WO1993001323A1

WO1993001323A1 - B4C/Al CERMETS AND METHOD FOR MAKING SAME

Info

Publication number: WO1993001323A1
Application number: PCT/US1991/004802
Authority: WO
Inventors: Aleksander J. Pyzik; Robert T. Nilsson
Original assignee: The Dow Chemical Company
Priority date: 1991-07-08
Filing date: 1991-07-08
Publication date: 1993-01-21
Also published as: EP0593474B1; JPH06508658A; EP0593474A1; DE69125033T2; DE69125033D1; US5039633A; EP0593474A4

Abstract

Reactive ceramic-metal compositions are described that include a ceramic phase of at least 70 percent by volume, 95 percent of theoretical density, and a metal phase that retains its chemical reactivity with the ceramic phase after the composition has been fully densified. The composition may be heat treated after densification to form additional ceramic phases in a controllable manner. Preferred ceramic metal compositions wherein the metal and ceramic components retain reactivity after densification include boron carbide ceramic and Al or Mg metals. The process employed in forming said compositions requires first forming a sintered porous body of the ceramic material followed by contacting with the metal component, which may be in chip or solid bar form. The system is then heated to the melting point of the metal and a pressure of at least 200 MPa is employed such that the porous body is filled with metal and the composition is substantially fully densified. Subsequent heating reacts the metal with the ceramic to form additional B-C-metal phases as desired.

Description

BnC Al CERMETS AND METHOD FOR MAKING SAME

The invention relates to ceramic-metal compositions or cermets. More particularly the invention relates to densified cermets that have selected desirable characteristics that are derived from the individual ceramic and metal starting components.

The potential of ceramic-metal compositions that include a unique combination of properties, such as the hardness of a ceramic material combined with the ductility of a metal, has long been of interest. It has, however, proved difficult to achieve cermet compositions that are fully densified and have a particularly desired range of properties. The difficulties arise from the conflicting physical and chemical nature of the starting materials.

Major areas of difficulties in processing of ceramic-metal composites are associated with:

(i) chemical reactivity of the starting materials resulting in oxidation and/or metal depletion and formation of undesirable phases between ceramic and metal; and (ii) non-wetting behavior of the metal with respect to the ceramic component.

Chemical reactions between composite ceramic and metal components that occur before density is achieved are often undesirable, because metal required for densification is reacted to form variety of phases. These cermet products will likely have a higher porosity than desired and lack sufficient quantities of desired ceramic-metal phases that would, if present, impart needed properties to the cermet.

Reactions after density is achieved can be beneficial because desired quantities of ceramic phases^' can be controllably developed to impart such qualities as hardness and wear resistance to resulting products.

Where articles having a high ceramic content are desired, in order to take advantage of the high hardness and wear resistance of the ceramic component, densification becomes particularly difficult. For example, in a highly reactive system such as B^C/Al, achieving a fully densified composition is difficult because there is significant reaction of Al with Bi_jC as the metal reaches a temperature where it wets the ceramic material and would otherwise completely fill the pores of or infiltrate into a porous ceramic body or preform.

Two general types of Bj_jC-Al cermets are known in the art heretofore. One type of B^C-Al cermet is characterized by high reactivity for forming B-C-Al phases and low, less than 70 volume percent, ceramic content. The second type of Bj_jC-Al cermet is characterized by low reactivity for developing desired ceramic phases and high, greater than 70 percent, ceramic content.

In light of the deficiencies of the known Bi_}C-Al cermets, it would be desirable to produce ceramic-metal compositions of reactive ceramic metal systems that have substantially greater ceramic content than 70 volume percent, are substantially fully densified and retain sufficient reactivity of the ceramic with respect to the metal to allow the controlled formation of further advantageous ceramic phases by subsequent processing.

The invention is a densified reactive ceramic- metal composition or cermet that comprises a ceramic phase that is permeated with a metal phase, wherein said ceramic phase comprises at least 70 percent by volume of said composition and said composition is at least about 95 percent of theoretical density. The cermets of the invention are further characterized by a metal phase that is, subsequent to densification, reactive with the ceramic phase. Such compositions, after densification, may be heat treated to form additional ceramic phases in a controllable manner. Preferred ceramic metal compositions wherein the metal and ceramic are reactive, comprise, for example, Bj_jC-Al or Bj_jC-Mg. Preferably, the Bj_jC ceramic phase comprises 70 to 95 volume percent of said composition, and most preferably, 80 to 95 volume percent Bj_jC ceramic. The cermets of the invention are particularly characterized by their greater hardness in comparison with cermets prepared by the infiltration methods of the prior art.

