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A synthetically controllable two-step spin transition was observed in iron(ii) spin crossover nanoparticles of the dehydrated one-dimensional coordination polymer [Fe(NH2trz)3]Br2 (NH2trz = 4-amino-1,2,4-triazole) using the reverse micellar method.

5 figures.-- Supplementary information available., Heterostructures of two-dimensional (2D) materials using graphene and MoS2 have enabled both pivotal fundamental studies and unprecedented sensing properties. These heterosystems are intriguing when graphene and MoS2 are interfaced with 2D sheets that emulate biomolecules, such as amino-terminated oligoglycine self-assemblies (known as tectomers). The adsorption of tectomer sheets over graphene and MoS2 modulates the physicochemical properties through electronic charge migration and mechanical stress transfer. Here, we present a systematic study by Raman spectroscopy and tectomer-functionalised scanning probe microscopy to understand mechanical strain, charge transfer and binding affinity in tectomer/graphene and tectomer/MoS2 hybrid structures. Raman mapping reveals distinctive thickness dependence of tectomer-induced charge transfer to MoS2, showing p-doping on monolayer MoS2 and n-doping on multilayer MoS2. By contrast, graphene is n-doped by tectomer independently of layer number, as confirmed by x-ray photoelectron spectroscopy. The interfacial adhesion between the amino groups and 2D materials are further explored using tectomer-functionalised probe microscopy. It is demonstrated here that these probes have potential for chemically sensitive imaging of 2D materials, which will be useful for mapping chemically distinct domains of surfaces and the number of layers. The facile tectomer-coating approach described here is an attractive soft-chemistry strategy for high-density amine-functionalisation of atomic force microscopy probes, therefore opening promising avenues for sensor applications., We would like to acknowledge strategic development funding from the University of Sussex. Additional funding from the Aragon Government is also acknowledged (Grupo de Nanosensores y Sistemas Bioanalíticos (N&SB), ref. E25_20R). [...] This work was also partially supported by a UKRI Future Leaders Fellowship (Grant No. MR/T042664/1).

Two-dimensional materials such as graphene and molybdenum disulfide are often subject to out-of-plane deformation, but its influence on electronic and nanomechanical properties remains poorly understood. These physical distortions modulate important properties which can be studied by atomic force microscopy and Raman spectroscopic mapping. Herein, we have identified and investigated different geometries of line defects in graphene and molybdenum disulfide such as standing collapsed wrinkles, folded wrinkles, and grain boundaries that exhibit distinct strain and doping. In addition, we apply nanomechanical atomic force microscopy to determine the influence of these defects on local stiffness. For wrinkles of similar height, the stiffness of graphene was found to be higher than that of molybdenum disulfide by 10–15% due to stronger in-plane covalent bonding. Interestingly, deflated graphene nanobubbles exhibited entirely different characteristics from wrinkles and exhibit the lowest stiffness of all graphene defects. Density functional theory reveals alteration of the bandstructures of graphene and MoS2 due to the wrinkled structure; such modulation is higher in MoS2 compared to graphene. Using this approach, we can ascertain that wrinkles are subject to significant strain but minimal doping, while edges show significant doping and minimal strain. Furthermore, defects in graphene predominantly show compressive strain and increased carrier density. Defects in molybdenum disulfide predominantly show tensile strain and reduced carrier density, with increasing tensile strain minimizing doping across all defects in both materials. The present work provides critical fundamental insights into the electronic and nanomechanical influence of intrinsic structural defects at the nanoscale, which will be valuable in straintronic device engineering.

We demonstrate a crystallographic configurational transformation from rhombohedral (ABC) to Bernal (ABA) stacking by exposing large area exfoliated trilayer graphene (3LG) to nitric acid vapors and...

In the present work, the effect of wettability on CaCO3 precipitation was approached by monitoring crystal formation in microchips of different wettability degree. Solutions of calcium chloride and...

Raman spectroscopy is employed to investigate the temperature dependence of the E2g phonon mode of single-layer, few-layer (FL), and bulk hexagonal boron nitride (hBN) sheets, situated over Si/SiO2...

