GB2033426A - Molybdenum-tungsten Carbide Products - Google Patents

Molybdenum-tungsten Carbide Products Download PDF

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Publication number
GB2033426A
GB2033426A GB7930720A GB7930720A GB2033426A GB 2033426 A GB2033426 A GB 2033426A GB 7930720 A GB7930720 A GB 7930720A GB 7930720 A GB7930720 A GB 7930720A GB 2033426 A GB2033426 A GB 2033426A
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molybdenum
carbide
tungsten
carbon
metal
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GB7930720A
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Cabot Corp
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Cabot Corp
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    • 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
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/32Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
    • B23K35/327Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C comprising refractory compounds, e.g. carbides
    • 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
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5626Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on tungsten carbides
    • 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
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06Alloys 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
    • C22C29/067Alloys 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 comprising a particular metallic binder

Abstract

A molybdenum-tungsten carbide product for use especially as a filter for welding rods for hard facing deposits. The product is believed to be principally complex carbides, (Mo, W)C+(Mo, W)2C. The optimum chemical composition comprises essentially about 30 w/o molybdenum, about 5 w/o carbon and the balance tungsten. The optimum metal-to-carbon ratio is recommended at about 1 to 1.48. The product is made by fusing and casting a powder mixture of Mo, W and C.

Description

SPECIFICATION Molybdenum-tungsten Carbide Products This invention relates to wear-resistant products and, more specifically, to articles composed of molybdenum-modified tungsten carbide.
Tungsten carbide is a very versatile commodity in many industrial and consumer uses. Its hardness and resistance to wear are outstanding features. For this reason, one of the principal uses is as a component in hardfacing applications, for example, filled tube rods, cast rods, powder mixtures and the like. In these applications, tungsten carbide may be used as a casting, as particles bound in a matrix, as particulates in a powder mixture, as sintered powder metallurgy products, and other forms.
For the purposes of this application, essentially all uses of tungsten carbide are included within the scope of this invention.
Molybdenum has been associated as interchangeable with tungsten for certain alloy systems in the metallurgical arts. Chemical and physical properties show tungsten and molybdenum as alloying agents to be somewhat similar in many respects. This invention is not concerned with elements in metal alloys. Some fundamental work has been reported in the concept of a molybdenum-tungsten monocarbide ((Mo,W)C). Several theories are available as exemplified in two recent studies: (1) "Progress summary" NSF Grant DNR 74-23256 August 1975 to August 1976, Oregon Graduate Centre, Albany, Oregon by E. Rudy and, (2) "Constitution Diagrams of Metallic Systems" Poroshkivaya Metallurgiya No. 3, 1973, (page 74) by L. W. Gorhkova et al. These studies are essentially concerned with opposing academic scientific theories, relating to phase diagrams.
U.S. Patent No. 4,066,451 discloses a method for making metal carbides.
