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GB1579417A - Method of producing silicon nitride - Google Patents

Method of producing silicon nitride Download PDF

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Publication number
GB1579417A
GB1579417A GB1562678A GB1562678A GB1579417A GB 1579417 A GB1579417 A GB 1579417A GB 1562678 A GB1562678 A GB 1562678A GB 1562678 A GB1562678 A GB 1562678A GB 1579417 A GB1579417 A GB 1579417A
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Prior art keywords
silicon nitride
mixture
si3n4
silicon dioxide
silicon
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GB1562678A
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Taiheiyo Cement Corp
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Onoda Cement Co Ltd
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Publication date
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Publication of GB1579417A publication Critical patent/GB1579417A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/06Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/068Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
    • C01B21/0685Preparation by carboreductive nitridation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Products (AREA)

Description

(54) METHOD OF PRODUCING SILICON NITRIDE (71) We, ONODA CEMENT COMPANY, LTD., a Japanese company, of 6276, Oaza Onoda, Onoda-shi, Yamaguchi, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a method of producing silicon nitride.
Silicon nitride is known for its various excellent properties, namely high refractoriness, thermal spalling resistance, and chemical resistance, and it is used as refractory articles in various forms. Therefore, various methods for the production of silicon nitride have been investigated. Typical procedures are as follows: (1) The interaction of metallic silicon powder and nitrogen and/or ammonia: (2) The interaction of silicon tetrachloride or silane and nitrogen and/or ammonia.
(3) The interaction of silicon dioxide and nitrogen and/or ammonia in the presence of carbon.
However, the procedure (1) has the disadvantage that the use of metallic silicon of high purity for the purpose of obtaining a product of high purity slows down the nitriding velocity and leaves metallic silicon as an impurity in the silicon nitride product, the procedure (2) is suitable for the production of silicon nitride of high purity, but it is difficult to use for large-scale production, because the silicon nitride product is prepared by the deposition of silicon nitride vapour on a heated surface, and the procedure (3) has the disadvantage that the completion of reaction requires a long time at high temperature as the reaction velocity is slow and therefore the silicon nitride product contains various impurities such as silicon oxy-nitride, silicon carbide and silicon oxide.
In order to eliminate these defects, a method of promoting the reaction velocity of silicon dioxide and nitrogen and/or ammonia gas with the use of a catalyst or a method of nitriding a mixture of silicon dioxide and an excess amount of a carbonaceous material and removing the remaining carbon in the product by low temperature oxidation after the nitriding procedure have been proposed. These methods are not satisfactory because the quality of the products is adversely affected.
A study was systematically initiated to attempt to formulate a procss which would overcome these disadvantages and we have found that the volume of a mixture of silicon dioxide and a carbonaceous material contracts considerably before the temperature of the mixture reaches the reaction temperature, which gives rise to delay in the reaction velocity. This is considered to be caused by the permeability of nitrogen and/or ammonia into the mixture. In order to eliminate this defect, the use of coarse particles of silicon oxide and carbonaceous material is not preferable because it results in an increase of unreacted material.
The present invention provides a method of producing silicon nitride, comprising shaping a mixture of silicon dioxide, a carbonaceous material and silicon nitride wherein the molar ratio of carbon to silicon dioxide in the mixture is from 2:1 to 5:1 and wherein the mixture has a silicon nitride content of 5-30% by weight relative to the amount of silicon dioxide and carbonaceous material present, and heating the mixture for from 1 to 20 hours at a temperature of 130(W1550 C under an atmosphere of nitrogen and/or ammonia.
The following description illustrates a typical one of various experimental results.
In these experiments, the silicon dioxide was amorphous silica the impurity of which was 0.14% and the specific surface area of which was 220 m2/g, and the carbonaceous material was carbon black the impurity of which was 0.08% and the specific surface area of which was 50 m2/g.
