大尺寸La2O3-TiO2-ZrO2非晶塑性烧结行为

La₂O₃-TiO₂-ZrO₂玻璃具有很高的折射率, 在镜头材料和上转换发光基质材料等领域表现出良好的应用前景, 但其玻璃形成能力低, 通常只能采用快速冷却的方法制备, 因此难以获得大尺寸材料。为了获得大尺寸La₂O₃-TiO₂-ZrO₂玻璃, 本研究采用La₂O₃-TiO₂-ZrO₂非晶粉末为原料, 利用非晶在玻璃转变温度以上的塑性行为, 在温度动力学窗口ΔT内进行热压烧结制备了大尺寸La₂O₃-TiO₂-ZrO₂玻璃, 在保持非晶的前提下实现了La₂O₃-TiO₂-ZrO₂粉末的完全致密化。采用SEM、XRD等方法研究了样品的显微结构和相组成。研究发现, 当烧结温度高于910 ℃时, 烧结过程中会析出La₄Ti₉O₂₄晶相; 当烧结温度低于900 ℃时, 样品保持良好的非晶性, 并随着烧结温度的增加, 样品的致密度有所升高。烧结压力也会影响烧结过程, 样品的致密度随着烧结压力升高而增加。大尺寸La₂O₃-TiO₂-ZrO₂非晶材料具有很高的折射率, 在587.6 nm处折射率可达到2.33。在La₂O₃-TiO₂-ZrO₂非晶粉末烧结过程中, 塑性流动是其主要的传质机理。     

Improved electrochemical performance of amorphous MnO2 modified by a novel supermolecular compound

A novel modification treatment to improve the electrochemical performance of amorphous, nano-sized MnO₂ is proposed in this paper. An “in situ polymerization reaction” method was employed to obtain the MPz(dtn)₄ or PMPzS₈–MnO₂ composition material. TG, IR, XRD and TEM methods were adopted for material characterization. The experimental results reveal that the amorphous nature and small particle size (10–20 nm) of the parent MnO₂ material can be preserved after MPz(dtn)₄ or PMPzS₈ modification treatment. Galvanostatic charge and discharge was carried out to test the electrochemical property of the resulting material. It indicates that all modified products show an improved electrochemical performance comparing with their parent MnO₂ phase as being reflected by the higher capacity and enhanced cycle life. To investigate the mechanism for improved electrochemical performance, ac impedance technique was employed. Preliminary results suggest that the capacity and the cycleability of the composition material are improved in some degree which may be ascribed to the increasing of intercalation/deintercalation from inter-granular modified compounds.     

Liquid-liquid phase transition in supercooled silicon

Silicon in its liquid and amorphous forms occupies a unique position among amorphous materials. Obviously important in its own right, the amorphous form is structurally close to the group of 4-4, 3-5 and 2-6 amorphous semiconductors that have been found to have interesting pressure-induced semiconductor-to-metal phase transitions. On the other hand, its liquid form has much in common, thermodynamically, with water and other 'tetrahedral network' liquids that show density maxima. Proper study of the 'liquid-amorphous transition', documented for non-crystalline silicon by both experimental and computer simulation studies, may therefore also shed light on phase behaviour in these related materials. Here, we provide detailed and unambiguous simulation evidence that the transition in supercooled liquid silicon, in the Stillinger-Weber potential, is thermodynamically of first order and indeed occurs between two liquid states, as originally predicted by Aptekar. In addition we present evidence to support the relevance of spinodal divergences near such a transition, and the prediction that the transition marks a change in the liquid dynamic character from that of a fragile liquid to that of a strong liquid.     

