WO1992006223A1 - Nickel or cobalt based cermet with dispersed niobium carbide - Google Patents
Nickel or cobalt based cermet with dispersed niobium carbide Download PDFInfo
- Publication number
- WO1992006223A1 WO1992006223A1 PCT/AU1991/000450 AU9100450W WO9206223A1 WO 1992006223 A1 WO1992006223 A1 WO 1992006223A1 AU 9100450 W AU9100450 W AU 9100450W WO 9206223 A1 WO9206223 A1 WO 9206223A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- matrix
- cermet material
- niobium carbide
- less
- vol
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
- B23K35/327—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C comprising refractory compounds, e.g. carbides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
Definitions
- the present invention relates to a cermet material suitable for use as a hardface of a composite roll, a composite roll comprising a metal core and a hardface of a cermet material, and a method of forming a hardface on a metal core.
- the present invention relates particularly, although by no means exclusively, to rolls used in the production of structural steel. Such rolls are usually chill cast from steel-based or iron-based materials.
- the main requirements of rolls used in the production of structural steel are:
- this situation has been contributed to by difficulties applying a seemingly suitable cermet material to a metal core to form a hardface which is acceptable in terms of microstructure and bonding to the metal core.
- the microstructure considerations include the need to have a uniform dispersion of carbide particles and minimal local defects.
- a further factor which has made it difficult to use cermet materials is that it must be possible to machine the hardface t. form a surface of acceptable quality.
- An object of the present invention is to alleviate the disadvantages described in the preceding paragraphs.
- cermet material suitable for use as a hardface of a composite roll comprising, a dispersion of niobium carbide particles in a cobalt based matrix or a nickel based matrix having a carbon concentration in the matrix of less than 0.3 wt.%.
- the matrix carbon concentration is less than 0.25 wt.%.
- the matrix carbon concentration is less than 0.22 wt.% for the cobalt based matrix and less than 0.20 wt.% for the nickel based matrix.
- the niobium carbide particles comprise less than 80 vol.% of the cermet material.
- the niobium carbide particles comprise less than 50 vol.% of the cermet material.
- cobalt based matrix is herein understood to mean a matrix formed from an alloy which comprises cobalt as the major component.
- the alloy may include any one or more of the following elements.
- the alloy may include up to 40 wt.% chromium. Chromium forms a solid solution with cobalt. Chromium carbides form in the presence of carbon.. In addition, chromium oxides form as a surface layer which provides excellent high temperature oxidation and corrosion resistance.
- the alloy may include up to 25 wt.% nickel.
- the nickel is added to improve the ductility of the matrix.
- the alloy may include up to 4 wt.% molybdenum.
- the molybdenum forms carbides and is added to increase the hardness and hot strength of the matrix.
- the molybdenum also allows the matrix to age harden.
- the alloy may include up to 15 wt.% tungsten, up to 6 wt.% niobium and up to 2 wt.% tantalum. These elements have generally the same effect as molybdenum on the properties of the matrix.
- the alloy may include up to 1 wt.% titanium.
- the titanium forms an intermetallic compound with nickel which allows the matrix to age harden.
- the alloy may include up to 1 wt.% aluminium.
- the aluminium forms an intermetallic compound with nickel which allows the matrix to age harden.
- the alloy may include up to 1.5 wt. % silicon.
- the silicon acts as a deoxidiser.
- the alloy may include up to 1.5 wt. % manganese.
- the manganese acts as a deoxidiser and a desulpheriser.
- the alloy may include up to 5 wt.% iron.
- the iron is used as a cheap alloying element which has no effect on the matrix when added in amounts less than 5 wt.%.
- the alloy may include up to 1 wt.% vanadium.
- the vanadium forms carbides which increase the hardness of the matrix.
- nickel based matrix is herein understood to mean a matrix formed from an alloy which comprises nickel as the major component.
- the alloy may include any one or more of the following elements.
- the alloy may include up to 20 wt.% chromium. Chromium forms a solid solution with nickel at room and at elevated temperatures. The chromium does not form intermetallic compounds and is not subject to phase changes which cause age hardening. Chromium oxides form as a surface layer which provides excellent high temperature oxidation and corrosion resistance.
- the alloy may include up to 10 wt.% iron. In amounts up to 5 wt.% the iron is used as a cheap alloying element with no disadvantageous effects on the matrix. However, higher amounts of iron may reduce corrosion resistance and hot strength of the matrix.
- the alloy may include up to 20 wt.% molybdenum.
- the molybdenum improves resistance to acids and increases the hot strength of the matrix.
- the alloy may include up to 20 wt.% cobalt.
