(en)Nanoscale, pyrogenically produced oxides and/or mixed oxides having a BET surface area of between 1 m 2 /g and 600 m 2 /g and a chloride content of less than 0.05 wt. % are produced by converting organometallic and/or organometalloid substances into the oxides at temperatures of above 200° C. The oxides may be used as a polishing agent in the electronics industry (CMP).

1.ApplicationNumber: US-73399807-A
1.PublishNumber: US-2007175362-A1
2.Date Publish: 20070802
3.Inventor: GUTSCH ANDREAS
HENNIG THOMAS
KATUSIC STIPAN
KRAMER MICHAEL
MICHAEL GUNTHER
VARGA GEOFFREY J.

4.Inventor Harmonized: GUTSCH ANDREAS(DE)
HENNIG THOMAS(DE)
KATUSIC STIPAN(DE)
KRAMER MICHAEL(DE)
MICHAEL GUNTHER(DE)
VARGA GEOFFREY J(DE)

5.Country: US
6.Claims:
(en)Nanoscale, pyrogenically produced oxides and/or mixed oxides having a BET surface area of between 1 m 2 /g and 600 m 2 /g and a chloride content of less than 0.05 wt. % are produced by converting organometallic and/or organometalloid substances into the oxides at temperatures of above 200° C. The oxides may be used as a polishing agent in the electronics industry (CMP).

7.Description:
(en)CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuing application of U.S. patent application Ser. No. 09/821,797, filed Mar. 30, 2001, which claims priority to U.S. Provisional Application Ser. No. 60/194,367, filed Apr. 4, 2000, and European Patent Application No. 00 107 237.0, filed Apr. 3, 2000, all of which are herein incorporated in their entirety by reference.


BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to nanoscale, pyrogenically produced oxides, to a process for the production thereof and to the use thereof.
2. Description of Related Art
It is known to produce pyrogenic oxides by flame hydrolysis of vaporisable metal chlorides or metalloid chlorides (Ullmanns Enzyklopädie der technischen Chemie, 4th edition, volume 21, page 44 (1982)).
These products produced in this manner have the disadvantage that, especially in the case of basic oxides, they have elevated chloride contents because they may be deacidified only very incompletely. The following chloride contents are typical of various oxides: titanium dioxide: approx. 3000 ppm, aluminium oxide: approx. 5000 ppm and zirconium oxide: approx. 6000 ppm.
Raising the temperature to higher levels during deacidification is not possible because this would amount to excessive exposure to elevated temperatures and result in an unwanted loss of surface area.
On the other hand, it is desirable that the chloride is removed as completely as possible, as this residual chloride content gives rise to corrosion problems when the oxides are used.
The known process for the production of pyrogenic oxides furthermore has the disadvantage that, for example in the case of aluminium chloride or zirconium tetrachloride, very high vaporisation temperatures must be used in order to be able to convert the starting materials into the gas phase. These vaporisation conditions place extremely stringent and thus very costly demands upon the materials of the production plant.
SUMMARY OF THE INVENTION
The object thus arises of producing nanoscale, pyrogenic oxides having a low chloride content and a BET surface area of between 1 and 600 m 2 /g, wherein these disadvantages do not occur.
The present invention provides nanoscale, pyrogenically produced oxides and/or mixed oxides of metals and/or metalloids, which oxides are characterised in that they have a BET surface area of between 1 m 2 /g and 600 m 2 /g and a total chloride content of less than 0.05%, preferably of less than 0.02 wt. %.
The present invention also provides a process for the production of the nanoscale, pyrogenically produced oxides and/or mixed oxides of metals and/or metalloids, which process is characterised in that organometallic and/or organometalloid substances, optionally dissolved in a solvent, are converted into the oxides, optionally in a flame, at temperatures of above 200° C.
The educts may be organometalloid and/or organometallic pure substances or any desired mixtures thereof or may be used as solutions in organic solvents.


BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic description of the process according to the invention.
FIG. 2 is a schematic representation of the burner arrangement usable according to the invention.


