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Preparation of nanocrystalline metal hydrides by ball milling

Article  in  Hyperfine Interactions · January 2000

DOI: 10.1023/A:1011081618311

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 Hyperfine Interactions 130: 109–126, 2000.
 2000 Kluwer Academic Publishers. Printed in the Netherlands.

Preparation of nanocrystalline metal hydrides by

ball milling
R.A. Dunlap ∗ , Z.H. Cheng, G.R. MacKay, J.W. O’Brien and D.A. Small
Department of Physics, Dalhousie University, Halifax, Nova Scotia B3H 3J5, Canada

The diffusion of hydrogen into metals during ball milling has been investigated. A sys-
tem is described that enables the milling to be done under approximately constant hydrogen
pressure and allows for the continuous measurement of the quantity of hydrogen absorbed.
This method has been used to prepare nanocrystalline hydrides of a variety of early transition
metals and alloys. X-ray diffraction studies are used to identify phases present before and af-
ter milling and the width of diffraction peaks is used to estimate average grain size. Changes
in the microstructure of Fe-containing samples during hydrogen absorption have been inves-
tigated by Mössbauer effect. Studies of the influence of milling conditions and the effect of
milling time are also presented.

1. Introduction

Metal hydrides have a number of important commercial applications such as hy-

drogen storage materials and electrodes for batteries (e.g., [1]). A number of elements
and alloys have shown the ability to absorb large quantities of hydrogen. In particular
materials involving early transition metals have shown considerable promise in this re-
spect. Titanium is a good example of such a material [2]. However, such applications
have been limited because of the difficulty in preparing titanium hydride. Typically hy-
drogenation is performed by exposing a sample of Ti to H2 gas at elevated temperature
and/or pressure for several hours. This is followed by slow cooling in order to maintain
maximum hydrogen content. A similar process is used for many other early transition
metal elements and alloys. The observation of the preparation of nitrides by the ball
milling of metals under a nitrogen atmosphere [3,4], suggests the possibility that metal
hydrides may be produced by milling under a hydrogen atmosphere. This process has
recently been reported for titanium [5–7] as well as Mg and Zr [6,7]. In these previ-
ous experiments, the milling process was stopped and the vial refilled with hydrogen
gas when the supply of hydrogen had been exhausted. Subsequently we have developed
a hydrogen reservoir system which allows us to maintain the pressure of the hydrogen
at approximately one atmosphere and to continuously monitor the amount of hydrogen
that is absorbed throughout the milling process. Using these methods we have investi-
gated the details of the hydrogen absorption process during ball milling for a number of
∗ Corresponding author. E-mail: dunlap@fizz.phys.dal.ca
110 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides

early transition metals [8–10] and alloys. We have also investigated the effects of differ-
ent milling conditions on hydrogen absorption. The present paper reviews our previous
investigations in these areas.

2. Experimental methods

All ball milling experiments described here were carried out using a SPEX Model
8000 Mixer/Mill. A custom made hardened steel vial as shown in figure 1 was used.
This had a chamber that was approximately ellipsoidal in shape and a vacuum coupling
to allow for control of the milling atmosphere. During milling the vial was connected
to a hydrogen gas reservoir system by means of a Norton Masterflex 6104-24 tygon
tube as shown in figure 2. The total volume of the hydrogen system was approximately

Figure 1. Ball milling vial as described in the text used for hydrogen absorption experiments.

Figure 2. Ball milling vial mounted in SPEX Model 8000 Mixer/Mill showing connection to hydrogen
system.
 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides 111

Figure 3. Typical hydrogen absorption curve showing the hydrogen pressure in the system as a function
of milling time. Data shown is for a 1 gram sample of −325 mesh elemental Ti powder milled using two
11.1 mm diameter hardened steel balls.

