H-Ni

The H-Ni (Hydrogen-Nickel) System

By M.L. Wayman University of Alberta and G.C. Weatherly University of Toronto

Equilibrium Diagram
At Low Pressures---0.1 MPa (< 1 atm)-- of H2
The behavior of the Ni-H system depends strongly on the activity (pressure) of H. In equilibrium with H 2 pressures on the order of I atm or less,Ni exhibits the features of a classical "endothermic occluder" of H [48Smi]--it reacts endothermically with H. The result is a very low solubility(interstitial) H in (Ni) at room of temperature (H/Ni - 3 10-5)* and most characteristically a positive temperature dependence of solubility.It has been possible to gather solubilitydata over a wide range of temperature, because the rapid rate of diffusion of H in (Ni) allows equilibrium conditions to be attained in reasonable periods of time c.g. 5 to 20 minutes at 250 ~ (523 K) for some experiments of [78Pon]. Solubility data for Ni in equilibrium with 1 atm of H2 gas have been compiled in several published reports [73Rob, 76Fro, 80Ser, 83Kiu, 84Mcl] representing the results of more than 20 different solubility investigations carried out since 1907. A recent compilation by [84Mcl] excluded all data that might be influenced by spurious surface-related experimental effects; these "clean" data for polycrystalline samples are shown, replotted, in Fig. 1.

At High Pressures-->100 MPa of H2

When Ni is exposed to environments in which the H activity is very high, corresponding to H2 pressures well in excess of 100 MPa, the behavior of the Ni-H system changes markedl:~ Such high H activity can be obtained by electrochemically (cathodically) charging the Ni in an electrolyte, for example 1N H2SO4 containing an H recombination poison such as thiourea or arsenic trioxide.

Fig. 1 Arrhenlue Plot of the Solubility of H In NI at Atmospheric Pressure

Atomic percent H
10.3

i0-2

10-I

1500 7

iiooo
700

50O
15 30o 19

At Moderate Pressures--10 to 100 MPa (100 to 1000 atm)--of H2

At H2 pressures in the range of 10 to 100 MPa, the H solubility and the effect of H2 pressure on melting behavior of Ni have been studied [79Shal, 79Sha2, 80Ser, 81Sha]. H appreciably reduces the melting point of Ni (Fig. 2), but this effect diminishes above 40 MPa H2 pressure. The Ni-H phase diagram in the vicinity of the melting temperature of 50 MPa of H2 is shown in Fig. 3. The system exhibits a eutectic point at 1406 ~ (679 K) and H/Ni = 0.036 [81Sha]. The behavior at H2 pressure of 100 MPa is comparable [80Ser]. The microstructure of Ni that was melted and then quenched from the liquid phase in H atmosphere (melt composition up to H/Ni = 0.02) consists of a eutectic mixture of solid metal with H2 gas bubbles, i.e. porosity [79Sha2]. Nickel hydride is not observed following such treatments. *Throughout this assessment, H concentrations are reported as the atomic ratio of H to Ni;

23

27

/
0

9 9 [3 x t~ o er

29 34 43 68 70 Z3 ?4 84

Sie Smi Arm 81a Cot. Mcl Sta Mc/

I00

50

35

~ 10-5

i0-4
A t o m i c ratio x = HINt

10-3

From [84Mcl].

M. Wayman and G.C. Weatherly, 1989.

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H-Ni
Fig. 2 Effect of H2 Pressure on the Melting Temperature of Ni Fig. 3 Upper Corner of the NI-H Phase Diagram at a H2 Pressure of 50 MPa

Atomic percent H
I 2
I

3
]

4
I

1460t

144C 142C

1460 1440 I0
I

,4o%

20

30

40

50

1420 1400
L~ O 011 ~ O. 0 3 6

H2

Hydrogen pressure (MPa)

From [79Sha2].

M. Wayman and G.C. Weatherly, 1989.

Ni

0.01

0.02

0.03

0.04

Alternatively, the Ni can be subjected to high pressures of H2 in a pressure cell; cells capable of hydrogenation at pressures as high as 7000 MPa of H2 were reported by [78Pon]. The electrochemical techniques are simple and flexible with regard to experimental conditions, being especially useful at low equilibrium H2 pressures [76Boe]. The high-pressure cell techniques give a controlled atmosphere of well-defined H activity, which can be maintained long enough to ensure that the system has reached equilibrium [72Bar, 78Bar, 81Bar]. The attainment of high H activity is facilitated by the high fugacity coefficient of H, which can often exceed a value of 100, thus permitting higher activity at lower H2 pressure than would otherwise be possible [72Bar, 84Bar]. The two techniques are sometimes combined, for example when samples charged with H electrochemically are placed in a high-pressure cell for the determination of the equilibrium pressure-temperature-composition relationships. The high-pressure technique often is considered to give more reproducible results; however, sample preparation normally plays a major role in determining reproducibility It is frequently advantageous to carry out "sample training," whereby a sample is pretreated by a series of charge-discharge cycles to activate the surface before carrying out the measurements of interest [67Barl, 78Bar]. With the application of pressure of H2 in excess of 1000 MPa, the Ni-H system exhibits an equilibrium surface in pressure-temperature-composition (P-T-X) space. This surface is markedly similar to the P-T-V surface for a free gas. The critical point, below which the Ni-H solid solution decomposes to form the H-poor (Ni) solid

Atomic ratio x = H / N i

From [79Sha2].

M. Wayman and G.C. Weatherly, 1989.

solution and the H-rich nonstoichiometric nickel hydride/3, liesin the vicinityof 350 to 430 ~ (623 to 703 K) and 1600 to 1900 M P a of H 2 [76Pon, 79Bar]. The strong pressure dependence of the Ni-H systenl corresponds to a transition from an endothermic reaction with H2 at low pressures to an exothemnic reaction at high H2 pressures. Such a transition is predicted by the model of [80Yur], which allows calculation of the T-P conditions at which a sign reversal occurs in the temperature dependence of H solubility. This transition can also be seen in the calculated solubilitiesof [83Fuk]. Absorption and desorption isotherms for the Ni-H system at 25 and 65 ~ (298 and 338 K) are shown in Fig. 4. This figure also illustratesthe marked hysteresis that occurs in the Ni-H system. The H2 pressure necessary for the formation of/J--about 600 MPa--is significantly higher than its decomposition pressu~ 340 MPa. The decomposition pressure is believed to represent the equilibriun~ value of pressure for (Ni)-/Jcoexistence [63Sch]. The absorption isotherms show that as H is absorbed at room temperature under high-pressure conditions, the terminal solid solubility--(Ni)max--is reached soon at H/Ni <0.1. Further absorption of H occurs by the formation of/3 in equilibrium with (Ni)./3phase has the same fcc crystal structure as Ni and the (Ni) solid

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H-Ni
Fig. 4 Absorption and Desorption Isotherms at 25 and 65 ~ for the NI.H System Fig. 5 NI-H T-X Phase Diagram

