Materials Dransactons, JIM, Vol. 41, No. $ (2000) pp. $77 to S80 Papers from JIM Fall Meeting (1999) (©2000 The Jpan Insitute of Metals Effects of Additions of BCC Former Elements on Protium Absorbing Properties of Cr-Ti-V Alloys*! ‘Takeshi Fuda*?, Kaname Matsumoto*?, Yukio Tominaga*?, Takuya Tamura*?, ‘Takahiro Kuriiwa*?, Atsunori Kamegawa"? and Masuo Okada Department of Materials Science, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan ‘Vanadium-based alloys with BOC structure are known to absorb high content of protium. The reduction of costs of the alloys requires to lower V conteat and to have higher protium capacity. The decrease of the V content in the alloys appears to form Laves phases, which resuls in reduced protium capaci: It is expected tht BCC former addition to the alloys wil form BCC phase with less V content nhbiing ormation of Laves phase. The effects ofthe addition of BOC former elements suchas Nb, Ts, Mo, and W on protium absorbing properties and the phases of Cr-T-V-M alloys have heen studied. It has been found that Nb, Ta, and Mo adions se effective ia forming BCC stactres ‘wih improved homogeneity ofthe alloys, resulting in Mattening the slope of plateau region oftheir PCT curves, (Received December 26,1999; ln Final Form February 10,2000) Keywords: protium storage alloy, chromium-itaniun-vanadiam alloy, adliona element, body centered cubic phase, homogeneity 1. Introduction Presently-used protium absorbing MmiNis alloys have the protium (H atom) capacity of ~1.2mass%H, and have been widely used as the negative electrode of secondary electric batteries. Recently, hydrogen fuel cell (FC) cars are actively proposed as a candidate of the emission-free vehicles. Uti- lization of protium absorbing alloys as the hydrogen storage tank for FC-cars is proposed for one of the possibilities. But the protium capacity of current alloys is insufficient for their usage as the hydrogen tank. Thus the development of high protium absorbing alloys is highly required. ‘Vanadium-based alloys with BCC structure are known to have protium absorbing capacities of more than 3.6mass% at room temperature,” but they desorb only about a half of the absorbed protium. It is reported that, in Ti-V-Ma al- loys, ‘Laves phase related BCC solid solution’ has a good bsorption- 99.6at%; V > 99.9 at%; and Cr > 99.99 at%. Samples ‘were remelted four times to ensure their homogeneity. Resultant phases and lattice parameters of the BCC phase ‘were determined by an X-ray diffractmeter (XRD) using Cu- Ka radiation (Rigaku, RINT2000 System). The microstruc- tures were observed by scanning electron microscopy (SEM, Hitachi $-530) with an energy dispersive X-ray spectrom- eter (EDX, Horiba EMAX-5770W). Pressure-composition- temperature (PCT) curves were measured with a Sieverts-type apparatus at 313 K without activation process. The alloy eas- ily absorb the hydrogen at room temperature at Ist cycle and there is no need to activate the alloy. The zero line of protium concentration on the PCT curves was reset in every cycle after evacuation 3. Results and Discussion Figure 1 shows XRD pattems of Cr-32.5T:-(20 — x)V- XM alloys (M_= Nb,Mo) (x = 0,2.5,5,10,20) in cast- state. The primary phase of each alloy (x = 0-5) was a BCC phase, but other phases such as Laves phase and residual added Mo appeared inthe alloys with more than 10at% of Nb and Mo, respectively. The obserbed phases in the Cr-32.5Ti— (20 — x)V-xM (M = Nb,Ta,Mo,W) (x = 0,2.5,5, 10,20) as-cast alloys are summarized in Table 1. The BCC phases ‘were formed mainly in the alloys with less than 5 at%Nb, Ta, Mo or W. However, ClS-type Laves phases appeared in the alloys withthe addition of more than 10%Nb and Ta, On other hand, all Mo or W added alloys have mainly BCC phase. But residual Mo or W appeared in the alloys with more than 10%Mo or S%W. The characteristics of additional ele-ss 1. Fada eral. Intensity (arb. units) Intensity (arb. units) 20 30 40 «50 60 70 80 20 Fig. 1 XRD pattems of C-32.511-(20 ~ x}V-xM as-castalloys (x = 0,25, ‘Table 1 The appeared phases ofthe Cr 51-20 ~ )V-aM alloys in as-catstate (= Nb T Mo, W) (5 0,25, 510,20. xe) re s 20 e as 10 Lives aves ” poe Swi ei) rn ™ Boc cc as Bee Mo noc Bec + + Mo Mo BOC BoC BoC w Boe + + + w w w ‘ments would be classified into two groups; Nb or Ta tends to form Laves phase as indicated in the binary phase diagram (NbCr, TaCr:), while Mo and W form complete BCC solid solutions with Cr. Figure 2 shows PCT absorption curves at 3rd cycle of C¥-32,5T-17.5V-2.5M alloys (M = V,Nb, Ta, Mo, W). The plateau pressures on the curves of the alloy were observed to decrease with Nb addition, and to increase with Ta, Mo and W addition. The slopes of plateau region on the curves was decreased by Nb, Ta and Mo addition but increased with W addition. ‘The Cr-Ti-V alloy without