared with different commercial glass reinforcements. Charalambides and Williams* concluded that the low fracture toughness they measured for a glass/phenolic composite was due t0 poor fibre-matrix bonding causing, mainly fibre debonding without achieving the resin's inherent toughness. Thus it is clear that the compatibility of resole resins with glass reinforcing fibres is an important issue in optimising composite performance. This problem is, accentuated by the fact that most commercially availableGlass-reinforced phenolic composites: N. A. St John and J. R. Brown oon ° H,CO--Si-CH,-CHy-CH,-O-C-C-CH, oct Hy Methacryloxypropyltimethoxysilane (MPS) cHy ° CH; CHy-CHy-O-CH, CH CH, oc, Glycidoxypropyitrmethoxysilane (GPS) oct, H,CO-Si CH, CH, Cll, NH, ook, ‘Aminopropyltrimethoxysilane (APS) Figure 1 Typical se coupling agents used ingles fre sizes glass reinforcements contain surface sizes developed for use with polyester and epoxy resins’. ‘The size that is applied (o glass fibres performs several functions during processing and end-use. the most immediate ‘of which is that it protects the fibre from breakage. Thus the size emulsion contains a “film former’ that then becomes a protective coating. Film formers or fibre finishes based on epoxy resin and poly(vinyl acetate) (PVAc) are usually used. The size emulsion also contains several additives whose function is to stabilise the emulsion. Fer GRP applications, the size must also provide a surface that promotes glass-resin compatibility. To achieve tais, the size must be sufficiently compatible with the resin to allow rapid wetting out of the fibres by the resin, followed by dissolution of the size in the resin (o allow direct interaction between the glass surface and the resin. Another important consideration is the strength of the bond between the resin and the glass surface. For most resin systems and clean glass surfaces, the interfacial bond strength is very weak”, Several approaches have been used to increase the interfacial bond strength in GRP composites: for example, treatment with chromium complexes has been used to improve compat- ibility with polyester resins’. However. the most widely used method of promoting the interfacial bond strength in GRP composites is the application of silane coupling agents to the glass filaments’. Silane coupling agents are organotrialkoxysilanes usually containing three ethoxy or methoxy groups that can condense to form covalent bonds with silanol groups on the surface of silaceous glasses’. Coupling agents also contain an organofunctional tail that can react with the ‘matrix resin to form a covalent bond. Examples cf three commonly used silane coupling agents are shown in Figure 1. The silanes are applied to the glass fibre as part of the size emulsion and thus are easily changed in th manufacturing process to provide glass fibres suitable for a variety of resin appl Previous studies have found that aminosilanes promote glass fibre adhesion with traditional thermally cured phenolic resins, and the use of epoxy silanes has also been 940 suggested". Both of these silanes are capable of chemical reaction with these phenolic resins. However. a study of the most suitable silane coupling agent for use with acid-cured resole phenolic resins has not previously been reported, In this paper, the flexural and ILSS properties of GRP composites fabricated from an acid-cured resole phenolic resin and glass fibres containing various silane coupling agents are characterised and compared with results. for similarly prepared glass/polyester composites. In addition, the effect of water ingress at 70°C and 90°C on the flexural ‘modulus and ILSS of the glass/phenolie composite material has been determined and is discussed in terms of the composite fibre/matrix interface. EXPERIMENTAL, ‘The phenolic resole resin (Resinox®CL1723) and acid hardener (Resinox®H1196), as well as the isophthalic polyester resin (Crystic®3-491 PS), were supplied by Hunts- man Chemical Company Australia Ltd. Glass fibre strands (100 filaments) prepared with the same size (epoxy-based fibre finish, which is commonly used for GRP applications) but with different organosilane coupling agents were produced and supplied by ACI Fibreglass Ltd. The organo- silanes used (see Figure 1) were the methacrylylsilane MPS (2-630; Dow Chemical Co.). the epoxy silane GPS (Z-6040: Dow Chemical Co.) and the aminosilane APS (1100: Union Carbide). A commercial roving (GUN900) that contained a PVAe-based size and the aminosilane coupling agent APS ‘was also supplied by