Non-Destructive Evaluation of Defects and Damage in Composite Materials and Structures

The mechanical behaviour of composite materials differs from that of conventional structural materials owing to their heterogeneous and anisotropic nature. Different types of defects and anomalies get induced in these materials during the fabrication process. Further, during their service life, the components made of composite materials develop different types of damage. The performance and life of such components is governed by the combined effect of all these defects and damage. While porosity, voids, inclusions etc., are some defects those can get induced during the fabrication of composites, matrix cracks, interface debonds, delaminations and fiber breakage are major types of service induced damage which are of concern. During the service life of components made of composites, one type of damage can grow and initiate another type of damage. For example, matrix cracks can gradually grow to the interface and initiate debonds. Interface debonds in a particular plane can lead to delaminations. Consequently, the combined effect of different types of distributed damage causes the failure of the component. A set of non-destructive evaluation (NDE) methods is well established for testing conventional metallic materials. Some of them can also be utilized for composite materials as they are, and in some cases with a little different approach or modification. Ultrasonics, Radiography, Thermography, Fiber Optics, Acoustic Emision Techniques etc., to name a few. Detection, evaluation and characterization of different types of defects and damage encountered in composite materials and structures using different NDE tools is discussed briefly in this paper.

Microstructure-Wear Resistance Correlation and Wear Mechanisms of Spark Plasma Sintered Cu-Pb Nanocomposites

The dispersion of a softer phase in a metallic matrix reduces the coefficient of friction (COF), often at the expense of an increased wear rate at the tribological contact. To address this issue, unlubricated fretting wear tests were performed on spark plasma sintered Cu-Pb nanocomposites against bearing steel. The sintering temperature and the Pb content as well as the fretting parameters were judiciously selected and varied to investigate the role of microstructure (grain size, second-phase content) on the wear resistance properties of Cu-Pb nanocomposites. A combination of the lowest wear rate (similar to 1.5 x 10(-6) mm(3)/Nm) and a modest COF (similar to 0.4) was achieved for Cu-15 wt pct Pb nanocomposites. The lower wear rate of Cu-Pb nanocomposites with respect to unreinforced Cu is attributed to high hardness (similar to 2 to 3.5 GPa) of the matrix, Cu2O/Fe2O3-rich oxide layer formation at tribological interface, and exuding of softer Pb particles. The wear properties are discussed in reference to the characteristics of transfer layer on worn surface as well as subsurface damage probed using focused ion beam microscopy. Interestingly, the flash temperature has been found to have insignificant effect on the observed oxidative wear, and alternative mechanisms are proposed. Importantly, the wear resistance properties of the nanocomposites reveal a weak Hall-Petch-like relationship with grain size of nanocrystalline Cu. (C) The Minerals, Metals & Materials Society and ASM International 2013

Direct Characterizing of Densification Mechanisms during Spark Plasma Sintering

Spark plasma sintering (SPS) is a convenient and rapid means of producing dense ceramic compacts. However, the mechanisms responsible for rapid densification have not been identified satisfactorily, with different studies using an indirect approach yielding varied values for the densification parameters. This study involved SPS in high purity nanocrystalline alumina with temperatures ranging from 1173 to 1423K and stresses from 25 to 100MPa. A direct approach, with analyses at a constant density, revealed a stress exponent of similar to 1 and an inverse grain size dependence of similar to 3, consistent with Coble creep process. Whereas the direct approach gives a stress exponent of similar to 1, the indirect approach used previously gives stress exponents ranging from similar to 2.2 to 3.5 with the same data, thereby revealing potentially spurious values of the densification parameters from conventional indirect approaches to characterizing densification. The rapid densification during SPS is related to the finer grain sizes retained with the rapid heating rates and the imposed stress that enhances the driving force for densification.

