EP1077272A1 - Revêtements en carbure de titane/borure de tungstène - Google Patents

Revêtements en carbure de titane/borure de tungstène Download PDF

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Publication number
EP1077272A1
EP1077272A1 EP99116068A EP99116068A EP1077272A1 EP 1077272 A1 EP1077272 A1 EP 1077272A1 EP 99116068 A EP99116068 A EP 99116068A EP 99116068 A EP99116068 A EP 99116068A EP 1077272 A1 EP1077272 A1 EP 1077272A1
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Prior art keywords
coating
tungsten
coatings
titanium
cobalt
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EP99116068A
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German (de)
English (en)
Inventor
Jiinjen Albert Sue
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Praxair ST Technology Inc
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Praxair ST Technology Inc
Praxair Technology Inc
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Priority to EP99116068A priority Critical patent/EP1077272A1/fr
Publication of EP1077272A1 publication Critical patent/EP1077272A1/fr
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    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material

Definitions

  • the present invention relates to titanium carbide/tungsten boride coatings having excellent corrosion and wear resistance and to a process for preparing such coatings. More particularly, the invention relates to hard, dense, low-porosity, corrosion and wear resistant coatings containing ultrafine particles of titanium carbide and tungsten boride precipitates dispersed in a metallic matrix. The invention also relates to a process for preparing such coatings in situ by thermal spray and diffusion reaction techniques.
  • Plasma arc spraying and detonation gun D-Gun
  • Typical detonation gun techniques are disclosed in U.S. Patent Nos. 2,714,563 and 2,950,867.
  • Plasma arc spray techniques are disclosed in U.S. Patent Nos. 2,858,411 and 3,016,447.
  • Other thermal spray techniques are also known, for example, so-called "high velocity" plasma and "hypersonic" combustion spray processes, as well as the various flame spray processes.
  • Heat treatment of the coatings is necessary and may be done after deposition in a vacuum or inert gas furnace or by electron beam, laser beam, induction heating, transferred plasma arc or other technique.
  • Alternative deposition techniques such as slurries, filled fabrics or electrophoresis, followed by heat treatment, are also known.
  • Still other methods include simultaneous deposition and fusion utilizing plasma transferred arc, laser or electron beam surface fusion with or without post deposition heat treatment.
  • Cutting tools are usually made of tungsten carbide-cobalt alloys. These alloys are extremely hard, strong and tough and exhibit excellent wear properties under most conditions of use. However, a problem with these alloys has been that tungsten carbide is subject to oxidation at temperatures above about 540°C. When operated at these elevated temperatures for any sustained period, cutting tools made of these alloys loose their wear properties and frequently crack, spall or chip.
  • TiB 2 titanium diboride
  • a thin film which is less than about 30 microns thick, is formed on the surface of the cutting tools which contains CoWB and TiC compounds.
  • Titanium carbide has a higher oxidation resistance than tungsten carbide and is more stable. Consequently, the formation of a film containing these compounds increases the wear resistance of the cutting tools.
  • Vapor deposited films containing CoWB and TiC are furthermore limited to use with only a few substrates, particularly tungsten carbide-cobalt alloys. It would be advantageous therefore to develop TiC/WCoB coatings which can be applied to a variety of substrate materials.
  • a family of titanium carbide/tungsten boride coatings having excellent abrasion and corrosion wear resistance and which are compatible with a variety of substrate materials.
  • These coatings comprise hard, ultrafine, titanium carbide particles and tungsten boride precipitates dispersed in a metallic matrix, the two phases constituting from about 30 to about 90 volume percent of the coating.
  • the coating has a hardness of about 700 to 1200 DPH 300 (HV.3) and is capable of withstanding temperatures up to about 800°C.