ACI Fiberglass Ltd, Phenolic resin castings were prepared between two glass plates separated by a rubber chord and clamped. then cured with 6.5 wt acid hardener for I h at 60°C and for 2h at 80°C to give flat sheets with a thickness of approximately 4.5 mm, The polyester resin castings were cured at room temperature for 4 h with 1% methyl ethyl ketone peroxide (10% active oxygen), then at 80°C for 2h. Castings for compression tests and density measurements were made in lass vials which were removed after cure and the speci- mens machined to yield the appropriate length. To evaluate different glass fibre treatments (organosilane coupling agents), unidirectional glass/phenolic and glass/ polyester composites were prepared by using a “leaky mould method. A split, open-ended stainless steel mould ‘was used to produce a bar specimen 240:mm long, 13 mm wide and 3.2 mm thick. The content of glass fibre strands ‘was adjusted to give composite bars with a glass content of approximately 62. wt%. The glass fibre impregnated with catalysed resin was compressed in the preheated mould (~SO°C) and entrapped air was removed. For the phenolic samples the mould was then placed in an oven and the resin cured at 60°C for | h; for the polyester resin the mould was left at room temperature for 4 h. The composite specimen ‘was then removed from the mould and post-cured for 2 h at 80°C. The composite specimens were designated as summarised in Table 1 ‘The flexural, tensile and compressive properties of the castings were determined according to ASTM Standard TestGlass-reinforced phenolic composites: N. A. St John and J. R. Brown ‘Table 1 Specimen designation Sample Resin ype Glass size pe Silane used Past Phenolic epoxy based MPs PHE Phelic epoxy based crs, PHA, Phenolic epoxy based APS PHG. Penslic PVAC APS PEM polyester epoxy bused ps PEE poljeser epoxy based Ges, PEA oljester epoxy based APS, Table 2 Mechanical and physical properties of eas resins Propeny Frenolc Polyester (Resinox®CL 1721196) Tensile strength (MPa) we Tensile ulus (GPA) Elongation to break (%) 20 008 Feu! song (MP) se FResual modulus (GPa) Sor oor Compresive stengt Ea) wos Compressive mde (GPa “6 + 002 Speci pravity (kgm) tian 10 on on R oh on, | 0 fe Ol tor “40. 2 on “ , R R R | = CHO) heat “10 y R R=H,CHOH a oH on 1 R oy | or R og ok Figure 2 Reaction scheme forthe aci-catlysed cure of « phenolic re resin, Hto yield ether crosslinks, 2, and medhylene crosslinks, 3 Methods D790M-86, D638M-89 and D69SM-89, respec- tively. The flexural modulus of each composite specimen was determined as a single measurement according to ASTM D790M-86 with a span-to-depth ratio of 64:1 Individual specimens were then cut into four lengths of approximately 60 mm for measurements of either flexural strength (ASTM D790M-86) in a three-point configuration and span-to-depth ratio of 16:1, oF ILSS using a four-point configuration (1:2:1 loading) as described by Browning er al.!! with a span to depth ratio of 12:1. The ILSS was calculated with eqn (J) where P, b and h are the load, specimen width and specimen thickness, respectively 0.75P. ILss bh ay ‘The results are the average of eight measurements for the ILSS and flexural strength, and four for the flexural modulus. 381 = 0.06 1S #2 221 006 160 = 10 After mechanical testing, the glass content in the specimens, was determined by ignition and burn-off to a constant weight in a fumace at 600°C. For water immersion, similar composite specimens were prepared and the ends sealed with resin to minimise wicking effects. The specimens were then immersed in water in sealed glass containers in an oven for 48 h at 90°C or for 240 h at 70°C, alter which the ILSS and flexural modulus were determined as above. The results are the average of four measurements for the ILSS and a single measurement for the flexural modulus, RESULTS AND DISCU! Phenolic matrix Resole phenolic resins are cured at low temperatures by the addition of a strong organic acid that catalyses polycondensation of the methylol groups present in the ‘The cure reaction proceeds rapidly under acidic conditions via the formation of water and benzyl carbonium ions that react with vacant phenyl substitution sites or hydroxymethyl groups to yield methylene or ether bridges, respectively. as shown in Figure 2. ‘The ether bridges thermally decompose, evolving formaldehyde which also reacts rapidly under acid conditions, to form a highly thermally stable three-dimensional_ network of ‘aromatic rings joined by methylene bridges. ‘As the molecular weight increases, the water