DETAILED DESCRIPTION
The following oxides may be produced using the process according to the invention: pyrogenically produced monoclinic zirconium oxide having a chloride content of less than 0.05 wt. %; pyrogenically produced amorphous aluminium oxide; pyrogenically produced alpha aluminium oxide; and pyrogenically produced titanium oxide having a rutile structure.
Suitable organometallic and/or organometalloid compounds may be fed in liquid form as a very finely divided spray into a high temperature reaction chamber, wherein particle formation may proceed in the high temperature reaction chamber, which preferably takes the form of a closed tubular reactor, at temperatures of above 400° C., wherein inert or reactive gases may additionally be fed into the high temperature reaction chamber as a carrier gas and the powders may be isolated by known gas/solid separation methods by means of a filter, cyclone, scrubber or other suitable separators.
To this end, solutions of organometallic and/or organometalloid substances (precursors) in organic solvents or also the pure substances (precursors) may be converted into the oxides, optionally in a flame, at relatively high temperatures, optionally of above 400° C.
Compounds of the type MeR may be used as precursors, wherein R represents an organic residue, such as for example methyl, ethyl, propyl, butyl, or the corresponding alkoxy variants or also a nitrate ion, and Me means a metal or a metalloid, such as for example Si, Ti, Ce, Al, Zr, Y, B, Ge, W, Nb, In, Sb, Zn, Sn, Fe, Mn, Mg, V, Ni, Cu, Au, Ag or Pt.
Solvents which may be used are organic solvents, such as alcohols, such as for example propanol, n-butanol, isopropanol and/or water.
The precursor may be fed at a temperature of 100 to 1000 bar.
The precursor may be atomised by means of an ultrasound nebuliser.
The temperature may be at least 200° C. for amorphous particles and compact spheres.
Fine particles may be obtained at a temperature of 1800° C. to 2050° C.
One advantage of the process according to the invention is that it is possible to introduce the precursors into the combustion chamber not in gaseous form, but instead in liquid form. In this process, at least one single-fluid nozzle at pressures of up to 3000 bar may produce a very fine droplet spray (average droplet size depending upon nozzle pressure of between 2 and 500 μm), which then combusts, so producing the oxide as a solid.
At least one two-fluid nozzle may furthermore be used at pressures of up to 100 bar.
The droplets may also be produced by using one or more two-fluid nozzles, wherein the gas used in two-fluid atomisation may be reactive or inert.
Using a two-fluid nozzle creates the advantage that the droplets are produced with a gas jet. This gas jet may contain oxygen or nitrogen or other reactive gases of the formula (MeCl x , such as for example silicon tetrachloride (Me corresponds to a metal or metalloid), H 2 , CH 4 ). In this manner, it is possible to achieve very intense mixing of the oxidising agent with the precursor. It is also possible to provide an additional fuel feed in the immediate vicinity of the droplets, in the event that the precursor is not reactive or the vapour pressure of the precursor is not sufficiently high to ensure a rapid reaction.
By using organometallic precursors in solvents, homogeneous solvent mixtures of various compounds of the formula MeR (precursors) may straightforwardly be produced in any desired concentration ratios and fed, preferably in liquid form, into a flame, in order to obtain the corresponding low-chloride, pyrogenic mixed oxides. Using the process according to the invention, it is straightforwardly possible to obtain mixed oxides which could previously be synthesised only with difficulty, if at all, due to widely differing vaporisation behaviour of the raw materials.
Another advantage of the process according to the invention is that it is possible not only to mix the liquid precursor with other liquid precursors but also optionally to disperse fine particles, such as for example pyrogenic oxides, such as Aerosil, precipitated silica, in the precursor, such that the particles dispersed in the precursor may be coated during the reaction.
The precursors may preferably be converted into the oxides in an oxyhydrogen flame. Apart from hydrogen, other flammable gases, such as for example methane, propane, ethane, may be used.
Since the organometallic precursors themselves constitute a good fuel, another advantage of the process according to the invention is that it is possible entirely to dispense with the supporting flame, so allowing savings to be made, for example, on hydrogen as a costly raw material.
Moreover, by varying the quantity of air (for combustion) and/or by varying nozzle parameters, it is possible to influence oxide properties, for example the BET surface area.
The low-chloride, pyrogenically produced oxides of metals and/or metalloids according to the invention may be used as a filler, as a support material, as a catalytically active substance, as a starting material for the production of dispersions, as a polishing material for polishing metal or silicon wafers in the electronics industry (CMP), as a basic substance in ceramics, in the cosmetics industry, as an additive in the silicone and rubber industry, for establishing the rheological properties of liquid systems, for providing thermal stabilisation, in the coatings industry as a thermal insulating material, as an antiblocking agent.
EXAMPLE 1
1 l/h of Zr(O-n-C 3 H 7 ) 4 as a 74% solution in n-propanol is atomised into the tubular reactor under nitrogen pressure using a nozzle. An oxyhydrogen flame of hydrogen and air burns in the reactor. The temperature 0.5 m below the flame is 800 to 1000° C. The ZrO 2 is separated in filters. Phase analysis reveals the principal constituent to be monoclinic ZrO 2 having a very low Cl content. As Table 1 shows, the BET surface area may be influenced by varying the nozzle diameter and the quantity of atomising air.
TABLE 1 Test 1 Test 2 Test 3 Delivery rate, l/h 1 1 1 Temperature, ° C. 800-1000 800-1000 800-1000 V H 2 , m 3 /h 1.5 1.5 1.5 V atomising gas, bar 2 7 14 V air, m 3 /h 13.5 16 20 Nozzle diameter, mm 1 0.8 0.8 BET surface area, m 2 /g 18 32 79 Colour white white white Cl, % 0.01 0.01 0.01 Tamped density, g/l 154 154 Phase analysis Monoclinic (principal constituent) Tetragonal and cubic (secondary constituent) Drying loss, % 0.5 Ignition loss, % 0.0 pH value 4.6 ZrO 2 , % 97.55 97.60 HfO 2 , % 2.14 2.14