Atomic percent H

0
I0 20
Atomic percent H 30 40
i

I0 20
l I

30
I

40
I

50
I

50
i

3501 300'-

T=65~ I00<:
T=25~

80C
_x ~x

250

60C

200
I
, I , I , I ~ I

0
200

0.2

0.4

0.6

0.8

1.0

Atomic ratio x = H / N /

0.2

04

0.6

0.8

1.0

!2

Atomic ratiox = H iN/

Open and closed circles show the data points for the (Ni),nax and/3min, respectively. From [77Anti. M. Waynmn and G.C. Weatherly, 1989. These electrical and nmgnetic effects are associated with the holes in the d band of Ni being filled with electrons from the H atoms. The P - T - X behavior of Ni-H is notably similar to that of the Pd-H system, but because the critical point of the latter system is at a much more easily obtainable pressure ( - 2 MPa, a factor of 1000 lower than that of Ni-H), Pd-H has been studied more widely. Other than the coordinates of the critical point, the major difference between the two systems is that the formation of #6 causes a much greater lattice expansion in Ni (5.8% increase in lattice parameter, compared with 3.5% in Pd); this clearly is related to the observation that #6rain, the minimum hydrogen content of#6 at room temperature, is higher in the Ni-H system than in Pd-H. Thereis also a much greater hysteresis in the Ni-H system. These are quantitative rather than qualitative differences; consequently, the Pd-H system has provided a valuable analog for Ni-H behavior.

From 178Bar].

M. Wayman and G.C. Weatherly, 1989.

solution, but with a high concentration of interstitial H atoms and consequently, a larger lattice parameter. As the temperature is increased, the maximum H content in (Ni) increases, while the minimum H content of (Ni) decreases; thus, the ndscibility gap narrows and finally disappears at the critical point. Above the critical point, a continuous range of H contents occurs, and the terms (Ni) and #6 then refer to the same phase. This is illustrated by the temperature-composition diagram, Fig. 5, which is a projection of the P-T-Xbehavior on an isobaric plane. Values of (Ni)n~ and #6rain measured in the vicinity of 25 ~ (298 K) by numerous workers [59Bar2, 61Bau, 63Szk, 63Wol, 64Bar2, 65Bin; 66StI; 67Barl, 67Maj, 77Ant, 78Bar, 78Pon] lie in the range 0.02 _< ( N i ) , ~ _< 0.1 and 0.6 < #6rain -< 1.0, respectively. At H contents between (Ni)n~x a n d / J n ~ (below the critical point) in the region of immiscibility, the (Ni) -~ #6 transformation can be followed by monitoring the electrical resistance, which decreases as #6 forms [67Barl, 76Pon]. Magnetic measurements are also helpful--~ is paramagnetic, whereas (Ni) is ferromagnetic; thus, as (Ni) transforms to/t, the saturation nmgnetization falls to zero in direct proportion to the anmunt of/3 (such a direct proportionality does not apply to electrical resistivity [77Bau, 81Bau]). In a similar manner, the high value of thermoelectrical power of #6 relative to (Ni) has been used to follow the (Ni) - - ~ and/~ -* (Ni) phase transformations [71Sko].

Techniques other than electrochemical and high-pressure H charging have produced nickel hydrides. Diatomic NiH has been detected spectroscopicallywhen nickel carbonyl was introduced into a burner flame [35Gay]. Hydrides have been produced as well by proton bombardment of Ni foils [64Pal] (see also [67Maj]). In all these, it is apparent that the hydride phases form only when the activity of H, especially atomic H, is high. Hence, the hydrides are unstable at room temperature and pressure, and they decay by transforming back across the miscibilitygap to (Ni), with a low H content.

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H-Ni
One consequence of the lattice expansion that occurs when/5 is formed from the (Ni) solid solution (5.8% linear expansion corresponds to 18.3% volume expansion) is that only thin pieces of Ni can be transformed to /5 during reasonable charging times. Thus, during electrochemical charging, a surface layer of hydride on the order of 30 p m maximum in thickness is formed on the cathode surface [59Bar1, 59Bar3]. The surface is seen by optical microscopy to be swollen and bulged outwards by its conversion to hydride [61Bon, 80Kit] with grain boundaries and slip lines readily visible. Under ambient conditions, the hydride decomposes over a period of a few tens of hours by evolution of H, and this process can be followed by using optical microscopy; scanning electron microscopy [80Kit], and a Bitter method of revealing ferromagnetic phases [78Jon] have also been employed in studies of/5 decomposition. These reveal that decomposition occurs by the formation and growth of plate-like(Ni) grains on the 15 surface, followed by the advance of the transformation front into the bulk/5. The volume shrinkage results in cracking from the surface inwards; both intergranular and transgranular cracks are normally observed. These changes in the surface must be related to the aforementioned "sample training" or surface activation, which when carried out prior to the measurement of absorption and desorption isotherms, improves the reproducibilityof the results. Terminal Solid Solution At low H2 pressure, below 1 MPa, Ni is a classical endothermic occluder, with a room-temperature H solubilityof about H/Ni - 3 10-5, increasing with temperature to about H/Ni - 10-3 at the melting point of 1455 ~C (1728 K) (Fig. I). Compilations of solubility data [73Rob, 76Fro, 80SeI; 83Kiu, 84Mcl] have been fittedto a solubilityequation of the form: log solubility= a - B / T
(Eq 1)

Fig. 6 Effect of H2 Pressure on the Solubility of H In (Ni)

Atomic percent H

0.5
I

1.0
I

. 1350~ o IO00~ A 800oc 9 600~

i t , /

O.

0.01

Atomic ratio x = H i N t

From |80Ser].

M. Wayman m~d G.C. Weatherly, 1989.

For example the [73Rob] compilation yielded "best fit" values: Solubility (H/Ni) = a' r exp - B ' / R T (E<t 2)

wide range of temperatures over which solubilitydata are available;because the chemical potentials of H both in the gas phase and in the solid are somewhat dependent on temperature, and because these parameters contribute to the term B' in Eq 2, their temperature dependence destroys what would otherwise be a linear relationship. The effectof the temperature dependency in the g a s p h a s e can be removed by plotting In(solubility x T7/4) vs 1/T (see [64Mcl]), but the plot remains nonlinear because of the s o l i d effects. The effect on H solubility of the transition from the ferromagnetic to the paramagnetic state at the Curie temperature is unclear. Some workers detected a drop in solubility in the vicinity of the Curie temperature [83Sha], as well as change in the heat of solution [83Vya, 83Sha]. On the other hand, in the data compiled by [84Mcl] (Fig. 1) and others, there is no discernable discontinuity at the Curie temperature. The effects of H2 pressure on solubility in the pressure range around 0.1 MPa are in accord with Sieverte' law, as given by the v ~ term in Eq 2 above [67Ebi, 71Jon, 83Vya]. The effects of H traps on solubility have also been considered. In addition to the contamination surfaces referred to above [83Kiu], dislocations and grain boundaries are potential trapping sites, and studies

where a' = 0.18 _ 0.007, P is pressure in MPa, B' = 12.5 _+ 0.3 kJ/nml, and Tis in K. Howevel; the envelope of results plotted by [73Rob] exhibited deviations from a linear relationship between log solubility and 1/T. This nonlinearity---an enhancement of H solubility at low temperatures, in contrast with values extrapolated from high temperatures--is visible in the data of other workers [71Vyk] and was both observed and considered by [84Mcl], who have compiled the data shown in Fig. 1. The nonlinearity is consistent with the trapping of H atoms in surface layers at sites provided by oxygen atoms [83Kiu]. Howevel; when data are screened to eliminate this spurious surface effect, the low-temperature enhancement remains [84Mcl]. [84Mcl] explained the nonlinearity as being a consequence of the usually