The densified, ceramic-metal compositions of the invention are prepared by a process that includes -it-

first forming a sintered porous body from a particulate ceramic powder. Following contacting the porous body with the metal, the process requires heating the metal and ceramic porous body to liquefy the metal. The process then requires applying pressure to the liquefied metal such that the metal is forced into, infiltrates and completely fills the pores of the porous body. The resulting ceramic-metal composition is fully densified. An advantage of the application of external force to the liquefying metal is that lower temperatures are required to densify the composition of the invention. For a preferred B^C-Al system, liquid metal-ceramic is introduced into the sintered B^C at below the metal wetting temperature, resulting in a substantially fully dense cermet having high post-densification chemical reactivity. Thus, a preferred composition of the invention, after post-densification heat treatment, is a BifC-Al cermet having a B^C content of greater than 70 volume percent, a B-C-Al phases content and a desired content of unreacted metal.

The cermet composition of the invention includes a high ceramic component content such that the cermet is characterized by high hardness, with respect to cermets of the prior art, while maintaining significant fracture toughness and flexural strength. The particular advantages achieved for a given ceramic- metal system depend upon the characteristics of the individual components selected.

The preferred ceramic component of the composition of the invention is B^C which is characterized by high hardness and superior wear resistance. The metal component of the composition of the invention is selected, in general, to impart toughness or ductility to the ceramic material. Preferred metal components include, for example, magnesium and aluminum. Ceramic systems are B^C-Al or B^C-Mg, for example.

The invention provides a process for producing the above-described cermets of the invention that are characterized by high continuity of ceramic phase and high ceramic content. The process produces products that retain a residual reactivity such that upon application of post-densification heat treating steps, the formation of additional ceramic-containing phases is possible.

The process first requires forming a porous body preform or greenware article from a ceramic particulate. In general, a fine ceramic powder, preferably having a particle diameter size range of 0.1 to 10 micrometers, is utilized. Ceramic materials in the form of platelets or whiskers may also be used. As is conventional, the particulate material is dry mixed or dispersed in a liquid followed by consolidation to form the porous green body.

The greenware is next sintered to achieve a ceramic content above 70 volume percent. Where the ceramic is B^C, the greenware is sintered at about 2000°C or higher to form porous compacts or preforms having a density ranging from greater than 70 to 95 percent of theoretical density.

The process then requires that the sintered porous preform be contacted with the selected metal component of the cermet and heated to at least about the liquefication temperature of the metal. Heating may take place in a vacuum or under an inert gas. Where the system of interest is B₂4C-AI, the porous preform is heated above metal melting temperature, but not higher than about 1100°C, which is about the temperature at which Al wets B^C. The metal placed in contact with the porous body prior to lique ication may be in the form of a particulate or solid bars or chips or any other suitable form.

Pressure is applied to the liquid metal such that the metal is pushed into the porous body structure of the porous compact or preform. Generally, any. pressure technique that exerts at least about 200 MPa on the metal is suitable. An external force or pressure is required to contain the preform when densities of products higher than 97 percent of theoretical density are required.

For the reactive B^C-Al system, an unexpected result is that, at densification temperatures below 1100°C, the resulting densified cermets of the invention retain a controllable chemical reactivity, in contrast to prior art systems. Thus, further heat treatment of the densified cermet is capable of forming a high content of B-C-Al phases in the cermet. For example, the resulting densified microstructure, consisting of a two-phase network of B₂1C-AIB24C₁J, interpenetrated with aluminum metal, can be post-depleted, by heating to 800°C, of Al metal in a desirable amount to form mainly AIB2 and Ali_jBC. The hardness of the cermet and all of the properties related to hardness increase during the post densification heat treatment. In general, a composition can be made that comprises 10 to 30 volume percent metal after densification and 6 to 10 volume percent metal after said metal and ceramic are reacted.

Reactive cermet products are produced when the chemically stable, high temperature-sintered Bj_jC is pressure densified with Al at temperatures above 660°C but below 1100°C. The result is an unexpected achievement regarding the Bj_jC-Al system. It is well known that there is a direct correlation between temperature and rate of diffusion such that increasing temperature increases the rate of diffusion.

