ARTICLE IN PRESS

Journal of Solid State Chemistry 179 (2006) 1110–1118

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Synthesis of layered zinc hydroxide chlorides in the presence of Al(III)

Tatsuo Ishikawaa,, Kumi Matsumotoa, Kazuhiko Kandoria, Takenori Nakayamab
a
School of Chemistry, Osaka University of Education, 4-698-1 Asahigaoka, Kashiwara, Osaka 582-8582, Japan
b
Materials Research Laboratory, Kobe Steel, Ltd., 5-5 Takatsukadai 1-Chome, Nishi-ku, Kobe, Hyogo 615-2271, Japan
Received 18 October 2005; received in revised form 24 December 2005; accepted 4 January 2006
Available online 7 February 2006

Abstract

Zinc hydroxide chloride particles were synthesized by hydrolysis of ZnCl2 solutions dissolving AlCl3 at different atomic Al/Zn ratios
from 0 to 1.0 and characterized by various techniques. Increasing Al/Zn ratio changed the crystal phases of the products as ZnO-
ZnO+ZHC (Zn5(OH)8Cl2
H2O)-ZHC-LDH (layered double hydroxides, Zn–Al–Cl) and the particle morphology as agglomerates
(ZnO)-fine particles (ZnO)-plates (ZHC)+rods (ZnO)-plates (ZHC)-plates (LDH). The atomic Cl/Zn ratios of LDH particles
formed at Al/ZnX0.3 were ca. 0.3 despite the increase of Al/Zn ratio, being due to the intercalation of CO2
3 into the LDH crystal. The
OH content of LDH estimated by TG was reduced by the deprotonation of OH to counteract the excess positive charge produced by
replacing Zn(II) with Al(III). ZHC exhibited a high adsorption selectivity of H2O.
r 2006 Elsevier Inc. All rights reserved.

Keywords: Layered compounds; Chemical reactions; Electron microscopy; Infrared spectroscopy; Thermogravimetric analysis; X-ray diffraction; Crystal
structure; XAFS; Gas adsorprion

1. Introduction sheet structures of these BSZ materials differ from that

Layered double metal hydroxides (LDH) receive atten-
tion in the material sciences of catalyst, adsorbent, anionic
exchanger, filler for polymer, nano-sheet for hetero
accumulated functional material, etc. The general formula
x n 2+
of LDH is ½M 2þ 3þ
1x M x ðOHÞ2  ðA Þn=x
mH2O where M
3+
and M are divalent and trivalent metal ions such as
Zn2+ and Al3+, respectively, and An is n-valent anion
[1–4]. On the other hand, hydroxy double salts (HDS) are
known as anion exchangers [5–7]. The general formula of
HDS is [(M2+ 1 xM
0 2+
)(OH)3(1y)]+An
(1+3y)/n
mH2O in
which M and M0 are divalent metal ions such as Zn2+.
Similar to LHD, the anions exist between the positive
charged hydroxide layers. There are another series of
layered basic salts of zinc (BSZ) such as zinc hydroxycar-
bonate (Zn5(CO3)2(OH)6, hydrozincite) [8], zinc hydro-
xychloride (Zn5(OH)8Cl2
H2O, simonkolleite) [9,10] and
zinc hydroxysulfate (Zn4SO4(OH)6
nH2O) [11,12]. The
Corresponding author. Fax: +81 729 78 3394.
E-mail address: ishikawa@cc.osaka-kyoiku.ac.jp (T. Ishikawa).
of LDH and HDS. The BSZ crystal has basal sheets
consisting of two kinds of Zn(II) ions octahedrally and
tetrahedrally coordinated by anions such as CO2 
3 , Cl and
2
SO4 , whereas the basal sheet of LDH crystal, i.e. brucitic
layer, consists of one kind of metal ions octahedrally
coordinated by OH. The anions of HDS are not
coordinated to Zn(II), so that they are easily exchanged
by other anions as well as those of LDH [13]. The
interaction between basal sheets of LDH or HDS is mainly
electrostatic attractive force between intercalated anion
and positively charged layer produced by the addition of
trivalent metal ion. On the other hand, the neutral basal
sheets of BSZ are bounded by different interactions
depending on kind of BSZ; coordination bonding of
CO23 between tetragonal and octahedral Zn(II) ions of
different hydroxide sheets in Zn5(CO3)2(OH)6 [8], weak
hydrogen bond of OH?Cl in Zn5(OH)8Cl2
H2O [10],
and strong hydrogen bonding of OH?OS between the
interlayer H2O molecules and the SO2 4 ions coordinating
to Zn(II) in the basal sheets of Zn4SO4(OH)6
nH2O [12].
Such a layered structure of BSZ allows us to prospect

