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Materials Chemistry and Physics: Research On The Methods To Determine Metallic Aluminum Content in Aluminum Nanoparticles
Materials Chemistry and Physics: Research On The Methods To Determine Metallic Aluminum Content in Aluminum Nanoparticles
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 (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-
Aluminum nanoparticles (ANPs) have a promising application lic Al in the raw particles, thus cannot be neglected. The existing
in propellants, explosives and pyrotechnics, which can add energy of this oxide layer and the high reactivity of the nanoparticles add
to the burning reaction in propellants and enhance the blast effect complexity to the determination of Al content for the virgin ANPs.
of explosives, as well as their underwater performance. A decrease To date, however, a main problem that has not been solved prop-
in particle size causes changes in the specific surface of the powder, erly in the application of ANPs is the determination of metallic Al
its structure, and phase composition. Especially when it comes to content in ANPs.
nano-scale, a large amount of aluminum (Al) atoms are on the sur- Many methods, such as volumetric and reductant–oxidant
face of the particle and it is easy to react with the environmental titration (e.g. permanganatometric), were investigated and made
atmosphere, oxygen, steam and carbon dioxide [1–3]. As a result, triumph in determining the Al content for the conventional micron-
the reactivity of ANPs is very high, and the oxidation and com- sized Al particles [18]. However, when they are used to analyze
bustion of them proceed in a manner differing from that of the ANPs, unsatisfactory results were obtained because of the high
micro-sized particles [4–7]. reactivity of the particles. The high reactivity caused early oxida-
A variety of techniques are developed to produce ANPs, includ- tion before their melting point (660 ◦ C) [19], which can be used
ing electro-exploded wire [8–10], plasma synthesized process [11], to estimate the Al content by themogravimetry analysis. A ceri-
wet chemical [12,13] and heating evaporation [14,15]. Whatever metric method [20] was also experienced to determine the Al
the method of production, the ANPs are subjected to passivation content but the high cost of the cerium (IV) sulphate as well as
to ensure their stability. The passivation involves the treatment of the difficulty to precisely determine the amount of the cerium (IV)
surface with either gaseous or liquid reagents that form a protec- sulphate consumed in the titration hindered the development of
tive layer [16,17]. In the simple and common case, this can be an this method. In this paper, modified volumetric, thermogravime-
oxide layer of a core-shell structure: the shell layer aluminum oxide 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
∗ Corresponding author at: State Key Lab of Materials Forming Simulation and Die
to find out the reasons that caused the underestimated results.
and Mould Technology, Huazhong University of Science and Technology, Wuhan
430074, PR China. Tel.: +86 27 87557453; fax: +86 27 87557453. Based on these measurements, a novel modified permanganato-
E-mail address: wulins@126.com (W. Song). 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
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.
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.
Fig. 5. TG results of the ANPs in oxygen environment. 5Fe2+ + MnO4 − + 8H+ = 5Fe3+ + Mn2+ + 4H2 O
674 L. Chen et al. / Materials Chemistry and Physics 120 (2010) 670–675
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