Application of nano-indentation, nano-scratch and single fibre tests in investigation of interphases in composite materials

Three novel experimental techniques were employed in this work in order to investigate the influence of the interphase region in polymer–glass composites on the bulk material properties: (i) the microdroplet test is a single fibre test designed to characterize the fibre–matrix bond (interface region) and to determine the interfacial shear stress in composite material; (ii) the nano-indentation test, a novel nano-hardness technique with ability to produce an indent as low as a few nanometres was employed in order to measure nano-hardness of the fibre–matrix interphase region; and (iii) the nano-scratch test, used in conjunction with the nano-indentation test for measurement of the interphase region width. The microdroplet test (MDT) has been used to characterize the interfacial bond in fibrous composite materials. The specimen consists of a fibre with a drop of cured resin pulled while the drop is being supported by a platinum disc with a hole. A properly tested specimen fails at the droplet’s tip–fibre interface, revealing the ultimate interfacial shear strength. In this study, finite element analysis (FEA) of the MDT has been focused toward simulation of the fibre–matrix interphase region. The influence of several functional variations of the material properties across the interphase layer on the stress distribution at the droplet’s tip was analysed. The results showed that the variation of the interphase properties significantly affects the stress distribution at the fibre–droplet interface, and, therefore, the stress redistribution to composite material. These results led to further experimental investigation of the interphase region, in order to obtain the material properties essential for the interfacial stress analysis. The interphase region in dry and water aged polymer–glass composite materials was investigated by means of the nano-indentation and the nano-scratch techniques. The nano-indentation test involved indentation as small as 30 nm in depth, produced along a 14 μm path between the fibre and the matrix. The distinct properties of the interphase region were revealed by 2–3 indents in dry materials and up to 15 indents in water aged, degraded materials. These results indicated interdiffusion in water aged interphase regions. The nano-scratch test involves moving a sample while being in contact with a diamond tip. The nano-scratch test, used in conjunction with the nano-indentation test, accurately measured the width of the interphase region. The results showed that the harder interphase region dissolved into the softer interphase region (both regions being harder/stronger than the matrix) expanding its width after aging in water.     

Improving the adhesion between a aqueous PU and a polyamide fibre with silane

Glycidoxypropyltrimethoxysilane (GPS) and γ-aminopropyltrimethoxysilane (APS) were used to modify the surface chemistry of polyamide fibre. The surface chemistry was characterised using X-ray photoelectron spectroscopy. The silanol functional group was designed to be introduced on the surface of polyamide fibre to increase its chemical activity by N-alkylation of GPS and hydrolysis of APS, and to improve the poor interfacial adhesion between a polyamide 66 fibre and an aqueous polyurethane polymer adhesive. The microbond test was used to measure the interfacial shear strength between the waterborne PU adhesive and the polyamide fibre. It has been found that APS hydrolysis and GPS-alkylated fibre surface can be used to improve the interfacial adhesion of polyamide fibre to PU. The IFSS can be improved by N-alkylation of GPS from 5.0 to 8.4?MPa. After water immersion at 50?°C for 48?h, then drying, the IFSS increased to 8.8?MPa due to the plasticisation of PU in water. Better interfacial adhesion was also observed by the hydrolysis of APS, but not significantly improved by this method due to the relatively weak hydrogen bond at the interface between APS and polyamide fibre.     

Multifunctional ToF-SIMS: combinatorial mapping of gradient energy substrates

We present a simple method for chemical modification of chlorosilane self-assembled monolayers (SAMs) on Si surfaces by exposure to a gradient of UV-ozone radiation to create stable substrates with a range of contact angles (θ_H2O≈5–95°) and surface energies on a single substrate. These gradient energy substrates are developed to potentially generate libraries for combinatorial studies of thin film phenomenology, where a systematic variation of interfacial surface energy represents one of the significant parameters along one axis. The graded oxidation process presents a systematic variation of surface chemical composition. We have utilized contact angle measurements and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to investigate this variation for a series of ions, among which are SiCH₃⁺, SiOH⁺ and COOH⁻. We show that the macroscopic measurements of surface free energy/contact angle correlate with the detailed analysis of surface chemistry (as assessed by ToF-SIMS) on these test substrates.     