The present invention provides an article of manufacture composed at least in part of a metal carbide, said metal consisting of molybdenum and tungsten, said carbide having essentially the hardness and wear resistance of tungsten carbide.
Preferably the molybdenum-tungsten carbide article consists essentially of 10 to 60 percent by weight molybdenum and more preferably 30% molybdenum. For best results, it is recommended a metal to carbon ratio be controlled between 1.2 and 2.0 and preferably over 1.48 up to 1.8.
The invention also includes articles in the form of material for making hard-face deposits, as filler material in filled tube rods and in the form of castings.
Although the exact structure is not completely understood, the molybdenum-tungsten carbide of this invention is believed to be a mixture of complex carbides with a crystal structure similar to principally (Mo,W)C+(Mo,W)2C. The molybdenum-tungsten carbide of this invention is produced by a mixture of molybdenum and tungsten metals together with carbon to yield the composition of this invention. Essentially, the molybdenum atoms are believed to replace some of the tungsten atoms thereby yielding a molybdenum-modified tungsten carbide.
All compositions given in this specification and claims are in percent by weight (w/o) unless otherwise stated.
Molybdenum may replace tungsten within the range about 10% to about 62% as shown by the examples described in Table 1. Preferably molybdenum content range may be about 17 to about 47%.
The molybdenum tungsten carbide product to this invention may contain up to about 1096 impurities including molybdenum carbide, tungsten carbide and free carbon.
Table 1 presents compositions and engineering properties data for experimental molybdenumtungsten carbide examples of this invention and Example No.001 represents unmodified tungsten carbide.
The first column in Table 1 presents the molybdenum to tungsten ratio (within the parentheses) and the ratio of metal to carbon. For example, the first one listed has a molybdenum-to-tungsten ratio of .21 to .79 and a metal-to-carbon ratio of 1 to 1.23.
The second column gives the example number. The third column presents the actual composition of the examples in weight percent w/o.
The fourth column presents the density of the examples in cast form, in grams per cubic centimeters.
The last column presents the hardness of the cast examples. Hardness was determined by a Kentron, Micro-hardness testing unit, Model No. AK.
The data appear to be totally random at first glance. It has been discovered that when the metal to-carbon ratio is 1.48 or more, the hardness is over 1800 Kg.mm2, in every example. When the metal to-carbon ratio is less than 1.48, the hardness is not consistent. Only 5 out of 13 examples had a hardness over 1800 Kg.mm2, as shown in Table 2. The 1.48 ratio number is effective regardless of the molybdenum-to-tungsten ratio. This discovery makes it possible to consistently control the product to a minimum of about 1800 Kg.mm2 hardness. For use where optimum hardness is not a requirement, the metal-to-carbon ratio does not need to be controlled to a 1.48 minimum.
X-ray analyses of the products of this invention show the carbide to have the crystal structure isomorphous with (Mo,W)C+(Mo,W)2C with minor impurities (less than 10%) of molybdenum carbides, tungsten carbides and free carbon. Samples of this invention wherein the metal-to-carbon ratio was about 1.8 or more tended to contain more free carbon.
The carbide article of this invention may be prepared by any means now known to commercially produce tungsten carbide. Instead of tungsten alone as the starting material, the article of this invention requires molybdenum together with tungsten as the starting metals to yield the molybdenum-tungsten carbide.
