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International Journal of Mineral s, Metallurgy and Materials Volume 16, Number 5, October 2009, Page

International Journal of Minerals, Metallurgy and Materials Volume 16, Number 5, October 2009, Page 592

Materials

Preparation of calcium carbonate particles coated with titanium dioxide

Hai Lin, Ying-bo Dong, and Le-yong Jiang

School of Civil and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China (Received 2008-12-23)

Abstract: The preparation of a new mineral composite material, calcium carbonate particles coated with titanium dioxide, was stud- ied. The mechanism of the preparation process was proposed. The new mineral composite material was made by the mechanochemi- cal method under the optimum condition that the mass ratio of calcium carbonate particles to titanium dioxide was 6.5:3.5. The mass ratios of two different types of titanium dioxide (anatase to rutile) and grinding media to grinded materials were 8:2 and 4:1 respec- tively, and the modified density was 60%. Under this condition, the new material was capable of forming after 120-min modification. The hiding power and oil absorption of this new material were 29.12 g/m 2 and 23.30%, respectively. The results show that the modi- fication is based on surface hydroxylation. After coating with titanium dioxide, the hiding power of calcium carbonate can be im- proved greatly. The new mineral composite materials can be used as the substitute for titanium dioxide.

Key words: calcium carbonate; mechano-chemical process; titanium dioxide film; hydroxylation

1. Introduction

Titanium dioxide (TiO 2 ) is of relevance to a num- ber of industrial products including dope, plastics, pa- per, printing ink, rubber, chemical fiber, and cosmet- ics. In recent years, the imbalance between the supply and demand of TiO 2 is more intensive because of the increasing demand of it [1]. More research is needed on TiO 2 , especially on looking for the substitute of it to reduce the cost. In the United States, Britain, Ger- many, Japan, and other industrialized countries, scien- tists began this work from the 1970s and gained great economic benefit. At present, this work is still in the primary stage in China, and the product performance is poor which can only replace 10%-30% of TiO 2 . The main reason is that the hiding power of the product is very low.

At present there are many reports on the organic modification of calcium carbonate (CaCO 3 ), but the inorganic modification reports are few at home and abroad. The modification of CaCO 3 is coating TiO 2 on the surface of CaCO 3 particles to improve the hiding power of CaCO 3 according to the application re- quirement. In this work, TiO 2 particles were used to coat on the surface of CaCO 3 particles by the mech- anochemical modification method. The best coating conditions were determined, and the hiding powers of

Corresponding author: Hai Lin, E-mail: linhai@ces.ustb.edu.cn © 2009 University of Science and Technology Beijing. All rights reserved.

CaCO 3 before and after modification were tested re- spectively. The study aims to use cheap CaCO 3 in- stead of expensive TiO 2 .

2. Experimental procedure

2.1. Material

Anatase TiO 2 was provided by Panzhihua Titanium Dioxide Plant in Sichuan Province, China. The per- formance of the sample was: blue-ray whiteness, 93%; particle size, 2 μm 93.66%; d 50 , 1.02 μm; specific area, 64155.65 cm 2 /cm 3 ; oil absorption value, 24.94%; hiding power, 21.16 g/m 2 .

Rutile TiO 2 (semi-finished products) was supplied by Shanghai Xinrun Limited Company. The perform- ance of the sample was: blue-ray whiteness, 88%; par- ticle size, 2 μm 92.29%; d 50 , 1.07 μm; specific area, 61492.57 cm 2 /cm 3 ; oil absorption value, 24.16%; hid- ing power, 17.47 g/m 2 .

Different CaCO 3 samples were bought from Guangxi, Guangdong, Benxi, and Shanghai. The whiteness of the samples were above 93% (blue-ray brightness), and the oil absorption values and the size of these samples were different.

Dispersant CHFS210M used for producing the ma-

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H. Lin et al., Preparation of calcium carbonate particles coated with titanium dioxide

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terials was supplied by CHI HE Chemical Engineering Limited Company, China.

