Evaluation of interface fracture energy for single-fibre composites

Raman and luminescence spectroscopy have been used for the first time to determine the interface fracture energy for single-fibre composites. By using the measured fibre stress distributions in single-fibre fragmentation composite specimens and a simple energy-balance scheme, the energy for the initiation of interfacial debonding has been estimated for carbon (T50) and α-alumina (PRD-166 and Nextel 610) fibres embedded in epoxy resins. It has been found that the interface fracture energy shows good sensitivity to changes in the level of fibre/matrix adhesion due to surface treatment and sizing of the fibres. It is also found that the values of interface fracture energy correlate well with measured values of interfacial shear strength determined for the same fibre/matrix systems.     

The relation of dynamic elastic moduli,mechanical damping and mass density to the microstructure of some glass-matrix composites

Dynamic elastic moduli and mechanical damping were measured with the PUCOT (piezoelectric ultrasonic composite oscillator) technique at room temperature for ceramic-matrix composites (CMCs) of the following compositions: PRD-166 (fibres)/N51A glass (matrix), PRD-166 fibres coated with SnO₂/glass, Nextel 480 fibres/glass, Nextel 480 fibres coated with SnO₂/glass, and Nextel 480 fibres coated with BN/glass. The fibres were continuous, and the volume fractions varied from 0.24 to 0.43. Some of the mechanical-property measurements correlated with the thickness of one of the coating materials, and with microstructural observations of the misorientation angle of the fibres and normalized fibre length. With increasing volume fractions of fibres, the fraction of broken fibres increased. For the PRD-166/glass and PRD-166/SnO₂/glass, a substantial fraction of the fibres were misoriented by angles of up to 15 °. Assessments were made of the measured properties in terms of the rule of mixtures and other theoretical estimations.     

Analysis of interfacial micromechanics of model composites using synchrotron microfocus X-ray diffraction

The deformation micromechanics of single-fibre embedded model composites of poly(p-phenylene benzobisoxazole) (PBO) and poly(p-phenylene terephthalamide) (PPTA) fibres, embedded in an epoxy resin have been examined using synchrotron microfocus X-ray diffraction. Single fibres (in air) were deformed and the c-spacing monitored to establish a calibration of crystal strain against applied stress. Subsequently, the variation in crystal strain along fibres, embedded in the resin matrix was mapped using synchrotron microfocus X-ray diffraction. Raman spectroscopy was then used to map molecular deformation on the same samples (recorded as shifts in the Raman band wavenumber) in order to provide a complementary stress data. A shear-lag analysis was conducted on the axial fibre stress data in order to calculate interfacial shear stress and identify different stress-transfer modes at fibre/resin interfaces. The results establish that the axial fibre stress distributions measured by synchrotron microfocus X-ray diffraction correlate well with those obtained using Raman spectroscopy. The interfacial shear stress data derived from the stress-transfer profiles also show a good degree of correlation.     

Fragmentation analysis of glass fibres in model composites through the use of Raman spectroscopy

Raman spectroscopy has been used to monitor deformation micromechanics in a model discontinuous fibre composite comprising a single glass fibre in an epoxy resin. The glass fibre was coated with a diacetylene-containing urethane copolymer that was subsequently cross-polymerised thermally. During composite deformation, the stress-induced Raman band shifts of the polydiacetylene sequences in the cross-polymerised coating were used to map the distributions of strain along glass fibres inside the epoxy resin matrix. The fragmentation of the fibre has been followed in detail and the behaviour analysed using classical shear-lag analysis. Values of the interfacial shear stress along fibre fragments were determined from the measured fibre strain distributions and were shown to be limited by the shear yield stress of the matrix. The effect of adhesion between the coating and the fibre upon the strain distributions has been investigated in detail. The fibre strain distributions can only be determined accurately when the adhesion is good. However, in the case of poor adhesion, although the strain distribution in the coating follows that of the matrix, the fragmentation process can still be monitored.     

