Calculation of anisotropic properties of dental enamel from synchrotron data

Obtaining information about the intrinsic structure of polycrystalline materials is of prime importance owing to the anisotropic behaviour of individual crystallites. Grain orientation and its statistical distribution, i.e. the texture, have an important influence on the material properties. Crystallographic orientations play an important role in all kinds of polycrystalline materials such as metallic, geological and biological. Using synchrotron diffraction techniques the texture can be measured with high local and angular resolving power. Here methods are presented which allow the spatial orientation of the crystallites to be determined and information about the anisotropy of mechanical properties, such as elastic modulus or thermal expansion, to obtained. The methods are adapted to all crystal and several sample symmetries as well as to different phases, for example with overlapping diffraction peaks. To demonstrate the abilities of the methods, human dental enamel has been chosen, showing even overlapping diffraction peaks. Likewise it is of special interest to learn more about the orientation and anisotropic properties of dental enamel, since only basic information is available up to now. The texture of enamel has been found to be a tilted fibre texture of high strength (up to 12.5×). The calculated elastic modulus is up to 155 GPa and the thermal expansion up to 22.3 × 10^?6 °C^?1.     

Preferred orientation in powder samples of magnesium and magnesium-cadmium alloys

Cylindrico-symmetrical needle-type texture has been observed in powder samples of magnesium and magnesium-cadmium alloys. Orientation distributions of crystallites determined by measurements of 002 reflexions on texture goniometer can be described by simple analytical expressions. Corrections for preferred orientation applied to measurements on powder diffractometer enable determination of Debye characteristic temperature≡ from the dependence of intensities on diffraction angle. The values of≡ determined after correction from samples with preferred orientation are in agreement with the value of randomly oriented sample.     

Evaluation of enamel crystallites in subsurface lesion by microbeam X‐ray diffraction

Early caries lesion is a demineralization process that takes place in the top 0.1 mm layer of tooth enamel. In this study, X‐ray microbeam diffraction was used to evaluate the hydroxyapatite crystallites in the subsurface lesion of a bovine enamel section and the results are compared with those obtained by transversal microradiography, a method commonly used for evaluation of tooth mineral. Synchrotron radiation from SPring‐8 was used to obtain a microbeam with a diameter of 6 µm. Wide‐angle X‐ray diffraction reports the amount of hydroxyapatite crystals, and small‐angle X‐ray scattering reports that of voids in crystallites. All three methods showed a marked decrease in the enamel density in the subsurface region after demineralization. As these diffraction methods provide structural information in the nanometre range, they are useful for investigating the mechanism of the mineral loss in early caries lesion at a nanometre level.     

Local study of fissure caries by Fourier transform infrared microscopy and X‐ray diffraction using synchrotron radiation

Investigations of intact dental enamel as well as carious‐affected human dental enamel were performed using infrared spectromicroscopy and X‐ray diffraction applying synchrotron radiation. Caries of enamel was shown to be characterized by an increase in the number of deformation and valence vibrations for N—C—O, N—H and C=O bonds, a decrease of the crystallinity index, and by the absence of the preferable orientation of hydroxyapatite crystals within the affected enamel. This indicates the presence of destructive processes in the organic matrix of hard tooth tissues.     

Effect of texture and grain shape on ultrasonic backscattering in polycrystals

An ultrasonic backscattering model is developed for textured polycrystalline materials with orthotropic or trigonal grains of ellipsoidal shape. The model allows us to simulate realistic microstructures and orthotropic macroscopic material textures resulting from thermomechanical processing for a broad variety of material symmetries. The 3-D texture is described by a modified Gaussian orientation distribution function (ODF) of the crystallographic orientation of the grains along the macroscopic texture direction. The preferred texture directions are arbitrary relative to the axes of the ellipsoidal grains. The averaged elastic covariance and the directional anisotropy of the backscattering coefficient are obtained for a wave propagation direction arbitrary relative to the texture and grain elongation directions. One particular application of this analysis is the backscattering solution for cubic crystallites with common textures such as Cube, Goss, Brass and Copper. In our analysis, in the texture-defined coordinates the matrix of elastic constants for cubic crystallites takes the form of orthotropic or trigonal symmetry. Numerical results are presented, discussed and compared to the experimental data available in the literature illustrating the dependence of the backscattering coefficient on texture and grain shape.     