High volume fraction carbon nanotube (CNT) composites (7.5&ndash, 16% vol.) were fabricated by the impregnation of CNT buckypapers into epoxy resin. To enhance the interfacial reaction with the epoxy resin, the CNTs were modified by two different treatments, namely, an epoxidation treatment and a chemical oxidation. The chemical treatment was found to result in CNT length severance and to affect the porosity of the buckypapers, having an important impact on the physico-mechanical properties of the nanocomposites. Overall, the mechanical, electrical, and thermal properties of the impregnated buckypapers were found to be superior of the neat epoxy resin, offering an attractive combination of mechanical, electrical, and thermal properties for multifunctional composites.

The accumulation efficiency and the properties of polyhydroxyalkanoates (PHAs) produced from acidified waste glycerol (AWG) and its derivatives via an enriched microbial consortium derived from soil, were investigated in this study. AWG consisted mainly from short chain fatty acids, 1,3 propanediol and residual glycerol, which were also evaluated individually as substrates. Accumulation capacity and yields were estimated after solvent extraction and purification and PHAs were further analyzed in terms of their chemical structure, thermal properties, molecular masses and mechanical properties. The lowest accumulation capacity was noticed for non-acidified waste glycerol as carbon source which led to the generation of P(3HB), whereas for the other carbon sources co-polymers of 3HB with 3HV or 3HHx were produced. Average molecular mass weights were quite high in all cases reaching ~1.8 × 106 Da. The thermal properties and the mechanical behavior of PHAs were shown to be highly affected by their monomeric composition, whereas it was also concluded that DSC and DMA results were in good agreement.

While synthetic methods for the grafting of nanoparticles or photoactive molecules onto carbon nanotubes (CNTs) have been developed in the last years, a very limited number of reports have appeared on the grafting of single-molecule magnets (SMMs) onto CNTs. There are many potential causes, mainly focused on the fact that the attachment of molecules on surfaces remains not trivial and their magnetic properties are significantly affected upon attachment. Nevertheless, implementation of this particular type of hybrid material in demanding fields such as spintronic devices makes of utmost importance the investigation of new synthetic protocols for effective grafting. In this paper, we demonstrate a new experimental protocol for the noncovalent grafting of DyIII2 SMM, [Dy2(NO3)2(saph)2(DMF)4], where H2saph = N-salicylidene-o-aminophenol and DMF = N,N-dimethylformamide, onto the surface of functionalized multiwalled CNTs (MWCNTs). We present a simple wet chemical method, followed by an extensive washing protoc...

The diamagnetic two-dimensional Hofmann-type metal-organic framework [Zn

Mechanical properties of graphene prepared by chemical vapour deposition (CVD) are not easily comparable to the properties of nearly perfect graphene prepared by mechanical cleavage. In this work, we attempt to investigate the mechanical performance of CVD graphene (simply supported or embedded in polymer matrix), transferred by two different techniques, under uniaxial loading with simultaneous in situ monitoring by Raman microspectroscopy. The level of charge transfer doping and strain is assessed using the vector analysis modified for uniaxial strain. The strain distribution across the samples varies significantly, owing to the growth and transfer process, which induces wrinkles and faults in the CVD graphene. In simply supported specimens, the stress transfer efficiency is generally very low and the changes in Raman spectra are dominated by variations in the charge transfer originating from the realignment of the domains on the substrate upon the application of strain. In contrast, samples covered with an additional polymer layer exhibit an improved stress transfer efficiency, and the alterations of charge doping levels are negligible. In fully embedded specimens, the variations in stress transfer efficiencies are caused by the size of the effective graphene domains defined by cracks, folds and/or wrinkles.

High volume fraction carbon nanotubes (CNTs) composites were fabricated by using the buckypaper approach. CNTs were modified by an epoxidation treatment to achieve high degree of chemical bonding with the epoxy matrix. The fabricated buckypapers exhibited high porosity, allowing the epoxy resin to fully penetrate inside the structure of the film. The hybrid material was found to exhibit specific strength of the same order of magnitude as aluminium-based industrial sheets. The usage of micro-Raman spectroscopy to assess the stress transfer from the polymer to the individual or bundled CNTs upon loading revealed that the enhanced mechanical integrity of such materials is due to the friction and contact forces of a huge number (∼10 23 m −3 ) of inter-bundle junctions. The proposed fabrication procedure can be easily extended towards the preparation of laminated composites at the industrial scale.

