Wenliang Zhu

On the annealing mechanism in PbWO4 crystals

To elucidate the annealing process in air, optical absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) measurements are conducted in PbWO4 crystals annealed in air at different temperatures. The annealing exhibits a complex phenomenon, but the essence is the exchange of oxygen components between the crystal and environment to modify the intrinsic defects in the crystal. Interstitial oxygen ions are found to play an important role in the process for the influence on the 350 nm absorption band. The mechanism of annealing is discussed in this paper

Raman tensor analysis of ultra-high molecular weight polyethylene and its application to study retrieved hip joint components

The angular dependences of the polarized Raman intensity of A(g), B(1g), B(2g), and B(3g) modes have been preliminary investigated on a model fiber sample of ultra-high molecular weight polyethylene (UHMWPE) in order to retrieve the Raman tensor elements, i.e. the intrinsic parameters governing the vibrational behavior of the orthorhombic structure of polyethylene. Based on this Raman analysis, a method is proposed for determining unknown crystallographic orientation patterns in UHMWPE biomedical components concurrently with the orientation distribution functions for orthorhombic lamellae. An application of the method is shown, in which we quantitatively examined the molecular orientation patterns developed on the surface of four in vivo exposed UHMWPE acetabular cups vs. an unused cup. Interesting findings were: (i) a clear bimodal distribution of orientation angles was observed on worn surfaces; and (ii) a definite and systematic increase in both molecular orientation and crystallinity in main wear zones vs. non-wear zones was found in all retrieved acetabular cups. The present crystallographic analysis is an extension of our previous Raman studies of UHMWPE acetabular cups related to assessments of oxidation and residual strain and suggests a viable path to track back wear-history information from the surface of UHMWPE, thus unfolding the in vivo kinematics of the bearing surfaces in hip joints on the microscopic scale.

Confocal Raman spectroscopic analysis of cross-linked ultra-high molecular weight polyethylene for application in artificial hip joints

Confocal spectroscopic techniques are applied to selected Raman bands to study the microscopic features of acetabular cups made of ultra-high molecular weight polyethylene (UHMWPE) before and after implantation in vivo. The micrometric lateral resolution of a laser beam focused on the polymeric surface (or subsurface) enables a highly resolved visualization of 2-D conformational population patterns, including crystalline, amorphous, orthorhombic phase fractions, and oxidation index. An optimized confocal probe configuration, aided by a computational deconvolution of the optical probe, allows minimization of the probe size along the in-depth direction and a nondestructive evaluation of microstructural properties along the material subsurface. Computational deconvolution is also attempted, based on an experimental assessment of the probe response function of the polyethylene Raman spectrum, according to a defocusing technique. A statistical set of high-resolution microstructural data are collected on a fully 3-D level on gamma-ray irradiated UHMWPE acetabular cups both as-received from the maker and after retrieval from a human body. Microstructural properties reveal significant gradients along the immediate material subsurface and distinct differences are found due to the loading history in vivo, which cannot be revealed by conventional optical spectroscopy. The applicability of the confocal spectroscopic technique is valid beyond the particular retrieval cases examined in this study, and can be easily extended to evaluate in-vitro tested components or to quality control of new polyethylene brands. Confocal Raman spectroscopy may also contribute to rationalize the complex effects of gamma-ray irradiation on the surface of medical grade UHMWPE for total joint replacement and, ultimately, to predict their actual lifetime in vivo.

Stress dependence of the polarized Raman spectrum of polycrystalline lead zirconate titanate

The stress dependence of the Raman spectrum of a relaxor-based polycrystalline ferroelectric lead zirconate titanate–lead nickel niobate–lead zinc niobate (PZT–PNN–PZN) has been investigated using polarized Raman microprobe spectroscopy. Emphasis has been placed on explicitly working out the second harmonic equations that relate Raman intensities to the angle between the laser polarization direction and selected crystalline axes. Based on these assessments, the effect under polarized light of crystal orientation on the intensity of selected Raman modes has been rationalized and the obtained experimental data interpreted. Raman spectra were collected with both parallel and cross polarization filters and their dependence on stress calibrated with loading the PZT–PNN–PZN samples in a four-point flexural jig. The use of polarized light allowed us to clarify the effect of domain orientation on the Raman spectrum of PZT–PNN–PZN and to perform precise calibrations of the stress dependence of the A1(TO4) Raman mo...

Spatially Resolved Stress Analysis in Al2O3/3Y-TZP Multilayered Composite Using Confocal Fluorescence Spectroscopy

Fluorescence piezo-spectroscopy (PS) was applied to evaluate the residual stress fields stored in a multilayered Al2O3/3Y-TZP (3 mol % Y2O3-stabilized ZrO2) composite using the chromophoric fluorescence spectra of Al2O3. The PS results were compared with a theoretical stress distribution in the laminate, calculated according to a repeating unit cell model. However, in practical fluorescence spectroscopy, each measurement point corresponded to a finite volume of material, within which the scattered light experienced fluorescence wavelengths characteristic of the local (weight-average) stress fields. Because of the finite volume of material probed in PS measurements, a comparison between the experimental and calculated values requires that the calculated stresses be convoluted according to the depth-response function of the probe. A pinhole aperture incorporated in the Raman microprobe was used to control the collection probe depth and to modulate the portion of the whole fluorescence emission reaching the detector. According to calibrations of the probe depth and probe response function, probe-convoluted stresses were obtained and a spatially resolved mapping of residual stresses could be obtained.