Formation of ⊥c texture of tungsten disulfide thin films with nickel

The formation of ⊥c texture of WS₂ thin films by solid state reaction between the spray deposited WO₃ and gaseous sulfur vapours with Ni interfacial layer has been reported. X-ray diffraction technique has been used to measure the degree of preferred orientation and texture of WS₂ films. Scanning electron microscopy, transmission electron microscopy and atomic force microscopy have been used to characterize the microstructure and morphology. The electronic structure and chemical composition was studied using X-ray photoelectron spectroscopy. The WS₂ films comprise single crystalline quality hexagonal crystallites of 15 μm × 15 μm size with their basal planes parallel to the substrate. The film consists of turbostratic stacking sequence of 2H and 3R polytypes of WS₂. The tungsten-to-sulfur ratio was estimated to be 1:1.8. The various qualitative models used to explain promotional effects are briefly outlined and the plausible underlying mechanism of formation of ⊥c texture with nickel, in this study, is given.     

Study of the growth of fullerene-carbonized epitaxial SiC thin films by synchrotron radiation

 Thin SiC films have been deposited on silicon(0 0 1) substrates by fullerene-carbonization. Using synchrotron radiation X-ray diffraction pole figure measurements have been employed in order to study the texture of the layers. It is qualitatively shown that the films contain epitaxially aligned β-SiC crystallites with the same orientation as the underlying substrate and their twins of first and second order. The orientational spread of the epitaxial crystallites in terms of tilt against and rotation around the substrate normal is smaller than 3°. The formation of twins as a growth defect plays a major role which is even more pronounced at a higher substrate temperature. Furthermore, an additional preferred orientation has been identified which can only be explained by a non-cubic SiC phase. The portion of these crystallites in the film can be considerably reduced by an increase of the deposition temperature. Received: 18 April 1996/Accepted: 12 August 1996     

Goldanskii-Karyagin effect versus preferred orientations (texture)

There are two main contributions influencing the relative line intensities in a hyperfine pattern of a polycrystalline material: 1) Lattice vibrational anisotropy-Goldanskii-Karyagin effect (GKE) and 2) preferred orientation of the crystallites (texture). We present the results of experiments and computer calculations of the line-intensity ratios for various orientation distributions. The two competing effects are hard to distinguish from an experimental point of view, and this evaluation should enable one to appreciate the magnitude of their respective contributions. A variety of textures is selected and discussed: For instance, the interesting case where the GKE and the texture produce the same effect on the relative line intensities. Generally speaking, it seems that in many qualitative discussions of quadrupole line asymmetries the influence of texture is underestimated, especially for small deviations from randomness. Conversely, the asymmetry in the spectra is often explained by making the ad hoc assumption of a GKE without realizing that this would require an unrealistic lattice vibration anisotropy. This work was done in partial fulfillment of the requirement for the degree “Dr. rer. nat.”.     

电沉积铁层晶体结构变化的第一性原理计算

研究了以氯化亚铁为主盐的电镀铁工艺,通过扫描电子显微镜微观形貌分析,铁镀层具有均匀致密结构,铁晶体具有较小的尺寸。通过X射线衍射测试发现,铝基底对铁镀层具有明显的诱导作用,然而随着沉积时间的增加,铁镀层逐渐趋向于Fe（211）晶面择优取向。采用第一性原理计算了不同晶面的表面能,铁晶体不同晶面的表面能依次为Fe（211）＜ Fe（110）＜Fe（200）,这很好地解释了Fe（211）晶面择优取向使体系的整体能量降低,有益于铁镀层的稳定性。     

Carbon ion beam-induced variation in orientation of crystal planes of polycrystalline Zn nanowires

In the present work, polycrystalline Zn nanowires are synthesised within polymeric templates by the electrochemical deposition technique. Free-standing Zn nanowires with diameters 100, 200, 400 nm were synthesised on copper substrate acting as cathode, using this technique. The synthesised nanowires were irradiated with 40 MeV C⁴⁺ ion beam for various fluencies at Inter University Accelerator Centre, New Delhi, India. The effect of carbon ion beam on the grain size and preferred orientation of crystal planes of Zn nanowires were studied. The Rigaku X-ray diffractometer was used for X-ray diffraction (XRD) spectra of pristine and irradiated Zn nanowires. Post irradiation XRD analysis showed variation in the intensity of peaks, indicating the change in the orientation of crystal planes of the material. The preferred orientation of the crystal lattice planes in the polycrystalline material was found using texture analysis. To quantitatively investigate the degree of preferred orientations, the texture coefficients (TC) were calculated. The variation of TC was used to demonstrate the effect of irradiation on preferred orientation.     