already present in the resin and that produced during the reaction becomes incompatible with the curing resin and phase- separates to produce water domains, ‘These are observed as tmicrovoids' 2~10 jm in diameter in the cured matrix, as shown in Figure 3. The size of these domains is governed by the surface tension of the resin and the rate and extent of the curing reaction, These microvoids can account for up t0 20% of the volume of the cured matrix 941Glass-reinforced phenolic composites: N. A. St John and J. R. Brown ‘Table 3. Flexural and interlaminar shear properties of glasvphnolic and glass/plyester composites Composite Flexural modulus Flexural GPa MPa) Pa e=09 2410 PHE 321 meu PHA avo 3 s= 12 PHG: wa = 08 PEM 318 = 05 866 = 33 PEE us209 26s PEA 21 sid = 38 Figure3_ Scanning electron micrograph of the surface of aresole phenolic resin sample cured with 65> acid catalyst for Ih at 60°C and 2F at 80°C. Showing phase-separted water domains or ‘microvoids” inthe resin ‘The mechanical and physical properties of resin castings of Resinox®CLI723/HI196 and Crystic®3-491 summarised in Table 2, The phenolic resin has si lower strength and modulus values than the polyester, as nerally quoted for other thermosetti such as epoxies and vinyl esters. This can be explained in part by the morphology of the phenolic material, with the microvoids having a significant effect on the bulk prope ties, For example, assuming a void content of 20%, the ‘measured tensile modulus of 2.3 GPa can be recalculated on a void-free resin basis to give 2.9 GPa. It is also likely that well as those resins the crosslink density for this class of phenolic resin is lower than for other thermosetting resins, and solvents such as water or glycols present in these phenolic resins may plasticise the cured matrix. ‘The low strength of the phenolic matrix is partly compensated by acceptable levels of fracture toughaess as lighted by Redjel'? and Charalambides and Williams" who reported fracture toughness values for similar phenolic materials comparable 10 those generally reported tor epoxies and polyesters. This is notably different to the fracture toughness of traditional thermally cured reso resins which are characterised by very brittle behaviour'™ Flexural modulus ‘The flexural and interlaminar shear properties of uni- directional GRP composites with different silane ccupling srength Interiaminar shear strength Fibre content (MPa) (wth) 96516 66522 157 = 07 643 =26 88209 50 = 21 103209 O48 = 06 27 £09 6h 205 BTS 20, 6L8 #09 5132 1a 622=01 agents on the glass fibres and either phenolic or polyester matrices are summarised in Table 3. The flexural moduli are independent of the silane coupling agent used, which is expected considering that this property is dominated by the high modulus of the glass fibres. The modulus was measured with a span-to-depth ratio of 64:1 to minimise any contribution of shear to the measured value'®, Thus the theoretical modulus of the composites can be estimated by use ofthe rule of mixtures, given as eqn (2), where & and V are the modulus and volume fraction with the subscripts f, m and ¢ referring to the fibre, matrix and composite values, respectively ELSViEV+ VE @ To obtain fibre content values, the composites were fist charred and then burnt in a furnace at 600°C for 4h to give a value for fibre weight. This yielded average fibre contents (Table 3) of 61.7 and 65.1 w1% for the glass/poty- ester and glass/phenolic composites, respectively, The higher glass contents determined for the glass/phenolic composites were inconsistent with the fact that both the polyester and phenolic composites were fabricated with the same amount of glass and compressed to the same volume in the mould, There are two possible reasons for the higher calculated fibre weights for the phenolic composites. The frst is that the resin contains inorganic salts from neutralisation of the base used in the resin manufacture which can account for 1-2% of the resin weight and will not be lost through combustion. The other is that the efficient char-forming properties of phenolic materials, which result in their good fire resistance, may result in trace amounts of very stable char remaining after 4h at 600°C. When a sample of phenolic casting was burnt it was found that substantial char remained after 4 h at 600°C: after a further heating at 800°C for 4h there still remained 7% by weight. It was thus concluded that burning of does not reliably remove all of the phenolic material and thus cannot yield reliable glass contents. This is not