  • the coatings of the present invention may be prepared by a process which comprises depositing onto a substrate a mechanically blended powder mixture composed of separate components including at least a first component containing tungsten carbide and a second component containing boron and at least one metal selected from the group consisting of nickel, cobalt and iron, said powder mixture including titanium in the first or second component or in a separate third component, at least one of the first, second or third components having a melting point below about 1200°C, and then heat treating the as-deposited coating.
  • the heat treatment effects a fusion reaction between the deposited elements resulting in the formation of ultrafine particles of titanium carbide and tungsten boride dispersed in a metallic matrix.
  • the coating can be deposited onto the substrate using any of the known deposition techniques above or a similar technique.
  • coatings containing titanium carbide and tungsten-boride precipitates are applied to various substrate materials.
  • Figure 1 is a photomicrograph taken at a magnification of 220X showing a typical as-deposited coating according to the present invention.
  • Figures 2 is a photomicrograph taken at a magnification of 440X showing a heat treated coating according to the present invention.
  • Figure 3 is a photomicrograph taken at a magnification of 3500X in a scanning electron microscope (SEM) showing in enlarged detail the microstructure of a typical coating according to the present invention.
  • Figure 4 is a group of curves comparing the weight gain of coatings prepared according to the present invention and conventional coatings when exposed to an oxidizing environment.
  • the coatings of the present invention are preferably applied to a substrate using thermal spray processes.
  • an electric arc is established between a non-consumable electrode and a second non-consumable electrode spaced therefrom.
  • a gas is passed in contact with the non-consumable electrode such that it contains the arc.
  • the arc-containing gas is constricted by a nozzle and results in a high thermal content effluent.
  • the powdered coating material is injected into the high thermal content effluent and is deposited onto the surface to be coated.
  • This process and plasma arc torch used therein are described in U.S. Patent No. 2,858,411.
  • the plasma spray process produces a deposited coating which is sound, dense, and adherent to the substrate.
  • the deposited coating also consists of irregularly shaped microscopic splats or leaves which are interlocked and mechanically bonded to one another and also to the substrate.
  • D-Gun detonation gun
  • a typical D-Gun consists essentially of a water-cooled barrel which is several feet long with an inside diameter of about one inch.
  • a mixture of oxygen and a fuel gas eg. acetylene, in a specified ratio (usually about 1:1) is feed into the barrel along with a charge of powder to be coated.
  • the gas is then ignited and the detonation wave accelerates the powder to about 2400 ft./sec. (730 m/sec.) while heating the powder close to or above its melting point.
  • a pulse of nitrogen purges the barrel and readies the system for the next detonation. The cycle is then repeated many times a second.
  • the D-Gun deposits a circle of coating on the substrate with each detonation.
  • the circles of coating are about one inch (25 mm) in diameter and a few ten thousandths of an inch (i.e., several microns) thick.
  • Each circle of coating is composed of many overlapping microscopic splats corresponding to the individual powder particles. The overlapping splats are interlocked and bonded to each other and to the substrate without substantial alloying at the interface thereof.
  • the placement of the circles in the coating deposit are closely controlled to build-up a smooth coating of uniform thickness and to minimize substrate heating and residual stresses in the applied coating.
  • the powdered coating material used in the thermal spray process will have essentially the same composition as the applied coating itself. With some thermal spray equipment, however, changes in composition may be expected. In such cases, the powder composition will be adjusted accordingly to achieve the desired coating composition.
  • wear and corrosion resistant coatings are applied to metallic substrates by plasma spraying a mechanically blended powder mixture containing separate components including a first component containing tungsten carbide and a second component containing boron and at least one metal selected from the group consisting of nickel, cobalt and iron.
  • the powder mixture will also include titanium in the first or second component or in a separate third component.
  • the first, second or third component, preferably the second component containing boron, should have a melting point less than about 1200°C.
  • the as-deposited coating is then heat treated at an elevated temperature sufficient to melt this component in the powder mixture.
  • the coatings of the present invention may be prepared using a two component system, that is, a first tungsten carbide component and a second boron-containing alloy component with either the first or second component or both containing titanium or alternatively, a multiple component system may be employed.
