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Materials Chemistry and Physics 120 (2010) 670675

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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 b c

State Key Lab of Materials Forming Simulation and Die and Mould Technology, Huazhong University of Science and Technology, Wuhan 430074, PR China Material Structure Department, Changjiang River Scientic Research Institute, Wuhan 430010, PR China 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
The high reactivity of aluminum nanoparticles (ANPs) made the determination of their metallic aluminum (Al) content difcult. Volumetric, thermogravimetry and permanganatometric methods were utilized to determine Al content. The reacted solution after volumetric measurement was further studied by 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) pattern of the powders after thermogravimetry analysis (TGA). The side reactions between ANPs and water made the result of permanganatometric measurement underestimated as by the former methods. A modied titration method, using anhydrous alcohol as solvent, was performed to reduce the inuence of water. The Al content of the ANPs produced by electro-exploded wire using this method was consistent with the quantitative phase analysis by Rietveld renement. 2009 Elsevier B.V. All rights reserved.

Article history: Received 17 July 2009 Received in revised form 6 December 2009 Accepted 15 December 2009 Keywords: Aluminum Nanoparticles Reactivity Metallic content Rietveld renement

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 specic 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 surface of the particle and it is easy to react with the environmental atmosphere, oxygen, steam and carbon dioxide [13]. As a result, the reactivity of ANPs is very high, and the oxidation and combustion of them proceed in a manner differing from that of the micro-sized particles [47]. A variety of techniques are developed to produce ANPs, including electro-exploded wire [810], 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 protective 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: (W. Song). 0254-0584/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2009.12.030

(Al2 O3 ) (25 nm in thickness) coats the core Al tightly. This oxide layer decreases the reactivity as well as the percentage of metallic 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 properly in the application of ANPs is the determination of metallic Al content in ANPs. Many methods, such as volumetric and reductantoxidant titration (e.g. permanganatometric), were investigated and made triumph in determining the Al content for the conventional micronsized 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 oxidation before their melting point (660 C) [19], which can be used to estimate the Al content by themogravimetry analysis. A cerimetric method [20] was also experienced to determine the Al content but the high cost of the cerium (IV) sulphate as well as the difculty to precisely determine the amount of the cerium (IV) sulphate consumed in the titration hindered the development of this method. In this paper, modied volumetric, thermogravimetry 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 nd out the reasons that caused the underestimated results. Based on these measurements, a novel modied permanganatometric method which used low concentration of aqueous solution

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was applied to measure the Al content of these ANPs. Quantitative phase analysis using Rietveld renement 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 synthesized process, got from Shandong Origine Nanomaterials Engineering Co., Ltd., China. Al-L and Al-I were experimental particles produced by laser heating evaporation and induction heating evaporation, respectively. The microstructures of these particles were examined by transmission electron microscope (TEM) (Tecnai G2 20, FEI, 200 KV), eld emission scanning electron microscope (FESEM) (Sirion 2000, FEI, 10 KV), BrunnerEmmettTeller (BET) method and X-ray diffraction (XRD). The volumetric method was based on the measurement of the hydrogen volume 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 L1 ). The volume of released H2 was measured by displacement volume of the water. Atmospheric pressure, room temperature and the temperature of the sealing water were measured. Thermogravimetry method was realized on TG-DTA equipment with a PerkinElmer TG/DTA 6300 thermal analysis system, which has an upper limit heating rate of 100 C min1 . The equipment consists of a pair of horizontal electro-balances, with a 0.1 g of resolution, a furnace and sensors of temperature, connected to a computer, using the Muse version 5.4 U thermal analysis systems. The crucibles used were 70 L alumina ones. The samples were heated at a rate of 10 C min1 from room temperature to 1000 C in dry oxygen (99.995%) atmosphere, with a gas ow of about 50 mL min1 . The conventional permanganatometric and a modied one were used as the reductant-oxidant titration method to analysis the Al content. In the conventional 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 2 h. The reacted solution was titrated by 0.1 mol L1 acid potassium permanganate. The X-ray diffraction data were measured over the scattering 2 angle range 1090 with 50 s per step (step-size 0.0167 ) using Cu K radiation ( k 1 = 1.54056 , k 2 = 1.54440 ) with a graphite monochromator in the reection geometry at 25 C (XPert PRO, PANalytical B.V.). The quantitative phase analysis based on Rietveld renement was also performed to prove the accuracy of the modied titration. Rietveld renement was carried out with FullProf program using a pseudoVoigt function with one Gaussian and one Lorentzian coefcient as the proles model.

