CN106975861A - A kind of hard material of tungsten carbide particle containing clad and preparation method thereof - Google Patents
A kind of hard material of tungsten carbide particle containing clad and preparation method thereof Download PDFInfo
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- CN106975861A CN106975861A CN201611193858.XA CN201611193858A CN106975861A CN 106975861 A CN106975861 A CN 106975861A CN 201611193858 A CN201611193858 A CN 201611193858A CN 106975861 A CN106975861 A CN 106975861A
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- tungsten carbide
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- 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
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- 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
Abstract
The present invention relates to for hard-face overlaying welding (welding or soldering) material, specially a kind of hard material of tungsten carbide particle containing clad and preparation method thereof.Hard material includes tungsten carbide particle and matrix alloy with clad, tungsten carbide particle at least includes one kind in cast tungsten carbide, Widia, macrocrystalline tungsten carbide and cemented tungsten carbide, tungsten carbide particles sized is more than 20 microns, and the clad of tungsten carbide particle at least includes one kind in metal carbides, metal boride, metal nitride or their complex chemical compound.The preparation of stiff dough is by overlaying method, at least with one of electric arc, oxy-acetylene, laser, plasma transferred arc, heating furnace or induction heating method.The invention further relates to prepare the halide activation solid powder vanning method with clad tungsten carbide particle.Clad on tungsten carbide particle eliminates or reduced the dissolving of the tungsten carbide particle in stiff dough preparation process, improves the wear-resisting of stiff dough and undermines shock resistance.
Description
Technical field
The present invention relates to for hard-face overlaying welding (welding or soldering) material, specially a kind of tungsten carbide containing clad
Hard material of grain and preparation method thereof, it is for improving wear-resistant metal material instrument and workpiece surface, shock resistance and corrosion resistant
Corrosion energy.
Background technology
Stiff dough (including stiff dough band in oil drilling and exploitation field) refers on metal material instrument and workpiece surface
Coat a high hardness spray coating, it can improve the wear-resistant of surface, shock resistance and decay resistance, stiff dough be widely used in machinery,
The field such as mining industry, agricultural, building and oil drilling and exploitation, it includes thin and thick two kinds of stiff dough.Wherein, thin stiff dough refers to thickness
No more than 50 microns；And thick stiff dough thickness is more than 50 microns, typically up to several millimeters, even more greatly.Thick stiff dough can be single
Metal or alloy, more commonly metal-base composites.In metal-base composites stiff dough, tungsten carbide particle is most normal
Enhancing phase, because it has high rigidity and good toughness.
The tungsten carbide particle that metal-base composites stiff dough typically contains 40~80wt.% is distributed in metal or alloy matrix
In.Tungsten carbide particle with high rigidity is wear-resistant constituent element, and the metal or alloy matrix with excellent toughness rises and holds enhancing
Phase separation, metal or alloy matrix is usually iron, cobalt, nickel or their alloy.
There are five kinds of methods to prepare the enhanced metal-base composites stiff dough of tungsten carbide particle：(1) particle is injected：Welding
Cheng Zhong, directly injects tungsten carbide particle, for example into molten bath：Consumable or non-consumable arc welding；(2) powder is sprayed into：In built-up welding
Cheng Zhong, to workpiece surface spraying tungsten carbide and matrix alloy mixed-powder, for example：Oxy-acetylene spraying melting, coating produced by laser cladding and wait
Ion-transfer arc-welding；(3) precoating：First workpiece surface smear one layer it is prefabricated containing tungsten carbide particle and matrix material cream,
Slurry lays built-up welding cloth, is then placed in heating furnace or realizes soldering using sensing heating, is typically in vacuum or lazy
Property gas in carry out；(4) welding rod or welding wire：Tungsten carbide particle, deoxidier and alloying element are mixed, inserted in metal tube, is made
Into flux-cored electrode or welding wire, them are then melted on the surface of the workpiece, form stiff dough；(5) welding：Welding be by wire core and
Surface coating material is constituted, and surface coating material contains tungsten carbide particle, deoxidier, alloying element and resinoid bond, in work
Fusion welding band, that is, form stiff dough on part surface.
