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Some Structural and Textural Aspects of Tribasic Lead


Sulfate Precipitation during the Mixing of
Lead-Acid Battery Positive Paste
F. Vallat-Joliveau, A. Delahaye-Vidal, and M. Figlarz
Laboratoire de Rdactivitd et de Chimie des Solides, Universitd de Picardie Jules Verne, URA CNRS 1211,
80039 Amiens Cedex, France

A. de Guibert
C.E.AC, 92111 Clichy Cedex, France

ABSTRACT
The reaction between PbO and H2SO4 in water leading to the formation of tribasic lead sulfate hydrate was studied
using pH measurements, x-ray diffraction, scanning and transmission electron microscopy, and infrared spectroscopy. We
examined the effect of different parameters such as temperature, starting composition, PbO source, order of the materials
addition, and presence of carbonates, on PbO-H2SO4 reaction. From this study, a mechanism is proposed for the reaction.
It explains why, by mixing PbO and H2SO4 in water, the tribasic lead sulfate cannot be obtained as a pure phase. Some
unreacted PbO always remains at the end of the reaction.

Introduction the mixing and curing operations. Indeed, a memory effect,


which could be related to the nature and the morphology of
Although lead-acid batteries have been extensively used
for one century, there always exists some limitations to the basic lead sulfate formed during the mixing and curing,
their performances due to the low mass utilization at the has been observed for the electrodes in cycling.l'2 For exam-
positive plate. Many improvements have been realized by ple, plates obtained from 4BS-type pastes exhibit better
empirical approaches but there is a lack of fundamental mechanical strength than the 3BS ones, but a complete
knowledge especially concerning the manufacture of flat conversion of 4BS into PbO2 is difficult to achieve during
positive electrodes. This process involves the following the final formation step. These facts are generally ascribed
steps. to the morphology of the 4BS phase which tends to form
1. The oxidation of metallic Pb to lead oxide PbO large needle-shaped crystals. However, since the exact
through processes called "Barton" or "mill" that produce mechanisms involved during both the manufacture a n d cy-
the "leady oxide" containing particles of aPbO and ~PbO cling operations are not yet well known, the cause of the
along with "free" lead. memory effect by the morphological features of the basic
2. The mixing of leady oxide in water with sulfuric acid lead sulfates has to be demonstrated. 1
which results in a paste containing free lead, lead oxide, Among the different transformations involved during the
and basic lead sulfates which are mainly 3PbO 9 PbSO~ 9 electrode preparation, only the mechanism of the 4BS --->
H20 (3BS) and 4PbO - PbSO4 (4BS) and, sometimes, acci- PbO2 transformation has been clearly elucidated. This was
dentally PbO - PbSO4 (1BS). initially done by Burbank 3 and latter confirmed by several
3. The pasting of the paste on lead alloy grids followed authors. 4'~ The interlocking macrotexture of the 4BS large
by a flash drying. needle-shaped crystals is retained after the formation; the
4. The curing during which the pasted flat electrodes are small PbO2 particles tend to form porous needle-shaped
subjected to a treatment in a humid and hot atmosphere agglomerates. This reaction was described by Burbank as a
(50-100~ depending on the manufacturing process). Dur- metasomatic process. In a recent article, Lam gave addi-
ing this stage, the remaining metallic Pb is oxidized and the tional results concerning the 4BS --~ PbSO4 --->P b Q and
basic lead sulfates recrystallize so that the plates exhibit 4BS -4 PbO2 transformations occurring during the soak-
improved mechanical strength and better adherence of the ing-formation stage. 6
active material to the current collector. For the other transformations involved during the prepa-
5. The soaking and formation of the cured plates, a step ration of the positive electrodes (PbO + H2SO4 ~-> 3BS;
in which the plates are immersed in sulfuric acid and PbO + H2SO4 --> 4BS; 3BS --~ PbO2) r/o clear mechanism can
electrochemically oxidized to ensure that the basic lead be found in the literature. In the case where only tribasic
sulfates are converted into the positive final active mate- lead sulfate is produced by mixing, Iliev and Pavlov7 tried
rial, PbO2. to understand how the tribasic lead sulfate precipitation
Each one of these five steps influences the positive active proceeds. The interpretation of their results is rather diffi-
mass behavior during cycling. This is particularly true for cult because they worked with industrial electrodes c o n -
2710 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.
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J. Electrochem. Soc., Vol. 142, No. 8, August 1995 © The Electrochemical Society, Inc. 2711

q
Fig. 1. SEM photographs of commercially available lead oxides:
(a, top left) red Merck (b, above) yellow Merck, and (c, left) Strem.