a problem for polyester resins, except where there are additives such as thixotroping agents. Ifthe resin content for the phenolic composites is adjusted to include a7 wi% resin residual amount after ignition, a fibre content of 62.7 wt% is obtained and this was used. Assuming a density for E-glass fibres" of 2560 kgm and the determined density for cured polyester resin of 1160 kg m_',a Vz, of 0.422 was calculated, Similarly, a Vp of 0.436 was obtained for the glasw/phenolic specimens. Ifa modulus of 70 GPa is assumed for the glass fibres", then ‘eqn (2) predicts flexural moduli for the glass/polyester andGlass-reinforced phenolic composites: N. A. St John and J. R. Brown 800 00 z | B «00 a 200 hh et | 00 08 10 48 20 25 30 35 Displacement (mm) Figure 4 Load vers dsplacement profes for Nese strength ts of lss/phenolie specimens PHM (-——-), PHA (yan PHE (=) glassphenolic composites of 31.5 + 0.6 and 31.8 0.6 GPa, respectively. This compares well with the average measured flexural moduli of 31.8 + 1.0 and 29.5 = I.1 GPa for the glass/polyester and glass/phenolic composites, respectively, which confirms the use of egn (2). The result shows that the lower modulus of the phenolic resin compared with that of the polyester resin probably has a greater contribution to the modulus of the composites studied than assumed. At lower glass contents and for glass reinforcement other than unidirectional, this enhanced Contribution of resin modulus to glass/phenolic composite ‘modulus could become significant Flexural strength The flexural strength values (Table 3) showed a lerge dependence on the resin used, with the glass/phenolic specimens giving much lower failure values than the glass/ polyester specimens. The silane on the glass fibres also had a significant effect for the glass/phenolic specimens, with the epoxy silane glass size giving nearly twice the strength of the other two sizes. Under tension the strength of a composite is almost entirely provided by the reinforcement: however, in flexure the resin contribution influences the bending moment to break and cannot be ignored. The glass polyester specimens were all observed to fail at the fibres located at the bottom surface, directly below the loading roller, A theoretical value for flexural strength can thus be calculated with eqn (3) if itis assumed that failure is due t0 tensile failure of the outer fibres, where o, is the flexural strength and o; and 0%, are the tensile strength of the glass fibre and the stress in resin matrix atthe Failure strain of the fibre, respectively. The second term is usually small in comparison to the firs term and so is often neglected. = OVE + nV Qa) The tensile strength of glass fibres is affected by the envir- ‘onment and the level of flaws'’, and thus can be different in a composite compared with the value for bare fibres. For the purpose of the calculation a typical value" of a; of 1700 MPa was used, which gives for the glass/polyester composites a value of 0, of 752 MPa; this is close to the measured value when the epoxy-silane-coated glass was used, The epoxy silane should produce no chemical bonding with the polyester matrix whereas the methacrylylsilane can react chemically with unsaturated groups in the polyester resin’. Aminosilanes, while apparently not being able to react through radical-initiated reaction, have been found'® to provide improved interfacial bonding with styrene-based, resins, possibly through the formation of an interpenetrating network. Thus it can be inferred that the o; value used is, reasonable, For the PEM and PEA composites there is sig- nificantly improved stress transfer between the fibres and the matrix owing to stronger interfacial bonding which is reflected in the higher flexural strength values The o, value for the glass/phenolic composites calculated with eqn (3) was 763 MPa, The measured values (Table 3) were considerably less than this, which is indicative of failure due to interlaminar shear or compressive failure and not through tensile failure of the fibres as assumed in eqn (3). Unfortunately. the opaque nature of the glass/phenolic composites made direct observation of the initial failure difficult, although on further loading failure of the outer fibres was evident. Daniels et al'® carried out an extensive study of shear failure under three-point loading and identified modes of failure for different load~displacement profiles. Figure 4 shows the load~displacement profiles for the glass/phenolic samples and. using the designation of Daniels et al.'