Each specimen was prepared from a desired ratio of molybdenum and tungsten thoroughly mixed into a powder blend. Five pounds of each powder blend was charged into a furnace containing carbon and resistance-heated by well-known means. As the heat increased, the carbon diffused into the powder blend. This lowered the melting point of the powders, thus melting the powder blend. The carbon content is controlled by the time the melt is held in the furnace. Longer hold times increase the carbon content. The melt was then centrifugally cast. Some of the cast carbide was tested as-cast and some of the cast carbide was crushed and screened into various mesh sizes. The crushed carbide was classified into various mesh sizes by the U.S. standard sieve series.
Portions of the various mesh sizes were used to produce filled rods for hardfacing as shown in Table 3. The crushed carbide was packed into AISI 1008 steel tubes to form filled tube rods for deposition testing, as shown in Table 3.
Deposits from each filled tube rod were made with an oxyacetylene gas torch with the flame at about 6,0000F. The deposition process was similar to the deposition of commercial tube rods filled with tungsten carbide. The deposits were ground flat to a 120-grit finish before abrasive testing.
The deposits were tested for abrasive wear characteristics on a Riley-Stoker unit as described in the "ASME 1977 Proceedings", Wear of Materials, Page 77, ASME, East 47th Street, New York, New York 10017. Briefly, in this test, the specimen is forced against a rotating rubber wheel while dry sand is fed between the specimen and the wheel. Metal loss from the specimen surface is measured to determine wear characteristics.
More specifically, the test consists of placing a flat specimen of each deposit in direct contact with a chlorobutyl rubber wheel under 28 pounds of force. Silica sand, screened to below 20 mesh (U.S. Standard sieve size), is then passed between the sample and the rotating wheel at a rate of 200 grams per minute. The nine-inch rubber wheel was rotated at a speed of 200 revolutions per minute.
The weight of each wear deposit was measured prior to and after each 1000 revolutions of the wheel.
The test was terminated after 5000 revolutions.
The volumen of metal loss is then calculated by dividing the actual weight loss by a calculated deposit density. The deposit density is defined as:
where Wc is the weight of the carbide filler material, WT is the weight of the tube rod sheath material, Pc is the carbide density, and PT is the density of the tube rod sheath material. The density of AISI 1008 steel is approximately 7.86 g/cc.
Date from Table 3 show the properties of the deposits of the examples of this invention are comparable to the deposits of unmodified tungsten carbide. There was no degradation of wearresistance characteristics with the addition of molybdenum up to 62%. In fact, many of the molybdenum modified tungsten carbide deposits were superior over the unmodified tungsten carbide deposits.