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doi:10.1016/j.jssc.2006.01.007
 ARTICLE IN PRESS
T. Ishikawa et al. / Journal of Solid State Chemistry 179 (2006) 1110–1118
intercalation, anion exchange, thermal transformation, and
exfoliation of BSZ in different processes from those of
LDH and HDS.
BSZ is a primary component of zinc rusts formed by
exposure to different environments [14–17]. Steels are
galvanized by zinc alloyed with metals such as Al, Ni,
Mg, etc. to enhance corrosion resistance of the steels.
Although the galvanized steel is an important industrial
material, the function of the alloying metals is still not
elucidated. We previously studied the influences of the
alloying metals such as Al, Fe, Co, Ni and Mg on the
formation of zinc rusts. It was found that the hexagonal
thin plate-like particles of simonkolleite, hereafter noted
ZHC, are produced from ZnCl2 solutions dissolving AlCl3,
FeCl2 and CoCl2 and that ZHC is formed by adding a very
low concentration of AlCl3 of 0.05 in atomic Al/Zn ratio
[18]. The fact that the ZHC formation is effectively
promoted by the addition of Al(III) is quite interesting in
concern with a high corrosion resistance of steels galva-
nized with a Zn–Al alloy (5% Al), because the preferred
orientation of thin plate-like ZHC particles leads to the
formation of compact rust layers. However, the structure
and property of the products at high Al(III) concentration
were still not explored.
The aim of the present study was to investigate the
structures and natures of hydrolysis products of ZnCl2
solutions dissolving AlCl3 at different atomic Al/Zn ratios
from 0 to 1.0. It was found by characterizing the products
that the crystal phase strongly depends on Al/Zn ratios;
ZHC and LDH are formed at Al/Znp0.2 and X0.3,
respectively. The difference in properties of these layered
materials is discussed in this article. The information
gained in this study is useful for not only developing
layered materials different from LDH and HDS but also
elucidating the corrosion resistance of Zn–Al alloys.
2. Experimental
2.1. Synthesis
Solutions (1 L) of 0.05 mol/L ZnCl2 dissolving AlCl3 at
different atomic Al/Zn ratios of 0–1.0 were prepared and
the solution pH was adjusted to pH 9 by dropping a
concentrated NH4OH (28%) with stirring. The resultant
precipitates were kept at 50 1C for 24 h in a capped
polypropylene vessel (2 L). After the aging the precipitates
were filtered out, washed with 2 L of deionized and distilled
water, and finally dried at 70 1C for more than 15 h. The
water used was not freed from CO2.
2.2. Characterization
The crystal phases of the products were determined by
powder X-ray diffraction (XRD) using a Rigaku diffract-
ometer with a CuKa irradiation (40 kV and 120 mA). The
morphology of the particles was observed by a JEOL
transmission electron microscope (TEM). The metal
1111
contents of the products were determined by a Seiko
induction coupled plasma atomic emission spectrometer
(ICP-AES). The samples were leached in concentrated HCl
solution and diluted the solutions with water. The Cl
content was determined by a JEOL electron probe
microanalyzer (EPMA). The IR spectra were taken using
a Nicolet FTIR spectrometer by a KBr method. The
sample concentration was 1 mg/100 mg KBr. The
DTA–TG curves were traced by a Seiko thermoanalyzer
at a heating rate of 5 1C/min in the air. X-ray absorption
spectroscopy was performed using an apparatus of the
BL16B2 station in SPring-8 (Nishiharima, Japan) at an
accelerating energy of 8.0 GeV. Transmisssion X-ray
absorption spectra of the ZnK edge were collected using
a Si(311) crystal monochromator. Extended X-ray fine
structures (EXAFS) at the ZnK edge were analyzed to gain
radial distribution function around the Zn atoms. The
adsorption isotherms of N2 were measured volumetrically
at the liquid nitrogen temperature and those of H2O were
determined gravimetrically at 25 1C using the automatic
adsorption apparatuses designed in our laboratory. The
specific surface areas of the products were calculated by
fitting the BET equation to the adsorption isotherms and
using the cross-sectional areas of 0.162 and 0.108 nm2 for
N2 and H2O molecules, respectively. Prior to the adsorp-
tion the samples were outgassed under less than 103 Torr
at 100 1C for 2 h.
3. Results and discussion
3.1. XRD and FTIR
Fig. 1 displays the typical XRD patterns of the products
at different atomic Al/Zn ratios. The products at
Al/Znp0.01 show the patterns characteristic of ZnO
(JCPDS 36-1451). At Al/ZnX0.05 the peaks due to ZHC
(JCPDS 7-195) appear in addition to the ZnO peaks. At
Al/Zn ¼ 0.1 only the peaks of ZHC are detected. The
product at Al/Zn ¼ 0.2 also showed only the ZHC peaks
(the patterns not shown). At Al/ZnX0.3 only LDH
peaks [19] appear and diminish with the increase of Al/
Zn ratio. The crystal phase of the products varies as
following ZnO-ZHC-LDH with increasing the Al/Zn
ratio and the addition of Al(III) facilitates the ZHC
formation. Thevenot et al. have reported that LDH
