铜模吸铸与高能球磨制备Zr46Cu46Al8非晶合金的组织结构及晶化动力学研究

采用铜模吸铸法制备出直径3 mm的Zr₄₆Cu₄₆Al₈块体非晶合金, 利用高能球磨法获得了不同粒径的合金粉体, 通过X射线衍射仪、示差扫描量热仪、扫描电镜等测试手段及热力学计算方法, 研究了制备方法对非晶合金组织结构及晶化动力学的影响。结果表明, 块体合金和粉体合金均可获得完全非晶结构; 块体非晶合金玻璃转变和晶化过程具有明显的动力学效应; 单因素变量法制备非晶粉体的最佳参数为: 转速300 r·min-1, 球料比30:1, 球磨时间15 h; 相同条件下, 除过冷液相区外, 块体非晶合金热力学参数普遍高于非晶粉体, 且晶化放热更剧烈; 随着加热速率增大, 二者热力学参数均向高温区移动, 过冷液相区的宽度也逐渐增加; 块体非晶合金和非晶粉体的特征温度表观激活能数值相近, 块体非晶态合金的表观激活能较非晶粉体高, 热稳定性更优。     

Al含量对Zr基块体非晶合金力学性能的影响

用铜模吸铸法制备了(Zr64.8/90Cu14.85/90Ni10.35/90)90+xAl10-x(x=-4,-3,-2,0,2,4,6)块体合金,利用X射线衍射仪(XRD)、万能试验机、显微硬度计和扫描电镜(SEM)研究了Al含量对Zr基块体非晶合金力学性能的影响。结果表明:随着Al含量的减小,合金先是从非晶相为主的非晶/晶体复合材料转变为完全非晶材料,接着转变为以晶体相为主的非晶/晶体复合材料,最后转变为完全晶体材料。表明通过调整Al的含量,可以制备出具有完全非晶结构的Zr基块体非晶合金。当x=-2时,即合金成分为Zr63.36Cu14.52Ni10.12Al12时,合金为完全非晶结构,该合金的室温压缩塑性应变达到20.6%,应力-应变曲线体现出了"加工硬化"特性,屈服强度σs、极限强度σm和断裂强度σf分别为1740.6,2030.7和1510.5 MPa。表明通过调整Al的含量,可以制备出具有优良室温压缩塑性的Zr基块体非晶合金。随着Al含量的减小,合金试样的显微硬度的总体趋势为先增大再减小。当x=2时,合金为非晶/晶体复合材料,该合金具有较高的显微硬度HV719.8。     

Al-Co-Y合金系非晶的形成及其晶化过程

利用熔体快淬法制备出了Al92-xCo8Yx（x=4,6,8,9,10）薄带,采用X射线衍射（XRD）和扫描电镜（SEM）进行结构分析,示差扫描量热仪（DSC）进行热稳定性分析。研究了Y的加入对合金的非晶形成能力的影响以及Al84Co8Y8合金薄带等温退火的晶化过程。结果表明：当Y的原子分数为8%时,合金系的非晶形成能力最好;非晶态Al84Co8Y8合金的晶化过程分为3个阶段进行,退火过程中的组织结构转变为：非晶合金→非晶基体＋初晶α-Al＋少量未知亚稳相→α-Al相＋未知亚稳相＋Al9Co2→α-Al相＋Al9Co2相＋Al3Y相。     

冷却介质对退火态Cu50Zr42Al8块体非晶合金力学性能的影响

考察在过冷液相区内790K+30min保温后炉冷和液氮冷却对Cu50Zr42Al8压缩断裂行为的影响。5mm铸态非晶复合棒的屈服强度、断裂强度和杨氏模量分别为1670MPa,1849MPa和104.4GPa,塑性应变为1.9%。经炉冷和液氮冷却试样的压缩断裂强度和杨氏模量下降,分别为912,678MPa和38,56.5GPa。液氮冷却试样为部分非晶结构,炉冷试样完全晶化。晶化相均为正交晶相Cu10Zr7,四角晶相CuZr2和DO3结构的AlCu2Zr三种脆化相。     