When preparing tungsten carbide grain reinforced metal base composite stiff dough, partially carbonized tungsten particle surface can evaporate, oxygen
Change or dissolve and lose, iron, cobalt, nickel and its alloy substrate melt can dissolve tungsten carbide.Carbonization tungsten loss not only cause material into
This raising, and its tungsten for discharging and carbon atom enter in metal or alloy matrix, forms brittlement phase, such as η phases (M6C),
This can seriously damage the toughness of stiff dough matrix, make its brittle.
(the August 14,1962 in a United States Patent (USP)；U.S.Pat.No.3,049,435；Process for
Applying Tungsten Carbide Particles to a Workpiece Surface), with nickel or nickel-phosphorus alloy bag
Tungsten carbide particle is covered, purpose reduces loss of the tungsten carbide during stiff dough is prepared.United States Patent (USP) (Dec.4,2007；
U.S.Pat.No.7,303,030B2；Barrier Coated Granules for Improve Hardfacing
Material it is) that, on drilling bit hard material, it uses iron, cobalt, nickel coated cemented tungsten carbide particles, purpose reduces sintering
Loss of the tungsten carbide in stiff dough preparation process.Although these metals and alloy cladding layer may play certain protective role,
It is their fusing point and not bery high, and solubility is very big in metal or alloy matrix melt, can very in stiff dough preparation process
Dissolve in soon into melt, their protective effect is very limited amount of.
United States Patent (USP) (November 15,2011；U.S.Pat.No.8,056,652B2；Barrier Coated
Granules for Improved Hardfacing Material Using Atomic Layer Deposition) it is another
One is related to drilling bit hard material, and it is to use double-coating cemented tungsten carbide particles, and internal layer is the thick pottery of nanometer scale
Ceramic material (1~500 nanometer), outer layer is metal or alloy.As noted above, metal or alloy outer layer can be dissolved into quickly
In matrix melt, they can not effectively shield.Internal layer ceramic material can be divided into two kinds, and one kind is that have high stable
Property, insoluble in matrix, such as oxide；It is another to have higher stability, be slightly soluble in matrix, such as carbide, nitride.
Those stability, the ceramics insoluble in matrix can not be infiltrated by matrix, and the interface of itself and matrix is non-coherence, therefore they
Interface binding power can be very weak.And higher stability, the ceramics that are slightly soluble in matrix can be infiltrated by matrix, the interface of they and matrix is
Coherence or half coherence, they have strong interface binding power.But, their thickness is only nanometer scale, is not enough to protect
They can retain enough time to card in matrix melt, to protect tungsten carbide particle.
Although the dissolving that these technologies alleviate tungsten carbide in stiff dough preparation process to a certain extent is changed in quality, result is simultaneously
It is unsatisfactory.Hard material still needs to further improvement, particularly to coating produced by laser cladding, plasma transferred arc and arc welding method,
Because there is very high heat input during these.
The content of the invention
It is an object of the invention to provide a kind of hard material of tungsten carbide particle containing clad and preparation method thereof,
Overcome the shortcomings of that existing tungsten carbide particle enhancing hard material is present, dissolved with solving the tungsten carbide particle in stiff dough preparation process
The problems such as transformation and its caused stiff dough penalty.
The technical scheme is that：
A kind of hard material of the tungsten carbide particle containing clad, including tungsten carbide particle and matrix with clad
Alloy, tungsten carbide particle, which at least includes cast tungsten carbide, Widia, includes carburizing cast tungsten carbide, macrocrystalline tungsten carbide and burning
Tie one kind in tungsten carbide；
Tungsten carbide particles sized is more than 20 microns；
The clad of tungsten carbide particle at least include metal carbides, metal boride, metal nitride or they answer
One kind in polymerisable compounds；
Tungsten carbide particle coating thickness is more than 0.5 micron.