- the cobalt forms intermetallic compounds with titanium, molybdenum and aluminium which allows the matrix to age harden.
- the alloy may include up to 15 wt.% tungsten, up to 6 wt.% niobium and up to 2 wt.% tantalum. These elements form carbides and are added to increase the hardness of the matrix.
- the alloy may include up to 3 wt.% titanium.
- the titanium forms intermetallic compounds with tungsten, cobalt and aluminium which allows the matrix to age harden.
- the alloy may include up to 6 wt.% aluminium.
- the aluminium forms intermetallic compounds with cobalt and titanium which allows the matrix to age harde .
- the alloy may include up to 1 wt.% vanadium.
- the vanadium forms carbides which increase the hardness of the matrix.
- the alloy may include up to 6 wt.% silicon.
- the silicon acts as a deoxidiser, a fluxing agent, and improves corrosion resistance of the matrix.
- the alloy may include up to 3.5 wt.% manganese.
- the manganese acts as a deoxidiser and desulphuriser and improves hot corrosion resistance of the matrix.
- a composite roll comprising a steel based or iron based core and a hardfacing of the cermet material described in the preceding paragraphs.
- a method of forming a composite roll comprising, welding a cermet material comprising particles of niobium carbide and a cobalt or nickel based alloy onto a core of steel based or iron based material to form a hardface comprising a dispersion of niobium carbide particles in a cobalt based matrix or a nickel based matrix having a carbon concentration in the matrix of less than 0.3 wt.%.
- the matrix carbon concentration is less than 0.25 wt.%.
- the matrix carbon concentration is less than 0.22 wt.% for the cobalt based matrix and less than 0.20 wt.% for the nickel based matrix.
- the niobium carbide particles comprise less than 80 vol.% of the cermet material.
- the niobium carbide particles comprise less than 50 vol.% of the cermet material.
- the metallic particles are spheroidal and comprise low oxygen and low slag concentrations. It is also preferred that the metallic particles are between 45 and 150 micron in diameter.
- the diameters of the niobium carbide particles are between 45 and 90 micron.
- the diameters of the niobium carbide particles may be within the following ranges:
- the method further comprises, welding a buffer material having a matrix carbon concentration of less than 0.3 wt.% onto the core prior to welding the cermet material onto the buffer layer.
- buffer layer One reason for the inclusion of the buffer layer is to avoid an increase of the matrix carbon concentration of the hardface above 0.3 wt.% due to dilution of the cermet material as a result of melting of the core in the molten pool formed during welding of the cermet material. Another reason for the inclusion of the buffer layer is to avoid an increase in the matrix iron concentration above that present in the cermet material.
- the method comprises plasma transferred arc welding of the cermet material and, where applicable, the buffer material onto the core.
- the powder and plasma gas comprises between 25 and 100 vol.% argon and up to 75 vol.% helium.
- 100 vol.% argon as the powder and plasma gas results in less primary niobium carbide dissolving in the molten pool formed during welding of the cermet material and hence less secondary carbide precipitating.
- 100 vol.% argon also results in a more uniform carbide distribution.
- the overall cermet material hardness is reduced for a given vol.% of niobium carbide when 100 vol.% argon is used as the powder and plasma gas.
- the use of helium in the powder and plasma gas has the beneficial effects of reducing nozzle build-up and allowing a thicker weld deposit.
- the shielding gas comprises argon 100 vol.%.
- the method comprises electromagnetic stirring of the weld pool.
- the present invention is based to a large extent on the realisation that, in order to minimise welding and machinability problems and to provide a hardfacing which has the optimum properties for use in rolling applications, the hardfacing should comprise a cermet material comprising a dispersion of niobium carbide particles in a cobalt or nickel based metallic matrix in which the carbon concentration is less than 0.3 wt.%, preferably less than 0.25 wt.%.
- the matrix carbon concentration influences the dispersion of niobium carbide in the matrix such that at low matrix carbon concentrations there is a uniform dispersion of niobium carbide and as the matrix carbon concentration increases there is an increase in the likelihood of segregation of the niobium carbides.
