Zr55Al10Cu30Ni5-xPdx块状非晶合金的玻璃形成能力和热稳定性

用铜模铸造方法制备了不同尺寸的Zr55Al10Cu30Ni5-xPdx(x=0,1,3,5)块状非晶合金，采用X射线衍射（XRD）、扫描差热分析（DSC）和透射电镜（TEM）分别为Zr55Al10Cu30Ni5-xPdx块状非晶样品的结构、热稳定性和微观组织进行了研究。结果表明：x=1时，合金具有最高的过冷液相区（高达100K）及最大的热稳定性，而对合金的玻璃形成能力影响不大，这说明用适量的Pd代表Zr55Al10Cu30Ni5合金中的Ni会提高合金的热稳定性；x=3时，合金的热稳定性有所提高，但降低了合金的玻璃形成能力；x=5时，非晶合金的热稳定性和玻璃形成能力同时降低。     

异质结构Zr基非晶合金的热稳定性及力学性能

通过铜模铸造法制备了具有异质结构的Zr64.2Ni16.2Cu14.6Al5和Zr63.4Ni16.2Cu15.4Al5块体非晶合金,利用X射线衍射(XRD)、高分辨透射电镜(HRTEM)和差示扫描量热法(DSC)研究了其微观结构及热稳定性。结果表明,与均匀结构的Zr65Al10Ni10Cu15块体非晶合金相比,异质结构降低了材料的热稳定性。在单轴压缩试验中,两种Zr基块体非晶合金具有大的塑性应变(>25%)和高的屈服强度(>1.6GPa)。低的STZs势能和高的剪切带扩展抗力是异质结构Zr基块体非晶合金塑性提高的主要原因。     

Zr-Cu-Fe-Al合金的非晶形成能力、热稳定性及组织结构特征

采用铜模铸造法制备了Zr-Cu-Fe-Al非晶合金,利用X射线衍射仪、差热分析仪及高分辨透射电镜,系统研究了Al含量和Cu与Fe摩尔比对Zr59(Cu0.5Fe0.5)33Al8合金的非晶形成能力、热稳定性及组织结构的影响。结果表明,随着Al含量增加,Zr59(Cu0.5Fe0.5)41-xAlx和Zr67-x(Cu0.5Fe0.5)33Alx合金的非晶形成能力均呈现先增加后降低的趋势。对于Zr59(Cu1-xFex)33Al8合金,当Cu与Fe摩尔比在5∶5~8∶2之间时,合金非晶形成能力较好。γ参数及晶化温度研究表明,Zr59(Cu0.7Fe0.3)33Al8合金具有大的非晶形成能力及高的热稳定性。此外,Zr59(Cu0.5Fe0.5)33Al8合金的HRTEM结果表明,由于Cu与Fe混合焓为正,在快速冷却条件下,合金将会发生液-液相分离,形成富Fe和富Cu两液相,之后两液相分别发生玻璃转变,最终形成高数量密度的纳米富Fe非晶粒子分布在富Cu非晶基体上的组织结构。     

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.     

添加剂对低压烧结Zr50Al15Ni10Cu25非晶态粉末力学性能的影响

以商业纯元素粉末为原料,用机械合金化方法在低真空条件下合成了以非晶态为主的Zr50Al15Ni10Cu25粉末。研究了一定量的外界添加剂C、Si3N4和SiC对体系热稳定性和晶化行为的影响。混合粉末用手工预压成形,然后在氩气氛下进行低压烧结。利用X射线衍射（XRD）、扫描电镜（SEM）、差热分析（DSC）和电子拉伸实验机对粉末样和块状样进行了测试。结果表明,合适的外界添加剂可以提高体系的析晶活化能,增强体系的热稳定性。适量的Si3N4能促进Zr50Al15Ni10Cu25非晶粉末的低压烧结性能,即有助于提高样品的烧结致密度和样品的抗弯强度。     

Crystallization of amorphous Zr70Cu30—xNix alloys

X－ray diffraction (XRD)and differential scanning calorimetry(DSC) were employed to investigate the influence of Ni content on the crystallization of amorphous Zr70Cu30-xNix(atom fration in%) alloys,Experimental results show that with the Ni content increasing the activation energies for crystallization of amorphous Zr70Cu30-xNix alloys increase correspondingly,indicating that the thermal stability is greatly improved.All the DSC traces of amorphous Zr70Cu30-xNix alloys exhibit two exothermic peaks,suggesting that the crystallization process via a double-stage ticles,while the second one corresponds to the precipitaion of nano-scale Zr2Ni phase and crystallization of residual amporphous phase,The mechanism on the crystallization of amorphous Zr70Cu30-xNix alloys was discussed.     