(Zn–Al–CO2 3 ) was formed at 0.43pAl//Znp0.67 [20],
which is in accordance with the present result in spite of the
difference of anions. The hydroxide sheet networks of
the LDH crystal are distorted by the large difference
in ionic radii of Zn(II) (0.74 nm) and Al(III) (0.51 nm), so
that increasing the Al/Zn ratio lowers the crystallinity of
LDH.
3.2. Unit cell dimension
According to Vegard’s law, the unit cell parameters of
ZHC and LDH crystals must be reduced by the exchange
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1112 T. Ishikawa et al. / Journal of Solid State Chemistry 179 (2006) 1110–1118
Fig. 1. XRD diffraction patterns of the products at Al/Zn ¼ 0–1.0. The
assignment of peaks: (J) ZnO; (W) ZHC; (K) LDH.
Fig. 2. Plots of unit cell parameter a (A) and d distance (B) of ZHC (J)
and LDH (K) against Al/Zn ratios in the starting solutions.
of Zn(II) with Al(III) because of the different sizes of
Zn(II) and Al(III). Fig. 2(A) shows the unit cell dimension
a of the ZHC and LDH crystals. The a dimensions of ZHC
and LDH decrease with the increase of Al/Zn except for
Al/Znp0.05 and ¼ 1.0 where the replacement of Zn(II) by
Al(III) may be insufficient. Similar results have been
reported for various LDH crystals such as Zn–Al–Cl [21],
Mg–Al–CO3 [22] and Mg–Ga–CO3 [23]; however, there has
been no published information on ZHC. The decrease of a
dimension is caused by the exchange of Zn(II) with smaller
Al(III). In general, the interlayer distance of layered
materials depends on the charge of layers. In Fig. 2(B)
the interlayer d distances estimated from the (003)
diffraction peak are plotted against Al/Zn ratios. Although
the d distances of ZHC are less than 0.788 nm reported for
pure ZHC [10], those of LDH are comparable to 0.77 nm
reported for the LDH synthesized at Al/Zn ¼ 0.5 [24]. The
increase of Al/Zn ratio slightly expands the d distance of
ZHC produced at Al/Znp0.2 even though the Al/Zn range
is narrow, whereas that of LDH formed at Al/ZnX0.3
steeply decreased with the increase of Al/Zn as well as the
dimension a. The replacement of Zn(II) with Al(III) in the
zinc hydroxide sheets of ZHC makes the layers positively
charged and slightly expands the interlayer due to
repulsion of the positive charges. On the contrary, the
increase of the excess charge of LDH sheets with the
addition of Al(III) reduces the interlayer distance. It has
been established that the interlayer distance of LDH
decreases with an increase in net charge of the layers
[25,26]. The increase of Al/Zn ratio strengthens the
electrostatic attraction between positive charge in hydro-
xide sheets and Cl or CO2 3 intercalated into interlayer to
compensate the excess positive charge, resulted in the
contraction of interlayer distance.
3.3. Particle morphology
TEM micrographs of the typical particles formed at
different Al/Zn ratios are shown in Fig. 3. The ZnO
particles formed at Al/Zn ¼ 0 are irregular aggregates
of fine particles and divided into fine particles at
Al/Zn ¼ 0.005. It is of interest that the aggregation of fine
ZnO particles is impeded by adding an extremely low
concentration of Al(III). This is ascribed to the surface
positive charge formed by adsorption of Al(III) or
replacement of Zn(II) by Al(III). The particles formed at
Al/Zn ¼ 0.025 and 0.05 are a mixture of thin hexagonal
particles and rod-like ones. According to the XRD pattern
the hexagonal and rod-like particles are identified as ZHC
and ZnO, respectively. Interestingly, the morphology of
ZnO particles strongly depends on the Al/Zn ratio; it turns
as aggregate-fine particle-rod particle with the increase
of Al/Zn ratio, though the reason for this is unclear at
present. The hexagonal ZHC particles grow with the
increase of Al/Zn ratio and at Al/Zn ¼ 0.1 only large
hexagonal ZHC particles are seen. In contrast to this, the
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T. Ishikawa et al. / Journal of Solid State Chemistry 179 (2006) 1110–1118
Fig. 3. TEM micrographs of the particles formed at Al/Zn ¼ 0–1.0.
plate-like LDH particles formed at Al/ZnX0.3 become
thinner and finer as the Al/Zn ratio increases.
3.4. Chemical composition
The Al/Zn ratios of the products were equivalent to
those of the starting solutions and no metal ions were
detected in the supernatant solutions after the reaction,
though the data are not shown here. This verifies that all
the Al(III) ions added to the starting solutions are
incorporated into the resultant particles. Further, the
products contained no other compounds than ZnO, ZHC
and LDH as confirmed by XRD and the particles of
amorphous materials were hardly detected in the TEM
micrographs (Fig. 3). Therefore, it is reasonable to consider
that Zn(II) of these materials is replaced by Al(III),
1113
resulting in the formation of excess positive charge in the
basal sheets. The positive charge produced is presumed to
be neutralized by intercalation of anions such as Cl and
CO23 and deprotonation of OH into O2. To confirm
this, the anions of Cl, CO2 3 , and OH

