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Materials Science and Engineering, 72 (1985) 171-176 171

The Influence of Inhomogeneous Rolling on the Capacity of Aluminium Anode


Foil Material

H. P. KNEYNSBERG*, C. A. VERBRAAK~ and M. J. TEN BOUWHUIJS


Department of Mechanical Engineering, Twente University of Technology, Enschede (The Netherlands)
(Received July 10, 1984; in revised form October 9, 1984)

ABSTRACT foil (on all walls of the pores) by electro-


chemically anodizing. To take advantage of
Several aluminium single crystals were cold the enlargement of the area of the anode foil,
rolled under different rolling conditions, char- the cathode of the capacitor is an electrolyte
acterized by the rolling parameter lid. The re- which is capable of penetrating into the pores,
sulting foil was subsequently electrochemi- thus contacting the dielectric at any site. The
cally etched and anodized, and the electrical electrolyte is absorbed in a thin layer of highly
capacity was measured. porous paper which covers the anode foil on
Inhomogeneously rolled foils showed a both sides, and the electrolyte is in contact
higher capacity than did homogeneously rolled with another foil, usually referred to as the
foils. This could be attributed to the develop- cathode foil.
ment o f layered structures in the case o f in- In this paper, investigations are described
homogeneous rolling; sharp orientation transi- o f the structure of the anode foil material in
tions in these layered structures in (123)(412) relation to its capacity.
foil gave rise to a higher capacity than did
gradual orientation changes in the other foils.
2. PRELIMINARY INVESTIGATIONS: STORED
ENERGY AND INHOMOGENEOUS DEFORMA-
1. INTRODUCTION TION

The most outstanding feature of an alumin- Adams and van de Broek [1] determined
empirically that the capacity of various hard
ium electrolytic capacitor is its capacity per
volume. This is partly caused by the relatively rolled aluminium foils with the same impurity
high value of the dielectric constant e~ of content, measured at 273 and 4.2 K after
A1203 which is the dielectric in an aluminium etching, increased with a decreasing value of
the electrical resistance of the unetched foils.
electrolytic capacitor. This dielectric layer can
be very thin because of the high dielectric Moreover, a low ratio of the electrical resis-
tance at 273 K to that at 4.2 K corresponded
strength o f A120 3 (1 V / 1 5 A ) .
The high capacity per volume of an electro- with a high capacity. The resistance at 273 K
lytic capacitor is caused mainly b y the tre- is caused b y atomic vibrations for the most
mendous enlargement of the geometrical area part; at 4.2 K, however, it is attributed mainly
which is obtained after electrochemically
etching the aluminium foil that is used as the
anode. This etching process creates a sponge-
like subsurface structure (Fig. 1). The dielec- ,o • v: oO • ocBe dw~
tric is applied directly onto the aluminium /~o~o, qjf.#~'. ~ d'o " Bm.'lO-~ot'Grtw
,,~* o - *-,, 4d'o ~* ¢ O ~ - o e * , O ' ~ O ; ~ . e Z . 6 " 7

*Present address: National Luxembourg Aluminium


Cie, Luxembourg.
J'Professor Verbraak passed away on March 23,
1983. Fig. 1. Schematic drawing of a foil after etching.

