Inert Gas Atomization of Chemical Grade Silicon

D. Rodrigues, J. B. Ferreira Neto, L. Salgado, P. F. Nogueira, J. G. R. Poo IPT Institute for Technological Research Metallurgy Division Cidade Universitria 05508-901 -So Paulo Brazil danielrd@ipt.br

Keywords: silicon; atomization; silicone; silicon powder; chemical grade silicon

Abstract: The use of inert gas atomization to obtain chemical grade silicon particles was investigated. Both cooling rate and chemical composition are very important regarding a tailored microstructure, related with silicon performance during the synthesis of the silanos, an intermediary raw material in the silicone production. Previously refined silicon was used as raw material. Silicon with different aluminum contents were atomized and analyzed. The atomization temperature was set around 1520 oC, and it was used a confined atomization nozzle. It was necessary to use a long atomization chamber to allow the cooling of the coarse silicon particles. After atomization, the powder was characterized and classified. The coarse fraction was milled. Two different particle size groups (different cooling rates) and the as atomized particles were investigated. The chemical behavior during the synthesis of the silanos was analyzed in a laboratory reactor. The relationship between cooling rate, aluminum content and silicon performance during the silanos synthesis is discussed.

Introduction The usual process to produce silanos (methylchlorosilanes), a raw material to synthesize silicones, is the Direct Process, that involves the reaction between chemical grade silicon particles and the gas (CH3Cl), carried out inside a reactor at 260-310oC and under 1-4 bar [1]. Copper and copper compounds can be used as a catalytic system [1]. The solidification process to produce the chemical grade silicon can be selected basically between two possibilities: mould cast followed by severe milling or granulation (atomization). The atomization advantages are: the possibility to produce particles directly, without milling steps; and the possibility to control the cooling rate, that is related with silicon performance during silicone synthesis. Typical granulation methods are based on the interaction between water and liquid metal. Most people in the metal producing industry have some experience of explosion connected to liquid metal and water [2]. The mechanisms for these explosions seems not to be fully understood but some reasons are often discussed: generation and expansion of steam at an explosive rate; generation of hydrogen at an explosive rate; and generation of hydrogen which reacts with oxygen. Considering this dangerous possibility, why not to eliminate water (steam) and oxygen? It would be possible through a specific atomization process, the inert gas atomization. The quality of the chemical grade silicon can be evaluated by tests in direct process laboratory reactors. Values like reactivity and selectivity can be determined in these reactors.

Reactivity is defined as the total amount of methylchlorosilanes per initial silicon mass and also reaction time (kgMCS/kgSi.h), and selectivity is the ratio between the amount of CH3SiCl3 (undesired product) and (CH3)2SiCl2 (desired product). The goal is always to develop a product with maximum reactivity and minimum selectivity. Reactivity and selectivity are both affected by microstructure. Two microstructural aspects are mostly important in this case: the grain size; and the distribution and morphology of the intermetallics. These two aspects are dependent of the cooling rate. The role of the intermetallic is to act as a catalytic system. The performance of this catalytic system depends on its chemical structure and physical characteristics. This paper will present results related with two microstructure sensitive variables, the cooling rate and aluminum content, that is present in many intermetallics. Sorhein et al [3], Larose et al [4], and Margaria et al [5] have investigated the relationships between intermetallics characteristics and silicon performance during synthesis. It was discussed in previous papers the relationships of particle size, grain size and the characteristics of the intermetallics [6,7]. Experimental Procedures Atomization The silicon powders were produced in a PSI-HERMIGA atomizer. Figure 1 shows the atomizer. A previously refined silicon [8] was used as raw material (300 g). Calcium and iron contents were, respectively, 0.028 %wt and 0.29 %wt. Different amounts of aluminum were added before atomizing. The melting temperature was 1520 oC, the atomizing gas was nitrogen, the melt chamber pressure was 0.25 bar, and the atomizing pressure was 5 bar. The variables liquid silicon stream diameter (tip) was used in three different levels, 1.5, 2.0 and 2.5 mm. Table 1 presents atomizing conditions.

Figure 1 Inert gas atomizer.

Table 1 - Atomizing conditions. Experiment tip silicon feed rate (grams/sec) (mm) H50 1,5 18 H52 2,5 21 H53 2,5 29 H54 2,0 23 1 chemical analysis of the atomized silicon.

