CN106975861B - A kind of hard material of tungsten carbide particle and preparation method thereof containing clad - Google Patents
A kind of hard material of tungsten carbide particle and preparation method thereof containing clad Download PDFInfo
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- CN106975861B CN106975861B CN201611193858.XA CN201611193858A CN106975861B CN 106975861 B CN106975861 B CN 106975861B CN 201611193858 A CN201611193858 A CN 201611193858A CN 106975861 B CN106975861 B CN 106975861B
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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
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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 and preparation method thereof containing clad.Hard material includes the tungsten carbide particle and matrix alloy with clad, tungsten carbide particle includes at least one of cast tungsten carbide, Widia, macrocrystalline tungsten carbide and cemented tungsten carbide, for tungsten carbide particles sized at 20 microns or more, the clad of tungsten carbide particle includes at least one of 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 the halide activation solid powder vanning methods that preparation has clad tungsten carbide particle.The dissolution of the tungsten carbide particle in stiff dough preparation process is eliminated or reduced to clad on tungsten carbide particle, 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
The hard material and preparation method thereof of grain, it is for improving wear-resistant metal material tool and workpiece surface, shock resistance and corrosion resistant
Corrosion energy.
Background technique
Stiff dough (including the stiff dough band in oil drilling and exploitation field) refers on metal material tool and workpiece surface
Coat a high hardness spray coating, it can improve the wear-resistant of surface, shock resistance and corrosion resistance, stiff dough be widely used in it is mechanical,
The fields 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 greater than 50 microns, generally 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 often
Reinforced 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 are usually iron, cobalt, nickel or their alloy.
There are five types of the metal-base composites stiff dough that method prepares tungsten carbide particle enhancing: (1) injecting particle: welding
Cheng Zhong directly injects tungsten carbide particle into molten bath, such as: 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, such as: it oxy-acetylene spraying melting, coating produced by laser cladding and waits
Ion-transfer arc-welding；(3) precoating: first workpiece surface smear one layer it is prefabricated containing tungsten carbide particle and basis material cream,
Slurry or laying built-up welding cloth, are then placed in heating furnace or realize using induction heating soldering, usually in vacuum or lazy
It is carried out in property gas；(4) welding rod or welding wire: tungsten carbide particle, deoxidier and alloying element are mixed, and are inserted in metal tube, system
At 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 material 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 at
This raising, and its tungsten for releasing and carbon atom enter in metal or alloy matrix, form brittlement phase, such as η phase (M6C),
This can seriously damage the toughness of stiff dough matrix, make its embrittlement.
(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 packet
Tungsten carbide particle is covered, purpose reduces loss of tungsten carbide during preparing stiff dough.United States Patent (USP) (Dec.4,2007；
U.S.Pat.No.7,303,030B2；Barrier Coated Granules for Improve Hardfacing
It Material is) about drilling bit hard material, it uses iron, cobalt, nickel coated cemented tungsten carbide particles, and 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, it, can very in stiff dough preparation process
It dissolves in fastly into melt, their protective effect is very limited.
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, it is to use double-coating cemented tungsten carbide particles, and internal layer is the pottery of nanometer scale thickness
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 is have high stable
Property, insoluble in matrix, such as oxide；Another kind has higher stability, is slightly soluble in matrix, such as carbide, nitride.
Those stability, the ceramics insoluble in matrix cannot be infiltrated by matrix, and the interface with 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
Enough time can be retained in matrix melt by demonstrate,proving them, to protect tungsten carbide particle.
Although the dissolution 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 be further improved, especially to coating produced by laser cladding, plasma transferred arc and arc welding method,
Because there is very high heat input during these.
Summary of the invention
The purpose of the present invention is to provide a kind of hard material of tungsten carbide particle and preparation method thereof containing clad,
Overcome deficiency existing for existing tungsten carbide particle enhancing hard material, is 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 include at least one in cast tungsten carbide, carburizing cast tungsten carbide, macrocrystalline tungsten carbide and cemented tungsten carbide
Kind；
Tungsten carbide particles sized is at 20 microns or more；
The clad of tungsten carbide particle include at least metal carbides, metal boride, metal nitride or they answer
One of polymerisable compounds；
Tungsten carbide particle coating thickness is at 0.5 micron or more.
The tungsten carbide particle clad includes at least carbide, the boron of a kind of titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or aluminium
Compound, nitride or their complex chemical compound.
The tungsten carbide particle clad has two layers or more structure, and wherein at least one layer is carbide, boride, nitrogen
Compound or their complex chemical compound.
