Materials Research Bulletin 41 (2006) 1638–1645

www.elsevier.com/locate/matresbu

Effect of acidity on the glycine–nitrate combustion

synthesis of nanocrystalline alumina powder
Tianyou Peng a,b,*, Xun Liu a, Ke Dai a, Jiangrong Xiao a, Haibo Song a
a
Department of Chemistry, Wuhan University, Wuhan 430072, PR China
b
Centre of Nanoscience and Nanotechnology, Wuhan University, Wuhan 430072, PR China
Received 23 June 2005; received in revised form 6 February 2006; accepted 20 February 2006
Available online 15 March 2006

Abstract
Nanocrystalline alumina powders were prepared by combustion synthesis using glycine as fuel and nitrate as an oxidizer. The
effect of the pH values in the precursor solutions on crystallite sizes, surface areas and morphologies of the synthesized alumina
powder has been investigated by X-ray diffractometry, thermal analysis, nitrogen adsorption–desorption, and transmission electron
microscopy. With decreasing the pH values in the precursor solutions, the obtained materials could be modified from segregated
nanoparticles (pH 10.5) to aggregates of nanoparticles (pH 6.0), and finally to a flaky morphology (pH 2.5). The rates of
decomposition, the interaction of coordination as well as the hydrogen bonding of the glycine and the Al-hydroxides species at
different pH values were found to be responsible for the generation of flake and/or segregated nanoparticles during auto-ignition
reactions. The as-prepared combustion ashes were converted into pure nanocrystalline alumina after calcination at elevated
temperatures. The specific surface areas of the products calcined at 800 8C ranged from 96 to 39 m2/g with the pH decreased from
10.5 to 2.5.
# 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Ceramics; A. Nanostructures; A. Oxides; B. Chemical synthesis

1. Introduction

In recent years, there has been an increasing interest in the synthesis of nanocrystalline metal oxides due to
important applications in advanced ceramics and as reinforcement in polymer and brittle matrix composites [1–7].
Nanocrystalline a-alumina (Al2O3) has considerable potential for various applications including high strength
materials, electronic ceramics and catalysis etc. In particular, high quality nanocrystals of a-Al2O3 are used as
electronic substrates and in fine precision equipment [2–9]. a-Al2O3 powders prepared by conventional methods
require high temperatures 1300–1600 8C for solid-state thermally driven decomposition of the hydrates of alumina.
The extent of conversion to the a-Al2O3 phase depends on the temperature and the time of calcinations [9]. Generally,
the following series of phase transformation may occur before conversion to a-Al2O3: hydrous
alumina ! boehmite ! g ! d ! u ! a. The average crystallite size increases to larger than 100 nm for a-
Al2O3 at the high temperature required for almost all these salt-derived aluminium hydroxides or hydrated aluminas to
form a-Al2O3 [6,9–11].

* Corresponding author. Tel.: +86 27 87218474; fax: +86 27 68754067.

E-mail address: typeng@whu.edu.cn (T. Peng).

0025-5408/$ – see front matter # 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2006.02.026
 T. Peng et al. / Materials Research Bulletin 41 (2006) 1638–1645 1639

Also, co-precipitation [10,11], sol–gel [12,13] and combustion synthesis [3–5] methods have been developed for
the preparation of nanocrystalline Al2O3 powers, but the processing routes of co-precipitation and sol–gel methods
are complicated and the duration times are long [14]. The combustion process to prepare the precursor powders of
high-tech ceramic materials, particularly the nanocrystalline ceramics, however, is of significant interest due to its
overall ease and less energy-intensive steps [3–5,15–21]. Moreover, the solution-based combustion synthesis is
advantageous over the solid-state synthesis in terms of better compositional homogeneity and purity of the final
product. Therefore, a series of such solution-based combustion decomposition techniques are developed to yield
single-phase products of various multi-component ceramics at relatively low temperatures [15,19–22]. This
technique involves the exothermic chemical reaction of a fuel (e.g. citric acid, urea, glycine or glycol, etc.) and an
oxidizer (e.g. nitrates) [3–5,15–19]. The exothermicity sometime appears in the form of a flame, which temperature
can be in excess of 1500 8C [15]. The large amount of gases generated during combustion synthesis rapidly cools the
product leading to nucleation of crystallites without any substantial growth. The gas generated also can disintegrate
the large particles or agglomerates; therefore, the resulted product consists of very fine particles of friable
agglomerates or nanoparticles [15–18]. The nature and amount of the fuel, and the pH of the starting solution are
important factors in preventing selective precipitation and/or phase separation during the evaporation of solvents,
which may result in phase and compositional inhomogeneities [16,19–22]. For example, Pathak et al. [3] found that
pH values in precursor solutions have important effect on the morphologies of nanocrystalline alumina powder
produced by citrate–nitrate combustion synthesis.
The zwitterionic character of glycine can effectively complex various metal ions which help in preventing their
selective precipitation and therefore in maintaining the compositional homogeneity among the constituents. Namely,
metal nitrates with glycine as complexing agent are highly promising in producing various amorphous and
nanocrystalline ceramic powders [15–22]. The solution-based combustion technique using glycine has been studied
widely, such as the effect of the fuel-to-oxidant ratio on the powder characteristics [16]. However, only a few efforts
have been made to investigate the effects of the pH on the glycine–nitrate combustion route to alumina. In this paper,
solution-based combustion synthesis is applied to prepare the Al2O3 powders from precursor solution of
Al(NO3)3
9H2O and glycine, in which nanocrystalline a-Al2O3 powders are obtained by heating the resultant
combustion ash at 1200 8C. The effect of pH values in the precursor solutions on the powder characteristics such as
crystallite sizes, surface areas and morphologies are described.