Described tungsten carbide particle clad at least includes carbide, the boron of a kind of titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or aluminium
Compound, nitride or their complex chemical compound.
Described tungsten carbide particle clad has more than two layers structure, and one layer of wherein at least is carbide, boride, nitrogen
Compound or their complex chemical compound.
The hard material of the described tungsten carbide particle containing clad, it is at least with welding rod, welding wire, welding, particle
One of or powdered, paste, pulpous state or cloth-like form.
The hard material of the described tungsten carbide particle containing clad, the preparation of stiff dough is by overlaying method, at least
With one of electric arc, oxyacetylene torch, laser, plasma transferred arc, heating furnace or induction heating method.
The preparation method of the hard material of the described tungsten carbide particle containing clad, solid powder is activated using halide
Last vanning method, tungsten carbide particle, which at least includes cast tungsten carbide, Widia, includes carburizing cast tungsten carbide, macrocrystalline tungsten carbide
With one kind in cemented tungsten carbide；
The clad of tungsten carbide particle at least include metal carbides, metal boride, metal nitride or they answer
One kind in polymerisable compounds；
Halide activation solid powder vanning method is included in a sealing container, and heating is intended to reacting metal or its alloyed powder
The mixture at end, halide powder and tungsten carbide particle, under holding temperature, is kept for the regular hour, is subsequently cooled to room temperature,
Broken, sieving, is isolated with clad tungsten carbide particle.
The preparation method of the hard material of the described tungsten carbide particle containing clad, is intended to reacting metal or alloy at least
Including one of titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or its alloy, halide is ammonium chloride.
The preparation method of the hard material of the described tungsten carbide particle containing clad, holding temperature be from 750 DEG C to
1250℃；Retention time is from 0.5 hour to 12 hours.
The preparation method of the hard material of the described tungsten carbide particle containing clad, in solid powder vanning method processing
Before or after, tungsten carbide particle, which carries out a kind of thermo-chemical treatment, includes carburizing, carbo-nitriding, boronising or nitriding.
The preparation method of the hard material of the described tungsten carbide particle containing clad, clad has more than two layers knot
Structure, one layer of wherein at least is metal carbides, metal boride, metal nitride or their complex chemical compound.
Advantages of the present invention and beneficial effect are：
Clad on tungsten carbide particle of the present invention eliminates or reduced the dissolving of the tungsten carbide particle in stiff dough preparation process,
Wearability, erosion drag and the shock resistance of stiff dough are improved, improved hard material will be in machinery, mining industry, agricultural, building
And be used widely in oil drilling and exploitation field.
Brief description of the drawings
Fig. 1 very diagrammatically show the tungsten carbide particle with one layer of clad of the present invention；
Fig. 2 very diagrammatically show a kind of tungsten carbide particle with two layers of clad of the present invention；
Fig. 3 very diagrammatically show another tungsten carbide particle with two layers of clad of the present invention；
The existing common tungsten carbide particle enhancing nickel that Fig. 4 is prepared for the plasma transferred arc process in the embodiment of the present invention 2
The microscopic structure of based alloy stiff dough；
The tungsten carbide with clad of the invention that Fig. 5 is prepared for the plasma transferred arc process in the embodiment of the present invention 2
The microscopic structure of particle enhanced nickel base alloy stiff dough；
The implication marked in figure：10 tungsten carbide particles；12 metal carbides, metal boride, metal nitride or they
Complex chemical compound clad；20 ceramics, the clad of metal or alloy；The clad of 30 metal or alloy.
Embodiment
In specific implementation process, the present invention relates to the tungsten carbide for hard-face overlaying welding material, including with clad
Grain and matrix alloy.Tungsten carbide particle at least includes in cast tungsten carbide, Widia, macrocrystalline tungsten carbide and cemented tungsten carbide
One kind, tungsten carbide particles sized is more than 20 microns, and the clad of tungsten carbide particle at least includes metal carbides, metal boron
One kind in compound, metal nitride or their complex chemical compound.