2.2. Method

A SDF-400 sand mill was used to prepare the modified product. A certain amount of CaCO 3 (as the core), water, grinding medium, and dispersant CHFS210M were added in the sand mill and the CaCO 3 was grinded until its particle size reached 2 μm 90%. Then TiO 2 was added in the SDF-400 sand mill and the core and TiO 2 were grinded together by the mechanochemical method until their particle size reached 2 μm 90%. The final modified products were obtained by medium draining, filtration, and drying.

2.3. Index testing

Coating effects, hiding power, and oil absorption value are the most important indexes reflecting the

performance of the white material, which were tested

in this work.

Coating effects were evaluated by transmission electron microscopy (TEM). The core in the single

modified particle, the morphology, and the thickness of the TiO 2 film could be observed clearly by TEM. In this test, the coating product acquired under the opti- mum modifying conditions was used for TEM analy- sis. After the treatment by the “ultrafine particles ion-shear method”, the coating product was tested by

a HITACHI model H-800 transmission electron mi-

croscopy with a 0.204-nm resolution and a PV9100/75 spectrometer.

The modified effect usually can be evaluated by hiding power and oil absorption values. In this work, the hiding powder and oil absorption were tested ac- cording to GB1709-79 [2] and GB1712-79 [3], re- spectively.

3. Results and discussion

This work aims to coat TiO 2 evenly on the surface of ultra-fine CaCO 3 particles through mechani- cal-chemical modification and make the coated CaCO 3 particles have the performance of TiO 2 . The production conditions were optimized to get the best performance in this work.

3.1. Type of ground calcium carbonate (GCC) test

In this work, CaCO 3 with the size of 43 μm were from different regions. The size, hiding power, and oil absorption value of CaCO 3 from different regions were different. To obtain the best performance, CaCO 3 should be in a certain size, neither too fine nor too big.

To study the effect of different types of GCC on coating, four different CaCO 3 were used in the work. The experimental result is shown in Figs. 1 and 2. The particle sizes of four different products are up to 2 μm 90% after 90-min modification and have met the requirements of the paint filler. Comparing the four products, the hiding power of the GCC from Guangxi is the highest, 32.80 g/m 2 , followed by the GCC from Guangdong and Shanghai. The hiding power of the GCC from Benxi is the lowest, 34.25 g/m 2 . For the oil absorption value, the GCC from Guangxi has the lowest, 23.35%. Therefore, the GCC from Guangxi is the best core according to the performance of the products.

the best core according to the performance of the products. Fig. 1. Effect of different types

Fig. 1. Effect of different types of CaCO 3 on the hiding power of modified products.

of CaCO 3 on the hiding power of modified products. Fig. 2. Effect of different types

Fig. 2. Effect of different types of CaCO 3 on the oil ab- sorption of modified products.

3.2. Mass ratio of CaCO 3 to TiO 2

This test was to study the effect of different mass ratios of CaCO 3 to TiO 2 . The experiments were done in the same modification conditions except the mass ratios. The result is shown in Fig. 3.

except the mass ratios. The result is shown in Fig. 3. Fig. 3. the hiding power

Fig. 3.

the hiding power and oil absorption of modified products.

Effect of different mass ratios of CaCO 3 to TiO 2 on

Fig. 3 shows that when the mass ratio of CaCO 3 to TiO 2 is low, the hiding power is low and the oil ab- sorption value is high, which are unfavorable. In the modification system, if the core material is too much it will lead to the coating process incompletely, and if the core material is too little it will increase not only

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International Journal of Minerals, Metallurgy and Materials, Vol.16, No.5, Oct 2009

the costs, but also the oil absorption value. Consider- ing the cost, the product index, and other factors, the mass ratio of CaCO 3 to TiO 2 should be 6.5:3.5. At this mass ratio, the hiding power is 32.00 g/m 2 and the oil absorption value is 22.50%.