raining a lot of different phases ((~ and ~PbO, Pb, 3PbO • nisms were not studied in detail. In this paper, the mecha-
PbSO~ • H~O, 4PbO • PbSQ, ...) with a not well-defined nism of formation of tribasic lead sulfate is discussed on
morphology. Rajah 8 and later Davies and Wright 9 suggested the basis of the characterization results of the different
that a passivating layer of PbSQ was formed on the surface phases observed during the reaction. X-ray diffraction
of the PbO particles when sulfuric acid is added without (XRD), infrared (IR) spectroscopy, scanning and transmis-
giving clear evidence of this suggestion. In fact, most pa- sion electron microscopy (SEM and TEM) were used for
pers related to the mixing and curing steps are more this purpose. Moreover, the influence on the reaction of
devoted to the determination of the factors which influence several experimental parameters (composition of the start-
the nature of the prepared basic lead sulfate (mono-, tri-, or ing PbO + H2SO4 + H20 mixture, temperature, morphology
tetrabasic one) than to the mechanisms involved in the re- of the reactants and reaction atmosphere) is investigated.
action. Pavlov 1° has shown that the nature of basic lead
sulfate changes depending on the sulfuric acid density and
Experimental
Starting PbO precursors.--Three lead oxides were used
the temperature. For low densities (i.e., with H2SOjPbO
in this study, yellow Merck PbO, red Merck PbO, and Strem
ratio less than 6%) and high temperatures (over 60°C), the
PbO. Commercial yellow Merck lead oxide is orthorhombic
tetrabasic lead sulfate precipitates, while for higher densi- while red Merck oxide is tetragonal. Both compounds show
ties and lower temperatures, the precipitation of the triba-
sic or monobasic sulfate is favored. The PbO structural
modification (~ or ~) is thought to influence the nature of
the basic lead sulfate formed, but there are controversies
on this subjectY '11'12Some think that the ~ modifica-
tion (orthorhombic PbO) favors the tetrabasic lead sulfate
production ~'7while others claim that it is the c~ one (tetrag-
onal PbO). 11,12
This work is part of an extended study of the mechanisms
involved during manufacture and formation of the positive
flat plates. 13 It is focused on the formation of 3BS by mix-
ing. In the industrial process, leady oxide is generally
added in excess with a low water content in order to obtain
a paste with a suitable consistency to fill the lattice struc-
ture of the grid. We chose to operate in more dilute solu-
tions than in real battery manufacture. Indeed, this method
is useful for investigating the reaction mechanisms of PbO
in sulfuric acid solution: dilute solutions allow an energic
stirring so that a good homogeneity is achieved inside the
reaction flask. Such dilute media were used by others for
preparing the 3BS or the 4BS phases, 3'4'14but the mecha- Fig. 2. SEM photography of lead oxide after grinding.
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2712 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.