EXAMPLE 2
Aluminium nitrate as a 3% (test 1) or 7.5% (test 2) aqueous solution, or liquid aluminium tri-sec.-butylate (tests 3 and 4) are atomised into the tubular reactor with compressed air and a nozzle (diameter 0.8 mm) or in the case of test 2 with an atomiser (diameter 1.1 mm). An oxyhydrogen flame of hydrogen, air and/or oxygen mixture burns in the reactor. The temperature 0.5 m below the flame is 250° C. to 1250° C. The aluminium oxide is separated in filters. The results are shown in Table 2.
TABLE 2 Test 1 Test 2 Test 3 Test 4 Delivery rate, ml/h 320 230 100 120 Temperature, ° C. 650-250 700-1200 560-900 1150-1300 V H 2 , m 3 /h 0.6 1.5 0.9 1.6 V atomising gas, 1.4 0 Two-fluid 0 carrier gas, bar nozzle, 0.8 mm diameter 2.3 V air, m 3 /h 1.0 2.2 2.8 2.1 BET, m 2 /g 3.1 9 205 16 D 50 (Cilas) 1.52 24.7 3.47 4.52 Phase 100% 70% alpha 16% delta 100% alpha amorphous 30% theta 84% gamma TEM, μm Compact Crystallites 0.005-0.0010 spheres up to 4 m 0.2-2 Cl content, % 0.018

EXAMPLE 3
Titanium bis(ammoniumlactato)dihydroxide ((CH 3 CH(O—) CO 2 NH 4 ) 2 Ti(OH) 2 ) as a 50% aqueous solution is atomised into the tubular reactor using compressed air and a nebuliser. An oxyhydrogen flame of hydrogen, air and/or oxygen mixture burns in the reactor. The temperature 0.5 m below the flame is 740° C. to 1 150° C. The titanium oxide is separated in filters. The data are shown in Table 3.
TABLE 3 Delivery rate, ml/h 200 Temperature, ° C. 740-1150 V H 2 , m 3 /h 1.8 V nebuliser carrier gas, bar 1.8 V air, m 3 /h 1.3 BET, m 2 /g 3.1 D 50 (Cilas) 0.92 Phase 100% rutile