Materials Chemistry and Physics 120 (2010) 670–675

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Research on the methods to determine metallic aluminum content in

aluminum nanoparticles
Liang Chen a,b , Wulin Song a,c,∗ , Jie Lv a , Xia Chen c , Changsheng Xie a
a
State Key Lab of Materials Forming Simulation and Die and Mould Technology, Huazhong University of Science and Technology, Wuhan 430074, PR China
b
Material Structure Department, Changjiang River Scientific Research Institute, Wuhan 430010, PR China
c
Analytical and Testing Center, Huazhong University of Science and Technology, Wuhan 430074, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The high reactivity of aluminum nanoparticles (ANPs) made the determination of their metallic aluminum
Received 17 July 2009 (Al) content difficult. Volumetric, thermogravimetry and permanganatometric methods were utilized
Received in revised form 6 December 2009 to determine Al content. The reacted solution after volumetric measurement was further studied by
Accepted 15 December 2009
transmission electron microscopy (TEM) and select area electron diffraction (SAED), which revealed that
there were unreacted Al particles. Peaks indexed to metallic Al were found in the X-ray diffraction (XRD)
Keywords:
pattern of the powders after thermogravimetry analysis (TGA). The side reactions between ANPs and
Aluminum
water made the result of permanganatometric measurement underestimated as by the former methods.
Nanoparticles
Reactivity
A modified titration method, using anhydrous alcohol as solvent, was performed to reduce the influence
Metallic content of water. The Al content of the ANPs produced by electro-exploded wire using this method was consistent
Rietveld refinement with the quantitative phase analysis by Rietveld refinement.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
Aluminum nanoparticles (ANPs) have a promising application
in propellants, explosives and pyrotechnics, which can add energy
to the burning reaction in propellants and enhance the blast effect
of explosives, as well as their underwater performance. A decrease
in particle size causes changes in the specific surface of the powder,
its structure, and phase composition. Especially when it comes to
nano-scale, a large amount of aluminum (Al) atoms are on the sur-
face of the particle and it is easy to react with the environmental
atmosphere, oxygen, steam and carbon dioxide [1–3]. As a result,
the reactivity of ANPs is very high, and the oxidation and com-
bustion of them proceed in a manner differing from that of the
micro-sized particles [4–7].
A variety of techniques are developed to produce ANPs, includ-
ing electro-exploded wire [8–10], plasma synthesized process [11],
wet chemical [12,13] and heating evaporation [14,15]. Whatever
the method of production, the ANPs are subjected to passivation
to ensure their stability. The passivation involves the treatment of
surface with either gaseous or liquid reagents that form a protec-
tive layer [16,17]. In the simple and common case, this can be an
oxide layer of a core-shell structure: the shell layer aluminum oxide
∗ Corresponding author at: State Key Lab of Materials Forming Simulation and Die
and Mould Technology, Huazhong University of Science and Technology, Wuhan
430074, PR China. Tel.: +86 27 87557453; fax: +86 27 87557453.
E-mail address: wulins@126.com (W. Song).
(Al2 O3 ) (2–5 nm in thickness) coats the core Al tightly. This oxide
layer decreases the reactivity as well as the percentage of metal-
lic Al in the raw particles, thus cannot be neglected. The existing
of this oxide layer and the high reactivity of the nanoparticles add
complexity to the determination of Al content for the virgin ANPs.
To date, however, a main problem that has not been solved prop-
erly in the application of ANPs is the determination of metallic Al
content in ANPs.
Many methods, such as volumetric and reductant–oxidant
titration (e.g. permanganatometric), were investigated and made
triumph in determining the Al content for the conventional micron-
sized Al particles [18]. However, when they are used to analyze
ANPs, unsatisfactory results were obtained because of the high
reactivity of the particles. The high reactivity caused early oxida-
tion before their melting point (660 ◦ C) [19], which can be used
to estimate the Al content by themogravimetry analysis. A ceri-
metric method [20] was also experienced to determine the Al
content but the high cost of the cerium (IV) sulphate as well as
the difficulty to precisely determine the amount of the cerium (IV)
sulphate consumed in the titration hindered the development of
this method. In this paper, modified volumetric, thermogravime-
try and conventional permanganatometric methods were used to
estimate the metallic Al content of ANPs prepared by four different
methods. The values of Al content determined by these methods
were underestimated, and then the results were further discussed
to find out the reasons that caused the underestimated results.
Based on these measurements, a novel modified permanganato-
metric method which used low concentration of aqueous solution

0254-0584/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2009.12.030
 L. Chen et al. / Materials Chemistry and Physics 120 (2010) 670–675 671

was applied to measure the Al content of these ANPs. Quantitative

phase analysis using Rietveld refinement was also performed to
prove the accuracy of the new titration method.