10 to 20 ~m edged octahedral particles (Fig. l a and b). 1BS


Strem PbO is a mixture of the two structural types (or- 10
thorhombic and tetragonal). Its particle morphology may 4BS
be described as platelets without a definite shape with a W 9
mean size of 4 ~m (Fig. lc).
In order to improve the reactivity of the oxides, the three e
starting materials were also subjected to a grinding in a i 8
SPEX 8000 mixer mill during 20 min. The resulting ground
materials were then used as starting PbO for some experi- g 7
ments. The grinding operation decreases the particle size
until about 1 to 2 ~m as shown in Fig. 2 b u t also changes the
h
structural type of PbO: orthorhombic PbO is partly con- t 6
verted into the tetragonal phase and vice versa.
Mixing experiments.-- The mixing of the starting mate-
% 5
rials was carried out in a flask equipped with a mechanical
stirrer, a mercury thermoregulator, a pH electrode, and a
condenser.
4
First, many experiments were performed under various H
conditions in order to study the following factors: (i) the
2 3
temperature, which varied between 5 to 60~ (if) the ratio
of PbO and H2SO4 (molar ratio: 3 < PbO/H2SO4 < 5); (iii) the S 2
PbO precursor (Merck and Strem commercial lead oxides,
ground or not); (iv) the addition order of the starting mate- O BURBANK
rials, and (v) the adsorption of carbonates on reactants and 4 1
products: most of experiments were performed under air BIAGETTI
but some of them under argon in order to avoid carbonation
of the solid phases. 0
For these experiments, the duration of the reaction was 0 20 40 60 80 100
fixed at least at 24 h, and no sample was removed during
the course of the reaction to be sure that a quasi-equi-
librium state is achieved. weight % PbO
In a second step, representative experiments were chosen Fig. 3. On this diagram, the point (0,0) corresponds to 100% in
among the previously investigated ones to study the mech- H20. Each of the three arrows corresponds to the stoichiometric
anism of the reaction. Typically, a suspension of ground compositions in H2S04 and PbO for preparing each of the three basic
Strem PbO (5.95 g) was introduced in a dilute sulfuric acid lead sulfates in a more or less dilute solution. It can be seen that
solution (1.88 g of 9N H2SO4 in 140.7 g of pure water) at Burbank and Biagetti worked in more dilute conditions than Pavlov
room temperature in air. The stirring was maintained for and Dapo (areas delimited by two I I ). The different points marked
24 h. Samples were periodically removed from the suspen- on this diagram show the various starting compositions we have
sion and characterized. chosen for the preparation of the basic lead sulfates.
Characterization techniques.-- The PbO precursors and
the solid phases obtained during or after mixing were char- ing composition is. If the composition corresponds to a
acterized by the following techniques. X-ray measure- point located above the tribasic lead sulfate straight line
ments were carried out using a Philips 1050 0-20 goniome- (see Fig. 3), tribasic and monobasic lead sulfates precipi-
ter (back monochromator, CuKa). IR spectra were recorded tate sometimes with a small quantity of PbO remaining
with a Nicollet 510 Fourier transform infrared (FTIR) spec- (Fig. 4a). Below the tribasic straight line, PbO is present in
trophotometer. The textural characterization of the sam- large amounts with 3BS (Fig. 4b). On the straight line, i.e.,
ples was performed either by scanning electron microscopy
with the stoichiometric composition, some unreacted PbO
(Philips SEM 505) or transmission electron microscopy
always remains along with 3BS (Fig. 5a), as evidenced by
(Philips STEM CM12). The solid phase identification by
the comparison with a reference 3BS sample (Fig. 5b). The
x-ray diffraction was not easy due to the overlapping of a
presence of unreacted PbO is not pointed out in the other
n u m b e r of peaks belonging to 1BS, 3BS, 4BS, aPbO, and
studiesY As mentioned in the experimental part, it is rela-
~PbO. Moreover, different x-ray diagrams have been pro-
posed for the 3BS phases in the literature. 15'16Recently, we tively difficult to identify all the solid phases in the paste
have established a new one from a pure 3BS sample13: this due to several phenomena (overlapping peaks, confused x-
phase was used as a reference material in this study. ray data for the 3BS phase, etc.).
PbO source infIuence.--In order to determine if the pres-
Influence of the Experimental Conditions ence of unreacted PbO after mixing could be related to the
Influence of the temperature and composition.--The reactivity of the starting lead oxide, the influence of the
temperature plays a predominant role on the reaction ki- morphological features of the available lead oxides (Strem,
netics. If the temperature of the reaction is lower than 10~ yellow Merck, and red Merck before and after grinding)
x-ray diffraction analysis reveals the presence of pure PbO was compared.
even after several days of mixing; this indicates that the No difference was noticed in the composition of the final
rate of the reaction is too slow in this range of temperature. mixed product with the different lead oxides, even after
Between 20 and 60~ the tribasic lead sulfate precipitates grinding. Mixtures of 3BS and PbO with the two structural
but a mixture of phases, whose nature depends on the start- types were prepared in all cases. Moreover, no influence of
ing composition, is obtained. the PbO type could be found. The morphology was only
In order to study the influence of the starting composi- found to influence the reaction kinetics. The change in the
tion of PbO + H2SQ + H20 mixtures, we varied the molar suspension coloration (from yellow-orange to white) indi-
ratio PbO/H2SO4 around the stoichiometric value, which is cating the precipitation of the 3BS phase occurs more
four for the tribasic lead sulfate. Figure 3 shows the differ- rapidly for smaller particles. The coloration was used to
ent starting compositions used in our experiments. The
measure the reaction time which appears to strongly de-
precipitation conditions corresponding to other reported
pend on the mean size of the PbO particles.
studies 3'4'1~ are also given on this diagram for comparison.
The x-ray study (Fig. 4 and 5) shows that the pure triba- Influence of order of materials addition.--The order of
sic lead sulfate is never obtained no matter what the start- materials addition was altered as follows: (i) sulfuric acid