  • the multiple component system is employed in those cases where titanium is not employed in either one of the first two components.
  • the multiple component system may also be employed in those situations where it is desirable to include additional elements in the metal matrix.
  • coatings containing titanium carbide and tungsten boride may proceed according to one of the following equations: (1) (W,Ti)C-M 1 + (M 2 -B) ⁇ W M ' / 1 B + TiC + (M 2 - M " 1 ) (2) WC-M 1 + Ti + (M 2 -B) ⁇ W M ' / 1 B + TiC + (M 2 - M " 1) (3) WC-M 1 + Ti-B + (M 2 -B) ⁇ W M ' / 1B + TiC + (M 2 -M " 1 ) wherein
  • M 1 and M 2 may also contain small amounts of other elements such as carbon, oxygen and nitrogen.
  • the proportion of titanium, tungsten, carbide and boron used in the powder mixture determines the volume fraction of both the titanium carbide and tungsten borides that precipitate in the metal matrix.
  • the ratio of tungsten to boron should be kept in a range from about 0.4 to about 2.0.
  • the ratio of titanium to carbon is about 1.0.
  • the volume fraction of titanium carbide and tungsten boride precipitates in the coating should be maintained in a range from about 30 to about 80 volume percent.
  • the volume fraction of the titanium carbide particles will be about 15 to 30 volume percent whereas the volume fraction of the tungsten boride precipitates will be about 30 to 50 volume percent.
  • coatings can be prepared with a volume fraction of tungsten borides in the above ranges if the elements in the boron-containing alloy are kept within the following proportions: from about 3 to about 20 wt. % boron, 0 to about 10 wt. % molybdenum, 0 to about 20 wt. % chromium, 0 to about 5 wt. % manganese, 0 to about 5 wt. % aluminum, 0 to about 1 wt. % carbon, 0 to about 5 wt. % silicon, 0 to about 5 wt. % phosphorus, 0 to about 5 wt. % copper and 0 to about 5 wt. % iron, the balance being nickel, cobalt or iron or combinations thereof.
  • any boron-containing alloy can be used to prepare coatings according to the present invention so long as the alloy satisfies the requirements of the diffusion reaction.
  • Alloys which are particularly suited for use in preparing coatings according to the present invention are given in Table I below.
  • BORON-CONTAINING ALLOYS Composition weight %) Alloy No. Ni Cr Si B Fe C 1 Balance 13-17 3-5 2.75-4 3-5 0.6-0.9 2 Balance 6-8 3-5 2.5-3.5 2-4 0.5-Max 3 Balance 3-4 3-5.4 8.8-10.8 2-3.5 0.32-Max 4 Balance 4.5-6 2.3-4 5.6-7 1.5-3.8 0.41-Max 5 Balance 3.2 2.5 6
  • the boron-containing alloy may not be required in those cases where the titanium-containing alloy or compound incorporates boron, e.g. TiB 2 .
  • the as-deposited coating It is important in the practice of the present invention to heat treat the as-deposited coating at a sufficiently elevated temperature for the boron-containing alloy to be fluid enough to promote the diffusion reaction, typically about 1000°C.
  • the heat treatment temperature can be substantially higher than 1000°C if desired, e.g. about 1200°C, but the temperature should not be so high as to detrimentally affect the substrate.
  • the as-deposited coating should be maintained at heat treatment temperature for times sufficient to promote the reaction and/or diffusion between the components of the coating. A limited, but important, amount of diffusion reaction occurs also with the substrate.
  • the heat treatment of the coating is generally carried out in a vacuum or an inert gas furnace.
  • the heat treatment can be achieved by surface fusion processes such as electron beam, laser beam, transferred plasma arc, induction heating or other techniques so long as the time at elevated temperature is sufficiently short or a protective atmosphere is provided such that no significant oxidation of the coating occurs.
  • An advantage of the present invention is that the coatings can be applied with success to many different types of substrates using the known deposition techniques described above or similar techniques.