2. Experimental procedure

All starting materials in the present experiment were of the analytical purity. In a cylindrical quartz container
(80 mm diameter  200 mm height), solution of aluminium nitrate (Al(NO3)3) were prepared and calculated
stoichiometric amount of glycine (NH2CH2COOH) was added. Subsequently, ammonia was added to neutralise the
pH of the solution at 6.0 and the final pH of the solution was adjusted to 2.5, 6.0 and 10.5 by adding either dilute HNO3
or liquid ammonia as required. The precursor solution containing aluminium nitrates and glycine was thermal
dehydration on a hit plate (80  5 8C), which resulted in viscous liquid. And then the viscous precursor was heated
rapidly in a pre-heated furnace maintained at 500 8C. Depending on the pH values, the material undergoes foaming
followed by decomposition generating large volume of gases, then spontaneous ignition occurred and underwent
smouldering combustion with enormous swelling, producing a grayish, foamy, voluminous mass in different fashion.
The whole process was complete in less than 2 min. The voluminous and foamy combustion ashes are easily crushed to
the precursor powders. The crushed precursor powders after calcinations at 800 and 1200 8C for 2 h transformed to
pure g- and a-Al2O3 powders, respectively.
The particle morphologies of products were observed on a JEM-100X/II transmission electron microscope (TEM).
Phase formation and estimation of the crystallite size of samples were carried out by means of an XRD-6000
´
diffractometer using Cu Ka radiation (l = 1.5406 Å). The dried precursors were collected prior to decomposition for
all the pHs and the TG-DTA analyses were conducted in flowing air up to 600 8C at a heating rate of 10 8C/min using a
Netzsch STA449 simultaneous thermal analyzer (TG-DTA) to study the decomposition behavior and nature of the
combustion reaction. The specific surface areas of the powders calcined at 900 8C were measured by liquid nitrogen
adsorption–desorption isotherms at 77 K on a Micrometrics ASAP 2010 system after samples were degassed at
120 8C.
1640 T. Peng et al. / Materials Research Bulletin 41 (2006) 1638–1645