®, the PHA composite has a profile consistent with homogeneous shear failure, the PHM profile is consistent with discrete shear failure and the PHE profile is consistent with tensile fibre failure. The fact that even the value for PHE is well below the theoretical value suggests that there is inefficient stress transfer between the glass fibres. It is possible to change the failure mode in the three- point flexure test by increasing the span-to-depth ratio, although a correction is then needed for the large deflections that result!*, Nevertheless, the results clearly indicate a poorer composite performance with the phenolic resin ‘matrix and the ILSS measurements discussed next more accurately characterise this deficiency interlaminar shear strength Tavakoli er al.” found the ILSS of acid-cured glass! phenolic composites to be @ sensitive indicator of fibre— resin compatibility because the principal failure mode is delamination. The ILSS was measured in a four-point bend configuration instead of the conventional three-point bend configuration used in the short-beam shear test to ensure that failure was by interlaminar shear'', The values in Table 3 for both the glass/phenolic and glass/polyester composites show that the silane used in the glass size has a marked effect on ILSS. For the glass/polyester composites the epoxy silane (PEE) gives a much weaker interface than when the other two silanes were used, which is consistent with previous studies™'* The glass/phenolic composites show a reverse trend, with the epoxy silane providing the largest [LSS with the PHE, composite. The epoxy group on the silane can readily reactGlass-reinforced phenolic composites: N. A. St John and J. R. Brown with phenols through the hydroxy! group". creating a covalent bond and thus strong. fibre-resin adhesion. Similarly, the low ILSS with the methacrylate silane (PHM) was not unexpected as the unsaturated methacrylate groups, which can react with styrene-based resins, are unlikely to react with any of the components of a phenolic resin. IL is noteworthy that the glass fibre size used with the PHM composite is similar to that commonly used on reinforcements for polyester and vinyl ester resis. A low ILSS was also obtained for the PHA composite ‘The aminosilane used is often suggested for use with phenolic resins and has been shown previously to be effective in improving interfacial strengths between glass and thermally cured resole resins". The ineffectiveness of the aminositane in this case, with an acid-cured phenolic resin, can be understood by the fact that in a highly acidic environment, amino groups are protonated and so present as ammonium ions. It is thus unlikely reaction can occur between the silane and the resin, as the only possible reactions require the amino group to be in the unprotonated state, It was also considered a possibility that the aminosilane might be masked by the epoxy-based size used on the fibres, rendering the amino groups unavailable for bonding with the phenolic resin. To investigate this, the ILSS was determined for the PHG composite prepared with a. commercial glass roving which has the same aminosilane (i.e, APS) but a PVAc-based size. A slightly better ILSS was obtained than for the PHA composite, although clearly the aminosilane used was of litle use in promoting imerfacial adhesion with acid-cured phenolic resins. Generally, the ILSS values for the glass/polyester composites are about three times those measured for the phenolic composites, which suggests a major effect on the interfacial strengths of glass/phenolic composites that is independent of the glass size used. Brelant and Pekter'” analysed results of studies of filament-wound GRP compo- sites and identified two important factors in determining the ILSS of composites: resin strength and composite void content, ‘These authors showed an essentially linear relationship between the tensile strength of the resin matrix used and the ILSS when “void-free” unidirectional composites were prepared'”. Unfortunately, no reference was made to suitability of glass sizes used with the different resins. By using their derived relationship fegn (4)], where ILSS,_ is the ILSS for a void-free unidirectional GRP composite, an ILSS of 59,8 and 35.0 MPa is predictad from resin tensile strengths for the glass/polyester and the glass/ phenolic composites, respectively. Considering the cifferent glass content and fabrication method! used in this study, the value predicted for the glass/polyester_ specimens. of 59.8 MPa compares reasonably well with those obtained, for