超声振动对Zr基大块非晶合金结构与显微力学行为的影响

在室温条件下对铸态Zr52Cu23Al14.5Ni10.5大块非晶合金进行5 h超声振动处理,通过X射线衍射(XRD)、高分辨透射电镜(HRTEM)、差示扫描量热分析(DSC)以及纳米压痕测试,研究长时间超声处理对大块Zr基非晶合金结构与显微力学行为的影响。结果表明,经过5 h超声振动处理后,Zr基非晶合金仍保留非晶态结构,没有发生晶化;超声振动对大块非晶合金的热力学特征温度如玻璃化转变温度(Tg)、晶化开始温度(Tx)以及晶化峰值温度(Tp)的影响都不大,但可诱导结构弛豫,使其自由体积明显减少;相比铸态合金,超声处理后的合金,其纳米压痕实验的载荷—位移曲线上的锯齿流变现象明显减少,显微硬度和弹性模量均明显提高,分别从铸态的5.7 GPa和102 GPa提高到6.5 GPa和122 GPa。表明超声振动处理是一种室温调控大块非晶合金力学性能的有效手段。     

非晶合金Cu77Ni8Sn8P7的玻璃转变和晶化激活能

通过对非晶合金Cu_(17)Ni_8Sn_8P_7的初淬和退火态进行DSC分析(差动扫描量热分析),得到多种加热速度下的玻璃化温度及晶化温度,用Henderson提出的变温动力学方法计算了非晶合金在晶化开始温度和蜂值温度下的转变激活能,并确定了非晶合金玻璃转变激活能的方法。最后讨论了转变激活能和温度的关系,并估算了晶化过程中成核和生长的激活能。     

Mg-TM-Ln型镁基纳米结构材料研究

讨论了Mg-Cu-Y、Mg-Ni-Y和Mg-Zn-Y等三种重要的Mg-TM-Ln型的多组元Mg基纳米结构材料的成分构成、制备过程、微观结构和力学性能以及它们的形成机制。其中,制备方法涉及非晶部分晶化法、机械合金化/粉末冶金法(MA/PM法)和快速凝固(原子雾化)/粉末冶金法(RS/PM法)。结果表明,在Mg-Cu-Y系合金中,分布于非晶相基体之上的纳米晶体相使非晶合金的断裂应力增加。而不同成分的旋淬Mg-Cu-Y非晶条带弯曲断裂韧性的不同,很可能是由于存在于它们之中的纳米晶颗粒的性质有别而造成;在Mg-Ni-Y系合金中,Y部分地置换Ni将严重地影响其晶化行为,使得Mg-Ni-Y三元非晶合金中的纳米晶体相颗粒变得更加细小,而合金晶化行为的改变则导致了其杨氏模量的明显变化;在所有的金属合金中,RS/PMMg97Zn1Y2合金的比强度是最高的。而在所有的Mg基合金中,RS/PMMg-Zn-Y合金具有最佳的综合性能。     

Al-Ni-Y合金雾化粉末的超高压固结成形及其机理研究

采用紧耦合惰性气体雾化技术制备具有非晶和纳米晶结构的Al82Ni10Y8(%)合金粉末, 粒径小于26μm粉末为非晶和纳米晶结构, 而粒径小于15μm粉末为非晶单相结构。在250, 310, 360, 400, 450℃5个不同温度下对粉末进行了超高压固结成形, 并对致密化后合金的显微结构进行了分析。致密化后粉末颗粒基本保持原有粉末形貌, 但随着致密化温度的升高, 晶化和晶化相长大愈发明显, 合金密度呈增高趋势。对粉末致密化的机理进行了讨论, 认为非晶相的粘滞流动是低温下获得高致密度的主要原因。     

Y基非晶合金的形成及晶化动力学

利用单辊急冷法制备Y56-xZrxA124Co20(x=0,5,10)非晶合金,研究Zr含量对该非晶合金的形成能力及热稳定性的影响.研究结果表明,添加元素Zr可以提高Y56A124Co20合金的非晶形成能力和热稳定性,而且随着Zr含量增加,合金的非晶形成能力提高.通过示差扫描量热法(DSC)研究了Y56A124Co20和Y46Zr10A124Co20的晶化动力学,前者的玻璃转变激活能和晶化激活能分别为366.5 KJ/mol和259.7 KJ/mol,后者的玻璃转变激活能和晶化激活能分别为415.6 KJ/mol和319.5KJ/mol,从理论上说明添加元素Zr可以改善Y56A124Co20合金的非晶形成能力和热稳定性.     