8×103 cm3 . For a starting pressure of 1 atmosphere, the absorption of 2 hydrogen atoms
per metal atom by a 1 gram sample corresponds to a decrease in the reservoir pressure of
about 5%, thus maintaining an approximately constant hydrogen pressure on the sample
during the milling process. During milling, small changes in the hydrogen pressure
representing absorption of hydrogen by the sample were measured continuously by an
Omega Model PX303-015ASV strain gauge type pressure transducer. Typical results are
illustrated in figure 3. The measured change in pressure may be related to the number of
hydrogen atoms absorbed per metal atom, H/M, as
H 2V A1P
= , (1)
M RmP0
where V is the volume of the reservoir system (in cm3 ), A is the average atomic weight
of the sample, 1P is the pressure change in the system, P0 is the initial pressure (in
the same units as 1P ), R is the standard volume of gas (in cm3 ) and m is the mass
of the sample (in g). Further details of the sample preparation for each experiment are
discussed below.
The structure of samples before and after milling was determined using room tem-
perature X-ray diffraction measurements. A Siemens D500 scanning diffractometer and
Cu-Kα radiation were used. Room temperature 57 Fe Mössbauer effect studies of Fe
containing samples have been performed with a Wissel System II constant acceleration
Mössbauer spectrometer.

3. Results and discussion

3.1. Hydride formation in early transition metals
Powders of Ti (2N), V (2N5), Zr (2N), Nb (2N8), Hf (2N6) and Ta (3N), of the
purities indicated were ball milled under hydrogen as described above. In all cases the
starting powders were −325 mesh and milling was performed on a 1.0 gram sample
using two 11.1 mm diameter hardened steel balls.
112 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides

Figure 4. Number of hydrogen atoms absorbed per metal atom (H/M) as a function of milling time for
various early transition metals.

Table 1
Saturation values of H/M, maximum hydrogen absorption rates and time before absorption begins, t0 , for
the elements studied here. The mean crystallite size as determined by X-ray diffraction peak widths is given
by hri.
M (H/M)sat [∂(H/M)/∂t]max [min−1 ] t0 [min] hri [nm]
Ti 2.0 0.158 10 8
V 0.8 0.030 54 5
Zr 2.0 0.18 5 7
Nb 0.9 0.071 21 6
Hf 1.8 0.12 17 7
Ta 0.7 0.10 18 9

The number of hydrogen atoms per metal atom (H/M) absorbed as a function of
milling time is illustrated in figure 4 for each of the samples. In all cases the hydrogen
absorption curves are characterized by an initial period during which there is little or
no hydrogen absorption. This is followed by a period of rapid hydrogen absorption and
saturation. In order to quantify these results we have defined three quantities as given
in table 1. These are the maximum hydrogen absorption rate, [∂(H/M)/∂t]max , defined
as maximum slope of a line tangent to the absorption curve, the time for the onset of
hydrogen absorption, t0 , defined as the H/M = 0 intercept of the line tangent to the
absorption curve at the point of maximum slope, and the saturation value of H/M, given
by the asymptotic value of H/M for long milling times. In general, it is seen that those
metals which have large values of t0 , also have small values of [∂(H/M)/∂t]max .
 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides 113

Figure 5. Room temperature X-ray diffraction scans of the early transition metal samples milled to satura-
tion. The symbols indicate the peaks expected for the hydride phases.

The structure of the samples milled to saturation have been determined by X-ray
diffraction techniques and show transition metal hydride phases as expected. Measured
diffraction patterns are illustrated in figure 5. In all cases the patterns of the samples
milled to saturation are consistent with those of metal hydrides with the stoichiometry
as indicated in table 1 and do not show the presence of any elemental metal. All X-ray
diffraction patterns of milled samples show measurable line broadening indicative of
small crystallites. The average crystallite size as determined by the Scherrer formula is
given in table 1.
Although the bulk diffusion rate of hydrogen in early transition metals is high,
diffusion rates during conventional hydrogenation are limited by the presence of sur-
face oxides. The greatly increased diffusion rates observed during ball milling has been
attributed to several factors [6]
(i) the formation of a large amount of oxide-free surface,
(ii) the rapid reduction in grain size, and
(iii) the introduction of significant lattice defects.
114 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides

In the first case, the chemisorption of H2 molecules and their dissociation to form
H atoms is promoted. In the second case, the reduced grain size means shorter diffusion
lengths are necessary. It is also relevant that the embrittlement of the metals which re-
sults from hydrogen absorption further increases the effectiveness of the milling process
at reducing the size of the grains. Finally it is known [7] that the introduction of lat-
tice defects, such as dislocations, provides convenient routes along which hydrogen can
diffuse through the metal.
In the present study the initial period during which there is little or no hydrogen ab-
sorption by the sample corresponds to a period during which sample grains are reduced
in size and lattice defects are introduced. This reduces the diffusion length necessary for
hydrogen absorption and introduces lattice defects such as dislocations along which hy-
drogen can readily diffuse. This is followed by a period during which hydrogen actively
diffuses into the sample. The rate at which hydrogen diffusion occurs does not show any
direct relationship with literature values of the bulk hydrogen diffusion coefficient [1,2].
However, table 1 illustrates that there is an inverse relationship [∂(H/M)/∂t]max and t0
measured in the present work. This suggests that the maximum rate at which hydrogen
diffuses into the sample is limited by the rate at which fresh surfaces and lattice defects
are produced by milling. Presumably, the effectiveness of the milling process at pro-
moting hydrogen absorption is determined to a large extent by the degree to which the
partially hydrogenated sample becomes embrittled. The average grain size of the fully
hydrogenated samples produced in the present investigation is in the range of 5–9 nm, as
indicated in table 1. This is somewhat smaller than that reported in earlier work for TiH2
produced by ball milling [6]. This suggests that the continuous supply of hydrogen gas
used in the present work may have been more effective at promoting rapid hydrogen dif-
fusion which resulted in more substantial grain size reduction and faster saturation times.
Thus rapid hydrogen absorption during ball milling appears to begin at some threshold
grain size and/or defect concentration and proceeds to saturation as a result of continued
particle size reduction. In order to better understand the details of the hydrogen diffu-
sion process and the suitability of ball milling as a means of producing metal hydrides,
we have undertaken additional experiments on the preparation of titanium hydride as
described below.

3.2. Effects of milling conditions

In order to investigate the effects of different milling conditions on hydride forma-

tion, 1.0 gram samples of −325 mesh titanium powder were ball milled using different
numbers and sizes of balls. The various milling conditions investigated in the present
work are summarized in table 2. In each case the number of hydrogen per Ti was mon-
itored as a function of milling time until saturation occurred. The time dependence of
the hydrogen absorption is illustrated in figure 6. The precision of the measurements is
limited by the sensitivity of the pressure transducer and is smaller than the size of the
data points shown in figure 1. Systematic errors in the measurement of H/Ti result from
uncertainties in the volume of the reservoir system and the absolute calibration of the
 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides 115

pressure transducer while variations between runs are the result of weighing accuracy
for the Ti sample, the fact that some portions of the Ti sample may become trapped in
the vial around the gas inlet and may not be effectively milled and variations in ambient
temperature. These latter factors probably account for an expected uncertainty in the
saturation value of H/Ti of about 0.1. This suggests that the variations in the saturation
value of H/Ti for different runs are probably not significant and all milled samples have
a stoichiometry of approximately TiH2 .

Table 2
Ball configurations for the runs reported here. In all cases
the sample mass was 1.0 gram.
Number of Diameter of Total ball
balls balls (mm) mass (g)
1 19.0 28.47
2 12.7 17.00
2 11.1 11.35
1 14.3 12.14
1 12.7 8.50
2 9.5 7.11
2 7.9 4.09
1 11.1 5.67
2 6.4 2.17

Figure 6. Number of hydrogen atoms absorbed per Ti atom as a function of milling time. The size and
number of balls is indicated in the insert. The order in which the data sets are listed corresponds to the
ordering of the curves in the graph from left to right. Ball to sample weight ratios are as given in table 2.
116 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides

Figure 7. Milling time required to absorb 1.0 H/Ti as a function of ball-to-sample weight ratio for milling
performed using one ball and two balls.