the PEM and PEA specimens of 52.7 MPa and $1.3 MPa respectively. The value for the glasvphenolic specimens (35.0 MPa) is. however, still considerably higher than the best result obtained (15.7 MPa) IL 0.9205, rh Brelant and Pekter!” also found that a nearly linear relation: ship existed between composite void content and ILSS, with, an increase of 1% in void content resulting in a 5% drop in ILSS up to @ void content of 16%. Judd and Wright'® reviewed previous studies of the effect of voids on compo- site mechanical properties and found that most work con- centrated on the effect on ILSS values. They found that, for a variety of resins and reinforcing fibres, a 1% increase in void content produced an average decrease of 7% in ILSS and this was approximately linear up to 4% voids, above which limited data were available. The majority of past studies have involved processing voids introduced by entrapment of air during resin impregnation, while as discussed earlier the voids present in an acid-cured phenolic matrix are much smaller and thus were referred to as microvoids. Wisnom et al." recently reported the results ofa study of ILSS reduction by voids in unidirectional glasslepoxy composites and char- acierised two types of void, discrete larger voids and small distributed voids. The larger voids acted as crack initiation sites under a shear stress, whereas the increase in stress due to the reduction in net cross-section was the main factor in shear failure of composites with smaller distributed voids. Greszezuk™ derived a theoretical relationship, eqn (5). between ILSS and composite void content based on net cross-section reduction, with V, being the volumetric void content. Eqn (5) assumes the voids are spherical and arranged in a cubic array, which is a reasonable assumption for the phenolic resin studied (Figure 1). ILss 1-7 ov, “ 5) iss, ~'~ a\ xv) ‘ For the glass/phenolic composites studied, the volumetric void content due to the microvoids was estimated to be 11.8%, so that eqn (5) predicts a 43% reduction in ILSS compared with the case of no microvoids. If an ILSS., value of 35.0MPa is assumed then an ILSS value of 20.1 MPa is predicted, which is close to the 15.7 MPa measured for the PHE composite when the assumptions made are considered. It is notable that eqn (5) predicts that the reduction in ILSS is independent of the fibre volume or the size of the individual microvoids. Greszezuk™” alse showed a void content dependence of compressive strength and interlaminar shear fatigue life and so it might be expected glas/phenolic composites will also have defi ciencies in these properties ‘The analysis described above highlights three factors that appear to be responsible for the low ILSS values obiained for glass/phenolic composites: the low strength of the resin, the microvoid structure of the resin and the suitability of the silane coupling agent used in the fibre size. Thus to obtain optimal composite properties with the acid-cured phenolic resins itis important to use the a lass reinforcement with a silane coupling agent capable of reaction with the resin (e.g. epoxy silane) and to minimise any additional processing voids. However, 10 raise the ‘maximum ILSS achievable, modification of the resin to increase the strength, reduce the degree of microvoiding or both would be necessaryGlass-reinforced phenolic composites: N. A. St John and J. R. Brown ‘Table 4 interlaminar shear stengths of GRPIphenoic composites after water immersion Composite ‘Water exposure ‘Water uptake Ge Punt ashowe 207 DOW TOC io PH a8 WAP 258 240 WTOC 203 Pua, ssn90rc 243 240 9s PGA, Seno0r 263 240 HTC 243 Water exposure Ina study of acid-cured phenolic composites fabricated from six different commercial chopped strand mat glass reinforcements, Tavakoli er al.’ found that exposure to boiling water for 16 h resulted in a decrease in the ILSS by about 25%, even though the initial ILSS values of each composite varied by up to 70%. It was also found that the water content increased and the ILSS decreased rapidly during the first 4h at 100°C and slowly thereafter”. Harper et al" observed that, on exposure to water, epoxy composites containing voids in the matrix undergo @ more rapid increase in water content to a higher final level than do composites with a low level of voids. It is likely therefore that the microvoid morphology of the phenolic max is involved in the fast water take-up observed with glass/ phenolic composites. It was thus of interest to investigate the mechanical performance of glass/phenolie composites