0025-5416/85/$3.30 © Elsevier Sequoia/Printed in The Netherlands


172

to dislocation density and impurity content. cessively removing layers and subsequent etch-
Since the low resistance ratio for aluminium ing, that the capacity strongly depends on the
foils in this case, where the impurity content quantity of the removed material. The influ-
did not vary, could be caused only by a high ence of layered structures on the recrystalliza-
dislocation density, the dislocation density tion behaviour o f an aluminium single crystal
was concluded to be an important parameter has been clearly demonstrated b y Heller et al.
for the capacity obtainable in a foil. [11], who investigated recrystallization after
Kneijnsberg [2 ] investigated various A1-Mg artificial nucleation in a rolled aluminium
foils. The capacity of the foils in the as-rolled single crystal. The first recrystallized grains
condition increased with increasing magnesium did not appear at those sites where preferred
content. Electron microscopy observations nucleation was expected but in a zone below
showed that the dislocation density after 99% and parallel to the surface. This anomalous
deformation also increased with increasing behaviour could be attributed to the forma-
magnesium content. Short heat treatments of tion of inhomogeneities in the deformed ma-
the A1-Mg foils before etching caused a strong trix, causing sites with a higher stored energy
decrease in capacity and a clearly recovered to act as nucleation sites. Both experiments
structure. The dislocation densities in the heat- clearly demonstrate the influence of layered
treated foils, however, were barely changed. structures on energy activated processes {e.g.
While recovery only slightly influences the nucleation, deep etching).
dislocation density, stored energy is strongly In order to investigate the role of stored
influenced because, in general, stored energy energy on the obtainable capacity, single-crys-
depends not only on the dislocation density tal experiments were chosen for two reasons:
but also on dislocation arrangements. Differ- (a) According to Haessner and Hoschek
ences in stored energy between the deformed [12], the initial orientation influences the
and the recovered state are due to differences amount of energy that can be stored during
in dislocation arrangements whereas differ- deformation; this is higher in { l l 2 ) ( l l l ) -
ences between the recovered state and the re- than in { l l 0 } ( l l 2 ) - o r i e n t e d single crystals. In-
crystallized state are due to a reduced disloca- vestigation of homogeneously rolled single
tion density in the recrystallized state. From crystals with different orientations will eluci-
the observations mentioned above, it might date the influence of the energy stored during
be assumed that the stored energy rather than rolling on the etchability.
the dislocation density as such is responsible (b) Inhomogeneous orientation distribu-
for the differences in capacity. tions over the cross section, which might cause
A second important aspect has to be con- an inhomogeneous distribution of stored ener-
sidered. According to many researchers [ 3 - 8 ] , gy over the cross section, thus influencing the
an inhomogeneous orientation distribution etching process, can be best investigated in
over the cross section in both single-crystal single crystals.
and polycrystalline materials can be developed
during rolling. This depends on the geometry
of the zone of deformation during rolling, 3. EXPERIMENTAL PROCEDURE
which is characterized by the ratio of the
zone contact length I to the zone thickness d. Single crystals with {123}(412), {110}(112)
The above-mentioned researchers state that an and {112}(111) orientations were produced
inhomogeneous orientation distribution over by the Bridgman technique from both high
the cross section is developed when rolling oc- purity (99.999%) and pure (99.99%) alumin-
curs with lid < 1. Strain distribution and the ium. The crystals were rolled with various
a m o u n t of redundant strain are also depen- l/d values on a Buehler rolling mill with a roll
dent on l/d or the parameter ~ = d/l [9]. In- diameter of 160 mm and a rolling rate of 24
homogeneous rolling leads to the development rev rain -1. The final rolling reduction for all
of layers with different orientations and sub- crystals amounted to 99%. The foil thickness
structures in the rolled sample. The presence was then about 100 pro. The orientation dis-
of layers with distinct substructures proved to tribution over the cross section was deter-
have a great impact on the capacity of the mined with a topographical X-ray technique
anode foil: van der Berk [10] found, b y suc- which enables determination of the orienta-
173

tions in the developed layers [2, 13, 14]. The


capacity was measured after deep etching and
forming the dielectric oxide layer. The foils
were etched in an aqueous solution, contain-
ing 20% NaC1 and 2.5% Na2SO4 at 90 °C. The
current density was 150 A dm -2 and the etch-
ing time 46.7 s (charge input, 700 C dm-2).
The foils were anodized in a borate-and-phos-
phate-based forming liquid until an oxide film
was formed which was sufficiently thick to
use the foil in low voltage (50 V) capacitors.
Capacity measurements were carried o u t at
100 Hz using a Hewlett-Packard capacity-
measuring bridge with the strips as the anode 6-

in a low resistance cell (100 ~2 cm). The cath-


ode was a silver cup sheathed with platinum.
The results obtained from the single-crystal
experiments were compared with t w o series
of experiments on polycrystalline 99.99%
pure aluminium. The material used for these
experiments was received from the manufac- f I I I
11231 < 4 1 2 > 11121 < 111 > 1110~ < 1 1 2 > polycrystalline
turer in the hot-rolled condition and showed a reference
strong hot-rolling texture and an inhomoge- orientation

neous grain size distribution over the cross Fig. 2. The capacity (in microfarads per square centi-
section. In one series of experiments, essen- metre) of 99.999% aluminium single-crystal foils with
tially texture-free samples (which had been both homogeneous and inhomogeneous orientation
obtained from this material by alternating de- distributions over the cross section and of a commer-
cially available foil (99.99%) which is used as the
forming and annealing) were rolled with vari- reference: ~, inhomogeneously deformed (l/d = 0.4);
ous l i d values. In the other series the sheet m, homogeneously deformed (lid = 1.2 for (110}(112)
was cold rolled with various l i d values. and {112}(111); lid = 2 for (123}(412)).

