Cu-Zr-Al-Y块体非晶合金复相材料的力学性能

利用铜模喷铸法和等温退火热处理,制备具有不同晶化程度的(Cu_(47)Zr_(45)Al)8)_(98.5)Y_(1.5)块体非晶基复相材料(BMGCs),研究了其显微组织与力学性能的关系。结果表明,随着退火温度增加,(Cu_(47)Zr_(45)Al)8)_(98.5)Y_(1.5)非晶基复相材料的晶化分数(V_f)上升,相转变进程为:非晶→非晶+Cu_(10)Zr_7→非晶+Cu_(10)Zr_7+AlCu_2Zr+Al_2Zr。晶化过程中结晶相的析出强化作用能明显提高合金的显微硬度,760K退火20min后合金最大硬度(HV)可达691。合金断裂强度随退火温度升高先增加后减小。680K等温退火后合金断裂强度达到最高,为1 950MPa。断口SEM显示随着热处理温度提高,非晶基复相材料断裂模式由韧-脆混合断裂模式向解理脆性断裂模式转变。试验结果表明,可以通过控制退火温度、退火时间等参数对Cu基块体非晶基复相材料的力学性能进行调控。     

微量元素对Cu-Zr基合金非晶形成能力的影响

采用铜模喷铸成形法制备Cu50Zr50、Cu62-xZr38-xAl2x(2x=2at％、4at％和6at％)和Cu46Zr47-xAl7Yx(x=4at％ ～7at％)大块非晶试样.通过X射线衍射分析、扫描电子显微镜和示差扫描量热计(DSC)分别研究添加元素Al与Y对Cu-Zr二元合金非晶形成能力、显微形貌和热稳定性的影响.结果表明:所制备的Cu50Zr50、Cu61Zr37Al2为非晶合金,基体中含极少量结晶相,非晶形成能力对Cu-Zr-Al成分较为敏感;Y含量对直径为4 mm的Zr47-xCu46Al7Yx非晶形成能力和显微组织有着显著影响,Y含量4at％时,基体中含极少量结晶相,Y含量5at％ ～ 7at％时,非晶合金呈现完全无特征组织.     

合金元素对Cu60Zr30Ti10合金的非晶形成能力与显微硬度的影响

用铜模吸铸法制备直径2~3 mm的Cu60-xZr30Ti10M2(M=Mg、Al、Sn)系列非晶合金。用X射线衍射、差式扫描量热仪和硬度实验等研究它们的非晶形成能力、热稳定性与显微硬度。该系列非晶合金均表现出两级晶化行为。Cu60Zr30Ti10的玻璃转变温度为426.5℃,晶化起始温度为467.7℃,过冷液相区为41.2℃。添加Mg、Mo、Al对过冷液相区影响比较小,而添加Sn则使过冷液相区明显增大,达到51.6℃,合金的非晶形成能力有较明显提高,热稳定性增强。Cu60Zr30Ti10非晶合金的显微硬度为HV594.3,添加2%(摩尔分数)的Mg、Mo和Al对显微硬度影响不大,而添加2%Sn(摩尔分数)却使显微硬度达到HV755.7,提高27%。     

Y、Sn对Cu60Zr30Ti10合金非晶形成能力及性能的影响

采用铜模喷铸法制备了φ4 mm×80 mill的Cu60Zr30Ti10、(Cu60Zr30Ti10)98 Sn2和(Cu60Zr30Ti10)98Y2合金棒试样.用X射线衍射仪(XRD)和差式扫描量热仪(DSC)分析了三合金内部结构及热稳定性.结果表明:合金元素Y、Sn均能提高Cu60Zr30Ti10合金的非晶形成能力,但添加Y的效果更佳.所制备的φ4 mm(Cu60Zr30Ti10)98Y2合金棒为完全非晶结构,且其热稳定性高于另外两种合金;非晶态(Cu60Zr30Ti10)98Y2合金的显微硬度低于由晶相/非晶组成的(Cu60Zr30Ti10)98Sn2、Cu60Zr30Ti10合金,且在该系列合金中,随着析出晶相增多,合金显微硬度下降.     

