Advanced Materials Research Vol.

66 (2009) pp 218-221
online at http://www.scientific.net
© (2009) Trans Tech Publications, Switzerland
Online available since 2009/Apr/01

Synthesis of Carboxylic Acids Intercalated Mg-Al Layered Double

Hydroxides by a Modified Reconstruction Method
Weidong Yang1, a, Sheng Li1,b, Dong Yang Wu1,c, Mark Spicer1,d,
Voytek Gutowski1,e, and Shirley Zhiqi Shen1,f
1
Division of materials Science & Engineering, CSIRO, Graham Rd. Highett, Vic. 3190, Australia
a b c d
weidong.yang@csiro.au, sheng.li@csiro.au, dong.yang.wu@csiro.au, mark.spicer@csiro.au,
e f
voytek.gutowski@csiro.au, shirley.shen@csiro.au

Keywords: Layered double hydroxide (LDH); fatty acid; calcination; rehydration; reconstruction.

Abstract. A series of saturated and unsaturated fatty acids (i.e. sorbic acid, octanoic acid, lauric acid,
stearic acid and oleic acid) were successfully intercalated into Mg-Al layered double hydroxides
(LDHs) using a modified reconstruction method, as confirmed by X-ray diffraction (XRD), Fourier
transformed infrared (FTIR) and thermal gravimetric analysis (TGA). The fatty acid intercalated
LDHs thus prepared exhibit much better well-defined hexagonal platelet structure than samples
prepared by the conventional reconstruction method.

Introduction
Layered double hydroxides (LDHs), also called hydrotalcite-like compound are available as naturally
occurring minerals and as synthetic materials. The structure of these materials is based on the stacking
of brucite [Mg(OH)2]-like layers, with hydrated anions in the interlayer. These materials have been
traditionally used in applications such as catalysis, adsorption, anion-exchange, medicine, and
recently as additives for nanocomposites [1,2]. The focus of the present work was the synthesis of
organophilic LDHs as an emerging class of nanoadditives for polymer reinforcement.
Pristine LDH is not suitable for melt intercalation by large species such as polymer matrices
because of their short intergallery space (about 7.6 Å) and their high layer charge density. It is
therefore necessary to modify the LDH materials prior to their inclusion in the polymer to increase the
intergallery distance and to improve the compatibility. These can be achieved by incorporating
suitable organic anion molecules. There are three main approaches for incorporating anionic
molecules into LDHs [3]: (i) anion-exchange of a precursor LDH, (ii) direct synthesis by
coprecipitation, and (iii) reconstruction through rehydration of a calcined LDH precursor. The
reconstruction method is by far the most common method for preparing fatty acid modified LDH.
Fatty acids were chosen as the organic modifiers for the LDH in this work because of their proven
effectiveness for surface treatment of mineral fillers (i.e. calcium carbonates) resulting in improved
compatibility and enhanced mechanical properties of the polymer composites. Potential oxygen
scavenging ability may also be possible when unsaturated molecules such as sorbic acid and oleic acid
are incorporated into the LDH for gas barrier applications. To our knowledge, no systematic study has
been reported on the synthesis and characterization of LDHs modified using the series of fatty acids
chosen in this work for their envisaged nanoadditives applications in polymers. A modified
reconstruction method was proposed and developed to effectively intercalate the series of fatty acids
with different chain lengths and degrees of unsaturation (e.g. sorbic acid, octanoic acid, lauric acid,
oleic acid, stearic acid) into the LDHs.

Experimental
The commercial Mg-Al LDH (Hycite 713, from Ciba Specialty Chemicals) with a Mg/Al ratio of 2.4
was used as a precursor material. Typically, LDH was calcined at 500°C for 14h, then cooled down to
room temperature under nitrogen. 100ml water was boiled for half an hour, and cooled to rehydration
temperature. 5.5g calcined LDH (Mg2.4AlO3.9, 0.0372 mol) was weighed and either directly added
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 Advanced Materials Research Vol. 66 219

into the fatty acid-containing aqueous solution at 1:1 mol ratio (LDH: fatty acid) under nitrogen and
agitation, or it was firstly rehydrated at 80°C for 3h in water before the fatty acid (lauric acid, octanoic
acid, oleic acid, stearic acid and sorbic acid from Aldrich) was added and stirred for another 18h.
After filtering, washing, drying, fine white powders were obtained with near 100% yield in all cases.
SEM was in a Philips XL 30 Field Emission Scanning Electron. The Diffuse Reflectance Infrared
Fourier Transformation (DRIFT) spectra were recorded on an Equinox 55 (Bruker) spectrometer
(4000-600 cm-1) (64 co-added interferograms were scanned at 4 cm-1 resolution) with a diffuse
reflectance attachment. Thermogravimetric analysis (TGA) was performed using a Perkin Elmer
Pyris TGA (Thermogravimetric analyser).