Weibull analysis of microbond shear strength at sisal fibre–polyester resin interfaces

An analysis has been made of the tensile strength of sisal fibres and the interfacial adhesion between fibres and polyester resin droplets. Density and microscopy methods were used to determine the cross-sectional area of the sisal fibres. The average tensile strength of treated sisal fibres decreased by a modest amount following treatment with 0.06 M NaOH. However, this treatment resulted in a substantial increase in the interfacial shear strength at the sisal fibre to polyester resin interface. Weibull analysis has been used successfully to analyse variability in tensile strengths and interfacial shear strength using probability of failure plots. Scanning electron microscopy has revealed the shape of resin droplets on the surface of treated and untreated sisal fibres and contact angles are much lower for droplets on treated fibres. Damage to the surface of fibres has been examined following shear testing. Weibull analysis is an effective tool for characterising highly variable fibre properties and evaluating the level of adhesion between polymer resin and the fibre surface.     

Numerical study of the single fibre push-out test: Part III. Singularity of interface stresses

The singular behaviour at the free edges of the fibre-matrix interface is analysed for the fibre push-out test geometry based on the boundary element method. The fibre push-out test has been extensively used to measure the fibre-matrix interfacial properties in polymer, ceramic and metal matrix composites. There are two free edges in the fibre push-out specimen: one is at the loaded fibre end and the other at the supported fibre end. The singular stresses can be expressed as a function of singular exponent and singular stress intensity. It is shown that the singular exponents obtained at both fibre ends are characteristic of composite constituent properties, such as Young's moduli of fibre and matrix, and does not vary with specimen dimensions. The singular exponents are real and identical for the shear and radial stress components at fibre ends where the wedge angles are the same. The singular stress intensities are also implicit in material properties, and vary with specimen dimensions, such as fibre to matrix radius ratio, fibre aspect ratio and support hole size. An interfacial failure criterion is proposed here based on the average stress concept to determine the critical singular stress intensities in mode I and mode II loads.     

Organic and inorganic discrimination of ballpoint pen inks by ToF-SIMS and multivariate statistics

Surface analysis by ToF-SIMS analysis of ballpoint pen ink markings was performed for discrimination. ToF-SIMS provided non-destructive analysis of ink's organic and inorganic components directly off paper with no interference from the paper substrate. Organic and inorganic information were collected simultaneously and processed with PCA, discriminating 41 out of 45 pairs (91%) of pens analysed. Minimal sample preparation and analysis time, the simultaneous acquisition of organics and metals, and ability to analyse trace amounts gives this technique advantages over others currently utilised in the forensic field. Simultaneous acquisition of organics and inorganics has not been presented before for the characterisation of these materials. It was indicated that pens from the same manufacturer, but discrete batches, can be significantly different.     

Imaging of aerosols using time of flight secondary ion mass spectrometry

Interest in environmental aerosol chemistry has grown over the last decade as a result of its role in both climate change and troposheric pollution. In this work, the combination of ToF-SIMS and SEM/EDX was employed to explore the surface chemistry of aerosols. The capabilities and limitations of ToF-SIMS were investigated using particles of known composition and size produced by a vibrating orifice aerosol generator (VOAG). Principal component analysis (PCA) proved to help in the distinction of particles of different types by consolidating the information generated by ToF-SIMS.     

Quantitative and high mass ToF-SIMS studies of siloxane segregation in hydrogel polymers using cryogenic sample handling techniques

This paper examines the capabilities of cryogenic sample handling to examine composition and structure of hydrogel materials where siloxane components are central to the analysis. XPS analysis of multicomponent polymers with cryogenic sample handling following exposure to aqueous environments has revealed the composition and kinetics of near surface reorganization for siloxane and fluorocarbon containing polymers. In this study we report results from a ToF-SIMS protocol for cryogenic sample handling applied to the analysis of surface changes upon hydration/dehydration of hydrogel polymers. Comparison of results from angle dependent XPS and ToF-SIMS are discussed for a range of commercial soft contact lens materials. Both methods detected changes in surface chemistry between the hydrated (frozen) and dehydrated surfaces. Analysis of the hydrated surfaces detected polymer components indicative of the commercial formulation as well as ice clusters. Analysis of the dehydrated materials detected changes in surface chemistry relative to the hydrated surface in addition to loss of water due to sample dehydration. A quantitative standard additions method for ToF-SIMS data was used to determine submonolayer amounts of PDMS impurities at the surface of the hydrogels. ToF-SIMS analysis of a series of seven poly (allyl methacrylate-g-dimethylsiloxane), AMA-g-DMS, graft copolymers in the hydrated state revealed high mass oligomeric ion distributions for systems with bulk PDMS content greater than 25 wt.%. This marks the first time that detection of high mass oligomeric ion distributions from hydrated (frozen) surfaces has been reported. Analysis of the dehydrated surface detected formation of high mass oligomeric ion distributions for systems with PDMS bulk content greater than 15 wt.%, but only detected these ion distributions in wet (frozen) samples when the bulk concentration was greater than 25 wt.%.     