正电子湮没技术研究Zr41Ti14Cu12.5Ni10Be22.5块体非晶合金的结构自由体积

采用X射线衍射(XRD)仪、正电子湮没光谱(PAT)研究Zr41Ti14Cu12.5Ni10Be22.5块体非晶合金的结构特性。结果表明:原始制备的Zr41Ti14Cu12.5Ni10Be22.5块体非晶合金其正电子湮没寿命为176ps(大于正电子在纯铁中点阵空位上湮没的寿命τVFe=165ps)。在过冷液区(T=400℃)等温退火中,正电子湮没寿命随着退火时间的增加而减小。在过冷液区退火,导致Zr41Ti14Cu12.5Ni10Be22.5块体非晶合金的结构更致密。     

Ti-Zr-Be-Cu-Co块体非晶合金形成能力及其耐蚀性的研究

采用磁控溅射法制备Dyx(Co21Cu79)100-x(x=0,4,8,9,12,14)颗粒膜.XRD结果表明:添加稀土元素Dy将促进CoCu过饱和固溶体分解,此外Dy元素还具有细化晶粒的作用.磁电阻测试发现:随着Dy含量的增加,Dyx(Co21Cu79)100-x薄膜的电阻逐渐增大,而薄膜的巨磁电阻(GMR)值先升后降,当退火温度Ta=425℃时,Dy4(Co21Cu79)96薄膜的GMR值达到最大,为-4.68％.薄膜的磁滞回线表明:矫顽力Hc随退火温度的升高逐渐增大,随Dy含量的增加,却单调减小.     

Nd对Zr基非晶合金形成能力、热稳定性及耐腐蚀性的影响

利用铜模吸铸法在水冷坩埚中制备了4种(Zr0.55Al0.1Ni0.05Cu0.3)100-xNdx(x=0,1,2,3)块体非晶合金。采用XRD和DSC检测了所获合金相组成、非晶形成能力及热稳定性,并采用盐酸溶液浸泡腐蚀试验评价了不同合金的腐蚀速率。结果表明,适量添加Nd可提高Zr0.55Al0.1Ni0.05Cu0.3非晶合金的形成能力和热稳定性,但非晶合金在2mol/L HCl溶液中的耐蚀性随Nd含量的增加而降低。该结果对进一步改善和提高非晶合金的性能具有重要的参考价值。     

二次急冷淬火成形SAF2507双相不锈钢螺旋桨在SRB+IOB海水中的腐蚀行为

为了研究SAF2507双相不锈钢（SAF2507 DSS）螺旋桨叶片在含硫酸盐还原菌(SRB)和铁氧化菌(IOB)海水中的耐腐蚀性能,提出一种二次急冷淬火成形技术来成形SAF2507DSS螺旋桨叶片。同时根据螺旋桨叶片在不同二次急冷淬火成形温度下析出相的类型和析出规律,研究螺旋桨叶片在含SRB和IOB海水中的耐腐蚀性能。结果表明,当二次急冷淬火成形温度在700℃时,螺旋桨叶片表面析出少量的χ相;达到850℃时,χ相停止析出并完全转化成σ相,析出的σ相达到最大值;超过850℃时,析出的σ相开始急剧减少,到950℃时仅有少量的σ相析出。螺旋桨叶片在不同二次急冷淬火成形温度下,腐蚀电流密度、交流阻抗等电化学性能变化规律与螺旋桨叶片表层χ相和σ相的析出规律、以及χ相和σ相自身的耐腐蚀特征相吻合。二次急冷淬火成形温度在750～1050℃之间,螺旋桨叶片的耐腐蚀性能随热成形温度的升高呈增强-降低-增强规律变化,850℃时螺旋桨叶片的耐腐蚀性能最差。螺旋桨叶片二次急冷淬火成形后富Fe的表面特征,使得在SRB+IOB的作用下,螺旋桨叶片表面钝化膜被破坏,导致耐腐蚀性能降低。     

