Boron nitride containing titanium nitride, method of producing the same and composite ceramics produced therefrom

• US 4,565,747 A
• Filed: 11/09/1984
• Issued: 01/21/1986
• Est. Priority Date: 11/11/1983
• Status: Expired due to Term

• Current Assignee: Furukawa Electric Company Limited, Japan Metals & Chemicals Co., Ltd., Research Development Corporation Of Japan (Japan Science And Technology Agency), NAOKI UNO, FURUKAWA DENKO KIBOGAOKA SHATAKU (5%), Toshio Hirai, Tsuyoshi Masumoto, YUKIO MATSUNAMI, NIHON JUKAGAKU KOGYO DAINI MITAKARYO (5%)
• Original Assignee: Hiroyuki Nakae, Naoki Uno, Toshio Hirai, Toshitsugu Matsuda, Tsuyoshi Masumoto, UAB Research Foundation (University of Alabama System), Yukio Matsunami
• Inventors: Hirai, Toshio, Masumoto, Tsuyoshi, Nakae, Hiroyuki, Uno, Naoki, Matsuda, Toshitsugu, Matsunami, Yukio
• Primary Examiner(s): McCarthy, Helen M.
• Application Number:
  US06/670,154
• Time in Patent Office: 438 Days
• Field of Search: 427/248.1, 427/255.2, 428/698, 501/96, 423/290, 423/297, 423/276, 423/411, 423/266, 423/275, 264/81
• US Class Current: 428/698
• CPC Class Codes: C03C 17/225 Nitrides
• CPC Class Codes: C03C 2217/281 Nitrides
• CPC Class Codes: C03C 2218/152 by cvd
• CPC Class Codes: C04B 35/583 based on boron nitride
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence

Abstract

Boron nitride containing titanium nitride in an amount of 0.05 to 10 wt. % which is produced at a relatively low temperature, utilizing a chemical vapor deposition technique. In the deposition process, boron, titanium and nitrogen source gases are introduced into an evacuated reactor together with a carrier and/or diluent gas and contacted with a heated substrate previously mounted in the reactor, whereby boron nitride with titanium nitride is deposited onto the substrate. The deposit thus obtained has a high density, a significantly improved heat-shielding ability, a high degree of anisotropy with respect to thermal diffusivity and a high chemical stability. By using such anisotropic boron nitride with BN ceramics, very useful BN type composite ceramics can be produced.

Claims

1. Boron nitride produced by chemical vapor deposition, said boron nitride containing titanium nitride in an amount of 0.05 to 10 wt. %.

2. Boron nitride as claimed in claim 1 in which said boron nitride contains titanium nitride in an amount of 0.05 to 2.0 wt. %.

3. Boron nitride as claimed in claim 1 in which said titanium nitride is contained in a fine particle form.

4. Boron nitride as claimed in claim 3 in which said titanium nitride is contained in the state of crystal.

5. Boron nitride as claimed in claim 4 in which said titanium nitride is contained in the state of crystal with a diameter of not greater than 100 Å

.

6. Boron nitride as claimed in claim 5 in which titanium nitride is contained in a single crystal particle form.

7. Boron nitride as claimed in claim 1 in which said boron nitride is in a turbostratic structure.

8. Boron nitride as claimed in claim 7 in which the interlayer spacing of said turbostratic structure is in the range of 3.35 to 3.45 Å

.

9. Boron nitride as claimed in claim 1 in which said boron nitride has a density of from 1.4 to 2.3 g/cm³.

10. Boron nitride as claimed in claim 9 in which said boron nitride has a density of from 2.0 to 2.2 g/cm³.

11. A method of producing boron nitride containing titanium nitride in an amount of 0.05 to 10 wt. % by a chemical vapor deposition, comprising the steps of:

(a) mounting a substrate shaped into a desired form in a reactor;

(b) evacuating said reactor and heating said substrate to the temperature range of 500°

to 2000°

C.;

(c) introducing a boron depositing source gas, a nitrogen depositing source gas, a titanium depositing source gas and carrier and/or diluent gas into said evacuated reactor, and then contacting said source gases with said substrate within the substrate temperature ranging from 500°

to 2000°

C. and at the total internal pressure of said reactor ranging from 0.1 to 770 torr, thereby depositing said boron nitride containing titanium nitride, the ratio of said titanium depositing source gas to said boron depositing source gas being controlled to give a Ti/B atomic ratio of 0.005 to 0.45;

(d) continuing to feed said source gases and said carrier and/or diluent gas while degassing to maintain said total internal pressure of said reactor within said pressure range until the desired amount of said boron nitride is deposited onto said substrate;

(e) cooling and taking out said substrate; and

(f) removing said deposited boron nitride from said substrate.

12. A method as claimed in claim 11 in which said temperature of said substrate is in the range of 1000°

to 1500°

C.

13. A method as claimed in claim 12 in which said temperature of said substrate is in the range of 1200°

to 1400°

C.

14. A method as claimed in claim 11 in which said total internal pressure of said reactor is maintained at 1 to 15 torr during the deposition process.

15. A method as claimed in claim 11 in which the ratio of said titanium depositing source gas to said boron depositing source gas is controlled to give a Ti/B atomic ratio ranging from 0.01 to 0.2.

16. A method as claimed in claim 11 in which said boron depositing source gas is one or more selected from the group consisting of BCl₃, BF₃, B₂ H₆, B₁₀ H₁₄, B₃ N₃ H₆ (borazine), B₃ N₃ H₃ Cl₃ (borazol trichloride), B(C₂ H₅)₃ and B(CH₃)₃.

17. A method as claimed in claim 11 in which said nitrogen depositing source gas is one or more selected from the group consisting of HN₃, NH₃, N₂ H₄, NH₄ Cl, NH₄ Br, NH₄ F, NH₄ HF₂, NH₄ I and N₂.

18. A method as claimed in claim 11 in which said titanium depositing source gas is one or more selected from the group consisting of TiCl₄, TiBr₄, TiF₄ and TiI₄.

19. A method as claimed in claim 11 in which one or more gases of nitrogen(N₂), argon(Ar), helium(He) and hydrogen(H₂) are employed as carrier and/or diluent gas.

20. A method as claimed in claim 11 in which said substrate is made of graphite, SiC, BN, TiB₂, metallic molybdenum, or quartz glass.

21. A method as claimed in claim 11 in which said source gases are introduced separately through two or more inlet passages.

22. Boron nitride type composite ceramics composed of (1) one or more boron nitride ceramic base layers containing titanium nitride in an amount of 0.05 to 10 wt. % which is produced by chemical vapor deposition and (b) one or more BN ceramic surface layers.