other additives ex- hibits a protium absorbing capacity of 2.6mass%. Nb and ‘Ta addtion slightly decreased the capacity, while Mo addition hardly affected the capacity of the original alloy. The addition of W to the alloys significantly decreased the capacity. Figure 3 shows a schematic illustration of a cross section, of arc-melted as-cast samples. The local compositions of the ‘cross section were analyzed at the upper (A), center (B), and ower (©) parts of the cross section. Table 2 summarized the results of EDX analysis of the various parts of arc-melted 20° 30° 40° 50 60° 70° 80° 20 10,20), (a) M-= Nb, (6) M= Mo, CAD SATTH IT SAN 2 SEM ‘Sedeyee, absorption wank PreyMPa ou oot og 04 G8 1218" 202428 Proium Concentration mass Fig. 2 PCT absorption curves of Cr-32STH-I7.SV-25M alloys (M =V,Nb,Ta Mo, W), SS — ® ® © Fig. 3. Schematic illustration of across section of ar-melted as-cast sam le (pont analyzed area by EDX) ingots as shown in Fig. 3 in Cr-32.5TI-(20 ~ x)V-xM al- loys without additives (a) and with M= (b) Nb, (c) Ta, (@) Mo, (e) W. There is a difference of the composition between the center (B) and other parts (A, C). Especially Ti content atfects of Additions of BCC Former Elements on Protium Absorbing Properties of Cr-Ti-V Alloys ‘Tle 2 EDX analysis of the various pars of arcmeted ingots in (Cr-32STi-(20 ~ x)V-xM (4) non aditon, M= (b) Nb, (0) T, (4) Mo, snd) W. ‘Addive Observed ‘Composition element postion Ty cr @ a 468 B “3 © 4s oN a a2 28 B 47428 c 46720 © tT A 467 B 4 ce 473 @ Mo a a2 B 320 180480 c 36 68479 ow fA 39°C TAT B 20 © 193027 c 38 mae 1S the center part of the alloys was less than other parts and V content was higher. It was found Nb addition gave decrease in difference of the content between center and other pars. It was observed that the homogeneity of the composition of the ingots was improved by Ta and Mo addition. Especially [Nb addition strongly improved the homogeneity of the alloy. However, W addition deteriorated the homogeneity ofthe in- got. The reason why Nb addition has a good effect would be due to lowering of the meting point of the alloys when judged from the Cr-Nb phase diagram (ie: -20K/ateNb), VENb (slightly decrease), Ti-Nb (almost no change). It is also expected that Ta, and Mo reduce the melting points of the ingots slightly (Le: -8K/at%Ta on Cr, —3.5 K/at%Mo in Cr). On the other hand, W addition will raise the melting point of Cr (i.e: +15K/at%W), Ti or V alloys, reducing the homogeneity ofthe Cr-Ti-V alloys. From Fig. 2 and Table 2, itis expected that the slope of the plateau regions on the PCT curves is related to the homogeneity ofthe ingots ofthe alloy. For example, the slope of Nb added alloys was flater than that of non-added alloy. Figure shows PCT curves of Cr-32.5Ti-17.5V-2Nb alloy (= 0,2.5,5). Itwas found that the flatness of plateau region ‘was improved and plateau pressure decreased with increas- ing Nb content. However, the protium capacity decreased for ‘SalNb addition. Figure 5 shows PCT curves of Cr-32,5Ti- 17.5V-2W alloy (x = 0,2.5,5). [twas found that slope and pressure of plateau region increased wit increasing W con- tent, and protium capacity decreased severely with W addi- tion 4. Conclusion ‘The effects of additive elements on protium absorption- desorption properties of the Cr-Ti-V alloys were investigated and the results are summarized as follows: (1) The addition of 2.5 or $at%Nb, Ta, Mo, and W to 37 10 Fyne ascast 3rd cycle at313K 1 i on 0.01 09°04 08 12 16 20 24 28 rotium Concentration /mass% Fig. 4 PCTreures of Cr-32.5T-17,5V-2Nb alleys (x = 0,25,5) 10 Pin/MPa on oot} Age 00-04 08 12 16 20 24 28 Protium Concentration /mass% Fig. 5. PCT curves of Cr-325T1-17.5V-0W alloys (x = 0,25,5). the alloys is effective on forming mainly BCC phase in the Cr-325THIS oF 17.5)V alloys. However, the alloys with ‘more than 10%Nb or Ta addition consisted of mainly C15- type Laves phase, and 10-20%Mo and 5-20%W additions have not only a BCC phase but unmelted Mo or W phase. (2) The flatness of plateau region in PCT curves of C~ ‘Ti-V-M alloys was improved by 2.5%Nb, Ta, Mo additions, because of their improvement of homogeneity of the ingots. However the W addition deteriorated the plateau region of PCT curves because oftheir inhomogeneity of the ingots. Es- pecially, the alloys with 2.5%Nb addition exhibit a protium absorbing capacity of about 2.6 mass% with flattened plateau region Acknowledgments This work has been supported in part by a Grantin-Aid for Science Research on Priority Area A of “New Protium Function” from Ministry of Education, Science, Sports and Calture,580 1 Fada eal 5) Akiba and H. tba Intermetallic, 6 1998), 461-470. REFERENCES {9 Ha, T. Mou, M, Shionoya and E. Akiba: Materia Japan, 36 1997), ‘40-649 (in Japanese), 1}, H. 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