2. Experimental

The investigated ANPs were labeled as Al-E, Al-P, Al-L and Al-I. The particles of
Al-E were commercial particles produced by electro-exploded wire (EEW) method,
got from Sina-Russian Joint Venture, Jiaozuo Banlv Nanomaterial Engineering Co.,
Ltd., China. The particles of Al-P were commercial particles produced by plasma syn-
thesized process, got from Shandong Origine Nanomaterials Engineering Co., Ltd.,
China. Al-L and Al-I were experimental particles produced by laser heating evapora-
tion and induction heating evaporation, respectively. The microstructures of these
particles were examined by transmission electron microscope (TEM) (Tecnai G2 20,
FEI, 200 KV), field emission scanning electron microscope (FESEM) (Sirion 2000, FEI,
10 KV), Brunner–Emmett–Teller (BET) method and X-ray diffraction (XRD).
The volumetric method was based on the measurement of the hydrogen vol-
ume released in the reaction of aluminum with sodium hydroxide solution. Before
the measurement, the air tightness was tested and the water for sealing released
H2 was saturated by H2 to exclude the systematic error. Accurately measured ANPs
(about 50 mg) were added to 50 mL sodium hydroxide solution (0.2 mol L−1 ). The
volume of released H2 was measured by displacement volume of the water. Atmo-
spheric pressure, room temperature and the temperature of the sealing water were Fig. 1. X-ray diffraction patterns of ANPs.
measured.
Thermogravimetry method was realized on TG-DTA equipment with a
PerkinElmer TG/DTA 6300 thermal analysis system, which has an upper limit heating particles of Al-E are sphere (Fig. 2a) and have a core-shell structure
rate of 100 ◦ C min−1 . The equipment consists of a pair of horizontal electro-balances, (Fig. 2b): Al in core with Al2 O3 layer (2–4 nm) as shell part. There
with a 0.1 ␮g of resolution, a furnace and sensors of temperature, connected to a is metallic magnesium (Mg) not be oxidized in the Al-E sample.
computer, using the Muse version 5.4 U thermal analysis systems. The crucibles
Mg may be formed as solid solution atoms in Al particles through
used were 70 ␮L alumina ones. The samples were heated at a rate of 10 ◦ C min−1
from room temperature to 1000 ◦ C in dry oxygen (99.995%) atmosphere, with a gas explosion of the raw material wires. The Al2 O3 layer prevents Mg
flow of about 50 mL min−1 . and Al to be further oxidized. Besides the sphere particles, there
The conventional permanganatometric and a modified one were used as the are rod-like ones in the sample of Al-L (Fig. 2c). This type of parti-
reductant-oxidant titration method to analysis the Al content. In the conventional cles also has the core-shell structure, but the shell part is 3–5 nm
permanganatometric, precise weighed of about 50 mg ANPs samples and 5 g ferric
chloride were added into 100 mL deionized water and then was stirred for about
(Fig. 2d). There is a certain amount of Ag in the sample of Al-P. The
2 h. The reacted solution was titrated by 0.1 mol L−1 acid potassium permanganate. contents of Al2 O3 are higher in samples of Al-L and Al-I, which is
The X-ray diffraction data were measured over the scattering 2 angle range consistent with the TEM observation of the thicker coating layers.
10–90◦ with 50 s per step (step-size 0.0167◦ ) using Cu K␣ radiation (k␣1 = 1.54056 Å, There is Si as an impurity phase in the sample of Al-I introduced in
k␣2 = 1.54440 Å) with a graphite monochromator in the reflection geometry at
the production process.
25 ◦ C (X’Pert PRO, PANalytical B.V.). The quantitative phase analysis based on
Rietveld refinement was also performed to prove the accuracy of the modified
titration. Rietveld refinement was carried out with FullProf program using a pseudo- 3.2. Volumetric measurement
Voigt function with one Gaussian and one Lorentzian coefficient as the profiles
model. The reaction involved in this measurement is followed by the
reaction below:
3. Results and discussion
2Al + 2NaOH + 2H2 O = 2NaAlO2 + 3H2
3.1. Microstructure characterization The content of the metallic ANPs is calculated by the volume of
generated hydrogen (H2 ) using the formula below. Here and below,
Characteristic of the four types of Al2 O3 passivated ANPs is listed mass percent values are used.
in Table 1. The mean diameter (Dm ) was calculated by XRD pat-
tern with an MDI jade 5.0 software assistant with TEM and FESEM (P1 − P2 − P3 )VK
CAl (wt.%) = × 100%
observation, the thickness of the coating layers (Tc ) was examined mT
by the high resolution TEM (HRTEM), the specific surface area (Sp ) P1 – atmospheric pressure, Pa; P2 – saturated water vapor pres-
was tested by the BET method. As can be seen from Table 1, the sure at T K, Pa; P3 – temperature correction value of atmospheric
mean diameters of the particles are around 50 nm and the parti- pressure, Pa; V – volume of generated H2 , L; T – temperature of
cles of Al-I have the smallest particles. The specific surface area the sealing water, K; m – mass of the sample, kg; K – conversion
increases with the decrease of the mean particle diameter of the coefficient, 2.88 × 10−4 . The duration of the analysis is about 10 h.
particles. XRD patterns of the four types of particles are shown in When the volume of the generated H2 kept invariable, the volume
Fig. 1. The appeared diffraction peak of Al2 O3 in these particles is at was read. Each result was got by the average value of three tested
the 2 position of 67.3◦ . The lowest intensity of Al2 O3 peak of Al-E results. The results of the volumetric measurement are listed in
means this type of particles has the thinnest coating layers as can Table 2.
be evidenced by Table 1. The morphologies and microstructures of To avoid the loss of H2 , the reaction must be initiated after
Al-E and Al-L are shown in Fig. 2. From Fig. 2 we can see that the tight sealing of the reactor vessel, because the most intense gas

