Preparation and crystallization of Ti53Cu27Ni12Zr3Al7Si3B1 bulk metallic glass with wide supercooled liquid region

Ti-based bulk metallic glass (BMG) alloy with the composition of Ti₅₃Cu₂₇Ni₁₂Zr₃Al₇Si₃B₁ was prepared by copper molder casting method and ribbon sample was prepared by melt spinning to compare. The thermal instability of this glass phase was examined by using differential scanning calorimetry (DSC) and differential thermal analysis (DTA). The results revealed that the supercooled liquid region (ΔT_x), glass transition temperature (T_g) and reduced glass transition temperature (T_g/T_m) of the glassy alloy are detected to be 69, 685 and 0.62 K, respectively. The crystallization behavior of the Ti-based glass phase was also investigated by annealing the glass phase at series temperatures above T_g. The annealed microstructures were examined by means of X-ray diffraction experiments. The crystallization process of the BMG can be characterized by metastable crystalline phases at the first crystallization step and further transition to stable crystalline phases at high temperature through metastable crystalline phase.     

The effect of cooling rate on the wear performance of a ZrCuAlAg bulk metallic glass

In the present work, the local atomic ordering and the wear performance of ZrCuAlAg bulk metallic glass (BMG) samples with different diameters have been studied using transmission electron microscopy (TEM) plus autocorrelation function analysis, and pin-on-disc dry sliding wear experiments. Differential scanning calorimetry and TEM studies show that smaller diameter BMG sample has higher free volume and less local atomic ordering. The wear experiments demonstrate that with the same chemical composition, the smaller BMG sample exhibits higher coefficient of friction, higher wear rate, and rougher worn surface than those of the larger ones. Compared with larger BMG sample, the faster cooling rate of the smaller sample results in looser atomic configuration with more free volume, which facilitates the formation of the shear bands, and thus leads to larger plasticity and lower wear resistance. The results provide more quantitative understanding on the relationship among the cooling rate, the local atomic ordering, and the wear performance of BMGs.     

A new TiCuHfSi bulk metallic glass with potential for biomedical applications

A new Ti_41.3Cu_43.7Hf_13.9Si_1.1 bulk metallic glass (BMG), free of Ni, Al and Be elements, was designed using the proper mixing of binary deep eutectics. The alloy exhibited excellent glass forming ability (GFA) and could be cast into single glassy rod up to 3 mm in diameter by copper mould casting method. The appropriate atomic-size mismatch, the large negative heat of mixing among constituent elements, and the possible formation of glassy HfSiO₄ facilitated its superior GFA. The BMG also showed good mechanical properties with fracture strength of 1685 MPa and Young’s modulus of 95 GPa as well as better corrosion resistance in both NaCl and Hank’s solutions, compared with pure Ti and Ti–6Al–4V alloy. The above results demonstrated that the developed BMG is promising in biomedical applications.     

Mg65Cu25Y10大块金属玻璃的玻璃转变行为与玻璃形成能力

简要回顾了Mg基大块金属玻璃(BMG)的历史,试图揭示其开发进程中所蕴藏的科学思想,以期能够给今后的研究工作带来某些启示;通过对一些实验结果的分析,探讨了Mg65Cu25Y10 BMG的玻璃转变行为与玻璃形成能力(GFA)之间的内在联系,并最终展示合金大的GFA.     

Enhanced glass forming ability of Fe-based alloys with minor additions

Minor Fe and Yof Fe_71.2B₂₄Y_4.8 bulk metallic glass (BMG) are replaced by Ni, Nd, and Ge, respectively, and glass-forming ability (GFA) influenced by these similar element substitutions are studied. Except Ge, Ni and Nd can both improve the critical diameter of base BMG from 2 to 3 mm. Therefore, substitutions with chemical similar elements are more effective on GFA enhancement than those with atom size similar elements.     

Investigation of glass-forming ability,deformation and corrosion behavior of Ni-free Ti-based BMG alloys designed for application as dental implants