572

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H-Ni
have been carried out on the effects of cold work and grain sizeon H solubility.The resultsof these studies do not give a clear picture. By comparing single-crystal behavior with that of polycrystals or by studying polycrystals of varying grain size, some workers [73Rob, 83Vya] found no evidence for the trapping of H at grain boundaries and arguments have been made [83Kiu, 64Mcl] as to why H-grain boundary or H dislocation interactions should not cause solubility anomalies. On the other hand, other studies [74Sta, 86Lee] showed an apparent trapping of H at grain boundaries. Similarly, there are reports of enhanced solubility in cold worked Ni as a result of H trapping by dislocations [86Lee], as well as reports of the absence of such an effect [59Gri]. Thus, at present, the effects of H traps on solubility remain uncertain.
In the intermediate range of H2 pressure (10 to 100 MPa), the H solubility has been measured over the temperature range 327 to 1077 ~ (600 to 1350 K) [79Sha2, 80Ser]; the data are shown in Fig. 6. The solubility of H can be seen to be an order of magnitude higher at 100 MPa than at 0.1 MPa. Sieverts' law is obeyed reasonably well over the full pressure range up to about 1027 ~ (1300 K), but above that temperature, negative deviations are observed (solubility lower than the Sieverts' law prediction). The deviations form ideality of the gas phase and any trapping of H would lead to positive deviations from Sieverts' law, possibly explaining the nonlinearity of the lower-temperature curves in Fig. 7. The negative deviations at higher temperature have been explained as due to hydrostatic compression, as well as to "the special features of the molecular- kinetic equilibrium at the gas-metal interface" [80Ser]. At H2 pressures high enough that/3 forms, terminal solubility is synonymous with (Ni)max, the maximum hydrogen content in the (Ni) solid solution in equilibrium with /3. The shapes of the absorption isotherms below the plateaus in Fig. 4 indicate that as the H2 pressure increases, the H solubility increases. Howeveg both the H2 gas and (Ni) increasingly deviate from ideality, causing strong positive deviations from Sieverts' law as (Ni)max is approached. Values of (Ni)max do not appear to be strongly dependent on temperature below 327 ~ (600 K), as seen in Fig. 5, but may increase as the critical temperature is approached. Data from above the critical point, where the terminal solid solubility is simply the H content in equilibrium with gaseous H2 (because (Ni) and/3 are no longer distinct entities), are not yet available. Increasing the H2 pressure has also been found to lower the Curie temperature of (Ni) from about 359 ~ (632 K) in pure Ni to about 277 ~ (550 K) at a H2 pressure of about 1200 MPa [76Pon, 77Ant, 78Pon], where (Ni)max is reached at H/Ni - 0.02 [77Ant]. This is shown in Fig. 7. The exothennic nature of the H-Ni system at these high H2 pressures, in contrast to the behavior at lower

Fig. 7

T-P Phase Diagram for the NI-H System

n Curie temperature
9 (N#~#

o ~ - - ~ (Ni)

40C
o

50C

I00

O0

I"

500

1000

1500

2000

Hydrogen pressure (MPa)

From 177Ant]. The horizontal displacement between the forward and reverse transformations at any temperature represents the hysteresis (see also Fig. 4). M. Wayman and G.C. Weatherly, 1989. pressures, has been attributed [83Fuk] to the fact that AV, the volume increase due to H in solution, is smaller than Vf, the atomic volume in fluid H. As a result, the term P ( A V - Vf) tends to offset the positive heat of solution at high values of P. The elastic H - H interaction in the solid solution also plays a role here, as well as being largely responsible for the immiscibility between (Ni) and/3 in the system [72Ale].

Nickel Hydride
/3 exists in equilibrium with high pressures of H2 at temperatures below the critical point. It consists of an fcc lattice of Ni atoms, with H atoms located in the octahedral interstices [63Wol]. Occupation of all the octahedral interstitial sites by H atoms would result in a hydride with H/Ni = 1.0; observed values for/3 lie in the range 0.6 to 1.0, with a most probable value of 0.8 to 0.9. Several studies have determined H/Ni in/3 to be higher than 1.0 [77Ant, 78Pon] (see also [79Kep]), but questions have been raised with regard to this possibility [79Kep]. Values of H/Ni > 1.0 imply some occupation by H atoms of tetrahedral interstices, as discussed by several workers [67Bar2, 78Pon]. However, whether or not the H/Ni values do exceed 1.0, it is clear that high H2 pressure can raise the H/Ni ratio o f / 3 above /3n~ [59Bar2, 67Barl, 68Bau, 71Way, 78Pon]. /3 is paramagnetic [61Bau, 77Bau, 81Bau]. It has a metallic character, with a positive temperature dependence of electrical resistivity.

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H-Ni
Table I EqulUbrlum DecomposlUon and Forma. tlon Pressures for/~
Reaction

Pressure, MPa

Temperature, ~

Reference

Decomposition ......... 340 7 335 356 Formation ................ 806 12 620 645

25 25 67 RT 25 67

[65Bar] [78Bar, 80Bar] [78Bar, 80Bar] [67Bar1] {78Bar, 80Bar] [78Bar, 80Bari

The experimentally determined H2 pressures at which#6 forms and decomposes are given in Table I, and their dependencies on temperature in Fig. 7. The hysteresisis obvious, as isitsdiminishing as the criticaltemperature is approached. The spread of values may be related to the necessity for "sample training." The high decomposition pressure means that #6 is unstable at room temperature and decomposes readily.The kinetics of this decomposition and of the formation of #6 are controlled by thermally activated processes, with activation energies in the range 56 to 62 kJ/mol (decomposition) and 27 kJ/mol (fornmtion) [59Bar4, 78Bau, 80Bor]. The decomposition rate was found to be the same in air and in vacuum [60Jan1] and to be affected by both the density and distribution of dislocations [78Pie]. Magnetic studies indicated that the amount of fl increases in proportion to the square root of time during cathodic charging and decomposition [78Bau]. As noted above, other nickel hydride phases have been reported by several workers, but their existence requires confirmation under a range of conditions to assess how general their formation is. They are discussed further below.

