Mining Science and Technology (China) 21 (2011) 7e10

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Mining Science and Technology (China)

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

Method for grinding and delaminating muscovite

Shirleny Fontes Santos a, *, Silvia Cristina Alves Frana b, Tsuneharu Ogasawara b
a b

Metallurgical and Materials Department, Federal University of Rio de Janeiro, RJ 21941-972, Brazil Centre for Mineral Technology, RJ 21941-980, Brazil

a r t i c l e i n f o
Article history: Received 20 January 2010 Accepted 15 May 2010 Keywords: Muscovite Grinding Ultrasound treatment Mineral processing

a b s t r a c t
A method of dry grinding muscovite based on the use of knife-mills is reported. It was possible to produce mica with a particle size below 100 and 45 mm. After grinding, the samples were submitted to sonication treatment, which promoted delamination of the material. The particle size distribution shows that sonicated mica has more particles in the size range 10e50 mm than does non-sonicated mica have. This also indicates a decrease in the average particle size. Characterization of the treated muscovite by scanning electron microscopy revealed a highly delaminated material with a plate-like structure. The products were characterized by chemical analysis and X-ray diffraction, too. This mica has already been used for the synthesis of pearlescent pigments. Copyright 2011, China University of Mining & Technology. All rights reserved.

1. Introduction Muscovite, KAl2[Si3AlO10](OH,F2), is a mineral of the mica group with many industrial applications such as use in condensers, insulators, plastic llers and pearlescent pigments [1]. For many applications it is necessary to reduce the particle size of the natural raw materials [2]. Grinding, either in the dry state or in the presence of water and chemical additives, is the common procedure used for particle size reduction of these materials [3]. In the case of phyllosilicates (layered minerals) such as muscovite two processes are possible when the mineral is ground: delamination by cleavage of the crystal leading to new basal surfaces; or comminution perpendicular to the cleavage planes giving rise to new lateral surfaces [4]. However, it is known that some grinding processes (ball, bar, vibratory mills) produce not only particle size reduction but also other effects on laminar silicates. These effects include amorphization, aggregation or modication of surface properties and they occur because of the plate-like shape, exibility and lubricant nature of the mineral. This is why special mills (the chaser mill for wet-ground or the uid-energy mill for dry ground) and long periods of grinding are necessary for comminution of micas and other layered minerals. This results in high-cost nal products [5]. Recent studies have described the use of a knife-mill for particle size reduction of micas, however. These mills are cheaper and

easier to use than conventional ones. Knife-mills are generally used for grinding of materials possessing high plasticity because they reduce size by cutting, which does not alter the structure of the material. Furthermore, they do not use water or other liquids, which represents a saving in the process [6]. Many properties of muscovite improve proportionally to the degree of delamination, which is not a technically easy process and is usually only achieved by wet-grinding methods [5,7]. Sonication has been recently proposed for processing laminar silicates. The micron- and sub micron-sized particles obtained thereby retained the plate-like shape and the crystalline structure of the material [8,9]. The effects of sonication are believed to be due to cavitation phenomena. This can be dened as the formation of tiny bubbles lled with vapor/gas, or their mixture, and the subsequent growth, collapse and rebound of the bubbles in liquids. Fan et al. have reported that cavitation is an extremely complex physicochemical process inuenced by many factors such as surfactant concentration, dissolved oxygen content, dissolved carbon dioxide gas content and others [10]. In this paper we describe an alternate route for producing dry-ground muscovite using a knife-mill. Particles in the micron-sized range (100e45 mm) may be produced this way. We also present a sonication process to improve delamination.

2. Experimental 2.1. Materials

* Corresponding author. Tel.: 55 21 87745929. E-mail address: shirleny@uezo.rj.gov.br (S.F. Santos).

The muscovite used in this work came from the Borborema-Serido region (Northeast of Brazil) and consisted of 2 cm diameter platelets.