CO2激光辐照工艺对非晶Fe73.5Cu1Nb3S13.5B9合金晶化的影响

在较低激光功率(40～170 W)和两种扫描速度(10mm/s,5mm/s)辐照条件下,研究了CO2激光辐照工艺对非晶Fe73.5Cu1Nb3S13.5B9合金晶化行为的影响.用穆斯堡尔谱(MS)技术对原始态和晶化后样品进行了结构分析.研究发现:非晶Fe73.5Cu1Nb3S13.5B9表面产生了少量晶化,晶化相为Fe-Si结构;晶化量在2.1%～3.57%内,随激光功率的增加而增加.当激光功率较低时,低扫描速度对晶化的促进作用大于激光功率的作用;但是,随激光功率增大,速度的影响变弱.表面微观硬度随激光功率的增加而增加.     

CaO-SiO2-Al2O3-V2O3四元系活度模型及其应用

根据熔渣结构的分子离子共存理论建立了CaO-SiO2-Al2O3-V2O3四元系活度模型,应用该模型计算出的活度数据,对用钒氧化物矿代替钒铁直接合金化冶炼高速钢的工艺过程进行了热力学计算和分析.用此活度数据计算了Al作还原剂时渣的平衡成分,计算结果表明渣中V2O3的含量极低,直接合金化的热力学条件好,钒理论最大还原率高.通过该活度数据计算钢中或渣中的各种还原剂还原渣中V2O3的△G和Lv,计算结果表明Al是所有还原剂中还原能力最强的.     

Segregation and wetting transition at dislocations

We investigate solute segregation and wetting transition at dislocations and the corresponding drag effect on dislocation glide using a continuum model developed previously for grain boundary and based on gradient thermodynamics. The dislocation core structure and stress field are described by the newly developed phase field model. This study differs from much previous work because it takes into account not only the long-range elastic interactions but the short-range chemical interactions between solute atoms and dislocation core as well as among solute atoms themselves. The latter leads to the prediction of a wetting transition at the dislocation core with respect to varying temperature, solute concentration, or dislocation velocity. The transition temperatures obtained during heating and cooling are different from each other, leading to a hysteresis loop in the solute concentration-temperature plot and the solute concentration-velocity plot. These predictions could provide new insights into the phenomena of sharp yield point drop and strain aging observed in metal alloys. This article is based on a presentation made in the “Hillert Symposium on Thermodynamics & Kinetics of Migrating Interfaces in Steels and Other Complex Alloys,” December 2–3, 2004, organized by The Royal Institute of Technology in Stockholm, Sweden.     

Intermediates and kinetic traps in the folding of a large ribozyme revealed by circular dichroism and UV absorbance spectroscopies and catalytic activity

The folding thermodynamics and kinetics for the ribozyme from Bacillus subtilis RNase P are analyzed using circular dichroism and UV absorbance spectroscopies and catalytic activity. At 37 degrees C, the addition of Mg2+ (Kd approximately 50 microM) to the unfolded state produces an intermediate state within 1 ms which contains a comparable amount of secondary structure as the native ribozyme. The subsequent transition to the native state (Kd[Mg] approximately 0.8 mM, Hill coefficient approximately 3.5) has a half-life of hundreds of seconds as measured by circular dichroism at 278 nm and by a ribozyme activity assay. Surprisingly, the formation of the native structure is accelerated strongly by the addition of a denaturant; approximately 30-fold at 4.5 M urea. Thus, the rate-limiting step entails the disruption of a considerable number of interactions. The folding of this, and presumably other large RNAs, is slow due to the structural rearrangement of kinetically trapped species. Taken together with previous submillisecond relaxation kinetics of tRNA tertiary structure, we suggest that error-free RNA folding can be on the order of milliseconds.     

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An information system of materials thermodynamics was built based on J2EE. This system was constructed of the popular structure SSH2. It can not only store and update basic thermodynamic data by Internet, but also do thermodynamic calculation and draw phase diagrams. This type of system is more individual and open, because it is cross-platform. The system can provide convenient conditions for materials researchers.     