  • the substrate must be able to withstand the effects of heat treatment without any harmful result.
  • Suitable substrate materials which can be coated according to the present invention include, for example, steel, stainless steel, iron base alloys, nickel, nickel base alloys, cobalt, cobalt base alloys, chromium, chromium base alloys, titanium, titanium base alloys, refractory metals and refractory metal base alloys.
  • Coatings of the present invention are most advantageously applied to substrates of carbon steel, stainless steels, and superalloys (e.g., iron, nickel and/or cobalt base alloys).
  • superalloys e.g., iron, nickel and/or cobalt base alloys.
  • the thickness of coatings prepared according to the present invention generally vary from about 0.005 to about 0.040 inch (1.3 X 10 2 to 1.0 X 10 3 micrometers).
  • the microstructures of the coatings of the present invention are somewhat complex and not fully understood. However, it is known from studies so far conducted that the coatings contain essentially two separate hard phases comprising ultrafine titanium carbide particles and tungsten boride precipitates dispersed in a metal matrix.
  • the metal matrix is essentially crystalline, relatively dense, softer than either hard phase and has a low permeability.
  • the size of the titanium carbide particles and tungsten boride precipitates will vary depending upon several factors including the heat treatment temperature and time. However, the average particle size will usually be sub-micron, typically from about 0.5 to about 3.0 microns.
  • the hardness of the coatings varies in direct proportion to the volume fraction of the hard phase. It is possible, for example, to tailor the hardness to a particular range of values by varying the atomic ratio of tungsten to boron within the powder mixture.
  • the hardness of the coatings is typically about 800 DPH 300 (HV.3).
  • An important advantage of the present invention is that the diffusion reaction between tungsten and the boron-containing alloy takes place at relatively low heat treatment temperatures, e.g., about 1000°C. Although the exact reason for this phenomenon is not understood, it is believed to be due to the build-up of high internal stresses and dislocations inside the lamellar splats or leaves that are deposited onto the substrate by thermal spraying. In contrast, metal borides and carbides are normally formed by conventional casting or hot pressed methods at significantly higher temperatures, i.e., greater than about 1300°C. These higher temperatures are usually detrimental to most steels. Due to the low heat treatment temperatures required in the present coating process, the substrates can now be coated without any harmful effects.
  • TiC/W 2 CoB 2 coatings were prepared by plasma spraying powder mixtures of a tungsten carbide-cobalt alloy, titanium diboride (TiB 2 ) and Alloy No. 2 on AISI 1018 1 steel specimens measuring 3/4 x 1/2 x 2-3/4 inches to a thickness of about 0.020 inch (0.5 mm).
  • the mix formulation was as follows: 50 wt.% (WC-10 Co) + 10 wt.% TiB 2 + 40 wt.% Alloy No. 2.
  • the W to B atomic ratio was about 1.
  • a polished cross-section of the as-deposited coating is shown in Figure 1.
  • the coating has a lamellar structure consisting of irregular shaped splats firmly adhered to one another and to the steel substrate.
  • the splats were formed by impact of WC-Co, TiB 2 and Alloy No. 2 powders in the molten or semi-molten condition on the substrate.
  • the as-deposited coating was then heat treated for one hour at a temperature of about 1000 to 1075°C in vacuum or argon.
  • Figure 2 shows the coating structure after heat treatment.
  • the coating consists of a primary coating and an interdiffusion zone formed by diffusion reaction between the coating materials and substrate.
  • the interdiffusion zone was about 50 to 60 micrometers wide with a finger-like iron-boride phase scattered along the diffusion zone/substrate interface.
  • the primary coating contains a great number of fine particles distributed uniformly in a Ni-Cr-Si-Fe matrix.
  • the particles were identified as TiC and W 2 CoB 2 phases by X-ray diffraction and EDX analyses.