Study of the influence of thermal history on the load transfer efficiency and fibre failure in carbon/polypropylene microcomposites using Raman spectroscopy

The influence of thermal history on the interfacial load transfer efficiency and fibre failure in carbon/polypropylene microcomposites has been studied using Micro Raman spectroscopy. Microcomposites were manufactured by cooling from the melt at different constant cooling rates or isothermally crystallized. Thermal residual strains were measured during and after manufacture of the microcomposites. The residual strains resulted in compressive fibre failure. Based on the experimental data, interfacial load transfer efficiency was determined quantitatively for the different cooling procedures. Results indicate that thermal history has a very large influence on the interfacial load transfer efficiency of the microcomposites. This was shown to be due to the influence of thermal history on transcrystallinity and interfacial residual stresses. A transcrystalline interphase provides a more effective load transfer compared to the non-transcrystalline interphase. Furthermore, decreasing cooling rates leads to an increase in load transfer efficiency due to increased transcrystallinity and higher crystallization temperature resulting in higher interfacial stresses.     

Evaluation of the geopolymer/nanofiber interfacial bond strength and their effects on Mode-I fracture toughness of geopolymer matrix at high temperature

The present article has reported the effects of several nanofiller’s aspect ratio, length and interfacial strength on Mode-I fracture toughness (K_IC) of geopolymer as the matrix of continuous fibre reinforced composites. These nanofillers have been chosen based on the variations in the surface chemistry and nature of interfacial bonding with geopolymer, which include Carbon, Alumina and Silicon carbide. Geopolymer matrix was subjected to the addition of single volume fraction, 2% of each type of nanofiller with two aspect ratios, designated as nanoparticles and nanofibers. Notched beam flexure tests (SEVNB) of neat and each nanofiller reinforced samples suggest that, while baseline K_IC of neat geopolymer improved with heat treatment, nanofibers with high interfacial bond strength showed maximum capability in further improving K_IC. Among those nanofibers, 2 vol% Silicon Carbide Whisker (SCW) showed the largest improvement in K_IC of geopolymer, which is ~164%. After heat treatment at 650 °C, SCW reinforcement was also found to be effective, with only ~28% lower than the reinforcing performance at 250 °C, while the performance of Alumina Nanofiber reinforced geopolymer notably reduced. SEM and EDS analysis suggested that the inhomogeneity in neat geopolymer and length of nanofibers control the reinforcing capability as well as crack propagation resistance of geopolymer. For instance, minimum length of nanofillers to toughen this geopolymer at 250 °C was required as ~2 μm. The results further suggested that the sample failure occurred due to the dominance of tensile failure of nanofibers over the interfacial separation.     

On the use of single fibre composites testing to characterise the interface in natural fibre composites

In recent years, natural fibre composites have received considerable attention as a serious contender to replace glass fibres in composite material applications. One of the key aspects in composite materials is the interface between the reinforcing fibres and the matrix and a critical assessment of the interfacial bond is needed for a successful design of the final component. Natural fibres possess many intriguing advantages over man-made fibres such as glass, but they also present serious difficulties, especially in terms of material heterogeneity and more specifically in terms of fibre diameter. In this sense, most of the traditional methods for interfacial characterisation are difficult to apply, since the required data reduction involves the use of stress analysis or fracture mechanics approaches in which the fibre diameter is a critical parameter. In the present study, interfacial characterisation is discussed for flax fibre/polypropylene composites and a sensitivity analysis is presented for the single fibre fragmentation test. The results indicate that traditional stress analysis fails to correctly assess the interface, whilst a statistical based data analysis can overcome the fibre heterogeneity problem.     

Relation between interfacial shear strength and compressive strength of carbon fiber/epoxy resin composite strands

The mechanism with which the fiber-matrix interfacial strength exerts its influence on the compressive strength of fiber reinforced composites has been studied by measuring the axial compressive strength of carbon fiber/epoxy resin unidirectional composite strands having different levels of interfacial shear strength. The composite strands are used for experiments in order to investigate the compressive strength which is not affected by the delamination taking place at a weak interlayer of the laminated composites. The interfacial strength is varied by applying various degrees of liquid-phase surface treatment to the fibers. The efficiency of the compressive strength of the fibers utilized in the strength of the composite strands is estimated by measuring the compressive strength of the single carbon filaments with a micro-compression test. The compressive strength of the composite strands does not increase monotonically with increasing interfacial shear strength but showes lower values at higher interfacial shear strengths. With increasing interfacial shear strength, the suppression of the interfacial failure in the misaligned fiber region increases the compressive strength, while at higher interfacial shear strengths, the enhancement of the crack sensitivity decreases the compressive strength.     