Widia is that it is typically many by the way that metal tungsten particle is through solid-state carburizing preparation under high temperature protection atmosphere
Brilliant tungsten carbide wc.In the present invention, Widia also includes thoseing the cast tungsten carbide through Carburization Treatment, and cast tungsten carbide is
WC and W2C eutectic phase, Carburization Treatment can be by W2C is transformed into WC.This transformation can be complete or occur over just superficial layer
Part, depending on handling process.Because WC compares W2C has higher thermodynamic stability, therefore Carburization Treatment can improve casting carbon
Change the heat endurance of tungsten.
In the present invention, cemented tungsten carbide refers to iron, cobalt, nickel or their alloy as binding agent, meanwhile, also wrap
Include the cemented tungsten carbide of binder free.
In the present invention, tungsten carbide particle can be with variously-shaped, it is regular or irregular, its size 20 microns with
On.
In the present invention, the clad of tungsten carbide particle at least includes metal carbides, metal boride, metal nitride
Or one kind in their complex chemical compound.Metal carbides refer to the carbide of a kind of titanium, niobium, zirconium, vanadium, tantalum, hafnium or chromium, i.e.,
TiC, NbC, ZrC, VC, TaC, HfC or Cr3C2.Metal boride refers to the boride of a kind of titanium, niobium, zirconium, vanadium, tantalum, hafnium or chromium,
That is TiB2、NbB2、ZrB2、VB2、TaB2、HfB2Or CrB.Metal nitride refers to a kind of titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or aluminium
Nitride, i.e. TiN, NbN, ZrN, VN, TaN, HfN, CrN or AlN.Complex chemical compound refers to containing more than two component
Compound, wherein at least one metallic element is titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or aluminium, and at least one nonmetallic member
Element is carbon, boron or nitrogen, for example, titanium carbonitride [Ti (CN)], TiAlN [(TiAl) N], carbonization titanium tungsten [(TiW) C] and carbon
Titanium tungsten nitride [(TiW) (CN)] etc..
Metal carbides, metal boride, metal nitride or their complex chemical compound selected by the present invention have height
Thermodynamic stability, their extents of reaction and reaction speed with metal bath are far below tungsten carbide, and they can be effectively
Prevent or reduce the transformation of tungsten carbide in stiff dough preparation process.It is them in metal bath that another reason, which selects these compounds,
There is certain solubility, can be infiltrated by matrix melt.Also, they with parent metal or alloy interface be coherence or half altogether
Lattice, bond strength is high.This is that they are better than the characteristics of oxide is as clad.In view of these compounds have in metal bath
Certain solubility, the clads of these compounds to have in certain thickness, the present invention coating thickness 0.5 micron with
On, preferred scope is 2-10 microns.In stiff dough preparation process, the clad dissolving on tungsten carbide particle can discharge a small amount of group
Into element into matrix, this microalloying will not only damage metal or alloy substrate performance, can benefit on the contrary.It is actual
On, the metallic element in the selected clad of the present invention is steel microalloying common element, for example：Titanium, niobium, zirconium, vanadium, tantalum and hafnium are
Important element in micro alloyed steel, they can crystal grain thinning tissue and the tiny precipitated phase of generation.
The clad of the present invention is individual layer.Fig. 1, which schematically illustrates a tungsten carbide particle, has individual layer clad.Tungsten carbide
Particle 10 is coated by individual layer clad, and individual layer clad is foregoing metal carbides, metal boride, nitride metal
The clad 12 of thing or their complex chemical compound.
The clad of the present invention may also be what is be made up of multilayer, and wherein outermost layer is foregoing metal carbides, gold
Belong to the clad 12 of boride, metal nitride or their complex chemical compound.For simplicity, Fig. 2 schematically illustrates one
Individual tungsten carbide particle 10 has two layers of clad, and outer layer is foregoing metal carbides, metal boride, metal nitride
Or the clad 12 of their complex chemical compound, internal layer is ceramics, the clad 20 of metal or alloy.