3.3. Modified concentration

The slurry concentration is a key factor in the modification process. Too high or too low concentra- tions are unfavorable for coating.

The effect of slurry concentration on the coating is shown in Fig. 4. The hiding power and the oil absorp- tion value both decreases at first and then increases. When the concentration is 60%, the hiding power reaches 31.30 g/m 2 and the oil absorption value is the minimum (22.44%). In addition, the product size test- ing shows that in the concentrations of 50% and 55%, the percent of the particle size of 2 m is lower than that of the product obtained in the concentrations of 60% and 65%. In these four different concentrations, the particle size of the final product can reach 2 μm 93%. This size has met its requirement as the paint filler. The result suggests that the optimal modified concentration is 60%.

suggests that the optimal modified concentration is 60%. Fig. 4. Effect of modified concentration of the

Fig. 4. Effect of modified concentration of the hiding power and oil absorption of modified products.

3.4. Time for modification

Time for modification is another important factor. Modification for a short time will be incomplete. Too long time modification would lead to the aggregates of fine particles, which would deteriorate the modifica- tion efficiency. In the same grinding and modified conditions, the effect of modification time on the coat- ing is shown in Fig. 5.

of modification time on the coat- ing is shown in Fig. 5. Fig.5. oil absorption of

Fig.5.

oil absorption of modified products.

Effect of modification time on the hiding power and

The result shows that when the modification time is 120 min, the hiding power and oil absorption of the product have optimal values. With 120-min modifica- tion, the hiding power and oil absorption value of the modification product are 30.48 g/m 2 and 22.37%, re- spectively.

3.5. Mass ratio of grinding media to grinded mate-

rials

The mass ratio of media to materials refers to the mass ratio of grinding media to slurry materials. This mass ratio reflects the contact opportunity among me- diums and grinding materials [4]. In the system of agitation mill, if the loadings of grinding mediums and materials can be effectively driven by a churn-dasher, the grinding efficiency will be proportion to the ratio of mediums to materials. The smaller the ratio, the less the contact opportunities among the materials and mediums. On the contrary, when the mass ratio of mediums to materials is high, the grinding effect will be good [5]. When the mass of grinding media is ex- cess, the loadings of the grinding medium and materi- als are too high to be driven by a churn-dasher, and the contact opportunities among grinding mediums will decrease, which can lead to low grinding effi- ciency [6]. Fig. 6 shows the effect of the mass ratio of mediums to materials. When the ratio is 4:1, the hid- ing power is the lowest (30.00 g/m 2 ), the lowest oil absorption value is 22.44%. This suggests that the mass ratio should be 4:1.

22.44% . This suggests that the mass ratio should be 4:1. Fig. 6. Effect of the

Fig. 6. Effect of the mass ratio of grinding media to mate- rials on the hiding power and oil absorption of modified products.

3.6. Mass ratio of anatase TiO 2 to rutile TiO 2

Anatase and rutile titanium dioxides were used as the coating materials in the experiment. The hiding power of rutile TiO 2 is better than that of anatase TiO 2 . The hiding power of the products can be improved if more rutile TiO 2 is used.

The effect of mass ratio of anatase TiO 2 to rutile TiO 2 on the coating is shown in Fig. 7. The experi- ment was done in the same grinding and modification conditions. The hiding power is better when the pro- portion of rutile TiO 2 increases. However, the oil ab- sorption value is higher and the cost is higher. The

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595

mechanical force is the main reason leading to surface modification. Mechanochemical variation of the coat- ing material during the grinding process is the main reason leading to the different effects of modification. In addition, the result of the size analysis test shows that the content ( 2 μm) of modified products can be 93% at least after 90-min modification. So the ratio of anatase TiO 2 to rutile TiO 2 has little effect on the ul- timate size of products. Therefore, the mass ratio of anatase TiO 2 to rutile TiO 2 is more important than the hiding power and the oil absorption value. Taking the product performance and the cost into account, the most suitable condition is 4:1 for the ratio of anatase TiO 2 to rutile TiO 2 where the hiding power is 29.12 g/m 2 and the oil absorption value is 23.30%.

is 29.12 g/m 2 and the oil absorption value is 23.30%. Fig. 7. Effect of different

Fig. 7. Effect of different mass ratios of anatase TiO 2 to rutile TiO 2 on hiding power and oil absorption of modified products.