A ToF-SIMS and XPS study of protein adsorption and cell attachment across PEG-like plasma polymer films with lateral compositional gradients

In this work we report a detailed X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) study of poly(ethylene glycol) PEG-like chemical gradients deposited via plasma enhanced chemical vapour deposition (PECVD) at two different load powers using diethylene glycol dimethyl ether (DG) as a monomer. Principal component analysis (PCA) was applied to the ToF-SIMS data both before and after protein adsorption on the plasma polymer thin films. Results of the PCA loadings indicated a higher content of hydrocarbon fragments across the higher load power gradient, which adsorbed higher amounts of proteins. Gradients deposited at a lower load power retained a higher degree of monomer like functionality as did the central region directly underneath the knife edge electrode. Analysis of the adsorption of serum proteins (human serum albumin and fetal bovine serum) was monitored across the gradient films and increased with decreasing ether (PEG-like) film chemistries. The effect of protein incubation time on the levels adsorbed fetal bovine serum on the plasma polymer films was critical, with significantly more protein adsorbing after 24 hour incubation times on both gradient films. The attachment of HeLa cells on the gradients appeared to be dictated not only by the surface chemistry, but also by the adsorption of serum proteins. XPS analysis revealed that at surface ether concentrations of less than 70% in the gradient films, significant increases in protein and cell attachment were observed.     

Structural and dielectric properties of Ru-based gate/Hf-doped Ta2O5 stacks

Hf-doped Ta₂O₅ thin films are studied with respect to their composition, dielectric and electrical properties. The incorporation of Hf is performed by sputtering of a 0.7 nm thick Hf layer on top of Ta₂O₅ and subsequent annealing to stimulate diffusion of Hf into Ta₂O₅ and their intermixing. The elemental in-depth distribution of the films is investigated by the time of flight secondary ion mass spectroscopy (ToF-SIMS), which has revealed that Hf and Ta₂O₅ are intermixed throughout the whole thickness. Two sub-layers exist in all the samples - an upper homogeneous Hf-doped Ta₂O₅ sub-layer and a near interfacial region which is a mixture of Ta- and Si-oxides. The X-ray reflectivity (XRR) analysis shows existence of interfacial layer with a thickness of about 1.9-2 nm, irrespectively of the total thickness of the stacks. Metal-oxide-Si structures with Ru and RuO₂ metal electrodes have been prepared and investigated in terms of dielectric constant, effective work function (EWF) and interfacial layer parameters. The influence of post-metallization annealing steps on these parameters was also studied.     

An energy criterion for the initiation of interface failure ahead of a matrix crack in brittle matrix composites

The mechanism of interfacial failure occurring as a consequence of the stress concentration induced by a matrix crack located in the vicinity of the interface is analysed. For this purpose, an asymptotic analysis is carried out to assess the competition between the propagation of the matrix crack towards the interface and the nucleation of an interfacial debond. An energetic approach provides a necessary condition comparing the ratio of the interfacial toughness over the matrix toughness to a critical value depending on the elastic mismatch between the fibre and the matrix and the ratio of the interfacial nucleation length over the width of the matrix ligament. Presented results show that the interfacial debonding is enhanced if the matrix is softer than the fibre. Further, a modified condition which does not involve the crack increment ratio is established if the matrix crack lies in the stiffest material.     