(Zr0.55Cu0.3Al0.1Ni0.05)98Er2非晶合金制备及其晶化动力学行为

为了研究SAF2507双相不锈钢（SAF2507 DSS）螺旋桨叶片在含硫酸盐还原菌( SRB)和铁氧化菌(IOB)海水中的耐腐蚀性能,提出一种二次急冷淬火成形技术来成形SAF2507 DSS螺旋桨叶片。同时根据螺旋桨叶片在不同二次急冷淬火成形温度下析出相的类型和析出规律,研究螺旋桨叶片在含SRB和IOB海水中的腐蚀性能。结果表明,当二次急冷淬火成形温度在700℃时,螺旋桨叶片表面析出少量的χ相;达到850℃时,χ相停止析出并完全转化成σ相,析出的σ相达到最大值;超过850℃时,析出的σ相开始急剧减少,到950℃时仅有少量的σ相析出。螺旋桨叶片在不同二次急冷淬火成形温度下,腐蚀电流密度、交流阻抗等电化学性能变化规律与螺旋桨叶片表层χ相和σ相的析出规律、以及χ相和σ相自身的耐腐蚀特征相吻合。二次急冷淬火成形温度在750℃-1050℃之间,螺旋桨叶片的耐腐蚀性能随热成形温度的升高呈增强—降低—增强规律变化,850℃时螺旋桨叶片的耐腐蚀性能最差。螺旋桨叶片二次急冷淬火成形后富Fe的表面特征,在SRB+IOB的作用下,螺旋桨叶片表面钝化膜被破坏,导致耐腐蚀性能降低。     

Ti-Zr-Ni-Cu非晶系的等电子浓度特征

以准晶成分Ti40Zr40Ni20为基准,在Ti—Zr-Ni-Cu系中设计出电子浓度为1.200和原子尺寸为0．1474nm的系列合金,并用铜模吸铸法制备直径为3mm的合金棒试样．结果表明,Ti12Zr55Ni13Cu20成分附近可形成块体非晶合金,而Ti3Zr60Ni12Cu25和Zr60Ni10Cu30成分点上形成了单一的四方Zr2Cu型非晶相关相．准晶、块体非晶合金和Zr2Cu相是具有相同电子浓度的电子化合物,它们在成分图上表现出鲜明的等电子浓度特征,表明块体非晶合金的等电子浓度判据适用于Ti-Zr-Ni-Cu非晶系．二十面体与截角八面体间的结构关联可作为准晶或非晶合金多型性转变成Zr2Cu相的结构模型．     

Zr57Nb5Cul5．4Nil2．6Al10大块非晶合金的晶化动力学及显微硬度

采用铜模铸造法制备直径10mm的圆柱状Zr57Nb5Cu15.4Ni12.6Al10大块非晶合金，并用X射线衍射(XRD)证明其为完全非晶态。应用示差扫描量热(DSC)分析方法测定该合金的玻璃转变的热学参量并分析其晶化过程。利用Kissinger法和Ozawa法计算了大块非晶合金表观晶化激活能。同时研究了退火温度对非晶合金显微硬度的影响。     

Effect of Si, Pd and La additions on glass forming ability and thermal stability of Zr-Ni-based amorphous alloys

In the present paper, the influence of minor additions of Si, Pd and La with representative atomic sizes on glass forming ability (GFA) and thermal stability of Zr-Ni-based amorphous alloys has been investigated using X-ray diffraction (XRD), differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and high resolution TEM (HRTEM). The results show that minor additions of La, Pd and Si can improve GFA of Zr-Ni-based alloys and La exhibits the optimum effect on enhancing GFA. The efficient cluster packing model can well explain the correlation between atomic sizes of additional elements and GFA of amorphous alloys. In addition, the relationship of the atomic size between the additional element and Zr has a more important effect on GFA than that between the additional element and Ni. The activation energy for crystallization of the Zr-Ni-based amorphous alloys with Si, Pd and La additions is obviously higher than that of the Zr_66.7Ni_33.3 amorphous alloy, and increases with decreasing distance between neighboring atoms. The thermal stability has a relation with topological short-range ordering of amorphous alloys. The proper addition of small atoms is preferential to enhance thermal stability of amorphous alloys due to stronger short-range ordering. Moreover, the small or intermediate atom addition can produce even better effect on thermal stability than the large atom addition.     