The clad of the present invention may also be another sandwich construction, and wherein outermost layer is a metal or alloy.Equally, in order to
For the sake of simplification, Fig. 3 schematically illustrates a tungsten carbide particle 10 with two layers of clad, and outer layer is the clad of metal or alloy
30, and internal layer is the cladding of foregoing metal carbides, metal boride, metal nitride or their complex chemical compound
Layer 12.To this multilayer coating structure layer, outer layer is the clad 30 of metal or alloy, its thermodynamic stability than metal carbides,
Metal boride, metal nitride or their complex chemical compound it is low.Thus, in stiff dough preparation process, metal or alloy
Outer layer can be dissolved, and cause metal carbides, metal boride, metal nitride or their complex chemical compound of internal layer sudden and violent
Dew, with substrate contact, forms compatible interface.
Preparing clad purpose on tungsten carbide particle in the present invention is prevention or reduces tungsten carbide in stiff dough preparation process
Dissolving.However, in stiff dough preparation process, these clads partly may be even completely dissolved, and this depends on bead-welding technology
Parameter.Even if these clads are completely dissolved, they have also necessarily play a part of to protect tungsten carbide particle, because selected cladding
Stratification compound has the stability higher than tungsten carbide and lower dissolution velocity.
Clad not only prevents or reduced the dissolving of tungsten carbide in stiff dough preparation process on tungsten carbide in the present invention, and
The interface compatible with matrix can be also produced, this is conducive to enhancing and the strong combination of metal or alloy matrix in stiff dough.
The invention further relates to prepare cladding layer method on tungsten carbide particle, preparation method includes chemical vapor deposition
(CVD), physical vapour deposition (PVD) (PVD), thermal response deposition (TD) and other suitable technologies.At chemical vapor deposition (CVD)
Or during physical vapour deposition (PVD) (PVD), tungsten carbide particle needs constantly to roll or move, to obtain uniform cladding
Layer, this can by fluidized bed, wave or the device realization such as vibrate.Industrially, fluidized bed CVD or PVD technique are applied to cladding
Grain and powder.For example, United States Patent (USP) (March 2,1999；U.S.Pat.No.5,876,793；Fine Powders and
Method for Manufacturing) it is exactly to be related to the quick fluidized bed CVD technology of circulation come cladded wolfram carbide powder.TD methods
Industrially it is mainly used in workpiece surface metallic cementation, but also can be used to coated particle.For example, U.S. Patent (April 20,
2006；U.S.Appl.Pat.No.2006/0,081,681A1；Coated Diamond Particles) be exactly with the technology come
Cladding diamond particle.Other any suitable technologies also can be used to prepare clad on tungsten carbide particle.
The present invention relates to clad is prepared on tungsten carbide particle with the monohalide activation solid vanning method of TD methods.Will
Carbide-forming metal or alloy powder, halide, such as：Ammonium chloride and tungsten carbide particle are sufficiently mixed, mixed powder
It is put into crucible and seals.Then, heating crucible is to predetermined temperature, and is kept for the scheduled time.Keeping temperature is 750 DEG C to 1250
DEG C, the retention time is 0.5 hour to 12 hours, and these parameters depend on desired clad classes of compounds, thickness and carbon
Change the species of tungsten particle.During keeping temperature, carbide former metal or alloy and the halide of gasification react, and are formed
Gaseous metal halogen, metal halide further reacts with hydrogen, produces carbide former metallic atom.These metal raws
Son is deposited on tungsten carbide particle surface, is reacted with the carbon atom in tungsten carbide, forms carbide, cladded wolfram carbide particle.
