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HYDROGEN SORPTION BY SOME EARLY-LATE TRANSITION METAL GLASSES
F. Spit, J. Drijver, W. Turkenburg, S. Radelaar
To cite this version:
F. Spit, J. Drijver, W. Turkenburg, S. Radelaar. HYDROGEN SORPTION BY SOME EARLY-LATE TRANSITION METAL GLASSES. Journal de Physique Colloques, 1980, 41 (C8), pp.C8-890-C8-893.
�10.1051/jphyscol:19808220�. �jpa-00220327�
JOURNAL DE PHYSIQUE CoZZoque C8, suppldment a u n08, Tome 41, aoCt 1980, page
C8-890
H Y D R O G E N
SORPTION BY SOME EARLY-LATE TRANSITION METAL
G L A S S E S F.H.M. Spit, J.W. Drijver, W.C. Turkenburg and S. RadelaarS t a t e U n i v e r s i t y l l t r e c h t , Department of ' ~ e c h n i e a Z P h y s i c s , P.O. Box 80.000, 3508 TA U t r e c h t , t h e N e t h e r l a n d s .
Abstract.- The hydrogen sorption behaviour of amorphous CU~,,Z~,~, Ni, Ti,,, Ni,,Ti3
,
Ni62Ti29Zr9, Ni Zr Ni6 Nb,, and Ni50NbSo obtained by melt spinning ISdescribes.
The first tiree alloys have6 4 36'
a relatively fow crystalllzatlon temperature and these alloys either could not be made completely amorphous or crystallized during hydrogen sorption. The highest absorption occurs in Ni6\Zr3 : about 0.6 hydrogen atom per metal atom at a temperature of 333 K and a hydrogen pressure of
80
bar.Pressure-composition isotherms of Ni6L1Zr36 show no pressure plateau in the range of temperatures and pressures investigated. The isotherms of crystalline ~ i and the intermetallic compound Ni,9Zr, ~ ~ ~ r ~ ~ do show such a plateau. During 100 cycles of hydration and dehydration of amorphous Ni,,Zr36 splinters of 0.1 mm spalled off from the pieces of ribbon, but disintegration into still smaller particles , was not observed. The X-ray diffraction and DSC-scan after 100 cycles are similar to those of as- quenched material. Magnetization and Rutherford-back-scattering results indicate surface segregation of Ni in a 100 times cycled sample.
INTRODUCTION
In recent years much attention is paid to metal hydrides, especially because of their possible application in hydrogen-storage systems.
In this paper we report about the hydrogen sorp- tion characteristics of amorphous CusoZrso,
Ni50Zr5~, Ni6tTi39, Ni6*Tiz9Zr9, Ni64Zr36, Ni60Nb40 and NisoNb~o. Amorphous alloys are of interest, because these may offer advantages over crystal- line materials. The well-known h~dride-forming compound LaNis for example disintegrates into a very fine powder, which is technologically un- desirable. Splat-quenched unhydrided alloys have a high yield stress and are ductile, contrary to intermetallic compounds and therefore will be less susceptible to disintegration.
EXPERIMENTAL DETAILS
Nominal compositions of the alloys investigated are CusoZrso, N ~ s o . o ~ ~ s o . o , Ni61.4Ti38.6,
Ni6,.7Ti2,.1Zr9.2, Ni63.7zr36.3, Xiso.oNh40.0, Ni~0.3Nb49.7.
The preparation of the amorphous alloys and the method to measure the pressure-composition iso- therms have been described in an earlier paper ( I ) . Calorimetric measurements are performed with a differential scanning calorimeter. The hydrogen content of the purge gas used in the DSC (purified Ar) is monitored. In this way the hydrogen evolu- tion and the heat effect are observed simultaneous- ly. The magnetization measurements are performed with a vibrating sample magnetometer. Measurements of the surface composition are done by Rutherford- backscattering of 2 MeV ~e+-ions.
RESULTS AND DISCUSSION
The crystallization temperatures and heats of crystallization measured by means of DSC are sum- marized in Table I. X-ray diffractograms of
Ni50 Zrso and of Ni6 1 Zr3 indicated the presence of
Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19808220
some c r y s t a l l i n e m a t e r i a l . A c t i v a t i o n o f most
l o o -
a l l o y s was p o s s i b l e a t a b o u t 530 K by c y c l i n g t h e hydrogen p r e s s u r e between vacuum (lo-' T o r r ) and 30-60 b a r . A c t i v a t i o n o f N i S 0 Z r 5 0 a l r e a d y o c c u r r e d a t 310 K. U n f o r t u n a t e l y c r y s t a l l i z a t i o n took p l a c e s i m u l t a n e o u s l y : t h e DSC-scan a f t e r h y d r a t i o n showed no amorphous t o c r y s t a l l i n e t r a n s i t i o n and t h e X-ray d i f f r a c t i o n p a t t e r n was v e r y s i m i l a r t o t h a t of c r y s t a l l i n e NiZrH3 (2; f i g . I ) . Also
Fig 2. P-C- isotherms of amorphous Ni64Zr36.