We developed new Ti-based bulk metallic glassy (BMG) alloys in Ti–Zr–Pd–Cu–Sn system without Ni element for application as biomaterials. These BMG alloys have a high potential to be applied as metallic biomaterials in various forms, such as melt-spun ribbons and cylindrical rods with a diameter of 4 mm. We also investigated of new Ti-based BMG alloys with higher glass-forming ability (GFA) for medical market as dental implants. These Ti-based BMG alloys do not contain Ni, Al and Be elements which are well known to be harmful for human body. In particular, a rod sample of the Ti_44.1Zr_9.8Pd_9.8Cu_30.38Sn_3.92Nb₂ BMG alloy with a diameter of 3 mm produced by copper mold casting exhibits a compressive strength of 1990 MPa and a Young's modulus of 99 GPa. In addition, the Ti_44.1Zr_9.8Pd_9.8Cu_30.38Sn_3.92Nb₂ BMG shows a large supercooled liquid region of 62 K and a reduced glass-transition temperature, T_rg( = T_g / T_m) of 0.61. The high thermal stability of the supercooled liquid allowed the fabrication of cylindrical rod specimens up to 5 mm in diameter. Thus the studied alloy exhibits high glass-forming ability (GFA) and a large size enough to be used for dental implants. The Ti_44.1Zr_9.8Pd_9.8Cu_30.38Sn_3.92Nb₂ BMG alloy also has a high corrosion resistance and is passivated at the lower passive current density of approximately 10^? 2 A m^? 2, 10^? 3 A m^? 2 and 10^? 2 A m^? 2, in 1 mass% lactic acid, PBS (phosphate-buffered saline without calcium and magnesium salts solution) and HBSS (Hank's balance salt solution without calcium, magnesium and phenol red), respectively, at 310 K, which are lower than those of pure Titanium and Ti–6Al–4V alloy.     

Quaternary Ti–Zr–Be–Ni bulk metallic glasses with large glass-forming ability

The glass-forming ability (GFA) of Ti–Zr–Be ternary alloys is dramatically improved by partially replacing Be with Ni. Centimeter-scale fully amorphous samples can be obtained in a wide Ni content range of 4 at.%–12 at.%. In particular, some of the developed Ti–Zr–Be–Ni alloys exhibit a critical diameter up to 20 mm, which is larger than that of other quaternary Ti-based bulk metallic glasses (BMGs). Moreover, Ni addition also enhances the yield strength and compressive plastic strain of Ti–Zr–Be alloys obviously. Based on the experimental results, the effect of substituting elements addition on the glass-forming ability of Ti–Zr–Be alloys has been systematically investigated and an empirical composition design method for the development of novel Ti-based BMGs with large GFA has been proposed.     

Diffusion bonding of Zr55Cu30Ni5Al10 bulk metallic glass to Cu with Al as transition layer

In this work we demonstrate the diffusion bonding of Zr₅₅Cu₃₀Ni₅Al₁₀ bulk metallic glass (BMG) to aluminum and copper alloy. The process parameters including temperature, pressure and time are investigated experimentally, and we obtain appropriate ones for accomplishing diffusion bonding of the BMG to aluminum alloy successfully. Then we present a two-step diffusion bonding process to bond the BMG to copper alloy by using aluminum alloy as transition layers, and achieve a five-layer bonded joint of BMG/Al/Cu/Al/BMG. The mechanical properties of the multilayer joint are examined. The hardness of the BMG in the joint is enhanced while the bending strength decreases significantly compared with the as-received BMG. Besides, the crystalline metals alleviate and block the extension of cracks in the BMG, which results in the joint fracturing in an explosion-proof glass manner, dissimilar to rupturing in a catastrophic manner that is always happened in the BMGs. Therefore, diffusion bonding of BMG to crystalline metals is a promising way to extend its application.     

Complete Composition Tunability of Cu(Ni)-Ti-Zr Alloys for Bulk Metallic Glass Formation

In the Cu-Zr-Ti ternary system, a new composition zone of bulk metallic glasses (BMGs) formation was discovered, locating at the 55-57 at. Pct Cu, 30-31 at. Pct Ti and 13-14 at. Pct Zr, and near Cu-Ti binary subsystem rather than the Cu-Zr binary. For these alloys, BMG rods of 2 mm in diameter can be fabricated by using copper mould casting. It is expected that these BMG-forming alloys correlate with (L→CuTi+Cu2TiZr+Cu61Zr14) eutectic reaction that the undercooled melt undergoes during solidification. Adopting "3D pinpointing ap-proach", compositional dependence of glass-forming ability (GFA) in Cu(Ni)-Ti-Zr pseudo ternary system was revisited. Optimized BMG-forming composition is located at Cu50.4Ni5.6Ti31Zr13, with a critical diameter of 6 mm for complete BMG formation. Its GFA is significantly superior to Vit 101 (Cu47Ni8Ti34Zr11) previously developed by Caltech group. The effect that the GFA of the ternary base alloy was improved by substitution of Ni for Cu is attributed to a role of retarding the crystallization of Cu51Zr14 intermetallics.     