in the products
were analyzed by EPMA, FTIR, TG, and EXAFS,
respectively. Fig. 4 plots the atomic Cl/Zn ratios in the
formed particles against those in the starting solutions. The
Cl/Zn ratio rises steeply with increasing the Al/Zn ratio up
to 0.2 and then remains at around 0.3 less than 0.4 of the
theoretical Cl/Zn ratio of ZHC crystal. The ZHC formed at
Al/Zn ¼ 0.1 shows rather low Cl/Zn ratio of 0.13, which is
due to the exchange of Cl with OH.
Fig. 5 depicts the IR spectra of the products at different
Al/Zn ratios. The product at Al/Zn ¼ 0 shows a broad
band at around 3500 cm1 due to the stretching vibration
 ARTICLE IN PRESS
1114 T. Ishikawa et al. / Journal of Solid State Chemistry 179 (2006) 1110–1118
Fig. 4. Atomic Cl/Zn ratios in the particles formed at Al/Zn ¼ 0–1.0.
Fig. 5. IR spectra of the particles formed at Al/Zn ¼ 0–1.0.
of OH and OH groups of H2O molecules and a strong
band at 434 cm1 due to the skeleton vibration of ZnO.
The OH bands of ZHC formed at Al/Zn ¼ 0.1–0.3 are
stronger than those of LDH formed at Al/ZnX0.4. The
reason for this is explained by the selective H2O adsorption
of ZHC and protonation of O2 in LDH as described later
in Section 3.5. The ZnO band at 434 cm1 diminishes on
increasing the Al/Zn ratio and at Al/ZnX0.05 the ZHC
band appears at 678 cm1. The OH stretching bands of the
products at Al/Zn ¼ 0.05–0.3 are divided into two bands at
3587 and 3455 cm1 of which the assignment is described in
this section.
All the samples show a weak deformation band of H2O
molecules at 1630 cm1 and two weak CO2 3 bands at 1490
and 1388 cm1. The detailed assignment of these CO2 3
bands will be described later. The FTIR result verifies that
the products vary as ZnO-ZHC-LDH with the increase
of Al/Zn ratio as shown by XRD.
As is seen from Fig. 5, the IR spectra of ZHC formed at
Al/Zn ¼ 0.05–0.2 show a strong OH band which is clearly
separated into two bands at 3587 and 3455 cm1. The ZHC
and LDH crystals have one kind of OH coordinating to
three octahedral Zn(II) ions in the basal hydroxide sheets.
Since the Cl ion of ZHC crystal coordinates to one
tetrahedral Zn(II) ion, the OH ion replacing Cl ion
coordinates to one Zn(II) ion. Therefore, the shoulder band
at 3587 cm1 is assigned to the OH ions coordinating to one
Zn(II) ion and the strong 3455 cm1 band to OH ions
coordinating to three Zn(II) ions and OH groups of H2O
molecules adsorbed and intercalated. On the other hand, as
is seen in Fig. 4, LDH formed at Al/ZnX0.3 shows
nearly constant Cl/Zn ratio of ca. 0.3 despite the increase
of Al/Zn ratio. For instance, LDH formed at Al/Zn ¼ 0.3
shows the Cl/Zn ratio of 0.29 and the Cl/Al ratio of 0.97
close to unity. This reveals that the excess positive charge
formed by the exchange of Zn(II) with Al(III) in the
hydroxide sheet is just canceled by Cl contained in the
interlayer. However, the product at Al/Zn ¼ 0.3 showed the
IR band of CO2 3 (Fig. 5). This conflict can be solved by
considering that a part of OH ions in the basal hydroxide
sheet are replaced with Cl similarly to HDS. The residual
positive charge of LDH formed at Al/ZnX0.3, which is
caused by an insufficiency of Cl, must be canceled by
intercalation of CO23 .
To verify the CO2 3 intercalation, the IR spectra
magnified are shown in Fig. 6. The spectra of all the
products show a band at 1626–1610 cm1 due to the
deformation vibration of H2O molecules adsorbed and
intercalated into the ZHC and LDH crystals. The spectra of
ZHC formed at Al/ZnX0.1 show two bands due to the
asymmetric and symmetric C–O stretching vibrations of
CO23 at 1490 and 1370 cm1, respectively [27]. The
1370 cm1 band is intensified by increasing Al/Zn ratio.
The spectra of LDH formed at Al/ZnX0.6 show an
additional band at 1410 cm1 due to the asymmetric
vibration of free CO2 3 ions and that of LDH formed at
Al/Zn ¼ 1.0 shows a weak band at 1264 cm1 in addition to
these three CO23 bands. Therefore, we can assign the bands
at 1490 and 1370 cm1 to the C–O stretching mode of CO2 3
hydrogen bonding to one OH ion and the 1264 cm1 band
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T. Ishikawa et al. / Journal of Solid State Chemistry 179 (2006) 1110–1118 1115

