Microstructure and compressive/tensile characteristic of large size Zr-based bulk metallic glass prepared by laser solid forming

The large size, crack-free Zr_(55)Cu_(30)Al_(10)Ni_(5) bulk metallic glass(BMGs) with the diameter of 54 mm and the height of 15 mm was built by laser solid forming additive manufacturing technology, whose size is larger than the critical diameter by casting. The microstructure, tensile and compressive deformation behaviors and fracture morphology of laser solid formed Zr_(55)Cu_(30)Al_(10)Ni_5 BMGs were investigated. It is found that the crystallization mainly occurs in the heat-affected zones of deposition layers, which consist of Al_5Ni_3Zr_2, NiZr_2, ZrCu, CuZr_2 phases. The content of amorphous phase in the deposit is about 63%.Under the compressive loading, the deposit presents no plasticity before fracture occurs. The fracture process is mainly controlled by the shear stress and the compressive shear fracture angles of about39?. The compressive strength reaches 1452 MPa, which is equivalent to that of as-Cast Zr_(55)Cu_(30)Al_(10)Ni_5 BMGs, and there exist vein-like patterns, river-like patterns and smooth regions at the compressive fractography. Under the tensile loading, the deposit presents the brittle fracture pattern without plastic deformation. The fracture process exhibits normal fracture model, and the tensile shear fracture angle of about 90?. The tensile strength is only about 609 MPa, and the tensile fractography mainly consists of micro-scaled cores and vein-like patterns, dimple-like patterns, chocolate-like patterns and smooth regions. The results further verified the feasibility and large potential of laser additive manufacturing on fabrication and industrial application of large-scale BMGs parts.     

Ti、La对贮氢合金ZrMn0.7 V0.2 Co0.1 Ni1.2相结构和电化学性能的影响

研究了贮氢电极合金Zr1-xTixMin0.7V0.2Co0.1Ni1.2的相结构和电化学性能。结果表明，随着掺Ti量的增加，该合金主相中C15型Laves相含量逐渐减少而C14型Laves相含量逐渐增加，同时非Laves相Zr7M10和TiNi相全部消失，说明元素Ti掺杂量的增加抑制了第二相的产生。当含Ti量x=0．2时，该合金具有最大放电容量Cmax为354mAh／g，在放电电流为300mAh／g条件下，高倍率放电性能比母体合金提高了15％。而对于合金Zr0.75Ti0.2La0.05Mn0.7V0.2Co0.1Ni1.2，其活化性能被大大提高，只需4次就能达到最大放电容量372mAh／g，而且经过30次循环仍能保持最大放电容量的93％。     

Plastic deformation of a Zr-based bulk metallic glass fabricated by selective laser melting

Fully amorphous Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ bulk metallic glass(BMG) samples with a relative density exceeding 98% were fabricated via selective laser melting(SLM).High fracture stresses of around1700 MPa and a reproducible plastic strain of about 0.5% were obtained for cylindrical SLM samples.The analysis of the observed serrations during compressive loading implies that the shear-band dynamics in the additively manufactured samples distinctly differ from those of the as-cast glass.This phenomenon appears to originate from the presence of uniformly dispersed spherical pores as well as from the more pronounced heterogeneity of the glass itself as revealed by instrumented indentation.Despite these heterogeneities,the shear bands are straight and form in the plane of maximum shear stress.Additive manufacturing,hence,might not only allow for producing large BMG samples with complex geometries but also for manipulating their deformation behaviour through tailoring porosity and structural heterogeneity.     