X-ray studies in the Ni-H system are complicated by several factors. First, the limiting thickness of the/3 layer produced by electrochemical charging (-30pro) is approximately the same as the analysis depth for X R D using CuIZ~ radiation. Thus, in many instances, the sample being X-rayed has a heterogeneous H/Ni ratio (and often phase structure) within the analyzed volume. Secondly, the formation of #6 in (Ni) matrix across the miscibilitygap gives rise to markedly broadened fllines. This isbelieved to be due to the creation of a dislocation structure as a consequence of the volume expansion that accompanies the (Ni) -* fl transfornmtion. Hence, the X R D pattern of fl created in this way and of (Ni) produced by subsequent decomposition offl consists of lines that are broadened sufficientlyto impair precise latticeparameter measurements. The third factor that must be considered in interpreting X R D results from the Ni-H system is the timedependent nature of the diffractionpattern as the H is desorbed at room temperature. #6 loses H as it approaches #6rain, so its lattice parameter changes during the first hour after H charging is stopped. A Debye-Scherrer pattern, with an exposure time of some tens of minutes, will therefore show extra broadening of the #3 lines caused by the shifting peak position. On the other hand, repeated scanning of a hydride peak with a diffractometer will detect the time dependence of the lattice parameter [68Bau, 71Way]. Despite these limitations, X R D has provided useful information on both the (Ni) and/3 phases of the Ni-H system.

(NI)
The (Ni) solid solution has the fcc crystal structure of Ni, with H dissolved interstitiallyBecause at 25 ~ (298 K), the m a x i m u m H content of the solidsolution is low (H/Ni - 6 10-5 in equilibrium with 0.1 M P a of H2 and H/Ni - 0.03 in equilibrium with#6 at H2 pressures above 340 MPa), latticeparameter changes are not expected to be large.Many workers [61Bon, 67Barl, 6TMaj] were unable to detect a change in the latticeparameter of the (Ni) phase as pure Ni absorbs H. Howevel; [67Jan] reported a slight but significant difference between the lattice parameter (measured at 25 ~ of Ni (0.35213 0.00005 nm) and that of (Ni) in equilibrium with/3 (0.35218 0.00005 nm). Using the lattice expansion data of [71Bar], this corresponds to H/Ni ~ 0.02, in agreement with the estimated values of (Ni)nmx as determined from absorption isotherms and electrochemical potential measurements [64Bar2, 78Pon]. An expansion of the lattice of the (Ni) phase above that of Ni was also observed by [68Bau]. O n the basis of results from the #6phase, itis likelythat the H atoms occupy octahedral interstices in the fcc lattice of the (Ni) solid solution, but there is only indirect evidence to confirm this.

Crystal Structures and Lattice Parameters

Crystallographic studies of the Ni-H system have been carriei out mainly by X-ray diffraction (XRD), although neutron diffraction has proved valuable for locating the positions of H atoms. XRD has been performed both during and after H charging by both the pressure and the electrochemical techniques. Most of the X-ray measurements have been made at room temperatures, although in a few instances, lower temperatures have been used.

As H is absorbed, littlechange in the X R D pattern is observed until the H content reaches (Ni)max, at which time theftpattern appears. With continued H charging, the (Ni) lines weaken, whereas the #6 lines strengthen, until at #6rain,the (Ni) lines are no longer present. Increases in the latticeparameter of a phase reflectits increasing H content, as shown for fcc metals in general by [71Bar], who found the partialmolar volume of H to be constant up to H]Ni - 0.75 at a value of 1.65 cm3/mol of H (as calculatedby [72Fla]).

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H-Ni
p Nlckel Hydrlde
Numerous XRD investigations [60Jan2, 61Bon, 67Maj, 67Jan, 71Way] have reported that ~ has the fcc Ni lattice, with the lattice parameter between 0.371 and 0.3735 nm at room temperature. Many of these authors reported no increase in the lattice parameter at H contents above ~min. However, as discussed above, this may in some instances reflect the use of powder cameras with exposure times too long to detect the decay of p to #6rain after the completion of charging [68Bau, 71Way]. The lattice parameter at #6rain should be that measured when/3 is in equilibrium with (Ni); under these conditions, [67Jan] reported a lattice parameter of 0.37251 0.00008 nm. Using this value for~n~, which is assumed to be at H/Ni = 0.9, and the partial molar volume data of [71Bar], the lattice parameter at H/Ni = 1.0 can be estimated to be 0.37318 nm, in rough agreement with the values measured by [68Bau] and by [71Way] immediately atter charging at the onset of the decay toward #6rain. The/~ lattice parameter of 0.37251 nm represents a linear expansion of 5.8%, or a volume expansion of 18.3%, compared with (Ni) at its solubility limit, (Ni)max [67Jan]. The hydride phase inherits the preferred orientation of the Ni from which it is formed [64Maj, 67Msj]. Neutron diffraction studies [63Wol] showed that the H atoms are located in the octahedral interstices, giving an NaCl structure and implying a m a x i m u m H]Ni ratio of 1.0. As mentioned above, it has been suggested [67Bar2, 78Pon] that at about H/Ni ffi 0.8, some tetrahedral site occupation begins, thus explaining t h e change in the H concentration dependence of the partial molar volume of H [71Bar]. This would also account for the H/Ni ratios greater than 1.0 (if indeed reports of H/Ni > 1.0 are correct; see above). Nickel hydrides other than the fi hydride discussed above have been reported. [48Snd] referred to a hexagonal nickel hydride, whereas the results of [59Bar4] suggested the possible existence of two hydrides. Finally, [60Janl] found by electron diffraction both /~ and another fcc hydride with t h e l a t t i c e parameter 0.383 to 0.387 nm; the latter disappeared during annealing at 400 ~ (673 K).

Thermodynamics
Heat of Solution The heats of solution of H in Ni have been determined by numerous workers from the temperature dependence of the H solubility. A "best fit" value as determined by [73Rob] was found to be 12.5 kJ/mol; values measured by various workers since the date of that compilation lie mainly in the range 8 to 18 kJ/mol (Table 2). Two reports [83Sha, 83Vya] of a nmrked difference between the heats of solution above and below the Curie temperature (14.25 and 16.93 kJ/mol in the ferromagnetic state and 8.03 and 10.64 kJ/mol in the paramagnetic state) are not in accord with t h e results of other workers. This magnetic effect clearly is not related to the nonlinearity of the log solubility vs 1/T curve (Fig. 1), because the magnetic effects acts to reduce the solubility in the ferromagnetic temperature range, whereas the observed nonlinearity is in the opposite sense.
The partial molar enthalpy and excess entropy of H atoms dissolved in Ni, with respectto H atoms at rest in a vacuum and also with respect to H2 gas at 1 atm pressure, are given in Table 3; these were calculated from solubility measurements [74Sta, 75Mcl, 86Suz]. Two experimentally determined values of the entropy of

Table 2

Heats of Solution of H In NI
Comment Reference

Heat of solution, kJ/mol of []

12.7 . . . . . . . . . . . . . . . . . . . . . . 15.1 0.3 . . . . . . . . . . . . 12.5 _+0.3 ......... Compilation of 12 experiments 15.5 . . . . . . . . . . . . . . . . . . . . . . 15.1 . . . . . . . . . . . . . . . . . . . . . .
17.9 ................... Average of seven experiments 23.0 . . . . . . . . . . . . . . . . . . . . . . 12.3 . . . . . . . . . . . . . . . . . . . . . . 14.25 ................. Ferromagnetic state 8.03 ................... Paramagnetic state

[57Lie] [67Ebi] [73Rob] [73Rob] [79Sha2]

[80Ser] [81Sha] [83Fuk] [83Sha] [83Sha]

16.93 0.41 ..... Ferromagnetic state 10.64 _+0.38 ..... Paramagnetic state 11.8 . . . . . . . . . . . . . . . . . . . . . .