Ag和Fe元素添加对Cu-Zr-Al系非晶形成能力和力学性能的影响

以Cu-Zr-Al三元系为基础,研究Ag和Fe合金组元添加对块体金属玻璃(BMG)及BMG基复合材料的非晶形成能力和力学性能的影响.在Cu-Zr-Al三元合金体系中,Cu50Zr42Al8系BMG的△Tx=61 K,Trg=0.624,γ=0.416.适量添加Ag元素能显著地提高非晶形成能力:在Cu-Zr-Al-Ag四元合金体系中,Cu43Zr45Al8Ag4、Cu45Zr42Al8Ag5、Cu40Zr44Al10Ag6、Cu43Zr41Al8A98和Cu36Zr48Al8Ag8的Trg分别为0.618、0.625、0.618、0.628和0.598,γ值分别为0.424、0.427、0.424、0.432和0.433,△TX分别为77、76、78、84和108 K.在(Cu0.36Zr0.48-Al0.08Ag0.08)100-XFex(x-=0,3,5,10,15,20)五元体系中,Fe的添加明显影响合金的非晶形成能力;尽管△TX和Trg呈下降趋势,但(Cu0.36Zr0.48Al0.08Ag0.08)97Fe3块体非晶合金仍具有较高的非晶形成能力,其△TX=103 K,Trg=566,γ=0.424:Fe的适量加入可显著提高合金的力学性能,其中(Cu0.36Zr0.48Al0.08Ag0.08)95Fe5合金的强度和塑性应变分别提高至2 249 MPa和4.9%.Fe元素的存在导致Cu36Zr48Al8Ag8合金中产生明显的相分离,使(Cu0.36Zr0.48Al0.08Ag0.08)100-xFex合金得到增强增韧.     

Y元素添加对Zr基非晶形成能力和力学性能的影响

在水冷铜坩埚中采用铜模吸铸法制备成直径为3mm的Zr65-xCu17.5Ni10Al7.5Yx(x=0、2、4at.%)合金圆棒。采用X射线衍射(XRD)、差热分析(DSC)和微机控制电子式万能试验机等技术手段对Zr基合金的非晶形成能力,热稳定性和力学性能进行研究。结果表明,当x=2时合金为完全非晶组织,此时非晶具有较高的热稳定性和非晶形成能力(△Tx=69K),此时断裂强度σmax为1518MPa,塑性变形εp为1.5%。随着Y含量的增加,非晶的形成能力、热稳定性和力学性能都有所降低。     

Al对Ti-Zr-Cu-Ni-Be非晶合金热稳定性和力学性能的影响

利用X射线衍射(XRD)、透射电镜(TEM)、差示扫描量热(DSC)和室温压缩试验等分析手段,通过替代(Ti40Zr20Cu8Ni9Be18Al5)和掺杂[(Ti40Zr25Cu8Ni9Be18)0.95Al0.05)]两种元素添加方法,研究了5%(摩尔分数)Al元素对Ti40Zr25Cu8Ni9Be18非晶合金铸态组织、热稳定性和力学性能的影响。替代和掺杂的Al元素使直径为3mm的非晶合金棒状试样中分别析出了纳米晶和准晶。Al替代Zr使非晶合金薄带试样的过冷液相区从46K升高到50K,而以掺杂方式添加时却使其降低为31K。替代方式添加的Al元素使非晶合金的压缩断裂强度从1924MPa提高到2121MPa,但塑性应变从3.9%降低到了0.2%;而掺杂方式添加的Al元素使非晶合金强度降低为1475MPa,并呈现零塑性。     