块体非晶合金剪切带温度的变化分析

通过对Zr41.2Ti13.8Cu12.5Ni10Be22.5(Vit 1)压缩实验,发现应力-应变关系曲线的锯齿流变特性随应变的增加而更为明显。并通过对简单剪切断裂面的分析,表明在剪切滑移过程中剪切带有一个形核和生长的过程。采用剪切带逐步扩展模型计算剪切带中温度的变化,通过计算表明剪切带形成中前期的温升不足以达到非晶合金的熔点,且剪切带温升与单个锯齿卸载部分形成过程所持续的时间和每次剪切滑移过程中载荷的变化量紧密相关。     

Al_(72)Ni_(12)Co_(16)/A365准晶颗粒增强铝基复合材料的制备及其力学性能

制备了增强相体积分数为5%~20%的系列Al72Ni12Co16P/A356准晶增强铝基复合材料。其中增强相Al72Ni12Co16通过将严格按化学成分配比的Al72Ni12Co16浇于水冷铜基板上激冷凝固而获得。TEM和XRD分析结果表明所获得的材料为单相准晶材料。准晶增强铝基复合材料经热挤压处理后,绝大部分的铸造缺陷被消除,力学性能测试显示当准晶相的加入量为20%时,铝基复合材料的抗拉强度、屈服强度、弹性模量等性能分别从基体材料的275 MPa、200 MPa和70 GPa提高至410 MPa、350 MPa和102 GPa,而延伸率却从6%降低至3%。分析了准晶增强铝基复合材料的断裂机制和增强机制,准晶颗粒增强铝基复合材料的断裂机制可能有如下3种:界面及其附近区域脱粘、基体在集中的滑移带内撕裂和颗粒断裂,而其增强机制主要是细晶强化、弥散强化和固溶强化。     

Approach to the Theoretical Strength of Ti—Ni—Cu Alloy Nanocrystals by Grain Boundary Design

The grain boundary design was used to introduce boride Ti_2B and TiB_2 nanoparticles of 5 nm in size into grain boundaries of nanocrystalline Ti_(50)Ni_(25)Cu_(25) alloy.As a result,the maximum normalized microhardness was increased by 20%and the theoretical limit of hardness is substantially approached.It is proposed that boride nanoparticles suppressed low-temperature grain-boundary sliding and,therefore,shifted the range of the anomalous behavior of Hall-Petch relation toward smaller sizes of the Ti-Ni-Cu nanocrystals.     

掺杂 Al_2O_3对 Ba_2Ti_9O_(20)相形成的影响

本文研究了在BaO-TiO_2-SnO_2固相反应系统中掺杂 Al_2O_3对 Ba_2Ti_9O_(20)相形成的影响。实验结果表明,即使掺杂少量的 Al_2O_3,在反应过程中 Ba_2Ti_9O_(20)相也变得更容易形成。微观结构分析结果表明,Ba_2Ti_9O_(20)晶体结晶时,由于具有层状结构特征,往往会出现结构层间应力;这种应力会严重制约Ba_2Ti_9O_(20)晶体的形核和长大。掺杂少量 Al_2O_3后,能形成与 Ba_2Ti_9O_(20)晶体共生的 BaAl_2Ti_6O_(16)晶体;这种共生机制抑制了应力的发展。Al_2O_3改善了 Ba_2Ti_9O_(20)结晶的动力学条件,促进了 Ba_2Ti_9O_(20)相的形成。     

大块非晶合金复杂应力状态塑性本构方程

为得到复杂应力状态下大块非晶合金的塑性本构方程,对Zr41.2Ti13.8Ni10Cu12.5Be22.5大块非晶合金进行简单拉伸、压缩和扭转实验,得到相应的一维本构关系,并应用弹塑性力学的相关理论,将一维本构方程延拓到多维应力空间.研究结果表明:该材料符合Mises屈服条件并具有强化特性;利用简单压缩和扭转实验结果可推导出材料在复杂应力状态下的塑性本构方程,且这两个塑性本构方程是一致的.     