- the matrix iron concentration has a marked effect on the properties of the hardfacing and it is important to avoid dilution of the cermet material with iron from the core;
- Fig. 1 is a series of schematic views illustrating the deposition structure of NbC/Nistelle C, NbC/Stellite 21 and NbC/316 stainless steel cermet material hardfacings and buffer layers welded onto steel substrates as part of an experimental procedure to evaluate the present invention
- Fig. 2 is a photomicrograph (magnification 160) of a typical view of a 50 vol.% NbC/Nistelle C hardfacing;
- Fig. 3 is a photomicrograph (magnification 160) of a typical view of a 30 vol.% NbC/Nistelle C hardfacing;
- Fig. 4 is a photomicrograph (magnification 160) of a typical view of a 20 vol.% NbC/Nistelle C hardfacing;
- Fig. 5 is a photomicrograph (magnification 160) of a typical view of a 50 vol.% NbC/Stellite 21 hardfacing;
- Fig. 6 is a photomicrograph (magnification 160) of a typical view of a 30 vol.% NbC/Stellite 21 hardfacing
- Fig. 7 is a photomicrograph (magnification 12.8) of a typical view of a 20 vol.% NbC/Stellite 21 hardfacing
- Fig. 8 is a photomicrograph (magnification 160) of a typical view of a 50 vol.% NbC/316 stainless steel hardfacing;
- Fig. 9 is a photomicrograph (magnification 12.8) of a typical view of a 30 vol.% NbC/316 stainless steel hardfacing;
- Fig. 10 is a photomicrograph (magnification 12.8) of a typical view of a 20 vol.% NbC/316 stainless steel hardfacing;
- Fig. 11 is a plot of Vickers hardness (HV30) versus vol.% NbC for the NbC/Nistelle C, NbC/Stellite 21 and NbC/316 stainless steel hardfacings.
- the cermet materials tested comprised:
- the buffer layer comprised Stellite 21 in the case of the NbC/Stellite 21 and NbC/316 stainless steel cermet materials and Nistelle C in the case of the NbC/Nistelle C cermet materials.
- FIGS. 2 to 4 show that the welding of 50 vol.%, 30 vol.% and 20 vol.% NbC/Nistelle C on a Nistelle C buffer layer produced a uniform distribution of primary NbC in a matrix displaying a dendritic dispersion of eutectoid with no weld defects or linear carbides.
- the photomicrograph in Fig. 5 shows that the welding of 50 vol.% NbC/Stellite 21 on a Stellite 21 buffer layer produced an uneven distribution of primary NbC particles in a matrix bearing a dendritic dispersion of rather course NbC precipitated from solution and a dendritic dispersion of finer carbides associated with the Stellite 21. There were no weld defects or linear carbides. Nevertheless, the uneven distribution of primary NbC particles is unacceptable from a rolling viewpoint. The results for the 30 vol.% NbC/Stellite 21 were equally if not more unfavourable. With reference to Fig. 6, the photomicrograph reveals pronounced segregation between primary and larger secondary NbC particles within a matrix bearing fine NbC and Stellite 21 carbides in dendritic arrangement.
- the photomicrographs in Figs. 8 to 10 show that the welding of 50 vol.%, 30 vol.% and 20 vol.% NbC/316 stainless steel revealed significant segregation of primary and larger secondary NbC particles.
- the matrix comprises coarse and fine NbC and fine unidentified carbides in a dendritic arrangement. There were no weld defects or linear carbides. Nevertheless, as noted above, the uneven distribution of primary NbC particles is unacceptable from a rolling viewpoint.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Powder Metallurgy (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3515700A JPH06501984A (en) | 1990-10-02 | 1991-10-02 | Nickel or cobalt based cermet with niobium carbide dispersed |
CA002093238A CA2093238A1 (en) | 1990-10-02 | 1991-10-02 | Nickel or cobalt based cermet with dispersed niobium carbide |
BR919106943A BR9106943A (en) | 1990-10-02 | 1991-10-02 | CERMET MATERIAL AND PROCESS TO FORM A COMPOUND LAMINATION CYLINDER |
AU86200/91A AU658371B2 (en) | 1990-10-02 | 1991-10-02 | Nickel or cobalt based cermet with dispersed niobium carbide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPK258490 | 1990-10-02 | ||
AUPK2584 | 1990-10-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992006223A1 true WO1992006223A1 (en) | 1992-04-16 |
Family
ID=3774982
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU1991/000450 WO1992006223A1 (en) | 1990-10-02 | 1991-10-02 | Nickel or cobalt based cermet with dispersed niobium carbide |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0552194A4 (en) |