d50 (m) 225 750 350 300

Al1 (wt. %) 0,25 0,08 0,16 0,38

The goal was to produce coarse particles with a broad size distribution. The atomized particles were divided in three different groups: a group C composed of coarse particles; a group F composed of fine particles; and a group A composed of as atomized particles. Table 2 presents these groups classified by opening particle size. Table 2 - Groups with different particle sizes (different cooling rate). coarse group (C) 35#<C<14# 500m<C<1410m fine group (F) 70#<F<35# 210m<F<500m as atomized group (A) 325#<A<70# 44m<A<210m Groups C and F were milled to a particle size similar to that one used in industrial synthesis reactors (44m - 210m). The group A was just classified between 325 # and 70# (44m and 210m). The target was to produce samples with different cooling rates, seen that there is a relationship between particle size and cooling rate. Reactivity and selectivity Figure 4 shows the apparatus for laboratory testing of silicon considering direct process. It is also presented the definitions of reactivity and selectivity. The measurement was based on the chemical reactions between the gas CH3Cl and silicon particles at 330 oC. The products of these reactions were analyzed and quantified. The basic chemical reaction is: Si + CH3Cl = (CH3)2SiCl2 + other silanos (1)

(2)

(3)

Figure 4 Apparatus to determine silicon reactivity and selectivity. The mass of (CH3)2SiCl2 was calculated considering the measured mass of CH3Cl that reacts with silicon to form (CH3)2SiCl2.

Results and discussion Figure 2a shows a log-normal plot of the experiments mentioned in table 1. During the H52 experiment, the liquid silicon stream becomes unstable, and coarse particles were produced. That is reason of the so much higher value of d50 obtained. The tip with a diameter of 2.5 mm associated with a quite low chamber melting pressure (0.25 bar), could explain this instability. Figure 2b shows the relationship between de diameter of the liquid silicon stream during atomization, defined by the tip diameter (tip), and mean particle size (d50). As expected, as higher is tip highest is d50. b) a)
400 350

d50 ( m)

300

250

200 1.0 1.5

tip(mm)

2.0

2.5

3.0

Figure 2 a) Log-normal plot of the four experiments mentioned in table I. b) Particle size versus liquid silicon stream diameter. Figure 3 compares size and morphology of the as atomized particles with atomized and milled ones, both classified between 44m and 210m. It is also presented a typical microstructure of gas atomized silicon. The presence of the intermetallics, specially in grain boundaries, is evident.

Figure 3 a) as atomized and classified between 44 and 210 m b) atomized and milled, classified between 44 and 210 m. c) typical atomized silicon microstructure.

Eie et al [9] showed that as atomized silicon particles present lower reactivity than milled ones, seen that the milling process promotes an exposition of the intermetallics. The catalytic action of the intermetallics was mentioned earlier and will be discussed later. Figure 4 presents results of reactivity and selectivity for the H52 experiment (0,082%Al). The values for reactivity and selectivity tend to stabilize after 700 minutes. The same measurements were carried out for samples with different aluminum contents. Table 3 and figure 5 summarize results considering 700 minutes.
0.30
F (fine) A (as atomized) C (coarse)

0.12
C (coarse) F (fine) A (as atomized)

0.25 reactivity

0.10 selectivity 0.08 0.06 0.04 0.02

1000
0.082%Al

0.20 0.15 0.10 0.05 0.00 0 200 400 600 time (minutes) 800
0.082%Al

0.00 0 200 400 600 800 time (minutes) 1000

Figure 4 Reactivity and selectivity determined in a laboratory reactor. Table 3 Results of reactivity and selectivity considering particle size and aluminum content. % Al 0.082 0.16 0.25 0.38 reactivity (700 min.) C (coarse) F (fine) A (as atomized) 0.19 0.16 0.12 0.21 0.16 0.17 0.25 0.20 0.11 0.19 0.16 0.16 selectivity (700 min.) C (coarse) F (fine) A (as atomized) 0.076 0.092 0.045 0.090 0.085 0.089 0.094 0.081 0.072 0.083 0.070 0.087

0.30 0.25

0.10 0.08 selectivity 0.06 0.04 0.02 0.00

0 0.1 0.2 aluminum (% wt.) C (coarse) F (fine) A (as atomized) 0.3 0.4

reactivity

0.20 0.15 0.10 0.05 0.00

0.1

0.2 aluminum (% wt.)

0.3

0.

C (coarse)

F (fine)

A (as atomized)

Figure 5 Reactivity and selectivity versus aluminum content. As atomized particles showed lower reactivity, and the reason is probably that the intermetallics (catalytic system mentioned before) are encapsulated (inside silicon particles).

The milling process can expose these intermetallics improving reactivity. Considering milled particles (F and C), there is an optimum value of aluminum, between 0.2 and 0.3 %wt. For these aluminum range, the intermetallics that can improve reactivity are not the same that can improve (reduce) selectivity [3] as confirmed in figure 5. Higher is the cooling rate, F compared with C, worst is reactivity and smallest is selectivity. Conclusions Coarse gas atomized silicon particles, around 0.3 mm, were obtained. During atomization, the silicon particle size increases with increasing liquid silicon stream. Reactivity showed maximum values for aluminum contents between 0.2 and 0.3 %wt. Selectivity decreases with increasing reactivity. As atomized silicon showed high selectivity but low reactivity. The milling can expose the intermetallic phases, so they can act as a catalytic system, improving reactivity.

Acknowledgement The authors are grateful to FINEP for the financial support of this work.

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