Journal of the Less-Common Metals, 120 (1986) 35 - 43 35

EFFECTIVE THERMAL CONDUCTIVITY OF A METAL HYDRIDE

BED AUGMENTED WITH A COPPER WIRE MATRIX

M. NAGEL, Y. KOMAZAKI and S. SUDA

Department of Chemical Engineering, Kogakuin University, 2665-1, Nakano-machi,

Hachioji-shi, Tokyo 192 (Japan)
(Received July 11,1985)

Summary

The effective thermal conductivity I(,’ of a copper wire matrix im-

proved metal hydride bed of MmNi4.46A1,,54 powder has been measured
using a steady state method. Effects of the copper wire matrix, the metal
hydride itself, the system pressures and the hydrogen-to-metal atom ratio
(~~~) on kr,’ are analysed and expressed through an empirical equation.

1. Introduction

Early experimental studies on metal hydride based heat-pump systems

[ 1 - 61 have clearly demonstrated the need for improving the heat transfer
through a metal hydride bed. Great improvement of the thermal conduct-
ivity of metal hydride powder (MHP) has been obtained when metal matrices
such as aluminium foams and copper nets are inserted. Aluminium foams
filled with MHP have been used in several applications [2, 31. They give a
K,’ value ranging from 5 to 7 W m-” K-l, but their high cost and poor com-
mercial availability make alternative methods necessary. One of these is a
material which is made by compacting the MHP together with flakes or
particles of high thermal conductivity. The heat conduction of such ma-
terials gives considerably improved values ranging from 10 to 12 W m-l
K-l [ 51. As an alternative, a new heat transfer scheme has been designed and
formed using a corrugated copper wire matrix. The fc,’ of this relatively
simple and easy-to-manufacture structure has been measured using a steady
state method [ 7, 81. An empirical equation is used for correlating K,’ values
with hydrogen gas pressure and hydrogen-to-metal atom ratio (H/M).

2. Configuration of the heat transfer device

Details of two different types of the heat transfer paths are shown in
Fig. 1, where Model I will provide the shortest path length S and Model II

0022-5088/86/$3.50 @ Elsevier Sequoia/Printed in The Netherlands

36

FtlELI mm II

FLAT WIFiE-KT CONTACT POINT CoRRUGtlED WIRE-MT

f HEAT FLCW f HEAT FLCW

.REFEREKE K4TEFtIAL

DIRECTION OF
HEAT Fu)c(

THEFK#JPLES

WRRUGATFD
WIRE-NET

‘FLAT WIRE-t.53

‘COOLING FUJID

Fig. 1. Structure model of a copper wire matrix to improve I&‘.

TABLE 1
Physical properties of the copper wire matrix

Material CU
Density (kg mm31 8920
Void fraction 0.91
Surface urea per unit volume (m2 mm3) 6882
Thermal conductivity -1 K-1 389
1
Wire diameter ;:;1 0.2 x 10-S
Matrix size (mesh) 50

will give the longer path S + 44. In each model the average values of L, S and
M are given as 2.2 mm, 3.5 mm and 5.0 mm respectively.
The maximum distance from the matrix to any part of the hydride bed
is less than 1.25 mm which enables rapid heat transfer and this distance is
well within the range recommended by Suda et al. [7]. The physical prop-
erties of the copper wire matrix are given in Table 1.
The heat transfer Q through the matrix can be calculated using the
Fourier equation:
 37

dQ = --&‘A g (1)

The resistance R to heat transfer is expressed in general as

R=fdX (2)
K,’ dA
By analogy with an electrical circuit, the resistance to heat flow in the
paths given by the two models can be expressed as a sum of the resistances.

Model I R, = Rs + R,
Model II RI1 =R,+R,+ZR, (3)

where (see Fig. 1)

Es = S/(&A,)
R, = ~/(K~A~)
R, = l/(&h,)
The value of R,
between two layers of
view, Model II occurs
the terms are included
matrix is found to be
(4)
depends on the conditions of the contact surfaces
the copper wire matrix. From a geometrical point of
about five times more often than Model I. When all
in Eqn. (1) the heat Q transferred by the copper wire

Q=
I_d!_
f&Ad
“I- -+
5&k
9
Tz) (5)

T, and T, are temperatures measured at two locations in the copper

wire matrix as shown in Fig. 1.

