Evaluation of interfacial shear stress between multi-walled carbon nanotubes and epoxy based on strain distribution measurement using Raman spectroscopy

This study investigated the stress recovery of aligned multi-walled carbon nanotubes (MWCNTs) embedded in epoxy using Raman spectroscopy, and evaluated interfacial shear stress between MWCNTs and epoxy using shear-lag analysis. To this end, ultralong aligned MWCNTs (3.8 mm long) were embedded in epoxy to obtain Raman spectra at multiple points along the MWCNTs. Downshift of the G′-band due to tensile strain was measured from the nanotube end to the center, and the strain distribution of embedded MWCNTs was evaluated successfully. Interfacial shear stress was then estimated by minimizing the error between the shear-lag analysis and measured strain distribution. The maximum interfacial shear stress between the embedded MWCNTs and epoxy was 10.3–24.1 MPa at the failure strain of aligned MWCNT-reinforced epoxy composites (0.46% strain). Furthermore, the interfacial shear stress between an individual MWCNT and epoxy was investigated.     

碳纤维增强环氧树脂基复合材料湿热残余应力的微Raman光谱测试表征

采用微Raman光谱仪对碳纤维增强环氧树脂复合材料CF/EP(纤维体积分数为30%)的湿热残余应力进行了研究。实验结果表明：湿热残余应力能够使碳纤维Raman光谱发生频移,根据频移可对纤维所受湿热残余应力进行表征;选择合适的试验点是复合材料湿热残余应力Raman测试成功的关键;在湿热环境下长期吸湿,纤维所受轴向残余应力由吸湿前的热残余压应力转变成吸湿后的湿热残余拉应力;由吸湿后碳纤维所受湿热残余拉应力减去吸湿前热残余压应力获得的吸湿拉应力非常大,平均为2272 MPa,接近所用碳纤维的拉伸强度(2800 MPa);适当的加工热残余压应力有利于降低吸湿导致的应力。     

Deformation of PBO/epoxy plain weave fabric laminae followed using Raman spectroscopy

Understanding of microscopic deformation behaviour of plain weave fabric lamina is essential in the analysis of the macroscopic mechanical properties of woven fabric composites. Many analytical models have been proposed to predict elastic properties of woven fabric laminae. The present paper is an attempt is made to fit experimental data obtained from the analysis of fibre deformation using Raman spectroscopy to the slice array model (SAM) to predict the local fibre strain distribution in the loading direction along the defined cell of a plain-weave lamina. Another model is proposed that combines the slice array and the off-axis (crimp) model and the experimental data are shown to fit this model rather better.     

Thermal stress hysteresis and stress relaxation in an epoxy film

Thermal cycling of an epoxy coating on silicon through the glass transition temperature (T _g) revealed a large stress hysteresis on the first thermal cycle through T _g and a change in the stress–temperature slope at T _g resulting from the change in the epoxy elastic properties due to the glass transition. This stress hysteresis was not observed on subsequent thermal cycles through T _g. However, after the coating was annealed (aged) below T _g (for hours or longer)—during which the stress relaxed exponentially with time—the stress hysteresis returned. The magnitude of stress hysteresis, on cycling through T _g, was found to correlate to the magnitude of long-time relaxation that occurred during annealing at temperatures below T _g.     

Measurement of interfacial residual stress in SiC fiber reinforced Ni-Cr-Al alloy composites by Raman spectroscopy

Raman spectroscopy was used to measure Raman spectra of the inner SiC fibers and surface C-rich layers of SiC fibers, composite precursors and SiCf/Ni-Cr-Al composites. The residual stresses of the inner SiC fibers and surface C-rich layers were calculated, and the effect of the(Al + Al_2O_3) diffusion barrier layer on the interfacial residual stress in the composites was analyzed in combination with the interface microstructure and energy disperse spectroscopy(EDS) elements lining maps. The results show that the existence of(Al + Al_2O_3) diffusion barrier improves the compatibility of the SiCf/Ni-Cr-Al interface,inhibits the adverse interfacial reaction, and relieves the residual stress inside SiC fibers and at the interface of composite material. Heat treatment can reduce the residual stress at the interface. As the heat treatment time increases, the residual stress at the interface decreases.     