In order to quantify the rate at which hydrogen is absorbed for different milling
conditions we define the mean hydrogenation time, tm , as the time required for the sam-
ple to absorb one hydrogen per titanium atom. Figure 7 shows tm as a function of ball-to-
sample weight ratio. The data shown here clearly indicate the differences between one
ball and two balls in terms of milling efficiency. It is also known that during ball milling
ball–ball and ball–vial collisions introduce substantial local temperature increases, al-
though the average temperature in the vial remains at about 40◦ C. The results of figure 7
are consistent with the importance of these local conditions for the diffusion of hydrogen.
The shorter milling times required for two balls (compared with one ball of similar total
weight), suggests the increased effectiveness of ball–ball collisions compared with ball–
vial collisions. This may be indicative of greater local heating as expected for the more
energetic ball–ball collisions. The importance of short-term local conditions on hydro-
gen absorption may be consistent with our observation that if the milling is stopped part
way through the hydrogenation process, the sample will continue to absorb hydrogen but
at a substantially reduced rate. The results of an experiment in which the milling was
periodically interrupted are illustrated in figure 8. It is clear that hydrogen absorption
rates are significantly higher during active milling.

3.3. Phase development during milling

We have further studied the processes that occur during milling by interrupting
the milling processes at intermediate stages and characterizing the sample. Elemental
titanium powders with particle size of −325 mesh were milled under hydrogen. In all
cases, about 1.0 g of titanium powder and two 11.1 mm diameters hardened steel balls
with a total weight of 11.19 g were used. The overall hydrogen absorption curve for
these conditions can be seen in figure 6.
The transformation of elemental Ti powder into titanium-hydride compound as
a function of milling time is observed in the X-ray diffraction patterns illustrated in
 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides 117

Figure 8. Effects of periodic interruption of the milling process on hydrogen absorption. Solid symbols
indicate times when the mill was on and open symbols indicate times when the mill was off. Milling
conditions consisted of two 8.5 g hardened steel balls and a 5.0 g sample of Ti.

figure 9. The pattern of elemental Ti powder is plotted for comparison. The X-ray
diffraction pattern indicates that the titanium hydride has a tetragonal or pseudo-faced-
centered-cubic structure with lattice constants a = 4.467 Å, c = 4.441 Å. Its unit cell
volume of 88.6 Å3 , is in good agreement with that of TiH2 (88.4 Å3 ) [2] confirming the
results of pressure measurements shown in figures 4 and 6. Tetragonal TiH2 transforms
to a cubic structure above 310 K, indicating that at room temperature the lattice constants
a and c are nearly same.
It is difficult to study the details of the phases of titanium and its hydride by X-ray
diffraction patterns due to the overlap of several peaks. Fortunately, we can select the
(0 0 2) peak of Ti and the (2 0 2) peak of TiHx as the characteristic peaks of these two
phases. These are marked by symbols “+” and “O” in figure 9, respectively. Figure 10
illustrates these two peaks measured over a small range of angles. After 7 minutes of
milling, the (2 0 2) peak of titanium-hydride phase is visible and its intensity increases
with increasing milling time. Meanwhile, the intensity of the (0 0 2) peak of Ti decreases.
For the sample milled at 35 minutes, no residual elemental Ti was detected by X-ray
diffraction.
The broadening of diffraction peaks with increasing milling time can be attributed
to the reduction of the grain size. Using the Scherrer formula the average grain sizes of
titanium and titanium-hydride as shown in figures 11 (top) and (bottom), respectively, are
obtained. During the first few minutes of milling, there is little or no hydrogen absorp-
tion, while the grain size of the Ti powders decreases rapidly. Within about 5.5 minutes
of milling, the grain size of Ti is reduced to about 30 nm and does not show any ob-
vious decrease with further milling. However, at this time, very fine Ti powders begin
to absorb hydrogen significantly to form titanium hydride. Due to the embrittlement of
titanium by hydrogen absorption the average grain size of the titanium hydride phase
118 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides

Figure 9. X-ray diffraction patterns of as-milled samples, (a) elemental Ti powder, (b) 13.5 minutes, (c) 18
minutes, (d) 35 minutes. Symbols indicate the (0 0 2) peak of Ti (+) and the (2 0 2) peak of TiHx (O).

