源自Ni--Nb共晶团簇式的Ni-Nb-(Zr, Ta, A

1、478Vol.47No.82011810031008ACTA METALLURGICA SINICA Aug. 2011pp.10031008 NiNbNiNb(Zr,Ta, Ag(, 116024 +NiNb .,Ni 59. 5Nb 40. 5(Ni0. 5Nb 0. 5Ni 6Nb 6Ni3, (Ni0. 5Nb 0. 5Ni 6Nb 6Ni 6Nb 7(Fe7W 6(Ni0. 5Nb 0. 5.,NiNbNi 62Nb 38NiNi 6Nb 6Ni3, ,Ni.NiNi 6Nb 6Ni3,3Zr, TaAg,NiNb-(Zr,Ta, Ag,3mm.,NiNi 6Nb 5TaNi3T g

2、 (935KT x (952K;(0.3%,NiNi 6Nb 5ZrNi3NiNi 6Nb 5TaNi33.23.4GPa. NiNb,+TG139.8A0412 1961(201108 1003 06COMPOSITION DESIGN OF NiNb(Zr,Ta, Ag TERNARY BULK METALLIC GLASSES BASED ON CLUSTER FOR-MULA OF NiNb EUTECTICYUAN Liang, QIANG Jianbing, PANG Chang, WANG Yinmin, WANG Qing, DONG ChuangKey Laboratory

3、of Materials Modication (DalianUniversity of Technology, Ministry of Education, Dalian 116024Correspondent:QIANG Jianbing, associate professor, Tel:(041184709336, E-mail:qiangSupported by National Science Foundation of China (Nos.50901012and 51041011, National Basic Re-search Program of China (No.20

4、07CB613902 and Cultivation Fund of the Key Scientic and Technical Innovation Project, Ministry of Education of China (No.707015Manuscript received 20110204, in revised form 20110415ABSTRACT A clusterplusglue atom model was employed to design NiNb based ternary bulk metallic glasses. The binary eutec

5、tic point Ni 59. 5Nb 40. 5was rst interpreted by the model in form of a cluster formula (Ni0. 5Nb 0. 5Ni 6Nb 6Ni3, where the cluster is (Ni0. 5Nb 0. 5centered icosahe-dron derived from a eutectic phase Ni 6Nb 7(Fe7W 6type. It was then pointed out that the best binary glass former Ni 62Nb 38could be

6、interpreted based on the eutectic cluster formula by replac-ing the cluster center Nb 0. 5with Ni 0. 5, namely NiNi 6Nb 6Ni3=Ni62. 5Nb 37. 5. To further improve the glassforming ability, Zr, Ta and Ag are selected as alloying additions to partially replace Nb in the NiNi 6Nb 6Ni3cluster formula, and

7、 glassy rods with a critical size of 3mm are achieved at ap-propriate ternary compositions by coppermould suctioncasting. DTA measurements indicate these bulk metallic glasses exhibit high thermal stabilities, among which the NiNi 6Nb 5TaNi3alloy has the highest T g (glasstransition temperatureof 93

8、5K and T x (crystallizationtemperature of 952K. Roomtemperature compressive curves of NiNi 6Nb 5ZrNi3and NiNi 6Nb 5TaNi3alloys show they*5090101251041011,2007CB613902707015:20110214,:20110415:, 1985,DOI:10.3724/SP.J.1037.2011.00074100447 have limited plasticity with a elongation of about 0.3%,fractu

9、re strength of the NiNi 6Nb 5ZrNi3and NiNi 6Nb 5TaNi3BMGs are about 3.2GPa and 3.4GPa, respectively.KEY WORDS NiNb-based bulk metallic glasses, composition design, clusterplusglue atom modelH 1 3. , , 4,. , . NiNb . 2070, Ruhl 5Splatcooling 40%60%Ni(. , Xia 6, NiNb ,Ni 62Nb 38, 2mm. 3NiNbSn 7, NiNbZ