After mixing the amorphous silica and carbon black in the proportion 1:2 mols (the mixture is designated by "a"), this mixture was formed into cylindrical tablets having a diameter of 14 mm and a height of 13 mm. The tablets were placed on a plate of carbonized resin !(carbon of high purity) in a muffle and were heated to 1500"C in 4 hours while passing nitrogen gas at the rate of 2.5 1/mien, and were thereafter left for 20 hours at the same temperature and were then cooled down, whereby silicon nitride containing 97.2% a-Si, N4 and 1.5% S-SirsN was produced (this product is designated by "b") Next, after adding silicon nitride thus obtained to the raw material mixture in the proportion of 5, 10, 25, 50 and 75%, respectively, the resultant mixture was formed into cylindrical tablets having a diameter of 14 mm and a height of 1S mm, and the tablets were nitrided at 1450"C for 2 hours in the same way as mentioned above, whereby silicon nitride products were obtained.
The results are listed in Table 1.
For a comparison, the nitriding reaction was performed without the addition of the silicon nitride "b" to the mixture "a" under the same conditions as mentioned above (comparative experimental example number 1), and also, in the place of the silicon nitride "b", carbon powder of high purity used for emission spectroanalysis the mean particle size of which was 1 micron (this carbon is designated by "c") was added to the above-mentioned raw material in proportions of 10 and 25%. After forming into the same size of cylindrical tablets as mentioned above, the tablets were nitrided by heating under the same temperature and time conditions as mentioned above. The analyses of silicon nitride in the comparative experimental example numbers 2 and 3 were done on the products from which carbon was eliminated by oxidation at 500 C after the nitriding procedure.
The analytical values of the products obtained in each case are listed in Table 1.
TABLE 1
Analytical Value Mixing Ratio (Weight SO) of Product (Weight %) Experimental Number a b c aSi31'14 ss-Si3N4 1 95 5 - 79 0.5 2 90 10 - 84 0.5 3 75 25 - 98 0.5 4 50 50 - 99 1.0 5 25 75 - 99 1.5 Comparative Experimental 1 100 - - 41 0 Example 2 90 - 10 58 0 Number 3 75 - 25 79 0.5 As apparent from Table 1, it can be seen that the tablets in which the silicon nitride "b" is added to the mixture "a" in place of the carbon powder "c" are converted to silicon nitride more effectively. From these results, it is supposed that the silicon nitride added to the mixture of silicon dioxide and a carbonaceous material not only acts to prevent the contraction of the raw material during the heating, but a!so acts to accelerate catalytically the interaction of silicon dioxide, carbon and nitrogen.
This invention is based on these exnerimental results, and relates to a method for the production of silicon nitride by heating a mixture of silicon dioxide and a carbol-raceous material in an atmosphere of nitrogen and/or ammonia, wherein silicon nitride is added to the mixture of silicon dioxide and a carbonaceous material.
In this invention, silicon dioxide such as amorphous silica and/or powdered quartz and a carbonaceous material such as carbon black, oil coke powder and/or carbonized resin are utilized. The molar ratio of carbon to silicon dioxide in the mixture is 2:1 to 5:1, and the preferable particle size of the carbonaceous material and silicon dioxide is less than 10 microns, respectively. Silicon nitride comprising a- and/or ss- Si3N4 is utilized as an additive. However, as is seen from the Table 3 in Example 2 below, it is preferable to use a-Si,N4 because the mechanical strength of refractory articles made of a-silicon nitride, especially refractory articles made by hot-pressing a-silicon nitride, is higher than that made of silicon nitride.The amount of silicon nitride added is 550% by weight relative to the amount of silicon dioxide and a carbonaceous material and its particle size is preferably 0.01-10 microns. The resultant mixture of silicon nitride is formed into for example plate, cylindrical or spherical shapes. The resultant mixture is heated at a temperature of 1300--1SSOOC and the heating period is from 1 to 20 hours.
By means of the method of the invention, silicon nitride products which have high purity can be effectively produced in a short time.
The invention will be further described with reference to the following illustrative examples.
Example 1.
Amorphous silica (specific surface area 180 m2/g, impurity 0.05%), quartz (specific surface area 7.5 m2/g, impurity 0.04%), carbon black (specific surface area 70 m2/g, impurity 0.02%) and silicon nitride prepared by the experimental example number 4 were mixed together in the proportions shown in Table 2, respectively, and the resultant mixtures were formed into cyllindrical tablets having a diameter of 14 mm and a height of 1S mm and the tablets were heated in a muffle to the temperature indicated in Table 2 in 4 hours while passing nitrogen and were thereafter left at that temperature for the time indicated in Table 2. After the nitriding procedure, the products were cooled down.
The analytical values of the products thus obtaned are shown in Table 2. TABLE 2
Condition of Analytical Value Mixing Ratio Heat Treatment of Product (wt. %) Amorphous Powdered Carbon Silicon Silica Quartz Black Nitride Temp. Time Test Number (mol %) (mol %) (mol %) (wt. %) ( C) (hours) α-Si3N4 ss-Si3N4 6 33.3 - 66.7 20 1500 2.5 99 1.0 7 20.0 - 80.0 50 1400 5.0 99 0.5 8 28.6 - 71.4 25 1350 20.0 98 1.0 9 - 30.0 70.0 10 1450 5.0 97 1.0 Comparative Example 28.6 - 71.4 0 1350 20.0 64 2 Note 1. The weight of silicon nitride in the mixing ratio indicates the ratio to the total amount of amorphous silica or quartz and carbon black.