In vitro/In vivo assessment and mechanisms of toxicity of bioceramic materials and its wear particulates

With the progress in modern technological research, novel biomaterials are being largely developed for various biomedical applications. Over the past two decades, most of the research focuses on the development of a new generation of bioceramics as substitutes for hard tissue replacement. In reference to their application in different anatomical locations of a patient, newly developed bioceramic materials can potentially induce a toxic/harmful effect to the host tissues. Therefore, prior to clinical testing, relevant biochemical screening assays are to be performed at the cellular and molecular level, to address the issues of biocompatibility and long term performance of the implants. Along with testing strategies in the bulk material toxicity, a detailed evaluation should also be conducted to determine the toxicity of the wear products of the potential bioceramics. This is important as the bioceramics are intended to be implanted in patients with longer life expectancy and notwithstanding, the material will eventually release finer (mostly nanosized) sized debris particles due to continuous wear at articulating surfaces in the hostile corrosive environment of the human body. The wear particulates generated from a biocompatible bioceramic may act in a different way, inducing early/late aseptic loosening at the implant site, resulting in osteolysis and inflammation. Hence, a study on the chronic effects of the wear particulates, in terms of local and systemic toxicity becomes the major criteria in the toxicity evaluation of implantable bioceramics. In this broad perspective, this article summarizes some of the currently used techniques and knowledge in assessing the in vitro and in vivo cytotoxicity and genotoxicity of bioceramic implant materials. It also addresses the need to conduct a broad evaluation before claiming the biocompatibility and clinical feasibility of any new biomaterial. This review also emphasizes some of the case studies based on the experimental designs that are currently followed and its importance in the context of clinical applications.

Photophysical, electrochemical and solid state properties of diketopyrrolopyrrole based molecular materials: importance of the donor group

Diketopyrrolopyrrole (DPP) based molecular semiconductors have emerged as promising materials for high performance active layers in organic solar cells. It is imperative to comprehend the origin of such a property by investigating the fundamental structure property correlation. In this report we have investigated the role of the donor group in DPP based donor-acceptor- donor (D-A-D) structure to govern the solid state, photophysical and electrochemical properties. We have prepared three derivatives of DPP with varying strengths of the donor groups, such as phenyl (PDPP-Hex), thiophene (TDPP-Hex) and selenophene (SeDPP-Hex). The influence of the donor units on the solid state packing was studied by single crystal X-ray diffraction. The photophysical, electrochemical and density functional theory ( DFT) results were combined to elucidate the structural and electronic properties of three DPP derivatives. We found that these DPP derivatives crystallized in the monoclinic space group P21/c and show herringbone packing in the crystal lattice. The derivatives exhibit weak p-p stacking interactions as two neighboring molecules slip away from each other with varied torsional angles at the donor units. The high torsional angle of 32 degrees ( PDPP-Hex) between the phenyl and lactam ring results in weak intramolecular interactions between the donor and acceptor, while TDPP-Hex and SeDPP-Hex show lower torsional angles of 9 degrees and 12 degrees with a strong overlap between the donor and acceptor units. The photophysical properties reveal that PDPP-Hex exhibits a high Stokes shift of 0.32 eV and SeDPP- Hex shows a high molar absorption co-efficient of 33 600 L mol -1 1 cm -1 1 with a low band gap of similar to 2.2 eV. The electrochemical studies of SeDPP- Hex indicate the pronounced effect of selenium in stabilizing the LUMO energy levels and this further emphasizes the importance of chalcogens in developing new n-type organic semiconductors for optoelectronic devices.

Mechanical and thermal modeling of In-Cu composites for thermal interface materials applications

In-Cu composite solders have been proposed as an effective thermal interface material. Here, finite element analysis and theoretical treatment of their mechanical and thermal behavior is presented. It was determined that the stresses and the strains were concentrated in the narrow and wider In channels, respectively. Furthermore, it is suggested that an In-Cu composite with disk-shaped Cu inclusions may not only further improve the thermal conductivity but may also reduce the stiffness of In-Cu composites in shear.

C. N. R. Rao and the Growth of Solid State and Materials Chemistry as a Central Domain of Research

In celebrating Professor C. N. R. Rao's 80th birthday, this article recalls his singular contributions to solid state and materials chemistry for about sixty years. In so doing, the article also traces the growth of the field as a central domain of research in chemical sciences from its early origins in Europe. Although Rao's major work lies in solid state and materials chemistry - a field which he started and nurtured in India while its importance was being recognized internationally - his contributions to other areas of chemistry (and physics), viz., molecular spectroscopy, phase transitions, fullerenes, graphene, nanomaterials and multiferroics are equally significant. Illustrative examples of his work devoted to rare earth and transition metal oxides, defects and nonstoichiometry, metal-insulator transitions, investigation of crystal and electronic structures of a variety of solids by means of electron microscopies and photoelectron spectroscopy, superconducting cuprates, magnetoresistive manganites, multiferroic metal oxides of various structures and, last but not the least, development of new strategies for chemical synthesis of a wide variety of solids including nanomaterials and framework solids in different dimensionalities, are highlighted. The article also captures his exemplary role as a science teacher, science educationist and institution builder in post-Independence India.