1674-5264/$ e see front matter Copyright 2011, China University of Mining & Technology. All rights reserved. doi:10.1016/j.mstc.2010.05.001

8 Table 1 Composition of the muscovite sample (%). Oxide SiO2 Al2O3 K2O Fe2O3 Na2O MgO Muscovite 46.37 38.35 11.67 1.88 0.40 0.25

S.F. Santos et al. / Mining Science and Technology (China) 21 (2011) 7e10

Theoretical value 45.4 38.5 11.8 e e e

a steel-coated laboratory knife-mill (EXPERT) equipped with four rotating knives was used. The material was ground in a batch circuit (50 g, 10 min) and dry sieved under 100e45 mm. The sonication procedure was performed with ultrasound equipment (sonics and materials) composed of a solid titanium rod connected to a piezoelectric element. A 20 kHz, 500 W power supply was used. In the sonication runs 5 g of <45 mm muscovite were mixed with 100 mL of distilled water for a period of 1 h. 2.3. Characterization methods

Intensity (u.a)

Muscovite (KAl2(Si3Al)O10(OH)2) (002) (024) (004) (029)

10

20

30

40 2

50

60

70

80

90

Fig. 1. X-ray diffraction of the muscovite sample.

Scanning electron microscopy of the samples was performed with a LEICA microscope. TGA (thermogravimetric analysis) and DTA (differential thermal analysis) were carried out in air with an automatic thermal analyzer system (TG/DTA INSTRUMENTS) at a heating rate of 10  C/min (25e1200  C). X-ray diffraction was done on a Bruker-AXS D5005 diffractometer at 35 kV and 40 mA with CuK radiation. The experimental patterns were compared with those calculated using PDF02 (ICDD, 1996) software. Particle size distribution was measured by a laser diffraction technique (Mastersizer 2000, Malvern Instruments) in aqueous suspensions. The chemical composition was determined by an X-ray uorescence technique with an S4 Bruker instrument.

2 100 99

exo

muscovite
610C 528C

0 -2 -4 -6

3. Results and discussion 3.1. Raw material characterization The elemental composition (by weight) of the muscovite is indicated in Table 1. The chemical composition of the sample is very close to that of pure muscovite [1]. X-ray diffraction analysis (Fig. 1) indicates that the structure of the sample is muscovite with a high degree of crystallinity. Additional characterization (MEV, EDS) revealed some impurities present in amounts too small to be detectable by X-ray diffraction. The TGA and DTA curves for the muscovite sample are shown in Fig. 2. Weight loss, 2a, begins at 610  C and nishes at 900  C, showing a total weight loss of 4.5% that corresponds to the expected value for the dehydroxylation of mica. The endotherm peak in the DTA curve corresponds to the same dehydroxylation process observed in the TG curve [11]. 3.2. Characterization of dry-ground material 3.2.1. First grinding (material smaller than 5 mm) The product of the rst step of grinding was analyzed by optical microscopy. As shown in Fig. 3a the micrograph revealed an intact plate-like structure with rounded aspect, but it was possible to verify the presence of impurity particles. So, the muscovite sample

TG (%)

(b)

DTA (V)

98 97 96 95 0 200 400

(a) 838C
600 800 1000

-8 -10

endo

Temperature (C)
Fig. 2. TG (a) and DTA (b) curves for the experimental muscovite.

2.2. Grinding conditions The rst step of the dry grinding process was performed with a steel-coated knife-mill (SEIBT A2/04) equipped with two rotating knives plus two xed knives. The material is fed into the knife-mill via a wide feeding chute. Size reduction takes place between the knives of the rotor and the stationary housing. The particle size of the reduced material is determined by the mesh of a screen installed at the bottom of the housing. The material was ground in an open circuit and sieved under 5 mm. After this step, the muscovite was concentrated by table gravity concentration (a wet method). In the second dry grinding step

Fig. 3. Analysis on product by optical microscopy. (a) Muscovite after the rst step of grinding (b) Tailings from tabling.