Cure kinetics characterization and monitoring of an epoxy resin using DSC,Raman spectroscopy,and DEA

The use of thick sections of fiber-reinforced polymers (FRPs) is increasing for numerous industrial applications such as wind turbine blades. In situ cure monitoring is very important to directly observe the cure process of FRPs during the manufacturing process. In this work, Raman spectroscopy and dielectric analysis (DEA) are investigated for in situ cure monitoring of an epoxy resin. The cure behavior is first characterized using differential scanning calorimetry (DSC) as a baseline comparison, and the best-fit phenomenological reaction model is determined to describe the cure behavior of the epoxy resin as well as the kinetic parameters. The relationship between T_g and degree of cure is also established. The degree of cure obtained from Raman spectroscopy and DEA under isothermal conditions is compared to that obtained from DSC. A good agreement is observed among the three methods, supporting the potential of these in situ cure monitoring methods during manufacturing. An implementation plan for in-plant monitoring is also discussed.     

Directivity enhanced Raman spectroscopy using nanoantennas

Directing the emission from optical emitters is highly desired for efficient detection and, by reciprocity, efficient excitation as well. As a scattering process, Raman benefits from directivity enhancements in both excitation and emission. Here we demonstrate directivity enhanced Raman scattering (DERS) using a nanoantenna fabricated by focused ion beam milling. The nanoantenna uses a resonant ring-reflector to shape the emitted beam and achieve DERS-this configuration is most similar to a waveguide antenna. The ring reflector boosts the measured Raman signal by a factor of 5.5 (as compared to the ground plane alone), and these findings are in quantitative agreement with comprehensive numerical simulations. The present design is nearly optimal in the sense that almost all the beam power is coupled into the numerical aperture of the microscope. Furthermore, the emission is directed out of the plane, so that this design can be used to achieve DERS using conventional Raman microscopes, which has yet to be achieved with Yagi-Uda and traveling wave antenna designs.     

Waterborne pathogen detection using Raman spectroscopy

Raman spectroscopy is being evaluated as a candidate technology for waterborne pathogen detection. We have investigated the impact of key experimental and background interference parameters on the bacterial species level identification performance of Raman detection. These parameters include laser-induced photodamage threshold, composition of water matrix, and organism aging in water. The laser-induced photodamage may be minimized by operating a 532 nm continuous wave laser excitation at laser power densities below 2300 W/cm(2) for Grampositive Bacillus atrophaeus (formerly Bacillus globigii, BG) vegetative cells, 2800 W/cm(2) for BG spores, and 3500 W/cm(2) for Gram-negative E. coli (EC) organisms. In general, Bacillus spore microorganism preparations may be irradiated with higher laser power densities than the equivalent Bacillus vegetative preparations. In order to evaluate the impact of background interference and organism aging, we selected a biomaterials set comprising Gram-positive (anthrax simulants) organisms, Gram-negative (plague simulant) organisms, and proteins (toxin simulants) and constructed a Raman signature classifier that identifies at the species level. Subsequently, we evaluated the impact of tap water and storage time in water (aging) on the classifier performance when characterizing B. thuringiensis spores, BG spores, and EC cell preparations. In general, the measured Raman signatures of biological organisms exhibited minimal spectral variability with respect to the age of a resting suspension and water matrix composition. The observed signature variability did not substantially degrade discrimination performance at the genus and species levels. In addition, Raman chemical imaging spectroscopy was used to distinguish a mixture of BG spores and EC cells at the single cell level.     

Three-dimensional imaging of objects embedded in turbid media with fluorescence and Raman spectroscopy

We present a single-ended technique for three-dimensional imaging of objects embedded in a turbid medium by the use of time-resolved fluorescence emission or Raman scattering. The technique uses the earliest arriving photons, which we show are not sensitive to the relatively long fluorescence lifetime, and thus can be used to extract the desired spatial information accurately, even at a distance equivalent to 100 mean free paths. The results also demonstrate the feasibility and the potential of one's combining time-resolved optical tomography with fluorescence or Raman spectroscopy to localize and identify the embedded objects. This technique may be valuable for the diagnosis of disease in highly scattering human tissue because it can provide spatial and biochemical information about the composition of embedded lesions.     

Discrimination of bacteria using surface-enhanced Raman spectroscopy

Raman spectroscopy has recently been shown to be a potentially powerful whole-organism fingerprinting technique and is attracting interest within microbial systematics for the rapid identification of bacteria and fungi. However, while the Raman effect is so weak that only approximately 1 in 10(8) incident photons are Raman scattered (so that collection times are in the order of minutes), it can be greatly enhanced (by some 10(3)-10(6)-fold) if the molecules are attached to, or microscopically close to, a suitably roughened surface, a technique known as surface-enhanced Raman scattering (SERS). In this study, SERS, employing an aggregated silver colloid substrate, was used to analyze a collection of clinical bacterial isolates associated with urinary tract infections. While each spectrum took 10 s to collect, to acquire reproducible data, 50 spectra were collected making the spectral acquisition times per bacterium approximately 8 min. The multivariate statistical techniques of discriminant function analysis (DFA) and hierarchical cluster analysis (HCA) were applied in order to group these organisms based on their spectral fingerprints. The resultant ordination plots and dendrograms showed correct groupings for these organisms, including discrimination to strain level for a sample group of Escherichia coli, which was validated by projection of test spectra into DFA and HCA space. We believe this to be the first report showing bacterial discrimination using SERS.     

