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Powder Technology 203 (2010) 389396

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Powder Technology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p ow t e c

Optimized experimental design for natural clinoptilolite zeolite ball milling to produce nano powders
Amir Charkhi a, Hossein Kazemian b,c,, Mohammad Kazemeini a
a b c

Chemical & Petroleum Eng. Department, Sharif University of Technology, Tehran, Iran SPAG Zeolite R&D Group. Technology Incubation Centre, Science and Technology Park of Tehran University, Tehran, Iran Department of Chemical and Biochemical Engineering, Faculty of Engineering, The University of Western Ontario, London, Ontario, Canada N6A 5B9

a r t i c l e

i n f o

a b s t r a c t
Nano powder of natural clinoptilolite zeolite was mechanically prepared by using a planetary ball mill. Statistical experimental design was applied to optimize wet and dry milling of clinoptilolite zeolite. To determine appropriate milling conditions with respect to the nal product crystallinity, particle size and distribution, different milling parameters such as dry and wet milling durations, rotational speed, balls to powder ratio and water to powder ratio (for the wet milling) were investigated. Laser beam scattering technique, scanning electron microscopy and X-ray diffraction analyses were carried out to characterize samples. Results showed that larger than 1 mm particle size of clinoptilolite powder may mechanically be reduced into the size range of less than 100 nm to 30 m by means of planetary ball milling. 2010 Elsevier B.V. All rights reserved.

Article history: Received 29 June 2009 Received in revised form 11 December 2009 Accepted 27 May 2010 Available online 4 June 2010 Keywords: Experimental design Planetary ball mill Natural zeolite nano powder Clinoptilolite

1. Introduction Zeolites are valuable inorganic materials having wide variety of applications including; molecular sieves, adsorbents, ion-exchangers and catalysts. These materials are microporous crystalline hydrated alumino-silicates composed of TO4 tetrahedral (T = Si, Al) with O atoms connecting neighboring tetrahedral in which the substitution of silicon by aluminum in framework positions leaves a negative charge behind which in turn may be compensated by some alkali or alkaline earth cations[14]. Nowadays, more than 150 different types of zeolites have been synthesized while more than 50 types have been discovered in the nature. Amongst natural zeolites; clinoptilolite, with the simpli ed ideal formula of (Na, K)6Si30Al6O72 nH2O; is one of the most commonly found mainly in sedimentary rocks of volcanic origin. Clinoptilolite-rich tuff is commercially very favorable due to its huge and easy mineable resources as well as, its high zeolite content. This well known zeolite may be utilized for purication and separation processes, removal of NH+ 4 and heavy cations from contaminated water and wastewater, aquaculture, soil fertilizers

Corresponding author. Department of Chemical and Biochemical Engineering, Faculty of Engineering, The University of Western Ontario, London, Ontario, Canada N6A 5B9. Tel.: +1(519) 661 2111x82209. E-mail addresses: Hossein.kazemian@uwo.ca, hosseinkazemian@gmail.com (H. Kazemian). 0032-5910/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.powtec.2010.05.034

and conditioners as well as, for dietary supplement in animal nutrition[410]. Recently there has been a considerable growing interest in utilizing nanozeolites due to their advantages over conventional micron sized materials. In other words, the reduction of the particle size of zeolites causes larger external surface areas available for interaction, shorter diffusion path lengths reducing mass and heat transfer resistances in catalytic and sorption applications, decreasing of side reactions, enhancing selectivity as well as, lowering tendencies to coke formation in some catalytic reactions. Up to now many different methods for synthesis of nanozeolites have been reported. All of these are based upon hydrothermal treatments which is performed by adjusting effective parameters such as temperature, process duration and ingredient concentrations in order to increase number of durable nuclei and reduce crystal growth [1]. It is reminded, however, that longer synthesis duration, expensive starting materials (specially organic template), lack of reproducibility of the synthesis processes and energy consumption for separation of nano powders by mean of high speed centrifugation are some main issues making the bottom-up chemical synthesis of nanozeolites techno-economically unviable processes [11]. As an alternative technique, the zeolite particle size may be reduced mechanically using specially designed ball mills [1217]. In previous researches, production of different synthetic zeolites such as Y, X, A, L, ZSM-5 and mordenite was considered utilizing this method [1217] where possible changes of milled zeolite characteristics when subjected to dry ball milling were well