3.7. Coating effect and performance evaluation

A TEM image of the coating material is shown in Fig. 8. The results of the energy spectra of the core and the coating film are shown in Figs. 9-10. The pic- tures show that there is a TiO 2 layer on the surface of CaCO 3 particles. The layer of TiO 2 is uniform and dense.

3 particles. The layer of TiO 2 is uniform and dense. Fig. 8. TEM image of

Fig. 8.

TEM image of the coating materials.

Through the optimization of influencing factors, the hiding power and the oil absorption value of modified products can reach 29.12 g/m 2 and 23.00%, respec- tively, and the content of 2 μm particles is 93.32%. The performance indexes of CaCO 3 , the final product

on the coating, and TiO 2 are shown in Table 1. The result shows that CaCO 3 after modification can be used to substitute some TiO 2 .

modification can be used to substitute some TiO 2 . Fig. 9. TEM energy spectrum of

Fig. 9.

TEM energy spectrum of the core.

some TiO 2 . Fig. 9. TEM energy spectrum of the core. Fig. 10. TEM energy

Fig. 10.

TEM energy spectrum of the coating film.

Table 1.

materials

Main performance evaluation indexes of three

 

Content of the 2 μm particles / %

Hiding

Oil absorp- tion value /

Material

power /

(g

m 2 )

%

Calcium

 

carbonate

7.02

180.00

13.37

Final product

93.32

29.12

23.00

on the

coating

Titanium

 

dioxide

95.60

23.68

20.36

4. Coating mechanisms

The mechanism of coating is proposed as follows. Large proportions of CO 2 on the surface of CaCO 3 particles react with water (absorbed in atmosphere) and produce CaCO 3 hydroxyl compounds. These hy- droxyl compounds are the active point to promote modification [7].

Crystal TiO 2 is one of the most typical oxides to form hydroxyl surface. The density of OH on the surface of anatase TiO 2 is as high as 2.8-4.5 nm 2 [8].

3

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International Journal of Minerals, Metallurgy and Materials, Vol.16, No.5, Oct 2009

In aqueous condition, Ti 4+ on the surface of TiO 2 par- ticles hydrolyzes and generates hydroxylation hy- drolysis products. With combined actions of each fac- tor, the surface morphology is formed, which is hy- droxyl-based and has the features of the active oxygen and electronic acceptance field [9-10].

Many studies show that mechanic-chemical effects promote phase reactions of solid particles. The active state of the particle surface generated from me- chanic-chemical effects promotes the direct or indirect phase reactions. The effect of mechanic-chemical on phase reactions between solid particles can be ex- plained by thermodynamics and dynamics between materials [11].

When solid particles in the ultra-fine process pre- sent the mechanochemical properties of crystal con- stitution integrated transfiguration, crystal lattice ab- errance and amorphization, there will be part of en- ergy existed on the surface. Therefore, solid matters can easily achieve the high energy state of reaction compensatory with surrounding particles [12]. Besides, chemical reactions could be promoted because of the high active surface of solid particles synchronously generated from the mechanic-chemical effect, in- creasing the unsaturated bond and strong compensate trend. Mechanic-chemical effects provide dynamic guarantee for the enhancement of modification iso- phase reaction [13]. Fine particles and crystal lattice limitation generated from mechanic-chemical effects reduce the activation energy of dissolution reaction and phase reaction, which could lead to the increase in the reaction velocity constant [14].