Cu基Cu-Zr-Al块体非晶合金的成分设计

利用变电子浓度经验判据，从Cu—Zr亚组元体系中的最深共晶点Cu61．8Zr38.2和次深共晶点Cu56Zr44出发，连接第三组元Al，建立(Cu61.8Zr38．2)1-xAlx和(Cu56Zr44)1-xAlx变电子浓度线．电子浓度在1．24—1．30的(Cu61．8Zr38．2)1-xAlx合金可通过铜模吸铸法形成直径为3mm的块体非晶；对于(Cu56Zr44)1-xAlx系列合金，块体非晶形成的电子浓度区间为1．28-1．36．热分析结果表明，每条变电子浓度线上块体非晶合金的热稳定性和玻璃形成能力随电子浓度增大而增加．其中，(Cu61．8Zr38.2)1-xAlx变电子浓度线上的非晶合金Cu58．1Zr35．9Al6(e／α=1．3)具有最高的热稳定性和最大的玻璃形成能力，其特征参数Tg=760K，Tg／Tl=0．648，皆高于已报道的最优成分Cu55Zr40Al5(Tg=722K，Tg／Tl=0．614)。     

半固态处理对Zr_(60)Cu_(17.5)Al_(7.5)Ni_(10)Ti_5非晶形成能力和力学性能的影响

采用铜模吸铸法将Ti元素添加到Zr65Cu17.5Al7.5Ni10非晶合金中,制备得到直径为3 mm的大块非晶合金。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、示差扫描量热仪(DSC)和微机控制电子式万能试验机等研究半固态处理对Zr60Cu17.5Al7.5Ni10Ti5大块非晶合金的微观组织结构、非晶形成能力、压缩力学性能以及断口形貌的影响。结果表明:半固态处理技术对非晶合金材料的组织结构和力学性能有很大的影响,能够提高非晶合金的强度和塑性;半固态下Zr60Cu17.5Al7.5Ni10Ti5表现出较好的非晶形成能力,表征非晶形成能力的参数Trg为0.618 9,过冷液相区△Tx达到40 K;且当吸铸电压为7 kV时试样的塑性最好,为1.94%,强度为1 487.411 MPa。     

Zr-Al-Co-Er-Cu系块体非晶合金的形成及其力学性能和腐蚀行为

制备了具有高非晶形成能力的Zr-Al-Co-Er-Cu系非晶块体合金,并研究了Cu元素对Zr-Al-Co-Er块体非晶合金的形成、力学性能和腐蚀行为的影响。研究表明以适量的Cu元素替代Zr-Al-Co-Er合金的Co元素有利于非晶形成能力的提高和力学性能的改善。其中,Zr49Al20Co23Er6Cu2非晶合金的临界直径达6mm,压缩断裂强度达到1950MPa,表现出1.4%的塑性变形。Zr49Al20Co25-xEr6Cux(x=0～8at%)非晶合金在1mol/LH2SO4、3%NaCl(质量分数,下同)溶液中的均发生自钝化,并且具有较低的钝化电流密度。Cu含量的变化对Zr-Al-Co-Er-Cu非晶合金的腐蚀行为没有明显影响。     

Effects of rare-earth elements on the glass-forming ability and mechanical properties of Cu46Zr47-xAl7Mx (M = Ce, Pr, Tb, and Gd) bulk metallic glasses

Cu46Zr47-xAl7Mx(M = Ce,Pr,Tb,and Gd) bulk metallic glassy(BMG) alloys were prepared by copper-mold vacuum suction casting.The effects of rare-earth elements on the glass-forming ability(GFA),thermal stability,and mechanical properties of Cu46Zr47-xAl7Mx were investigated.The GFA of Cu46Zr47-xAl7Mx(M = Ce,Pr) alloys is dependent on the content of Ce and Pr,and the optimal content is 4.at %.Cu46Zr47-xAl7Tbx(x = 2,4,and 5) amorphous alloys with a diameter of 5 mm can be prepared.The GFA of Cu46Zr47-xAl7Gdx(x = 2,4,and 5) increases with increasing Gd.Tx and Tp of all decrease.Tg is dependent on the rare-earth element and its content.△Tx for most of these alloys decreases except the Cu46Zr42Al7Gd5 alloy.The activation energies △Eg,△Ex,and △Ep for the Cu46Zr42Al7Gd5 BMG alloy with Kissinger equations are 340.7,211.3,and 211.3 kJ/mol,respectively.These values with Ozawa equations are 334.8,210.3,and 210.3 kJ/mol,respectively.The Cu46Zr45Al7Tb2 alloy presents the highest microhardness,Hv 590,while the Cu46Zr43Al7Pr4 alloy presents the least,Hv 479.The compressive strength(σc.f.) of the Cu46Zr43Al7Gd4 BMG alloy is higher than that of the Cu46Zr43Al7Tb4 BMG alloy.     

