超声波筛选激光增材制造非晶合金

目的 快速优化出无缺陷非晶合金激光增材制造工艺。方法 以Zr51Ti5Cu25Ni10Al9非晶合金为模型材料,利用超声波对金属内部缺陷的衰减,来快速筛选激光增材制造非晶合金的最佳工艺组合(激光功率和扫描速度)。结果 超声波检测可以准确有效地检测出非晶合金试件的晶化比例,并且当激光功率为1 300 W、扫描速度为600 mm/min时超声波衰减系数降至最低。进一步对该工艺下获得的样品分析发现,该工艺成型的Zr51Ti5Cu25Ni10Al9非晶合金缺陷最少、晶化程度最低、性能最佳。结论 超声波技术是快速筛选激光增材制造非晶合金等高性能金属最佳工艺参数的有效技术手段。     

Fabrication of Cu rich bulk metallic glass composites via solidification method

Abstract

Cu based bulk metallic glasses and composites with tiny crystalline phases embedded in metallic glass matrix have been successfully fabricated by solidification technique in the present work. The formation of crystalline phases and structure inhomogeneity in bulk metallic glasses was characterised. Al is used as the minor alloying element to partly substitute Cu element in 61Cu–34Zr–5Ti. The results show that quarternary 60Cu–34Zr–5Ti–1Al alloy exhibits monoamorphous feature, and 56Cu–34Zr–5Ti–5Al alloy has a few crystalline peaks superimposed on a broad diffraction peak, suggesting that a composite structure forms in certain solidification conditions. To further identify the microstructure of the as cast rod, all samples were characterised by scanning electron microscopy (SEM). Small size phases are found in 2 mm diameter 56Cu–34Zr–5Ti–5Al rod, which has larger plastic deformation. The composition of those crystalline phases is also investigated. All results indicate that the presence of certain phases in metallic matrix benefits the mechanical properties of the as cast bulk metallic glasses.     

锆基大块非晶合金及其晶化合金在0.5mol/L H2SO4中的腐蚀行为研究

根据合金的DSC曲线制定了Zr60Al15Ni25、Zr52.5Al10Ni10Cu15Be12.5和Zr65Al10Ni10Cu15等锆基大块非晶合金的等温退火工艺,获得了与非晶态合金具有相同成分的晶化合金。通过研究非晶态合金和晶化合金在0.5mol/L H2SO4中的极化曲线,结合扫描电镜(SEM)和能量散射X射线谱(EDS)分析,发现,在0.5mol/LH2SO4中非晶态合金和晶化合金都具有非常优异的耐腐蚀性能,但非晶合金的耐腐蚀性能要比晶化合金稍好。这主要是因为晶态合金的结构中不存在晶界、位错等缺陷,同时非晶态合金中的组元具有很高的活性,使合金更快地进入钝态。     

A Group of Cu（Zr）-based BMGs with Critical Diameter in the Range of 12 to 18 mm

A group of Cu（Zr）-based bulk metallic glasses （BMGs） with critical diameter （De） in the 12 to 18 mm range have been obtained using copper mould casting. In the Cu-Zr-Y-Al quaternary system, a new record of Dc=14 mm was established for Cu-based compositions, and 16 mm for compositions based on equi-atomic CuZr. Additional partial substitution of Hf for Zr further elevated the Dc to 18 mm at Cu42Zr43Hf1.5Y3.5Al10.     

Zr-Al-Ni-Cu块体非晶合金的制备及其耐蚀性能

块体非晶合金的耐蚀性能与合金元素本身的特性及合金成分密切相关.采用铜模吸铸法制备了Zr_(55)Al_(10)Ni_5Cu_(30)块体非晶合金,用X射线衍射(XRD)、差示扫描量热分析法(DSC)和差热分析法(DTA)考察了合金的非晶特性和热力学属性,通过电化学极化试验和盐雾腐蚀试验测试了合金的耐蚀性.结果表明,制备的Zr_(55)Al_(10)Ni_5Cu_(30)合金为完全的非晶相,且具有较大玻璃形成能力和热稳定性;腐蚀电流密度仅为12.6 nA/cm~2,经144 h盐雾试验无质量变化,表明合金具有优异的耐腐蚀性能.     