In aqueous conditions, both of the surfaces of CaCO 3 and TiO 2 particles present strong hydroxyl properties. The IR spectra of CaCO 3 before and after coating with TiO 2 show that a chemical bond forms between CaCO 3 and TiO 2 through the surface hy- droxyl [15]. Based on the studies of surface morphol- ogy and the formation of chemical bonds, the reaction model between CaCO 3 and TiO 2 is proposed, as shown in Fig. 11.

CaCO 3 and TiO 2 is proposed, as shown in Fig. 11. Fig. 11. Reaction model

Fig. 11.

Reaction model between CaCO 3 and TiO 2 .

4. Conclusions

(1) In the optimum condition, the hiding power and the oil absorption value of the coating materials are 29.12 g/m 2 and 23.30%, respectively.

(2) The materials after coating can be used to some substitute TiO 2 because of the similar properties com- pared to pure TiO 2 . From economic aspects, coating materials are better than pure TiO 2 . This work gives a reference for combined mineral materials with other non-metallic minerals for further use.

(3) The mechanism of coating TiO 2 on the surface of CaCO 3 is based on the chemical bonding between hydroxyl compounds on the surface of the particles under mechanochemical reactions.

References

[1] F. Deng and L.F. Wu Titanium, Dioxide Application

Manual (in Chinese), Chemical Industry Press, Beijing,

2005.

Applied Technology Room of Shanghai Organic Chemis-

[2]

try Industrial Company, GB1709-79, Determination of Hiding Power of Pigment (in Chinese), National Standards Administration, Beijing, 1980. [3] Shanghai Jinghua Chemical Factory, GB1712-79, Deter-

mination of Oil Absorption of Pigment (in Chinese), Na- tional Standards Administration, Beijing, 1988. Z.X. Li and Y. Fang, Effect and application in processing

[4]

mineral particle by mechanochemistry, China Non Met. Min. Ind. Herald (in Chinese), 50(2005), No.5, p.39. [5] H. Honda, K. Ona, T. Ishizaka, et al., Surface modifica- tion of powders by high speed impact treatment method, J. Soc. Powder Technol. Jpn., 24(1987), No.2, p.593. [6] S.C. Lu, Performance Modulation and Processing of In- dustry Suspension (in Chinese), Chemical Industry Press,

Beijing, 2003. [7] X.L. Su, Z. Cao, and Z.J. Zhang, Progress in research of preparation of modified ultrafine powders by mechano- chemical method, Met. Mine (in Chinese), 374(2007), No.8, p.1. [8] H. Ding and F. Xing, Behavior of grinding media in wet ultrafine grinding of mineral powder using stirred mill and its effect, China Powder Technol. (in Chinese), 6(2000), No.4, p.9. [9] E. Ivanov and C. Suryanarayanao, Materials and Process through mechanochemical routes, J. Mater. Synth. Proc- ess., 8(2000), No.3, p.235. [10] S.L. Zheng, The Modification of Powder Surface (in Chi- nese), China Building Materials Industry Press, Beijing,

1995.

[11] R.I. Josep, CaCO 3 fillers-market trends and developments, Ind. Miner., 326(1994), p.62. [12] M. Alonso, M. Satoh, and K. Miyanami, Mechanism of the combined coating-mechanofusion processing of pow- ders, Powder Technol., 59(1989), No.1, p.45. [13] Y.M. Lian, Effects of surface treatments and deposition conditions on the adhesion of silicon dioxide thin film on

H. Lin et al., Preparation of calcium carbonate particles coated with titanium dioxide

597

polymethylmethacrylate, Surf. Coat. Technol., 71(1995), No.2, p.142. [14] E. Gaffet, F. Bernard, J.C. Niepce, et a1., Some recent developments in mechanical activation and mechano-

[15]

chemistry, J. Mater. Chem., 132(1999), No.9, p.305. Y.X. Han, W.Z. Yin, Z.H. Wang, et a1., Mineral Mate- rial (in Chinese), Science Press, Beijing, 2006.