Strain measurement in diacetylene-containing copolymers using Raman spectroscopy

Rigid diacetylene-containing block copolymers are shown to have Raman spectra similar to those of polydiacetylene single crystals. The vibrational frequencies of certain main-chain Raman-active modes of the copolymers are sensitive to deformation which enables strain measurement to be made by following the shift in the Raman band positions. Measurements of the stress concentrations around defects in copolymer specimens during deformation have been carried out using Raman spectroscopy and they have been compared with theoretical analyses of stress concentrations. There is good agreement between the theoretical and experimental measurements and it has been demonstrated that the use of Raman spectroscopy allows the measurement of stress or strain in complex situations for which no theoretical solutions exist.     

Studying bacterial metabolic states using Raman spectroscopy

Natural metabolic variability expected during characteristic growth phases in batch cultures of Escherichia coli and Staphylococcus epidermidis were studied by Raman spectroscopy. Spectral changes induced by metabolic changes found in the growth phases (i.e., lag, exponential, stationary, and decay) were identified. Maximum intensity of bands assigned to DNA and RNA bases are seen at the beginning of the exponential phase, when cells are metabolically active, and minimum intensities are seen when cells are decaying. High agreement in spectral variation due to growth phases was seen for all the trials that were performed, four growth cycles for E. coli and two for S. epidermidis. Batch cultures were monitored by standard plate counts to identify all growth phases, including decay. Spectral data were analyzed by principal component analysis (PCA) and discriminant analysis to identify similarities and differences and to estimate a classification performance based on growth phases. For the species evaluated, spectra during decay are grouped closer to each other and separated from lag, exponential, and stationary cells. These results suggest that Raman spectroscopy can be used to study metabolic states in bacteria and in particular cell viability.     

Measurement of strains in plain and perforated epoxy models by means of embedded strain gauges

In the embedded strain gauge technique, the use of miniature gauges with very thin copper leads minimises reinforcing effect on the model. The technique. in this form, was applied to the investigation of three–dimensional strain distributions. Suitability of the method was assessed by determining the mechanical properties of epoxy resin from strains measured in cylindrical and rectangular models subjected to uniaxial tension and in a rectangular beam model subjected to pure bending. The central portion of the beam was subsequently perforated with a triangular array of holes to simulate the geometry of a heat exchanger tube plate. Strains in the ligaments were then measured for various ligament efficiencies, with the model under bending and under tension.     

Effect of oxygen plasma treatment of PPTA and PBO fibers on the interfacial properties of single fiber/epoxy composites studied by Raman spectroscopy

The interfacial micromechanics of single poly(p-phenylene terephthalamide (PPTA) and poly(p-phenylene benzobisoxazole (PBO) fibers embedded in an epoxy resin has been investigated by determining the interfacial shear stress distributions along the fiber length. The effects of an oxygen plasma treatment on the interfacial shear stress of the fiber-epoxy systems are analyzed. Raman spectroscopy was used to map the stress distributions along the fiber when the composite is subjected to a small axial tensile strain (3.5% for PPTA and 2.5% for PBO). The quality of the interface or adhesion was improved after the surface treatment, supporting the ability of plasma oxidation to enhance the adhesion of high-performance fibers to epoxy resins. The tensile behavior of fiber-reinforced systems was different in each case. PPTA reinforcements underwent fragmentation, likely by fiber microfailure, whereas debonding or bridging is the most probable fragmentation mechanism in the case of PBO.     

Detection of alkaline phosphatase using surface-enhanced Raman spectroscopy

A new approach was developed to detect the activity of alkaline phosphatase (ALP) enzyme at ultralow concentrations using a surface-enhanced Raman scattering (SERS) technique. The approach is based on the use of gold nanoparticles as a SERS material whereas 5-bromo-4-chloro-3-indolyl phosphate (BCIP) is used as a substrate of ALP. The enzymatic hydrolysis of BCIP led to the formation of indigo dye derivatives, which were found to be highly SERS active. For the first time, we were able to detect ALP at a concentration of approximately 4 x 10(-15) M or at single-molecule levels when ALP was incubated with BCIP for 1 h in the Tris-HCl buffer. The same technique also was successfully employed to detect surface-immobilized avidin, and a detection limit of 10 ng/mL was achieved. This new technique allows the detection of both free and labeled ALP as a Raman probe in enzyme immunoassays, immunoblotting, and DNA hybridization assays at ultralow concentrations.     

