WO1981001143A1 - Ceramic compositions - Google Patents

Ceramic compositions Download PDF

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Publication number
WO1981001143A1
WO1981001143A1 PCT/US1980/001262 US8001262W WO8101143A1 WO 1981001143 A1 WO1981001143 A1 WO 1981001143A1 US 8001262 W US8001262 W US 8001262W WO 8101143 A1 WO8101143 A1 WO 8101143A1
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Prior art keywords
weight percent
ceramic composition
alumina
compositions
transverse rupture
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Application number
PCT/US1980/001262
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French (fr)
Inventor
S Lee
Original Assignee
Minnesota Mining & Mfg
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Publication date
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Publication of WO1981001143A1 publication Critical patent/WO1981001143A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111Fine ceramics
    • C04B35/117Composites

Definitions

  • the present invention relates to ceramic compositions with superior mechanical properties of wear resistance and transverse rupture strength.
  • the ceramic compositions of the present invention comprise aluminum oxide and titanium carbonitride with or without metal phases.
  • oxides will, in general, exhibit higher wear resistance than the corresponding carbides or pure metals probably due to their chemical stability resulting from their more negative standard free energy of formation. This is especially evident when the materials are used in wear applications such as in metal cutting in which relatively high interface temperatures are generated thereby making diffusion of atoms across the interface a rate-controlling step for the wear process.
  • the overall wear resistance ranking of ceramic materials in metal cutting is, in general, in the order of oxides, nitrides, and finally, carbides with their correspondingly lower negative free energy of formation. Yates, U.S.
  • Patent 3,409,419 which is directed to ceramic compositions consisting of essential nitrides bonded with iron, cobalt, or nickel and wherein up to fifty percent of the essential nitride can be substituted with a carbide provided that the carbide cannot reduce the nitride content below 20 volume percent is another attempt to provide wear resistant compounds with exceptional properties.
  • the present invention provides ceramic compositions having improved toughness properties without materially affecting the inherent wear resistance characteristics thereof. This is achieved by adding an intermediate nitride phase to the alumina-titanium carbide compositions. It was found that in so doing, the titanium carbide and titanium nitride form a solid solution in the hot forming step thereby resulting in an alumina-titanium carbonitride composition of increased strength and wear resistance.
  • the ceramic compositions of the present invention comprise 10-90 weight percent alumina and 90-10 weight percent titanium carbonitride, viz.
  • c is titanium carbide and n is titanium nitride and wherein said carbonitride includes 0-30 weight percent of a metal phase comprised of Group IVB or Iron group elements including Mo or combinations thereof.
  • Articles made of such compositions are especially effective in applications where both wear resistance and toughness are required such as in metal cutting operations.
  • compositions of the present invention have average transverse rupture strengths above such alumina-TiC compositions and also possess generally improved wear resistance properties.
  • Example 1 A 700 gram mixture of alumina having an average particle size of 0.65 micron, titanium carbide powder having an average particle size of 3-5 micron, titanium nitride powders having an average particle size of 1 micron, and molybdenum powders having an average particle size of 1 micron, in a weight ratio of 10 percent, 41 percent, 40 percent, 4.5 percent and 4.5 percent, respectively, was ball milled in Soltrol for 40 hours. The milled powder mixture was vacuum dried at 240°C for 14 hours and subsequently hot pressed at 1550°C for 7 minutes under a presure of 280 kg/cm 2 .
  • Example 16 is directed to a conventional composition of alumina-TiC for comparison with the compositions of the present invention, alumina-titanium carbonitride composition where the titanium nitride is the major phase, i.e.,
  • Example 17 should be compared with Examples 1 and 2 where only the ratios of titanium carbide and titanium nitride have been changed leaving the alumina and metal phase constant. One can see similar differences by comparing Example 18 to Example 6 and also comparing Example 19 to Example 12.
  • compositions of the present invention are significantly tougher than pure alumina materials and are generally superior to the alumina-titanium carbide composition of Example 14 in either machining tests and/or transverse rupture strength, Furthermore, it can be seen that having titanium carbide as the major phase of the titanium carbonitride generally gives superior results to compositions where titanium nitride is the major component.
  • Example 10 In addition to the machining tests described previously, a comparative wear machining test was conducted for the compositions of Example 10 and Example 16. In this test, SNG 432 tools were used to turn 4142 steel having a Rockwell C hardness of 57 at 101.6 surface cm per sec, 0.38 mm DOC (Depth of Cut) and a feed rate of 0.254 mm per revolution for 30 minutes. The uniform flank wear of the tools was read every two minutes. The results are given in Table 2.
  • compositions of the present invention show greater wear resistance than currently commercially available compositions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

Ceramic compositions with mechanical properties, namely, wear resistance and transverse rupture strength, far exceeding that of conventional ceramic materials have been prepared. Said compositions comprise aluminum oxide and titanium carbonitride with or without metal phases. Articles made of such compositions can be used efficiently in such areas as metal cutting and other wear resistance applications.