4. RESULTS
creased by inhomogeneous rolling. The capaci-
In Fig. 2 the capacities of the foils of ho- ty of the {112}<111> foil is only slightly influ-
mogeneously and inhomogeneously rolled enced by changing the rolling geometry. The
99.999% pure aluminium single crystals are results presented in Fig. 2 clearly demonstrate
plotted as a function of the initial orientation. the influence of this inhomogeneity on the
The inhomogeneously rolled foils are made by capacity, which was caused by changing the
rolling with I / d = 0.4, whereas the homoge- rolling geometry.
neously rolled foils are made by rolling either Figure 3 shows the capacities of foils ob-
with I / d = 1.2 ({110}(112) and {112}<111> tained by inhomogeneously rolling single crys-
crystals) or with l / d = 2 ({123}(412> crystal). tals of the 99.99% pure material with differ-
The capacity of a polycrystalline 99.99% pure ent orientations. These crystals were rolled
commercially available foil which was used as with l i d = 0.4. The influence of inhomoge-
a reference is also indicated. neous rolling on the capacity of the {112}-
As to the homogeneously rolled crystals, <111) and {110}(112> crystals is somewhat dif-
Fig. 2 shows that the capacity of the (123}- ferent in this case. However, again the foil
(412> foil is the highest although there is little made by inhomogeneously rolling a crystal
difference from the capacity of the {112}- with the {123}(412> orientation has by far the
(111) foil. When the inhomogeneously rolled highest capacity.
crystals are considered, the {123}<412> foil Figure 4 shows the structures as revealed in
shows an especially high capacity, while the the optical microscope o f these single crystals
capacity of the {110}(112) foil was also in- after 50% deformation. The differences in
174

9- rolling conditions as a function of the applied


ratio lid. It can be seen that the capacity de-
creases with increasing value of l/d. From pole
figure measurements it could be concluded
that in these foils, although the major part
8- was rolled with lid > 1 and different rolling
conditions were applied, no homogeneous
orientation distribution over the cross section
developed and also that the inhomogeneity of
the texture distribution (especially that ob-
7- served in the band-like structure (Fig. 4(c)))
decreases with increasing lid value.
In Fig. 6 the capacities of the polycrystal-
line foils as a function of lid are given. The
figure demonstrates that the capacity of the
foils obtained by rolling the texture-free ma-
6-
terial (indicated by open squares) decreases
with increasing lid value. From topographical
X-ray measurements it could be concluded
that rolling with lid = 0.4 resulted in a fine
multiple-layered structure, whereas a coarse
5- layered structure developed when rolling with
lid = 5. In the foils produced b y further cold
rolling the hot-rolled material (full squares)
i i I
the capacity is only slightly influenced by
:123:<412> :112:<111> 110: < 1 1 2 >
variation in the rolling parameter. The layered
orientation
structure as observed in these foils was not in-
Fig. 3. The capacity (in microfarads per square centi- fluenced by changing the cold-rolling geom-
metre) of 99.99% a l u m i n i u m single-crystal foils ob- etry.
tained by rolling with l / d = 0.4.

5. D I S C U S S I O N A N D F I N A L R E M A R K S
contrast make clear that a layered structure
has been developed during rolling in all three The results presented above show that the
crystals. From topographical X-ray photo- capacity after etching can be influenced by
graphs and electron microscopy observations, the rolling parameter lid in single crystals as
it can be concluded that, in the (110}(112) well as in polycrystalline material. Rolling
and (112}(111) crystals, mainly gradual orien- with lid < 1 leads to layered structures in all
tation changes are found between the differ- rolled single crystals (Fig. 4), whereas rolling
ent layers whereas, in the band-like structure with I/d > 1 results in a layer-free structure.
observed in the upper part of the rolled (123}- An exception has to be made in the last case
(412) crystal (Fig. 4(c)), very sharp discontin- for (123}(412) crystals with 99.99% purity.
uous orientation transitions are found. The In general, the capacity of the crystals with
same features are found in the 99.999% pure a homogeneous structure, i.e. homogeneous
material. On the basis of the development of orientation distribution over the cross section
the layered structures as observed in the opti- after rolling, is lower than the capacity of the
cal microscope as well as in topographical X- crystals with the same initial orientation b u t
ray photographs taken from samples with with an inhomogeneous structure over the
higher rolling reductions, it can be stated that cross section. In crystals with a homogeneous
the same t y p e of structure and orientation structure over the cross section, the capacity
transition over the cross section are also pres- depends on the orientation in the same way as
ent after higher degrees of deformation. does the stored energy, as measured by Haess-
Figure 5 shows the capacity of several net and Hoschek [12]. In crystals with an in-
99.99% pure (123}(412) foils under different homogeneous structure the capacity depends
175