Table 1 Composition and Property Data for Experimental Examples Ratios Cast Vickers (Mo:W) Composition, W. Density Hardness Metal: Carbon Example Mo W C {g/cc) (kg/mm2) (Mo21W79)123C 905 11.70 Bal. 5.60 13.85 1920 (Mo32W68)124C 102 18.57 Bal. 5.86 12.08 1469 (Mo50Wso)129c 703 32.24 Bal. 6.24 11.40 2167 (Mo.80W.20),1.30C 403 62.00 Bal. 7.48 9.75 1727 (Mo5W.25)134c 303 38.97 Bal. 6.48 10.21 1763 (Mo.36W64),.3sC 404 54.89 Bal. 6.97 9.75 1785 (Mo2,W,9),37C 304 47.25 Bal. 6.61 10.75 1890 (Mo.sOW.s0)1 39C 907 11.83 Bal. 5.04 13.79 1637 (MQsoW.Eo)lAoC 203 32.22 Bal. 5.81 11.92 2087 (MO.soW.so)lA2C 606 32.17 Bal. 5.78 11.64 1595 (MO.2lW.7s)lA3C 603 32.63 Bal. 5.72 11.97 1485 (Mo.50W.50.145C 906 11.86 Sal. 46.7 14.09 1837 (MO.69W.3l)1.46C 605 32.67 Bal. 5.61 11.91 1595 (MO.2lW.79)lABC 503 32.69 Bal. 5.51 12.22 2103 (MO.2lW3g)lAsC 904 11.90 Bal. 4.70 14.18 2003 Table 1 continued (Mo.50W.50)1.51C 903 11.86 Bal. 4.67 14.20 1917 (Mo s0W 50),51C 504 32.78 Bal. 5.38 12.22 1870 (Mo.50W.50)1.52C 611 32.68 Bal. 5.35 12.35 1993 (Mo.50W.50)1.55C 604 32.45 Bal. 5.35 12.32 2010 W154C(1 001 - Bal. 4.08 15.91- 2293 16.01 1857 (Mo.50W.50)1.55C 610 32.77 Bal. 5.25 12.36 2010 (Mo.47W.53)1.55C 204 29.72 Sal. 5.15 12.47 1927 (Mo34W66),.56C 103 20.01 Bal. 4.77 13.53 2253 (MOAsW.5l)l.eoC 608 32.02 Bal. 5.07 12.53 1920 (Mo50W50),68C 609 32.55 Bal. 4.86 12.45 1980 (Mo.29W.71)1.68C 803 17.11 Bal. 4.33 13.98 2057 (Mo.32W.68)1.80C 101 19.12 Sal. 4.12 13.84 1805 (1) Commercial Tungsten Carbide Product (Comparative) Table 2 Metal-to-carbon Ratio vs Hardness Vickers (Kg/mm2) Over 1800Kg/mm Under 1800Kg/mm Example No. Ratio No. Example No. Ratio No.
101 1.80 605 1.46 803 1.68 603 1.43 609 1.68 606 1.42 608 1.60 907 1.39 103 1.56 404 1.35 204 1.55 303 1.34 610 1.55 403 1.30 001(WC) 1.54 102 1.24 604 1.55 611 1.52 504 1.51 903 1.51 904 1.49 503 1.48 906 1.45 203 1.40 304 1.37 703 1.29 905 1.23 Table 3 Abrasive Wear Test Results Filled Tube Rod Deposits Deposit Volume Metal Loss, mm3 Total Example Filler Density 1000 2000 3000 4000 5000 Metal Number Mesh Size (g/cc) Rev. Rev. Rev. Rev. Rev.Loss, g 001 20x30 11.21 7 13 18 24 27 0.30 Tungsten Carbide 30x40 11.49 7 14 19 23 27 0.31 11.49 7 15 22 27 32 0.37 11.49 5 11 16 22 27 0.31 11.29 6 8 11 14 16 0.18 40x60 11.32 7 13 18 21 26 0.29 11.32 7 14 20 23 27 0.30 11.32 10 16 21 25 28 0.32 11.29 5 8 11 13 16 0.18 101 20x30 10.49 9 14 18 22 25 0.26 30x40 10.37 6 11 16 20 23 0.24 Table 3 continued Abrasive Wear Test Results Filled Tube Rod Deposits Deposit Volume Metal Loss, mm3 Total Example Filler Density 1000 2000 3000 4000 5000 Metal Number Mesh Size (g/ccJ Rev. Rev. Rev. Rev. Rev.Loss, g 40x60 10.43 6 9 13 16 21 0.22 103 20x30 10.27 7 15 21 26 31 0.31 10.27 2 5 7 9 12 0.12 30x40 10.27 5 10 12 16 19 0.20 10.27 2 5 8 10 12 0.12 40x60 10.33 4 7 9 12 15 0.15 10.33 2 4 6 7 9 0.09 203 20x30 9.37 7 11 15 19 22 0.21 9.37 4 3 11 13 15 0.14 30x40 9.37 6 9 13 17 20 0.18 9.37 5 10 5 21 26 0.25 40x60 9.37 5 10 13 16 19 0.18 9.37 4 7 9 12 14 0.13 303 30x40 8.87 5 10 14 17 21 0.19 8.87 5 9 13 17 21 0.19 40x60 8.87 5 9 13 16 19 0.17 8.87 5 11 14 16 17 0.15 304 30x40 9.02 7 9 13 16 20 0.18 9.02 6 12 17 22 27 0.24 40x60 9.02 6 10 13 16 19 0.17 9.04 7 9 13 17 21 0.19 403 40x60 8.63 7 13 17 22 26 0.22 8.63 5 8 12 16 18 0.15 8.63 4 6 9 12 14 0.12 8.63 5 9 12 15 19 0.16 60x 100 8.63 6 10 16 20 25 0.21 8.63 9 14 19 23 27 0.23 100xD 8.66 6 10 15 18 22 0.19 8.74 11 19 25 31 33 0.33 609 20x30 9.82 6 11 15 19 23 0.23 9.75 4 8 13 17 21 0.20 30x40 9.75 10 16 23 28 33 0.32 9.75 5 9 13 18 22 0.22 40x60 9.81 4 7 10 13 17 0.17 9.75 5 9 13 16 22 0.21 9.75 4 7 9 11 13 0.13 60x100 9.75 5 8 11 15 18 0.17 9.75 4 8 9 12 15 0.15 611 20x30 9.74 6 11 14 18 20 0.20 9.74 3 6 9 12 15 0.14 30x40 9.74 8 13 17 21 25 0.25 9.75 4 8 13 17 20 0.19 40x60 9.78 4 7 10 12 14 0.14 9.78 4 7 9 12 14 0.14 803 20x30 10.47 6 15 19 22 25 0.26 30x40 10.54 6 10 14 17 20 0.21 40x60 10.60 3 6 8 10 11 0.12 904 20X30 10.60 5 10 14 18 22 0.23 30X40 10.60 5 9 13 17 20 0.21 40x60 10.60 4 7 10 13 15 0.16 906 20x30 10.50 5 10 15 19 22 0.23 10.50 2 6 10 13 16 0.16 30x40 10.50 4 7 10 12 15 0.16 10.50 4 8 12 15 19 0.20 40x60 10.52 4 8 11 14 17 0.18 10.56 2 4 7 10 12 0.12 10.42 3 4 6 7 9 0.10 60x100 10.58 3 5 7 9 10 0.11 10.58 4 6 8 10 12 0.13