S.F. Santos et al. / Mining Science and Technology (China) 21 (2011) 7e10

Fig. 4. Muscovite structure projected on the (010) plane.

10 8

Volume (%)

6 4 2 0 0,1 1

d(0,1)= 13,31m d(0,5)= 34,53m d(0,9)= 71,11m

10 100 1000 Particle Size (m)

10000

Fig. 5. Particle size distribution of the muscovite sample.

an Al3 ion producing a total negative charge in the layer. This negative charge is compensated by a K cation located between the two layers. This facilitates the perfect cleavage through basal plane, as can be seen in Fig. 4 [3]. Due to this structural conguration friction forces and impact during ne grinding can destroy or alter the platelets of the mica while reducing their size. A process of grinding by cutting could minimize the attrition and impact forces, as was observed for the rst step of grinding. Hence, the material from the primary grinding in the knife-mill was re-ground in a second knife-mill (laboratory scale) appropriate for obtaining a ne particle size (45e100 mm). This method yielded material about 67% of which was smaller than 100 mm and 36% of which was below 45 mm in size. Fig. 5a shows the particle size distribution of this ground muscovite. Fig. 6a illustrates the morphology of the ground mica produced in the laboratory knife-mill. The plate-like structure can be easily recognized despite the very tiny particle size. These results indicate that a knife-mill does not produce morphological or structural damage. This was conrmed by the X-ray diffraction patterns of these samples (not shown). For comparison, Fig. 6bed shows other muscovite samples ground using other comminution methods. These micrographs illustrate that reducing the particle size in a ball mill or a vibratory mill does not retain the plate-like shape of the original mica (Fig. 6c and d). In a bar mill, Fig. 6d, the plate-like structure was maintained but the platelets did not delaminate. Besides, the three products from alternate grinding methods were completely opaque while the product from the laboratory knife-mill is bright and transparent mica, as expected [5]. 3.2.3. Delamination Morphologic analysis revealed that the thickness of the muscovite was between 1.0 and 5.0 mm. However for many applications a mica thickness around 500 nm is requested [5]. The ground muscovite sample was treated with ultrasound using the method previously described. Characterization of this material by scanning electron microscopy conrmed the existence of ner platelets with a thickness between 0.5 and 1.0 mm, Fig. 7. The sonicated mica was also evaluated in terms of particle size, see Fig. 8. Sonicated mica has a larger volume of particles falling in the

was submitted to table gravity concentration before the second grinding step. The highest efciency tabling gravity concentration split the sample into two parts: 98.5% (by weight) of almost pure muscovite and 1.5% (by weight) of impurities. Fig. 3b shows quartz, iron oxides and tourmalines in the tailings, as conrmed by X-ray diffraction (not shown). 3.2.2. Second grinding (material smaller than 100 and 45 mm) The muscovite chemical structure is a superposition of tetrahedral SiO4 sheets and octahedral sheets containing hexacoordinate Al3 ions. One Si4 out of four in the tetrahedral sheets is replaced by

Fig. 6. SEM Micrograph of muscovite dry ground in different mills. (a) A knife-mill; (b) A ball mill; (c) A vibratory mill; (d) A bar mill.

10

S.F. Santos et al. / Mining Science and Technology (China) 21 (2011) 7e10

Fig. 7. SEM Micrograph of sonicated muscovite.

Volume (%)

10 8 6 4 2 0 10 8 6 4 2 0

Non sonicated muscovite

without morphologic or structure alterations. These alterations often occur when other dry grinding methods are used. 2) We also veried the applicability of sonication as a delamination treatment for muscovite. This treatment decreased 1.0e5.0 mm thick muscovite to a thickness of 0.5e1.0 mm. This mica has already been used for preparing pearlescent pigments. Acknowledgments The authors are grateful to CNPq for the nancial support and to CETEM/MCT and COPPE/UFRJ for the laboratorial facilities.