[83Yva]
[86Lee]

Table 3
Reference

Enthslples and Entropies of NI-H Solutions Temperature, HH,

K kJ/mol

~V~H,
kJ/mol

SetH,
J/K.moi

~eXll,
JfK. mol

[73Mcl, 75Mcl] .........................1000 to 1516 [74Sta] ...................................... 613 to 1573 [86Suz] ..................................... 673 to 1273
Entropies of solution obtained from solubility data

-180.4 -180.1 -186 to -196

16.6 27.0 ...

37.8 35.3 21.1 to 34.4 31.3 34.08

-48.72 -49.21 ...

[71Jon] ......................................... [83Fuk] ........................................

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H-Ni
Table 4 Enthalples of Formation and Decompoaltlon of Nlckel Hydrlde (NIHx) as Determined Calorlmetrlcally
P/T,
Reference Reaction X(H/Ni) 0.3 to 0.5 0.5 ... ... ... ... atm/K 1/298 ... 6200/298 34001298 1/298 1/298 [64Barl] ........................ Decomposition [66Cza] .......................... F o r m a t i o n [85Tka] ......................... Formation Decomposition Formation Decomposition Enthalpy, kJ/mol of H2 10.0 _ 0.4 -8.8 -10.0 0.21 6.27 0.42 -16.3 0.21 8.95 0.21

Note" [71Wol] reported values of"thermal contribution of the enthalpy" of NiH:~ wherex = 0.50, 0.58, and 0.68. These enthalpy values were calculated from specificheat measurements nmde between 0 and 200 K and by extrapolation to 300 K. This enthalpy at 300 Kis roughly 6 kJ/mol of NiI~.

Table 5 Standard Entropies of Formation of Nickel Hydride (NIHx)

Reference X(H/Ni) Entropy of formation -107 2 J/K.mol of H2 -106 J/K.mol of H2 -26.1 J/K.mol of NiHx -31.0 J/K.mol of NiH.~ -36.4 J/K.mol of NiI-[~

Table 7 (NiHx)

Heat Capacities

(Cp) of Nickel Hydride

Temperature, K

Heat Capacity (Cp), J/mol.K NiHo~o NiH0~ NiHo.as 0.139 0.502 1.55 3.27 5.52 8.16 10.5 12.6 14.6 16.4 18.3 20.0 21.6 22.7 23.6 24.5 25.4 26.1 26.8 27.4 28.0 28.6 29.2 29.8 30.4 30.9 31.5 32.0 32.5 33.0 0.140 0.494 1.52 3.34 5.65 8.19 10.5 12.6 14.6 16.4 18.3 20.0 21.6 22.9 24.0 25.0 25.9 26.7 27.4 28.0 28.6 29.2 29.8 30.3 30.8 31.4 31.9 32.5 33.0 33.5

[65Bar] ..................... 0.5 [71WolJ ..................... 0.5(?} 0.5 0.59 0.68

Note.' Values of the s t a n d a r d entropy of NiHx from 171Wol]: forX ffi 0.5, +36.3 J/K.mol of NiI-I~; f o r X = 0.59, +37.3 J/K.mol of NiHx; a n d for X = 0.68, +37.7J/K.mol of NiH,~.

Table 8 Glbba Energies of Formation of Nlckel Hydrlde

Reference Conditions Gibbs energy, kJ/mol of H2 23.6 0.08 34.4 +_0.16 25 27.2

[65Bar] ..................... S t a n d a r d 3400 a t m [68Sie] ...................... F r o m electrode potential 180Bar] ..................... 340 K

s o l u t i o n of H i n N i a r e also given. T h e d a t a s h o w n i n T a b l e 3 c o m e p r i n c i p a l l y f r o m t h e g r o u p [73Mcl, 74Sta, 75Mcl, 86Suz] w h o u s e m o l e s of H a t o m s r a t h e r t h a n m o l e s o f H2 gas, so t h a t t h e i r d a t a m u s t be m u l t i p l i e d by t w o before c o m p a r i n g w i t h those o f o t h e r w o r k e r s . H H a n d SeXH a r e t h e p a r t i a l m o l a r e n t h a l p y a n d excess e n t r o p y o f H i n t h e s o l u t i o n w i t h r e s p e c t to H a t o m s a t r e s t i n a v a c u u m . AHH a n d ASeXH a r e t h e r e l a t i v e p a r t i a l m o l a r e n t h a l p y a n d excess e n t r o p y o f a t o m s i n t h e s o l u t i o n w i t h r e s p e c t to H2 g a s a t 1 a t m p r e s s u r e . T h e h e a t of s o l u t i o n g i v e n i n T a b l e 1 is t h e slope o f t h e log solubility vs 1 / T line, h e n c e c o r r e s p o n d i n g to t h e H H i n T a b l e 3.

10 ............................ 0.125 20 ............................ 0.473 30 ............................ 1.141 40 ............................ 3.07 50 ............................ 5.31 60 ............................ 7.87 70 ............................ 10.2 80 ............................ 12.0 90 ............................ 14.0 100 ............................ 15.9 110 ............................ 17.7 120 ............................ 19.4 130 ............................ 20.8 140 ............................ 22.0 150 ............................ 23.0 160 ............................ 24.0 170 ............................ 25.1 180 ............................ 25.8 190 ............................ 26.4 200 ............................ 27.0 210 ............................ 27.7 220 ............................ 28.3 230 ............................ 28.9 2 4 0 ............................ 29.4 250 ............................ 30.0 260 ............................ 30.5 270 ............................ 31.0 280 ............................ 31.6 290 ............................ 32.1 300 ............................ 32.6 From [71Wol].

Calorimetry
Very few c a l o r i m e t r i c i n v e s t i g a t i o n s h a v e b e e n c a r r i e d o u t i n t h e N i - H s y s t e m , a t l e a s t p a r t l y b e c a u s e of t h e difficulty of m a k i n g such m e a s u r e m e n t s at high pressure. The e n t h a l p y of desorption of nickel hydride (at 2 9 8 K a n d i a t m o f H2 p r e s s u r e ) h a s b e e n m e a s u r e d

576

Bulletin of Alloy Phase Diagrams Vol. 10 No. 5 1989

H-Ni
Table 8 Heat Capacities (Cp) of Nickel Hydride (NiHx) from 10 to 20 K

NIHo.es NIHos NiHo~o [TemperaTemperaTempera| [Tempera. Tempera[ [Tempera. Tempera. I ture, Cp. ture, Cp, ture, Cp. ture. Cp, ture, Cp, ture, Cp, ture, Up, K J/tool. K K J / m o l 9K K J / m o l -K K J / m o l 9K K J / m o l -K K J / m o l 9K K J / m o i 9K

10.18 ..... 0.148 12.75 ..... 0.213 13.45 ..... 0.227 14.10 ..... 0.252 14.74 ..... 0.266 16.10 ..... 0.323 16.70 ..... 0.341 17.30 ..... 0.356 17.85 ..... 0.389 18.37 ..... 0.407 18.83 ..... 0.427 19.27 ..... 0.452

10.93 ..... 11.81 ..... 12.62 ..... 13.31 ..... 13.93 ..... 14.54 ..... 15.17 ..... 17.18 ..... 17.75 ..... 19.28 .....

