CN106995910A - A kind of metal_based material and preparation method for being covered with carbide coating - Google Patents
A kind of metal_based material and preparation method for being covered with carbide coating Download PDFInfo
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- CN106995910A CN106995910A CN201610052852.4A CN201610052852A CN106995910A CN 106995910 A CN106995910 A CN 106995910A CN 201610052852 A CN201610052852 A CN 201610052852A CN 106995910 A CN106995910 A CN 106995910A
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
- C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
- C23C10/22—Metal melt containing the element to be diffused
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
- C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
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- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a kind of metal_based material and preparation method for being covered with carbide coating.It comprises the following steps：Under inert atmosphere or vacuum atmosphere, metal_based material is added to the fluoride molten salt contained for penetration enhancer of molten condition, insulation reaction；It is the one or more simple substance or its oxide in chromium, vanadium, niobium, titanium, silicon and zirconium for penetration enhancer.The preparation method technique of the present invention is simple, and to techniques such as batch mixing orders without considered critical, applicability is extensive；The present invention is controllable in carbide coating dense uniform, thickness made from metal_based material surface, firm metallurgical binding is formed between matrix, adhesion is strong, the surface property of matrix material is improved, is made a concerted effort with high rigidity, high-wearing feature, anti-bite, the excellent properties such as high temperature oxidation resisting and environmental corrosion；Material surface performance is significantly improved, the service life of hardware is extended, the industrial applicability of metal material has been widened.
Description
Technical field
The present invention relates to a kind of metal_based material and preparation method for being covered with carbide coating.
Background technology
Metal plays great effect, especially big as important structural material in commercial Application
It is widely used in the essential industry field of the decision national economic development of type, such as automobile making, aviation system
Make, the industry such as Naval Architecture and Ocean Engineering, and in fields such as mould processing, forging molding, accurate devices
It is used as instrument and mold materials.But hardware under arms during, the abrasion of generally existing, plasticity
The failure phenomenons such as the corrosion under deformation, scuffing, occlusion, surrounding medium effect so that the life-span of component asks
Topic becomes increasingly conspicuous.The Surface Technics that 1960s flourishes, are directed generally to pass through
Physics, chemistry and other means change material surface state, obtain the surface texture that performance is much better than matrix.
The technology is applied to rapidly metal surface properties modification field, with strengthening material surface, improves machinery production
The service life of product and hardware.
In metal material surface intensive treatment technology, mainly there are high energy beam heat source surface reinforcement technique, gas
The methods such as phase deposition technique, plasma spray technology and thermo-chemical treatment.Every kind of reinforcement technique has it unique
Advantage, but equally there is also limitation.
High energy beam process for modifying surface makes processed surface produce high temperature by carrying out local high energy beam irradiation,
Then rapid cooling is so as to reach the purpose of surface peening.Advantage is the hardened layer for resulting in high-quality, energy
It is self cooling, skin layer and selective hardening can be achieved.But its have the disadvantage it is expensive, by high energy beam power limit
System, can only replace part to be heat-treated, and can not implement very well for shaped piece, interior surface processing etc..
Gas phase deposition technology includes chemical and physical vapor deposition, using the reaction between gas phase,
Single or multiple lift film is deposited on surface, so that material or product obtain required various excellent properties.
The maximum feature of this technology is to result in high rigidity, such as dystectic overlay film, TiC or TiN.But
It is that vapor deposition reaction temperature is high, it is high to equipment requirement, cause coating cost high, effluent pollution environment,
And for it is in irregular shape and it is internal need the workpiece of overlay film, its coat effect it is poor.
Plasma spray technology is to utilize Special Equipment by certain solid material heating and melting or softening and accelerate, and is sprayed
It is mapped on matrix surface, so as to form a kind of special coating.Its major defect is that coating binding force is poor,
Low for small size workpiece spray efficiency, coating uniformity is poor.
Thermo-chemical treatment is to make a kind of surface of infiltration layer element infiltration metal surface strong using the diffusion of element
Change technology, including carburizing, nitriding, boronising, carbo-nitriding and TD processing (Toyota Diffusion
Coating Process) etc. method.Wherein TD processing is a very excellent process for modifying surface,
Almost take into account the advantage of every other process for treating surface.TD treatment technologies are initially by Japanese Toyota's vapour
Car center research institute research and development a kind of process for modifying surface (Toyota Diffusion), be fused salt immersion plating,
The processing of the general name of electrolysis and powder method, also commonly known as metallic cementation.TD processing gained film layers have
Excellent abrasion resistance properties and high hardness, form metallurgical binding between coating and matrix, with other
The adhesion that method does not possess, substantially prolongs the workpiece life-span.Although TD treatment technologies have above-mentioned excellent
Gesture, but the key factor of its development of restriction is there is in commercial Application：Borax base salt divides at high temperature
Solution, causes molten salt composition to change, catabolite has severe corrosive, perishable processing equipment and fixture；
Borax base salt is very low to the dissolving activity for penetration enhancer metal, it is impossible to directly dissolve simple metal, can only be by also
Virgin metal oxide obtains simple metal element, therefore addition reducing agent and activator are needed in processing procedure.
The continuous consumption of the decomposition of salt bath, reducing agent and activator and addition, can cause salt bath component change and
Salt bath aging phenomenon.Salt bath aging can not only reduce reactivity, and generation does not plate or coated uneven etc.
Phenomenon, can also make fused salt mobility be deteriorated, stick to workpiece surface, the defect for causing cleaning difficult.
In practical application, fused salt several times was used, due to the fused salt that serious aging must more renew, was added
The cost of TD processing, is that abraum salt processing and environmental protection bring pressure.