Effects of oxidation on surface stresses and mechanical properties of liquid phase pressureless-sintered SiC–AlN–Y2O3 ceramics

The understanding of the oxidation mechanism of 50 wt% SiC–50 wt% AlN composites obtained by means of pressureless sintering without the protective powder bed and with Y₂O₃ as sintering-aid were significantly improved by means of Raman spectroscopy. These analyses put in evidence that “amorphous carbon” started to be formed at 1300 °C as main effect of active oxidation of SiC. At higher temperature the crystallization process began and it was completed at 1500 °C when only graphite could be recognized. On the basis of these new evidences, oxidation effects on the mechanical properties of SiC–AlN–Y₂O₃ composites were defined. First of all, heat treatment in air was able to induce a compressive surface stress due to the volume gain associated to the oxidation of the intergranular phase. As a consequence apparent fracture toughness showed a value of 6.6 MPa m^1/2 after a heat treatment at 1300 °C, while at higher temperature effects of active oxidation caused a decreasing up to 4.7 MPa m^1/2. This toughening mechanism was also used to improve the resistance to thermal shock, which was evaluated by performing quenching tests. Furthermore, passive oxidation induced the healing of superficial flaws by means of the formation of -cristobalite. This phenomenon was assumed to be responsible for the increasing of the flexural strength.     

Revealing the Origins of Mechanically Induced Fluorescence Changes in Organic Molecular Crystals

Mechanofluorochromic molecular materials display a change in fluorescence color through mechanical stress. Complex structure–property relationships in both the crystalline and amorphous phases of these materials govern both the presence and strength of this behavior, which is usually deemed the result of a mechanically induced phase transition. However, the precise nature of the emitting species in each phase is often a matter of speculation, resulting from experimental data that are difficult to interpret, and a lack of an acceptable theoretical model capable of capturing complex environmental effects. With a combined strategy using sophisticated experimental techniques and a new theoretical approach, here the varied mechanofluorochromic behavior of a series of difluoroboron diketonates is shown to be driven by the formation of low‐energy exciton traps in the amorphous phase, with a limited number of traps giving rise to the full change in fluorescence color. The results highlight intrinsic structural links between crystalline and amorphous phases, and how these may be exploited for further development of powerful mechanofluorochromic assemblies, in line with modern crystal engineering approaches.     

Pressure-induced amorphization and polyamorphism: Inorganic and biochemical systems

Pressure-induced amorphization (PIA) is a phenomenon that involves an abrupt transition between a crystalline material and an amorphous solid through application of pressure at temperatures well below the melting point or glass transition range. Amorphous states can be produced by PIA for substances that do not normally form glasses by thermal quenching. It was first reported for ice I_h in 1984 following prediction of a metastable melting event associated with the negative initial melting slope observed for that material. The unusual phenomenon attracted intense interest and by the early 1990s PIA had been reported to occur among a wide range of elements and compounds. However, with the advent of powerful experimental techniques including high resolution synchrotron X-ray and neutron scattering combined with more precise control over the pressurization environment, closer examination showed that some of the effects previously reported as PIA were likely due to formation of nanocrystals, or even that PIA was completely bypassed during examination of single crystals or materials treated under more hydrostatic compression conditions. Now it is important to understand these results together with related discussions of polyamorphic behavior to gain better understanding and control over these metastable transformations occurring in the low temperature range where structural relaxation and equilibration processes are severely constrained. The results will lead to useful new high-density amorphous materials or nanocrystalline composites containing metastable crystalline varieties and the experiments have driven new theoretical approaches to modeling the phenomena. Here we review the incidence and current understanding of PIA along with related phenomena of density- and entropy-driven liquid–liquid phase transitions (LLPT) and polyamorphism. We extend the discussion to include polymeric macromolecules and biologically-related materials, where the phenomena can be correlated with reversible vs irreversible unfolding and other metastable structural transformations.     

Amorphous silicon exhibits a glass transition

Amorphous silicon is a semiconductor with a lower density than the metallic silicon liquid. It is widely believed that the amorphous-liquid transition is a first-order melting transition. In contrast to this, recent computer simulations and the experimental observation of pressure-induced amorphization of nanoporous silicon have revived the idea of an underlying liquid-liquid phase transition implying the existence of a low-density liquid and its glass transition to the amorphous solid. Here we demonstrate that during irradiation with high-energy heavy ions amorphous silicon deforms plastically in the same way as conventional glasses. This behaviour provides experimental evidence for the existence of the low-density liquid. The glass transition temperature for a timescale of 10 picoseconds is estimated to be about 1,000 K. Our results support the idea of liquid polymorphism as a general phenomenon in tetrahedral networks.     