Fragmentation of aramid fibres in single-fibre model composites

Raman spectroscopy has been used to monitor the state of axial stress along fragmented, high-modulus Kevlar 149 aramid fibres in an epoxy resin matrix by monitoring the peak position of the strain-sensitive 1610 cm^–1 aramid Raman band along individual fragments. It is shown that the interfacial shear stress along each fragment, derived from the strain distribution profiles, is not constant as assumed by conventional fragmentation analysis. The fragmentation process of as-received Kevlar 149 fibres is compared to that of irradiated Kevlar 149 fibres exposed to ultraviolet light where the tensile strength and modulus of the fibres have been reduced. It is found that the derived interfacial shear stress and interfacial shear strength values are higher for those fibres exposed to ultraviolet light compared with the as-received fibres. It is also clearly demonstrated that the values of interfacial shear strength calculated at high matrix strains from conventional fragmentation analysis are considerably lower than the maximum value of interfacial shear stress prior to fibre fracture that was found to be close to the shear yield stress of the resin matrix. Hence the determination of the interfacial shear strength following the saturation of the fragmentation process may give rise to misleading results.Nomenclature e _f Fibre strain - e _m Matrix strain - e _f ^max Maximum strain along each fragment - e _f ^* Failure strain of the fibre - E _f Fibre tensile modulus - l _c Critical fragment length - l _c Mean critical fragment length - l _f Fragment length - r Fibre radius - x Distance along the fibre - _f ^max Maximum stress along each fragment - _f ^* Fibre tensile strength - Interfacial shear stress - _s Interfacial shear strength     

Crack bridging and fibre pull-out in polyethylene fibre reinforced epoxy resins

An investigation has been undertaken of the stress distributions in high-performance polyethylene fibres bridging cracks in model epoxy composites. The axial fibre stress has been determined from stress-induced Raman band shifts and the effect of fibre surface treatment has been followed using untreated and plasma-treated polyethylene fibres. It is found that when the specimen is cracked, the fibres do not break and stress is transmitted from the matrix to the fibre across the fibre/matrix interface. A debond propagates along the fibre/matrix interface accompanied by friction along the debonded interface. The axial stress distributions in the fibres can be analysed using a partial-debonding model based upon shear-lag theory and it is found that the maximum interfacial shear stress at the bond/debond transition is a function of the debond length. The debonding process has been modelled successfully in terms of the interfacial fracture energy-based criterion developed by Hsueh for the propagation of a debond along a fibre/matrix interface accompanied by constant friction along the interface.     

SWNT composite coatings as a strain sensor on glass fibres in model epoxy composites

The preparation of a model glass-fibre/epoxy composite with single-walled carbon nanotubes (SWNTs) incorporated as a strain sensor on the fibre surface is described. A micromechanical study of stress transfer at the fibre–matrix interface followed using Raman spectroscopy properties is reported. The SWNTs were distributed along the fibre surface either by dispersing them in an amino-silane coupling agent or coating with an epoxy resin solution containing the SWNTs. The point-by-point mapping of the fibre strain in single fibre fragmentation tests has been undertaken for the first time using SWNTs on the fibres and the interfacial shear stress distribution along the fibre length was determined using the embedded SWNTs. The behaviour was found to be consistent with the classical shear-lag model. The effects of SWNT type and preparation procedure on the sensitivity of the technique were evaluated and optimized from single fibre deformation tests.     

Effects of plasma oxidation on the surface and interfacial properties of ultra-high modulus carbon fibres

An ultra-high modulus (UHM) carbon fibre was submitted to an oxygen plasma treatment. The effects of this treatment on the physical and chemical properties of the carbon surfaces were investigated by using surface characterisation techniques. SEM and STM studies were performed in order to determine the changes in the surface morphology. Observations on the nanometre scale lead to the conclusion that the plasma oxidation “cleaned” the original surfaces of carbonaceous impurities. XPS analysis of the treated fibres revealed a very significant increase of oxygen content. Single-fibre epoxy composites were prepared from as-received and plasma-treated fibres, and fragmentation tests were performed in order to characterise fibre/matrix interfacial adhesion. Raman spectroscopy has been used to map the strain along the fibre during tensile loading of the matrix, and the distribution of interfacial shear stress has been obtained. The quality of the interface improved dramatically after the surface treatment, supporting the ability of cold plasma oxidation to enhance the adhesion of UHM carbon to epoxy matrices. It is concluded that the increase of the oxygen surface content and the removing of the outermost layers may contribute in a co-operative way to the improvement on fibre/matrix adhesion.     