  • the TiC and W 2 CoB 2 phases were formed by substituting Ti for W in the carbide and reacting W and Co with B during diffusion, and chemical reaction between WC-Co and TiB 2 splats, because the affinity of Ti to C is greater than that of W to C.
  • a scanning electron micrograph reveals TiC and W 2 CoB 2 phases with a particle size less than 1 micrometer.
  • the W 2 CoB 2 phase exhibits a characteristic light contrast, while the TiC phase exhibits a dark contrast dispersed in the matrix.
  • the TiC/W 2 CoB 2 coatings were also subjected to erosion tests. These tests were conducted according to standard procedures using alumina particles with a nominal size of 27 microns, and a particle velocity of about 91 meters/sec. at two impingement angles of 90° and 30°. The erosion rates were found to be about 128 and 26 micrometers/gm, respectively.
  • the abrasion and erosion resistance of the coatings were considered to be excellent when compared to other conventional coatings.
  • TiC/WCoB coatings were prepared by plasma spraying powder mixtures of a tungsten carbide-cobalt alloy, titanium diboride (TiB 2 ), cobalt and Alloy No. 2 onto AISI 1018 steel specimens measuring 3/4 x 1/2 x 2-3/4 inches to a thickness of about 0.020 inch (0.5 mm). Additional cobalt was used in the powder mixture to favor the formation of WCoB rather than W 2 CoB 2 as in Example I.
  • the mix of formulation was as follows: 50 wt.% (WC-10 Co) + 10 wt.% TiB 2 + 20 wt.% Alloy No. 2 + 20 wt.% Co.
  • the W to B atomic ratio was about 1.
  • the as-deposited coatings were heat reated for one hour at temperatures of about 1050 to 1075°C in vacuum or argon. After heat treatment, the coatings were cooled and examined. The coatings had a lamellar structure of splats containing TiC and WCoB precipitates dispersed in a Ni-Cr-Si-Fe matrix. The size of the precipitates was less than about 1 micron.
  • the hardness of these TiC/WCoB coatings was in the range of 700 to 1100 DPH 3000 (HV.3).
  • Abrasive wear and erosion properties of the coatings were determined using the same test procedures described in Example I.
  • the sand abrasion wear rate of these coatings was about 1.9 mm 3 /1000 revolutions.
  • the erosion wear rate to alumina particles at 30° and 90° impingement angles were found to be approximately 30 and 130 micrometers per gram, respectively.
  • the abrasion and erosion properties of these coatings were considered to be good to excellent.
  • a number TiC-rich TiC/W 2 NiB 2 /WC/WC 2 coatings were prepared by plasma spraying powder mixtures of tungsten - titanium carbide-nickel alloy and Alloy No. 5 onto AISI 1018 steel specimens measuring 3/4 x 1/2 x 2-3/4 inches to a thickness of about 0.020 inch (0.5 mm).
  • the mix formulation was as follows: 60 wt.% (W, Ti) C - Ni + 40 wt.% Alloy No. 5.
  • the as-deposited coatings were heat treated for one hour at a temperature of about 1045°C in vacuum or argon and then cooled.
  • the coatings had a lamellar structure of fine precipitates of TiC and W 2 NiB 2 dispersed between WC or WC 2 particles in a Ni-Cr-Si-Fe matrix.
  • the hardness of these coatings was about 900 DPH 300 (HV.3).