Before clad is prepared with halide of the present invention activation solid vanning method, tungsten carbide particle can be carried out at carburizing
Reason, to improve its surface region layer carbon content, Carburization Treatment can avoid or reduce fragility η phases and be formed.Such as to produce carbonitride,
Boride or nitride clad, then need to be carried out corresponding before halide activation solid vanning method processing to tungsten carbide particle
Carbo-nitriding/nitriding, boronising or Nitrizing Treatment, to improve the content of tungsten carbide particle surface region layer carbon/nitrogen, boron or nitrogen.
The clad with sandwich construction can be prepared on tungsten carbide with the halide activation solid vanning method of the present invention.Such as
Fruit metal deposition capability is excessive, will be formed outer layer be metal or alloy and internal layer be compound multilayer coating structure layer.Such as to produce
Outer layer is the clad of compound, can be after halide activation solid vanning method processing, to metal or alloy outer layer
Tungsten carbide particle carries out carburizing, carbo-nitriding, boronising or Nitrizing Treatment, and outer layer metal or alloy are changed into compound.
The TD methods of the present invention-halide activation solid cases method compared with CVD and PVD methods, with investment of production equipment
The advantages of small, raw material are cheap, technique is simple.
The tungsten carbide particle with clad of the present invention is positioned in hard-face overlaying welding solder, various built-up welding welderings are made
Material.These built-up welding solders can be the single tungsten carbide particle with clad, with the mixture of metal or alloy matrix powder,
Thread, strip, banding, paste, pulpous state or cloth-like etc..Heap postwelding, these tungsten carbide particles for having clad are uniformly distributed in base
In body.Preparing the overlaying method of stiff dough includes arc welding, oxy-acetylene welding or soldering, induction welding or soldering, plasma transfer
Arc welding, laser melting coating and heating furnace brazing etc..
For electric arc and plasma transfer arc-welding, the tungsten carbide particle with clad can be direct plungeed into by loading hopper
In the molten bath of workpiece surface, these particles are caught up in stiff dough matrix, form stiff dough.Also can be by the tungsten carbide with clad
Grain is inserted in continuous metal or alloy pipe, flux-cored wire is made, while can also dose other materials such as alloying element etc., metal
Pipe skin as stiff dough matrix.In these welding wires feeding workpiece surface matrix melt, stiff dough is formed.
, can be by nozzle by the carbonization with clad for spraying and fusing, plasma transfer arc-welding and laser melting coating
Tungsten particle and matrix powder spray to workpiece surface together.Tungsten carbide particle and matrix powder can be fed with different nozzles, more
Commonly, they are sufficiently mixed in advance, then fed with nozzle.In workpiece surface, with oxyacetylene torch, plasma arc or
Laser fusion solder, forms stiff dough.
For oxygen-acetylene repairing and non-consumable arc welding, the tungsten carbide particle with clad is inserted into metal or alloy pipe
In, flux-cored electrode is made, these surfacing weldings can include alloying element and deoxidier, metal sheath as stiff dough matrix.
Workpiece surface, with oxyacetylene torch or arc-melting flux-cored electrode, forms stiff dough.
For oxygen-acetylene repairing, the welding of the tungsten carbide particle containing clad also can use.By the carbonization with clad
Tungsten particle, alloying element, deoxidier and mixed with resin, are applied to the surface of wire core, form coating layer, welding is made.
Workpiece surface, with oxyacetylene torch fusion welding band, forms stiff dough.
It is for heating furnace brazing, the tungsten carbide particle with clad and matrix material and additive such as flux is abundant
Mixing, the soldering soldering paste being made, slurry or soldering weldering cloth.Workpiece surface is smeared or are placed on to soldering soldering paste, slurry or soldering weldering cloth
On, it is then placed in stove and heats, carries out soldering.Heat stove to predetermined temperature, kept for predetermined time, subsequent stove is cold or sky
It is cold, just form stiff dough in workpiece surface, it is also possible to which sensing or oxyacetylene torch heating carry out soldering.
Embodiment given below is only that the present invention is further described, and claim includes but is not limited to described
Embodiment content.