Single- and bi-layer MoS2 are two-dimensional semiconductors able to withstand very large deformations before failure, standing out as suitable templates for strain engineering applications and flexible electronics. It is imperative, for the proper integration of this material in practical applications, that the relationship between material property and strain is well understood. Two dimensional MoS2 crystals fabricated by chemical vapor deposition or micromechanical exfoliation are transferred onto flexible substrates and subjected to biaxial tension on a carefully designed and assessed loading stage with high accuracy and control. The successful stress transfer from substrate to the overlying 2D crystal is identified by in-situ monitoring of the strain-induced phonon frequency and photoluminescence peak shifts. Reliable values for the mode Grüneisen parameters and exciton deformation potentials were obtained by studying a significant number of crystals. The experimental results are backed by density functional theory calculations and are in good agreement with the experiments. This work highlights the potential of these materials in strain engineering applications and gives accurate values for single- and bi-layer MoS2 thermomechanical parameters.

Enhancement of thermal properties of epoxy resins was achieved by incorporation of polybenzimidazole (PBI) fibermats filled with carbon nanomaterials, prepared by the solution electrospinning technique. Different type of carbon nanostructures (carbon nanotubes, graphite flakes, graphene nanoplatelets and carbon black) were compared as fillers in polybenzimidazole fibers. The carbon-PBI-fibermats showed remarkable thermal transport properties and therefore, they were studied as thermal reinforcement material for epoxy composites. Mechanical and thermal properties of produced composites were evaluated and the effectiveness of different types of carbon fillers examined. Results showed that the produced carbon filled fibermats can be used effectively as a thermal reinforcing material in epoxy resins, offering several advantages.

A controlled and eco-friendly, scalable CVD method for the production of single and few layer MoS2 crystals is proposed. The MoS2 crystals are fabricated at atmospheric pressure through the reaction of pre-deposited sodium molybdate (Na2MoO4) in solution and elemental sulfur at 800 degrees C, offering the flexibility to achieve two growth regimes-either homogeneously distributed single layer MoS2 crystals or continuous MoS2 films-by varying the Na2MoO4 solution concentration. In particular, for low precursor concentrations, isolated single layer MoS2 crystals with controllable mean lateral size were produced. Higher concentrations resulted in continuous single layer films grown in tandem with highly oriented few layer epitaxial domains. The area of the monolayer relative to the few-layer domains can be adjusted. The significant impact on the optical properties of single layer MoS2 crystals due to the growth induced strain is also examined. The grown monolayer crystals are found to experience similar to 0.3% biaxial tensile strain relative to the exfoliated ones, while a strain relief of 0.6% is measured when these CVD crystals are transferred to another plastic substrate. Moreover, in their photoluminescence (PL) spectra, the neutral exciton and negative trion peaks are shifted linearly with biaxial strain. By correlating PL and Raman spectroscopies the deformation potential of the direct optical transition in single layer MoS2 can be determined.

While synthetic methods for the grafting of nanoparticles or photoactive molecules onto carbon nanotubes (CNTs) have been developed in the last years, a very limited number of reports have appeared on the grafting of single-molecule magnets (SMMs) onto CNTs. There are many potential causes, mainly focused on the fact that the attachment of molecules on surfaces remains not trivial and their magnetic properties are significantly affected upon attachment. Nevertheless, implementation of this particular type of hybrid material in demanding fields such as spintronic devices makes of utmost importance the investigation of new synthetic protocols for effective grafting. In this paper, we demonstrate a new experimental protocol for the noncovalent grafting of Dy

A methodology is presented here for deriving true experimental axial stress-strain curves in both tension and compression for monolayer graphene through the shift of the 2D Raman peak that is present in all graphitic materials. The principle behind this approach is the observation that the shift of the 2D wavenumber as a function of strain for different types of PAN based fibres is a linear function of their Young's moduli and, hence, the corresponding value of the shift of the 2D Raman peak over axial stress is, in fact, a constant. By moving across the length scales we show that this value is also valid at the nanoscale as it corresponds to the in plane breathing mode of graphene that is present in both PAN based fibres and monolayer graphene. Hence, the values of the shift of the 2D Raman peak can be easily converted to values of stress in the linear elastic region without the aid of modelling or the need to resort to cumbersome experimental procedures for obtaining the axial force transmitted to the material and the cross sectional area of the two dimensional membrane.

