Powder Technology 153 (2005) 153 158 www.elsevier.

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Preparation and properties of composite mineral powders

Guo-Sheng Gaia, Yu-Fen Yanga,b,*, Shi-Min Fana, Zhen-Fang Caia
b

Powder Technology R&D Group, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China School of Chemistry and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China Received 27 October 2003; received in revised form 28 March 2005

Abstract Mineral powders such as ground calcium carbonate (GCC) and wollastonite are widely used as fillers in plastics, rubber, paper, paints and other fields. The interface compatibility between the polymer matrix and the mineral particles is relatively weak, both because of the smooth cleavage surface and the sharp particle edges formed during pulverizing. It is beneficial therefore to modify the surface properties of mineral powders before they are used in a polymer composite. In this paper, we report the successful preparation of composite mineral particles, coated by nanoparticles of calcium carbonate of 20 100 nm particle size, by chemical reaction using the Ca(OH)2 H2O CO2 system. The degree of nanoparticle coverage can reach 100% if the operating parameters are effectively controlled, and the specific surface area can be increased to three times the value before modification. Mechanical testing of polypropylene containing composite wollastonite powder as a filler shows an increase in the impact strength of 65% compared to similar samples prepared using conventional filler powder. D 2005 Elsevier B.V. All rights reserved.
Keywords: Mineral powders; Nanometer calcium carbonate; Coating; Surface modification

1. Introduction China has a plentiful supply of industrial minerals such as ground calcium carbonate (GCC), talcum, kaolin, glimmer, wollastonite and dolomite. Among these, GCC and wollastonite are widely used as fillers in plastics, rubber and paints. Extensive supplies of GCC ores are found widely throughout China, and wollastonite reserves of up to 200 million tons exist in China, the highest figure in the world [1,2]. However, because of limitations in processing technology, the interface compatibility between GCC and wollastonite filler powders and the polymer matrices in which they are used is often inadequate. Several common surface modification technologies, involving addition of either coupling-agents or surfactants followed by mechanical mixing, have been widely used to
* Corresponding author. School of Chemistry and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China. Tel.: +86 10 62781144; fax: +86 10 62791258. E-mail address: yangyufen@mail.tsinghua.edu.cn (Y.-F. Yang). 0032-5910/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.powtec.2005.03.013

modify the surface properties of these powders, and these techniques are well developed. However, the sharp edges and the smooth cleavage surfaces formed during pulverizing cannot be modified using these methods. These intrinsic defects can provide nucleation sites for failure of composite polymer-based materials, and the existence of such defects therefore has a direct effect on the amount of mineral powder that can be filled into a given composite material [3]. Technology for the nanosurface coating of mineral powders has been developed by the Powder Technology R&D Group, Department of Material Science and Engineering, Tsinghua University (patents applied for). The idea is to use a chemical reaction to deposit nanosized particles of calcium carbonate on the surface of micron-sized particles of GCC or wollastonite. The composite particles formed by the depositing or coating not only possess the same dispersive properties as the original mineral particles, but also possess outstanding characteristics due to the nanoparticles on the surface. The technology allows a series of new and valuable methods for the preparation of mineral powders.

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2. Experiment 2.1. Materials The GCC powders, with average size grain 5.200 Am, were supplied by Shandong LuFen Hongda Cement Co. Ltd. Wollastonite powders with 4.890 Am of average particle size, supplied by the Beijing Guoli Ultrafine Powder Company, were used. Lime from Beijing Fangshan lime factory was used. Polypropylene (PP) was sourced from the 3rd. chemical plant of Beijing Yanshan Petroleum Chemical Corporation (product Nos. P1340 and K8303). MgCl2 was used to increase ion concentration and the reaction velocity; hexa-poly-partial atrium phosphate was used to control crystal type, and sucrose was used as a dispersing agent. All these products, as well as the pure CO2 gas used in the experiments, were bought from standard commercial sources. 2.2. Experimental units The test device has a processing capacity of 2 kg/h, and the pilot installation in our lab has a 3050 kg/h capacity, respectively. The specific conductance meter (DDS-307) used in the system was made by Shanghai Lenci Instrument Factory. The standard pH instrument (Basic pH Meter PB20) used was produced by the Germany Saduolixi Stock Company. 2.3. Chemical and physical analyses A JSM-6301F (JEOL, Japan) scanning electron microscope (SEM) was used to observe the surface morphology of mineral particles before and after coating, and to observe the morphology of the fracture surface of compound polypropylene (PP) materials produced using different filler powders. The specific surface area was determined from the nitrogen adsorption data by the BET method, using a NOVA4000 high-speed automatic surface area analyzer. An ultrasonic vibrator (JY96-II, made by the Shanghai Xinzi Biotechnology Research Institute and the Ningbo Xinzi Science Instrument Research Institute) was used to assess the bonding strength between the nanoparticles and the core particles. Tensile testing equipment (LJ-1000) and impact test equipment (JB6/3), purchased from the Guangzhou Material Testing Machine Factory, were used to test the mechanical properties of compound PP materials produced using either original mineral powders or composite mineral powders.