Embodiment 1：Halide solid vanning method prepares the tungsten carbide particle with clad
The tungsten carbide to be coated is spherical cast tungsten carbide particle, and weight is 100 grams, and its size is 45 microns to 150 micro-
Rice.Deposition reaction material includes 20 grams of titanium valves (25 microns~37 microns) and 12 grams of ammonium chlorides.Before use, ammonium chloride is through 120 DEG C
Dehydration is handled for 1 hour.Casting carbon tungsten carbide particle, titanium valve and ammonium chloride powder are put into ball mill, mixed 4 hours.Then, will
Batch mixing is put into a stainless steel crucible, is capped and is sealed with aluminum oxide cream.Sealed stainless steel crucible is put into resistance furnace,
Under the argon gas protection of flowing, 1000 DEG C are heated to 10 DEG C/min., 2 hours are incubated, then furnace cooling.By the material after processing
Material is put into ball mill and crushed, sieving, isolates the tungsten carbide particle with clad, it is micro- that tungsten carbide particle surface forms about 2
The titanium carbide clad of rice.
Embodiment 2：Plasma transferred arc process prepares stiff dough
Two kinds of stiff dough are prepared for plasma transferred arc process：The first is existing common tungsten carbide particle as enhancing
Phase, second is that their stiff dough matrix alloy is same nickel as enhancing phase with the tungsten carbide with clad of the invention
Based alloy.In their experimentations, keep other materials identical with technique, imitated with the effect for disclosing clad on tungsten carbide
Really.Original silicon carbide tungsten particle is spherical cast tungsten carbide, and size is 45 microns to 150 microns, and the clad of tungsten carbide is about 2 micro-
The thick titanium carbide of rice.The matrix material of stiff dough be nickel-base alloy, its nominal chemical composition (percetage by weight) be 0.35~
0.45%C, 1.3~1.9%Fe, 2.7~4.3%Si, 1.3~1.9%B, 8.1~11.0%Cr, surplus are nickel, and its name is hard
Spend for HRc 38~43.Superalloy Substrate powder size is 45 microns to 150 microns.The base material of built-up welding is AISI4140
Low-alloy steel, size is tungsten carbide particle containing 60wt.% in 25mm × 100mm × 12mm, design hard material.By 300 grams of carbon
Change tungsten particle to be well mixed with 200 grams of Superalloy Substrate powder, be put into dispenser.95 amperes of welding current, powder carrier gas
For argon gas, its cubic feet/hour of flow 3.Single-layer surfacing, 1.5 millimeters of hardstanding target thickness.Saw to cut at a slow speed with diamond
Stiff dough sample is cut, cross-sectional metallographic sample is made, structure observation and micro-hardness measurement is carried out.
Fig. 4 is the scanning electricity of existing conventional cast tungsten carbide enhancing nickel-base alloy stiff dough prepared by plasma transferred arc process
Sub- microphotograph.It can be seen that, tungsten carbide particle there occurs significant dissolving, while Precipitation a large amount of strips in the base
Two-phase.Fig. 5 is the enhancing nickel-base alloy stiff dough of the cast tungsten carbide with clad of the invention prepared by plasma transferred arc process
Electron scanning micrograph.It can be seen that, tungsten carbide particle dissolution degree substantially mitigates, while precipitating second number of phases in the base
Amount is decreased.The microhardness result measured is converted into Rockwell hardness to show, conventional cast tungsten carbide enhancing nickel-base alloy
The average hardness of stiff dough matrix is HRc 58.5, and the cast tungsten carbide for having clad strengthens being averaged for nickel-base alloy stiff dough matrix
Hardness HRc 49.0.Compared with matrix material nominal hardness, heap postwelding stiff dough matrix hardness is all improved, and this is due to enhancing phase
Particle surface dissolve and caused by alloying matrix.As can be seen that there is the cast tungsten carbide enhancing nickel-base alloy stiff dough of clad
The increase rate of matrix hardness strengthens nickel-base alloy stiff dough matrix much smaller than conventional cast tungsten carbide.Microstructure observation and hard
Degree measurement all shows：The casting carbon tungsten carbide particle dissolution degree for having clad is substantially less than conventional cast tungsten carbide.This explanation
Titanium carbide clad on tungsten carbide particle effectively prevents or alleviated the dissolving of tungsten carbide.