Methods of piezo-spectroscopic calibration of thin film materials: II. Tensile stress field at indentation crack tip

A new method is reported for determining the piezo-spectroscopic (PS) coefficient of brittle materials using the stress field generated at the tip of a Vickers indentation crack. The method requires a minimum amount of material (e.g., small areas of devices or thin films) and can be applied to both Raman and fluorescence spectra. Applications are shown for sapphire and silicon single-crystalline thin plates as paradigm examples of highly transparent and opaque materials, respectively. The crack opening displacement was preliminarily measured in a field emission scanning electron microscope, and fitted by a recently proposed theory to obtain an in situ estimate of the crack stress intensity factor. Taking advantage of an automated travelling jig, capable of submicrometric lateral displacements, spectral shifts typical of the K-dominated zone (i.e., the zone along the axis of crack propagation) were recorded as a function of distance from the crack tip. To assess the reliability of the indentation method for PS calibration, the interaction between the sample and laser probe was also analysed in detail. A confocal configuration was required in highly transparent materials to reduce the probe depth and convolution error as well. This study confirms the possibility of extending Raman and fluorescence piezo-spectroscopy to the high-resolution quantitative stress analysis of transparent materials.

Silicon Nitride Bioceramics Induce Chemically Driven Lysis in Porphyromonas gingivalis

Organisms of Gram-negative phylum bacteroidetes, Porphyromonas gingivalis, underwent lysis on polished surfaces of silicon nitride (Si3N4) bioceramics. The antibacterial activity of Si3N4 was mainly the result of chemically driven principles. The lytic activity, although not osmotic in nature, was related to the peculiar pH-dependent surface chemistry of Si3N4. A buffering effect via the formation of ammonium ions (NH4(+)) (and their modifications) was experimentally observed by pH microscopy. Lysis was confirmed by conventional fluorescence spectroscopy, and the bacterias metabolism was traced with the aid of in situ Raman microprobe spectroscopy. This latter technique revealed the formation of peroxynitrite within the bacterium itself. Degradation of the bacterias nucleic acid, drastic reduction in phenilalanine, and reduction of lipid concentration were observed due to short-term exposure (6 days) to Si3N4. Altering the surface chemistry of Si3N4 by either chemical etching or thermal oxidation influenced peroxynitrite formation and affected bacteria metabolism in different ways. Exploiting the peculiar surface chemistry of Si3N4 bioceramics could be helpful in counteracting Porphyromonas gingivalis in an alkaline pH environment.

On the role of oxygen vacancies, aliovalent ions and lattice strain in the in vivo wear behavior of alumina hip joints.

We have visualized at the nanometer scale the topological, chemical and mechanical characteristics of long-term in vivo exposed bearing surfaces of femoral heads made of monolithic alumina. Four self-mated alumina retrievals were studied, which were exposed in the human body for relatively long periods of time ranging between 7.7 and 10.7 yrs. Besides conventional morphological features, monitored by atomic force microscopy, the topographic distributions of point defects and lattice strain on the surface of the heads were systematically probed by collecting high spatially and spectrally resolved cathodoluminescence spectra from zones of different wear severity. Three types of optically active point-defect site could be detected: (i) oxygen vacancies; (ii) substitutional (aliovalent) cations; and, (iii) interstitial aluminum cations. These luminescent sites represent the main defects progressively developed in the alumina lattice during exposure in human hip joints. A clear evolution toward (environmentally driven) off-stoichiometry was found with progressing wear. Moreover, the shallow electro-stimulated optical probe also detailed the presence of lattice strain fields (of both elastic and plastic nature) stored in the very neighborhood of the bearing surface. The present spectroscopic characterizations enable substantiating important tribochemical interactions between bearing surfaces and in vivo environment as pivotal parts of progressive events of wear degradation.

Raman tensor elements for wurtzitic GaN and their application to assess crystallographic orientation at film/substrate interfaces

This study is aimed at establishing a method of polarized/confocal Raman spectroscopy capable of quantitatively assessing crystallographic orientation in wurtzitic GaN with a micron-scale resolution. First, Raman selection rules are explicitly put forward from a theoretical viewpoint in their complete form; then, experimentally retrieved intensities of the Raman signal as a function of Euler angles are fitted to the obtained theoretical dependencies in order to quantify a set of Raman tensor elements using experiments on known crystallographic planes of a wurtzitic GaN single-crystal. According to the above two procedures, a spectroscopic algorithm, incorporating the use of Raman tensor elements and Euler angles in tandem, becomes available for estimating unknown crystallographic orientations. As an application of the developed method, a confocal Raman probe was used to non-destructively unfold the relative orientation of a wurtzitic GaN epilayer with respect to (0001)-oriented sapphire substrate. The mic...

Spatially resolved crack-tip stress analysis in semiconductor by cathodoluminescence piezospectroscopy

A spatially resolved cathodoluminescence piezospectroscopic analysis is attempted for the high-resolution evaluation of the stress field developed ahead of the tip of an equilibrium crack propagating in a semiconductor. GaN was selected for this assessment as a paradigm semiconductor material. Quantitative measurements of in-plane luminescence probe response function (PRF) were preliminarily performed at different acceleration voltages upon scanning across a straight and atomically sharp interface between GaN and gold metal. Then, based on the knowledge of PRF, the convoluting effect due to the finite size of the electron probe could be corrected and an improved plot of the crack-tip stress field could be retrieved by a computer-aided data restoration procedure. The crack-tip stress intensity factor KI obtained by the cathodoluminescence piezospectroscopic method was compared with that obtained on the same crack path according to high-resolution measurements of crack-tip opening displacement. This study n...