Structure and deformation of high-modulus alumina-zirconia fibres

The relationship between structure and mechanical properties for high-modulus alumina-zirconia fibres PRD-166 has been examined in detail. The structure has been characterized using a combination of wide-angle X-ray diffraction and scanning and transmission electron microscopy. The fibres have been found to have a Young's modulus of at least 280 GPa and a fracture strength of up to 1.2 GPa. The deformation of the fibres has also been followed using Raman microscopy where it is found that the wave numbers of the two -alumina Raman bands and two zirconia Raman bands shift on the application of strain. This is interpreted as being due to macroscopic stressing of the fibres leading to direct stressing of the metal oxide grains in the fibres. The possible application of this phenomenon for the investigation of the micromechanics of deformation of composites reinforced with PRD-166 fibres is discussed.     

Effect of surface treatment upon the pull-out behaviour of aramid fibres from epoxy resins

A detailed study has been undertaken of the pull-out behaviour of aramid fibres with different surface characteristics from blocks of an epoxy resin matrix. The fibres employed had either no surface treatment (HM), a standard surface finish (HMF) or had been treated with a special epoxy-based adhesion-activating finish (HMA). The point-to-point variation of axial fibre strain along the fibres both inside and outside of the resin matrix has been determined from stress-induced Raman band shifts. This has enabled the distribution of interfacial shear stress along the fibre/matrix interface to be determined and, in combination with scanning electron microscope analysis of the specimens following pull-out testing, the failure mechanisms to be elucidated. It is found that pull out of the HM fibre takes place by a debond propagating along the fibre/matrix interface at a low level of interfacial shear stress. The HMF fibre showed better adhesion to the epoxy matrix with pull out occurring in a complex manner through both separation of the fibre skin and failure at the fibre/finish interface. No evidence of debonding was found for the HMA fibre and failure occurred by fracture of the fibre at the point where it entered the resin block.     

Analysis of the fragmentation test for carbon-fibre/epoxy model composites by means of Raman spectroscopy

The interfaces between high-modulus PAN-(T50) and mesophase pitch-based (P55) carbon fibres and an epoxy matrix have been studied by using the conventional fragmentation test in conjunction with polarised-light optical microscopy. Raman spectroscopy has also been used to follow stress transfer from the matrix to the fibres for the same fragmentation geometries. The level of fibre/matrix adhesion and mechanisms by which the stress is transfered from the matrix to the fibres has been determined from both the stress birefringence patterns and strain-induced Raman band shifts in the fibres. The values of interfacial shear strength have been determined by means of both the conventional analysis and the Raman technique. It is found that the Raman method gives a much more detailed picture of stress transfer in the test specimens and that the two methods give somewhat different values of the interfacial shear strength. The values of interfacial shear stress have been discussed with respect to fibre surface energy, surface chemistry and surface morphology. It was found that the surface chemical functional groups appear to have no direct correlation with interfacial shear strength. Furthermore, it appears that mechanical interlocking due to surface roughness could contribute to the higher values of interfacial shear strength determined for the PAN-based fibre.     

Strain-sensitive Raman spectroscopy and electrical resistance of carbon nanotube-coated glass fibre sensors

This paper presents the development of glass fibres coated with nanocomposites consisting of carbon nanotubes (CNTs) and epoxy. Single glass fibres with different CNT content coating are embedded in a polymer matrix as a strain sensor for composite structures. Raman spectroscopy and electrical response of glass fibres under mechanical load are coupled for in situ sensing of deformation in composites. The results show that the fibres with nanocomposite coating exhibit efficient stress transfer across the fibre/matrix interface, and these with a higher CNT content are more prone to fibre fragmentation at the same matrix strain. A relationship between the fibre stress and the change in electrical resistance against the fibre strain is established. The major finding of this study has a practical implication in that the fibres with nanocomposite coating can serve as a sensor to monitor the deformation and damage process in composites.     