Raman spectroscopy explores molecular structural signatures of hidden materials in depth: Universal Multiple Angle Raman Spectroscopy

Non-invasive 3D imaging in materials and medical research involves methodologies such as X-ray imaging, MRI, fluorescence and optical coherence tomography, NIR absorption imaging, etc., providing global morphological/density/absorption changes of the hidden components. However, molecular information of such buried materials has been elusive. In this article we demonstrate observation of molecular structural information of materials hidden/buried in depth using Raman scattering. Typically, Raman spectroscopic observations are made at fixed collection angles, such as, 906, 1356, and 1806, except in spatially offset Raman scattering (SORS) (only back scattering based collection of photons) and transmission techniques. Such specific collection angles restrict the observations of Raman signals either from or near the surface of the materials. Universal Multiple Angle Raman Spectroscopy (UMARS) presented here employs the principle of (a) penetration depth of photons and then diffuse propagation through non-absorbing media by multiple scattering and (b) detection of signals from all the observable angles.

Detailed understanding of the excitation-intensity dependent photoluminescence of ZnO materials: Role of defects

The photoluminescence (PL) of ZnO is shown to be dependent on the excitation intensity (EI) of the laser, and the substantial shift observed in the band to band transition is attributed to the heating effect. In order to understand this phenomenon in detail, we investigate the EI dependent PL of various ZnO samples systematically from liquid nitrogen (LN) to room temperature by varying the laser power. Some of the samples exhibit substantial red shift in the band to band transition with increasing EI even in LN environment, negligible effect is observed for others. Hence, our results strongly suggest that the EI dependent PL is not a characteristic of all ZnO samples. This indicates that laser-induced heating effect is not the dominant factor that governs the shifts in the PL spectra. Rather, the defect level excitation accounts for such observation. (C) 2014 AIP Publishing LLC.

Effect of Post-Deposition Annealing on the Al2O3/Si(100) Interface Properties

In the present investigation, Al2O3 thin films were deposited onto Si < 100 > substrates by DC reactive magnetron sputtering. The films were annealed in vacuum for one hour at 623, 823 and 1023 K. The composition of the films was quantitatively estimated using X-ray photoelectron spectroscopy (XPS) and the O/Al ratio was found be in the range 1.19 to 1.43. Grazing incidence X-ray diffraction (GIXRD) results revealed that the annealed films are amorphous in nature. Cross sectional transmission electron microscopy (X-TEM) analysis was carried out to study the microstructure and nature of the Al2O3-Si interface as a function of post-deposition annealing. TEM results revealed the presence of nanocrystalline gamma-Al2O3 in the annealed films and an amorphous interface layer was observed at the Al2O3 Si interface. The thickness of the amorphous interface layer was determined from the TEM analysis and the results are discussed.

Generalized scaling of misorientation angle distributions at meso-scale in deformed materials

Scaling behaviour has been observed at mesoscopic level irrespective of crystal structure, type of boundary and operative micro-mechanisms like slip and twinning. The presence of scaling at the meso-scale accompanied with that at the nano-scale clearly demonstrates the intrinsic spanning for different deformation processes and a true universal nature of scaling. The origin of a 1/2 power law in deformation of crystalline materials in terms of misorientation proportional to square root of strain is attributed to importance of interfaces in deformation processes. It is proposed that materials existing in three dimensional Euclidean spaces accommodate plastic deformation by one dimensional dislocations and their interaction with two dimensional interfaces at different length scales. This gives rise to a 1/2 power law scaling in materials. This intrinsic relationship can be incorporated in crystal plasticity models that aim to span different length and time scales to predict the deformation response of crystalline materials accurately.