3. Results and discussion

Upon heating, the precursor solutions containing nitrate–glycine transformed into viscous liquids, which
further spontaneously ignited to yield a grayish, foamy, and voluminous mass. It is known that the exothermic heat
generated in this combustion process is governed by a thermally induced redox reaction involving glycine and
nitrate in the precursor, where the nitrate anions act as oxidant and the glycine act as reductant [15,16]. The
appearance of the combustion decomposition is also evident from the thermal analysis of the dried precursors
collected prior to pyrophoric decomposition. A typical TG-DTA plot for the sample obtained at pH 10.5 is shown
in Fig. 1. The exothermic behavior of auto-ignition can be clearly seen at about 288.8 8C with concurrently weight
loss of about 82.4% (200–300 8C). The appearance of the exothermic peak in DTA curve at 288.8 8C for sample
prepared at pH 10.5 clearly indicates the nitrate–glycine redox reaction in this system. The maximum weight loss
(TGA-curve) occurs in a very narrow temperature range, which corresponds to the auto-ignition step. The
expected weight losses corresponding to the complete conversion of the precursor to Al2O3 in case of precursor
powder during auto-ignition is 85.0%. The difference (2.6%) in expected and observed weight losses may be
attributed to the remained carbon contamination, which can be inferred from the fact that a grayish product was
obtained. The total weight loss (about 2.9%) above 320 8C of TGA curve also indicates that the remaining carbon
is combustible as.
The appearances of exothermic peaks at 287.5 8C (Fig. 2) and 277.4 8C (Fig. 3) also clearly indicate auto-
ignition reactions for samples prepared at pH 6.0 and 2.5, respectively. The observed weight losses during the auto-
ignition reactions of the pH 2.5 and 6.0 (150–320 8C) precursors were 84.5 and 82.1%, respectively. The
differences in the observed weight losses are consistent with the shades of grayish products generated from
different pH values solutions. The decomposition of the precursor with pH 2.5 composition is very near to the
single step decomposition as described by Purohit et al. [16]. However, TG-DTA plots of products show a multi-
steps decomposition of precursors for pH 6.0 and 10.5, which is likely to produce some different intermediates as
compared to that for pH 2.5. Furthermore, the rapid decomposition of the precursor at pH 10.5 has been observed to
be associated with a very sharp DTA peak (Fig. 1), whereas the exothermic peaks of dried precursors are weakened
and broadened with the pH decreasing from 10.5 to 2.5, implying the reduced exthermicity and prolonged time of
the auto-ignition reactions.
This variety of TG-DTA of precursors for different pHs is a direct consequence of the different prevailing glycine
and Al-hydroxide species. For example, the NH3+CH2COOH and NH2CH2COO species are the dominant species for
pH 2.5 and 10.5, respectively. At the isoelectric point of glycine (pH 6.0), NH3+CH2COO is thus the dominant one.
Whereas, the reaction (1) is also affected by varied pHs of the precursor solution. The pyrophoric pyrolysis of NH4NO3
formed in the reaction (1) is known to yield nitrogen, H2O and nascent oxygen [3], and this excludes the possibility of
formation of NOx and HCN species in the process, which makes the process less hazardous:

AlðNO3 Þ3 þ 3NH4 OH ¼ AlðOHÞ3 þ 3NH4 NO3 (1)

Fig. 1. Simultaneous TG-DTA curves of the dried nitrate–glycine precursor (pH 10.5) collected prior to decomposition.
 T. Peng et al. / Materials Research Bulletin 41 (2006) 1638–1645 1641

Fig. 2. Simultaneous TG-DTA curves of the dried nitrate–glycine precursor (pH 6.0) collected prior to decomposition.

For the pH 2.5, the rate of both protonation and dissolution of Al-hydroxides derived from the reaction (1) is high,
and the NH3+CH2COOH is the dominant glycine species, the coordination interactions between the aluminium ions
and glycine species are limited, whereas the absorbed glycine seems to have attacked the surface hydroxyls. According
to Shafei and Philip [24], the glycine interacted dissociatively via a protonation of surface hydroxyls and the rest of the
molecule has hydrogen bonded with an adjacent hydroxyl or surface oxygen. The possibility of the redox reaction can
be understood from the comparison of the TG-DTA analysis of free glycine (Fig. 3). Shafei et al. [24] have reported the
appearance of one endothermic peak at 265 8C followed by exothermic peak at 290 8C in the thermal analyses
investigation of the free glycine. The appearance of exothermic peaks and rapid weight loss at 277.4 8C for sample
prepared at pH 2.5 clearly indicates the nitrate–glycine reaction in the case [3].
Whereas for the pH 6.0, the ziwitterionic forms is the dominant glycine species, the coordination interactions,
maybe with hydrogen bonding, between the aluminium ions from the Al-hydroxide and the –COO of zwitterionic
will be the main interactions. For the 10.5, the glycine existed mainly as NH2CH2COO forms, there may exist
coordination interaction between the aluminium ions of Al-hydroxide and the –NH2 of NH2CH2COO, the target sites
on the surface are the coordinatively unsaturated Al3+ ions [24]. These coordinated glycines for precursors pH 6.0 and
10.5 are beneficial for the dispersivity of the Al-hydroxides by inhibiting selective precipitation during the evaporation
of solvents, which is facilitated to the formation of segregated particles and prevention of agglomerates. These
interactions of coordination and hydrogen bond between Al-hydroxide and glycine seem need more energy and hence,
the auto-ignition decompositions need higher temperature. Moreover, these interactions also resulted in a multi-step
decomposition of precursors for pH 10.5 and 6.0 as observation from the TG-DTA plots.