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Table 1 Variable parameters and their level in designed experiments in this study. Level Milling Balls to speed powder (rpm) ratio in wet milling (wt.%) 1 2 3 4 450 500 550 600 4.5 5 9 Ball to powder ratio in dry milling ( No./weight) 0.1 0.2 Wet Milling period of time (h) 2 3 4 Dry milling period of time (min) 10 20 Water to Powder ratio (vol/weight) 1 1.2 1.5 3

investigated. However, results have ascertained that high energy ball milling, decreased the size of aforementioned zeolites. Furthermore, the XRD patterns revealed that the crystallinity of the milled zeolites was also reduced. Thus, collapse of the zeolite crystal structure renders them useless as molecular sieves, adsorbents or shape selective catalysts. In order to overcome this crystallinity problem, wet ball milling of the HY zeolite was investigated. Previous results indicated that by omitting the dry milling step, the crystalline structure of the ground HY zeolite did not collapse completely, even at long milling durations [13]. Furthermore, higher energy ef ciencies, lower magnitude of excess enthalpies and elimination of dust formation may also be mentioned as some other added advantages of grinding in aqueous compared to dry medium [13]. In order to evaluate the possibility of production of natural clinoptilolite nano-particles, in this study a combination of wet and dry milling was investigated using a planetary ball mill. To optimize grinding conditions, effective parameters were selected and several sets of experiments were designed based upon statistical methods. Zeolites were milled at different periods of time, milling speed, balls to powder and water to powder ratios. Characteristics of nal products such as particle size and distribution as well as, crystallinity of samples were examined by Laser particle size analyzer, scanning electron microscopy (SEM) and Xray diffraction (XRD) techniques. 2. Experimental section 2.1. Ball milling of clinoptilolite zeolite Powders of natural zeolite (clinoptilolite-rich tuff) were obtained from a mine located in north of Iran near the city of Semnan. Ball milling of clinoptilolite zeolite was performed by mean of a planetary ball mill (PM100; Retsch Corporation). To optimize the milling conditions with respect to size reduction and crystallinity retention, milling parameters such as rotational speed, ball to powder and water to powder ratios as well as, grinding time were varied for different experiments. In most of the

performed tests a clinoptilolite powder with particle size of larger than 1 mm was utilized as the starting material in dry milling for a time period of about 1020 min. The wet milling in water media was then carried out at different periods of time between 2 to 4 h. All of the tests were done in a 250 ml stainless steel jar with protective jacket of zirconium oxide. Zirconium oxide balls of 20 and 3 mm were utilized for dry and wet millings; respectively. The grinding jars were arranged eccentrically on the sun wheel of the planetary ball mill. The direction of movement of the sun wheel being opposite to that of grinding jars was selected with the ratio of 1:1. A certain amount of zeolite and balls as well as, water in wet milling were placed in the jar at room temperature and atmospheric pressure then sealed and imposed to milling. Due to lack of appropriate accessories to control the temperature and pressure of the jar during grinding , sampling was carried out at the end of this period, at which time the jar was allowed to be cooled down to room temperature. For characterization step the ground powders was dried at 30 C for 24 h. 2.2. Design of experiments Different sorts of experiments were designed in order to optimize the appropriate milling conditions for the production of natural clinoptilolite nano-powders with higher crystallinity and lower particle size and distributions. Selected variable parameters and their levels are provided in Table 1. For convenience, the shorthand nomenclature of a, b, c, d, e, f, and g were assigned in which, (a) the dry milling speed, (b) the dry milling time, (c) the ball to powder ratio for dry state, (d) the wet milling speed, (e) the wet milling time, (f) the balls to powders ratio for the wet state and nally (g) the water to powder ratio; were set. Moreover, different conditions for each experiment are presented in this table. 2.3. Characterization The ground clinoptilolite zeolite was characterized with different instrumental techniques. The morphology of the ground powders as well as its size studied by means of Scanning Electron Microscopy utilizing a LEO 1455vp SEM instrument. XRD patterns to evaluate the crystallinity of the ground powders determined by mean of a STOE STAD-MP Diffractometer in which a copper target at 40 kV and 30 mA (2 h b 10_) followed. Furthermore, Particle size measurements of the ground samples performed by laser beam scattering technique through means of a Master sizer 2000 apparatus (MALNERN Instruments). 3. Result and discussion In order to investigate the effect of different ball milling conditions on size distribution of the ground clinoptilolite zeolite,