10、r 8, 9NiNbSb 10 , 3mm NiNb ., ,.11,12, ( . , 1315. , , fcc . , . Dong 16+, ,17 19. 20NiNbZr ,.+NiNb , NiNb, NiNbZr, NiNbTa NiNbAg , .1+11, , ( x, x ., , fcc , ,x =1;bcc, , x =3.21. NiNb 2Ni 59. 5Nb 40. 5Ni 84. 5Nb 15. 5, Ni 59. 5Nb 40. 5 Ni 62Nb 38,. Ni 6Nb 7(Fe7W 6 Ni 3Nb(Al3Ti . Ni 6Nb 7M M Ni 6Nb

11、 6, , M , Ni Nb 50%, M =0.5Ni+0.5Nb.M Ni 6Nb 6, Ni , +,M Ni 6Nb 6Nix , x =3, M Ni 6Nb 6Ni3Ni 59. 4Nb 40. 6Ni 59. 5Nb 40. 5, . 20M Ni 6Nb 6Ni3, , 1M 1 Zr 2Nb NiNb Zr M Ni 6Nb 4MZrNi3. Goldschmidt R R Zr = 0.16nm, R Nb =0.147nm, R Ni =0.125nm, R M =Ni0. 5Nb 0. 5=0.136nm, R M0. 5Zr 0. 5=0.148nm 22. AlN

12、iZr 23, +, , . , . , , ,Z , Z , . NiNb, 1. , Ni 3Nb 3CN12, , , ; Ni 6Nb 75 , 15. M M Ni 6Nb 6M Ni 6Nb 2, 4Ni, Ni 6Nb 7M Ni 6Nb 2Ni4, Z =13, , M Ni 6Nb 6, 20,8:NiNbNiNb(Zr,Ta, Ag10051Ni 6Nb 7Ni 3NbTable 1Cluster formulae of the Ni 6Nb 7and Ni 3Nb eutectic phasesPhase (typeCN cluster Cluster formula (

13、numberof atoms in unit formula, Z Ni 6Nb 7(Fe7W 6CN13NiNi 5Nb 7M NiNbM 1/6(2.17CN12M Ni 6Nb 6M Ni 6Nb 2Nb4(13CN17NbNi 9Nb 5M 3Nb2Ni 3M 1/2Nb(6.5CN15NbNi 6Nb 9Nb2Ni 3NbM 1/2(6.5CN14NbNi 6Nb 8Nb3Ni 3M (6.5Ni 3Nb (Al3TiCN12NiNi 8Nb 4Ni3Nb(4CN12NiNi 8Nb 4Ni1. 5Nb 0. 5(2CN12NbNi 12NbNi3(4 1Ni 6Nb 7Fig.1C

14、lusters centred by ve nonequivalent atomic sites in Ni 6Nb 7(Nb1, Nb 2and Nb 3are three kinds Nb atomwith dierent atom occupied position(acentered by Ni (bcentered by M (ccentered by Nb 1(dcentered by Nb 2(ecentered by Nb 3.M Ni 6Nb 6Ni3,MNi,NiNi 6Nb 6Ni3(Ni62. 5Nb 37. 5,Ni 62Nb 38.,NiNb NiNi 6Nb 6N

15、i3.NiNi 6Nb 6Ni3,3.Nb,NbZr,NbTa(R Ta =0.14nm,Nb Ag(R Ag =0.145nmNb,NiNi 6Nb 6 x Zr x Ni3,NiNi 6Nb 6 y Ta y Ni3NiNi 6Nb 6 z Ag z Ni33.299.99%Ni, 99.95%Nb,99.99%Zr, 99.95%Ta99.99%Ag100647, Ar , , 34 . 23mm, 30mm . Bruker D8X(XRD,Cu K . TA Q600 (DTA, 0.33K/s. 2mm, 4mm , Instron , 5×10 4s 1. JSM560