3. ~pe~en~l apparatus

The experimental apparatus consists of two annular chambers shown

schematically in Fig. 2. Lead shot and ethyl alcohol were used as the refer-
ence material in the inner chamber. The physical properties of the copper
wire matrix and the reference material are listed in Table 1 and Table 2
respectively. The heat flow was kept constant between the reference bed
and the testing chamber by producing temperature gradients between the
heating tube placed in the centre and the outer cooling jacket. The tem-
peratures of the heating and cooling fluids were controlled to within +I “C.
Eight thermocouples of 0.3 mm diameter were placed in the reference and
in the testing chambers to measure the temperature distribution in the radial
direction. Two fluorocarbon polymer (Difron) blocks were used for insula-
tion at each end of the testing chamber. A porous sintered filter with a pore
diameter of 2 X low6 m was used to prevent the fine particles from leaving
38

HEATING FWID

cm FOXEN
FLU

CUT

TESTING CM8BER ( METAL HYDRIDE PCKER OF i’h Nqa6 h,~

INNER CfIPPER WIR-NET MRIX)

REFERENCE CHMBER ( LEAC SHOT AM ETHYL ALCDHOL )

INSULATION

COJLING FLUID

HEATING FLUID
5 3 OUTLET
THEMJX#JPLES

Fig. 2. Experimental apparatus used to measure K,‘.

TABLE 2
Physical properties of the reference materials

Lead shot
Average particle size (m) 2.24 X 1O-3
Density (kg me3) 11,320
Void fraction 0.418
Sample weight (kg) 1.815
Thermal conductivity (W m-l K-l) 35.3
Ethyl alcohol
Thermal conductivity (W m-l K-l) 0.168
Reference material
Thermal conductivity (W m’-’ K-l) 1.64 - 0.00192’,”

aIn the range (0 =GT, < 60 “C).

the chambers. Details of the experimental apparatus are shown in Fig. 3,

and they are described in detail elsewhere [ 7, 81.
The particle size distribution of the testing material was determined
and the results are shown in Table 3.
 39

Fig. 3. Details of experimental apparatus: (1) Piping for heating fluid; (2) Difron insu-
lator; (3) O-ring seal; (4) reference bed; (5) metal hydride bed; (6) cooling jacket; (7)
pipes for thermocouples; (8) inlet for hydrogen gas; (9) sintered metal filter (2 pm);
(10) Difron insulator.

TABLE 3
Particle size distribution of MmNi 4.46A1e.s4 hydride after 15 sorption cycles

Diameter Distribution
(Pm) (%)

22 7.65
16 21.98
11 25.54
7.8 24.64
5.5 13.05
3.9 5.37
2.8 1.63
1.9 0.12
40

4. Experimental procedure

Activation of MmNi4.46A10.54powder was achieved by first outgassing

the testing chamber for 6 - 7 h at 1.2 Pa at a temperature of 90 “C. The
alloy powder was then hydrided under a pressure of 4 MPa. The hydriding
and dehydriding process was repeated 10 times to ensure the powder was
completely hydrided. The temperature of the heating fluid was adjusted to
constant conditions of 30, 40 or 60 “C, and that of the cooling fluid was
kept constant at 20 “C.

5. Results and discussion

K,’ values obtained under three different temperature conditions are

shown in Fig. 4 as a function of system pressure, as well as the values ob-
tained under helium atmosphere. As the pressure increases, typical S-shaped
curves [9] are observed for both hydrogen and helium atmospheres. The
steep increase in K,’ values can be explained by means of the kinetic gas
theory [lo].
m%liE (AT,,)
0.1 0.5 1 5 10 9
I I
I

0.01 0.05 0.1 0.5 1 5

FiEsYJllE@PAPA)

Fig. 4. K,' vs.P for an improved metal hydride bed, showing the effects of temperature
and hydrogen or helium atmosphere.

5.1. Low pressure region (less than 0.02 MPa)

In this region, the system pressure has no influence on K,‘as the mean
free path of the gas molecules (0.1177 X 10e6 m) is considerably smaller than
the characteristic length of the space between the grains of the powder. The
K,’ values obtained under vacuum conditions and at pressures up to 0.02
 41

MPa are attributed to particle-to-particle heat conduction with a minor con-

tribution from heat radiation. Because of the average size of the particles and
the relatively low temperature, radiation heat transfer, Krad = 5 X 10M4 W
m-i K-’ [lo] c an be neglected. The pressure independent particle-to-particle
heat conduction is of the order of 0.1 W m-i K-l as in the evacuated condi-
tion [ 111. The thermal conductivity of the copper wire matrix packed with
hydride particles is 0.3 - 0.4 W m-’ K-i under evacuated conditions as shown
in Fig. 4. This is believed to be caused by extremely poor surface contact
between the particles.