0.163 0.188 0.210 0.227 0.243 0.264 0.282 0.353 0.378 0.451

11.19 ..... 0.167 12.07 ..... 0.196 12.80 ..... 0.210 13.46 ..... 0.228 14.09 ..... 0.254 14.63 ..... 0.267 15.15 ..... 0.284 16.25 ..... 0.323 16.88 ..... 0.351 17.49 ..... 0.375 18.07 ..... 0.393 18.58 ..... 0.412 19.07 ..... 0.439 19.53 ..... 0.465

10.31 .... 0.136 11.32 .... 0.163 12.91 .... 0.205 13.58 .... 0.222 15.97 .... 0.299 16.66 .... 0.331 17.30 .... 0.351 17.92 .... 0.380 18.48 .... 0.402 19.47 .... 0.449

10.32 ..... 11.40 ..... 12.33 ..... 13.86 ..... 14.54 ..... 15.16 ..... 15.76 ..... 16.42 ..... 17.11 ..... 17.77 ..... 18.92 ..... 19.94 .....

0.135 0.160 0.184 0.223 0.256 0.274 0.303 0.316 0.348 0.370 0.426 0.483

10.90 ..... 11.81 ..... 12.58 ..... 13.27 ..... 13.90 ..... 14.47 ..... 15.15 ..... 15.65 ..... 16.35 ..... 16.99 ..... 18.20 ..... 18.69 ..... 19.16 .....

0.158 0.185 0.206 0.226 0.243 0.256 0.280 0.309 0.330 0.362 0.406 0.428 0.462

10.44 ..... 12.11 ..... 13.58 ..... 14.21 ..... 14.76 ..... 15.29 ..... 15.91 ..... 16.59 ..... 17.20 ..... 17.79 ..... 18.84 ..... 19.94 .....

0.146 0.193 0.236 0.255 0.275 0.290 0.313 0.347 0.359 0.386 0A~ A 0.515

From [71Woll.

Table 9 Electronic Specific Heat Coefficients (7) and Oebye Temperatures (0D) for NI and NIHx
Composition,
H/Ni

},,
J/mol.K

0D,
K

0 .......................... 0.50 ..................... 0.59 ..................... 0.68 ..................... From [71Wol].

7.299 x 10-3 (9.29 0.21) x 10-~ (9.92 0.06 10-3 (11.09 0.17) x 10-3

380 376 4 372 1 388 3

Gibbs energies of formation have b e e n d e t e r m i n e d by calculation from calorimetrically determined entropies and enthalpies of formation, from electrode potential m e a s u r e m e n t s , a n d also b y m e a s u r e m e n t s o f t h e d e c o m p o s i t i o n p r e s s u r e p l a t e a u s . T a b l e 6 gives m e a s u r e d v a l u e s o f t h e G i b b s e n e r g y o f f o r m a t i o n offl n i c k e l hydride. I t h a s b e e n p o i n t e d o u t [ 6 5 B a r ] t h a t o n l y a m i n i m a l difference can be expected b e t w e e n the Gibbs energies of formation at equilibrium pressure and at 1 a t m of H2 pressure.

Low-Temperature Heat Capacity

in a differential calorimeter [64BArl] u s i n g a "static-dynamic" method, whereas later measurements by a d y n a m i c m e t h o d [66Cza] yielded v a l u e s for its s t a n d a r d e n t h a l p y of f o r m a t i o n . T h e d a t a o b t a i n e d a r e s h o w n i n T a b l e 4. More r e c e n t l y [85Tka], c a l o r i m e t r i c m e a s u r e m e n t s u n d e r high p r e s s u r e h a v e y i e l d e d v a l u e s for t h e f o r m a t i o n a n d d e c o m p o s i t i o n e n t h a l p i e s o f ~6 n i c k e l h y d r i d e ; t h e s e w e r e t h e n c o n v e r t e d to e n t h a l p i e s a t n o r m a l p r e s s u r e of H2. T h e d a t a o b t a i n e d (also g i v e n i n T a b l e 4), a r e i n r e a s o n a b l e a g r e e m e n t w i t h t h e e a r l i e r work. At l o w e r H c o n t e n t , t h e a b s o l u t e v a l u e s o f t h e s e e n t h a l pies d e c r e a s e u n t i l a t H / N i 0.02, a c h a n g e o f s i g n occurs, i n a g r e e m e n t w i t h t h e e n d o t h e r m i c n a t u r e o f s o l u t i o n of g a s e o u s H a t 1 a t m p r e s s u r e i n Ni.
-

T h e h e a t c a p a c i t i e s o f N i - H alloys of c o m p o s i t i o n s H / N i ffi 0.50, 0.59, a n d 0.68 h a v e b e e n m e a s u r e d o v e r t h e t e m p e r a t u r e r a n g e 10 to 2 0 0 K a n d e x t r a p o l a t e d to 3 0 0 K [71Wol]. T h e s e d a t a , s h o w n i n T a b l e 7 a n d i n m o r e d e t a i l b e t w e e n 10 a n d 2 0 K i n T a b l e 8, fit t h e e q u a t i o n :

Cp = y T + fl'T 3

(Eq 3)

T h e e l e c t r o n i c specific h e a t c o e f f i c i e n t s , 7, a n d D e b y e t e m p e r a t u r e s (OD, c a l c u l a t e d f r o m t h e / ~ ' coefficients) a r e s h o w n i n T a b l e 9. T h e s e d a t a a r e for alloys l y i n g i n t h e (Ni) + /~ m i x e d - p h a s e r e g i o n , a n d so do n o t r e p r e s e n t e i t h e r p h a s e alone.

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Bulletin of Alloy P h a s e Diagrams Vol. 10 No. 5 1989