Co_(41)Ni_(33)Al_(26)合金冷轧带材相变与阻尼能力

通过热轧和冷轧工艺制备了0.2mm厚的Co41Ni33Al26合金带材,采用1350℃×5h水冷对该带材进行了淬火热处理,用金相显微镜观察了其组织。用微分差热分析仪(DSC)测定了其马氏体转变温度,并用动态热机械谱仪(DMS)研究了其相变及阻尼能力。结果表明,0.2mm的Co41Ni33Al26合金带材的基体为竹节状的粗大再结晶晶粒,其马氏体相变温度比1.5mm厚的板材高约45℃;降温过程中合金带材在140~25℃温度范围出现阻尼峰,其阻尼峰宽明显大于马氏体相变温度范围,后者为121~78℃,表明有新的应力诱发马氏体相变出现;Co40Ni33Al27合金带材的阻尼能力超过0.04,并且温度范围宽,有望成为新型阻尼材料。     

Characterization,Removal and Evaluation of Oxide Film in the Diffusion Bonding of Zr55Cu30Ni5Al10 Bulk Metallic Glass

The composition of oxide film of ZrssCu3oNi5Al10 bulk metallic glass was identified by X-ray photoelectron spectroscopy. In addition, the relatively sound joints of bulk metallic glass without macroscopic deformation were obtained by removing the oxide film before diffusion bonding. The joint interfaces were observed by scanning electron microscopy and atomic force microscopy. The hardness of joints near the interface was higher than that far away from the interface, which is attributed to the difference of structural relaxation. According to the result of micro-focused X-ray diffractometry and transmission electron microscopy, the joints retained the amorphous structure when the holding time is less than 20 min. The surface area fraction of oxide film on the interface of joints was detected by ultrasonic inspection. Moreover, the surface area fraction of oxide film is in excellent agreement with the theoretical value calculated by shear strength. The result indicated that surface oxide film is the dominant barrier on the diffusion bonding of bulk metallic glass rather than low atomic diffusion coefficient.     

Dy替代M1对低钴贮氢合金组织和性能的影响

采用多元合金化及A侧稀土元素Dy取代M1的方法，制备出了多元低钴贮氢合金M1（1-x）DyxNi3．90 Co0．3 M0．4 Cu0．15 Fe0．1 Sno．1 Ti0．05（x=0．00、0．05、0．10、0．15），研究了加Dy对合金的微观结构、组织以及电化学性能的影响。XRD及EDS分析表明，Dy能很好融入主相晶格中，未单独形成第二相。电化学测试表明，适量Dy的加入能够提高低钴舍金的放电容量，以及合金的充放电循环稳定性。     

退火温度对Pb(Zr_(0.53)Ti_(0.47))O_3薄膜结构及其性能的影响

采用sol-gel法在Pt/Ti/SiO_2/Si衬底上制备Pb(Zr_(0.53)Ti_(0.47))O_3薄膜.利用X射线衍射仪(XRD)和原子力显微镜(AFM)对其晶格结构和微观形貌进行了表征,通过改变退火温度制得了具有单一钙钛矿结构的Pb(Zr_(0.53)Ti_(0.47))O_3薄膜.然后将该薄膜与环氧树脂形成复合结构材料.对其铁电性能以及复合材料的阻尼性能进行了测试,结果表明,退火温度的升高有利于改善薄膜的铁电性能,在750℃下退火的Pb(Zr_(0.53)Ti_(0.47))O_3薄膜,其剩余极化值2Pr达到了68.6μC/cm~2, 矫顽场强2E_c达到158.7kV/cm;同时退火温度的升高还有利于薄膜致密度的提高,对复合材料的阻尼性能也有一定的改善,当退火温度达到800℃,复合材料的阻尼损耗因子达到最大值,阻尼温域最宽,阻尼性能最好.     

Towards the diffusion source cost reduction for NdFeB grain boundary diffusion process

Aiming at improving the performance/cost ratio in grain boundary diffusion process(GBDP),the critical RE containing Pr-Al-Cu alloy,less expensive RE containing La-Al-Cu alloy and non-RE Al-Cu alloy were employed as the diffusion sources.The preliminary results show that the coercivity was successfully enhanced from 1000 kA/m to 1695,1156 and 1125 kA/m by Pr70Al20Cu10,La70Al20Cu10 and Al75Cu25(at.%) alloys diffusion,respectively,due to the formation of(Nd,Pr)-Fe-B,La2 O3 and c-Nd2 O3 phases respectively,after diffusion.It is also found that the corrosion resistance can be improved by Al-Cu diffusion due to the positive effects of Al and Cu elements in grain boundary.The present results demonstrated the various coercivity enhancement mechanisms for the GBDP based on different diffusion sources,and provided feasible solutions for cost reduction of GBDP and NdFeB production by saving RE resource.     