Fig. 3. Simultaneous TG-DTA curves of the dried nitrate–glycine precursor (pH 2.5) collected prior to decomposition.
1642 T. Peng et al. / Materials Research Bulletin 41 (2006) 1638–1645

Fig. 4. X-ray diffraction patterns of the Al2O3 powder prepared from nitrate–glycine precursor (pH 10.5): (a) as-prepared, (b) calcined at 800 8C, (c)
calcined at 1000 8C and (d) calcined at 1200 8C.

X-ray diffraction patterns show that the as-synthesized combustion ashes prepared at pH 10.5 are basically g-Al2O3
in nature (Fig. 4a), which need to be calcined at elevated temperatures to yield pure a-Al2O3 powders (Fig. 4b–d). The
auto-ignition of viscous liquids with different pHs resulted in grayish powders containing considerable amounts of
carbonaceous residue, which indicates the incomplete combustion probably due to the less dwell time for the auto-
ignition. Hence, this grayish powder needs calcination at a higher temperature to be converted into pure alumina
powder. Purohit et al. have also observed a similar behavior in the nitrate–glycine combustion synthesis of
nanostructured thoria powders [16]. As can be seen form Fig. 4a, no peak corresponding to any of the source material
was observed. Diffraction peaks corresponding to g-Al2O3 have been found for the as-synthesized samples. No
significant change in the structure except for the increased diffraction intensities has been found after calcinations at
800 8C (Fig. 4b). A small amount of a-Al2O3 has been detected after calcinated at 1000 8C (Fig. 4c), which coexists
with the major phase g-phase. A typical X-ray diffraction pattern of the resultant a-Al2O3 powders after calcinations at
1200 8C (2 h) are shown in Fig. 4d, as can be seen, a pure phase diffraction peaks of a-Al2O3 are predominant in the
XRD patterns, which is similar with the earlier results [3,10]. The line broadening feature in Fig. 4d can be observed
due to their small crystallite particle size, indicting that the nanocrystallines can be prepared in a relatively low
temperature (1200 8C). The crystallite sizes, calculated by a X-ray line broadening using the Scherrer formula, for the
pH 10.5, 6.0 and 2.5 products calcined 1200 8C were found to be about 19.8, 16.9 and 9.6 nm, respectively.
Some representative TEM images of the alumina powders prepared at different pHs are shown in Fig. 5. The TEM
images of products calcined at elevated temperature show a clear change in morphology as the pH of the solution
decreased from 10.5 to 2.5 (Fig. 5a–f). The particle morphology of alumina calcined at 800 8C changes from
segregated nanoparticles (Fig. 5a, pH 10.5) to aggregates of nanoparticles (Fig. 5c, pH 6.0), and finally to flaky
structures (Fig. 5e, pH 2.5). After calcinations at 1200 8C, most of the Al2O3 particles appear to be irregularly
elliptical, which is different form the morphologies of products calcined at 800 8C, indicating that the calcinations
resulted in the restructures of alumina. For the pH 10.5, the TEM images (Fig. 5b) of the segregated a-Al2O3
nanoparticles exhibited a sharp particle distribution with an average particle diameter of 21 nm. This value is very
closed to that of the crystallite size (19.8 nm) calculated from XRD pattern for the same powder, implying the obtained
nanoparticles have good crystallinity and low agglomeration. For the pH 2.5, the particle morphology changes from
flaky form to network-like morphologies (Fig. 5f). The hard agglomeration companying with the formation of necked
crystallites (about 9 nm in size, which is again close to the crystallite size obtained from XRD) can be clearly observed.
The morphology (Fig. 5d) of the product for pH 6.0 exhibits particles characteristics between those of pH 10.5 and 2.5.
The products have much larger aggregates consist of primary particles with particle distribution of 20–80 nm (centered
at 41 nm) and smaller average crystallite size (16.9 nm) as compared to products for pH 10.5.
The specific surface areas of the pH 10.5, 6.0 and 2.5 products calcined at 800 8C were found to be about 96, 64 and
39 m2/g, respectively. In general, the glycine–nitrate combustion produces powder with high surface area as compared
 T. Peng et al. / Materials Research Bulletin 41 (2006) 1638–1645 1643