The properties of graphene depend sensitively on strain and doping affecting its behavior in devices and allowing an advanced tailoring of this material. A knowledge of the strain configuration, i.e. the relative magnitude of the components of the strain tensor, is particularly crucial, because it governs effects like band-gap opening, pseudo-magnetic fields, and induced superconductivity. It also enters critically in the analysis of the doping level. We propose a method for evaluating unknown strain configurations and simultaneous doping in graphene using Raman spectroscopy. In our analysis we first extract the bare peak shift of the G and 2D modes by eliminating their splitting due to shear strain. The shifts from hydrostatic strain and doping are separated by a correlation analysis of the 2D and G frequencies, where we find ∆ω2D/∆ωG = 2.21 ± 0.05 for pure hydrostatic strain. We obtain the local hydrostatic strain, shear strain and doping without any assumption on the strain configuration prior to the analysis, as we demonstrate for two model cases: Graphene under uniaxial stress and graphene suspended on nanostructures that induce strain. Raman scattering with circular corotating polarization is ideal for analyzing frequency shifts, especially for weak strain when the peak splitting by shear strain cannot be resolved., 2D Materials, 5 (1), ISSN:2053-1583

Multilayered graphitic materials are not suitable as load-bearers due to their inherent weak interlayer bonding (for example, graphite is a solid lubricant in certain applications). This situation is largely improved when two-dimensional (2-D) materials such as a monolayer (SLG) graphene are employed. The downside in these cases is the presence of thermally or mechanically induced wrinkles which are ubiquitous in 2-D materials. Here we set out to examine the effect of extensive large wavelength/ amplitude wrinkling on the stress transfer capabilities of exfoliated simply-supported graphene flakes. Contrary to common belief we present clear evidence that this type of "corrugation" enhances the load bearing capacity of few-layer graphene as compared to 'flat' specimens. This effect is the result of the significant increase of the graphene/polymer interfacial shear stress per increment of applied strain due to wrinkling and paves the way for designing affordable graphene composites with highly improved stress-transfer efficiency., Comment: 20 pages, 6 figures

The design, fabrication and evaluation of a low-cost and low-power, continuous-flow microfluidic device for DNA amplification by polymerase chain reaction (PCR) with integrated heating elements, on a commercially available thin polymeric substrate (Pyralux® Polyimide), is presented. The small thermal mass of the chip, in combination with the low thermal diffusivity of the polymeric substrate on which the heating elements reside, yields a low power consumption PCR chip with fast amplification rates. A flow-through μPCR device is designed and fabricated using flexible printed circuit (FPC) technology on a foot-print area of 8 cm × 6 cm with a meandering microchannel realized at a very small distance (50 μm) above 3 independently operating resistive (copper) serpentine microheaters, each one defining one of the three PCR temperature zones. The 145 cm-long microchannel is appropriately designed to cross the alternating temperature zones as many times as necessary for the DNA sample to perform 30 PCR cycles. Numerical computations lead the design so that there is no thermal crosstalk between the 3 zones of our chip and indicate excellent temperature uniformity in each zone. In addition, the total power consumption during the chip operation is calculated to be in the order of a few Watts, verified experimentally by means of thermal characterization of our heaters. Thermal camera measurements also verified the excellent temperature uniformity in the three thermal zones. An external, home-made temperature control system was utilized to maintain the heater temperatures in the designated values (±0.2 °C). The PCR chip was validated by a successful amplification of a 90 base-pairs DNA template of the mouse GAPDH housekeeping gene within 5 min.