Results and Discussion

The conventional reconstruction method involves calcination of a LDH by heating at 500-800 °C to
transform it into an amorphous mixed magnesium aluminium oxide. Subsequent rehydration of the
mixed oxide in the presence of water and anions results in the intercalation of the anions into the
LDH. However, it is important to note that the conventional reconstruction method has been proven
suitable mainly for incorporating small anions such as Cl− , NO3- etc instead of the much larger
organic anions as investigated in this and other previous studies [4]. Therefore, a modified
reconstruction method has been developed in this study in order to prepare carboxylic acid
intercalated LDHs with well-organised layer structures. This involved a separate rehydration step of
the calcined LDH to enable the formation of a well-organised lamellar structure before addition of the
fatty acids.
The characteristic lamellar peak of the Mg-Al LDH at 2θ=11.6° as determined by XRD was used to
optimise the rehydration step as part of the modified reconstruction method. At room temperature, the
rehydration process is very slow, and takes 24h to restore the lamellar structure of the LDH. When the
rehydration temperature was increased to 80°C, a large proportion of the lamellar structure of the
Mg-Al LDH has been restored even after 1h. The reaction is complete after 3h. Therefore, the
rehydration condition at 80°C for 3h was chosen in the subsequent experiments to produce suitable
LDHs structure for intercalation with the carboxylic acids.
Fig.1 compares the XRD patterns of the ‘as received’, calcined, and rehydrated LDHs. The ‘as
received’ LDH exhibits a XRD pattern characteristic of a crystalline lamellar material. Subsequent to
the calcination treatment, the crystalline diffraction peaks of the LDH completely disappear,
indicating that the layered structure has been destroyed by the calcination process. After rehydration
in water at 80°C for 3h, the diffraction peaks of the LDH sample appeared at the same 2 theta angles
as the ‘as received’ LDH, suggesting that the lamellar structure was restored. However, the rehydrated
sample appears to be less crystalline than it was before the heat treatment, as shown by the reduced
peak intensities and the broadened peak widths. The representative XRD patterns of the LDHs
intercalated with the smallest (sorbic acid) by the above two methods are displayed in Fig.2. The fatty
acid intercalated LDHs synthesised by the modified reconstruction method exhibit a well-organised
layer structure in contrast to the disordered structure obtained from the conventional method. During
the conventional reconstruction process, the anions quickly adsorb on the surface of the positively
charged hydroxide layers once they are formed, and become a platform for generating the next layer.
While the presence of the small anions (i.e. Cl−, NO3- etc) have been shown to cause minimum
disruption to the reconstruction of the layer structure of the LDH, the adsorption of the relatively large
and hydrophobic anions such as the fatty acids onto the hydrophilic hydroxide layers is expected to
lead to a loose and disordered layer structure due to incompatibility and steric hindrance. Such a
problem is avoided in the case of the modified reconstruction process because the rehydration step of
the calcined LDH in water is known to firstly produce LDHs with a well-organised layer structure
containing OH− as interlayer anions [5]. Subsequent addition of the fatty acid anions led to their
intercalations into the LDH by replacing the hydroxyl anions with minimum interruption of the layer
structure.
220 Advanced Synthesis and Processing Technology for Materials

4500 0.76nm 6000

4000
5000
3500
Intensity (Counts)

3000

Intensity (counts)
4000
Sorbic acid-LDH
2500 Rehydrated (conventional)
3000
2000
LDH
1500 2000
Sorbic acid-LDH
1000 Rehydrated (Modified)
0.77nm Calcined LDH 1000
500 Rehydrated LDH
0
0
3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33
5 10 15 20 25 30 35 40 45 50
2 Theta
2 Theta

Figure 1. Comparison of XRD spectra of LDH Figure 2. XRD spectra of sorbic acid
intercalatedCalcined LDH and rehydrated LDH LDH with conventional and modified method

Successful intercalation of all the carboxylate anions investigated in this work is confirmed by
their XRD patterns (Fig.3). In all cases, one observes broadening and shifting of the basal reflection
peaks towards lower field once the carboxylate molecule is intercalated in comparison with the ‘as
received’ LDH. As the size of the carboxylate molecule is increased, the distance between the LDH
platelets is also enlarged in a linear fashion. This expansion of the space between the platelets is
expected to facilitate their separation and dispersion into a polymer matrix for the formation of
nanocomposites. These results also suggest that the intercalation reaction is not significantly affected
by the alkyl chain length or whether or not the alkyl chain is saturated or unsaturated. This broadening
indicates the presence of some turbostratic effect caused by a decrease of the ordering along the
stacking axis due to the loss of van de Waals interaction between adjacent layer and the absence of a
densely packed interlayer space formed by high-charge-density anions such as carbonate or halides. In
addition, a broad scattering hump is observed between 20-30° in 2θ for the stearic modified LDHs,
suggesting that a part of the stearic molecules is adsorbed on the surface of the LDH similar to the
cases of LDHs modified by polyethylene oxide derivatives and oleate ions.
FTIR analysis was used to confirm the presence of the fatty acid anions in the LDH. The ‘as received’
LDH has an intense absorption peak at 1361cm−1 due to the ν (asym) stretching mode of the carbonate
anion, which is not present in the spectra of any of the fatty acid modified LDHs. Subsequent to the
incorporation of the fatty acid anions into LDH, one can observe the characteristic peaks of the COO-
group at 1600cm-1 (sym) and 1400cm−1 (asym) instead of the free acid (COOH) peak at 1705cm-1.
Weaker bands arising from the alkyl C–H stretches of the fatty acid molecules are observed in the
range 3000–2800cm−1.
100
Stearic acid 90
80
Weight Loss (%)
Intensity (counts)