The hard material of the tungsten carbide particle containing clad, it is at least with welding rod, welding wire, welding, particle
Or one of powdered, paste, pulpous state or cloth-like form.
The hard material of the tungsten carbide particle containing clad, the preparation of stiff dough are 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 tungsten carbide particle containing clad activates solid powder using halide
Last vanning method, tungsten carbide particle include at least in cast tungsten carbide, carburizing cast tungsten carbide, macrocrystalline tungsten carbide and cemented tungsten carbide
One kind；
The clad of tungsten carbide particle include at least metal carbides, metal boride, metal nitride or they answer
One of 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, then cooled to room temperature,
Broken, sieving, is isolated with clad tungsten carbide particle.
The preparation method of the hard material of the 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 tungsten carbide particle containing clad, holding temperature be from 750 DEG C to
1250℃；Retention time is from 0.5 hour to 12 hour.
The preparation method of the hard material of the tungsten carbide particle containing clad, in solid powder vanning method processing
Before or after, it includes carburizing, carbo-nitriding, boronising or nitriding that tungsten carbide particle, which carries out a kind of thermo-chemical treatment,.
The preparation method of the hard material of the tungsten carbide particle containing clad, clad, which has two layers or more, to be tied
Structure, wherein at least one layer is metal carbides, metal boride, metal nitride or their complex chemical compound.
The invention has the advantages and beneficial effects that:
The dissolution of the tungsten carbide particle in stiff dough preparation process is eliminated or reduced to clad on tungsten carbide particle of the present invention,
Wearability, erosion drag and the shock resistance of stiff dough are improved, improved hard material will be in machinery, mining industry, agricultural, building
And it is used widely in oil drilling and exploitation field.
Detailed description of the invention
Fig. 1 very diagrammatically show the tungsten carbide particle with one layer of clad of the invention；
Fig. 2 very diagrammatically show a kind of tungsten carbide particle with two layers of clad of the invention；
Fig. 3 very diagrammatically show the tungsten carbide particle that another kind of the invention has two layers of clad；
Fig. 4 is that the existing common tungsten carbide particle of the plasma transferred arc process preparation in the embodiment of the present invention 2 enhances nickel
The microscopic structure of based alloy stiff dough；
Fig. 5 is the tungsten carbide with clad of the invention of the plasma transferred arc process preparation in the embodiment of the present invention 2
The microscopic structure of particle enhanced nickel base alloy stiff dough；
Meaning marked in the figure: 10 tungsten carbide particles；12 metal carbides, metal boride, metal nitride or they
Complex chemical compound clad；The clad of 20 ceramics, metal or alloy；The clad of 30 metal or alloy.
Specific embodiment
In the specific implementation process, the present invention relates to hard-face overlaying welding material is used for, including the tungsten carbide with clad
Grain and matrix alloy.Tungsten carbide particle includes at least in cast tungsten carbide, Widia, macrocrystalline tungsten carbide and cemented tungsten carbide
One kind, for tungsten carbide particles sized at 20 microns or more, the clad of tungsten carbide particle includes at least metal carbides, metal boron
One of compound, metal nitride or their complex chemical compound.
Widia be by under high temperature protection atmosphere metal tungsten particle prepare through solid-state carburizing, it is usually more
Brilliant tungsten carbide wc.In the present invention, Widia also includes those cast tungsten carbides through Carburization Treatment, and cast tungsten carbide is
WC and W2The eutectic phase of C, Carburization Treatment can be by W2C is transformed into WC.This transformation can be completely or occur over just superficial layer
Part depends on treatment process.Due to WC ratio W2C has higher thermodynamic stability, therefore casting carbon can be improved in Carburization Treatment
Change the thermal stability of tungsten.
In the present invention, cemented tungsten carbide, which refers to, uses iron, cobalt, nickel or their alloy as binder, meanwhile, also wrap
Include the cemented tungsten carbide of binder free.
In the present invention, tungsten carbide particle can be with various shape, regular or irregular, size 20 microns with
On.