reduces from 15 to 6 nm with subsequent milling. This result may be compared with the
situation for an as-milled TiN compound, where it requires about 36 hours of milling to
obtain TiN powders with grain size of 9 nm [3]. This indicates that, by comparison, the
absorption of hydrogen during ball milling is a very rapid process.
Within the experimental errors, the position of the (0 0 2) diffraction peak of ti-
tanium does not change as a function of milling time (see figure 12(a)), implying that
hydrogen does not enter titanium to form a Ti(H) solid solution. Instead, partially hy-
drided powders consist of a mixture of fine-grained non-stoichiometric titanium-hydride
powders and unhydrided titanium grains. The X-ray diffraction pattern of titanium hy-
dride as initially formed by ball milling indicates approximate composition of TiH1.9
and, as seen in figure 12(b), additional hydrogen is absorbed after prolonged milling.
 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides 119

Figure 10. The (0 0 2) diffraction peak of Ti and the (2 0 2) diffraction peak of TiHx for samples milled for
different times. Solid lines are computer fits to a Gaussian and were used to determine grain sizes.

A random solid solution of dilute hydrogen might exist in a well-ordered single

crystal of a metal. However, in the nanosized grains of metal produced by ball milling,
hydrogen is trapped at a variety of possible sites resulting from the large number of
lattice defects and grain boundaries [11]. The trapping of hydrogen in as-milled pow-
ders characterizes a relatively slow diffusion process compared with free diffusion. The
trapped hydrogen has enough time to form clusters, react with titanium, and conse-
quently form titanium hydride. On the other hand, the high mobility of hydrogen in
metals permits the establishment of an equilibrium condition at a much lower temper-
ature and after a much shorter time than those of other interstitial atoms, such as C, N
or O. Moreover, the embrittlement of titanium caused by hydrogen absorption aids in
the further reduction of the grain size of the hydride phase. Therefore, as-milled pow-
ders can easily absorb hydrogen to form titanium hydride. The change in the X-ray
peak position for longer milling times as seen in figure 12(b) indicates that continued
milling results in the absorption of a small amount of additional hydrogen to yield the
equilibrium TiH2 phase.
120 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides

Figure 11. Average grain size of Ti and its hydride in the samples milled for different times.

Figure 12. Position of (a) the (0 0 2) peak of Ti and (b) the (2 0 2) peak of titanium hydride in the samples
milled for different times.
 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides 121

3.4. Hydrogen absorption in quasicrystalline Ti–Zr–Ni–Fe

Quasicrystalline materials have been shown to exhibit favorable properties as hy-

drogen absorbers and may have important commercial applications as hydrogen storage
materials and as electrodes for batteries. Bahadur et al. [12] have shown that Ti-based
quasicrystals absorb a substantial quantity of hydrogen. More recent studies have shown
that titanium/zirconium-3d transition metals quasicrystals are particularly promising
[13–19]. Of these, Ti–Zr–Ni icosahedral (i-phase) quasicrystals are the best ordered
and are thermodynamically stable [15,20]. Previous studies of hydrogen diffusion [21]
have used conventional hydrogenation techniques such as exposing the sample to H2 gas
at elevated temperatures and pressures for several hours, and gentle ball milling, using
a sealed H2 filled vial rotated on a metal lathe. These studies have yielded hydrogen to
metal ratios (H/M) in the range of 1.6–1.7. In many cases hydrogen diffusion is inhib-
ited by an oxide layer on the sample, as is generally the case for crystalline Ti alloys [5].
We have recently extended our investigations of hydrogen absorption during ball milling
under a hydrogen atmosphere to include some quasicrystalline materials.
Alloys of composition Ti45 Zr38 Ni17−x Fex , with x = 0 and 5 were prepared by
arc melting high-purity elemental compounds followed by conventional melt spinning
methods to produce the quasicrystalline phase. Ball milling was performed as described
above using a 1.0 gram sample and two hardened steel balls with a diameter of 11.1 mm
and a combined mass of 11.19 g.
The hydrogen absorption curves for the two samples studied here are illustrated in
figure 13. The saturation H/M values of about 1.4 and 1.7 were reached in about 17 and
13 minutes for x = 0 and x = 5, respectively. The presence of iron in the x = 5 sample
increased the saturation H/M value and shortened the time to saturation appreciably.
Typical X-ray diffraction patterns for samples before and after milling under hy-
drogen are illustrated in figure 14. The X-ray diffraction patterns for the as-quenched