Table 1
Characteristic of the tested ANPs.

Type Preparing method Shape Dm (nm) Tc (nm) Sp (m2 g−1 )

Al-E Electro-exploded wire Sphere 56.1 2–4 27.1

Al-P Plasma synthesized process Sphere 57.0 2–5 33.8
Al-L Laser heating evaporation Sphere, rod-like 51.9 3–5 45.7
Al-I Induction heating evaporation Sphere, rod-like 44.1 3–5 60.1
672 L. Chen et al. / Materials Chemistry and Physics 120 (2010) 670–675

Fig. 2. Morphologies and microstructures of the particles: (a) TEM image of Al-E, (b) HRTEM image for a single particle of Al-E, (c) TEM image of Al-L, (d) HRTEM image for a
single particle of Al-L.

release occurs at the first moment. A special reactor shown in Fig. 3 the measured Al content of the volumetric is lower than the real
was designed to exclude the contact of reagents before closing. value. The thicker Al2 O3 layers in the small particles prevent the
After sealing the reactor vessels, the reactor was tilted by clock- reaction between Al particles and NaOH solution, which makes the
wise rotation (as the arrow shows in Fig. 3) to trigger the reaction reaction uncompleted and thus makes the results lower than the
between ANPs and sodium hydroxide (NaOH). The amount of NaOH real value.
could be controlled by the rotation angle, and then the intensive
reaction became controllable. The use of a set of such facilities
was more convenient compared to standard equipment for serial
analyses.
In order to investigate whether the ANPs (take Al-E as an exam-
ple) reacted completely or not, the reacted solution was tested by
TEM (Fig. 4) after this measurement. As can be seen from Fig. 4,
particles with several nanometers in diameter (<10 nm) still exist
in the reacted solution. Further analysis using selected area elec-
tron diffraction (SAED) proves that the particles are unreacted Al
particles (Fig. 4, insert). Because there are unreacted Al particles,

Table 2
Results of the metallic Al content (wt.%) determined by different methods.

Type Volumetric Thermogravimetry Permanganatometric Modified

perman.

