Nanocomposites of silicon nitride, silicon carbide, and boron nitride
View Patent ↗Densified composites of silicon nitride, silicon carbide, and boron nitride that exhibit high creep resistance are obtained by sintering a mixture of amorphous powders of silicon nitride, silicon carbide, and boron nitride in the presence of an electric field under high pressure. The grain size in the resulting composite is less than 100 nanometers for all components of the composite, and the composite exhibits high creep resistance.
1. A method for forming a dense Si—C—B—N composite, said method comprising:
(a) mechanically activating a powder mixture comprised of silicon nitride, silicon carbide, and boron nitride; and
(b) consolidating said powder mixture so activated into a continuous mass by compressing said powder mixture so activated in the presence of 0 to 1% by weight of metal oxide densification aids relative to said powder mixture, while passing an electric current through said powder mixture, to achieve a fused Si—C—B—N mass comprised of crystals less than 100 nanometers in diameter.
2. The method of claim 1 wherein said powder mixture of step (a) is substantially amorphous.
3. The method of claim 1 wherein said crystals of said fused Si—C—B—N mass are less than 50 nm in diameter.
4. The method of claim 1 wherein any metal densification aid present in step (b) is from 0 to 0.5% by weight of said powder mixture of step (b).
5. The method of claim 1 wherein any metal densification aid present in step (b) is from 0 to 0.1% by weight of said powder mixture of step (b).
6. The method of claim 1 wherein step (b) is performed in the absence of metal oxide densification aids.
7. The method of claim 1 wherein said powder mixture of step (a) consists essentially of from about 10 to about 60 parts by volume silicon, from about 10 to about 60 parts by volume carbon, from about 10 to about 60 parts by volume nitrogen, and from about 2 to about 30 parts by volume boron, based on a total of 100 parts by volume of said powder mixture of step (a).
8. The method of claim 1 further comprising forming said powder mixture of step (a) by combining decaborane with a polyorganosilazane, followed by crosslinking and pyrolysis.
9. The method of claim 8 wherein said polyorganosilazane is a polyureasilazane.
10. The method of claim 1 wherein step (b) comprises compressing said powder mixture so activated at a pressure of about 10 MPa to about 200 MPa and a temperature of about 900° C. to about 3,000° C., and said electric current is a pulsed direct current of about 1,000 A/cm 2 to about 10,000 A/cm 2 .
11. The method of claim 10 wherein said pressure is about 40 MPa to about 100 MPa.
12. The method of claim 10 wherein said temperature is about 1,000° C. to about 2,000° C.
13. The method of claim 10 wherein said pulsed direct current is about 1,500 A/cm 2 to about 5,000 A/cm 2 .
14. The method of claim 1 wherein step (b) is performed to achieve a fused mass with a density of at least 95% relative to a volume-averaged theoretical density.
15. The method of claim 1 wherein step (b) is performed to achieve a fused mass with a density of at least 98% relative to a volume-averaged theoretical density.
16. The method of claim 1 wherein step (b) is performed to achieve a fused mass with a density of at least 99% relative to a volume-averaged theoretical density.
17. The method of claim 1 wherein step (a) comprises milling said powder mixture by high-energy ball milling.
18. The method of claim 17 wherein said high-energy ball milling is performed with silicon nitride milling balls in an oscillating mill at about 6 or more impacts per second and a charge ratio of at least about 10:4.