Table 2 Different conditions of designed experiments in this research. No. code Dry milling Zeolite powder amount (g) 1 2 3 4 5 6 7 8 9 10 3223311 4224311 3223313 4223313 3112221 0001322 2121233 3121234 3111213 3212113 50 50 50 50 100 0 50 50 100 100 Ball No. 10 10 10 10 10 0 10 10 10 10 Rotational speed (rpm) 550 600 550 600 550 0 500 550 550 550 Duration (min) 20 20 20 20 10 0 10 10 10 20 Wet milling Zeolite amount (g) 50 50 50 50 100 100 50 50 100 100 Balls weight (g) 225 225 225 225 500 500 450 450 450 450 Rotational speed (rpm) 550 600 550 550 450 450 450 450 450 500 Water volume (cm3) 50 50 75 75 100 120 50 150 150 150 Duration (h) 4 4 4 4 3 4 3 3 3 2

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Fig. 1. Volume particle size distribution at different milling condition (experiments 1 and 3; see Table 2.).

volume mean size and the size span were studied. The span is a measure of the size distribution, which may be dened as follow: Span = d0:9d0:1=d0:5 1

where d(0.1), d(0.5) and d(0.9) represent sizes for which 10, 50 and 90% by volume of particles in ground samples are smaller than these sizes, respectively. It is to be noted that smaller span corresponds to narrower size distribution. The particle size distribution of ground zeolite powders milled according to conditions provided in Table 2 and measured by means of laser beam scattering demonstrated in Fig. 1. By utilizing these results, the span was calculated and shown in Fig. 2. The volume weighted mean size and d(0.1) are also shown in Figs. 3

Fig. 3. Variation of volume weighted mean size in designed experiments.

Fig. 2. Variation of span in designed experiments.

Fig. 4. Variation of d(0.1) in designed experiments.

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and 4; respectively. The d(0.1) results indicate that through utilizing planetary ball mill, production of submicron powders is possible and at different ball milling conditions this value may be varied between 0.56 and 2 m for natural clinoptilolite zeolite with initial size of larger than 1 mm. The volume mean sizes of these samples were also changed in the range of 3.3 to 15 m. In order to evaluate the inuence of each factor on the volume weighted mean size and span, an arithmetic calculation was

carried out. The average effect of each level of variable parameters was calculated by averaging the results of those experiments which were carried out at that level. For example, to calculate the average effect of second level of wet speed milling (500 rpm), results of all experiments which were performed at that rotation speed under wet condition (results of 311-2221 and 321-2113 experiments) were averaged. Results of these calculations are displayed in Figs. 5 and 6. Data in Fig. 5 indicated that an increase in

Fig. 5. Inuences of milling conditions on volume weighted mean size.

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rotational speed under dry conditions caused initially a decrease in volume mean size of ground zeolite while at faster speed of 600 rpm, this value increased again. Moreover, increasing of the milling time as well as, ball to powder ratio under dry conditions caused an enhancement in the volume mean size of ground powders. On the other hand, increasing of the rotational speed from 450 to 550 rpm under wet conditions, decreased the volume mean size; while, at a little bit higher speed of 600 rpm, the volume

mean size started to rise again. In addition, the reduction in water to powder ratio caused lowering of volume mean size. Ultimately, form the data in Fig. 5, it is a foregone conclusion that the volume mean size increased due to the raised ball to powder ratio. It may further be concluded that for production of clinoptilolite powders with the smallest volume mean size, planetary ball milling should be performed at 1) for dry conditions: i- milling speed of 550 rpm, ii- milling time of 10 min and iii- 5 balls of 20 mm per 50 g of

Fig. 6. Inuences of milling conditions on span.

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powders and 2) for wet conditions: i- milling speed of 500 rpm, iiball to powder weight ratio of 4.5, iii- water to powder ratio of 1 (e.g.; 50 g of water per 50 g of zeolite) and iv- milling time of 3 h. It is emphasized through Fig. 6 that increased in milling speed, time and balls to powder ratio caused a raise in the span of ground powders. Furthermore, it is seen that amongst parameters studied, the rotation speed variations had the most inuence on this span. On the other hand, increase in speed and time of wet milling led to a wider span. From this gure, it also is understood that increased ball to powder and water to powder ratio under wet milling makes narrower span. To study probable changes of morphology for ground powders after ball milling as well as to conrm the PSA results, samples were subjected to SEM investigation. Some of the SEM images of ground samples are shown in Fig. 7. SEM images indicated that almost in all samples, zeolite powder with particles size less than 100 nm may be recognized as a separated particle or in the form of larger agglomerates. Moreover most particles have lost their initial octahedral shape and converted into spherical, elliptical or irregular shapes. By careful considerations of SEM images, some crystals with sharp edges and clean surfaces observed; which are about 200 nm in size. Therefore, it may be concluded that careful selection of milling conditions may result in production of nano clinoptilolite zeolite with desirable crystalline structure. Nevertheless, mechanical production of zeolitic nano-particles by mean of planetary ball mills may also reduce zeolite crystallinity. As mentioned in a previous study [14], milling at high speed and prolonged time resulted in collapsed crystalline structure of