A versatile approach is developed to fabricate strong multi walled carbon nanotube/epoxy composites, based on the buckypaper approach. The crucial factors affecting their mechanical performance are the porosity of the carbon nanotube preform, the presence of reactive functional groups onto the CNT surface and the pressure-assisted impregnation. This fabrication procedure can be easily extended towards the preparation of CNT-based composites in industrial scale.

A chemical vapor deposition (CVD) process for the production of continuous-high quality-graphene layers based on camphor decomposition on polycrystalline Ni foil, is demonstrated. In situ X-ray diffraction at the pyrolysis temperature of the Ni foil indicates the presence of dominant Ni grains which play an important role in the carbon nucleation and growth. The topography of the grown graphene layers is studied by scanning electron microscopy and atomic force microscopy which show that the Ni surface is covered by continuous and wrinkled graphene carpets. Raman spectroscopy reveals the high quality of the graphene film which appears to be only a few monolayers thick. X-ray photoelectron spectroscopy indicates the existence of graphitic layers and the absence of any spectral features associated with carbides (Ni x C). The proposed CVD process is a sufficient method for large scale production of graphene films.

Thin membranes, such as monolayer graphene of monoatomic thickness, are bound to exhibit lateral buckling under uniaxial tensile loading that impairs its mechanical behaviour. In this work, we have developed an experimental device to subject 2D materials to controlled equibiaxial strain on supported beams that can be flexed up or down to subject the material to either compression or tension, respectively. Using strain gauges in tandem with Raman spectroscopy measurements, we monitor the G and 2D phonon properties of graphene under biaxial strain and thus extract important information about the uptake of stress under these conditions. The experimental shift over strain for the G and 2D Raman peaks were found to be in the range of 62.3 ± 5 cm–1/% and 148.2 ± 6 cm–1/%, respectively, for monolayer but also bilayer graphenes. The corresponding Grüneisen parameters for the G and 2D peaks were found to be between 1.97 ± 0.15 and 2.86 ± 0.12, respectively. These values agree reasonably well with those obtained from small-strain bubble-type experiments. The results presented are also backed up by classical and ab initio molecular dynamics simulations and excellent agreement of Γ-E2g shifts with strains and the Grüneisen parameter was observed.

We present the first Raman spectroscopic study of Bernal bilayer graphene flakes under uniaxial tension. Apart from a purely mechanical behavior in flake regions where both layers are strained evenly, certain effects stem from inhomogeneous stress distribution across the layers. These phenomena such as the removal of inversion symmetry in bilayer graphene may have important implications in the band-gap engineering providing an alternative route to induce the formation of a band-gap., Comment: 21 pages, 7 figures

In this communication an extended ‘‘in–out’’ polymerization method is presented, which leads to the synthesis of novel heteroarm star block terpolymers of the type An(B-b-C)n. A four step/one-pot synthetic procedure is pursued using anionic polymerization under an inert atmosphere. The resulted star-shaped terpolymer consists of a divinyl benzene nodule bearing pure polystyrene and poly(hexyl methacrylate)-block-poly(methyl methacrylate) diblock copolymer arms. It is shown that this kind of star terpolymers can self-assemble in the bulk forming lamellae mesophase by arm and block segregation. The mechanical properties of the terpolymer have been examined in detail. Finally, the proposed synthetic procedure can be easily employed in other controlled polymerization methods.

Carbon nanotube thin sheets – buckypapers – were prepared from multi-walled carbon nanotubes oxidised with different oxidation agents. Prepared buckypapers were characterized by mechanical testing, surface conductivity and mercury porosimetry. It was found that their mechanical properties were increased by increasing the power of oxidation agents. Nitric acid-treated buckypapers showed the highest structural integrity and surface conductivity.