Correlation between deformation behavior and atomic-scale heterogeneity in Fe-based bulk metallic glasses

The correlation betweent deformation behavior and atomic-scale heterogeneity of bulk metallic glasses(BMGs)is critical to understand the BMGs'deformation mechanism.In this work,three typical[(Fe_0.5Co_0.5)_0.75B_0.2Si_0.05]₉₆Nb_4,Fe₃₉Ni₃₉B_14.2Si_2.75P_2.75Nb_2.3,and Fe₅₀Ni₃₀P₁₃C₇BMGs exhibiting different plasticity were selected,and the correlation between deformation behavior and atomic-scale heterogeneity of Fe-based BMGs was studied.It is found that the serrated flow dynamics of Fe-based BMGs transform from chaotic state to self-organized critical state with increasing plasticity.This transformation is attributed to the increasing atomic-scale heterogeneity caused by the increasing free volume and short-to-medium range order,which facilitates a higher frequency of interaction and multiplication of shear bands,thereby results in a brittle to ductile transition in Fe-based BMGs.This work provides new evidence on heterogeneity in plastic Fe-based BMGs from the aspects of atomic-scale structure,and provides new insight into the plastic deformation of Fe-based BMGs.     

Effect of ECAP consolidation temperature on the microstructure and mechanical properties of Al-Cu-Ti metallic glass reinforced aluminum matrix composite

Al_(65)Cu_(20)Ti_(15)metallic glass(AMG) reinforced Al matrix composites were consolidated by equal channel angular pressing(ECAP) process. The effects of ECAP consolidation temperature ranging from room temperature to just below the first crystallization temperature of metallic glass on the consolidation of composites were investigated in terms of the relative densities, structural evolutions and mechanical properties of composites. Some intermetallic compounds included Al_5CuTi_2, Al_3Ti and Al_4Cu_9 precipitated from metallic glass particles at consolidation temperature of 300?C. Consolidation temperature did not affect the matrix grains size of the composite. Quantitative analysis revealed that the distribution of reinforcing particles was considerably dependent on consolidation temperature. Density of the composite was increased by increasing the consolidation temperature to 250?C. The composite consolidated at250?C through ECAP process, exhibited the best combination of yield strength and ductility of 184 MPa and 48%, respectively.     

Effects of High Temperature Oxidation on Mechanical Properties of Ti_3AlC_2

The oxidation tests of Ti_3AlC_2 were conducted at 1100 and 1200?C in air for 48 and 360 h, respectively,and the effects of high temperature oxidation on the flexural strength and hardness of Ti_3AlC_2 were investigated. The microstructure, grain size and phase compositions of Ti_3AlC_2 substrate didn't change after oxidation, hence the oxide removed Ti_3AlC_2 substrate maintained its initial flexural strength and hardness. However, the flexural strength of oxide retained Ti_3AlC_2 decreased by about 5%. Acoustic emission monitoring indicated that during the process of three-point bending test, the formed Al_2O_3 scale on Ti_3AlC_2 surface fractured firstly in a cleavage manner, then the substrate/oxide interface cracked,and finally the Ti_3AlC_2 substrate fractured. The mechanical degradation was caused by the preferential formation of cracks in brittle Al_2O_3 scale as well as at defective and lacunose grain boundaries of the substrate where stress concentration generated. The mechanical degradation was insensitive to oxidation temperature and time in the present conditions. In addition, the surface hardness increased significantly after oxidation due to the formed hard Al_2O_3 scale on the surface of Ti_3AlC_2 substrate.     