电脉冲孕育处理对Zr基块体非晶热稳定性及退火晶化的影响

通过先对Zr55Ni5Al10Cu30合金熔体施加脉冲电流处理,再利用非真空吸铸法制备出Zr55Ni5Al10Cu30块体非晶合金的方式,研究了电脉冲孕育处理对非晶热稳定性及退火晶化的影响。差分扫描量热(DSC)及X射线衍射(XRD)分析结果表明:经电脉冲孕育处理后Zr55Ni5Al10Cu30块体非晶合金的玻璃转变温度上升,晶化温度降低,过冷液相区变窄,同时玻璃转变激活能和晶化激活能有所减少。电脉冲孕育处理没有改变Zr55Ni5Al10Cu30块体非晶合金退火晶化相演变过程,但提高了非晶退火晶化率。电脉冲孕育处理对Zr55Ni5Al10Cu30块体非晶合金的晶化起到了促进作用。     

Zr-Al-Ni-Cu-Nb块体非晶复合材料的制备及热稳定性

采用结构分析和热分析手段研究了Nb对Zr65(Cu0.4Al0.3Ni0.3)35-xNbx(x=0, 3, 5, 6 7) (at%)合金玻璃形成能力和热稳定性的影响,采用铜模吸注法成功制备了非晶基体上均匀分布枝晶相的Zr65(Cu0.4Al0.3Ni0.3)28Nb7块体非晶复合材料.Nb的添加导致合金的过冷液相区间的宽度显著减小,同时,Nb的加入使得合金的原子结构更加无序化,因而合金具有更好的热稳定性.     

Crystallographic and electrochemical characteristics of melt-spun Ti-Zr-Ni-Cu alloys

Ti44Zr32Ni22Cu2 and Ti41Zr29Ni28Cu2 alloys were prepared by the melt-spinning method. The phase structure was analyzed by X-ray diffraction,and the electrochemical performances of the melt-spun alloys were investigated. The results indicated that the Ti44Zr32Ni22Cu2 alloy was composed of the icosahedral quasicrystals and amorphous phases,and the Ti41Zr29Ni28Cu2 alloy comprised icosahedral quasicrystals,amorphous,and Laves phases. The maximum discharge capacity was 141 mAh/g for the Ti44Zr32Ni22Cu2 alloy and 181 mAh/g for the Ti41Zr29Ni28Cu2 alloy,respectively. The Ti41Zr29Ni28Cu2 alloy also showed a better high-rate dischargeability and cycling stability. The better electrochemical properties should be ascribed to the high content of Ni,which was beneficial to the electrochemical kinetic properties and made the alloy more resistant to oxidation,as well as to the Laves phase in the Ti41Zr29Ni28Cu2 alloy,which could work as the electro-catalyst and the micro-current collector.     

Ti-Zr-Ni-Cu非晶钎料

根据Si3N4陶瓷钎焊性和非晶形成能力的要求，确定非晶钎料合金成分为Tj40Zr25Nj15Cu20；采用单辊熔体快淬法成功制备了箔带状Ti40Zr25Ni15Cu20钎料合金，并通过X射线衍射、差热分析、电镜线扫描等分析手段证实其为非晶态。试验结果表明，Ti40Zr25Ni15Cu20合金其约化玻璃温度Trg=0．76，过冷液相区△Tx=78K。     

Zr-Ti-Cu-Ni-Be大块非晶合金等温晶化过程相分离研究

利用差示扫描量热法(DSC)和透射电镜(TEM)对Zr41.2Ti13.8Cu12.5Ni10Be22.5(at％)大块非晶合金的等温晶化过程和析出相进行了研究。结果表明，大块非晶合金在等温晶化过程中表现出多阶段相析出行为，并且在不同的晶化阶段，析出相也有所不同。在第1个晶化阶段，析出相主要是体心四方(b.c．t)结构的Zr2Cu相；而在晶化的第2个阶段，晶化相主要为简单六方结构的ZrBe2相。从一定程度上证实了Zr41.2Ti13.8Cu12.5Ni10Be22.5大块非晶合金在发生晶化时会形成富Zr区和富Be区，即有相分离的趋势。XRD测试的结果也证实了非晶合金在发生完全晶化时，主要的晶化产物为Zr2Cu和ZrBe2相。     

Zr55Al10Ni5Cu30块状非晶合金靠近玻璃转变点的等温纳米晶化

研究了Zr55Al10Ni5Cu30块状非晶合金靠近玻璃转变点等温晶化过程。结果表明：420℃退火5h,出现了尺寸为20nm左右的晶相,同时,非晶基体也出现了尺寸为1－2nm分布均匀的团簇状结构;退火10h,析出的晶相尺寸为20－50nm,所占的体积分数为40％;退火20h之后,非晶相完全转变为亚稳相,析出的晶相尺寸为50nm左右,并没有出现明显的长大现象。退火得到的晶相为Cu10Zr7,Zr2Ni及一些未能标定的相,这些相在420℃具有相对的稳定性,没有问题稳定相转变。退火后,残余非晶相的热稳定性降低。等温退火过程经历了从非晶相→团簇状结构→亚稳相的转变过程。