The effect of oxidation on the structural integrity of multiwalled carbon nanotubes through acidic (nitric acid and a mixture of sulfuric acid and hydrogen peroxide) and basic (ammonium hydroxide/hydrogen peroxide) agents has been studied. In order to purify the as-received material, a non-oxidative treatment (with hydrochloric acid) was also applied. Electron microscopy and thermogravimetric analysis clearly revealed that the nitric acid-treated material under reflux conditions suffered the highest degree of degradation, such as, nanotube shortening and additional defect generation in the graphitic network. Basic oxidative treatment led to the complete removal of amorphous carbon and metal oxide impurities but the structural integrity was found to be intact. X-ray photoelectron spectroscopy was employed to confirm the different functionalities produced for each oxidation agent, whereas titration measurements determined the relative concentration of carboxylic functions onto the graphitic surface. Moreover, a general relationship between the chemical treatment and the amount of non-graphitic carbon was established by means of Raman spectroscopy measurements. The possibility of controlling the required amount of functionality, carboxylic and hydroxyl, via these oxidation procedures is discussed.

In this work, the thermal stress development in anisotropic fiber-reinforced polymer composites is investigated for temperatures below the glass transition temperature of the resin. By applying two independent experimental methodologies, it was found that the initial thermal (residual) strain in the reinforcing fibers is compressive of about − 0.04% at ambient temperatures. This is due to the mismatch of the thermal expansion coefficient between the polymer matrix and fiber, as the material is cooled down from the processing temperature. However, on reheating the composites the compressive stress in the fiber gradually diminishes and becomes zero at 50 °C. Further heating to 100 °C introduces tensile strains in the fiber of maximum of 0.13%. The conformity of these results to analytical models that relate the composite thermal strain to the thermal expansion coefficients of fiber and resin, as well as, the fiber volume fraction, is examined. Finally, the possibility of tailoring the sign (positive, negative or, even, zero) of the composite thermal expansion coefficient of certain advanced composites by simply varying the thermal expansion of the polymer matrix, is discussed.

Single-walled carbon nanotubes were functionalized along their sidewalls with hydroxyalkyl groups using a radical addition scheme. These moieties were found to be active in the polymerization of acrylic acid from the surface of the nanotubes by a redox radical mechanism. The resulting polymerized nanotubes were analyzed by UV-Vis, XPS, Raman and SEM techniques. The composite material was found to be soluble in aqueous media (pH > 5) and polar organic solvents. The reported grafting technique is expected to be suitable for industrial production of modified carbon nanotubes.

The present work deals with the stress generation capability of nickel?titanium shape memory alloys (SMAs) under constrained conditions for two well-defined loading modes: recurrent crystalline transformation (transformation fatigue) and a one-step continuous activation (generated stress relaxation). The data acquired will be very useful during the design process of an SMA Ni?Ti element as a functional part of an assembly. Differential scanning calorimetry (DSC) was employed in order to investigate the transformation characteristics of the alloy before and after the tests. Transformation fatigue tests revealed that the parameter that affects more the rate of the functional degradation is the number of crystalline transitions the wire undergoes. Thus, the service life limit of this material as a stress generator can be reduced to a few thousand working cycles. For stress relaxation, the main factor that affects the ability for stress generation is the working temperature: the higher the temperature above the austenite finish?(TAf) limit the higher the relaxation effect. Thermomechanical treatment of the alloy during the tests reveals the 'hidden' transformation from the cubic structure (B2) of austenite to the rhombohedral structure of the R-phase. It is believed that the gradual loss of the stress generation capability of the material under constrained conditions must be associated to a gradual slipping relaxation mechanism. Scanning electron microscopy (SEM) observations on as-received, re-trained, fatigued and stress-relaxed specimens in the martensitic state provide further support for this hypothesis.

The stress sensitivity of two aramid fiber optical phonons at 1611 and 1648 cm −1 has been employed to conduct stress as well as interface measurements in aramid/epoxy resin composites at ambient and elevated temperatures (60–100 °C). It was found that when the stress/interface measurements were conducted via the 1648 cm −1 phonon, which is practically insensitive to thermal effects, there was an upper limit of temperature beyond which the results were scattered and important information on the interface integrity was lost. Alternatively, it has been shown here that at elevated temperatures one can obtain the interfacial shear stress directly from the 1611 cm −1 shift and then the axial stress by integration. Useful results were obtained both on the applicability of both techniques and also on the interface yield stress of these composites as a function of temperature.