Microstructure and mechanical properties of Cu/Al joints brazed using (Cu,Ni, Zr,Er)-modified Al—Si filler alloys

To design a promising Al—Si filler alloy with a relatively low melting-point, good strength and plasticity for the Cu/Al joint, the Cu, Ni, Zr and Er elements were innovatively added to modify the traditional Al—Si eutectic filler. The microstructure and mechanical properties of filler alloys and Cu/Al joints were investigated. The result indicated that the Al—Si—Ni—Cu filler alloys mainly consisted of Al(s,s), Al₂(Cu,Ni) and Si(s,s). The Al—10Si—2Ni—6Cu filler alloy exhibited relatively low solidus (521 °C) and liquidus (577 °C) temperature, good tensile strength (305.8 MPa) and fracture elongation (8.5%). The corresponding Cu/Al joint brazed using Al—10Si—2Ni—6Cu filler was mainly composed of Al₈(Mn,Fe)₂Si, Al₂(Cu,Ni)₃, Al(Cu,Ni), Al₂(Cu,Ni) and Al(s,s), yielding a shear strength of (90.3±10.7) MPa. The joint strength was further improved to (94.6±2.5) MPa when the joint was brazed using the Al—10Si—2Ni—6Cu—0.2Er—0.2Zr filler alloy. Consequently, the (Cu, Ni, Zr, Er)-modified Al—Si filler alloy was suitable for obtaining high-quality Cu/Al brazed joints.     

Microstructure and mechanical properties of Zr-Cu-Al bulk metallic glasses

Zr49Cu46Al5 and Zr48.5Cu46.5Al5 bulk metallic glasses（BMGs） with diameter of 5 mm were prepared through water-cooled copper mold casting. The phase structures of the two alloys were identified by X-ray diffractometry（XRD）. The thermal stability was examined by differential scanning calorimetry（DSC）. Zr49Cu46Al5 alloy shows a glass transition temperature, Tg, of about 689 K, an crystallization temperature, Tx, of about 736 K. The Zr48.5Cu46.5Al5 alloy shows no obvious exothermic peak. The microstructure of the as-cast alloys was analyzed by transmission electron microscopy（TEM）. The aggregations of CuZr and CuZr2 nanocrystals with grain size of about 20 nm are observed in Zr49Cu46Al5 nanocrystalline composite, while the Zr48.5Cu46,5Al5 alloy containing many CuZr martensite plates is crystallized seriously. Mechanical properties of bulk Zr49Cu46Al5 nanocrystalline composite and Zr48.5Cu46.5Al5 alloy measured by compression tests at room temperature show that the work hardening ability of Zr48.5Cu46.5A15 alloy is larger than that of Zr49Cu46Al5 alloy.     

Microstructure and thermal expansion of copper-based amorphous alloys during structural relaxation

(Cu43Zr48Al9)98Y2 amorphous alloy bar was prepared by the arc melting copper mold absorption casting method,and then,the amorphous alloy was annealed at different temperatures for different times.The influence of heating rate on thermal expansion and thermal stability was studied by thermomechanical analysis(TMA),and the microstructure evolution of the amorphous alloy during structural relaxation and crystallization was studied by XRD and TEM.Results show that the structural evolution behavior of the(Cu43Zr48Al9)98Y2 amorphous alloy can be divided into five different stages(structural relaxation preparation stage,structural relaxation stage,first crystallization stage,second crystallization stage,and grain growth stage).When the heating rate is 20 K/min,the amorphous alloy has the smallest thermal expansion coefficient and the best thermal stability.The width of the supercooled liquid region is 66.42 K.Samples with different relaxation states were prepared by annealing at the heating rate of 20 K/min.The structural evolution of amorphous alloys with different relaxation states is as follows:amorphous→CuZr2+AlCu2Zr7→CuZr2+AlCu2Zr7+CuZr(B2)+CuZr(M)+Cu10Zr7→CuZr2+AlCu2Zr7+CuZr(B2)+CuZr(M).After annealing at 706 K and 726 K(in the supercooled liquid region)for 1.5 h,the amorphous-nanocrystalline composites were obtained.When the annealing temperature is 706 K,the crystallization process of the sample is as follows:amorphous→Cu10Zr7→Cu10Zr7+CuZr,and for the sample at 726 K,it is as follows:amorphous→CuZr2+AlCu2Zr7+Cu10Zr7→Cu10Zr7+CuZr2→CuZr2+CuZr(B2)+Cu10Zr7.     