20

40

60

80

100

120

Sonicated muscovite

20

40

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100

120

References
[1] Barlow SG, Manning AC. Inuence of time and temperature on reactions and transformations of muscovite mica. British Ceramic Transactions 1999;98 (3):122e6. [2] Prez-Rodrguez JL, Wiewira A, Drapala J, Prez-Maqueda LA. The effect of sonication on dioctahedral and trioctahedral micas. Ultrasonics Sonochemistry 2006;13(1):61e7. [3] Papirer E, Eckhardt A, Muller F, Yvon J. Grinding of muscovite: inuence of the grinding medium. Journal of Materials Science 1990;25(12):5109e17. [4] Balard H, Aouadj O, Papirer E. Monitoring, by inverse gas chromatography, of the variation of the surface energetic heterogeneity of ground muscovite samples. Langmuir 1997;13:1251e5. [5] Kogel JE, Trivedi NC, Barker JM, Krukowski ST. Industrial minerals and rocks: commodities, markets and uses. Washington: SME; 2006. [6] Docar M. Knife mill for use in grinding of material, has rotor rotationally xed to its housing with specic angle and at rotor knife with different inclination. European Patent: WO2007011316eA2, WO2007011316-A3; 2007. [7] Kobayashi M, Ishimori R, Senna T. Delamination of sericite into thin platelets in the presence of titania sol. Journal of Materials Science Letters 1998;17:789e93. [8] Poli AL, Batista T, Schmitt CC. Effect of sonication on the particle size of montmorillonite clays. Journal of Colloid and Interface Science 2008;325 (2):386e90. [9] Wiewiora A, Perez-Rodriguez JL, Perez-Maqueda LA. Particle size distribution in sonicated high and low charge vermiculites. Applied Clay Science 2003;24 (1/2):51e8. [10] Fan M, Tao D, Honaker R, Luo Z. Nanobubble generation and its application in froth otation (part I): nanobubble generation and its effects on properties of microbubble and millimeter scale bubble solutions. Mining Science and Technology 2010;20(1):1e19. [11] Schomburg J, Zwahr H. Thermal differential diagnosis of mica mineral group. Journal of Thermal Analysis 1997;48(1):135e9. [12] Franco F, Perez-Maqueda LA, Perez-Rodriguez JL. The effect of ultrasound on the particle size and structural disorder of a well-ordered kaolinite. Journal of Colloid and Interface Science 2004;274(1):107e17. [13] Wang JH, Chen QR, Kuang YL, Lynch AJ, Zhuo JR. Grinding process within vertical roller mills: experiment and simulation. Mining Science and Technology 2009;19(1):97e101. [14] Hao XD, Zhu DM, Bian ZR, Wang X. Numerical analysis of grinding power consumption of a vertical planetary mill. Journal of China University of Mining & Technology 2008;18(2):311e5.

Particle size distribution (m)

Fig. 8. Particle size distribution.

size range between 10e50 mm than does non-sonicated mica. This also indicates a decrease in particle size. Preservation of the crystalline phase was veried by X-ray diffraction. These results indicate that sonication is a useful method for delamination of mica. This mica was used for synthesis of pigments, an application which needs mica platelets as ne as 500 nm, but only after ultrasound treatment could the pigments be obtained. The efcacy of sonication is probably related to the formation of vapor bubbles and gases (cavitation phenomena). Compression stages (positive pressure) and expansion stages (negative pressure) occur during production of ultrasound, which generates the cavities. Gases adsorbed in the pores of the particles are compressed to the interior of the particle in the compression stage and, in the expansion stage, those gases or vapor bubbles are expelled from the particle. However, the bubbles are not all totally expelled, resulting in an effective increase of the cavity size [12e14]. In the case of the micas, it is believed that generation of those cavities at the interface of the perpendicular direction of the cleavage plane of the material could be the decisive factor for separation of the platelets.

4. Conclusions 1) It was possible to develop an alternative route for dry grinding muscovite using knife-mills. Comminution by cutting was shown to efciently produce material with a size below 100 mm