ToF-SIMS characterisation of diterpenoic acids after chromatographic separation

Microcolumn liquid chromatography (μHPLC) coupled on-line with time of flight secondary ion mass spectrometry (ToF-SIMS) was applied for mixture of diterpenoic acids (abietic, gibberellic and kaurenoic) analysis. Chromatographic effluent, with analytes separated, was carried out directly onto different, ToF-SIMS compatible surface substrates, for further ToF-SIMS analysis. Silica gel Si₆₀, aluminium backplate modified Si₆₀, monolithic silica gel and Raman spectroscopy chromatographic thin layers were used as the deposition substrates in this experiment. By ToF-SIMS surface imaging the deposition trace picture has been obtained. Effluent deposition surface area was scanned for diterpenoic acid fragment mass values based on mass spectrometric library. Measured ToF-SIMS dataset of fragment abundance and intensities were used for preliminary fragmentation schemes construction. The lowest substrate background activity has been established for monolithic silica gel thin layer and aluminium backplate modified Si₆₀ thin layer. In the case of Raman spectroscopy pre-treated thin layer or conventional chromatographic thin layer Si₆₀, the both, high background signal intensity and impossibility to construct negative ions surface image, were observed. Diterpenoic acids studied serve the similar mass spectrum but ToF-SIMS coupled with liquid chromatographic separation brings new impact to the positive identification of analytes studied.     

Dielectric properties of short sisal/coir hybrid fibre reinforced natural rubber composites

The dielectric properties, such as dielectric constant, volume resistivity and dielectric loss factor, of sisal/coir hybrid fibre reinforced natural rubber composites have been studied as a function of fibre loading, fibre ratio, frequency, chemical modification of fibres and the presence of a bonding agent. The dielectric constant values have been found to be higher for fibre filled systems than pure natural rubber. This has been attributed to the polarization exerted by the incorporation of fibres into the matrix. Dielectric constant values were observed to be decreased with increase in frequency due to the decreased interfacial and orientation polarization at higher frequencies. Whereas dielectric constant increases with fibre loading because of the increment in number of polar groups after the addition of hydrophilic lignocellulosic fibres. The volume resistivity of the composites was found to be decreased with fibre loading and a percolation threshold has been obtained at 15.6% volume of fibres. Fibre treatment, such as alkali, acetylation, benzoylation, peroxide and permanganate, were carried out to improve the adhesion between fibres and matrix. The dielectric constant values were lower for systems consisting of fibres subjected to chemical treatments due to the increased hydrophobicity of fibres. The addition of a two-component dry bonding agent consisting of hexamethylene tetramine and resorcinol, used for the improvement of interfacial adhesion between the matrix and fibres, reduced the dielectric constant of the composites. When the weight percentage of sisal fibre was increased in the total fibre content of the hybrid composites, the dielectric constant was found to increase. The added fibres and different chemical treatments for them increased the dielectric dissipation factor. A dielectric relaxation has been observed at a frequency of 5 MHz.     

An appraisal of composite interface mechanics models and some challenging problems

A critical review of previous mechanics models proposed for the evaluation of interfacial properties from single fibre tests is presented with regard to their applicability and limitations. New results which include the effects of some important factors, such as pre-existing fibre flaws. thermal residual stresses and matrix cracks. are provided for a single fibre fragmentation test. By comparing the stress distributions of single fibre fragment and multi-fibre fragment, a basic method to study the multi-fibre composite is introduced in order to relate the interfacial parameters to the mechanical properties of the bulk composite. Some challenging problems on fibre-matrix interfaces are discussed for future research work.     

Detection of chromium in liquids by laser induced breakdown spectroscopy (LIBS)

Environmental concerns about the amount of dissolved heavy metals in coastal tidal waters have led to investigations into possible ways to detect chromium dissolved in water. A method using fluorescence spectroscopy in solution has been proposed. However, such optical emission spectroscopic methods tend to suffer from a lack of sensitivity caused by the strong quenching processes in liquids. In this investigation, Nd:YAG Q-switched laser pulses were utilised to generate a plasma filled bubble in a chromium solution. Fluorescence in the plasma was detected using an optical fibre tip placed adjacent to the bubble. Light wavelengths characteristic of chromium were detected and spectral images recorded using an optical multi-channel analyzer. PACS 39.30.+w; 42.62 Fi; 52.38 Mf; 92.20 Ny     

The preparation of optical fibre nanoprobe and its application in spectral detection

As an important component of scanning near-field optical microscope (SNOM), optical fibre nanoprobe has been applied to many fields extensively. A melt-stretched etching method is proposed to produce optical fibre nanoprobe with low cost. Firstly, optical fibre tip with micrometer-sized diameter is created by the melt-stretched measure. Next, it is dipped into hydrofluoric acid (HF), and a fine optical fibre nanoprobe will be made after a short-time etching. Owing to the taper structure of tip, it can be etched again in acid if a nanoprobe is not constructed when the first etching is completed. In addition, optical fibre nanoprobe is applied to spectral investigation, and the fluorescence spectroscopy of rhodamine B (Rh B) solution is collected by an optical investigation system with a bifurcated fibre.