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71Jon: EG. Jones and R.D. Pehlke, "Solubilityof Hydrogen

in Solid Ni-Co and Ni-Cu Alloys," Me(all. Trans., 2, 26552663 (1971). (Equi Diagram, Thermo; Experimental) 71Sko: T. Skoskiewicz, "Investigationsof the ThermoelectricalPower at High Hydrogen Pressure in the Ni-H and Pd-H Systems," Phys. Status Solidi (a), 6, 29-32 (1971). (Equi Diagram; Experimental) 71Vyk: V.B.Vykhodets, V.B. Detain, P.B.Geld, A.H. Men, A.Y. Fyshman, and G.I. Chufarov, "Solubility of Hydrogen in F.C.C. Metals," Izv.Akad. Nauk SSSR, Met., 6(6), 71-77 r in Russian; TR: Russ. Me(all., (6), 55-59 (1971). (Equi Diagram; Theory) 71Way: M.L. Wayman and G.C. Smith, "Hydride Formation in Nickel-Iron Alloys," J. Phys. Chem. Solids, 32, 103-108 ( 1971). (Equi Diagram, Crys Structure; Experimental) 71Woh G. Wolf and B. Baran0wski, "Specific Heat of Nickel Hydride from 10~ to 200 ~ J. Phys. Chem. Solids, 32, 1649-1655 ~1971). (Thermo; Experimental) 72Ale; G. Alefeld, "Phase Transitions of Hydrogen in Metals Due to Elastic Interaction," Ber. Bunsenges. Phys. Chem., 76, 746-755 (1972). (Equi Diagram; Theory) 72Bar: B. Baranowski, "Thermodynamics of Metal/Hydrogen Systems at High Pressures," Bet. Bunsenges. Phys. Chem., 76, 714-724 (1972). (Equi Diagram; Review) 72Fla: T.B. Flanagan and W.A. Oates, "Thermodynamics of Metal/Hydrogen Systems," Ber. Bunsenges. Phys. Chem., 76, 706-714 (1972). (Crys Structure; Review} 73Mch R.B. McLellan and W.A. Oates, "The Solubility of Hydrogen in Rhodium, Ruthenium, Iridium and Nickel," Acta Metall., 21,181-185 ( 1973~. (Equi Diagram, Thermo; Experimental) * 73Rob: W.M. Robertson, "Hydrogen Permeation, Diffusion and Solution in Nickel," Z. Metallkd., 64, 436-443 (1973). (Equi Diagram, Thermo; Experimental, Compilation) 74Sta: S.W. Stafford and R.B. McLellan, "The Solubilityof Hydrogen in Nickel and Cobalt," Acta Me(all., 22, 14631468 (1974).~Equi Diagram, Thermo; Experimental} "75McI: R.B. McLellan and C.G. Harkins, "Hydrogen Interactions with Metals," Mater. Sci. Eng., 18, 5-35 (1975). (Thermo; Review) 76Boe: N. Boes and H. Zuchner, "Electrochemical Methods for Studying Diffusion, Permeation and Solubility of Hydrogen in Metals," J. Less-Common Met., 49, 223-240 11976). (Equi Diagram; Review) 76Fro: E. F r o m m and E. Gebhardt, Ed., Gase und Kohlens(offin Metallen, Springer, Berlin (1976) in German. (Equi Diagram; Review) 76Pon: E.G. Ponyatovskii, V.E. Antonov, and I.T Belash, "The T-P Phase Diagram of the Ni-H System for Temperatures up to 630 K and Pressures up to 18 Kilobars," Dokl. Akad. Nauk SSSR, 229, 391-393 (1976) in Russian. (Equi Diagram; Experimental 1 77Ant: VE. Antonov, I.T Belash, and E.G. Ponyatovskii, "The T-P Phase Diagrams of the Ni-D and Ni-H Systems for Temperatures up to 375 ~ and Pressures up to 20 Kilobars," Dok l. Akad. Nauk SSSR, 223, 1114-1117 (1977) in Russian. (Equi Diagram; Experimental; #) 77Bau: H.J. Bauer and B. Baranowski, "In-Situ Observation of the Disappearance of the Ferromagnetism of Nickel Under High Pressure Gaseous Hydrogen," Phys. Status Solidi is), 40, K35-K38 (1977). (Equi Diagram; Experimental) 78Bar: B. Baranowski, "Metal-Hydrogen Systems at High Hydrogen Pressures," Topics in Applied Physics, Vol. 29,

Hydrogen in Metals H, G. Alefeld and J. Volkl, Ed., SpringerVerlag, Berlin, 157-200 (1978). (Equi Diagram; Review) 78Bau: H.J. Bauer, M. Becker, H. Pretsch, and M. Zwick, "Magnetic Study of the Activation Energy of the Phase Transition Kinetics Between Nickel and Nickel Hydride," Phys. Status Solidi (a), 47, 445-450 (1978). {Equi Diagram; Experimental) 78Jon: D. Jonitz and H.J. Bauer, "Studiee of the Decomposition Process of Nickel Hydride by Bitter Powder Pattern and the Laue Method," Hydrogen in Metals, III, Proc. 2nd Int. Cong. Hydrogen in Metals, Paris, 1977, Pergamon Press, New York, Vol. III, Paper No. 1E3, 1-5 (1978). (Equi Diagram; Experimental) 78Pie: J. Pielaszek and E. Lunarska, "Effect of the Real Structure of Nickel on the Kinetics of Nickel Hydride Decomposition," Bull. Akad. Pol. Sci., Chim., 26, 87-90 (1978). (Equi Diagram; Experimental) *78Pon: E.G. Ponyatovskii, V.E. Antonov, and I.T Belash, "Group VI-VIII Transition Metals at High Hydrogen Pressures," Neorg. Mater., 14, 1570-1580 (1978) in Russian. (Equi Diagram, Crys Structure; Experimental; #) 79Bar: B. Baranowski, "Metal-Hydrogen Systems in the High Pressure Range," Z. Phys. Chem. (Neue Folgr 114, 71-93 (1979). (Equi Diagram; Review ) 79Kep: J.B. Kepka and E.W. Czaputowicz, "Analysis of Some Results on Pd-H and Ni-H Systems Studied in High-Pressure-Hydrogen Conditions," Phys. Rev. B, 19, 2414-2416 (1979). (Equi Diagram; Experimental) 7 9 S h a l : V.I. Shapovalov and N.P Serdyuk, "On the Phase Diagrams of the Nickel-Hydrogen and Cobalt-Hydrogen Systems," Dop. Akad. Nauk Ukr. RSR A, Fiz.-Mat. Tekh., 151-154 (1979) in Ukrainian. (Equi Diagram; Experimental; #~ 79Sha2: V.I. Shapovatov and N.E Serdyuk, "Certain Thermodynamic Characteristics of the Nickel-Hydrogen and Cobalt-Hydrogen Systems," Zh. Fiz. Khim., 53, 2187-2191 (1979) in Russian; TR: Russ. J. Phys. Chem., 53, 1250-1252 11979) (Equi Diagram, Thermo; Experimental; #) 80Bar: B. Baranowski and M. Tkacz, "Ab- and Desorption Isotherms of Hydrogen in Ni-Cu Alloys in the High Pressure Range," Pol. J. Chem., 54, 819-825 (1980). (Equi Diagram, Thermo; Experimental} 80Bor: P.C. Borbe, F. Erdmann-Jesnitzer, and W. Schoebel, "Studies of Formation and Decomposition of NickelHydride," Z. Metallkd., 71, 227-230 (1980) in German. (Equi Diagram; Experimentall 80Kit: S. Kitagawa, "Mechanism of Surface Crack Formation by Hydrogen in Pure Nickel," Hydrogen in Metals, Proc. 2nd Jpn. Inst. Met. Int. Syrup., suppl, to Trans. dpn. Inst. Met., 21,497-501 (1980). (Equi Diagram; Experimentad *80Set: N.P. Serdyuk and A.L. Chuprina, "High Pressure Anomalies in the Solubility of Hydrogen and Nickel and Cobalt," Russ. d. Phys. Chem., 54, 1615-1618 ~1980). (Equi Diagram, Thermo; Experimental; # I 80Yur: I.A. Yurichev and E.G. Ponyatovskii, "Isomorphic Transitions and Critical Phenomena in EC.C. Metals under Hydrogen Pressure," Phys. Status Solidi (a), 58, 5766 ( 1980 I. (Equi Diagram; Theory) *81Bar: B. Baranowski, "Hydride Formation at High Hydrogen Pressure," Metal Hydrides, G. Bambakidis, Ed., Plenum Press, New York, 193-213 (1981). (Equi Diagram; Review} 81Bau: H.J. Bauer, "Phase Transitions in Hydrogenated Nickel and Nickel Alloys Investigated by Magnetic