Dynamics and mechanics below the glass transition: The non-equilibrium state

There is much interest in the dynamics of glass-forming systems above the glass transition temperature. However, in many applications the behavior of the systems needs to be understood in the glass-transition T_g range and particularly in the non-equilibrium state. We present a set of empirical observations for the dynamics of material behaviors near to, but below the glass transition for polymer glass formers and outline a “minimal” set of requirements that might be expected of computer simulations in the non-equilibrium glass near to T_g. The survey includes the kinetics and nonlinearity of the structural (volume or enthalpy) recovery of the glass and its impact on the mechanical response (physical aging). These are presented with the thought that computer simulations may well be able to provide insights to the origins of an extremely complicated set of experimental observations.

Additionally, we present some results of glass formation of simple liquids constrained to nanometer size pores with the expectation that such experiments may be readily simulated because of the small number of molecules in such pores.     

Critical optimization

Critical optimization is a remarkable recently discovered thin film deposition phenomenon. Its extraordinary reproducibility, its applicability to an extremely wide range of properties and materials, its really accurate (and theoretically explicable) correlation with a simple fundamental property of the materials, and its ability to predict and explain technologically important property optima make it perhaps unique in thin film science. We here present a review, discussing both what is known and what remains to be done; we also propose a possible new mechanism, involving a connection with the “ideal amorphous state”, and point out that critical optimization could be applicable to deposition methods other than the presently considered vacuum evaporation and sputtering, and to an even wider range of materials.     

A mechanistic model for the influence of stress ratio on the LEFM fatigue crack growth behavior of metals and alloys—I. Crack-ductile materials

Concentrating on local behavior of a highly stressed zone ahead of the crack tip, a recent mechanistic approach to analyse LEFM fatigue crack growth behavior in three stages at stress ratio R = 0 is extended here to include the effect of a positive stress ratio. This paper is limited to analysing primarily the stages I and II of “crack-ductile” materials, characterised by a purely “reversed shear” (or ductile “striation”) growth mechanism in stage II. It is shown that in these materials stage I is R-sensitive and stage II is insensitive, and these can, without invoking crack closure arguments, be rationalised alternatively by considering the dominance of a K_max-controlled “Submicroscopic Cleavage” and a ΔK-controlled “ reversed shear ” fracture mechanism, respectively. Assuming Paris type power relations to hold, a predictive model is developed that contains separate growth equations with R-effect for stages I and II and shows the existence of a characteristic “master shear-curve” and a “moving pivot-point” on this curve for a class of materials. Good agreement was found between quantitatively predicted growth curves at selected R-values and a relatively large volume of available experimental data for low strength steels, aluminum alloys and titanium alloys. Besides providing more physical explanations for the observed growth behavior, the model may also be useful as a convenient alternative to crack closure for obtaining fairly accurate and conservative estimates of fatigue life for design applications.     

Defect formation in amorphous structures as revealed by computer simulation

Various types of defect in amorphous structures are discussed. It is shown that the formation, migration, redistribution and annihilation of defects in amorphous solids can be fully understood only by using computer simulation. More insight into the physics of amorphous thin films is given by the simulation of columnar growth and of the interface between a crystalline phase and an amorphous phase.     

Joining Technology in Metal-Ceramic Systems

Metallic alloys and ceramic materials are employed in aggressive and hostile environments, ranging from aerospace to energy production, from offshore to biological applications. Today, production requires materials able to survive for a long time at high temperatures, in highly aggressive atmospheres, both from the chemical and the mechanical points of view. No single material can offer these characteristics, so that “composite” structures (composites, multilayer materials, metal-ceramic joints) are designed and tested under extreme conditions.