Effect of Minor Alloying on Crystallization Behavior and Thermal Properties of Zr_(64.5)Ni_(15.5)Al_(11.5)Cu_(8.5) Bulk Amorphous Alloy

Minor alloying plays an important role in the synthesis and improvement of thermal stability of bulk metallic glasses(BMGs).The present study was conducted to investigate the effect of minor additions of Y,Ti and Nb on the crystallization behavior and the thermal properties of Zr64.5Ni15.5Al11.5Cu8.5 alloy.Thermal parameters and the activation energies for crystallization were calculated for four(Zr0.645Ni0.155Al0.115-Cu0.085)100-xMx(M=Y,Ti and Nb,while x=0,2 at.) alloys.The present alloys have wide supercooled liquid region of ≥87 K.Maximum activation energy was found to be greater than 300 kJ/mol for the base alloy.Four crystalline phases were identified in the samples annealed at 823 K for 20 min.Reduced glass transition temperature(Trg) and other thermal parameters such as γ,δ and β were improved by Y and Ti addition.Nb addition resists crystallization below annealing temperature 713 K,however,its effect on thermal properties is not very promising.     

On the Atomic Anisotropy of Thermal Expansion in Bulk Metallic Glass

Glass transition temperature and plastic yield strength are known to be correlated in metallic glasses. We have observed by in situ synchrotron high energy X‐ray diffraction anisotropy of the thermal expansion behavior in the nearest neighbor and second nearest neighbor atomic distances in the building blocks of Zr? Cu? Ni? Al based bulk metallic glass, leading inevitably to shear. Mechanical yielding of the latter on the atomic scale leads to the glass transition and the increase of the free volume. These experimental results uncover the mechanism, how glass transition and yield strength are linked.     

Microstructure Evolution of Zr50Cu18Ni17Al10Ti5 Bulk Metallic Glass during Cold-rolling

Zr50Cu18Ni17Al10Ti5 bulk metallic glass has been rolled at room temperature up to 95% in thickness reduction, and the dependence of microstructure on the strain was investigated. With increasing thickness reduction, the full width at half maximum (FWHM) and crystallization enthalpy decrease gradually till 80%, and then increase evidently at 95%. It is revealed that the reversible transition between the ordered and disordered atomic configurations was found in the metallic glass as the deformation proceeds, which is further verified by the high-resolution transmission electron microscopy images. The final microstructure in metallic glass during cold-rolling is the net result of two competing processes between shear-induced disordering and diffusion controlled reordering.     

Zr基大块非晶合金成分的等电子浓度和等原子尺寸判据

制备了6种合金Zr65.5Al5.6Ni6.5Cu22.4,Zr65.3Al6.5Ni8.2Cu20,Zr65Al7.5Ni10Cu7.5,Zr64.8Al8.3Ni11.4Cu5.5,Zr64.5Al9.2Ni13.2Cu13.1和Zr63.8Al11.4Ni17.2Cu7.6,共晶成分位于合金Zr64.5Al9.2Ni13.2Cu13.1和合金Zr63.8Al11.4Ni17.2Cu7.6的成分之间，这6种合金均显示了非晶相的形成和较宽的过冷液相区范围△Tx值，以及较大的约化玻璃转变温度Trg值，除合金Zr63.8Al11.4Ni17.2Cu7.6的△Tx值为87K外，其余5种成分合金的△Tx值均在97K以上，最宽的达105K，表明这6种合金是一个具有大玻璃形成能力和高热稳定性的非晶合金系列，合金Zr63.8Al11.4Ni17.2Cu7.6是6种合金中玻璃表成能力和热稳定性最高的，其Tg，Tx和Trg值最高，Inoue非晶合金Zr65Al7.5Ni10Cu17.5并不是最佳非晶成分，提出以等电子浓度和等原子尺寸规律作为设计大块非晶合金成分的判据。     

In vitro and in vivo studies on Ti-based bulk metallic glass as potential dental implant material