Construction of novel TiO_2/Bi_4Ti_3O_(12)/MoS_2 core/shell nanofibers for enhanced visible light photocatalysis

TiO2/Bi4 Ti3 O12 hybrids have been widely prepared as promising photocatalysts for decomposing organic contaminations.However,the insufficient visible light absorption and low charge separation efficiency lead to their poor photocatalytic activity.Herein,a robust methodology to construct novel TiO2/Bi4 Ti3 O12/MoS2 core/shell structures as visible light photocatalysts is presented.Homogeneous bismuth oxyiodide(BiOI) nanoplates were immobilized on electrospun TiO2 nanofiber surface by successive ionic layer adsorption and reaction(SILAR) method.TiO2/Bi4 Ti3 O12 core/shell nanofibers were conveniently prepared by partial conversion of TiO2 to high crystallized Bi4 Ti3 O12 shells through a solid-state reaction with BiOI nanoplates,which is accompanied with certain transition of TiO2 from anatase to rutile phase.Afterwards,MoS2 nanosheets with several layers thick were uniform decorated on the TiO2/Bi4 TiO3 O12 fiber surface resulting in TiO2/Bi4 Ti3 O12/MoS2 structures.Significant enhancement of visible light absorption and photo-generated charge separation of TiO2/Bi4 Ti3 O12 were achieved by introduction of MoS2.As a result,the optimized TiO2/Bi4 Ti3 O12/MoS2-2 presents 60% improvement for photodegrading RhB after 120 min irradiation under visible light and 3 times higher of apparent reaction rate constant in compared with the TiO2/Bi4 Ti3 O12.This synthetic method can also be used to establish other photocatalysts simply at low cost,therefore,is suitable for practical applications.     

0.94[(Na0.96-xKxLi0.04)0.5Bi0.5]TiO3-0.06Ba(Zr0.055Ti0.945)O3无铅压电陶瓷的压电介电特性

对无铅压电陶瓷0.94[(Na0.96-xKxLi0.04)0.5Bi0.5]TiO3-0.06Ba(Zr0.055Ti0.945)O3的性质随K含量的变化进行了系统研究,获得压电应变常数d33高达185pC/N的0.94[(Na0.80K0.16Li0.04)0.5-Bi0.5]TiO3-0.06Ba(Zr0.055Ti0.945)O3压电陶瓷.随着K掺杂量的增加,该陶瓷材料的介电温谱峰值向右明显移动,其介电峰温度明显升高.     

Sol-gel方法制备BiFeO_3/Bi_4Ti_3O_(12)多层薄膜及其电性能

采用溶胶-凝胶方法在FTO/glass底电极上制备了BiFeO3/Bi4Ti3O12和Bi4Ti3O12/BiFeO3多层薄膜。研究了室温下薄膜的结构,铁电性质和介电性质,并将其与纯的BiFeO3薄膜的性质进行了比较。从薄膜的XRD模式中可以观察到共存的BiFeO3相和Bi4Ti3O12相。通过电滞回线测量可以看出,相对于纯的BiFeO3薄膜,BiFeO3/Bi4Ti3O12和Bi4Ti3O12/BiFeO3多层薄膜能够承受更高的测试电场而获得充分极化,从而表现出较强的铁电性,在450kV/cm测试电场下,薄膜的剩余极化强度分别为37μC/cm2和23μC/cm2。     

La、V掺杂对SrBi4Ti4O15性能影响对比研究

采用传统固相烧结工艺,制备了掺杂量分别为0．00～1．00、0．00～0．06的La、V掺杂SrBi4Ti4O15铁电陶瓷。X射线衍射结果显示,La、V对SrBi4Ti4O15的A、B位掺杂都未影响材料的晶体结构。A、B位掺杂均改善了材料的铁电性能。La掺杂量为0．25时,SBTi的剩余极化(2P1)增大50％,同时矫顽场(2Ec)下降了25％。少量的V取代SBTi的B位Ti离子后．2Ec虽无明显变化,但2P,却可增大近两倍．并且不影响材料的居里温度,而A位掺杂导致了材料的居里温度的明显下降。这与A、B位掺杂对材料晶格畸变程度的影响有关。