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J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc. 2713

was added to a suspension of PbO in water; (ii) PbO was o PbO


added to a mixture of water and sulfuric acid; and (iii) PbO
was added to acidified water (pH 2), and the remaining
sulfuric acid was then allowed to react.
In all the above cases, mixtures of 3BS with PbO and/or
1BS were identified by x-ray diffraction.
Influence of carbonates presence.--The IR spectra of the
3BS phase (Fig. 6) shows several bands due to sulfate ions
at 1130, 1095, 1033, 960, and 600 cm -1. Three peaks at 473,
446, and 411 cm -~ may be ascribed to the Pb-O vibration
modes. The narrow b a n d at 3570 cm -~ is probably due to
hydroxyl groups of water molecules H-bonded to sulfates 10 15 20 25 30 35 28
ions. Besides these SO4, O-H, and Pb-O bands, two peaks at
1400 and 700 cm -1, which are due to carbonate ions, clearly
appear in the spectra even if mixing is performed under an
argon atmosphere. Carbonation of samples is then very dif-
ficult to avoid. The fact that the peak at 1400 cm -~ is a
singlet indicates that these ions exhibit the D3h symmetry.
This means that the carbonate ions in our samples are
rather free t h a n coordinated to metallic cations. For coor-
dinated carbonates, the corresponding symmetries (Cs or
C2v) of these structures involve the splitting of the D3h de-
generate modes leading to a doublet peak in the 1300 to
1500 cm -1 range. Actually, there are two different types of
- - i . . . . . . 9 . . . . . . . . . 9 . . . . . . l - i . . . . s . . . . . .

10 1s 20 zs 30 35 20
o PbO
9 3BS Fi9. 5. X-Ray study of the final product vs. the starting composition
in PbO and H2S04. (a, top) When the starting composition is the
~IBS staichiometric one far 3BS, we obtain a mixture of 3BS and PbO. (b,
bottom) For comparison, here is the diagram of pure tribasic lead
sulfate.

carbonation for powder lead compounds. The carbonate


species can be adsorbed on the surface of the products be-
cause of the small size of the particles. This adsorption can
o occur during the grinding of the starting material or during
the drying of the final powder so that even if the experi-
ments are made under argon the final product can be car-
9 9 | bonated. However, adsorbed carbonates are generally coor-
|

/,/
w, 9
dinated to metallic ions: .they show the C2v symmetry with
the doublet peak between 1300 and 1500 cm -1. 18As the D3h
symmetry seems to predominate in our spectra, another
form of carbonation has to be considered. In water or in
8 t2 i6 20 24 28 32 36 humid air containing carbon dioxide, a small amount of
2e PbO or 3BS can be partly dissolved and converted into lead
carbonate phases (hydrocerussite or plumbonacrite) con-
~ PbO taining carbonate ions in the D3h symmetry. However, the
9 3BS amount of these carbonate compounds is often too small to
be identified on the x-ray patterns. By contrast, IR spec-
troscopy reveals the presence of these compounds as sur-
face phenomena are enhanced by this technique. It is also
possible to identify a few hexagonal particles of lead car-
bonate by TEM (Fig. 7). In fact, our starting lead oxides,