Al-E 75.75 70.58 74.40 90.75

Al-P 52.04 60.24 57.31 76.20
Al-L 52.51 52.43 52.02 74.54
Al-I 47.37 43.87 48.13 62.12 Fig. 3. The modified reactor for H2 generator in volumetric measurement.
 L. Chen et al. / Materials Chemistry and Physics 120 (2010) 670–675
Fig. 4. TEM images of the solution after volumetric measurement for Al-E (insert:
SAED of the unreacted particles).
3.3. Thermogravimetry measurement
When Al reacts with oxygen (O2 ), Al is oxidized into Al2 O3 , as
illustrated in the equation below. The mass of the original particles
increases because of the oxidation of Al.
4Al + 3O2 = 2Al2 O3
The mass of the ANPs reacted in the oxidation can be calculated
by the following formulation:
4 M
mAl = × Al mO2 = 1.125mO2
3 MO2
MAl and MO2 are formula weight of Al and O2 , respectively. In this
reaction, the mass of the reacted O2 is the mass gain of the sample,
i.e. mO2 = m. From the TG curves (Fig. 5), we can see that there is a
weight decrease (4–7%) in each TG curves from room temperature
to about 400 ◦ C because of the outgassing of the absorbed gas (car-
bon dioxide and water vapor) after preparation of the ANPs and the
mass percentage of the sample reaches its minimum value (define
it as  0 ). When the temperature increases, ANPs react with O2 and
Fig. 5. TG results of the ANPs in oxygen environment.
673
Fig. 6. XRD patterns of the particles (Al-E) after TG analysis.
the mass percentage of the sample increases to its maximum value
(define it as  f ) as the temperature reaches to 1000 ◦ C. The mass
percentage gain of the sample is  =  f −  0 , and then the content
of the metallic Al is calculated by this equation:
CAl (wt.%) = 1.125 = 1.125 (f − 0 )
Based on this equation, the results are calculated and listed in
Table 2. After TG analysis of the particles Al-E, the reacted powders
are collected and further tested by XRD and the result is shown in
Fig. 6. From Fig. 6, we can see that there are patterns that can be
indexed to metallic Al, which means that there are unreacted ANPs
remained in the collected powders after TG analysis. Al is also found
by XRD for the other powders after TGA. These results prove that
the TG measurement underestimates the Al content too.
The uncompleted oxidation of ANPs can be explained by the
two intensive mass gain stages phenomenon in each TG curve
(Fig. 5). The first intensive mass gain stage begins at 450 ◦ C and fin-
ishes at about 660 ◦ C. The second one ranges from 750 ◦ C to 900 ◦ C.
This two-stage mass gain phenomenon can be explained by the
mechanism of low temperature oxidation of ANPs. The low tem-
perature oxidation of Al particles occurs at least in two steps [21].
The first step, dominated by chemical kinetics, builds a layer (␥-
Al2 O3 and ␪-Al2 O3 ) of 6–10 nm thickness composed of crystallites
of the same size independent on the initial particle size. The sec-
ond step combines diffusion and chemical reaction and therefore,
proceeds slowly. The lower slope of the second mass gain stage
than the slope of the first one also proves that the second oxidation
step proceeds lower than the first one. As the aluminum oxide layer
grows, the diffusion of O2 into the core Al becomes difficult. When
the temperature reaches to 900 ◦ C, O2 cannot diffuse from the thick
layer into the core part and then the chemical reaction between Al
and O2 terminates.
3.4. Permanganatometric measurement
The permanganatometric method, as one of the indirect redox
titrations, has been successfully used to analyze both the virgin
micro-sized aluminum particles and the condensed combustion
products (in general, consisting of Al2 O3 and unburned Al). The
reaction principle for the permanganatometric measurement is
represented by the following equations.
Al + 3Fe3+ = Al3+ + 3Fe2+
5Fe2+ + MnO4 − + 8H+ = 5Fe3+ + Mn2+ + 4H2 O
674 L. Chen et al. / Materials Chemistry and Physics 120 (2010) 670–675