Interface stress relaxation in magnesium matrix composites studied by mechanical spectroscopy

Abstract

Mechanical spectroscopy has been used to study magnesium matrix composites reinforced either by long SiC fibres or randomly distributed Al₂O₃ (Saffil) short fibres. It is well known that, in metal matrix composites, thermal stresses can be built up at the interface due to the mismatch between the thermal expansion coefficients of matrix and reinforcements. In magnesium matrix composites, these thermal stresses are relaxed by dislocation motion in the matrix. This mechanism of thermal stress relaxation yields an extra transient component in the mechanical loss spectrum, which depends on the heating/cooling rate and disappears in isothermal condition in the behaviour of the shear modulus G with temperature has been observed during thermal cycling between 100 K and 500 K. The intensity of this phenomenondepends on the spatial distribution of the reinforcements in the matrix. In particular, composites reinforced with long fibres exhibit a more pronounced anomaly. This is interpreted by the modification of the interface strength when temperature is changed.     

Observation of ferroelectric domains in bismuth-layer-structured ferroelectrics using Raman spectroscopy

Raman spectroscopy has been used to investigate the domain structures in bismuth-layered-structured ferroelectrics (BLSFs). In Bi₄Ti₃O₁₂ single crystal, the lowest frequency mode (soft mode) at 30 cm⁻¹ appears exclusively for the xx polarization configuration (xpolar axis). We found that the polarization dependence of the Raman signal exhibits spatial symmetries that reflect the presence of different domain variants present in Bi₄Ti₃O₁₂. This highly anisotropic character of the soft mode shares with other BLSFs such as Bi_3.25La_0.75Ti₃O₁₂ and SrBi₂Ta₂O₉, which demonstrate the usefulness of the soft-mode spectroscopy for the study of ferroelectric domain structures in BLSFs. We also applied Raman spectroscopy to in situ observation of domain structures in Bi₄Ti₃O₁₂ under applied electric field.     

Raman spectroscopy for characterization of interfacial debonds between carbon fibers and polymer matrices

A systematic study on Raman spectroscopy of carbon fibers, both experimental and commercial, has been undertaken. The objectives of this study are to (i) use the Raman spectra of carbon fibers to quantify the degree of chemical bonding and interdiffussion across the fiber–matrix interface, and (ii) to characterize interfacial debonds. Key experimental results include: (i) spectra from the same location of a fiber, repeated thrice, (ii) spectra from three different locations of a particular fiber, (iii) spectra from the same location of a fiber as a function of laser power, and (iv) comparison of the spectra of commercial fibers (AS4), manufactured at Hercules, Inc. (presently Hexel), Magna, with those of the experimental fibers, produced in a more controlled laboratory environment at the Hercules Research Center, Wilmington, DE. In the present investigation, the experimentally determined crystallite size (inversely proportional to the ratio of the relative intensities of the Raman peaks corresponding to the week (A_1g) and strong (E_2g) modes) is correlated to the deformation and stress states in the vicinity of the circumferential tip of a fiber–matrix interfacial debond under the combined mode I/II. The experimental results obtained by means of Raman spectroscopy in combination with a three-dimensional eigenfunction approach can provide a powerful tool for characterization of interfacial debond nucleation and propagation in real-life carbon fiber/polymer matrix composites.     

Evaluation of time-dependent change in fiber stress profiles during long-term pull-out tests at constant loads using Raman spectroscopy

Constant-load pull-out tests were carried out on single-fiber model composite specimens for 500 to 1,000 hours in order to investigate the time-dependent change in fiber axial stress profiles resulting from matrix creep in unidirectional continuous fiber-reinforced composites. Three resins used as the matrix materials, in which single carbon fibers were embedded, were normal epoxy, a blend with a more flexible epoxy, and UV-curable acrylic. The time-dependent change in fiber stress profiles in the constant-load pull-out tests was measured using Raman spectroscopy, and creep and relaxation tests for the matrix resins themselves were performed. It was observed that the normal epoxy matrix composite exhibited only a negligible change in the fiber stress profile with time whereas the flexible epoxy and UV-curable acrylic matrices allowed, respectively, considerable and significant changes. These observations were shown to be consistent with the creep and stress relaxation test results of the matrix resins. It was also found that the time-dependent change in fiber stress was much slower in the experiment than in the prediction based on perfect bonding at the fiber/matrix interface. The interfacial slip that occurred in the composites tested could be responsible for the gradual variation in fiber stress profiles.