In the present invention, the clad of tungsten carbide particle includes at least metal carbides, metal boride, metal nitride
Or one of 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 selected by the present invention, metal boride, metal nitride or their complex chemical compound have height
Thermodynamic stability, for the extent of reaction and reaction speed of they and metal bath far below tungsten carbide, 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, the interface of they and parent metal or alloy is that coherence or half are total
Lattice, bond strength are high.This is that they are better than the characteristics of oxide is as clad.Have in metal bath in view of these compounds
Certain solubility, the clad of these compounds will have certain thickness, in the present invention coating thickness 0.5 micron with
On, preferred scope is 2-10 microns.In stiff dough preparation process, the clad dissolution on tungsten carbide particle can discharge a small amount of group
At element into matrix, this microalloying will not only damage metal or alloy substrate performance, can benefit instead.It is practical
On, the metallic element in clad selected by the present invention is steel microalloying common element, such as: titanium, niobium, zirconium, vanadium, tantalum and hafnium are
Important element in micro alloyed steel, they can refine grain structure and generate tiny precipitated phase.
Clad of the invention is single layer.Fig. 1 schematically illustrates a tungsten carbide particle with single layer clad.Tungsten carbide
Particle 10 is coated by single layer clad, and single layer clad is foregoing metal carbides, metal boride, nitride metal
The clad 12 of object or their complex chemical compound.
Clad of the invention can also be to be made 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
A 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 are the clads 20 of ceramics, metal or alloy.
Clad of the invention can also be another multilayered structure, 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, 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 dissolve, and cause metal carbides, metal boride, metal nitride or their complex chemical compound of internal layer sudden and violent
Dew forms compatible interface with substrate contact.
It is to prevent or reduce tungsten carbide in stiff dough preparation process the purpose of preparing clad on tungsten carbide particle in the present invention
Dissolution.However, these clads partially may be even completely dissolved, this depends on bead-welding technology in stiff dough preparation process
Parameter.Even if these clads are completely dissolved, they have also centainly play a part of to protect tungsten carbide particle, because of selected cladding
Layer compound has stability more higher than tungsten carbide and lower solution rate.
Clad not only prevents or reduces the dissolution of tungsten carbide in stiff dough preparation process on tungsten carbide in the present invention, but also
The interface compatible with matrix can be also generated, this is conducive to the strong combination of reinforced phase and metal or alloy matrix in stiff dough.
The invention further relates to the preparation cladding layer methods on tungsten carbide particle, and 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, the devices realization such as wave or vibrate.Industrially, fluidized bed CVD or PVD technique have been 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 method
Industrially it is mainly used in workpiece surface metallic cementation, but can also 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 can also be used to prepare clad on tungsten carbide particle.
The present invention relates to clad is prepared on tungsten carbide particle with the monohalide of TD method activation solid vanning method.It 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 predetermined time.Keeping temperature is 750 DEG C to 1250
DEG C, the retention time is 0.5 hour to 12 hours, these parameters depend on desired clad classes of compounds, thickness and carbon
Change the type of tungsten particle.During keeping temperature, carbide former metal or alloy is reacted with the halide of gasification, is formed
Gaseous metal halogen, metal halide are further reacted with hydrogen, generate carbide former metallic atom.These metals are former
Son is deposited on tungsten carbide particle surface, is reacted with the carbon atom in tungsten carbide, and carbide, cladded wolfram carbide particle are formed.
Before preparing clad 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 brittleness η phase and formed.Such as to generate carbonitride,
Boride or nitride clad need to then carry out tungsten carbide particle corresponding before halide activates solid vanning method processing
Carbo-nitriding/nitriding, boronising or Nitrizing Treatment, to improve the content of tungsten carbide particle surface region layer carbon/nitrogen, boron or nitrogen.
Clad with multi-layer structure can be prepared on tungsten carbide with halide activation solid vanning method of the invention.Such as
Fruit metal deposition capability is excessive, just will form that outer layer is metal or alloy and internal layer is the multilayer coating structure layer of compound.Such as to generate
Outer layer is the clad of compound, can be after halide activates 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.
TD method of the invention-halide activation solid vanning method has investment of production equipment compared with CVD and PVD method
The advantages that small, raw material are cheap, simple process.
Tungsten carbide particle with clad of the invention is placed 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,
Filiform, strip, band-like, paste, pulpous state or cloth-like etc..Heap postwelding, these have the tungsten carbide particle of clad to be uniformly distributed in base
In body.The overlaying method for preparing 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 by loading hopper
In the molten bath of workpiece surface, these particles are caught up in stiff dough matrix, form stiff dough.It can also be by the tungsten carbide with clad
Grain is inserted in continuous metal or alloy pipe, flux-cored wire is made, while other materials such as alloying element can also be dosed etc., metal
Matrix of the pipe skin as stiff dough.These welding wires are fed in workpiece surface matrix melt, form stiff dough.