<112>

(b)
1.4mm I I
~
<111>
<110>_~

<110>
1 mm
t
~..1 >
I I
(a) <112>

<123>
1.4mm
t
rL <112)
I I ~
(c) <412>

Fig. 4. Photomicrographs of rolled 99.99% aluminium single crystals ( l / d = 0.4; viewing plane perpendicular to
the rolling direction): (a) {110}(112}, 50% rolling reduction;(b) {112}(111), 75% rolling reduction;(c) {123}(412),
50% rolling reduction.

also on the orientation b u t far more on the changes between narrow layers. This t y p e of
t y p e o f inhomogeneity and their distribution inhomogeneity is mainly observed in inhomo-
over the cross section. The inhomogeneities geneously rolled {123)(412} crystals. From
and their distribution have been analysed the recrystallization experiments carried o u t
more thoroughly by Kneijnsberg and co- by HeUer e t al. [11] it can be concluded that
workers [2, 13, 14]. From these analyses it these inhomogeneities create places with a
could be concluded that high capacities were high local stored energy. It can thus be con-
measured in foils containing sharp orientation cluded from the single-crystal experiments
176

9-
line material are in accordance with those ob-
~ nolrotated
served in single crystals. The influence of the
~ nolrolated
rolling geometry on a material with a hot-
rolling structure is less evident. This is attrib-
8- uted to the layered structure present in the
as-delivered material. The experiments of
~ reversed
Kneijnsberg and coworkers have shown that
this layered structure, which was developed
7-
during hot rolling, is only slightly influenced
~embedded + reversed by additional cold rolling. This is also true for
the capacity. In spite of this, experiments on
ireversed
polycrystalline materials show that, in these
materials as well, the layered structure (and
6-
notrotated hence the distribution of stored energy)
strongly influences the capacity.
(J

ACKNOWLEDGMENTS

// This work has been financially supported


I I I I ff I
04 08 12 2 5
by Philips Elcoma for the major part. Addi-
lld tional support was obtained from the Founda-
Fig. 5. The capacity (in microfarads per square centi- tion Twente University of Technology and
metre) of several (123)(412) aluminium foils (99.99% from the Foundation for Technical Research
purity) obtained by rolling with different rolling con- (FOM-STW).
ditions.

REFERENCES
11"--~

1 J. Adams and J. van de Broek, personal communi-


10~
cation, 1977.
2 H.P. Kneijnsberg, Ph.D. Thesis, Twente Universi-
ty of Technology, 1982.
g~ 3 R. E. Bauer, H. Mecking and K. Liicke, Mater. ScL
Eng., 27 (1977) 163.
4 H. O. Asbeck and H. Mecking, Mater. ScL Eng.,
8 m 34 (1978) 111.
5 J. Hansen and H. Mecking, in G. J. Davies et al.
(eds.), Proc. 4th Int. Conf. on the Texture o f Ma-
7-- teriais, Cam bridge, Cam bridgeshire, 1975, Metals
o Society, London, 1976, p. 147.
g 6 P. S. Mathur and W. A. Backofen, Metall. Trans.,
"~ 6--
4 (1973) 643.
7 W. Truszkowski, J. Krol and B. Major, Metall.
I i i // , //--T-- Trans. A, 13 (1982) 665.
0.4 0.8 1.2 3.75 5
8 R. A. Vandermeer and J. B. Bernal, Texture
Cryst. Solids, 2 (1977) 183.
Fig. 6. The capacity (in microfarads per square centi- 9 W.A. Backofen, Deformation Processing, Addison-
metre) of polycrystalline aluminium foils (99.99% Wesley, Reading, MA, 1972.
purity) obtained by a 99% rolling reduction of essen- 10 P. van der Berk, personal communication, 1977.
tially texture-free material (D) and material in the hot- 11 H.W.F. Heller, J. H. van Dorp, G. Wolff and C. A.
rolled state (m) with various I/d values. Verbraak, Met. Sci., 15 (1981) 333.
12 F. Haessner and G. Hoschek, Scr. Metall., 10
(1976) 63.
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bution of the stored energy) strongly influ- Nagashima (ed.), Proe. 6th Int. Conf. on the Tex-
ture o f Materials, Tokyo, 1981, Japan Iron and
ences the capacity. Steel Institute, Tokyo, 1982, p. 356.
The phenomena observed in the foils made 14 H. P. Kneijnsberg, C. A. Verbraak and M. J. ten
by rolling essentially texture-free polycrystal- Bouwhuijs, Acta. Metall., to be published.