5.2. Intermediate pressure region (0.02 - 3 MPa)

For pressures up to 3 MPa, K,’ is dependent on free molecule conduc-
tion, K’ which is directly proportional to the system pressure as described
mathematically by Kennard [12]. In order to evaluate the influence of
system pressure separately from that of the H/M ratio, K,’ of the well acti-
vated MHP samples was measured in vacuum, and in hydrogen and helium
atmospheres. Helium was chosen because it does not react with the hydride
powder and has a thermal conductivity close to that of hydrogen (Ku, =
Kue X 1.25).
Up to 3 MPa, K,’ increases linearly with helium gas pressure with only
minor influence of the system temperature. The difference between the
values of K,’ obtained under helium and hydrogen atmospheres is due pri-
marily to the presence of hydrogen in each hydride particle. The main cause
is the volume increase of the hydrided particles which leads to a larger con-
tact area; the particle-to-particle conduction is improved and the void frac-
tion of the hydride bed is reduced.

5.3. High pressure region (greater than 3 MPa)

After the metal hydride bed reaches fully hydrided conditions no
distinctive increase of K,’ is expected with further increase of hydrogen gas
pressure.
In Fig. 5, changes of K,’ are shown as a function of the H/M ratio. The
curves obtained are quite similar to those of the pressure-temperature-
composition (P-T-C) as given in Fig. 6. In this region, a strong influence of
hydrogen gas pressure on K,’ is obviously observed. A marked deviation of
K,’ is observed between absorption and desorption processes. As K,’ de-
creases when the temperature difference between the heating and cooling
fluids decreases, K,’ also increases with the average bed temperature.
K,’ can be separated into the following terms:

K,’ = &as(fH/M + f,) + &u + KMH(~ + gH/M) (6)

which are defined in Appendix A.

Finally, the empirical expression for K,’ was found as a function of P
and the H/M ratio, being valid between 1 and 40 atm:

K,‘= 0.44 + (0.55H/M - 0.025P) + ln(1.734 + 0.375P) (7)

 -1

-0.5

6
F

k!
-0.1 3

ii!

I I I II 1 I II 1
0 0.1 0.2 0,3 04 0,s 0.6 0.7 0.8 0. 0.2 089 0,6 0,X 1.0
HITIM TO - PETAL ATCtl RATIO ( HM ) HYDROGEN - TO - t’ETA1 ATOM RATIO (H/N)

Fig. 5, K,’ vs. H/M ratio for absorption (solid symbols) and desorption (open symbols)
processes at various temperatures.

Fig. 6. P us. H/M ratio for absorption (solid symbols) and desorption (open symbols) of
~rn~i~,~**s~ at 40 and 60 “C.

6. Conclusions

K,’ of a hydride reaction cell with a copper wire matrix has been mea-
sured in vacuum and under helium and hydrogen atmospheres, and analysed
to separate the effects of several parameters such as system pressure, particle-
to-particle heat conduction, and hydrogen-to-metal atom ratio. An empirical
equation is presented for a MrnNieSG6A1 e-s4 hydride bed. The copper wire
matrix will improve I&’ by 0.4 W m-l K-r.

We wish to thank undergraduate students Y. Kondo and Y. Shin for

their experimental assistance.
 43

References

1 S. Suda, F’roc. 5th World Hydrogen Energy Conf., Toronto, Canada, 15 - 20 July
1984, Hydrogen Energy Prog. V, Pergamon, Oxford, 1984, p. 1201.
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Meeting, Sendai, Japan, 1983, Society of Chemical Engineering of Japan, Tokyo.
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319 - 327.
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(1983) 325 - 332.
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9 Y. Ishido, M. Kawamura and S. Ono, Int. J. Hydrogen Energy, 7 (1982) 173 - 182.
10 N. Wakao and D. Vortmeyer, Chem. Eng. Sci., 26 (1971) 1753 - 1765.
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12 E. H. Kennard, Kinetic Theory of Gases, McGraw-Hill, New York, 1938, p. 311.

Appendix A: Nomenclature

A area (m2)
AC cross sectional area of contact (m2)
cross sectional area of a wire (m2)
$M
fP
H/M ratio correlation factor
system pressure correlation factor
gH,M H/M ratio correlation factor to MHP conduction
4 heat transfer coefficient (W m-l K-i)
HIM hydrogen-to-metal atom ratio
&h thermal conductivity of copper (W m-l K-l)
K,’ effective thermal conductivity (W m-’ K-l)
K gas conduction from gas to solid (W m-’ K-l)
K MH thermal conductivity of MHP under vacuum conditions (W m-l K-l)
K rad radiation heat transfer (W m-’ K-l)
K ref thermal conductivity of reference material (W m-l K-l)
P system pressure (Pa)
Q heat transfer (W m-l K-l)
R resistance to heat transfer (K W’)
RI. II thermal resistance of Model I or Model II (K W-l)
RC thermal resistance of contact points (K W-l)
R S,M thermal resistance of the wire length S or M (K W’)
T temperature (K)
X length, distance (m)