Interfacial micromechanics of technora fibre/epoxy composites

The application of Raman spectroscopy using a near-infrared laser (IR) for the study of the deformation micromechanics of Technora fibres and single Technoras fibre embedded in epoxy composites is reported. The shift with strain of the Raman band approximately at 1613 cm⁻¹ corresponding to p-phenylene ring deformation is studied. It is shown that the shift of the Raman band can be used to monitor the deformation micromechanics of the Technora/epoxy composites allowing the interfacial shear stress (ISS) to be determined. It was found that the maximum ISS was close to the shear yield stress of the resin indicating that there is good adhesion between the Technora fibres and the epoxy resin matrix.     

Comparing single-walled carbon nanotubes and samarium oxide as strain sensors for model glass-fibre/epoxy composites

The study of the interfacial stress transfer for glass fibres in polymer composites through the fragmentation test requires certain assumptions, such as a constant interfacial shear stress. In order to map the local interfacial properties of a composite, both Raman spectroscopy and luminescence spectroscopy have been independently used. Unlike other polymer fibre composites, the local strain state of a glass fibre cannot be obtained using Raman spectroscopy, since only very broad and weak peaks are obtainable. This study shows that when single-walled carbon nanotubes (SWNTs) are added to the silane sizing as a strain sensor, it becomes possible to map the local fibre strain in glass fibres using Raman spectroscopy. Moreover, if this model glass fibre contains a small amount of Sm₂O₃, as one of the components, luminescence spectroscopy can be simultaneously used to confirm this local fibre strain. A combined micromechanical properties study of stress transfer at the fibre–matrix interface using luminescence spectroscopy, together with Raman spectroscopy, is therefore reported. The local strain behaviour of both Sm³⁺ doped glass and SWNTs in the silane coating are shown to be consistent with a shear-lag model. This indicates that Sm³⁺ dopants and SWNTs are excellent sensors for the local deformation of glass fibre composites.     

Deformation micromechanics of a model cellulose/glass fibre hybrid composite

Interfacial stress transfer in a model hybrid composite has been investigated. An Sm³⁺ doped glass fibre and a high-modulus regenerated cellulose fibre were embedded in close proximity to each other in an epoxy resin matrix dumbbell-shaped model composite. This model composite was then deformed until the glass fibre fragmented. Shifts of the absolute positions of a Raman band from the cellulose fibre, located at 1095 cm⁻¹, and a luminescence band from a doped glass fibre, located at 648 nm, were recorded simultaneously. A calibration of these shifts, for both fibres deformed in air, was used to determine the point-to-point distribution of strain in the fibres around the breaks in the glass fibre. Each break that occurred in the glass fibre during fragmentation was shown to generate a local stress concentration in the cellulose fibre, which was quantified using Raman spectroscopy. Using theoretical model fits to the data it is shown that the interfacial shear stress between both fibres and the resin can be determined. A stress concentration factor (SCF) was also determined for the regenerated cellulose fibre, showing how the presence of debonding reduces this factor. This study offers a new approach for following the micromechanics of the interfaces within hybrid composite materials, in particular where plant fibres are used to replace glass fibres.     

The interfacial properties of aramid/epoxy model composites

Many attempts have been made to measure, evaluate and improve the level of interfacial adhesion in aramid/epoxy composites. Different surface treatments have been developed in order to promote chemical bonding between the fibre and the matrix but it is found that most of the surface treatments developed have shown little or no improvement in the level of interfacial adhesion. The interfacial properties of a model composite are often determined by measuring the interfacial shear strength using micromechanical test methods that employ different loading configurations. However, the values of interfacial shear strength determined using different test methods are found to be dependent upon the variation of localized stress in the samples due to the different loading configurations and often give different results. Using Raman spectroscopy it is shown that the strain-dependent shift of the 1610 cm^–1 aramid Raman band can be used to determine the point-to-point variation of axial fibre strain along aramid fibres embedded in epoxy resin matrices from which the interfacial properties can be derived. The interfacial properties of aramid/epoxy model composites have been determined using Raman spectroscopy where the properties of the fibre, including different surface treatments, and the matrix have been changed systematically. The results are reviewed here and compared to those obtained using conventional micromechanical test methods. It is also demonstrated that the Raman technique can be used to characterize the interfacial properties of aramid/epoxy model composites deformed using different micromechanical test methods. In this way the interfacial properties can be determined at different loading levels enabling the progressive failure of the fibre/matrix interface to be monitored and defined accurately.     