fixed amounts and concentrations of GCC or wollastonite powder and either lime cream or Ca(OH)2 solution to the reactor, the slurry was stirred for 10 15 min to ensure homogeneous mixing. Next, a mixture of air and carbon dioxide was injected into the reactor. During this step, the slurry was continuously stirred to ensure uniform gas liquid solid mixing. In this system, carbon dioxide reacts with calcium hydroxide resulting in nanoparticles of calcium carbonate which are deposited on the surface of the larger GCC or wollastonite particles. The Ca(OH)2 H2O CO2 system comprises the following reactions: CaOH2 sYCa2 aq 2OH aq CO2 gYCO2 aq CO2 aq OH aqYHCO aq
HCO aq OH aqYH2 O CO2 3 aq Ca2 aq CO2 3 aqYCaCO3 s

1 2 3 4 5

According to the principle of heterogeneous nucleation, the CaCO3 nanoparticles directly nucleate and grow on the surface of micron-sized GCC or wollastonite particles. During heterogeneous nucleation, the micron-sized host/ core particle can be taken as the nucleation core. According to the thermodynamics of phase transformation, the relation* ship between the heterogeneous nucleation free energy DG h * and the homogeneous nucleation free energy DG r is as follows [4,5]: DG h 16pc3 LS 3DGv 2 2 cosh1 cosh2 DG r f h 4

3. Surface coating mechanism Preparation of the composite mineral particles was done using the Ca(OH)2 H2O CO2 system. After addition of

where c LS is the liquid solid interface energy; DG v is the free energy change per unit volume [6]; h is the contact angle between the new-phase crystal-nucleus and the base of the host particle such that f ( h ) is equal to (2 + cosh )(1 cosh )2/4. In general, h ranges from 0- to * 180-, and f (h ) ranges from 0 to 1. Consequently DG h is * always less than DG r . The smaller the value of h , the * smaller will be the value of DG h , and therefore the easier the heterogeneous nucleation. The process of heterogeneous nucleation is one of reactants deposition, nucleation and growth on the coated particles [7,8]. Heterogeneous nucleation is promoted in cases where the atom arrangements are similar in both the coating and the substrate materials. XRD analyses show that the reactants, nanoparticles of calcium carbonate, easily deposit, nucleate and grow on GCC or wollastonite particle surfaces, because they have a similar crystalline structure to both of these materials. Nucleation of nanoparticles of calcium carbonate on GCC or wollastonite particle surfaces is therefore thermodynamically easy.

G.-S. Gai et al. / Powder Technology 153 (2005) 153 158 Table 1 Special surface area of mineral powders before and after coating Samples Special surface area (m2/g) Before coating Wollastonite GCC 1.74 0.66 After coating in pilot installation 7.36 2.06

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4. Results and discussion 4.1. Surface morphology of particles In order to prepare different kinds of composite particles, several parameters must be effectively controlled and adjusted during the reaction. These parameters include the concentration, the gas flow rate, the quantity and average size of the mineral powders, the temperature and the mixing intensity [9,10]. Composite GCC or wollastonite particles coated by nanoparticles of calcium carbonate have successfully been prepared in the experimental pilot production unit under suitable operating conditions. For production of composite GCC material, the conditions used were GCC/ Ca(OH)2 weight ratio of 10:1, CO2/air flow ratio of 3:7, 28 -C slurry temperature and 400 r/min stirring speed. Composite wollastonite powders were prepared under similar conditions. It is important to note that formation reaction of nanometer CaCO3 stops when the pH value of the slurry reaches 7. For the given conditions, the reaction lasted about 15 20 min. After the reaction was completed, the slurry was filtered and solid material was dried using an oven or a spray dryer. SEM photomicrographs showing the surface morphology of the mineral particles before and after coating in the pilot installation are given in Fig. 1. It can be seen from Fig. 1(a) and (c) that the degree of coverage is close to 100%. The nanoparticles of calcium carbonate coated on the surface of

After coating in test device 3.53 8.16 1.47 1.98

Note: Results provided by the Monitoring and Inspection Center of the State Inorganic Salt Quality of Product in Tianjin.

the GCC or wollastonite particles have sizes in the range of 20 100 nm. Compared with the uncoated GCC (Fig. 1(b)) or wollastonite (Fig. 1(d)), the nanoparticle-coated (composite) mineral particles possess blunt edges and a rough surface: the sharp edges and the smooth surface caused by pulverizing have thus been transformed. 4.2. Specific surface area The BET method was used to measure the specific surface area of the powders before and after coating. The results, given in Table 1, show that the specific surface area of composite GCC powder is three times greater than that of the original powder, and that the specific surface area of composite wollastonite powder is four times greater than that of the original powder. Compared to the original powders, the composite mineral powders can be expected to

Fig. 1. SEM photographs of surface morphology of mineral particle before and after coating.