Oleic acid 70
60 LDH
Lauric acid 50

Octanoic acid
40 StA-LDH

30 Stearic Acid
Sorbic acid
20
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 50 250 450 650
2 Theta Temperature (degree)

Figure 3. XRD spectra of reconstructed LDHs Figure 5. TGA of stearic acid, LDH and
Intercalated with fatty acids of different chain lengths stearic acid intercalated LDH
 Advanced Materials Research Vol. 66 221

Figure 4. SEM images of (a) rehydrated LDH@80C, 3h; (b) sorbic acid modified LDH. The bar in the
image is 500nm.

SEM analysis reveals that the LDHs intercalated with the smaller carboxylate anions such as sorbic
acid; octanoic acid and lauric acid maintain the well defined and regular hexagonal-shaped platelet
structure (Fig.4). On the other hand, longer molecules such as stearic acid appear to be present on the
surface of the LDH as well as being inserted into the platelet structure as confirmed by XRD analysis.
TGA curves (Fig.5) of the selected fatty acid samples indicate that the thermal stability of the fatty
acid-intercalated LDH materials is superior to that of the free acid molecules because the inorganic
structure protects and delays the decomposition of the fatty acid molecules. The 10% weight loss from
room temperature to 250°C as a continuous step for the fatty acid intercalated samples corresponds to
desorption of physisorbed and interlayer water molecules. This indicates that the modified LDHs
should be thermally stable under the processing condition of the polymer nanocomposites (i.e.
polyolefins based matrix). Above 400°C, the dehydroxylation of the lattices and decomposition of the
interlayer anions are observed for the modified LDH samples.

Conclusions
Mg-Al LDHs intercalated with saturated and unsaturated fatty acids were successfully synthesised
using the modified reconstruction method developed in this work. The modified LDHs maintain
well-ordered layer structures and exhibit significantly increased interlayer distances as the length of
the fatty acid molecules increases. The fatty acid (i.e. stearic acid) modified LDH exhibits
hydrophobic properties making it feasible for their intended application as nanoadditives in polymers.
The stearic, oleic modified LDHs may also be good candidates for drug delivery system to the
intestines in which the Mg-Al LDH readily dissolves in acid whilst the stearic, oleic molecules are
insoluble in the acid.

References
[1] A. Vaccari: Appl. Clay Sci. Vol. 14 (1999), p. 161.
[2] S.Sinha Ray, Okamoto and M. Prog: Polym. Sci. Vol. 28 (2003), p. 1539.
[3] T.Hibino, Tsunashima: A. Chem. Mater. Vol. 10 (1998), p. 4055.
[4] Y. Kameshima, H. Yoshizaki, A. Nakajima and K. Okada: J. Coll. Inter. Sci. Vol. 298 (2006), p.
624.
[5] F. Prinetto, G. Ghiotti, P. Graffin and D. Tichit: Micro. and Meso. Mater. Vol. 39 (2000), p. 229.
222 Advanced Synthesis and Processing Technology for Materials

Advanced Synthesis and Processing Technology for Materials

doi:10.4028/www.scientific.net/AMR.66

Synthesis of Carboxylic Acids Intercalated Mg-Al Layered Double Hydroxides by a

Modified Reconstruction Method
doi:10.4028/www.scientific.net/AMR.66.218

References
[1] A. Vaccari: Appl. Clay Sci. Vol. 14 (1999), p. 161.
doi:10.1016/S0169-1317(98)00058-1

[2] S.Sinha Ray, Okamoto and M. Prog: Polym. Sci. Vol. 28 (2003), p. 1539.

[3] T.Hibino, Tsunashima: A. Chem. Mater. Vol. 10 (1998), p. 4055.

[4] Y. Kameshima, H. Yoshizaki, A. Nakajima and K. Okada: J. Coll. Inter. Sci. Vol. 298
(2006), p. 624.
doi:10.1016/j.jcis.2006.01.033
PMid:16529762

[5] F. Prinetto, G. Ghiotti, P. Graffin and D. Tichit: Micro. and Meso. Mater. Vol. 39 (2000),
p. 229.