Fig. 6. Magnified IR spectra of the products at Al/Zn ¼ 0–1.0.

to that of CO2 
3 bridging two adjacent OH ions within the
basal hydroxide sheet of LDH as follows [27].

O O O
O
C O O O
O O
H H H
O O O
1410 cm-1 1490, 1370 cm-1 1264 cm-1

Increasing the Al/Zn ratio promotes the CO2 3 incor-

poration to balance the excess positive charge and
produces various kinds of CO2 3 species in the LDH
crystal. This is because the addition of Al(III) distorts and
collapses the layered structure of LDH. Actually, the
particle growth and crystallization of LDH were interfered
with by adding Al(III) as confirmed by XRD, TEM, and Fig. 7. TG–DTA curves of the products at Al/Zn ¼ 0–1.0.
N2 adsorption.

3.5. Thermal analysis
Fig. 7 depicts the TG–DTA curves of the products at
different Al/Zn ratios. The TG curves of the products at
Al/ZnX0.05 show a steep mass loss below ca. 300 1C and a
gradual one at ca. 350–ca.650 1C. The mass loss accom-
panies endothermic peaks in the DTA curves though the
mass loss at a wide range of ca. 350–ca.650 1C accompanies
no clear endothermic peak. As described above, the
products contain H2O, OH, Cl and CO2 3 which are
 ARTICLE IN PRESS
1116 T. Ishikawa et al. / Journal of Solid State Chemistry 179 (2006) 1110–1118
Fig. 8. Mass loss in TG curves at ca. 350–ca.650 1C of the products at
Al/Zn ¼ 0–1.0.
supposed to be eliminated when heated up to 800 1C. The
release of CO2
3 in ZHC and LDH took place at lower than
200 and 300 1C, respectively, as confirmed by FTIR. The
products at Al/Zn ¼ 0.05 and 0.1 show a strong endother-
mic peak at ca. 170 1C due to the desorption of intercalated
H2O. The shoulder peaks of these peaks at ca. 200 1C are
assigned to release of Cl, because these peaks were found
to be weakened by ion exchange with anions such as SO2 4
and CO2 3 as will be reported elsewhere. The products at
Al/ZnX0.2 show a strong endothermic peak at ca. 260 1C
which is also weakened by anion exchange and ascribed to
the removal of Cl. The several weak endothermic peaks of
the products at Al/ZnX0.2 due to the desorption of
intercalated H2O suggests that the LDH crystal contains
different kinds of H2O; however, the details remain unclear
at the present. The gradual mass loss at ca. 350–ca.650 1C
can be ascribed to release of OH as H2O. The mass loss by
this dehydroxylation is plotted as a function of the Al/Zn
ratio of starting solutions in Fig. 8. The mass loss
corresponding to the OH content of the products steeply
increases with increasing the Al/Zn ratio and then
decreases, showing a maximum at Al/Zn ¼ 0.3. This can
be interpreted by considering that the increase in OH
content is caused by the formation of ZHC crystal and the
decrease in OH content by the deprotonation of OH into
O2 in basal hydroxide sheets to compensate the positive
charge generated by the replacement of Zn(II) with Al(III).
The deprotonation of OH was confirmed by the radial
distribution functions of the products obtained from
EXAFS shown in Fig. 9. The radial distance of the
products is shorter than the theoretical distance estimated
from the crystal structures of the products, because the
phase shift is not corrected in the functions. The ZnO