Description

CERAMIC COMPOSITIONS
Technical Field
The present invention relates to ceramic compositions with superior mechanical properties of wear resistance and transverse rupture strength. The ceramic compositions of the present invention comprise aluminum oxide and titanium carbonitride with or without metal phases.
Background Art
Although ceramic materials, especially alumina, have been used in many wear applications, their use has been severely limited due to their brittle nature or lack of toughness. Consequently, in applications where both wear resistance and toughness are needed, tungsten carbide and other complex carbides have been the materials of choice.
Numerous efforts have been made to improve the toughness of ceramic oxides while retaining their inherent wear resistant character, but such efforts have met with only limited success. The combination of alumina with titanium carbide is one such example.
It is commonly believed that oxides will, in general, exhibit higher wear resistance than the corresponding carbides or pure metals probably due to their chemical stability resulting from their more negative standard free energy of formation. This is especially evident when the materials are used in wear applications such as in metal cutting in which relatively high interface temperatures are generated thereby making diffusion of atoms across the interface a rate-controlling step for the wear process. According to this theory, the overall wear resistance ranking of ceramic materials in metal cutting is, in general, in the order of oxides, nitrides, and finally, carbides with their correspondingly lower negative free energy of formation. Yates, U.S. Patent 3,409,419 which is directed to ceramic compositions consisting of essential nitrides bonded with iron, cobalt, or nickel and wherein up to fifty percent of the essential nitride can be substituted with a carbide provided that the carbide cannot reduce the nitride content below 20 volume percent is another attempt to provide wear resistant compounds with exceptional properties.
Disclosure of Invention
The present invention provides ceramic compositions having improved toughness properties without materially affecting the inherent wear resistance characteristics thereof. This is achieved by adding an intermediate nitride phase to the alumina-titanium carbide compositions. It was found that in so doing, the titanium carbide and titanium nitride form a solid solution in the hot forming step thereby resulting in an alumina-titanium carbonitride composition of increased strength and wear resistance.
The ceramic compositions of the present invention comprise 10-90 weight percent alumina and 90-10 weight percent titanium carbonitride, viz.
Figure imgf000004_0001
wherein c is titanium carbide and n is titanium nitride and wherein said carbonitride includes 0-30 weight percent of a metal phase comprised of Group IVB or Iron group elements including Mo or combinations thereof. Articles made of such compositions are especially effective in applications where both wear resistance and toughness are required such as in metal cutting operations.
Detailed Description Recent trends and more demanding conditions both in metal cutting operations and other wear applications have created the need for materials which are more wear resistant and tougher than conventional ceramic materials. As hereinabove noted, pure alumina cutting tools have been used in only limited cases such as in simple turning due to their lack of toughness. The highest strength hot pressed alumina may have a transverse rupture strength of about 7000 kg/cm2. Alumina-TiC cutting tools were more recently introduced and have successfully overcome some of the difficulties encountered with pure alumina tools. The transverse rupture strength of alumina-TiC materials is about 8400 kg/cm2. While it is common for both metallic and ceramic materials that any gain in toughness, measured by transverse rupture strength of the material is accompanied by some sacrifice in wear resistance such as measured by turning tests, the compositions of the present invention have average transverse rupture strengths above such alumina-TiC compositions and also possess generally improved wear resistance properties.
The following specific examples are intended to illustrate more clearly the nature of the present invention.
Example 1 A 700 gram mixture of alumina having an average particle size of 0.65 micron, titanium carbide powder having an average particle size of 3-5 micron, titanium nitride powders having an average particle size of 1 micron, and molybdenum powders having an average particle size of 1 micron, in a weight ratio of 10 percent, 41 percent, 40 percent, 4.5 percent and 4.5 percent, respectively, was ball milled in Soltrol for 40 hours. The milled powder mixture was vacuum dried at 240°C for 14 hours and subsequently hot pressed at 1550°C for 7 minutes under a presure of 280 kg/cm2. The resulting hot pressed parts had a density of 5.31 g/cc and a Rockwell A (RA) hardness of 94. Cutting tool inserts having a geometry of 12.7 mm x 12.7 mm x 4.75 mm have been fabricated from hot pressed blanks. These tools have been used, in machining tests, to turn 4142 alloy steel tube of Rockwell hardness of RQ 52-58. The results, given in Table 1, represent the surface speed of the work material at which the tool broke in this machining test where the surface speed was increased at an increment of 25.4 surface cm per minute (scps), two minutes at each increment starting from 50.8 scps.
Samples of transverse rupture test of geometry, 1,7 in x 1.7 m x 19 mm, were also made and tested in 3-point bending tests. The results are given in Table 1.
Examples 2-16 In these Examples, ceramic compositions were produced as 700 gram mixtures with the indicated components in the proportions shown in Table 1 , following the procedure of Example 1 and tested in the same manner hereinbefore set forth.
Figure imgf000007_0001
Figure imgf000008_0001
Figure imgf000008_0002
Example 16 is directed to a conventional composition of alumina-TiC for comparison with the compositions of the present invention, alumina-titanium carbonitride composition where the titanium nitride is the major phase, i.e.,
Figure imgf000009_0001
where c represents titanium carbide and n represents titanium nitride. Example 17 should be compared with Examples 1 and 2 where only the ratios of titanium carbide and titanium nitride have been changed leaving the alumina and metal phase constant. One can see similar differences by comparing Example 18 to Example 6 and also comparing Example 19 to Example 12.
Examination of Table I will show that the compositions of the present invention are significantly tougher than pure alumina materials and are generally superior to the alumina-titanium carbide composition of Example 14 in either machining tests and/or transverse rupture strength, Furthermore, it can be seen that having titanium carbide as the major phase of the titanium carbonitride generally gives superior results to compositions where titanium nitride is the major component.
In addition to the machining tests described previously, a comparative wear machining test was conducted for the compositions of Example 10 and Example 16. In this test, SNG 432 tools were used to turn 4142 steel having a Rockwell C hardness of 57 at 101.6 surface cm per sec, 0.38 mm DOC (Depth of Cut) and a feed rate of 0.254 mm per revolution for 30 minutes. The uniform flank wear of the tools was read every two minutes. The results are given in Table 2.
Figure imgf000010_0001
As can be seen in Table 2, the compositions of the present invention show greater wear resistance than currently commercially available compositions.