ground zeolite. Therefore, apart from size distribution, the crystallinity study of ground powders is also very important when a choice for appropriate conditions for ball milling of clinoptilolite samples has to be made. Patterns of XRD for all samples were obtained and some of them are displayed in Fig. 8. Results showed the increase in time and rotational speed of milling caused reduction in crystallinity. In the ground clinoptilolite samples, major peak observed at 2 equal to 22.49o. With regards to the intensity ratio of aforementioned peak in original parent clinoptilolite to the ground samples, crystallinity reduction due to the milling processes was calculated. Results are provided in Table 3. In order to determine best milling conditions amongst those mentioned in Table 2 above, the following normalized expression; so-called objective function (O.F.), dened to give each experiment a weight for this purpose as a result. The biggest O.F., thus, indicated best milling conditions in which highest crystallinity retained while smallest volume mean size and narrowest size distribution also obtained. The weighting factor for each term of this expression selected according to its importance for these authors. It is given by:

 O:F : = 1

Vol weighted Mean Max Vol weighted Mean

 0:35 + 1

 Span 2 Max Span

0:15 + 0:5 Crystalinity:

Fig. 7. SEM images of original and ground clinoptilolite zeolite.

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Furthermore, results of experiment 000-1322 in Table 2 designed under wet conditions indicated that omitting dry milling may cause an enhancement in crystallinity. This issue may be explained in terms of the following mechanism. Different methods of grinding may impose different forces upon particles, such as compression, shear, attrition, impact or internal forces [18]. In ball milling, the grinding of samples is carried out by balls which are swept along by the wall and then fall onto the load. The fragmentation of particles in samples results from the stress, which may be due to compression or shear, imposed upon the bed of particles by the balls. It has been proposed that wet grinding causes shearing along the cleavage planes whereas dry grinding fractures the crystals [13,19]. It has also been suggested that wet grinding proceeds with the preferential formation of new surfaces while little bulk deformation takes place in the particles [13,20]. Thus, crystallinities of zeolite samples obtained by wet ball milling were considerably larger than those prepared by the dry counterpart. On the other hand, amorphization of crystalline zeolites may be attributed to breaking the structural SiOSi and SiOAl bonds and collapsing of the original crystal structure under the action of intensive mechanical forces [1417] mainly occurring at the dry stage.

4. Conclusion In this work the possibility of production of nano clinoptilolite zeolite by mean of a planetary ball mill utilizing a combination of wet and dry conditions was investigated. Statistical experimental design incorporated in order to optimize the effect of key parameters. Results revealed that by application of appropriate milling conditions obtained in this study, clinoptilolite powders with particle sizes less than 100 nm and desirable crystallinity may be produced. Nevertheless this method led to a wide size distribution of ground powders in the range of less than 100 nm to 30 m and crystallinity loss of about 55100%. Furthermore, based upon experiments performed under wet milling conditions in this work, it may be concluded that under certain situations one may go thru wet milling without any needs for dry milling pretreatments.

Fig. 8. XRD patterns of a) original clinoptilolite zeolite and b) milled clinoptilolite zeolite under condition of experiments 311-2221, c) 422-4311 and d) 321-2113.

As shown in Table 3, best milling conditions belonged to experiment No. 7 with sample code of 311-2221. It meant that choosing following conditions for milling of clinoptilolite gives the best result with respect to crystallinity and size distribution. These included; for dry milling i)milling speed of 550 rpm, ii) milling duration of 10 min and iii) balls to powder ratio of 0.1 and for wet milling; i) rotational speed of 500 rpm, ii) milling duration of 3 h, iii) ball to powder ratio of 4.5 and iv) water to powder ratio of 1. To nd the inuence of different levels of milling parameter on crystallinity, a simple arithmetic calculation similar to what was done previously for size distribution performed. Results showed that the increase in milling time and speed under dry and wet conditions caused crystallinity to reduce. In addition, for maintaining the crystallinity, the second level of ball to powder and water to powder ratios in wet milling had to be selected.