In this study, a high glass forming system, Ti41.5Zr2.5Hf5Cu37.5Ni7.5Si1Sn5 (TZHCNSS) bulk metallic glass (BMG), is studied in terms of microstructure, surface analysis, mechanical properties, corrosion resistance, in vitro cytotoxicity and in vivo biocompatibility. It is found that the as-prepared TZHCNSS samples are fully amorphous by XRD and TEM observations, as well as DSC curve. Comparing with pure Ti, TZHCNSS BMG shows superior mechanical properties with higher hardness and better wear resistance. Due to the oxide film formed on its surface, TZHCNSS BMG shows great corrosion resistance close to pure Ti in electrochemical measurements. The pitting corrosion potential in artificial saliva solution is much higher than that in SBF solution. The indirect and direct cytotoxicity results show that TZHCNSS extracts had obvious low cell viability on both L929 and NIH3T3 cells. However, the in vivo testing results proved that TZHCNSS BMG could integrate with bone tissue, showing excellent osseointegration.     

微量Al添加对铜基大块非晶合金性能的影响

为了进一步提高铜基大块非晶合金的玻璃形成能力及力学性能,采用添加微量Al元素的方法对块体非晶合金Cu52.5Ti30Zr11.5Ni6进行了成分优化.热分析与X射线衍射结果显示,随着微量Al的添加,液相线温度从非晶合金Cu52.5Ti30Zr11.5Ni6的1150 K逐步降低到Cu50.5Ti30Zr11.5Ni6Al2的1134 K,临界直径相应的从5 mm提高到6 mm.大块非晶Cu50.5Ti30Zr11.5Ni6Al2的压缩断裂强度达到2286 MPa,比经典的铜基非晶合金Cu47Ti34Zr11Ni8提高约100 MPa,表明微量Al的添加在有效提高玻璃形成能力的同时,强度也略有提高.     

Preparation of Cu-based Bulk Metallic Glass Matrix Composites

Cu47Ti34Zr11Ni8 bulk metallic glass （BMG） matrix composites containing in situ formed TiC particles and 5-TiCu dendrite phase were developed by copper mold cast. The thermal stability and microstructure of the composites are investigated. Room temperature compression tests reveal that the composite samples exhibit higher fracture strength and distinct plastic strain of 0.2%-0.5%, comparing with that of the corresponding Cu47Ti34Zr11Ni8 monolithic BMG.     

大块玻璃合金射流成形方法的研究

用射流成形方法制备出直径从Φ５ｍｍ到Φ１０ｍｍ的Ｚｒ基大块玻璃离态合金，研究了样品尺寸大小以及保护气氛中含氧量对形成玻璃态合金的影响，结果表明，样品尺寸越上，则合金达到的冷却速率越大，形成的玻璃态合金中析出结晶相越少，消除氧非均匀核的影响，可以减少消除大块玻璃态合金基体中的结晶析出，有利于获得更大尺寸的大块玻璃合金。     

Gibbs Free Energy and Activation Energy of ZrTiAlNiCuSn Bulk Glass Forming Alloys

The Gibbs free energy differences between the supercooled liquid and the crystalline mixture for the (Zr_(52.5)Ti_5Al_(10)-Ni_(14.6)Cu_(17.9))_((100-x)/100)Sn_x (x=0, 1, 2, 3, 4 and 5) glass forming alloys are estimated by introducing the equationproposed by Thompson, Spaepen and Turnbull. It can be seen that the Gibbs free energy differences decrease firstas the increases of Sn addition smaller than 3, then followed by a decrease due to the successive addition of Snlarger than 3, indicating that the thermal stabilities of these glass forming alloys increase first and then followed by adecrease owing to the excessive addition of Sn. Furthermore, the activation energy of Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9) and(Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9))_(0.97)Sn_3 was evaluated by Kissinger equation. It is noted that the Sn addition increases theactivation energies for glass transition and crystallization, implying that the higher thermal stability can be obtainedby appropriate addition of Sn.     