Claims

WHAT IS CLAIMED IS:
1. Ceramic composition having superior mechanical properties of wear resistance and transverse rupture strength comprising about 10 to 90 weight percent aluminum oxide and about 90 to 10 weight percent titanium carbonitride, the major phase of said carbonitride comprising titanium carbide, said carbonitride including up to 30 weight percent of a metal phase comprised of group IVB or Iron group elements including molybdenum or combination thereof.
2. Ceramic composition according to claim 1 wherein the metal phase comprises nickel and molybdenum.
3. Ceramic composition according to claim 1 comprising 30 weight percent alumina, 49 weight percent titanium carbide and 21 weight percent titanium nitride, said ceramic composition having a transverse rupture strength of 11,130 kg/cm2.
4. Ceramic composition according to claim 1 comprising 10 weight percent alumina, 61 weight percent titanium carbide, 20 weight percent titanium nitride, 4.5 weight percent nickel and 4.5 weight percent molybdenum, said ceramic composition having a transverse rupture strength of 17,500 kg/cm2.
5. Ceramic composition according to claim 1 comprising 68.7 weight alumina, 22.2 weight percent titanium carbide, 7.5 weight percent titanium nitride, 0.8 weight percent nickel and 0.8 weight percent molybdenum, said ceramic composition having a transverse rupture strength of 9660 kg/cm2.
PCT/US1980/001262 1979-10-26 1980-09-22 Ceramic compositions WO1981001143A1 (en)

Applications Claiming Priority (2)

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US8837779A 1979-10-26 1979-10-26
US88377 1987-08-24

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4964540A (en) * 1984-10-17 1990-10-23 Exxel Container, Inc. Pressurized fluid dispenser and method of making the same
EP0443624A1 (en) * 1990-02-23 1991-08-28 Mitsubishi Materials Corporation Alumina based ceramics
CN102029298A (en) * 2010-12-22 2011-04-27 济南大学 Al2O3/TiC ceramic drawing die and manufacturing method thereof