Fig. 5. TEM micrographs of Al2O3 powders prepared from nitrate–glycine precursors: (a) and (b), pH 10.5; (c) and (d), pH 6.0; (e) and (f), pH 2.5;
whereas, (a), (c) and (e) calcined at 800 8C; (b) (d) and (f) calcined at 1200 8C.

to the citrate–nitrate combustion process [16]. The substantial reduction of the surface area in case of the pH 2.5
product as compared to the pH 10.5 product is due to the broadening exothermic peaks and longer dwell times of auto-
ignition reaction in this case, which might have facilitated hard agglomeration among active primary crystallites
produced in the process. As described above, the DTA plots showed that the nature of the exothermic peaks for the
chemical decomposition reactions of the samples changes with the pH of the solution (Figs. 1–3). The rapid
decompositions of the precursors at pH 10.5 are associated with a very sharp DTA peak (Fig. 1). This rapid pyrophoric
pyrolysis at pH 10.5 has led to generation of large amount of gases (such as, CO, CO2, NO, NO2, NH3, water vapor,
1644 T. Peng et al. / Materials Research Bulletin 41 (2006) 1638–1645

etc.). It not only helps in preventing the formation of a dense structure and results in a higher surface area, but also
disintegrates the large particles to yield nanoparticles. However, the exothermic peaks for the pH 2.5 are relatively
weak in nature (Fig. 3) and they are associated with slow rate of weight loss during heating (Fig. 3). The alterations of
chemical species and the interactions of coordination and hydrogen bond in glycine and Al-hydroxide compositions
due to varying the pH of the solution precursor are possibly the reason for this decrease of exothermic peaks, which
further induce the morphological and microstructural variations of the obtained powders.
It is known that glycine–nitrate stoichiometry in the precursor composition is the primary factor in controlling the
reaction enthalpy in such a redox reaction [16]. If the oxidant ratio (nitrate anions in this case) in the precursor solution
is increased in comparison to glycines, then the exothermicity of the reaction is reduced. In the present system, the
glycine ion composition is fixed, whereas adding nitric acid to attain low pH values increases the nitrate ion
concentration. Therefore, the increase of nitrate ions in the low pHs is expected to decrease the enthalpy of the
exothermic reaction [3,16], which is also in agreement with the experimental results. Therefore, the slow
decomposition of the precursor in the pH 2.5 has enabled the alumina particles to come closer to form flakes. But the
longer dwell time of combustion process for the pH 2.5 precursor solution facilitated the crystalline agglomerates as
described above. The crystallite size of the pH 10.5 product is larger than that of the pH 2.5 product probably due to
higher crystal growth assisted by a high enthalpy or flame temperature of the combustion reaction in this case. In
addition to narrow exothermicity associated with the rapid auto-ignition of the pH 10.5 precursor, another crucial
factor is the fast cooling due to the rapid evolution of the gases during auto-ignition in the basic solution. Moreover, the
increased ammonia concentration for attaining the high pH values also resulted in more gases during combustion, and
such a vigorous process not only helps to disintegrate the agglomerated particle with each other to obtain nanoparticles
but also helps to dissipate the heat of combustion, thus inhibiting the sintering of nanocrystalline powders [20–24],
which is also in agreement with the experimental results (Fig. 5 a and b). Moreover, the interaction of coordination and
hydrogen bonding also play an important role in the formation of segregated nanoparticles by affecting the behavior of
combustion and formation homogeneity composition.

4. Conclusion

The a-Al2O3 nanocrystalline was synthesized by combustion synthesis processing along with heating the resultant
combustion ash precursor powder at 1200 8C. A systematic investigation of acidity effect in precursor solution on the
morphology and microstructure of the alumina powder synthesized by a pyrophoric reaction using nitrate–glycine
route is carried out. The pH of the precursor solution bears a great influence in controlling the morphology and
microstructure of the obtained powder. The sluggish decomposition of the precursors at pH 2.5 yielded flaky powders,
whereas the rapid decomposition at high pH 10.5 produced segregated nanoparticles. The process is shown to have a
considerable potential for producing alumina powders with high surface area, which subsequently may be sintered at
relatively lower temperature and in shorter time.

Acknowledgements

Financial support from the Natural Science Foundation (20573078) of China, the Natural Science Foundation
(2004ABA083) of Hubei Province, and the Project sponsored by SRF for ROCS, SEM of China are gratefully
acknowledged. Authors are also indebted to Mr. Ren from Center for Electron Microscopy of Wuhan University, for
the TEM images.

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