9 v(c03-)
1~(S04Z-)
o 40
o_
tq

3o
m
~- Pbo)
20

_j 8 t2 t6 20 24 28 32 36
10
211
Fig. 4. X-Ray study of the final product vs. the starting composition 3500 3000 2S00 2000 1500 1000 500
in PbO and H2S04. (a, top) When Ihe starting composition is too rich Wavelength (crn-1)
in H2S04 compared to the stoichiometric composition for 3BS,
the prepared mixture is "3BS + 1BS + PbO." (b, bottom) When the Fig. 6. Infrared spectroscopy diagram of the powders after mixing.
starting composition is too rich in PbO, the final mixture is "3BS + The sulfate and carbonate bonds are indexed. The vibrations due to
PbO." PbO and H20 can he seen, too.
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2714 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.

Fig. 7. TEM photography of


lead carbonate.

before mixing, always contain more or less lead carbonates nearly stabilized and reaches a pseudo plateau: the reac-
depending on the storing conditions (duration and hy- tion then becomes very slow.
grometry). The carbonation cannot then be avoided even Samples taken in the first part of the curve contain
under argon atmosphere. mainly P b S Q , PbO, and ]BS, but also 3BS in a very small
In short, from the investigation of a lot of experimental amount (Fig. 9). This indicates that PbSO4 and monobasic
conditions, it appears that some unreacted PbO always re- lead sulfate are intermediate species in the reaction. Scan-
mains along with the 3BS phase during mixing. This means ning electron micrographs of such samples (Fig. 10a) re-
that the reaction cannot be complete using this method. In vealed the presence of three types of particles: (i) squared
the following section, a possible explanation is given from particles, which ca n be easily identified as PbSO4 particles
the study of the reaction mechanism. by comparison with micrographs of a pure PbSO4 powder;
(it) needles, which are generally observed for the 1BS and
3BS phases; and (iii) agglomerates of small particles, which
Study of the ReactionMechanism probably correspond to the PbO phase.
Characterization of the solid phases during the course of Samples taken in the second part of the curve contain the
the reaction.-- In order to understand better how the 3BS 3BS phase along with small amount of PbO. The 1BS and
phase forms, samples were taken from the mixture during PbSO4 phases are not identified in the mixture at this stage
the course of the reaction and studied by x - r a y diffraction of the reaction. The corresponding SEM micrographs show
and SEM (see Experimental section). Simultaneously, the agglomerates of small particles and needles (Fig. 10b). The
pH curves were recorded during the reaction. needles, sometimes broken, can also be observed by TEM
The pH curve typically obtained at 20~ is shown in (Fig. 11). The corresponding selected area electron diffrac-
Fig. 8. Similar curves are obtained at higher temperatures. tion (SAED) patterns clearly indicate that these needles are
Two parts can be distinguished in this curve. In a first due to the tribasic lead sulfate phase. The identification of
stage, the p H rapidly increases indicating that the rate of the agglomerates of small particles is not possible because
reaction is relatively high. In the second stage, the pH is SAED spots cannot be indexed with accuracy due to the
large number of crystallites. Such agglomerates may corre-
spond to PbO. However, it seems hard to attribute them
only to PbO in view of their large number compared with
pH=f(t) ~, 20~ the small amount of PbO detected by x - r a y diffraction
(Fig. 3a). The 3BS phase probably crystallizes in two differ-
ent ways leading to two types of morphology: needles
10 (about 5 ~m in length and 1 ~m in thickness) and micronic
particles without a definite shape.
~ f
8
o PbO

6 ~IBS
+PbS04
pH *3BS
4

2 &
+

0 I I I ~ I 1

20 40 60 80 100 120
+ + I :J,
temps (rain) 10 1S 20 25 30 35 20

Fig. 8. pH curve typically obtained at 20~ during the mixing of Fig. 9. X-RoydiffTocfion pattern of samples taken at the start of the
PbO, H2S04, and H20. mixing, in the first port of the pH curve (pH < 8).