冷却速率对Zr61.6N16.6Cu13.8Al8非晶合金力学性能的影响

采用铜模吸铸法制备了阶梯形的Zr61.6N16.6Cu13.8Al8非晶合金，利用x射线衍射（XRD）分别对不同直径的合金试样进行结构分析，利用万能试验机及扫描电镜对试样进行压缩试验和断口形貌分析。研究表明，由于冷却速度的影响，合金试样直径为3mm时是非品结构；直径为4mm和6mm时晶体相增多，甚至为完全晶体相结构；对于Zr61.6N16.6Cu13.8Al8合金，直径为3mm时的断裂强度可达到1703MPa，塑性变形可达到1．7％，适当体积晶体相的加入可以有效提高非晶材料的塑性。     

新型铜合金/非晶复合材料的挤压成形特性

基于大块非晶在过冷液相区间具有较好的热塑性成形特点,选择铜基非晶Cu40Zr44Ag8Al8和铜合金,通过挤压成形工艺,制备出一种新型的铜合金/非晶复合材料;在703 K和挤压速度为0.4 mm/min下对该复合材料进行挤压,获得铜合金、非晶复合材料棒材.通过光学金相(OM)、X射线衍射(XRD)、示差扫描量热分析(DSC)和维氏硬度测试(HV)对挤压变形前、后芯部非晶进行形貌观察和结构分析.结果表明:芯部非晶在挤压前期呈不均匀分布,而后分布非常均匀;结合XRD、DSC和硬度的结果分析,在703 K下挤压后,芯部非晶没有发生晶化.     

Refinement of primary Si in Cu–50Si alloys with novel Al–Zr–P master alloy

In this article, a novel Al-6Zr-2P master alloy with ZrP particles was successfully synthesized, and the refining performance of this novel master alloy for the primary Si in Cu-50Si alloys was also investigated. By means of the fracture plane observation, it is found that the ZrP phase would precipitate first in the solidification process, and then, the ZrAl 3 phase grows around them. Furthermore, it is observed that the refining effect can be remarkably improved by changing the addition sequence of the raw materials. After the melting of commercial Cu, the 2.0 wt% Al-6Zr-2P master alloy and crystalline Si were added in sequence, and the mean size of the primary Si in Cu-50Si alloy can be significantly refined from 255.7 to 75.3 lm. Meanwhile, the refining mechanism was discussed in detail.     

快速压铸法制备(Zr_(0.55)Al_(0.10)Ni_(0.05)Cu_(0.30))_98Er_2多孔非晶合金

采用快速压铸法制备了多孔非晶合金。利用NaCl颗粒作为预制型,将熔融的合金倒入卧式压铸机的容杯中进行快速压铸,然后去除盐型,得到直径达40mm、长度大于10mm、孔隙率大于50%、孔隙直径可控制在0.3～3mm之间的(Zr0.55Al0.10Ni0.05Cu0.30)98Er2多孔非晶合金。XRD分析表明所制备的多孔试样组织为非晶结构。采用SEM观察到孔隙之间具有良好的连通性,孔壁厚度小于1mm。热分析结果表明该泡沫的玻璃转变温度、晶化温度和晶化放热量分别为388℃、476℃和-37J/g,与实体非晶合金一致。