One skilled in the art would expect that increasing the temperature at which the prior art vacuum infiltration occurs, that is, above the wetting temperature of Al for B^C, between 1100 and 1200°C, would increase the reactivity of the resulting Bj_jC-Al system. In the work leading to the present invention, it was discovered that the opposite result occurs, that is, the sintered Bj_jC becomes much more stable and unreactive. The present invention solves the problems of the lack of reactivity of Bj_jC and Al after densification, in addition to overcoming the low ceramic content characteristic of prior art reactive ceramic- metal compositions.

The following examples further define, but are not intended to limit the scope of the invention.

Example 1

BJJC (ESK specification 1500, manufactured by Elektroschemeltzwerk Kempten of Munich, Germany, and having an average particulate size of 3 micrometers) powder was dispersed in water at pH 6.5. The suspension was cast on a plaster of Paris mold to form a porous cera ic body having a density of 63 volume percent of theoretical (100 percent) density. The B^C greenware was dried for 24 hours at 105°C and then sintered at 2250°C for 30 minutes in a graphite element furnace to a density of 82 volume percent of theoretical. The resulting preform was cut into two parts. The first part was filled with molten aluminum (a specification 6061 alloy, manufactured by Aluminum Company of America that is a commercial grade of aluminum, comprising less than 4 percent other metals) by using the prior art vacuum infiltration process at 1180°C for 30 minutes. The second part of the Bj_jC preform was filled with the 6061 Al alloy, in accord with the present invention, by applying pressure at 700°C. A pressure of 830 MPa was used. Both parts were then heat treated at 800°C to deplete remaining metal. Vickers hardness was measured using a Vickers indentor and 30 pound (13.6 kg) load. Hardness as a function of the heat-treatment time is shown in Table 1. The metal content of the cermet during processing was monitored by the differential thermal colorimetry technique and data are presented in Table 2.

Table 1

Hardness as a Function of Time at 800°C Heat Treatment After Densification/Infiltration

Vickers Hardness ²

^Pressure densification at 830 MPa - product and process of the invention

²Comparative vacuum infiltration process - not of the invention

Table 2

Metal Remaining in Cermet After Heat Treatment, Following Metal

Densification/Infiltration

Amount of

Amount of Al Amount of Metal

Metal after introduced to After densifi¬

Heat-treatment the System cation Process at 800°C

(Vol ) (Vol )

(Vol %)

Comparative 30 26 25 Vacuum¹ Infiltration

Pressure 30 23 10 densification

2 Comparative vacuum infiltration process - not of the invention P Prreessssuurree metal infiltration - product and process of the invention Example 2

A porous greenware body of Bi_jC was prepared and sintered as described in Example 1. Then, samples were filled with Al by using vacuum infiltration of the prior art and the pressure densification process of the invention. A BiC-Al cermet having a density of 82 volume percent of theoretical 100 volume percent was produced. The mechanical properties of the densified products are presented in Table 3.

Table 3 Mechanical Properties of Example 2 Cermets

Strength¹ Toughness² Hardness³ (MPa) (MPa m^1/2) (k /mm²)

Comparative 480 7.19 1200

Vacuum infiltration

Pressure 440 6.93 1413

Infiltration,

Process of

Invention

¹4-point bend test according to Military Standard 1942 ²Chevron notch method

Vickers microhardness method using 30 pound (13.6 kg) load.

Table 3 shows the improved hardness of the product of the invention, while strength and toughness are insignificantly slightly lower than the comparative process products.

1. A densified reactive ceramic-metal composition, comprising:

a ceramic phase wherein said ceramic phase comprises before densification at least 70 percent by volume of said composition; and

a metal phase permeating said ceramic phase wherein said metal after densification remains reactive with said ceramic phase such that new ceramic-metal phases can be formed,

10 wherein said composition is at least about 95 percent of theoretical density.

2. The composition of Claim 1 wherein said ceramic phase before densification is 70 to 95 volume

-_t- percent of said composition.

3. The composition of Claim 1 wherein said ceramic phase before densification is 80 to 95 volume percent of said composition. 0 4. The composition of Claim 1 wherein said ceramic-metal composition after densification is heat treated such that additional ceramic phases are formed therein. 5 5. The composition of Claim 1 wherein said ceramic-metal composition comprises Bi_|C-Al or Bj_jC-Mg.

6. The composition of Claim 1 wherein said ceramic phase is a porous body that is sintered prior to infiltration.

7. The composition of Claim 6 wherein said porous body is sintered at greater than 2000°C.

8. A densified ceramic-metal composition comprising boron carbide that is about 70 to 95 volume percent of said composition and aluminum wherein said composition is fully densified and said metal remains reactive with said boron carbide at full density.