CusoZrso c r y s t a l l i z e d d u r i n g hydrogen s o r p t i o n and t h e d i f f r a c t o g r a m showed l i n e s c o r r e s p o n d i n g t o
l O o ~ ~ , ~ r . ~ . , ~ r . ! . ~
c r y s t a l l i n e Cu and ZrHz; t h e NiNb- and N i T i - a l l o y s d i d remain amorphous ( s e e T a b l e I ) . By h e a t i n g hy- d r i d e d N L ~ Z Q ~ , N i b l T i 3 9 , N i 6 D N b 4 ~ and N i s 0 k % ~ o i n t h e DSC u n d e r A r purge g a s hydrogen d e s o r b e d from 300 K, 500 K and 700 K r e s p e c t i v e l y . Ni,zTizu Zr9 a b s o r b e d a b o u t 0 . 2 hydrogen atom p e r m e t a l atom and Ni64Zr36 about t w i c e t h a t amount a t
j y : :
,
001 , , , , CRYSTAL1 ye;i'?6,3\ IN€0.0 . I .2 . 3
.
. S . 6 . 7X - r a y D I F F R A C T O G R A M S 0 1 N ~ ~ ~ z ~ ~ ~ H/V
I N T E N S I T Y Fig 3. p-C-isotherms of crystalline Ni64Zr36.
D I F F R A C T I O N ( o r b u n t l ~ )
n e a r l y t h e same t e m p e r a t u r e .
Research was c o n c e n t r a t e d on Ni64Zrj6 and r e l a t e d
4.0 1.5 3 0 2 0 7 0 c r y s t a l l i n e compounds. The i s o t h e r m s o f amorphous
A Y G L E Of D I F F R A C T I O N ( 2 8 8n d e g r e e s )
Fig 1. X-ray diffractogram of N i 5 g Z r ~ in the Ni64Zr36 d i d n o t show a p r e s s u r e p l a t e a u ( f i g . 2 ) . asquenched state and after hydrogen sorption.
The 5 3 3 K P-C i s o t h e r m s o f amorphous and c r y s t a l - TABLE I
ALLOY
CUSO Zrs o N ~ S O Z ~ S O
N i 6
1 Ti3 9Ni62Ti29Zr9
N i 6 4 Z ~ J 6
NiboNb40 N ~ S O N ~ S O
X-RAY DIFFRACTION DATA A=Amorphous, C = C r y s t a l l i n e TC=Traces o f C r y s t a l l i n i t y DSC-DATA
CRYSTALLIZATION TEMPERATURE 8 HEAT
MAXIrilTM AMOUNT OF, ABSORBED HYDROGEN
AS-QUENCHED A TC T C A A
A A
L
K
720 730 750 835 84 0
9 30 940
HIMmax
0 . 2 1
.o
0.2 0 . 4 0 . 6 HYDRIDED
c c
TC A A
A A kJ/mol
4.6 4.0 2.4 2.4 3.5
3 4
measured a t
-
30 b a r and a t e m p e r a t u r e o f :
K 350 300
420 433 333
JOURNAL DE PHYSIQUE
l i n e N i 6 4 Zr36 w e r e a l m o s t s i m i l a r , b u t t h e 433 K and 333 K i s o t h e r m s showed a c l e a r d i f f e r e n c e ( f i g . 3 ) . Because c r y s t a l l i n e N i 6 4 Zra6 i s a n e u t e c - t i c a l l o y composed of . t h e i n t e r m e t a l l i c compounds N i l o Z r 7 and NisZr2 a l s o t h e 433 K and 333 K i s o - t h e r m of t h e s e compounds were measured ( f i g . 4 ) .
took
,
I I I I 1 I I' f .
= Nlto Z r 7.
= NI, Zr,0.01 1
I
00 01 02 0 3 04 0.5 0.6 07 0 8 09 10
HIM
Fig 4. P-C-isotherms of the intermetallic compounds NiloZr7 and NigZr2.
The i s o t h e r m of c r y s t a l l i n e N i 6 4 Z r 3 6 c l o s e l y a p p r o x i m a t e a weighted a v e r a g e o f t h e i s o t h e r m s of N ; ~ Zr2 and N i l Zr7
.