Fig. 1. X-ray diffraction patterns of ANPs.

particles of Al-E are sphere (Fig. 2a) and have a core-shell structure (Fig. 2b): Al in core with Al2 O3 layer (24 nm) as shell part. There is metallic magnesium (Mg) not be oxidized in the Al-E sample. Mg may be formed as solid solution atoms in Al particles through explosion of the raw material wires. The Al2 O3 layer prevents Mg and Al to be further oxidized. Besides the sphere particles, there are rod-like ones in the sample of Al-L (Fig. 2c). This type of particles also has the core-shell structure, but the shell part is 35 nm (Fig. 2d). There is a certain amount of Ag in the sample of Al-P. The contents of Al2 O3 are higher in samples of Al-L and Al-I, which is consistent with the TEM observation of the thicker coating layers. There is Si as an impurity phase in the sample of Al-I introduced in the production process. 3.2. Volumetric measurement The reaction involved in this measurement is followed by the reaction below: 2Al + 2NaOH + 2H2 O = 2NaAlO2 + 3H2 The content of the metallic ANPs is calculated by the volume of generated hydrogen (H2 ) using the formula below. Here and below, mass percent values are used. CAl (wt.%) = (P1 P2 P3 )VK 100% mT

3. Results and discussion 3.1. Microstructure characterization Characteristic of the four types of Al2 O3 passivated ANPs is listed in Table 1. The mean diameter (Dm ) was calculated by XRD pattern with an MDI jade 5.0 software assistant with TEM and FESEM observation, the thickness of the coating layers (Tc ) was examined by the high resolution TEM (HRTEM), the specic surface area (Sp ) was tested by the BET method. As can be seen from Table 1, the mean diameters of the particles are around 50 nm and the particles of Al-I have the smallest particles. The specic surface area increases with the decrease of the mean particle diameter of the particles. XRD patterns of the four types of particles are shown in Fig. 1. The appeared diffraction peak of Al2 O3 in these particles is at the 2 position of 67.3 . The lowest intensity of Al2 O3 peak of Al-E means this type of particles has the thinnest coating layers as can be evidenced by Table 1. The morphologies and microstructures of Al-E and Al-L are shown in Fig. 2. From Fig. 2 we can see that the
Table 1 Characteristic of the tested ANPs. Type Al-E Al-P Al-L Al-I Preparing method Electro-exploded wire Plasma synthesized process Laser heating evaporation Induction heating evaporation Shape

P1 atmospheric pressure, Pa; P2 saturated water vapor pressure at T K, Pa; P3 temperature correction value of atmospheric pressure, Pa; V volume of generated H2 , L; T temperature of the sealing water, K; m mass of the sample, kg; K conversion coefcient, 2.88 104 . The duration of the analysis is about 10 h. When the volume of the generated H2 kept invariable, the volume was read. Each result was got by the average value of three tested results. The results of the volumetric measurement are listed in Table 2. To avoid the loss of H2 , the reaction must be initiated after tight sealing of the reactor vessel, because the most intense gas