Figure 13. Hydrogen per metal atom (H/M) as a function of milling time for Ti45 Zr38 Ni17 (0% Fe) and
Ti45 Zr38 Ni12 Fe5 (5% Fe).
122 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides

Figure 14. X-ray diffraction patterns Ti45 Zr38 Ni17 (a) before milling and (b) after milling.

samples show predominantly the characteristic i-phase peaks, which are labeled by their
conventional indices [22,23]. A minor MgZn2 -type (C14 Laves phase) impurity phase
is also observed as previously reported by Nicula et al. [13] and Viano et al. [14]. The
quasilattice constant of the unmilled x = 0 sample was found to be 5.18 Å, consistent
with the value previously reported in the literature [17].
The X-ray diffraction patterns for the milled sample shows that the principal qua-
sicrystal peaks have shifted to lower angle and have broadened. The broadening of the
peaks is due to the smaller grain size induced by the milling process, while the shifting to
lower angle is an indication that the addition of hydrogen has expanded the quasilattice.
The quasilattice constant for the x = 0 hydride sample is found to be 5.52 Å, consis-
tent with the literature value [17]. The X-ray diffraction patterns for the milled samples
exhibit primarily the hydrogenated i-phase with evidence of an amorphous phase and
a small quantity of unhydrogenated i-phase. The presence of an unhydrogenated qua-
sicrystalline phase explains the difference between our H/M values (1.4 for x = 0) and
the literature values (1.6 for x = 0) [17].
The iron-containing sample was further analyzed using 57 Fe Mössbauer spec-
troscopy. The Mössbauer spectra of the x = 5 sample before and after milling are
illustrated in figure 15 and a summary of these results is presented in table 3. The spec-
trum of the unmilled sample was fitted to a doublet. The small quadrupole splitting
observed in this spectrum indicates a lack of symmetry in the iron environment. This is
in contrast to the Mössbauer effect spectra of quasicrystalline Ti–Ni–Fe–Si which shows
a singlet, indicating a highly symmetric Fe environment. In both quasicrystalline Ti–
Ni–Fe–Si and quasicrystalline Ti–Zr–Ni–Fe the Fe center shift is substantially negative
relative to α-Fe (for Ti–Ni–Fe–Si quasicrystals the center shift is around −0.2 mm/s
[27]). A slightly negative center shift has been reported for dilute Fe in Ti [28,29]. The
 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides 123

Figure 15. Mössbauer spectra for Ti45 Zr38 Ni12 Fe5 (a) before milling and (b) after milling.

Table 3
57 Fe Mössbauer effect parameters for Ti Ni Zr Fe before and after milling under hydrogen. The
45 38 12 5
values of the center shift, δ, are given relative to room-temperature α-Fe and the linewidth, 0, is the full
width at half maximum of the Lorentzian line shape. Errors on all fitted velocities are approximately
± 0.01 mm/s. The relative area of the various spectral components is given by A1 /(A1 + A2 ).
δ1 11 01 A1 /(A1 + A2 ) δ2 12 02
(mm/s) (mm/s) (mm/s) (mm/s) (mm/s) (mm/s)
Before milling −0.153 0.217 0.29 1.0 – – –
After milling −0.104 0.172 0.30 0.71 0.386 0.417 0.40