X-ray diffraction and IR spectroscopy investigation of synthesized and biogenic nanocrystalline hydroxyapatite

The results of the X-ray diffraction analysis (XRD) and optical (IR) investigations of hydroxyapatite (HAP) produced from the egg-shell of birds and biogenic HAP (a slice of tooth enamel) are presented. The synthesized material is a nanocrystalline hydroxyapatite with an average crystal size ∼35 nm. The outer and inner sides of the tooth enamel slice include HAPs with a different structural organization. The inner side of the tooth slice containing HAP nanocrystals, with an average size of ∼15 nm, demonstrates the most similarity with the synthesized material. Hydroxyapatite of the outer enamel consists of hydroxyapatite with a strong texture organization whose common elements, namely hexagonal prisms, are predominantly oriented along the [001] crystallographic direction. The IR spectra of the tooth enamel (in addition to fundamental HAP vibration modes) revealed the vibration modes of the collagen protein. The comparison of the characteristics of the synthesized and biogenic HAP show that synthesized HAP is a promising candidate for medical applications, e.g., for improving the adhesion properties of dental cement pastes.     

FT‐Raman investigation of human dental enamel surfaces

FT‐Raman spectra of human enamel surfaces from sound, affected (with 1 cavity) and highly affected (with at least 3 cavities) tooth samples were analyzed by principal component analysis (PCA). Major differences between the unaffected and affected tooth samples seem to arise from the structural changes along the c‐axis of hydroxyapatite, the chief crystalline component of human dental enamel. Based on Fisher index calculations, the most discriminative value was obtained for the intensity of the only Raman active ν₂PO₄³⁻ (E₁) symmetric deformation mode at 428 cm⁻¹. Moreover, these changes can be observed through the whole tooth enamel surface, establishing a predisposition to caries correlated to chemical and structural composition of tooth enamel. No spectral changes regarding the CO₃²⁻ substitution were detected by both nondestructive FT‐Raman and FTIR (Fourier transform infrared) spectroscopy of the powdered teeth samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Functional mapping of carious enamel in human teeth with Raman microspectroscopy

We employed Raman microspectroscopy to measure the Raman spectra of phosphate in sound and carious tooth substance. The peak intensity at 960 cm⁻¹ of the phosphate (PO₄³⁻) symmetric stretching vibrational mode (υ₁) in sound enamel was stronger than that of sound dentin, which indicated that sound enamel contained more phosphate than sound dentin. Furthermore, the element analysis of phosphate in sound teeth substance, measured using a scanning electron microscope (SEM) equipped with an energy dispersive X‐ray spectroscope (EDX), gave similar results to those of the Raman measurement. In addition, the border between sound enamel and dentin was clearly demonstrated by mapping the image of the Raman spectrum of phosphate. The mapping image of phosphate in the carious enamel region revealed a heterogeneous low Raman spectrum intensity of phosphate in the area surrounding carious enamel; this finding indicates that phosphate had dissolved from the tooth substance in such areas. In contrast with the decrease in the Raman spectrum intensity of phosphate, the intensity of amide I increased mainly in the low‐phosphate area. Although it remains very difficult to clinically identify the accurate border between sound and carious tooth substance, this distinction may be enabled by using the Raman spectrum of carious tooth substance. Copyright © 2008 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of teeth affected with molar–incisor hypomineralisation

Raman spectroscopy was used to chemically map lesions associated with molar–incisor hypomineralisation in human teeth. Three teeth with hypomineralised lesions of differing severity, described as white, yellow or brown, were mapped using integral ratios of major component bands (hydroxyapatite, amide I and b‐type carbonate) and principal component analysis scores values. These lesions were found to contain depleted levels of mineral (hydroxyapatite) compared with those of healthy enamel. Principal component analysis also highlighted changes in the phosphate structure and variations in various organic constituents. These variations were consistent with increased disorder in the mineral component of the hypomineralised tooth lesions. Scanning electron microscopy–energy dispersive X‐ray spectroscopy supported the findings based on Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

用于YBCO高温超导涂层的立方织构铜基带制备

Cu是制备双轴织构YBCO高温超导涂层的优良基带材料之一,立方织构的铜带可以提供良好的外延生长环境。文中采用轧制辅助双轴织构基带技术(RABiTS),研究了立方织构铜基带的制备工艺。将铜锭在初轧变形量达到88.4%后,进行400℃退火30min,再经二次轧制总变形量达到99.07%后,在氩气环境125—850℃之间不同温度下退火30min。用March-Dollase函数计算该系列样品的r值,其中850℃退火的样品具有最强的200择优取向,r值为0.25,用不完整极图对该样品的织构情况做进一步分析,用ODF函数定量计算了该样品立方织构的体积百分含量。该样品形成了较强的{001}<100>立方织构,体积百分含量为70.8%。     