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H-Ni In-La
Methods," Metal Hydrides, G. Bambakidls, Ed., Plenum Prem, New York, 313-327 (1981). (Equi Diagram; Review) 81Sha: V.I. Shapovalov, L.M. Poltoratskii, V~. Trofimenko, and N.P Serdyuk, "Phase Diagram of a Metal-Hydrogen System," Fazorye Ravnovesiya Met. Splavakh, M.E. Drits, Ed., Izd. Nauka, Moscow, 280-285 (1981) in Russian. (Equi Diagram, Thermo; Experimental) 83Fuk: Y. Fukai and H Sugimoto, "Enhanced Solubility of Hydrogen in Metals under High Pressure: Thermodynamical Calculation," Trans. Jpn. Inst. Met., 24, 733-740 (1983). (Equi Diagram, Thermo; Theory) 83Klu: I~ Kiuchi and R.B. McLellan, "The Effect of Surface Contamination on the Measured Hydrogen Solubilities of Metals," J. Less-Common Met., 95, 283-292 {1983L (Equi Diagram; Experimental) 83Sha: V.I. Shapovalov and L.B. Boyko, "Anomaly of Hydrogen Solubility in Ferromagnetic Metals near the Curie Point," Fiz. Met. Metalloved., 55, 1220-1221 (1983) in Russian. {Equi Diagram, Thermo; Experimental) 83Vya: A.F. Vyatkin, P.V. Zhorin, and E.M. Tseitlin, "Influence of Magnetic Ordering on the Solubility of Hydrogen in Pure Nickel," Zh. Fiz. Khim., 57, 419-422 (1983) in Russian; TR: Russ. J. Phys. Chem., 57, PA9-251 (1983). (Equi Diagram, Thermo; Experimental) 84Bar: B. Baranowski, "Investigation of Some MetalHydrogen Systenm in the High Pressure Region," J. LessCommon Met., 101, 115-129 (1984). (Equi Diagram; Review) "84Mc1: R.B. McLellan and EL. Sutter, "Thermodynamicsof the Hydrogen-Nickel System," Acta Metall., 32, 2233-2239 (1984). (Equi Diagram; Experimental, Compilation) 85Tka: M. Tkacz and B. Baranowski, "Heats of Formation and Decomposition of Nickel and Ni0.sCu0.2 Hydrides Measured in High Pressures of Gaseous Hydrogen," J. Less-Common Met., 113, 83-87 (1985). (Thermo; Experimental) 86Lee: S.-M. Lee and J.-Y Lee, "The Trappingand Transport Phenomena of Hydrogen in Nickel," Metall. Trans. A, 17, 181-187 (1986). (Equi Diagram, Thermo; Experimental) 86Suz: Y. Suzuki and R.B. McLellan, "Thermodynamic Study of Ternary Nickel-Cobalt-Hydrogen So]id Solutions," Acta MetaU., 34, 125-130 (1986). (Thermo; Experimental) *Indicates key paper. #Indicates presence of a phase diagranl.

Ni-HevaluationcontributedbyM.Wayman,DepartmentofMining,Metallurgicaland PetroleumEngineering,UniversityofAlberta, Edmonton, CanadaT6G2G6,and G.C.Weatherly,DepartmentofMetallurgyand MaterialsScience,UniversityofToronto,Toronto,CanadaM5S 1A4.This work was supportedby OntarioHydroas a contributionfromthe CanadianCouncilof ASMINTERNATIONALto the joint ASM/NISTBinary AlloyPha~ DiagramProgram. Literaturesearchedthrough 1986.Part ofthe bibliographicsearch was prodded byASMINTERNATIONALand part byother sources.ProfessorWeatherlyis the ASM/NISTData ProgramCo-CategoryEditor forbinaryhydrogenalloys.

The In-La (Indium-Lanthanum) System

By A. Palenzona and S. Ciraficl University of Genova, Italy

Equilibrium Diagram
The assessed In-La phase diagram (Fig. i) is based on the work of [74Mcm], and the equilibrium phases include: (1) the liquid, L; (2) seven intermetallic compounds-In3La, In2La, In5La3, InxLa, InLa, InLa2, and InLa3; and (3) three terminal solid solutions, (yLa), (~La), and (In). No information is available for the solid solution of In in c~La. The a ,~/3 transformation for La is indicated by a dashed line at 310 ~ [74Mcm] investigated the In-La system by thermal analysis,ndcroscop~ and X-ray diffraction.The In used was 99.999% (weight percent?) pure. The La was prepared in their laboratory by Ca reduction of the fluoride, followed by a vacuum casting of the La. The major impurities (in atomic ppm) were: 1000 each oxygen and Ta, 370 each carbon and nitrogen, 690 hydrogen, and smaller quantities of Fe, Y, Ce, Gd, and fluorine. Eight master alloys,with compositions of 1.0, 48.4, 50.3, 55.9, 62.5, 85.1, 97.4, and 98.2 at.% La were prepared by arc melting and heat treated in sealed tantalum crucibles.Weighed amounts of either La or In were added to these master alloys, for a total of 60 samples for differential thermal analysis (DTA)

investigations. The accuracy in the temperature measurements was _+ 5 ~

The phase diagram of [74Mcm] showed seven intermetallic compounds In3La, In5La3, and InLa (congruently melting at 1140, 1185, and 1125 ~ respectively), In2La, InLa2, and InLa3 (forming peritectically at 1153, 955, and 816 ~ respectively) and InxLa, which exists in the temperature range 905 to 1073 ~ between 38.5 and 50 at.% La. Four eutectic reactions were reported at 155 ~ and < 0.5 at.% La, at 1120 ~ and 28.8 at.% La, at 1086 ~ and 46.0 at.% La, and at 742 ~ and 86.5 at.% La. A eutectoid reaction was observed at 702 ~ and 91.9 at.% La, resulting from the lowering of the 865 ~ Y "~ ~ transformation temperature of La by In additions. At the eutectoid temperature, the solubility of In in (~La) and in (yLa) was shown as 3.5 and 8.1 at.% In, respectively, and at the 742 ~ eutectic temperature, the solubility was reported as 10.2 at.% In in (TLa). No appreciable solid solubility of La in (In) was observed. Only InsLa3 seemed not to be a line compound; [74Mcm] found a variable composition, but did not give the range.

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Bulletin of Alloy Phase Diagrams Vol. 10 No. 5 1989