JP (1) | JPH06501984A (en) |
BR (1) | BR9106943A (en) |
CA (1) | CA2093238A1 (en) |
WO (1) | WO1992006223A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0593408A1 (en) * | 1992-09-11 | 1994-04-20 | BÖHLER Edelstahl GmbH | Compound roll |
WO1994011128A1 (en) * | 1992-11-18 | 1994-05-26 | The Broken Hill Proprietary Company Limited | A composite roll |
US20150044088A1 (en) * | 2013-08-08 | 2015-02-12 | Ut-Battelle, Llc | Creep-Resistant, Cobalt-Free Alloys for High Temperature, Liquid-Salt Heat Exchanger Systems |
US9540714B2 (en) | 2013-03-15 | 2017-01-10 | Ut-Battelle, Llc | High strength alloys for high temperature service in liquid-salt cooled energy systems |
US9605565B2 (en) | 2014-06-18 | 2017-03-28 | Ut-Battelle, Llc | Low-cost Fe—Ni—Cr alloys for high temperature valve applications |
US9683280B2 (en) | 2014-01-10 | 2017-06-20 | Ut-Battelle, Llc | Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems |
US9683279B2 (en) | 2014-05-15 | 2017-06-20 | Ut-Battelle, Llc | Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems |
CN117966083A (en) * | 2024-04-02 | 2024-05-03 | 西安理工大学 | Surface boronizing method for mirror symmetry double-gradient laminated composite material |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1001186A (en) * | 1961-03-23 | 1965-08-11 | Birmingham Small Arms Co Ltd | Improvements in or relating to powder metallurgy |
US4089466A (en) * | 1977-03-30 | 1978-05-16 | Lomax Donald P | Lining alloy for bimetallic cylinders |
-
1991
- 1991-10-02 JP JP3515700A patent/JPH06501984A/en active Pending
- 1991-10-02 EP EP91917318A patent/EP0552194A4/en not_active Withdrawn
- 1991-10-02 WO PCT/AU1991/000450 patent/WO1992006223A1/en not_active Application Discontinuation
- 1991-10-02 CA CA002093238A patent/CA2093238A1/en not_active Abandoned
- 1991-10-02 BR BR919106943A patent/BR9106943A/en unknown
Non-Patent Citations (5)
Title |
---|
Derwent Abstract Accession No. 87-351459/50, class P53, JP,A,62253747 (HITACHI METAL KK) 5 November 1987 (05.11.87) see Abstract. * |
Derwent Abstract Accession No. 88-342806/48, class P51, P55, JP,A,63256275 (KUBOTA KK), 24 October 1988 (24.10.88) see Abstract. * |
PATENTS ABSTRACTS OF JAPAN, C-302, page 18, JP,A,60082644 (HITACHI KINZOKU KK) 10 May 1985 (10.05.85) see Abstract. * |
PATENTS ABSTRACTS OF JAPAN, C-77, page 3549, JP,A,52103307 (MITSUBISHI KINZOKU KK) 30 August 1977 (30.08.77) see Abstract. * |
See also references of EP0552194A4 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0593408A1 (en) * | 1992-09-11 | 1994-04-20 | BÖHLER Edelstahl GmbH | Compound roll |
WO1994011128A1 (en) * | 1992-11-18 | 1994-05-26 | The Broken Hill Proprietary Company Limited | A composite roll |
US9540714B2 (en) | 2013-03-15 | 2017-01-10 | Ut-Battelle, Llc | High strength alloys for high temperature service in liquid-salt cooled energy systems |
US20150044088A1 (en) * | 2013-08-08 | 2015-02-12 | Ut-Battelle, Llc | Creep-Resistant, Cobalt-Free Alloys for High Temperature, Liquid-Salt Heat Exchanger Systems |
US9435011B2 (en) * | 2013-08-08 | 2016-09-06 | Ut-Battelle, Llc | Creep-resistant, cobalt-free alloys for high temperature, liquid-salt heat exchanger systems |
US9683280B2 (en) | 2014-01-10 | 2017-06-20 | Ut-Battelle, Llc | Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems |
US9683279B2 (en) | 2014-05-15 | 2017-06-20 | Ut-Battelle, Llc | Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems |
US9605565B2 (en) | 2014-06-18 | 2017-03-28 | Ut-Battelle, Llc | Low-cost Fe—Ni—Cr alloys for high temperature valve applications |
US9752468B2 (en) | 2014-06-18 | 2017-09-05 | Ut-Battelle, Llc | Low-cost, high-strength Fe—Ni—Cr alloys for high temperature exhaust valve applications |
CN117966083A (en) * | 2024-04-02 | 2024-05-03 | 西安理工大学 | Surface boronizing method for mirror symmetry double-gradient laminated composite material |
CN117966083B (en) * | 2024-04-02 | 2024-06-04 | 西安理工大学 | Surface boronizing method for mirror symmetry double-gradient laminated composite material |
Also Published As
Publication number | Publication date |
---|---|
JPH06501984A (en) | 1994-03-03 |
BR9106943A (en) | 1993-08-03 |
EP0552194A4 (en) | 1995-09-27 |
CA2093238A1 (en) | 1992-04-03 |
EP0552194A1 (en) | 1993-07-28 |
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