2D crystals, such as graphene, exhibit the higher strength and stiffness of any other known man-made or natural material. So far, this assertion has been primarily based on modelling predictions and on bending experiments in combination with pertinent modelling. True uniaxial loading of suspended graphene is not easy to accomplish; however such an experiment is of paramount importance in order to assess the intrinsic properties of graphene without the influence of an underlying substrate. In this work we report on uniaxial tension of graphene up to moderate strains of 0.8% ca.. This has been made possible by sandwiching the graphene flake between two polymethylmethacrylate (PMMA) layers and by suspending its central part by the removal of a section of PMMA with e-beam lithography. True uniaxial deformation is confirmed by the measured large phonon shifts with strain by Raman spectroscopy and the indication of lateral buckling (similar to what is observed for thin macroscopic membranes under tension). Finally, we also report on how the stress is transferred to the suspended specimen through the adhesive grips and determine the value of interfacial shear stress that is required for efficient axial loading in such a system.

The problem of efficient stress transfer in two-phase composites is very intriguing as it is a prerequisite for the attainment of satisfactory mechanical performance in these materials. Many micromechanical models are now available for the prediction of the stress distribution on either phase or at the interface. Some of the existing models are based on poor assumptions while others are too complex to be applied directly without prior knowledge of all the elastic constants of the constituent materials and their inter-dispersion in the composite. In this paper, an attempt is made to revisit the shear-lag type of model applying it to a specific class of two-phase materials, that of long-fiber polymer composites. The experimental tool used to verify the theoretical stress distributions is the technique of laser Raman microscopy (LRM). By introducing, a local fiber discontinuity in a composite of high volume fraction we could determine both the axial fiber build-up and the corresponding interfacial shear-stress distribution at all strain levels using LRM. The results are compared to the theoretical shear-lag curves (elastic region) and useful conclusions are drawn for the universality of these models and their applicability to high volume fraction polymer composites.

The Raman response of aramid fibers is examined as a function of the applied stress and temperature. Noticeable wavenumber shifts are recorded for the 1611 and 1648 cm −1 Raman bands with increasing stress. In contrast, only the 1611 cm −1 band is affected by temperature within the −50 to 200 °C range. The existence of two adjacent vibrational modes sensitive to stress with only one of the two being temperature dependent, allows the development of a simultaneous stress and temperature spectroscopic sensor. The applicability of this sensor is evaluated on an epoxy resin – aramid fiber composite activated by a shape-memory-alloy actuator.

A multifunctional non-destructive technique, based on the Raman response of aramid fibers, is employed for (a) assessing the interface integrity and the overall stress distribution in a unidirectional Kevlar 29®/epoxy composite (b) measuring the stress concentration and its development with applied load in Kevlar 49®/epoxy composites incorporating a circular notch and finally, (c) determining the strain arising in 0° plies due to partial and full crack growth within the θ° plies in multidirectional 0°/θ°/0° composites. It is shown that this technique can be used effectively to study the damage development in composite materials that arise from the presence of different length scale discontinuities.

Shape memory alloy (SMA) wires have been integrated in composite laminates consisting of an epoxy resin reinforced by aramid fibres. In the first part of this series, a new methodology was proposed for the simultaneous measurement of stress and temperature in the reinforcing fibres during shape memory wire activation. Those tests were conducted at three activation temperatures (40, 60 and 100°C) and the internal compressive stress distribution was extracted for low wire volume fraction composites. It was observed that for higher wire volume fractions the high compressive recovery stresses generated during electrical resistive heating of the wires led to the geometric failure of the composite coupons. In this work, measurements are conducted on hybrid laminate coupons of dimensions that prevent geometric (global) specimen failure. The internal stress distribution is measured at relatively high activation temperatures of 80 and 100°C and a filtering technique based on fast Fourier transform (FFT) is employed to simulate the stress and temperature variability and to filter the associated experimental noise. The results show that the higher stresses appear in the middle of the mid-wire distance and that the values at 100°C activation are not significantly different than those at 80°C indicating the presence of an upper limit in the transmission of wire recovery stresses in these systems.