2. The analytical value of the product except that of test No. 6 indicates the analytical value of the product from which carbon residue was eliminated by oxidation at 500 C.
3. The analytical value of the nitrogen component of test No. 6 was 37.4%.
It was confirmed by emission spectroanlysis of the product obtained from test No. 6 that it was silicon nitride of especially high purity, and the X-ray diffraction pattern of this product is illustrated in the accompanying drawing.
Example 2 After mixing α-Si3N4 (purity 99.9%, average particle size 0.03 micron) or ss-Si3N4 (purity 98%, average particle size 0.2 micron) into a mixture of amorphous silica (specific surface area 320 m2/g, impurity 0.05%) and carbon black (specific surface area 110 m2/g, impurity 0.03%) in the proportions shown in Table 3, the mixtures were formed into cylindrical or spherical tablets in the same way as in Example 1 and the tablets were heated in a muffle to 1450 C in 4 hours in a stream of nitrogen or a mixture of nitrogen and ammonia and were thereafter left at this temperature for 6 hours. After the nitriding procedure, the products were cooled down.
The analytical values of the products thus obtained are shown in Table 3.
TABLE 3
Mixing Ratio Analytical Shape of Value of Amorphous Carbon Raw Mixture Product (wt. %) Silica Black α-Si3N4 ss-Si3N4 Nitriding Test Number (mol %) (mol %) (wt. %) (wt. %) Cylinder Sphere Gas α-Si3N4 ss-Si3N4 10 33.3 66.7 20 - O N2 99 1.0 11 " " " - O " 89 1.7 12 " " - 20 O " 69 30.5 13 " " - " O " 61.5 29.5 14 " " - " O N2+NH3 64 30.5 Comparative example " " - - O N2 56 0.5 Note 1. Cylindrical shapes have a diameter of 14 mm and a height of 15 mm.
2. Spherical shapes have diameters between 8-12 mm.
WHAT WE CLAIM IS:1. A method of producing silicon nitride, comprising shaping a mixtur of silicon dioxide, a carbonaceous material and silicon nitride wherein the molar ratio of carbon to silicon dioxide in the mixture is from 2:1 to 5:1 and wherein the mixture has a silicon nitride content of 5-50% by weight relative to the amount of silicon dioxide and carbonaceous material present, and heating the mixture for from 1 to 20 hours at a temperature of 1300-1550 C under an atmosphere of nitrogen and/or ammonia.
2. A method as claimed in claim 1, wherein the silicon nitride product obtained contains α- and/or ss-Si3N4 3. A method as claimed in Claim 2, wherein the silicon nitride product obtained is substantially α-Si3N@@ 4. A method as claimed in Claim 1 or 2, wherein the particle size of the silicon nitride is from 0.01 to 10 microns.
5. A method as claimed in any of Claims 1, 2 and 4, wherein the silicon dioxide is amorphous silica and/or quartz having a particle size of less than 10 microns.
6. A method as claimed in any of Claims 1, 2, 4 and 5, wherein the carbonaceous
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (8)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    TABLE 3
    Mixing Ratio Analytical Shape of Value of Amorphous Carbon Raw Mixture Product (wt. %) Silica Black α-Si3N4 ss-Si3N4 Nitriding Test Number (mol %) (mol %) (wt. %) (wt. %) Cylinder Sphere Gas α-Si3N4 ss-Si3N4 10 33.3 66.7 20 - O N2 99 1.0 11 " " " - O " 89 1.7 12 " " - 20 O " 69 30.5 13 " " - " O " 61.5 29.5 14 " " - " O N2+NH3 64 30.5 Comparative example " " - - O N2 56 0.5 Note 1. Cylindrical shapes have a diameter of 14 mm and a height of 15 mm.
    2. Spherical shapes have diameters between 8-12 mm.
    WHAT WE CLAIM IS:1. A method of producing silicon nitride, comprising shaping a mixtur of silicon dioxide, a carbonaceous material and silicon nitride wherein the molar ratio of carbon to silicon dioxide in the mixture is from 2:1 to 5:1 and wherein the mixture has a silicon nitride content of 5-50% by weight relative to the amount of silicon dioxide and carbonaceous material present, and heating the mixture for from 1 to 20 hours at a temperature of 1300-1550 C under an atmosphere of nitrogen and/or ammonia.
  2. 2. A method as claimed in claim 1, wherein the silicon nitride product obtained contains α- and/or ss-Si3N4
  3. 3. A method as claimed in Claim 2, wherein the silicon nitride product obtained is substantially α-Si3N@@
  4. 4. A method as claimed in Claim 1 or 2, wherein the particle size of the silicon nitride is from 0.01 to 10 microns.
  5. 5. A method as claimed in any of Claims 1, 2 and 4, wherein the silicon dioxide is amorphous silica and/or quartz having a particle size of less than 10 microns.
  6. 6. A method as claimed in any of Claims 1, 2, 4 and 5, wherein the carbonaceous
    material is carbon black, oil coke and/or a carbonized resin having a particle size of less than 10 microns.
  7. 7. A method as claimed in any of Claims 1, 2, 4, 5 and 6, wherein the said mixture is formed in a plate, a cylinder or a sphere.
  8. 8. A method according to Claim 1 for the production of silicon nitride, substantially as herein described in any of the foregoing Examples.
GB1562678A 1977-04-28 1978-04-20 Method of producing silicon nitride Expired GB1579417A (en)