Evaluation of glass forming ability in binary and ternary metallic alloy systems – an application of thermodynamic phase diagram calculations

Abstract

The glass forming ability (GFA) of a wide range of binary and ternary alloy systems (Au–Si, Pd–Si, Ti–Be, Zr–Be, Hf–Be, Cu–Ti, Co–Zr, Ni–Zr, Cu–Zr, Ni–P, Pd–P, Ni–Pd–P, Cu–Pd–P, Co–Ti–Zr, Zr–Be–Hf, Ti–Be–Hf, Ti–Be–Zr) was calculated using a combined thermodynamic and kinetic approach. There is good agreement between the predicted glass forming ranges and those experimentally observed. By using this combined approach it has also proved possible to estimate critical cooling rates for phases not observed in the equilibrium phase diagram. A significant advantage of the approach is that, for multicomponent alloys, the melting temperatures and thermodynamic input parameters for the kinetic equations are derived using the constituent binary thermodynamic phase diagram calculations and, therefore, it has the potential to predict GFA in multicomponent systems using information from mainly binary systems.

MST/788     

Main α relaxation and slow β relaxation processes in a La30Ce30Al15Co25 metallic glass

Dynamic relaxation processes are fundamental to understand the mechanical and physical properties of metallic glasses. In the current work, mechanical relaxations in a La₃₀Ce₃₀Al₁₅Co₂₅ bulk metallic glass were probed by dynamic mechanical analysis. In contrast to many metallic glasses, La₃₀Ce₃₀Al₁₅Co₂₅ metallic glass shows a pronounced slow β relaxation peak. Physical aging below the glass transition temperature T_g leads to an increase of the apparent activation energy and a decrease of the slow β relaxation magnitude. The correlation between the slow β relaxation and the main α relaxation is discussed.     

含Be多元合金非晶形成能力的替代效应研究

利用晶胞平移和分子动力学模拟建立了Zr4lTil3.8Be22.5Ni17.5Cu5．2晶态和非晶合金的原子结构模型，利用递归方法研究了Zr4lTi13.8Be22．5Ni17．5Cu5．2晶态及非晶态合金中元素的替代效应．Be与B、Al、Si状态密度形状相似表明Be与B、Al、Si具有相似的性质，可以用Al、B、Si代替Be；非晶态相对于晶态的结构能差表明，用Al、B、Si代替Be后均使合金的非晶形成能力下降，只是Al、B下降的幅度较小；用Al、B替代Be，再用其它过渡金属替代Cu、Ni或zr、Ti可使非晶形成能力达到含Be合金的水平．     

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.     

Friction Stir Welding of Zr_(55)Al_(10)Ni_5Cu_(30) Bulk Metallic Glass to Crystalline Aluminum

The Zr55Al10Ni5Cu30 bulk metallic glass plate were successfully welded to crystalline aluminum plates by using a friction stir welding (FSW) method. The welded zone was examined. No defects, cracks or pores were observed and no other crystalline phases except for aluminum were found in the welded joint. The strength of the joint is higher than that of aluminum. The glassy phase in the stir zone keeps the amorphous state, showing a successful welding. The storage modulus softens over the glass transition. An...     

In vivo evaluation of Zr-based bulk metallic glass alloy intramedullary nails in rat femora

Zr-based bulk metallic glasses (BMG) show high corrosion resistance in vitro and higher strength and lower Young’s modulus than crystalline alloys with the similar composition. This study aimed to perform an in vivo evaluation of Zr₆₅Al_7.5Ni₁₀Cu_17.5 BMG. Osteotomy of the femur was done in rats and stabilized with intramedullary nails made of Zr₆₅Al_7.5Ni₁₀Cu_17.5 BMG, Ti–6Al–4V alloy, or 316L stainless steel. Systemic and local effects of each type of nail were evaluated by measuring the levels of Cu and Ni in the blood and the surrounding soft tissue. Changes of the surface of each nail were examined by scanning electron microscopy (SEM). Healing of the osteotomy was evaluated by peripheral quantitative computed tomography and mechanical testing. No increase of Cu and Ni levels was recognized. Surface of the BMG showed no noticeable change, while Ti–6Al–4V alloy showed Ca and P deposition and 316L stainless steel showed surface irregularities and pitting by SEM observation. The stress strain index, maximum torque, torsional stiffness, and energy absorption values were larger for the BMG than those for Ti–6Al–4V alloy, although there was no significant difference. The Zr-based BMG can promote osteotomy healing as fast as Ti–6Al–4V alloy, with the possible advantage of the Zr-based BMG that bone bonding is less likely, allowing easier nail removal compared with Ti–6Al–4V alloy. The Zr-based BMG is promising for the use in osteosynthetic devices that are eventually removed.