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1072182B (en) * 1959-12-24 VEB Hartmetallwerk Im'meib'orn, Imirmel'born (Thur.) Process for the production of ceramic composites
US3143413A (en) * 1960-06-03 1964-08-04 Siegfried G Krapf Ceramic materials and methods for their manufacture
FR1600142A (en) * 1968-12-31 1970-07-20
US3565643A (en) * 1969-03-03 1971-02-23 Du Pont Alumina - metalline compositions bonded with aluminide and titanide intermetallics
US3580708A (en) * 1969-03-06 1971-05-25 Nippon Tungsten Method of forming cutting tool materials consisting of alumina and titanium carbide
US3669695A (en) * 1969-11-21 1972-06-13 Du Pont Titanium and/or zirconium nitride based articles of jewelry
US3705025A (en) * 1968-11-18 1972-12-05 Du Pont Cutting tool
DE2334172A1 (en) * 1972-07-11 1974-01-24 Combustion Eng METHOD OF MANUFACTURING A MOLDED BODY
US4022584A (en) * 1976-05-11 1977-05-10 Erwin Rudy Sintered cermets for tool and wear applications
NL7605917A (en) * 1976-06-02 1977-12-06 Philips Nv Sintered articles of aluminium oxide and iron, cobalt or nickel - have good electrical and thermal conductivity e.g. for semiconductors
SU565488A1 (en) * 1974-11-12 1979-05-30 Всесоюзный научно-исследовательский и проектный институт тугоплавких металлов и твердых сплавов Ceramic cutting material
JPS54134717A (en) * 1978-04-12 1979-10-19 Nippon Tungsten Cutting tool material and its manufacture
US4204873A (en) * 1978-06-13 1980-05-27 Ngk Spark Plug Co., Ltd. Sintered ceramic body for cutting tools
US4217113A (en) * 1977-06-13 1980-08-12 Massachusetts Institute Of Technology Aluminum oxide-containing metal compositions and cutting tool made therefrom
JPH0589410A (en) * 1991-09-30 1993-04-09 Toshiba Corp Floppy disk device
JPH05226682A (en) * 1992-02-14 1993-09-03 Sanyo Electric Co Ltd Solar cell tree
JPH05237913A (en) * 1992-02-27 1993-09-17 Mitsubishi Heavy Ind Ltd Screw for high kneading

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1072182B (en) * 1959-12-24 VEB Hartmetallwerk Im'meib'orn, Imirmel'born (Thur.) Process for the production of ceramic composites
US3143413A (en) * 1960-06-03 1964-08-04 Siegfried G Krapf Ceramic materials and methods for their manufacture
US3705025A (en) * 1968-11-18 1972-12-05 Du Pont Cutting tool
FR1600142A (en) * 1968-12-31 1970-07-20
US3565643A (en) * 1969-03-03 1971-02-23 Du Pont Alumina - metalline compositions bonded with aluminide and titanide intermetallics
US3580708A (en) * 1969-03-06 1971-05-25 Nippon Tungsten Method of forming cutting tool materials consisting of alumina and titanium carbide
US3669695A (en) * 1969-11-21 1972-06-13 Du Pont Titanium and/or zirconium nitride based articles of jewelry
DE2334172A1 (en) * 1972-07-11 1974-01-24 Combustion Eng METHOD OF MANUFACTURING A MOLDED BODY
SU565488A1 (en) * 1974-11-12 1979-05-30 Всесоюзный научно-исследовательский и проектный институт тугоплавких металлов и твердых сплавов Ceramic cutting material
US4022584A (en) * 1976-05-11 1977-05-10 Erwin Rudy Sintered cermets for tool and wear applications
NL7605917A (en) * 1976-06-02 1977-12-06 Philips Nv Sintered articles of aluminium oxide and iron, cobalt or nickel - have good electrical and thermal conductivity e.g. for semiconductors
US4217113A (en) * 1977-06-13 1980-08-12 Massachusetts Institute Of Technology Aluminum oxide-containing metal compositions and cutting tool made therefrom
JPS54134717A (en) * 1978-04-12 1979-10-19 Nippon Tungsten Cutting tool material and its manufacture
US4204873A (en) * 1978-06-13 1980-05-27 Ngk Spark Plug Co., Ltd. Sintered ceramic body for cutting tools
JPH0589410A (en) * 1991-09-30 1993-04-09 Toshiba Corp Floppy disk device
JPH05226682A (en) * 1992-02-14 1993-09-03 Sanyo Electric Co Ltd Solar cell tree
JPH05237913A (en) * 1992-02-27 1993-09-17 Mitsubishi Heavy Ind Ltd Screw for high kneading

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4964540A (en) * 1984-10-17 1990-10-23 Exxel Container, Inc. Pressurized fluid dispenser and method of making the same
EP0443624A1 (en) * 1990-02-23 1991-08-28 Mitsubishi Materials Corporation Alumina based ceramics
US5188908A (en) * 1990-02-23 1993-02-23 Mitsubishi Materials Corporation Al2 O3 Based ceramics
CN102029298A (en) * 2010-12-22 2011-04-27 济南大学 Al2O3/TiC ceramic drawing die and manufacturing method thereof
CN102029298B (en) * 2010-12-22 2013-03-06 济南大学 Al2O3/TiC ceramic drawing die and manufacturing method thereof

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