Photon migration in Raman spectroscopy

Monte Carlo simulation has been applied to study time-resolved Raman and Tyndall photon migration in opaque samples under isotropic and forward scattering conditions. For isotropic scattering, Raman and Tyndall intensities are predicted to decay according to t((1-n)) and t(-n), respectively, where the value of n depends on the ratio of the optical collection aperture to the mean scattering length. The simulation correctly reproduced the analytical results of n = 3/2 and n = 5/2 for a point source in infinite and semi-infinite media, respectively. In addition the model can be used to relate the time at which a Raman photon exits the sample to the mean depth at which it was generated. This could provide a useful tool for depth profiling the chemical composition of turbid systems, and hence be a useful addition to the established array of photon-migration techniques. The model was applied to analyze experimentally observed Raman and Tyndall decay profiles from powdered trans-stilbene. The transport mean free path (l(t)) was calculated to be approximately 400 microm, which was significantly larger than the particle sizes present in the sample (approximately 10-100 microm). This implies that the particles were highly forward scattering, as would be expected for this size range. When highly anisotropic scattering was introduced into the model a much more reasonable scattering length (l(s) approximately 40 microm) was obtained. Finally, a simple analytical model was developed that gives the correct relationship between the Raman and Tyndall decay exponents for isotropic scattering. To the best of our knowledge this work represents the first detailed study of Raman photon migration under time-resolved conditions.     

Fabrication of Porous Bulk Metallic Glass

1. IntroductionBulk metallic glasses (BMGs) exhibit many uniquproperties, including mechanical properties (e.g., higstrength, high elastic deformation, low Young's modulus) , good corrosion resistance and biologic compatibilitas well as homogeneousness in structure[1,2]. But monolithic BMGs fail by shear localization with almost nmacroscopic plastic strain, limiting their use as structuramaterials[3]. However, Conner et al.[4] have compiled extensive literature documenting high bending duct…     

Surface features of Zr-based and Ti-based metallic glasses by ion irradiation

Due to a lack of crystalline structures and grain boundaries, metallic glasses exhibit extremely high strength and superior resistance to corrosion. They are also supposed to be resistant against displacive irradiation due to their inherent disordered structure, thereby are potential candidates for applications in irradiation environments. In this work, the irradiation effects of Zr- and Ti- based bulk metallic glasses (BMGs) under heavy ions irradiation were investigated. The results showed that the Zr-based BMG is more resistant to the Cl ion irradiation with no structural transition and distinct damage subjected to high irradiation fluence. In contrast, the Ti-based BMG exhibits unique damage morphology with respect to the Zr-based BMG and other reported metallic glasses material. Two kinds of damage pits in micrometer scale form on the irradiated surface, and distinct viscous flow takes place. The formation mechanism of the unique irradiation damage feature is discussed.     

类金刚石薄膜的紫外辐照研究

对射频等离子体方法制备的类金刚石（以下简称DLC）薄膜样品进行了紫外辐照，采用电阻率，Raman光谱及红外光谱研究了紫外光（以下简称UV）辐照对DLC薄膜结构与特征的影响，Raman光谱表明：紫外光对DLC薄膜中SP^3C-H键的破坏作用非常明显，红外（IR）光谱结果进一步验证了这一结果，经UV辐照后，DLC薄膜的电阻率呈变小趋势，这说明薄膜被强烈氧化，最后呈现石墨化趋势。     

激光功率对多孔硅微Raman谱的影响

运用微Raman谱仪以不同功率的激光入射到用阳极脉冲腐蚀制备的多孔硅样品以研究多孔硅的稳定性.用斯托克斯与反斯托克斯散射强度的比率确定样品的温度.观察比较不同温度下多孔硅样品的Raman谱趋向,发现在激光功率和样品温度之间的关系曲线上有3个过程,与Raman频移和Raman强度的曲线相一致.所有现象都可以用Si-O键和非晶Si被氧化的机制进行解释.     

Highly controlled surface-enhanced Raman scattering chips using nanoengineered gold blocks

Well defined gold nanostructures of various sizes are fabricated on glass substrates using high-resolution electron-beam lithography/lift-off techniques and detailed surface-enhanced Raman scattering (SERS) properties of crystal violet molecules are studied in order to elucidate electromagnetic (EM) field enhancement effects on the fabricated structures. SERS measurements are performed with high reproducibility using in situ Raman microspectroscopy in aqueous solution. An analysis based on EM theory is performed using field-enhancement factors obtained from finite-difference time-domain (FDTD) simulations and the analysis reproduces experimental results very well. It is noteworthy, furthermore, that the proposed analytic method of EM effects on SERS allows the estimate of the ideal local temperature of gold nanostructures by canceling out the difference in EM field factors at Stokes and anti-Stokes Raman scattering wavelengths. Thus, these experimental results demonstrate that quantitative analysis based on EM theory can be obtained using highly controlled gold nanostructures for SERS measurements with high reproducibility, a result that is promising for the construction of a SERS analysis chip. Although no SERS chip reported so far has been usable for quantitative analysis, this study opens the door for construction of a quantitative SERS chip.     