containing glass fibres treated with different silane coupling agents afier water immersion at elevated temperatures. Immersion in water for 48 hat 90°C or for 240 h at 70°C resulted in an average increase in composite specimen mss of 2.6 and 2.1%, respectively. The average flexural modulus (Table 4) after water exposure was 28.8 * 018 GPa compared with 29.5 + 1.1 GPa for unexposed glass/phenolic com po- sites, The difference is not statistically significant and suggests that there was only minimal plasticisation of the resin matrix at the water levels achieved. A significant decrease in ILSS after water exposure was observed (Table 4) for all the glass/phenolic composites studied. The aminosilane-treated glasses (PHA and PGA) showed the smallest decrease, although the ILSS values for the corresponding unexposed specimens were also low, ‘The PHM and PHE samples showed similar decreases. of approximately 30%. These results are similar to those of Tavakoli er a.”, showing that even a short exposure to water can lead to significant loss of [LSS and that the percentage decrease in ILSS is similar with different glasses, although the absolute values vary considerably. One of the main advantages of using silane coupling agents with other resin systems has been an improvement in strength retention on water exposure and this has been tributed (0 the improved resin-fibre bonding’. In the case of acid-cured phenolics, the improved ILSS with an epoxy silane was not translated into any relative improvemen: in ILSS retention on water exposure. This suggests that the observed decrease of ILSS occurs by a mechanism other than degradation of the resin-silane bond. Any decrease in Interlaminaesheaesteength Pa 60=03 72204 los +06 Has 03 loo 2 03 strength of the matrix resulting from water ingress is unlikely to be significant enough to explain the observed decrease in ILSS. The decrease in ILSS is also observed to be relatively fast and does not deteriorate further over time or higher water contents’, suggesting a mechanism that is acting only in the interfacial region between the resin matrix and the glass fibres E-glass fibres contain alkali metals such as sodium, and Metcalfe et al”? have shown that dissolution of these through hydrogen-ion substitution can result in a reduction of fibre strength through weakening of the glass structure at the fibre surface—a process that is accelerated in acidic conditions. Ashe and Wyatt” have proposed a mechan- ism for degradation of the resin—fibre bond in composites driven by inereased osmotic pressure at the interface generated by the water-soluble constituents leached from the glass fibre. When it is also considered that phenolic resins contain water-soluble ions from the neutralisation step in their manufacture, it can be postulated that on exposure fo water a high osmotic pressure at the resin/ibre interface draws the water directly tothe interface. This then results in a rapid deterioration of the imerfacial region, leading 10 the observed decrease in ILSS for the glass/ phenolic composites. If this is correct. then a strategy for improving the durability of glasVphenolic composites under wet conditions may be to reduce the ion concentrations in the resin, protect the glass fibre from attack or use & glass that is more stable such as CR glass CONCLUSION ‘The glass/phenolic composites were found to yield ILSS values that were substantially lower than those obtained for similar glass/polyester composites, and this was attributed (o the lower resin strength and the high level of microvoids present in the phenolic matrix. The silane coupling agent used on the glass reinforcement was also found to have a large effect on the ILSS values obtained. An epoxy- functional silane yielded the highest ILSS with a phenolic matrix whereas an amino-functional silane, which is commonly recommended for heat-cured phenolic resins, was found to yield a low ILSS. The ILSS of the glass! phenolic composites was found to decrease after exposure to water at elevated temperatures, with the relative decrease being essentially independent of the silane coupling agent used.Glass-reinforced phenolic composites: N. A. St John and J. R. Brown The inherently fire-retardant properties of the phenolic resins combined with their relatively low cost means that they ate very attractive for applications where fire risks exist: however, the poor performance of gliss/shenolic composites under shear loads needs to be considered when assessing their use. 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