In this paper are presented the basic principles underlying joining technologies, a short discussion of the thermodynamic background of wetting processes, recent developments related to non-reactive and reactive wetting, the influence of trace chemical elements (in the solid, liquid and gaseous phases), and some specific aspects of diffusion bonding, brazing and transient liquid phase joining processes.     

二元脂肪酸/生物基SiO_2复合相变材料的制备与性能

为了获得适用于建筑领域的相变材料和相变温度,选用月桂酸(LA)和棕榈酸(PA)共混制备的二元低共熔脂肪酸(LA-PA)作为储能材料,废弃稻草和稻草灰提取的生物基SiO_2(b-SiO_2)粉末作为载体,采用熔融浸渗法制备了LA-PA/b-SiO_2定形相变储能材料。采用FTIR、XRD、比表面测试、SEM、DSC、TGA对LA-PA/b-SiO_2复合相变材料的结构与性能进行分析。结果表明:LA-PA和b-SiO_2并不是简单的物理相互作用;LA-PA被束缚在b-SiO_2多孔网络中,从而在固相变为液相时,相变材料不会泄露。通过XRD分析可得,随着b-SiO_2含量的增加,LA-PA/b-SiO_2复合相变材料的结晶度降低。由DSC和TGA分析可知,LA-PA/b-SiO_2复合相变材料具有良好的相变性质和热稳定性,相变焓在67.36~146.0J/g之间。     

The upgrade of intense pulsed neutron source (IPNS) through the change of coolant and reflector

The current intense pulsed neutron source (IPNS) depleted uranium target is cooled by light water. The inner reflector material is graphite and the outer reflector material is beryllium. The presence of H₂O in the target moderates neutrons and leads to a higher absorption loss in the target than is necessary. D₂O coolant in the small quantities required minimizes this effect. We have studied the possible improvement in IPNS beam fluxes that would result from changing the coolant from H₂O to D₂O and the inner reflector from graphite to beryllium. Neutron intensities were calculated for directions normal to the viewed surface of each moderator for four different cases of combinations of target coolant and reflector materials. The simulations reported here were performed using the MCNPX (version 2.1.5) computer program. Our results show that substantial gains in neutron beam intensities can be achieved by appropriate combination of target coolant and reflector materials. The combination of D₂O coolant and beryllium inner and outer reflectors improves facility performance about 1.3 times. The purpose of this summary is to report our simulation and to recommend to change target coolant and inner reflector materials based on our simulation results.     

CaO-Al2O3-SiO2系玻璃分相的计算机模拟

据结晶学、热力学与动力学理论, 利用 Ｔ Ｅ Ｍ、图象分析仪和计算机, 模拟了 ＣaO-Ａｌ_２ Ｏ_３-Ｓｉ Ｏ_２ 系玻璃的液滴状分相过程, 研究中, 结合相变理论与实验数据, 建立了数学 逻辑复合分相模型, 模拟结果表明, 由成核 生长机理控制的玻璃液滴状分相, 形成对数分布的主要条件是： 液滴相临界半径必须在某一特定范围内波动; 液滴相生长相对线速度应是５ ％ ～１０ ％ ; 而开始分相液滴相临界半径和终止分相时液滴相半径的绝对值与分布类型无关本模拟方法为控制玻璃的纳米结构、研制特殊性能的玻璃材料提供了一种新的手段     

C.V.D. Coating of Alumina Reinforcing Particles to Improve the Wear Resistance of H.S.S. Based Composites