It, can be by nozzle by the carbonization with clad for spraying and melting, 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, are then fed with nozzle.In workpiece surface, with oxyacetylene torch, plasma arc or
Laser melts 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 may include alloying element and deoxidier, matrix of the metal sheath as stiff dough.?
Workpiece surface forms stiff dough with oxyacetylene torch or arc-melting flux-cored electrode.
For oxygen-acetylene repairing, the welding of the tungsten carbide particle containing clad also can be used.By the carbonization with clad
Tungsten particle, alloying element, deoxidier and resin mixing, are applied to the surface of wire core, form coating layer, welding is made.?
Workpiece surface forms stiff dough with oxyacetylene torch fusion welding band.
For heat furnace brazing, by with clad tungsten carbide particle and basis material and additive such as flux it is abundant
Mixing, manufactured soldering soldering paste, 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 furnace and heats, be brazed.Stove is heated to predetermined temperature, holding scheduled time, subsequent furnace is cold or empty
It is cold, stiff dough is just formed in workpiece surface, it is also possible to which induction or oxyacetylene torch heating are brazed.
Embodiment given below is further described to of the invention, and claim includes but is not limited to described
Embodiment content.
Embodiment 1: the vanning method preparation of halide solid has the tungsten carbide particle of clad
The tungsten carbide to be coated is spherical cast tungsten carbide particle, and weight is 100 grams, micro- having a size of 45 microns to 150
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
It is dehydrated 1 hour and handles.Casting carbon tungsten carbide particle, titanium valve and ammonium chloride powder are put into ball mill, mixed 4 hours.Then, will
Mixing is put into a stainless steel crucible, is covered and is sealed with aluminium oxide cream.The stainless steel crucible of sealing is put into resistance furnace,
Under the argon gas protection of flowing, 1000 DEG C are heated to 10 DEG C/min., keeps the temperature 2 hours, then furnace cooling.It will treated material
Material is put into ball mill and is 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
Use plasma transferred arc process to be prepared for two kinds of stiff dough: the first is existing common tungsten carbide particle as enhancing
Phase, second is to use the tungsten carbide with clad of the invention as reinforced phase, their stiff dough matrix alloy is same nickel
Based alloy.In their experimentations, keep other materials identical with technique, to disclose the effect effect of clad on tungsten carbide
Fruit.Original silicon carbide tungsten particle is spherical cast tungsten carbide, and having a size of 45 microns to 150 microns, the clad of tungsten carbide is about 2 micro-
The thick titanium carbide of rice.The basis material of stiff dough is nickel-base alloy, nominal chemical component (weight percent) is 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 name is hard
Degree is 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 designs tungsten carbide particle containing 60wt.% in hard material having a size of 25mm × 100mm × 12mm.By 300 grams of carbon
Change tungsten particle to be uniformly mixed with 200 grams of Superalloy Substrate powder, be put into dispenser.95 amperes of welding current, powder carrier gas
For argon gas, 3 cubic feet/hour of flow.Single-layer surfacing, 1.5 millimeters of hardstanding target thickness.It is sawed at a slow speed with diamond to cut
Stiff dough sample is cut, cross-sectional metallographic sample is made, carries out structure observation and micro-hardness measurement.
Fig. 4 is that the existing conventional cast tungsten carbide of plasma transferred arc process preparation enhances the scanning electricity of nickel-base alloy stiff dough
Sub- microscope photo.As it can be seen that significant dissolution has occurred in tungsten carbide particle, while Precipitation a large amount of strips in the base
Two-phase.Fig. 5 is that the cast tungsten carbide with clad of the invention of plasma transferred arc process preparation enhances nickel-base alloy stiff dough
Electron scanning micrograph.As it can be seen that tungsten carbide particle dissolution degree is substantially reduced, while second number of phases is precipitated in the base
Amount decreases.The microhardness result measured is converted into Rockwell hardness and shows that conventional cast tungsten carbide enhances nickel-base alloy
The average hardness of stiff dough matrix is HRc 58.5, and has the cast tungsten carbide of clad to enhance being averaged for nickel-base alloy stiff dough matrix
Hardness HRc 49.0.Compared with basis material nominal hardness, heap postwelding stiff dough matrix hardness is all improved, this is because reinforced phase
Particle surface dissolution 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 is much smaller than conventional cast tungsten carbide enhancing nickel-base alloy stiff dough matrix.Microstructure observation and hard
Degree measurement all shows: having the casting carbon tungsten carbide particle dissolution degree of clad to be substantially less than conventional cast tungsten carbide.This explanation
Titanium carbide clad on tungsten carbide particle effectively prevents or alleviates the dissolution of tungsten carbide.