Elasticity tensor and ultrasonic velocities for anisotropic cubic polycrystal

The orientation distribution of crystallites in a polycrystal can be described by the orientation distribution function (ODF). The ODF can be expanded under the Wigner D-bases. The expanded coefficients in the ODF are called the texture coefficients. In this paper, we use the Clebsch-Gordan expression to derive an explicit expression of the elasticity tensor for an anisotropic cubic polycrystal. The elasticity tensor contains three material constants and nine texture coefficients. In order to measure the nine texture coefficients by ultrasonic wave, we give relations between the nine texture coefficients and ultrasonic propagation velocities. We also give a numerical example to check the relations. Supported by the National Natural Science Foundation of China (Grant Nos. 10562004 and 10662004), the Jiangxi Project to Nature Academic and Technical Leaders in Targeted Areas, and Research Fund for the Doctoral Program of Higher Education (Grant No. 20070403003)     

Applications of Raman Spectroscopy in Dentistry: Analysis of Tooth Structure

Abstract: Tooth enamel is the most mineralized tissue in the human body, and in this article the use of Raman spectroscopy for the analysis of tooth structure, a comparison with synthetic apatites, and use in dentistry are described. Spectral peaks that are related to dental hard and soft tissues are discussed, which provide crucial data in understanding the chemical structural properties of dentin and enamel. The Raman spectrum of dentin confirms the presence of crystalline phosphate-based minerals in dentin. Both dentin and enamel consist of two primary components: an inorganic or mineral phase that closely resembles hydroxyapatite and the Raman spectrum of dentin that confirms the presence of crystalline phosphate-based minerals in dentin. Hence, the mineral phase in dentin and enamel may be characterized essentially as nonstoichiometric substituted apatite. The presence of carbonate (A and B type) incorporated in the hydroxyapatite lattice is also confirmed by the presence of spectral bands. The organic phase, which is mainly composed of type I collagen, is confirmed by the spectral bands of amide I and amide II bands, tryptophan, and phenylalanine. Furthermore, these spectral bands associated with organic and inorganic parts of the enamel and dentin are useful in predicting early formation of carries formation.     

Electromechanical properties of a textured ceramic material in the (1 − <Emphasis Type="Italic">x</Emphasis>)PMN-<Emphasis Type="Italic">x</Emphasis>PT system: Simulation based on the effective-medium method

A complete set of dielectric, piezoelectric, and elastic parameters for the textured ceramic material 0.67PMN-0.33PT is calculated by the self-consistency method with due regard for the anisotropy and piezoelectric activity of the medium. It is shown that the best piezoelectric properties corresponding to those of a single crystal are observed for the ceramic material with a texture in which all crystallites are oriented parallel to the [001] direction of the parent perovskite cubic cell. The simplest models of the polarization of an untextured ceramic material with a random initial orientation of crystallites are considered. The results obtained are compared with experimental data.     

Strain energy effects on the ordering process in diblock styrene-butadiene copolymer

The technique of time-resolved small-angle x-ray scattering is used to monitor the disorder-order transformation occurring in asymmetric, diblock styrene-butadiene. A rapid thermal quench is applied to drive the system from its initial high-temperature disordered state to a low-temperature ordered structure, a body-centered cubic lattice of styrene spheres characterized by a series of concentric Debye rings in the two-dimensional scattering profile. At relatively late times in the microdomain ordering process, the uniform Debye rings were seen to rapidly develop nonuniformities indicating the existence of preferred orientation with a fiber texture, the 110] axis of the bcc structure defining the fiber axis. These results are interpreted in the context of a developing transformation strain energy during the ordering process and shown to be consistent with accompanying changes in lattice spacing as well as earlier observations of apparent fluctuations in the ordering process.     

High-pressure torsion applied to nickel single crystals

Nickel single crystals with different crystallographic orientations were deformed by high-pressure torsion. Special attention is devoted to examining the evolution of the micro-texture and microstructure. The initial crystal orientation was found to have a significant effect on the mechanical hardening and evolution of micro-texture at low and medium equivalent strains, whereas at very high strains no effect of the initial orientation was observed and the behaviour was very similar to a polycrystal. The evolution of micro-texture is in good qualitative agreement with the full constrained Taylor model. At very high equivalent strains the initial crystal orientation has no influence on micro-texture. At such strains, the hardening, the refinement of the structure and the texture reaches a saturation. The final micro-texture is explained by the change from one preferred crystallographic orientation to another.