CaO-SiO_2-Al_2O_3-V_2O_3四元系活度模型

根据熔渣结构的分子离子共存理论建立了CaO-SiO2-Al2O3-V2O3四元系活度模型。应用该模型计算出的活度数据,对用钒氧化物矿代替钒铁直接合金化冶炼高速钢的工艺过程进行了热力学计算和分析。用此活度数据计算了Al作还原剂时渣的平衡成分。计算结果表明,渣中V2O3的质量分数极低,直接合金化的热力学条件好,钒的理论最大还原率高。通过计算钢中或渣中的各种还原剂还原渣中V2O3的ΔG和LV,表明在炼钢工艺常用的所有还原剂中,Al的还原能力最强。     

Computer Model of Phase Transformation From Hot-Deformed Austenite in Niobium Microalloyed Steels

Based on thermodynamics and kinetics, a new mathematical model was developed to calculate the CCT diagrams and the transformation kinetics in low carbon niobium steels, in which the effect of deformation on the degree of supercooling was taken into account. The undercooling caused by deformation is the major reason for the increase of the starting transition temperature during continuous cooling. The critical cooling rate of bainite formation is within 2--5 ℃s for the studied niobium steels and deformation is suitable for the occurrence of pearlite. The ferrite volume fraction increases with the increase of the austenite boundary area, and decreases with the increase of the cooling rate. The calculated CCT diagrams and the volume fraction of each phase are in good agreement with the measurements.     

Effect of metal ion substitutions in concanavalin A on the binding of carbohydrates and on thermal stability

Isothermal titration calorimetry (ITC) measurements were performed on the binding of alpha methyl-D-mannopyranoside, D-mannopyranose, alpha methyl-D-glucopyranoside, and D-glucopyranose (Glu) to cobalt, nickel, and cadmium substituted concanavalin A (Con A) derivatives at pH = 6.9 and at 25 degrees C. The metal substituted Con A derivatives consisted of Co2+, Ni2+, and Cd2+ substituted for the Mn2+ ion in the S1 site of Con A which is about 12.8 A away from the center of the carbohydrate binding site of Con A. The thermodynamic quantities determined from the ITC measurements were the same for most of the binding reactions indicating that the structure of the binding site in solution is the same for all the Con A derivatives in solution and that the presence of different 2+ metal ions in the S1 site has little effect on the binding reactions. Differential scanning calorimetry scans of solutions of the metal ion derivatives of Con A show that the thermodynamics of the unfolding transition for the cobalt and nickel substituted derivatives are the same as for Con A: they dissociate from tetramers into monomers as they unfold around 85 degrees C. The cadmium substituted Con A derivative, however, exhibits an additional transition around 93 degrees C which also appears following the addition of Cd2+ to the Con A solutions. This transition results from the unfolding of a species of Con A with Cd2+ substituted into a third binding site at the monomeric interface of the Con A tetramer. The higher stability of this species is not only exemplified by the higher thermal transition temperature but also by the lack of dissociation as it unfolds. Cd2+ is released from the S3 site upon decreasing the pH from 6.9 to 6.4. ITC measurements on the binding reaction of Cd2+ to Con A show that the binding enthalpy is 40.2 +/- 0.4 kJ mol-1 at 23.4 +/- 0.2 degrees C and the binding reaction exhibits a large heat capacity change of 1.43 +/- 0.41 kJ mol-1 K-1.     

Differences in crystallisation behaviours during cooling and post-heating processes of Ti based metallic powders

Abstract

The different crystallisation behaviours of Ti based metallic powders were systematically investigated. Governed by a higher transition temperature (a lower supercooling degree), the composition of the microsized precipitations (Sn and Ti rich) of cooling significantly varies from that of the glassy matrix (Cu and Zr rich). On the other hand, a kinetics limited condition (a lower transition temperature) results in nanocrystals and various compositional regions between small atoms (Ti, Ni and Cu) and large atoms (Sn and Zr) for the post-heating. The different crystallisation mechanisms are considered to be determined by the synergetic effect of thermodynamics (supercooling degree) and kinetics (transition temperature).     

CO-H_2-H_2O气氛下金属尘化腐蚀的热力学分析

金属材料在CO-H2-H2O合成气氛使用过程中会发生金属尘化腐蚀。运用化学热力学理论与计算方法对在CO-H2-H2O气氛下发生金属尘化腐蚀时的标准反应吉布斯函数进行计算,得到了气氛碳活度与温度的关系式。通过气氛碳活度与材料碳活度的比较,获得两种金属尘化类型。CO-H2-H2O气氛碳的化学势受温度、气氛组成、总压的影响,减少H2O的含量,升高总压,会使发生金属尘化的温度范围扩大。