Claims (11)

Claims
1. An article of manufacture composed at least in part of a metal carbide, said metal consisting of molybdenum and tungsten, said carbide having essentially the hardness and wear resistance of tungsten carbide.
2. An article according to claim 1 wherein the carbide consist of 10 to 62 w/o molybdenum and the balance tungsten, carbon and incidental impurities.
3. An article according to claim 2 wherein the carbides consist of 17 to 37 w/o molybdenum and the balance tungsten, carbon and incidental impurities.
4. An article according to claims 1,2 or 3 wherein the carbide has a metal-to-carbon ratio between 1.23 and 2.0.
5. An article according to claim 4 wherein the metal-to-carbon ratio is between 1.48 and 1.80.
6. An article according to claim 5 wherein the hardness of the carbide is at least 1800 Kg/mm2 Vickers scale.
7. An article according to any one of the preceding claims containing less than 10% total content of molybdenum carbide, tungsten carbide and carbon.
8. An article of any one of claims 1 to 7 in the form of a material for making hardfacing deposits.
9.An article of any one of claims 1 to 7 as filler material in filled tube rods.
10. An article of any one of claims 1 to 7 in the form of a casting.
11. An article substantially as hereinbefore described with reference to the Examples.
GB7930720A 1978-10-11 1979-09-05 Molybdenum-tungsten Carbide Products Withdrawn GB2033426A (en)

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JP (1) JPS5554545A (en)
AU (1) AU5160579A (en)
BE (1) BE879332A (en)
BR (1) BR7906433A (en)
DE (1) DE2937807A1 (en)
FR (1) FR2438636A1 (en)
GB (1) GB2033426A (en)
IT (1) IT1121481B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601189A (en) * 2013-11-30 2014-02-26 吉林大学 High-temperature high-pressure preparation method for tungsten molybdenum dicarbide
WO2019169744A1 (en) * 2018-03-09 2019-09-12 自贡硬质合金有限责任公司 (wmo)c-based cemented carbide material and preparation method therefor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3100266C2 (en) * 1981-01-08 1993-11-18 Sumitomo Electric Industries Process for the production of mixed carbides or mixed carbonitrides
US5076225A (en) * 1989-12-28 1991-12-31 Toyota Jidosha Kabushiki Kaisha Piston for an internal combustion engine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601189A (en) * 2013-11-30 2014-02-26 吉林大学 High-temperature high-pressure preparation method for tungsten molybdenum dicarbide
CN103601189B (en) * 2013-11-30 2015-06-03 吉林大学 High-temperature high-pressure preparation method for tungsten molybdenum dicarbide
WO2019169744A1 (en) * 2018-03-09 2019-09-12 自贡硬质合金有限责任公司 (wmo)c-based cemented carbide material and preparation method therefor

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AU5160579A (en) 1980-04-17
JPS5554545A (en) 1980-04-21
BE879332A (en) 1980-02-01
DE2937807A1 (en) 1980-04-24
IT1121481B (en) 1986-04-02
FR2438636A1 (en) 1980-05-09
BR7906433A (en) 1980-05-27
IT7968970A0 (en) 1979-10-10

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