New columnar liquid crystal materials based on luminescent 2-methoxy-3-cyanopyridines

A new series of donor-acceptor-donor (D-A-D) type luminescent mesogens carrying 2-methoxy-3-cyanopyridine as a central core linked with variable alkoxy chain lengths (m = 6 and 8) as terminal substituents was synthesized and characterized using spectral methods. The newly synthesized molecules were subjected to single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), differential scanning calorimetric (DSC), polarizing optical microscopy (POM), and fluorescence emission studies in order to ascertain their mesogenic and photophysical properties. The SCXRD data on 4a and 4b reveal that the presence of short intermolecular contacts, viz. C-H center dot center dot center dot N, C-H center dot center dot center dot O, C-H center dot center dot center dot pi, and pi center dot center dot center dot pi interactions, is responsible for their crystal packing. The measured torsion angle values indicate that molecules possess distorted non-planar structure. The DSC, POM, and PXRD studies confirm that all the molecules show thermotropic liquid crystalline behaviour and exhibit rectangular columnar phase. Further, their UV-visible and fluorescence spectral studies reveal that the target molecules are luminescent displaying a strong absorption band in the range of 335-340 nm and a blue fluorescence emission band in the range of 395-425 nm (both in solution and film state) with good fluorescence quantum yields (10-49 %).

Electromagnetic Interference Shielding Materials Derived from Gelation of Multiwall Carbon Nanotubes in Polystyrene/Poly(methyl methacrylate) Blends

Blends of polystyrene (PS) and poly(methyl methacrylate) (PMMA) with different surface-functionalized multiwall carbon nanotubes (MWNTs) were prepared by solution blending to design materials with tunable EMI (electromagnetic interference) shielding. Different MWNTs like pristine, amine (similar to NH2), and carboxyl acid (similar to COOH) functionalized were incorporated in the polymer by solution blending. The specific interaction driven localization of MWNTs in the blend during annealing was monitored using contact mode AFM (atomic force microscopy) on thin films. Surface composition of the phase separated blends was further evaluated using X-ray photoelectron spectroscopy (XPS). The localization of MWNTs in a given phase in the bulk was further supported by selective dissolution experiments. Solution-casted PS/PMMA (50/50, wt/wt) blend exhibited a cocontinuous morphology on annealing for 30 min, whereas on longer annealing times it coarsened into matrix-droplet type of morphology. Interestingly, both pristine MWNTs and NH2-MWNTs resulted in interconnected structures of PMMA in PS matrix upon annealing, whereas COOH-MWNTs were localized in the PMMA droplets. Room-temperature electrical conductivity and electromagnetic shielding effectiveness (SE) were measured in a broad range of frequency. It was observed that both electrical conductivity and SE were strongly contingent on the type of surface functional groups on the MWNTs. The thermal conductivity of the blends was measured with laser flash technique at different temperatures. Interestingly, the SE for blends with pristine and NH2-MWNTs was >-24 dB at room temperature, which is commercially important, and with very marginal variation in thermal conductivity in the temperature range of 303-343 K. The gelation of MWNTs in the blends resulted in a higher SE than those obtained using the composites.

Organic white-light emitting materials

Full-color emissive organic materials have attracted significant attention in recent years as key components in display and lighting devices based on OLEDs. An ideal white-light emitter demands simultaneous emission of red, green and blue with nearly similar distribution of intensities covering the entire region of visible spectra. However, the design of such white-light emitters is not straightforward. Mixing several emitters is seldom successful owing to the negative effects of intermolecular interactions and energy transfer processes. Nonetheless, these fundamental questions have been addressed in recent times by several research groups of vastly different expertise leading to a considerable progress in the field of organic white-light emitters. The designs cover a large area of the chemistry ranging from frustrated energy transfer to simple protonation or from designed self-assembly to simple mixing of materials. In this review, the concepts and rational approaches underlying the design of white-light emissive organic materials are described. (C) 2014 Elsevier Ltd. All rights reserved.

Electron microscopy of Ag-(Ni-O) core-shell nanowires

This report provides information about an electrodeposition based two-step synthesis methodology for producing core-shell Ag-(Ni-O) nanowires and their detailed structural and compositional characterization using electron microscopy technique. Nanowires were produced by employing anodic alumina templates with a pore diameter of 200 nm. In the first step of the synthesis process, nanocrystalline Ni-O was electrodeposited in a controlled manner such that it heterogeneously nucleated and grew only on the template pore walls without filling the pores from bottom upwards. This alumina template with pore walls coated with Ni-O was then utilized as a template during the electrodeposition of Ag in the second step. Electrodeposited Ag filled the template pores to finally produce Ag-(Ni-O) core-shell nanowires with an overall diameter of 200 nm.