It is to be understood that the above is only one of embodiment of the present invention, for those of ordinary skill in the art
For, without departing from the principle of the present invention, also it can make several improvements and polish, these are improved and polishing also should be regarded as
Protection scope of the present invention.
Claims (9)
1. a kind of hard material of the tungsten carbide particle containing clad, including with clad tungsten carbide particle and matrix close
Gold, it is characterised in that: tungsten carbide particle includes at least cast tungsten carbide, carburizing cast tungsten carbide, macrocrystalline tungsten carbide and sintering carbon
Change one of tungsten；
Tungsten carbide particles sized is at 20 microns or more；
The clad of tungsten carbide particle is in metal carbides, metal boride, metal nitride or their complex chemical compound
At least one formation layer；Wherein, metal carbides refer to the carbide of a kind of titanium, niobium, zirconium, vanadium, tantalum, hafnium or chromium, metal
Boride refers to the boride of a kind of titanium, niobium, zirconium, vanadium, tantalum, hafnium or chromium, metal nitride refer to a kind of titanium, niobium, zirconium, vanadium, tantalum,
The nitride of hafnium, chromium or aluminium, complex chemical compound refer to the compound containing more than two component, wherein at least one metal
Element is titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or aluminium, and at least one nonmetalloid is carbon, boron or nitrogen；
Tungsten carbide particle coating thickness is at 0.5 micron or more.
2. the hard material of the tungsten carbide particle according to claim 1 containing clad, it is characterised in that: the carbon
Changing tungsten particle clad has two layers or more structure, and wherein at least one layer is carbide, boride, nitride or theirs is compound
Compound.
3. the hard material of the tungsten carbide particle according to claim 1 containing clad, it is characterised in that: hard material
It is at least one of in the form of welding rod, welding wire, welding, particle or powdered, paste, pulpous state or cloth-like.
4. 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 at least to use electric arc, oxyacetylene torch, laser, plasma transferred arc, heating furnace or induction heating method by overlaying method
One of.
5. the preparation method of the hard material of the tungsten carbide particle containing clad described in a kind of one of Claims 1-4,
Be characterized in that: tungsten carbide particle of the preparation containing clad is using halide activation solid powder vanning method, and tungsten carbide particle is extremely
It less include one of cast tungsten carbide, carburizing cast tungsten carbide, macrocrystalline tungsten carbide and cemented tungsten carbide；
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, then cooled to room temperature, be crushed,
Sieving, is isolated with clad tungsten carbide particle.
6. the preparation method of the hard material of the tungsten carbide particle according to claim 5 containing clad, feature exist
In: it is intended to reacting metal or alloy includes at least one of titanium, niobium, zirconium, vanadium, tantalum, hafnium, chromium or its alloy, halide is ammonium chloride.
7. the preparation method of the hard material of the tungsten carbide particle according to claim 5 containing clad, feature exist
In: holding temperature be from 750 DEG C to 1250 DEG C；Retention time is from 0.5 hour to 12 hour.
8. the preparation method of the hard material of the tungsten carbide particle according to claim 5 containing clad, feature exist
In: before solid powder vanning method processing or after, it includes that carburizing, carbon nitrogen are total that tungsten carbide particle, which carries out a kind of thermo-chemical treatment,
Infiltration, boronising or nitriding.
9. the preparation method of the hard material of the tungsten carbide particle according to claim 5 containing clad, feature exist
There is two layers or more structure in: clad, wherein at least one layer be metal carbides, metal boride, metal nitride or it
Complex chemical compound.
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| CN110385545B (en) * | 2018-10-25 | 2022-01-11 | 唐山师范学院 | Welding wire steel for manual argon arc welding |
| US11000921B2 (en) * | 2019-04-26 | 2021-05-11 | Kennametal Inc. | Composite welding rods and associated cladded articles |
| CN110394568B (en) * | 2019-08-07 | 2022-03-25 | 西安石油大学 | Double-layer core-shell structure cast tungsten carbide particle welding wire and preparation method thereof |
| CN110394566B (en) * | 2019-08-07 | 2022-03-25 | 西安石油大学 | Double-layer core-shell structure cast tungsten carbide particle welding rod and preparation method thereof |
| CN113319466B (en) * | 2021-06-15 | 2022-07-26 | 磐固合金(常州)有限公司 | Surfacing welding method for inner wall of thin-wall cylinder |
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