formed at Al/Zn ¼ 0 shows Zn–O and Zn–Zn peaks at
0.142 and 0.285 nm, respectively. The Zn–O and Zn–Zn
Fig. 9. Radial distribution functions of the products at Al/Zn ¼ 0–1.0.
peaks of the product at Al/Zn ¼ 0.2 appear at 0.165 and
0.278 nm, respectively. The increase of Al/Zn ratio moves
the Zn–O peak to a short radial distance and the Zn–O and
Zn–Zn peaks of the product at Al/Zn ¼ 1.0 are 0.149 and
0.286 nm, respectively. This supports the fact that OH
converts to O2 because O2 (0.140 nm radii) is smaller
than OH (0.151 nm radii).
3.6. Selective adsorption
To characterize layered structures of ZHC and LDH, we
determined the specific surface areas of the products at
varied Al/Zn ratios from the adsorption isotherms of N2
and H2O molecules with different sizes and polarity. The
specific surface areas determined by the adsorption of N2
and H2O are noted as SN and SW, respectively, and they
are plotted against Al/Zn ratio of starting solutions in
Fig. 10(A). The SW steeply increases with increasing the
Al/Zn ratio and then reaches a constant high value of ca.
200 m2/g. On the other hand, the SN gradually increases
with the increase of Al/Zn ratio though a maximum SN
appears at a low Al/Zn ratio of 0.01 owing to the formation
of fine ZnO particles as is seen in the TEM micrograph
(Fig. 3). The SW of all the products is larger than their SN,
indicating that H2O molecule adsorbed preferably to N2
molecule. This fact testifies that the ZHC and LDH crystals
possess interlayer spaces accessible to H2O molecule but
 ARTICLE IN PRESS
T. Ishikawa et al. / Journal of Solid State Chemistry 179 (2006) 1110–1118 1117

the ZHC particles was less than its theoretical value,

showing that a part of Cl ions of the ZHC crystals are
replaced by OH. The excess positive charge formed by the
replacement of Zn(II) with Al(III) is neutralized by the
intercalation of CO23 . The ZHC crystals exhibited a high
selective adsorption of H2O compared to the LDH crystals,
indicating that interlayer spaces less than 0.32 nm develop
in the ZHC crystal.
The plate-like LDH particles formed at Al/ZnX0.3
intercalated H2O, CO2 
3 , and Cl . The excess positive
charge produced by the lack of Cl in LDH crystals
formed at Al/ZnX0.4 is counteracted by deprotonation of
OH to O2 and intercalation of CO2 3 . The CO3
2

intercalated in LDH crystal exists in three different modes;

single CO2 2
3 ions, and two kinds of CO3 ions hydrogen

bonding to one and two OH ions.
The fact that the formation of plate-like ZHC and LDH
particles is promoted by the addition of Al(III) pertains to
the high corrosion resistance of Zn–Al alloys which are
widely used to galvanize steels, because plate-like rust
particles form compact and protective rust layers through
their preferred orientation.

Acknowledgments

The authors gratefully acknowledge Mr. Masao Fuku-

sumi of Osaka Municipal Technical Research Institute for
help with the TEM observations. This study was supported
in part by the Grant-in-Aid for Science Research Funds (B)
from the Ministry of Education, Science, Sports and
Culture, Japanese Government.

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