more negative value observed here may result from a greater Ti s-band contribution to
the electron density at the Fe nucleus due to a greater Ti (or Zr) coordination around
the Fe sites. The relatively narrow spectral lines as given in the table indicate the well
ordered nature of the Fe sites in this alloy. The spectrum of the sample after ball milling
was fit to two doublets as shown in figure 15 with fitting parameters as given in table 3.
One of the doublets corresponds to a remaining unhydrogenated component of the sam-
ple as indicated by the hyperfine parameters given in the table. The similarity of these
parameters, including the line width, suggests that the unhydrogenated component of
the sample was affected very little by the milling process. This component accounts for
about 30% of the Mössbauer absorption and is consistent with our interpretation based
on X-ray diffraction results. The second doublet is due to the hydride phase and as shown
in table 3 has a larger quadrupole splitting, a greater linewidth and a substantially more
positive center shift. These results may be contrasted with the Mössbauer spectra of
Ti–Ni–Fe–Si quasicrystals before and after hydrogen absorption [12]. In these previous
investigations the absorption of hydrogen had relatively little effect on the Mössbauer
effect spectrum of the sample. The present results indicate that in the Ti–Zr–Fe–Ni al-
124 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides

loys hydrogen has a much more substantial effect on the Fe environments. The greater
quadrupole splitting of the hydride sample indicates that the hydrogen has reduced the
symmetry of the Fe site environment. The excess linewidth is an indication for Fe sites
that are not uniquely defined. This is understandable in terms of the X-ray studies if the
hydride component of the spectrum results from both quasicrystalline and amorphous
components. The substantial positive change of the center shift indicates a reduction in
electron density at the Fe nuclear sites. This is consistent with the overall expansion
of the quasilattice indicated by the shift in the X-ray diffraction peaks. In general the
Mössbauer effect parameters of the hydride sample are consistent with changes in the
microstructure of the quasicrystal phase caused by hydrogen bonding to Ti and/or Zr in
the near neighbor shell around the Fe probe sites. This will have the observed effect on
the center shift and will, most likely, reduce the local symmetry.

4. Conclusions

The formation of hydrides of early transition metals and their alloys may be accom-
plished by ball milling under a hydrogen atmosphere at room temperature for relatively
short periods of time. Although the bulk diffusion rate of hydrogen in early transition
metals is very high, conventional hydrogenation methods require elevated temperature
and/or pressure and extended periods of time are required for the hydrogen atoms to
penetrate the strongly adherent oxide layer. The ball-milling method is, therefore, a
simple and efficient means of producing single phase hydrides from elemental and alloy
precursors containing early transition metals.
The results presented here represent our investigations aimed at quantifying the
rate of hydrogen absorption in metals during ball milling and at relating this rate to the
milling parameters. They also include our observations of the microstructural phase
development during the milling process and an investigation of hydride phases formed
in quasicrystalline materials. In general the diffusion of hydrogen into a sample during
ball milling may be characterized by the following features:
(i) the formation of a large amount of oxide-free surface,
(ii) the rapid reduction in grain size, and
(iii) the introduction of significant lattice defects.
Our detailed studies of titanium indicate that during the initial phase of milling there
is a rapid reduction of grain size to about 30 nm. This is followed by the formation of
titanium hydride. The titanium hydride, when formed, is slightly non-stoichiometric and
has a grain size of about 15 nm. It is reasonable to assume that those titanium grains that
contain sufficient defects and grain boundaries absorb hydrogen fairly rapidly and frag-
ment into smaller non-stoichiometric titanium hydride grains. These non-stoichiometric
titanium-hydride grains absorb a small amount of additional hydrogen over a period of
time and fragment into smaller grains. The formation of other early transition metal
 R.A. Dunlap et al. / Preparation of nanocrystalline metal hydrides 125

hydrides show similar features in the hydrogen absorption curves and it is likely that
similar process occur on a microscopic scale as those observed for titanium.
In the case of the quasicrystalline materials studied here, substantial quantities of
hydrogen are absorbed. The addition of a small amount of Fe seems to increase both
the hydrogen absorption rate and the saturation value of H/M. These results suggest the
possibility of commercial utilization of these materials for hydrogen storage. Mössbauer
effect studies have shown that microstructural changes resulting from the absorption of
hydrogen correspond to hydrogen bonding to Ti and/or Zr in the near neighbor shell
around the Fe probe sites.

Acknowledgements

This work was supported in part by grants from the Natural Sciences and Engi-
neering Research Council of Canada. One of the authors (Z.H.C.) thanks the Killam
Foundation for financial support.

References
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[2] K.M Mackay, Hydrogen Compounds of the Metallic Elements (Spon, London, 1965).
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