From t h e absence o f a p r e s s u r e p l a t e a u i n t h e P-C- c u r v e s of amorphous N i a 4 Z r 3 6 i t can b e concluded t h a t no h y d r i d e w i t h a d i s c r e t e c o m p o s i t i o n i s f o r - med a t t e m p e r a t u r e s between 333 K and 533 K. How- e v e r t h e p r e s e n c e o f h y s t e r e s i s a t t h e l o w e s t tem- p e r a t u r e p o i n t s t o h y d r i d e f o r m a t i o n i n s t e a d o f an e x t e n d e d H-solution. Also t h e i s o t h e r m s do n o t obey S i e v e r t s ' l a v .
From t h e P-C i s o t h e r m s we c a l c u l a t e d t h e e n t h a l p y of f o r m a t i o n of t h e t e r n a r y h y d r i d e s of N i 6 4 Z r 3 6 and t h e r e l a t e d c r y s t a l l i n e a l l o y s . I n T a b l e 2 t h e s e v a l u e s a r e compared'with t h e r e s u l t s o b t a i n e d from t h e a l l o y model developed by Miedema and co- workers (3-5). Only t h e v a l u e s f o r N i s Zrz d i f f e r w i d e l y , p r o b a b l y due t o t h e low amount o f hydrogen absorbed by t h i s compound. These r e s u l t s w i l l b e
TABLE 2
The e n t h a l p i e s o f f o r m a t i o n o f Zr-, Ti- and Nb-hy- d r i d e a r e -163, -125 and -25 kJ/mol Hz r e s p e c t i v e l y . Not u n d e r s t o o d i s why t h e sequence of t h e tempera-
t u r e s a t which hydrogen s t a r t s t o d e s o r b by h e a t i n g i n t h e DSC (300 K , 500 K and 700 K r e s p e c t i v e l y )
A l l o y
i s j u s t opposed t o t h e s e q u e n c e o f t h e s t a b i l i t y o f t h e b i n a r y Zr-, Ti- and Nb-hydrides.
The amorphous N i 6 4 Z r 3 6 samples d i d remain amor- phous even a f t e r 100 hydrogen a b s o r p t i o n - d e s o r p t i o n c y c l e s ( f i g . 5 ) . I n t h e h y d r i d e d s t a t e t h e samples were b r i t t l e ( p i e c e s of a b o u t 0 . 1 mm s p a l l e d o f f
from t h e r i b b o n (10 mn x 1 mm x 0.04 m m ) ) , b u t a f - t e r d e h y d r a t i o n t h e d u c t i l i t y was r e c o v e r e d , a l s o of t h e s m a l l s p l i n t e r s . B e s i d e s t h e s i z e o f t h e s p l i n t e r s was s t i l l l a r g e compared t o t h e p a r t i c l e s i z e of t h e LaNis-hydride powder (< 0.005 mm).
E n t h a l p y of f o r m a t i o n (kJ/mol Hz)
d i s c u s s e d i n d e t a i l e l s e w h e r e .
From PC i s o t h e r m s
T E M P E R A T U R E ( K )
Fig 5. DSC- and hydrogen desorption-scan of hydrided Ni64Zr36.
From Miedema mode 1
-
20-
48-
48-
52Nis Zrz
N & 4 Zr36 amorph.
N i a 4 Z r 3 , C r y s t . N i l 0 Z r 7
- 3 9 t 4
-
41 f 4-
44 f 6 - 4 7 t 5As-quenched samples of Ni642r36 were p a r a m a g n e t i c , w h i l e samples which had undergone 100 s o r p t i o n cy- c l e s Were s u p e r - p a r a m a g n e t i c . The s a t u r a t i o n v a l u e o f t h e m a g n e t i z a t i o n c o r r e s p o n d e d t o t h e
s e g r e g a t i o n o f 1.7 % of t h e Ni-atoms i n t h e form of m e t a l l i c N i - c l u s t e r s .