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JP4837377A JPS53133600A (en) 1977-04-28 1977-04-28 Production of silicon nitride

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DE (1) DE2818545A1 (en)
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GB (1) GB1579417A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514370A (en) * 1981-11-25 1985-04-30 Tokyo Shibaura Denki Kabushiki Kaisha Process for preparing silicon nitride powder
GB2159506A (en) * 1984-03-29 1985-12-04 Toshiba Kk Method for production of ceramic powder silicon nitride material
US5075091A (en) * 1986-04-11 1991-12-24 Bayer Aktiengesellschaft Process for the preparation of silicon nitride
CN116813354A (en) * 2023-06-06 2023-09-29 东莞理工学院 A method for in-situ preparation of silicon nitride ceramics, the prepared silicon nitride ceramics and their applications

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4590053A (en) * 1983-07-14 1986-05-20 Sumitomo Chemical Company, Limited Method for producing α-form silicon nitride fine powders
JPS6021804A (en) * 1983-07-14 1985-02-04 Sumitomo Chem Co Ltd Manufacture of finely powdered alpha type silicon nitride
US4724131A (en) * 1984-06-07 1988-02-09 Sumitomo Chemical Company, Limited Method for producing α-form silicon nitride
JPS61146797A (en) * 1984-12-14 1986-07-04 Tateho Kagaku Kogyo Kk Continuous manufacture of silicon nitride and silicon carbide
FR2687393B1 (en) * 1992-02-18 1994-04-15 Elf Atochem Sa CONTINUOUS PROCESS FOR THE PREPARATION OF SILICON NITRIDE BY CARBONITRURATION AND THE SILICON NITRIDE THUS OBTAINED.
RU2137708C1 (en) * 1998-03-13 1999-09-20 Институт структурной макрокинетики и проблем материаловедения РАН Method of preparing silicon nitride with elevated content of alpha-phase
RU2149824C1 (en) * 1999-01-29 2000-05-27 Институт структурной макрокинетики и проблем материаловедения РАН Silicon nitride with increased alpha-phase content
JP7341038B2 (en) * 2019-11-25 2023-09-08 日本バイリーン株式会社 Method for manufacturing silicon nitride fiber

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR433995A (en) * 1910-11-12 1912-01-20 Ottokar Serpek Manufacturing process of nitrogen compounds of silicon
FR489063A (en) * 1915-12-08 1918-12-13 Axel Rudolf Lindblad Method and apparatus for the production of nitrogen compounds and especially azides
GB1206468A (en) * 1967-04-10 1970-09-23 Lucas Industries Ltd Method of manufacturing silicon nitride powder
GB1470171A (en) * 1974-07-31 1977-04-14 Lucas Industries Ltd Method of producing silicon nitride
JPS53102300A (en) * 1977-02-18 1978-09-06 Toshiba Corp Preparation of type silicon nitride powders

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514370A (en) * 1981-11-25 1985-04-30 Tokyo Shibaura Denki Kabushiki Kaisha Process for preparing silicon nitride powder
EP0082343B1 (en) 1981-11-25 1986-08-13 Kabushiki Kaisha Toshiba Process for preparing silicon nitride powder
GB2159506A (en) * 1984-03-29 1985-12-04 Toshiba Kk Method for production of ceramic powder silicon nitride material
US4911870A (en) * 1984-03-29 1990-03-27 Kabushiki Kaisha Toshiba Method for production of sintered silicon nitride article
US5075091A (en) * 1986-04-11 1991-12-24 Bayer Aktiengesellschaft Process for the preparation of silicon nitride
CN116813354A (en) * 2023-06-06 2023-09-29 东莞理工学院 A method for in-situ preparation of silicon nitride ceramics, the prepared silicon nitride ceramics and their applications

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Publication number Publication date
FR2388763A1 (en) 1978-11-24
JPS53133600A (en) 1978-11-21
FR2388763B1 (en) 1984-01-27
DE2818545A1 (en) 1978-11-09

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