Dm (nm) 56.1 57.0 51.9 44.1

Tc (nm) 24 25 35 35

Sp (m2 g1 ) 27.1 33.8 45.7 60.1

Sphere Sphere Sphere, rod-like Sphere, rod-like


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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 rst moment. A special reactor shown in Fig. 3 was designed to exclude the contact of reagents before closing. After sealing the reactor vessels, the reactor was tilted by clockwise rotation (as the arrow shows in Fig. 3) to trigger the reaction between ANPs and sodium hydroxide (NaOH). The amount of NaOH 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 example) 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 electron 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 Al-E Al-P Al-L Al-I Volumetric 75.75 52.04 52.51 47.37 Thermogravimetry 70.58 60.24 52.43 43.87 Permanganatometric 74.40 57.31 52.02 48.13 Modied perman. 90.75 76.20 74.54 62.12

the measured Al content of the volumetric is lower than the real value. The thicker Al2 O3 layers in the small particles prevent the reaction between Al particles and NaOH solution, which makes the reaction uncompleted and thus makes the results lower than the real value.

Fig. 3. The modied reactor for H2 generator in volumetric measurement.

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Fig. 6. XRD patterns of the particles (Al-E) after TG analysis.

Fig. 4. TEM images of the solution after volumetric measurement for Al-E (insert: SAED of the unreacted particles).

the mass percentage of the sample increases to its maximum value (dene 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 (

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: mAl = 4 M 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 (47%) in each TG curves from room temperature to about 400 C because of the outgassing of the absorbed gas (carbon dioxide and water vapor) after preparation of the ANPs and the mass percentage of the sample reaches its minimum value (dene it as 0 ). When the temperature increases, ANPs react with O2 and

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 rst intensive mass gain stage begins at 450 C and nishes 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 temperature oxidation of Al particles occurs at least in two steps [21]. The rst step, dominated by chemical kinetics, builds a layer ( Al2 O3 and -Al2 O3 ) of 610 nm thickness composed of crystallites of the same size independent on the initial particle size. The second step combines diffusion and chemical reaction and therefore, proceeds slowly. The lower slope of the second mass gain stage than the slope of the rst one also proves that the second oxidation step proceeds lower than the rst one. As the aluminum oxide layer grows, the diffusion of O2 into the core Al becomes difcult. 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+

Fig. 5. TG results of the ANPs in oxygen environment.

5Fe2+ + MnO4 + 8H+ = 5Fe3+ + Mn2+ + 4H2 O


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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 permanganate 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 content 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 underestimated. So how to exclude or reduce the inuence 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 L1 was added into the stirrer. Step 3: Ten hours later, the metallic Al in the ANPs sample was oxidized and reacted completely and then the reacted solution was titrated by 0.1 mol L1 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 process: rstly, 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 oxidativereductive 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 L1 is proper for the 50 g ANPs samples, otherwise, side reactions and poor repeatability may occur. The results determined by the modied 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 renement 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 renement of the X-ray diffraction data for Al-E. The bottom line in the gure is the difference cure of the intensity of observed prole subtracts calculated prole. The little uctuation of this difference cure shows the calculated prole

Fig. 7. Rietveld renement 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 renement is good. The phase composition content (wt.%) determined by the renement 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 determined by the modied permanganatometric method in Table 2. The Rietveld renement method is a full pattern analysis method in which all factors contributing to the intensity measured for each 2 step may be simultaneously rened by a least-square procedure 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 [2224]. The precondition for the renement is that all phases in the mixture are correctly determined and the amorphous phase may make the renement difcult [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 renement in turn can prove the correctness of the other determination methods. 4. Conclusions The volumetric, thermogravimetry and conventional permanganatometric methods estimates the metallic Al content in ANPs. Anhydrous alcohol and ferric nitrate are used as solvent and oxidizer, respectively in a new modied permanganatometric method to eliminate the inuence 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 1520% higher than by the former ones. Especially, the Al content of ANPs produced by EEW reaches to 90.75%, which is consistent with the quantitative phase analysis by Rietveld renement. The modied permanganatometric method can be used to accurately 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 requirement 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

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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 Foundation of China. We would like to thank Analytical and Testing Center, Huazhong University of Science and Technology for the measurements and analysis. References
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