Fabricating Au–Ag core-shell composite films for surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) integrates high levels of sensitivity with spectroscopic precision, and thus, has tremendous potential for chemical and biomolecular sensing. The key to the wider application of Raman spectroscopy using roughened metallic surfaces is the development of highly enhancing substrates for analytical purposes, i.e., for better detection sensitivity of trace contaminants and pollutants. Here, we have prepared Au, Ag, AuAg multilayer, and Au@Ag films on glass substrates for SERS-active substrates. The Au@Ag film shows a much stronger SERS signal for trans-bis(4-pyridyl)ethylene (BPE) molecules than those from pure Au, Ag, and AuAg films, indicating the Au@Ag film is more powerful than pure Au, Ag, and AuAg film as SERS active substrates. The enhanced surface Raman scattering signals were attributed to the local field enhancement in the core-shell structure.     

Near-Field Surface-Enhanced Raman Imaging of Dye-Labeled DNA with 100-nm Resolution

Raman chemical imaging on a scale of 100 nm is demonstrated for the first time. This is made possible by the combination of scanning near-field optical microscopy (SNOM or NSOM) and surface-enhanced Raman scattering (SERS), using brilliant cresyl blue (BCB)-labeled DNA as a sample. SERS substrates were produced by evaporating silver layers on Teflon nanospheres. The near-field SERS spectra were measured with an exposure time of 60 s and yielded good signal-to-noise ratios (25:1). The distinction between reflected light from the excitation laser and Raman scattered light allows the local sample reflectivity to be separated from the signal of the adsorbed DNA molecules. This is of general importance to correct for topographic coupling that often occurs in near-field optical imaging. The presented data show a lateral dependence of the Raman signals that points to special surface sites with particularly high SERS enhancement.     

Nanophotonic crescent moon structures with sharp edge for ultrasensitive biomolecular detection by local electromagnetic field enhancement effect

We present novel gold nanophotonic crescent moon structures with a sub-10 nm sharp edge, which can enhance local electromagnetic field at the edge area. The formation of unconventional nanophotonic crescent moon structure is accomplished by using a sacrificial nanosphere template and conventional thin film deposition method, which allows an effective batch nanofabrication and precise controls of nanostructure shapes. Unique multiple scattering peaks are observed in a single gold nanocrescent moon with dark-field white light illumination. A 785 nm near-infrared (NIR) diode laser was used as the excitation source to induce the amplified scattering field on the sharp edge of the single gold nanocrescent moon. The Raman scattering spectrum of Rhodamine 6G molecules adsorbed on the single gold nanocrescent moon are characterized, and the Raman enhancement factor of single gold nanocrescent moon is estimated larger than 10(10), which suggests the potential applications of gold nanocrescent moons in ultrasensitive biomolecular detection and cellular imaging using surface enhanced Raman spectroscopy.     

Comparing single-walled carbon nanotubes and samarium oxide as strain sensors for model glass-fibre/epoxy composites

The study of the interfacial stress transfer for glass fibres in polymer composites through the fragmentation test requires certain assumptions, such as a constant interfacial shear stress. In order to map the local interfacial properties of a composite, both Raman spectroscopy and luminescence spectroscopy have been independently used. Unlike other polymer fibre composites, the local strain state of a glass fibre cannot be obtained using Raman spectroscopy, since only very broad and weak peaks are obtainable. This study shows that when single-walled carbon nanotubes (SWNTs) are added to the silane sizing as a strain sensor, it becomes possible to map the local fibre strain in glass fibres using Raman spectroscopy. Moreover, if this model glass fibre contains a small amount of Sm₂O₃, as one of the components, luminescence spectroscopy can be simultaneously used to confirm this local fibre strain. A combined micromechanical properties study of stress transfer at the fibre–matrix interface using luminescence spectroscopy, together with Raman spectroscopy, is therefore reported. The local strain behaviour of both Sm³⁺ doped glass and SWNTs in the silane coating are shown to be consistent with a shear-lag model. This indicates that Sm³⁺ dopants and SWNTs are excellent sensors for the local deformation of glass fibre composites.     

Detection of nano-oxidation sites on the surface of hemoglobin crystals using tip-enhanced Raman scattering

Hemoglobin nanocrystals were analyzed with tip-enhanced Raman scattering (TERS), surface-enhanced resonance Raman scattering (SERRS) and conventional resonance Raman scattering (RRS) using 532 nm excitation. The extremely high spatial resolution of TERS enables selective enhancement of heme, protein, and amino acid bands from the crystal surface not observed in the SERRS or RRS spectra. Two bands appearing at 1378 and 1355 cm(-1) assigned to the ferric and ferrous oxidation state marker bands, respectively, were observed in both TERS and SERRS spectra but not in the RRS spectrum of the bulk sample. The results indicate that nanoscale oxidation changes are occurring at the hemoglobin crystal surface. These changes could be explained by oxygen exchange at the crystal surface and demonstrate the potential of the TERS technique to obtain structural information not possible with conventional Raman microscopy.