It is to be understood that, described above is only one of embodiment of the present invention, for those of ordinary skill in the art
For, under the premise without departing from the principles of the invention, some improvement and polishing can be also made, these are improved and polishing also should be regarded as
Protection scope of the present invention.
Claims (10)
1. a kind of hard material of the tungsten carbide particle containing clad, including the tungsten carbide particle with clad and matrix are closed
Gold, it is characterised in that：Tungsten carbide particle, which at least includes cast tungsten carbide, Widia, includes carburizing cast tungsten carbide, macrocrystalline
One kind in tungsten carbide and cemented tungsten carbide；
Tungsten carbide particles sized is more than 20 microns；
The clad of tungsten carbide particle at least includes metal carbides, metal boride, metal nitride or their Composite
One kind in compound；
Tungsten carbide particle coating thickness is more than 0.5 micron.
2. the hard material of the tungsten carbide particle according to claim 1 containing clad, it is characterised in that：Described carbon
Change tungsten particle clad at least include the carbide of titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or aluminium a kind of, boride, nitride or it
Complex chemical compound.
3. the hard material of the tungsten carbide particle according to claim 1 containing clad, it is characterised in that：Described carbon
Changing tungsten particle clad has more than two layers structure, and one layer of wherein at least is carbide, boride, nitride or theirs is compound
Compound.
4. the hard material of the tungsten carbide particle according to claim 1 containing clad, it is characterised in that：It is at least
With one of welding rod, welding wire, welding, particle or powdered, paste, pulpous state or cloth-like form.
5. the hard material of the tungsten carbide particle according to claim 1 containing clad, it is characterised in that：The system of stiff dough
Standby is by overlaying method, at least with electric arc, oxyacetylene torch, laser, plasma transferred arc, heating furnace or induction heating method
One of.
6. the preparation method of the hard material of the tungsten carbide particle containing clad described in a kind of one of claim 1 to 5, its
It is characterised by：Using halide activation solid powder vanning method, tungsten carbide particle at least includes cast tungsten carbide, Widia
Including one kind in carburizing cast tungsten carbide, macrocrystalline tungsten carbide and cemented tungsten carbide；
The clad of tungsten carbide particle at least includes metal carbides, metal boride, metal nitride or their Composite
One kind in compound；
Halide activation solid powder vanning method is included in a sealing container, and heating is intended to reacting metal or its alloy powder, halogen
The mixture of compound powder and tungsten carbide particle, under holding temperature, is kept for the regular hour, is subsequently cooled to room temperature, crush,
Sieving, is isolated with clad tungsten carbide particle.
7. the preparation method of the hard material of the tungsten carbide particle according to claim 6 containing clad, its feature exists
In：Being intended to reacting metal or alloy at least includes one of titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or its alloy, and halide is ammonium chloride.
8. the preparation method of the hard material of the tungsten carbide particle according to claim 6 containing clad, its feature exists
In：Holding temperature is from 750 DEG C to 1250 DEG C；Retention time is from 0.5 hour to 12 hours.
9. the preparation method of the hard material of the tungsten carbide particle according to claim 6 containing clad, its feature exists
In：Before solid powder vanning method processing or after, tungsten carbide particle carries out a kind of thermo-chemical treatment and includes carburizing, carbon nitrogen being total to
Ooze, boronising or nitriding.
10. the preparation method of the hard material of the tungsten carbide particle according to claim 6 containing clad, its feature exists
In：Clad has more than two layers structure, one layer of wherein at least be metal carbides, metal boride, metal nitride or it
Complex chemical compound.
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