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Fig. 2. SEM photographs of surface morphology of composite mineral powders after oscillation testing.

have a better contact interface with the polymer matrix when used as a filler material, on account of their larger specific surface areas. 4.3. Bonding strength of composite particles In order to examine the bonding strength between the coating particles and the coated material, a slurry of each composite powder was put into a supersonic oscillator,

operated at a power of 400 W. SEM photomicrographs showing the surface morphology of the composite GCC and composite wollastonite particles after 8 min oscillation time are given in Fig. 2. The specific surface areas of the particles following the oscillation testing were 1.83 m2/g and 6.45 m2/g, for the GCC and wollastonite samples, respectively. It can be seen from Fig. 2 that no obvious separation of nanoparticles from the core particles takes place. This observation shows that the coating particles are strongly

6000

intensity (cps)

wollastonite calcite 4000

2000

0 10 20 30 40 50 60 70 80

2 (degree)

(a) XRD pattern of composite wollastonite powder

10000 calcite

intensity (cps)
0 10 20 30 40 50 60 70 80

2 (degree)

(b) XRD pattern of composite GCC powder

Fig. 3. XRD patterns of the composite mineral powders.

G.-S. Gai et al. / Powder Technology 153 (2005) 153 158 Table 2 Mechanical properties of composite PP materials filled with different powders Samples Properties Tensile strength (MPa) Filling wollastonite powders Pure PP (K8303) 24.69 Composite wollastonite 22.65 Original wollastonite 21.32 Filling GCC powders Pure PP (P1340) Composite GCC Original GCC Impact strength (J/m) 256.34 235.58 140.98 Tensile elongation (%) 286 260 80 Bending modulus (MPa) 2250 3590 3950 Young modulus (MPa) / 62.31 61.22

157

Bending strength (Mpa) 52.81 55.66 51.73

25.2 23.6 20.8

254.5 191.8 149.6

570 560 520

935.0 1110.9 /

496.7 549.6 519.6

26.3 28.6 28.3

adhered to the core particles. The coating particles would, however, be detached from the core particles following 400 W supersonic oscillation if the adhesion between them was only a physical one. 4.4. XRD analyses XRD patterns (Fig. 3) show that the coating material for both the composite GCC and wollastonite particles is a calcium carbonate component, which has the same hexagonal structure as calcite (card No. 50586), as indicated by , 2.285 A and the characteristic diffraction peaks at 3.036 A 2.095 A. The strongest peak is at 3.036 A. 4.5. Mechanical properties of compound PP materials To compare their filling properties, wollastonite and GCC powders, both in the before and after coating conditions, were used to produce different compound polypropylene (PP) materials. The powder:PP filling ratio in each case was fixed at 30:100. It can be seen from Table 2 that the mechanical properties of compound PP materials using composite powder fillers are better than those of PP materials produced using the original untreated powders. The results confirm that the composite mineral powders have a better interfacial compatibility with the PP matrix compared to the original powders. The tensile elongation of PP composites filled using the composite wollastonite powder is three times greater than that of similar composites filled using the original untreated wollastonite powder. Similarly, the impact strength of PP materials produced using composite powders was increased by as much as 65%. Such improvements may be attributable to the rough surface and large surface area of the composite mineral powders following coating of calcium carbonate nanoparticles on the surface of the original powders.

a chemical method. The degree of nanoparticle coverage can reach 100% if the operating parameters are effectively controlled. (2) Compared with the original/untreated powders, the specific surface area of the composite GCC powders is increased by 300%. For the composite wollastonite powders, the specific surface area is increased by 400%. (3) The nanometer-sized calcium carbonate particles coated on the surface of the larger original mineral particles possess the same hexagonal structure as calcite. (4) Supersonic oscillating experiments show that the coating particles are strongly adhered to the surface of the core original mineral particles. (5) The mechanical properties of compound PP material containing composite GCC or wollastonite powders are improved compared to those containing the original mineral powders. (6) The production capacity has been successfully increased, from 2 kg/h in a test device to 30 50 kg/ h in a pilot installation.

Acknowledgement Financial support for this work provided by the National Natural Science Foundation of China (project number 50474003) is gratefully acknowledged. The authors would also like give special thanks to Miss Xu Li and Mr. Liu Hongda for their contribution to our research work, and to Prof. A. Godfrey for assistance with proof-reading of the text.

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