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J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc. 2715

Fig. 10. SEM photographs:


(a, left) of the samples taken in
the first part of the pH curve and
(b, right) of the final product.

Fig. 11. TEM photography of


the needles of 3BS and corre-
sponding electron diffraction
pattern.

Discussion sively disappear as shown by x-ray diffraction due to their


The study of the pH and of the nature of the solid phases dissolution
during the course of mixing clearly suggests that the reac- PbSO4 --+ Pb 2§ + SO4
tion of PbO with H2SO4 proceeds in two steps.
During the first step, which is the most rapid, as clearly PbO 9PbSO4 + H20 --~ 2Pb 2+ + SO4 + 2 OH
indicated by the pH curve, the lead sulfate PbSO, is prefer-
entially formed. The change in the morphology of the solid Simultaneously, 3BS forms by consuming Pb 2+species from
particles (agglomerates of pellets for the PbO starting the solution
product/squared monocrystalline particles for the PbSO~
phase formed at this stage) indicates that the reaction oc- 4Pb 2§ + SO4 + 6 OH- -~ 3PbO 9PbSO4 - H20 + 2H20
curs via the solution. The concentration of the different
Hence, the Concentration of Pb 2§ in the solution during
species in solution and the low pH values at the beginning
the second step remains relatively low, It is probably not
of the reaction allow the nucleation and growth of the lead
high enough to permit an homogeneous nucleation of the
sulfate from the solution. PbO dissolves and dissociates in
3BS phase. Homogeneous nucleation would occur if an
the acidic solution. This reaction produces Pb 2§ and OH-
oversaturation of the Pb ~§species was achieved in the solu-
ions. These hydroxide ions react and neutralize the H30 §
tion so that nuclei of the 3BS solid phase formed in the
species in the solution so that the pH increases. It may be
solution. The increasing amount of 3BS in the mixture dur-
concluded that the chemical reactions that prevail in this
ing the second step can probably be explained as follows.
first step are
There is heterogeneous nucleation of tribasic lead sulfate
PbO + H20 -e Pb 2§ + 2 0 H - on the surface of solid germs and then growth from the
solution. These solid germs could be either PbSO4, PbO -
Pb 2§ + SO~ --~ PbSO4 PbSO4, or PbO particles. However, the germination of the
tribasic lead sulfate seems to be more probable at the sur-
2 O H - + 2H* ~ 2H20 face of PbO and PbO 9PbSO4 particles as: (i) the morphol-
ogy of the 3BS final particles seems to derive from that of
However, mono- and tribasic lead sulfates begin to precipi- PbO (micronic particles without definite shape) or PbO -
tate in very small amounts during this stage. PbSO, (needles) but not from that of PbSO~ (no squared
The second step of the reaction is slower as the pseudo- particles at the end of reaction) and (it) the local pH at
plateau is achieved when the pH value becomes 8 or more. the surface of PbO and PbO 9 PbSO4 particles is more
For such values of pH, PbO is rather stable but intermedi- basic than for PbSO4 and favors the nucleation of tribasic
ate reaction products, PbSO4 and PbO 9 PbSO4 progres- lead sulfate.

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2716 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.

Such a mechanism may explain why there always re- CEAC company for their financial support and fruitful
mains some unreacted PbO even when the starting condi- discussions.
tions are the best ones for producing the tribasic lead sul- Manuscript submitted Dec. 29, 1994; revised manuscript
fate (stoichiometric composition and temperature between received March 22, 1995.
20 and 60~ During the second step of the reaction, the
dissolution of PbO becomes negligible and the nucleation Universitd de Picardie Jules Verne assisted in meeting the
of 3BS mainly occurs on the surface of the remaining p a r t i - publication costs of this article.
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Acknowledgments 17. R. F. Dapo, This Journal, 121, 253 (1974).
The authors would like to thank the ADEME (Agence de 18. M.J. Hernandez-Moreno, M. A. Ulibarri, J. L. Rendon,
l'Environnement et de la Maitrise de l'Energie) and the and C. J. Serna, Phys. Chem. Miner., 12, 34, (1985).

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