16、0LV(SEM. Vickers HV1000, 0.98N. 323mm XRD . , NiNi 6Nb 6 x Zr x Ni3(x =0.8 1.2, Ni Ni 6Nb 6 y Ta y Ni3(y =0.9 1.1 NiNi 6Nb 5. 95-Ag 0. 05Ni3XRD, , , Zr, Ta Ag NiNb;NiNb(Ni 6Nb 7 Ni 3Nb . XRDNiNbZr NiNb-Ta 3mm , NiNb-Ag , 3. Nb Zr Ta NiNi 6Nb 6Ni3Nb. Zr , Nb Ta , 3mm ; Ag Nb , , Ni , Nb NiNb , , Nb A

17、gZr Ta , z =0.5 NiNi 6Nb 5. 5Ag 0. 5Ni3, Ni Ni 6Nb 5. 95Ag 0. 05Ni3, 2c . Ag NiNb , Ag O , NiNb , Ag24. Zr, Ta Ag Nb,NiNb , .33mm NiNi 6Nb 5ZrNi3, NiNi 6Nb 5TaNi3NiNi 6Nb 5. 95Ag 0. 05Ni3 DTA . , DTA, .23mm XRDFig.2XRD patterns of ascast NiNbbased ternary alloy rods with a diameter of 3mm(aNiNi 6Nb

18、6 x Zr x Ni3(bNiNi 6Nb 6 y Ta y Ni3(cNiNi 6Nb 6 z Ag z Ni3DTA 2. 2 , NiNi 6Nb 5ZrNi3, NiNi 6Nb 5TaNi3Ni Ni 6Nb 5. 95Ag 0. 05Ni3, 3 T g T x890K 915K, NiNi 6Nb 5TaNi3T g , 935K; NiNi 6Nb 5ZrNi3NiNi 6Nb 5TaNi3 T rg ,. NiNi 6Nb 5ZrNi3T rg 0.626, T rg 9.8:NiNbNiNb(Zr,Ta, Ag10074NiNi 6Nb 5ZrNi3NiNi 6Nb 5-

19、TaNi3 ., NiNi 6Nb 5ZrNi3NiNi 6Nb 5TaNi3 6-Fig.3DTA curves of NiNi 6Nb 5ZrNi3, NiNi 6Nb 5Ta-Ni 3and NiNi 6Nb 5. 95Ag 0. 05Ni3BMGs at a heat-ing rate of 0.33K/s0.3%. 5NiNi 6Nb 5ZrNi3NiNi 6Nb 5TaNi3SEM., NiNi 6Nb 5ZrNi3Ni4NiNi 6Nb 5ZrNi3NiNi 6Nb 5TaNi3Fig.4Roomtemperature engineering stressstrain curve

20、sof NiNi 6Nb 5ZrNi3and NiNi 6Nb 5TaNi3glassy rods (strainrate is 5×10 4s 12NiNi 6Nb 5ZrNi3, NiNi 6Nb 5TaNi3NiNi 6Nb 5. 95Ag 0. 05Ni3Table 2Thermal parameters of the ascast NiNi 6Nb 5ZrNi3, NiNi 6Nb 5TaNi3and NiNi 6Nb 5. 95Ag 0. 05Ni3BMGsSampleT g , K T x , K T m , K T l , K T x , K T rg , K NiN

21、i 6Nb 5ZrNi389892714141434290.6260.398NiNi 6Nb 5TaNi393595214711492170.6260.392NiNi 6Nb 5. 95Ag 0. 05Ni391993514541477160.6220.390Note:T g glass transition temperature, T x crystallization temperature, T m melting point, T l liquidus tempera-ture, T x undercooled liquid span, T rg reduced glass tran