Precise weighed ANPs are oxidized by molysite (Fe3+ ) salt,

simultaneously the molysite (Fe3+ ) salt is partially deoxidized
to ferric (Fe2+ ) salt by the ANPs, and then acid potassium per-
manganate solution is used to titrate the amount of the ferric
(Fe2+ ) salt. The content of the metallic Al in ANPs is determined
by the amount of the acid potassium permanganate solution
and the mass of the ANPs samples. The results of the Al con-
tent determined by this method are listed in Table 2. Compared
with the results of the former methods, the results maintain
the same level, which means the permanganatometric method
based on aqueous solution underestimates the Al content too. The
nanoparticles behave as stronger reducing agent than the coarse
particles or the bulk samples and easily interact with the protons
of acids and water. The reaction between water in the aqueous
solution and the ANPs makes the results of Al content underes-
timated.
So how to exclude or reduce the influence of water to some
extent is the main problem to solve the underestimated results
in the titration method. Another problem that should be solved is
the existence of the alumina on the surface of each particle, which
hinders the reaction of metallic Al and the oxidant. In this paper, we
designed a novel permanganatometric method to determine the Al
content of ANPs. In this method, the main goals were to reduce the
amount of water in the solution and dissolve the alumina on the
surface of each particle. This method was realized by the following
three steps:
Step 1: Precise weighed of about 50 mg ANPs samples and about
5 g ferric nitrate (FeNO3 ) were added into 80 mL anhydrous
alcohol and then was stirred for about 2 h.
Step 2: 28 mL nitric acid (HNO3 ) at a concentration of 0.1 mol L−1
was added into the stirrer.
Step 3: Ten hours later, the metallic Al in the ANPs sample was oxi-
dized and reacted completely and then the reacted solution
was titrated by 0.1 mol L−1 acid potassium permanganate
(KMnO4 /H+ ).
The Step 1 is to mix the reducer ANPs and the oxidizer ferric
nitrate uniformly in the solvent anhydrous alcohol. In this step, the
redox reaction occurs partially because the ferric nitrate cannot
be ionized in the anhydrous solution. A cloud of alcohol molecular
above the solution because of the volatilization of the anhydrous
alcohol prevents the ANPs from oxidization by the oxygen in the air.
The diluted nitric acid plays an important role in the titration pro-
cess: firstly, water in the acid, which helps the ferric ions (Fe3+ )
ionize makes the redox reaction perform completely; secondly,
hydrogen ions (H+ ) dissolve the oxide coating layers to make the
internal aluminum oxidized more easily; Finally, the acidity of the
solution is a necessary for the potassium permanganate to improve
the oxidative–reductive potential in the following titration in Step
3. The amount and concentration of the nitric acid is important
in this method and they are related to the amount of the tested
ANPs samples. In our practice, 28 mL 0.1 mol L−1 is proper for the
50 g ANPs samples, otherwise, side reactions and poor repeatability
may occur.
The results determined by the modified permanganatometric
method are listed in Table 2. From Table 2 we can see that the
tested results are higher than the results tested by other methods,
especially the Al content of Al-E that reaches to 90.75%. Rietveld
refinement was used to perform the quantitative phase analysis
and then to prove the accuracy of the Al content of Al-E. Fig. 7
shows the Rietveld refinement of the X-ray diffraction data for
Al-E. The bottom line in the figure is the difference cure of the
intensity of observed profile subtracts calculated profile. The lit-
tle fluctuation of this difference cure shows the calculated profile
Fig. 7. Rietveld refinement results of Al-E.
is in good agreement with the experimental diffraction data. The
three agreement factors, Rp = 8.52, Rwp = 9.24, Rexp = 4.10, as well
as the reduced Chi2 = 5.07, mean the quality of the refinement
is good. The phase composition content (wt.%) determined by
the refinement is: 90.44% Al, 8.34% ␥-Al2 O3 and 1.22% Mg. This
Al content is in good agreement with the result of Al-E deter-
mined by the modified permanganatometric method in Table 2.
The Rietveld refinement method is a full pattern analysis method
in which all factors contributing to the intensity measured for
each 2 step may be simultaneously refined by a least-square pro-
cedure until the difference between the observed and calculated
pattern is minimized. This method provides a quantitative phase
analysis of much higher accuracy compared to any peak-intensity
based method [22–24]. The precondition for the refinement is
that all phases in the mixture are correctly determined and the
amorphous phase may make the refinement difficult [25]. The
phases in the ANPs are complicated to be determined because
the compositions of the ANPs vary with the preparing methods.
So it is important to develop other methods such as titration to
determine the Al content in ANPs. The Rietveld refinement in
turn can prove the correctness of the other determination meth-
ods.
4. Conclusions
The volumetric, thermogravimetry and conventional perman-
ganatometric methods estimates the metallic Al content in ANPs.
Anhydrous alcohol and ferric nitrate are used as solvent and oxi-
dizer, respectively in a new modified permanganatometric method
to eliminate the influence of water and other side reactions. Diluted
nitric acid solution plays an important role in this titration process.
The volume and concentration of the nitric acid depends on the
weight of the ANPs sample. The Al content of the ANPs determined
by this method is 15–20% higher than by the former ones. Espe-
cially, the Al content of ANPs produced by EEW reaches to 90.75%,
which is consistent with the quantitative phase analysis by Rietveld
refinement.
The modified permanganatometric method can be used to accu-
rately determine the Al content of ANPs. Only two parameters,
weight of the samples and amount of potassium permanganate,
should be precisely measured. The relatively short time require-
ment and the low cost of the titrants make this method a promising
titration method. Further work should be done to determine the Al
content of the ANPs passivated by other layers other than Al2 O3 or
 L. Chen et al. / Materials Chemistry and Physics 120 (2010) 670–675
even condensed combustion products and develop other methods
to verify the validity of this new method.
Acknowledgements
This work was funded by the National Natural Science Founda-
tion of China. We would like to thank Analytical and Testing Center,
Huazhong University of Science and Technology for the measure-
ments and analysis.
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