EP99116068A 1999-08-16 1999-08-16 Revêtements en carbure de titane/borure de tungstène Withdrawn EP1077272A1 (fr)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2067872A3 (fr) * 2007-11-28 2011-06-08 United Technologies Corporation Article doté d'une couche composite
WO2012009509A1 (fr) * 2010-07-14 2012-01-19 Praxair Technology, Inc. Revêtements composites par projection thermique pour applications de semi-conducteur
US20140076467A1 (en) * 2012-09-17 2014-03-20 Glassimetal Technology Inc. Bulk nickel-silicon-boron glasses bearing chromium
US9534283B2 (en) 2013-01-07 2017-01-03 Glassimental Technology, Inc. Bulk nickel—silicon—boron glasses bearing iron
US9556504B2 (en) 2012-11-15 2017-01-31 Glassimetal Technology, Inc. Bulk nickel-phosphorus-boron glasses bearing chromium and tantalum
US9816166B2 (en) 2013-02-26 2017-11-14 Glassimetal Technology, Inc. Bulk nickel-phosphorus-boron glasses bearing manganese
US9863024B2 (en) 2012-10-30 2018-01-09 Glassimetal Technology, Inc. Bulk nickel-based chromium and phosphorus bearing metallic glasses with high toughness
US9863025B2 (en) 2013-08-16 2018-01-09 Glassimetal Technology, Inc. Bulk nickel-phosphorus-boron glasses bearing manganese, niobium and tantalum
US9920400B2 (en) 2013-12-09 2018-03-20 Glassimetal Technology, Inc. Bulk nickel-based glasses bearing chromium, niobium, phosphorus and silicon
US9920410B2 (en) 2011-08-22 2018-03-20 California Institute Of Technology Bulk nickel-based chromium and phosphorous bearing metallic glasses
US9957596B2 (en) 2013-12-23 2018-05-01 Glassimetal Technology, Inc. Bulk nickel-iron-based, nickel-cobalt-based and nickel-copper based glasses bearing chromium, niobium, phosphorus and boron
US10000834B2 (en) 2014-02-25 2018-06-19 Glassimetal Technology, Inc. Bulk nickel-chromium-phosphorus glasses bearing niobium and boron exhibiting high strength and/or high thermal stability of the supercooled liquid
US10287663B2 (en) 2014-08-12 2019-05-14 Glassimetal Technology, Inc. Bulk nickel-phosphorus-silicon glasses bearing manganese
US10458008B2 (en) 2017-04-27 2019-10-29 Glassimetal Technology, Inc. Zirconium-cobalt-nickel-aluminum glasses with high glass forming ability and high reflectivity
CN111962022A (zh) * 2020-09-07 2020-11-20 西安石油大学 一种wb2/wbc多层硬质涂层及其制备方法和应用
US11371108B2 (en) 2019-02-14 2022-06-28 Glassimetal Technology, Inc. Tough iron-based glasses with high glass forming ability and high thermal stability
US11905582B2 (en) 2017-03-09 2024-02-20 Glassimetal Technology, Inc. Bulk nickel-niobium-phosphorus-boron glasses bearing low fractions of chromium and exhibiting high toughness

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7998604B2 (en) 2007-11-28 2011-08-16 United Technologies Corporation Article having composite layer
EP2067872A3 (fr) * 2007-11-28 2011-06-08 United Technologies Corporation Article doté d'une couche composite
WO2012009509A1 (fr) * 2010-07-14 2012-01-19 Praxair Technology, Inc. Revêtements composites par projection thermique pour applications de semi-conducteur
US9920410B2 (en) 2011-08-22 2018-03-20 California Institute Of Technology Bulk nickel-based chromium and phosphorous bearing metallic glasses
US20140076467A1 (en) * 2012-09-17 2014-03-20 Glassimetal Technology Inc. Bulk nickel-silicon-boron glasses bearing chromium
US11377720B2 (en) * 2012-09-17 2022-07-05 Glassimetal Technology Inc. Bulk nickel-silicon-boron glasses bearing chromium
US9863024B2 (en) 2012-10-30 2018-01-09 Glassimetal Technology, Inc. Bulk nickel-based chromium and phosphorus bearing metallic glasses with high toughness
US9556504B2 (en) 2012-11-15 2017-01-31 Glassimetal Technology, Inc. Bulk nickel-phosphorus-boron glasses bearing chromium and tantalum
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CN111962022B (zh) * 2020-09-07 2022-05-06 西安石油大学 一种wb2/wbc多层硬质涂层及其制备方法和应用

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