22、sition temperature, parameter 5NiNi 6Nb 5ZrNi3NiNi 6Nb 5TaNi3SEMFig.5SEM images of the fractured NiNi 6Nb 5ZrNi3(a,b and NiNi 6Nb 5TaNi3(c,d glassy rods 1008 3 NiNb Table 3 Property data of the NiNbbased ternary BMGs Compositions NiNi6 Nb5 ZrNi3 =Ni62.5 Nb31.25 Zr6.25 NiNi6 Nb5 TaNi3 =Ni62.5 Nb

23、31.25 Ta6.25 NiNi6 Nb5.95 Ag0.05 Ni3 = Ni62.5 Nb37.1875 Ag0.3125 Tg , K f , GPa E, GPa p , % HV, GPa P , g/cm3 898 935 919 3.2 3.4 162 168 0.3 0.25 9.14 9.42 9.34 8.75 9.68 8.93 Dc , mm 3 3 3 ¨    ¯ § Þ © ж Ï©À µ 47 Þ Note:

24、f fracture strengh, EYoungs modulus, p plastic strain, HVVickers hardness, mass density, Dc critical diameter · ѳº Ò Ñ Ë Ä, ѳ ½Ò ¼Ú¦¿, Ý Ôª Ñѧ ¤ . ¬ , Ag · º · &#

25、214; É , ´ ÖÍ Ê ° 2 mm · ¤, · , § ± . Å4 Í ª Ñ· ѳ f ¡ Youngs E ´¾ªºÆ p ± 3, ± ¯· Vickers ¼ ± . 3 £ , NiNi6 Nb5 TaNi3 Ñ· Ý ¬

26、ѳ ¡Youngs ´¼ , Ý ° ¾ªÆ¦Á , Ñ ° · ªÁ. 25 × ÚÒ Ñ· ѳ Tg × , Tg À¬, ѳ À¬, « Tg ¬ NiNi6Nb5 TaNi3 ª Ñ, ѳ ¬, 

27、1; 25 ° . Ni6 Nb5 TaNi3 ¢ 4 ° Û ¢¢ Ñ· È + NiNb(Zr, Ta, Ag , NiNi6 Nb6x Zrx Ni3 (x=0.81.2, Å ß ª ´ Þ ¤£ À Ѽ¢, Ni ¼¢ £ ͵ Õ Ì Ñ. NiNb(Zr, Ta, Ag ª Ñ

28、83; Ý ¸¬ ÙÆ À Ó ª, , NiNi6 Nb5TaNi3 935 K. NiNb(Zr, Ta ß ª ÑÝ ° · ªÁ, NiNi6 Nb5TaNi3 Ñ Ñ³ ¬À 3.4 GPa. Ni6 Nb6y Tay Ni3 (y=0.91.1 Ag0.05 Ni3 NiNi6 Nb5.95 3 mm © ¼¾ 1 Inoue A. Acta M

29、ater, 2000; 48: 279 2 Inoue A, Shen B L, Takeuchi A. Mater Trans, 2006; 47: 1275 3 Kimura H, Inoue A, Yamaura S. Mater Trans, 2003; 62: 1167 4 Xu D H, Duan G, Johnson W L, Garland C. Acta Mater, 2004; 52: 3493 5 Ruhl R C, Giessen B C, Cohen M, Grant N J. Acta Metall, 1967; 15: 1693 6 Xia L, Li W H,

30、Fang S S, Wei B C, Dong Y D. J Appl Phys, 2006; 99: 26103 7 ChoiYim H, Xu D H, Johnson W L. Appl Phys Lett, 2003; 82: 1030 8 Chen L Y, Hu H T, Zhang G Q, Jiang J Z. J Alloys Comp, 2007; 443: 109 9 Zhu Z W, Zhang H F, Ding B Z, Hu Z Q. Mater Sci Eng, 2008; 492: 221 10 Zhang J L, Wang Y M, Shek C H, Wang Q, Dong C. J Alloys Comp, 2010; 491: 513 11 Eckert J, Mattern N, Zinkevitch M, Seidel M. Mater