Tensile properties of real unidirectional Kevlar/epoxy composites

Mechanical behaviour, tensile strength and failure modes in real unidirectional Kevlar/epoxy composites, loaded parallel to the fibres, at volume fraction (V_f) range 0.26–0.73, were investigated. It was found that the measured tensile strengths deviated from the expected values calculated from the Rule of Mixture. The deviation, which was minimal at V_f of about 0.5, was mainly due to geometrical deficiencies typical of real composites. At V_f<0.5 it could be explained by non-homogeneous fibre spread and distribution of fibres. At V_f>0.5 the deviation was explained by the increasing lack of matrix between some adjacent fibres and by squeezing of fibres. The initial part of loading was typified by straightening out of non-axial fibres, accompanied by fibre/matrix debonding. The straightening process was completed at a stress level of about 0.6–0.7 of the composite strength. Matrix damage began at this stress level and continued to develop up to final failure. Failure of Kevlar fibres was noted to occur only at an extremely short loading interval coinciding with the catastrophic final failure. This was due to the small scatter of Kevlar fibre strength.     

Hybrid C/Pet/epoxy composites

Hybrid carbon/PET/epoxy composites were prepared by a wet layup technique and characterized by standard methods of fracture and impact tests. The influence of PET fibre surface treatment with polyfunctional amine on the composite properties has been studied in order to determine the role of the fibre/matrix interface. The state of the fibre/matrix interface has been examined by several techniques, such as SEM, differential scanning calorimetry (DSC) and contact angle measurements. A significant hybrid effect of the PET/aminated fibres on the curing reaction and T _g of the epoxy matrix in the composites was established. It is probably due to the reaction between the amine groups of the fibre surface and the epoxy component of the resin, as determined by DSC.     

Stress induced twinning of polydiacetylene single crystal fibres in composites

Scanning electron microscopy has been used to show that twins induced by compression of DCHD-polydiacetylene fibres occur on a single crystallographic plane. Other twinning modes appear to be prohibited by the nature of the sidegroup packing. Under the optical microscope identical twinning patterns have been observed on fibres in composite specimens where matrix shrinkage had been induced by post-curing the epoxy at 100°C. Resonance Raman spectroscopy has been used to monitor the strain in a single fibre embedded in an epoxy matrix which was subjected to uniaxial compressive stress. The initiation of twinning was found to occur when the axial strain in the fibre was approximately 0.2%.     

A study of mechanisms of stress transfer in continuous- and discontinuous-fibre model composites by laser Raman spectroscopy

The micromechanics of stress transfer in single-fibre/epoxy-resin model composites has been investigated. Two specimen geometries are examined incorporating both continuous and discontinuous fibres in epoxy resin blocks. In both cases, the point-by-point strain in the fibre is measured from the fibre Raman spectrum and its strain dependence. The continuous-fibre model composites (CFMC) are subjected to incremental tensile loading and the fibre fragmentation process is continuously monitored. The short-fibre model composites (SFMC) are loaded incrementally to levels of stress of sufficient magnitude to cause interfacial failure and the fibre strain profiles are obtained at each level of applied stress.

In addition to fibre strain measurements, the interfacial shear stress distribution is derived at each increment of applied stress by means of a balance-of-forces argument. The effects of fibre surface treatment and fibre modulus on the strain transfer profile and the distribution of the interfacial shear stress along the fibre are examined. The importance of parameters such as fibre/matrix debonding and interphase yielding in the vicinity of fibre breaks or fibre ends is discussed.