Acknowledgments The Authors acknowledge Dr. Azizollah Kamalzadeh from the Institute of Scientic-Applied Higher Education of Jihad_e_Agriculture of Iran and Animal Sciences Research Institute in Karaj, Iran, for providing the ball mill equipment. The authors have declared no conict of interest.

Table 3 Milling results in terms of size distribution, crystallinity and dened objective function. No. Exp. 5 6 7 4 9 10 1 3 8 2
a

Code 3112221 0001322 2121233 4223313 3111213 3212113 3223311 3223313 3121234 4224311

d(0.1) (m) 0.849 1.601 1.199 0.559 1.448 0.746 0.8 0.675 1.904 0.85

d(0.5) (m) 2.462 3.814 7.935 4.514 8.093 6.687 5.347 7.944 8.728 4.65

d(0.9) (m) 6.72 8.059 20.03 20.496 22.91 20.911 23.37 31.418 35.628 38.265

Volume weighted mean size (m) 3.309 4.41 9.598 8.074 10.763 9.078 9.466 12.622 15.005 13.378

span 2.384 1.693 2.373 4.417 2.65 3.015 4.221 3.87 3.864 8.046

Crystallinitya 0.45 0.45 0.38 0.33 0.38 0.28 0.30 0.28 0.38 0

O.F. 0.604 0.591 0.419 0.392 0.387 0.370 0.351 0.271 0.265 0.038

Normalized O.F. 1.000 0.979 0.694 0.649 0.641 0.612 0.580 0.449 0.440 0.063

crystallinity is the ratio of major intensity of ground sample to original Clinoptilolite zeolite.

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396 A. Charkhi et al. / Powder Technology 203 (2010) 389396 [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] F.A. Mumpton, P.H. Fishman, J. Anim. Sci. 45 (1977) 1188. K.T. Matin, D. Bastani, H. Kazemian, Chem Eng. Technol. 32 (7) (2009) 1. J. Xie, S. Kaliaguine, Appl. Catal.: A 148 (1997) 415. K. Akcay, A. Sirkecioglu, M. Tather, O.T. Savasci, A. Erdem-Senatalar, Powder Technol. 142 (2004) 121. P.A. Zielinski, A. van Neste, D.B. Akolekar, Micropor. Mater. 5 (1995) 123. C. Kosanovic, et al., Zeolites 15 (1995) 247. A.S. Kharitonov, et al., Zeolites 15 (1995) 253. C. Kosanovic, B. Subotic, A. Cizmek, Therm. Acta 276 (1996) 91. C. Frances, N. Le Bolay, K. Belaroui, M.N. Pons, Int. J.Miner. Process. 61 (2001) 41. G. Suraj, C.S.P. Iyer, S. Rugmini, M. Lalithambika, Appl. Clay Sci. 12 (1997) 111. D. Feng, C. Aldrich, Int. J. Miner. Process. 60 (2000) 115.

References
[1] L. Tosheva, V.P. Valtchev, Chem. Mater. 17 (2005) 2494. [2] R.M. Milton, Molecular Sieves, Soc. of Chem. Ind. London (1968). [3] D.W. Breck, Zeolite Molecular Sieves: Structure, Chemistry and Uses, John Wiley & Sons, New York, 1974. [4] J.D. Sherman, Proc. Natl. Acad. Sci. (PNAS), USA 96 (7) (1999) 3471. [5] H. Kazemian, M.H. Mallah, Iran. J. Chem. Chem. Eng. 25 (4) (2006) 91. [6] A. Ansari Mahabadi, M.A. Hajabbasi, H. Kazemian and H. Khademi, Geoderma 137 (34) (2007) 388. [7] S.J. Shahtaheri, H. Kazemian, R. Menhaje-Bena, Studies in Surface Science and Catalysis, 154 B, 2004, p. 1892. [8] H. Faghihian, H. Kazemian, Iranian J Sci. Technol. 26 (A2) (2002) 357. [9] H. Asilian, S.B. Mortazavi, H. Kazemian, S. Phaghiehzaadeh, S.J. Shahtaheri, M. Salem, Iranian J. Public Health 33 (1) (2004) 45.