F i g . 6 shows t h e R u t h e r f o r d - b a c k s c a t t e r i n g r e s u l t s f o r an as-quenched and a 100 t i m e s c y c l e d sample of amorphous Ni64Z1-36. We i n t e r p r e t e t h e d i f f e r e n - c e s between b o t h p r o f i l e s a s a Ni-enrichment n e a r t h e s u r f a c e of t h e h y d r i d e d sample. From t h e e l e c -
SlTY ( a r b
"nits)
I
R U T H - B A C K - S C A T T E R I N G
2 MeV He'- N I ~ ~ Z ~ ~ ~
1
ENERGY 0:. Of B A C K - S C A T T E R E D P A R T I C L E S 1.0 1 1 47
( M e V ).J
F i g . 6 . R u t h e r f o r d - b a c k s c a t t e r i n g o f 2 MeV ~ e + - i o n s on an as-quenched and a 100 t i m e s h y d r i d e d
~ i 6 4 Z r 3 6 sample. The e n e r g y s c a l e c o r r e s p o n d s w i t h a d e p t h - s c a l e d e p e n d e n t on t h e mass o f t h e atom, by which t h e ~ e + - i o n i s b a c k s c a t t e r e d .
t r o n i c s t o p p i n g power, which i s about 500 eV/nm, i t i s c a l c u l a t e d t h a t t h e t h i c k n e s s o f t h e Ni-en- r i c h e d s u r f a c e l a y e r i s a b o u t 0.05 pm. Comparison w i t h t h e m a g n e t i z a t i o n measurements i n d i c a t e s
t h a t t h e s e g r e g a t i o n of m e t a l l i c N i a l s o t a k e s p l a c e i n t h e bulk. F o r c r y s t a l l i n e TiFe and LaNis Schlapbach e t a 1 ( 6 ) and Siegmann e t a 1 (7) found o n l y a s u r f a c e s e g r e g a t i o n of t h e second component
(Fe, N i r e s p e c t i v e l y ) . For a 1500 t i m e s c y c l e d sample of FeTi f o r example t h e y found a n Fe-en- r i c h e d l a y e r w i t h a t h i c k n e s s o f a b o u t 0.05 u m j u s t below t h e s u r f a c e .
CONCLUSIONS
-
Of t h e a l l o y s w i t h a r e l a t i v e l y low c r y s t a l - l i z a t i o n t e m p e r a t u r e (750 K o r l e s s ) , C u ~ o Z r s o , N i 5 0 Z r 5 0 and N h l T i 3 9 , t h e f i r s t two c r y s t a l l i z e d u r i n g hydrogen s o r p t i o n . The amount of c r y s t a l - l i n e m a t e r i a l p r e s e n t i n N b j T i 3 9 does n o t i n - c r e a s e .-
The a l l o y s w i t h a r e l a t i v e l y h i g h c r y s t a l l i z a - t i o n t e m p e r a t u r e (835 K o r h i g h e r ) , N i 6 2 Ti29 Zr9,
N i 6 4 Z r 3 6
,
Ni60Nbq0 and Nis0Nb50,
do n o t c r y s t a l - l i z e d u r i n g hydrogen s o r p t i o n .-
Under Ar amorphous N i ~ , 4 Z r 3 ~ d e s o r b s hydrogen a t lower t e m p e r a t u r e s t h a n amorphous NiTi- and NiNb-alloys of comparable c o m p o s i t i o n .-
The i s o t h e r m s o f amorphous Ni64Zr36 do n o t show a p r e s s u r e p l a t e a u .- The d i s i n t e g r a t i o n of amorphous samples d u r i n g hydrogen s o r p t i o n i s l e s s s e v e r e t h a n t h a t of c r y s t a l l i n e i n t e r m e t a l l i c compounds
-
I n a 100 t i m e s c y c l e d sample o f N L j 4 Z r 3 6 s e g r e - g a t i o n of N i found p l a c e .LITERATURE
I ) F.H.M. S p i t , J . W . D r i j v e r and S . R a d e l a a r . Z . S c h r . Phys. Chem. N . F . , G (1979) 225.
2 ) J-L. Baron, A. V i r o t e n J . D e l a p l a c e . J . Nucl.
Mat.
83
(1979) 286.3) A.R. Miedema, R. Boom, F.R. d e Boer. J . L e s s Corn. M e t a l s
41
(1975) 283.4) A.R. Miedema. J . Less Corn. M.
66
(1976) 67.5) A.F. Miedema, K.H.J. Buschow, H.H. van Mal.
J . L e s s C o w . M.
49
(1976) 463.6 ) J . S c h l a p b a c h , A. S e i l e r and F. S t u c k i . Mat.
Res. B u l l .
2
(1978) 697.7) H . C . Siegmann, L. Schlapbach and C.R. B r u n d l e . Phys. Rev. L e t t .
40
(1978) 972.ACKNOWLEDGEMENTS
The a u t h o r s a r e v e r y g r a t e f u l t o E . K u i p e r s f o r p e r f o r m i n g m a g n e t i z a t i o n measurements. P a r t i c i p a - t i n g s t u d e n t s were K. Blok, W. C l a a s s e n , E . Hen- d r i k s , M. Kramer, B. Wevers and G . Winkels