C.V.D. coating of the reinforcing ceramic particles used in particulate metal matrix composites allows the control of reactivity at the particle/matrix interface. Wear resistant high speed steel-based composites containing uncoated A1₂0₃, uncoated TiC and C.V.D. coated A1₂0₃ were liquid phase sintered, then characterized using “pin-on-disc” wear testing. TiC or TiN C.V.D. coatings of A1₂0₃ were tested to determine die increase in reactivity of the particles with the liquid phases formed during sintering. This resulted in a porosity decrease at the particle/matrix interface in addition to a better ceramic/metal cohesion due to improved wettability. Reactivity and wettability were studied using differential thermal analysis, electron microprobe analysis, transmission electron microscopy, and image analysis. Results from pin-on-disc wear testing illustrated the role of the C.V.D. coating on the wear behavior of the studied materials. Lower wear rates were obtained with the composites containing TiC or TiN-coated Al₂0₃. These results showed that there is a relation between wettability of ceramic particles by the metallic phases and wear resistance of the composites.     

不同结构铝氧化物对磷的吸附特征

磷是影响藻类生长的重要营养元素, 它在沉积物界面上的吸附是海洋环境中磷循环的重要环节, 金属氧化物是吸附磷沉积物的重要活性组分之一。采用批量实验法研究不同结构的氧化铝对无机磷的吸附特征, 分别使用二段一级动力学方程和Freundlich等方程对其动力学曲线和平衡吸附等温线进行定量描述, 并对介质盐度、温度等影响因素进行研究。结果发现, 无定型氧化铝结晶弱且比表面积大, 该特点使其吸附容量大于γ-Al₂O₃, 结合表面酸碱滴定的结果, 可知吸附也与铝氧化物的表面酸碱性质相关。分析影响因素可知, 与NaNO₃介质相比, 氧化铝吸附海水中的磷受到阻滞, 且随着介质离子强度增大, 吸附量均呈现降低趋势; pH显著影响磷的吸附量, 在pH=5左右, 两种氧化铝表面对磷酸根的吸附达到最大值; 温度升高, 有利于吸附的进行, 该吸附为吸热、自发、熵增加的过程, 两种结构氧化铝的吸附热力学参数无显著差异。     

Investigation of stress behaviors and mechanism of void formation in sputtered TiSix films

We have investigated the stress behaviors and a mechanism of void formation in TiSi_x films during annealing. TiSi_x thin films were prepared by DC magnetron sputtering using a TiSi_2.1 target in the substrate temperature range of 200–500 °C. The as-deposited TiSi_x films at low substrate temperature (<300 °C) have an amorphous structure with low stress of 1×10⁸ dynes/cm². When the substrate temperature increases to 500 °C, the as-deposited TiSi_x film has a mixture of C49 and C54 TiSi₂ phase with stress of 8×10⁹ dynes/cm². No void was observed in the as-deposited TiSi_x film. Amorphous TiSi_x film transforms to C54 TiSi₂ phase with a random orientation of (311) and (040) after annealing at 750 °C. The C49 and C54 TiSi₂ mixture phase transforms to (040) preferred C54 TiSi₂ phase after annealing over 650 °C. By increasing substrate temperature, the transformation temperature for C54 TiSi₂ can be reduced, resulting in relieved stress of TiSi₂ film. The easy nucleation of the C54 phase was attributed to an avoidance of amorphous TiSi_x phase. We found that amorphous TiSi_x→C54 TiSi₂ transformation caused higher tensile stress of 2×10¹⁰ dynes/cm², resulting in more voids in the films, than C49→C54 transformation. It was observed that void formation was increased with thermal treatment. The high tensile stress caused by volume decreases in the silicide must be relieved to retard voids and cracks during C54 TiSi₂ formation.     

激光致溅射沉积Ge2Sb2Te5薄膜的结晶行为研究

利用ＸＲＤ研究了激光致溅射沉积Ｇｅ_２Ｓｂ_２Ｔｅ_５薄膜的结晶行为;研究发现,与热致相变不同的是,激光致相变只发生从非晶态到ＦＣＣ晶态结构的转变,从ＦＣＣ到ＨＣＰ的结构转变不再发生,这有利于提高相变光盘的信噪比．Ｇｅ_２Ｓｂ_２Ｔｅ_５薄膜的结晶程度受初始化功率和转速的影响．