9. The composition of Claim 8 characterized by a fracture toughness that is 200 percent greater than B^C, above 6.5 MPa^mJ.

10. The composition of Claim 8 wherein said metal and ceramic are reacted to form B-C-metal phases.

11. The composition of Claim 10 wherein said densified composition comprises a two-phase network of B_2jC-AlB₂4Ci_j interpenetrated with aluminum metal and said metal is subsequently reacted with said ceramic phase network to form mainly A1B and Ali_}BC.

12. The composition of Claim 1 comprising about 10 to 30 volume percent metal after densification and 6 to 10 volume percent metal after said metal and ceramic are reacted.

13. A process for making a densified reactive ceramic-metal composition, comprising: forming a porous body from a particulate ceramic powder;

sintering said porous body at 2000°C or greater;

contacting said porous body with a metal;

heating said ceramic and metal to a temperature that liquefies said metal, but is below the temperature at which said metal wets said ceramic; and

applying pressure to said liquefied metal such that said metal is forced into and substantially completely fills the pores of said porous body and said ceramic-metal composition is fully densified,

wherein said metal remains reactive with said ceramic phase such that additional ceramic-metal phases can be formed.

14. The process of Claim 13 wherein said pressure is at least about 200 MPa.

15. The process of Claim 13 wherein said ceramic is B]_jC and said metal is Al.

16. The process of Claim 15 wherein heating said metal in contact with said ceramic is at about 660 to 1100°C.

17. The process of Claim 15 wherein additional B-C-metal phases of said densified ceramic-metal composition are formed by heating said composition at about 900°C for about 25 hours.

18. The process of Claim 17 wherein said heating is at about 800°C for about 20 hours.

Claims

1 .

AMENDED CLAIMS

[received by the International Bureau on 18 February 1992 (18.02.92); original claims 6 and 7 cancelled; original claim 1 amended; claims 8-18 renumbered as claims 6-16; wherein original claims

9,10,11,14-18 are amended; other claims unchanged (3 pages)]

l.A densified reactive ceramic-metal composition, comprising:

a ceramic phase wherein said ceramic phase is a sintered porous body that comprises before densification at least 70 percent by volume of said composition; and

a metal phase that permeates without wetting said ceramic phase wherein said metal after densification remains reactive with said ceramic phase such that new ceramic-metal phases can be formed,

wherein said composition is at least about 95

10 percent of theoretical density.

2. The composition of Claim 1 wherein said ceramic phase before densification is 70 to 95 volume nt- percent of said composition.

3. The composition of Claim 1 wherein said ceramic phase before densification is 80 to 95 volume percent of said composition. 0

4. The composition of Claim 1 wherein said ceramic-metal composition after densification is heat treated such that additional ceramic phases are formed therein. 5

5. The composition of Claim 1 wherein said ceramic-metal composition comprises B^C-Al or B^C-Mg.

6. A densified ceramic-metal composition comprising boron carbide that is about 70 to 95 volume percent of said composition and aluminum wherein said composition is fully densified and said metal remains reactive with said boron carbide at full density.

7. The composition of Claim 6 characterized by a fracture toughness that is 200 percent greater than Bi_jC, above 6.5 MPa-mJ.

8. The composition of Claim 6 wherein said metal and ceramic are reacted to form B-C-metal phases.

9. The composition of Claim 8 wherein said densified composition comprises a two-phase network of BJJC-A1B2 CIJ interpenetrated with aluminum metal and said metal is subsequently reacted with said ceramic phase network to form mainly A1B₂ and Alj_jBC.

10. The composition of Claim 1 comprising about 10 to 30 volume percent metal after densification and 6 to 10 volume percent metal after said metal and ceramic are reacted.

11. A process for making a densified reactive ceramic-metal composition, comprising:

forming a porous body from a particulate ceramic powder;

sintering said porous body at 2000°C or greater;

contacting said porous body with a metal; heating said ceramic and metal to a temperature that liquefies said metal, but is below the temperature at which said metal wets said ceramic; and

12. The process of Claim 11 wherein said pressure is at least about 200 MPa.

13. The process of Claim 11 wherein said ceramic is B^C and said metal is Al.

14. The process of Claim 13 wherein heating said metal in contact with said ceramic is at about 660 to 1100°C.

15. The process of Claim 13 wherein additional B-C-metal phases of said densified ceramic-metal composition are formed by heating said composition at about 900°C for about 25 hours.

16. The process of Claim 15 wherein said heating is at about 800°C for about 20 hours.