Therefore, there is a kind of components of molten salt stabilization to be developed, corrosivity is controllable, operation is simple, avoid aging
Technology prepare the metal_based material for being covered with uniform coating and coating with matrix is metallurgical binding.
The content of the invention
Technical problem solved by the invention is to overcome existing is modified skill on metal_based material surface
Equipment cost height, complex process, the medium of art are serious to equipment corrosion, plating binding force of membrane is not strong, and
The overlay film of homogeneous coating, especially shaped piece and hidden face can not be obtained for the sample of unconventional size
There is provided a kind of metal_based material and preparation method for being covered with carbide coating for the defect that can not implement.This
The preparation method technological process of invention is simple, to techniques such as batch mixing orders without considered critical；Raw material type is few,
It is environment-friendly without additionally adding the adjuvant such as reducing agent and activator；Salt bath component is stable, without frequency
Numerous replacing salt bath；Applicability extensively, has no special requirements to specimen shape and size, and sample cleaning is easy,
Sample multiplicating can be handled, still ensure that thicknesses of layers is uniform, reduce production cost, be conducive to
Industrialized production.The present invention can in carbide coating dense uniform, thickness made from metal_based material surface
Control, forms firm metallurgical binding between matrix, and adhesion is strong, and film layer species is more, can meet not
Same use demand, significantly improves the surface property of matrix material, with high rigidity, high-wearing feature, resists
The excellent properties such as snap-in force, high temperature oxidation resisting and environmental corrosion.Carbide coating significantly improves material list
Face performance, with excellent properties such as high rigidity, high-wearing feature, resistance to high temperature oxidation and environmental corrosions, significantly
The service life of hardware is extended, the industrial applicability of metal material has been widened.
The present invention solves above-mentioned technical problem by the following technical programs.
The invention provides a kind of preparation method for the metal_based material for being covered with carbide coating, it is included such as
Lower step：Under inert atmosphere or vacuum atmosphere, metal_based material is added to molten condition containing confession
The fluoride molten salt of penetration enhancer, insulation reaction produces the metal_based material for being covered with carbide coating；Wherein, institute
It is the one or more simple substance or its oxide in chromium, vanadium, niobium, titanium, silicon and zirconium to state for penetration enhancer.
In the present invention, the inert atmosphere is the conventional inert atmosphere in this area, preferably argon gas atmosphere
And/or nitrogen atmosphere, it is more preferably argon gas atmosphere.
In the present invention, the metal_based material is conventional use of metal_based material in industrial circle, preferably
Ground is iron-based material, more preferably the iron-based material for phosphorus content 0.014~6%, is most preferably phosphorus content 3~6%
Iron-based material, above-mentioned percentage is mass percent.The iron-based material is that this area is conventional, example
Such as carbon steel, stainless steel or cast iron.
In the present invention, the form of described metal_based material can be various Metal Substrates commonly used in the art
Material shape, generally sheet material, tubing, strip, bulk and/or powder.
In the present invention, the metal_based material before addition, preferably first passes through pretreating process.It is described
Pretreating process can be the conventional pretreating process in this area, preferably be carried out by operations described below：Polishing,
Solvent cleans and removed solvent.
Wherein, the polishing is this area routine operation, is preferably polished using sand paper.According to
Common sense in the field, the surface after polishing generally only need to reach surfacing using application request as standard
.
Wherein, the solvent is the solvent that this area routine cleansing operation is used, preferably absolute ethyl alcohol.
The mode for removing solvent is conventional for this area, is preferably dried up using cold wind.
In the present invention, the form of the confession penetration enhancer can be various forms commonly used in the art, generally
Block or powder.
In the present invention, the confession penetration enhancer is preferably one kind or many in chromium, vanadium, niobium, titanium, silicon and zirconium
The simple substance planted, is more preferably simple substance chromium and/or elemental vanadium.
In the present invention, the confession penetration enhancer is before use, preferably pass through pretreating process.The pretreatment
Technique can be the conventional pretreating process in this area, and the drying of 1~2 hour is preferably carried out in an oven
Processing.The temperature of the baking oven is preferably more than 100 DEG C, is more preferably 120 DEG C.The baking oven one
As be vacuum drying chamber.
In the present invention, the mass ratio of the confession penetration enhancer and the fluoride molten salt is preferably 5~20%, more
It is 7.5~15% goodly.
In the present invention, the fluoride molten salt is the conventional fluoride molten salt of chemical field, preferably alkali
Metal fluoride, alkali earth metal fluoride, zirconium fluoride (ZrF4) and sodium fluoborate (NaBF4) in
It is one or more；More preferably it is lithium fluoride-sodium fluoride (LiF-NaF) fused salt, lithium fluoride-potassium fluoride (LiF-KF)
Fused salt, potassium fluoride-sodium fluoride (KF-NaF) fused salt, potassium fluoride-zirconium fluoride (KF-ZrF4) fused salt,
Lithium fluoride-sodium fluoride-potassium fluoride (LiF-NaF-KF) fused salt；Most preferably it is lithium fluoride-sodium fluoride-fluorination
Potassium (LiF-NaF-KF) fused salt；It is capitally lithium fluoride, sodium fluoride and potassium fluoride using mol ratio as 46.5：
11.5：42 lithium fluoride mixed-sodium fluoride-potassium fluoride (LiF-NaF-KF) eutectic fused salt.This Shen
Inventor please it has been investigated that, the fused salt mixt of above-mentioned mol ratio composition takes into account the low melting point of fused salt, height
The excellent heat physical performance such as boiling point, low viscosity.
Wherein, described alkali metal fluoride be preferably lithium fluoride (LiF), sodium fluoride (NaF) and
One or more in potassium fluoride (KF).Described alkali earth metal fluoride is preferably magnesium fluoride (MgF2)
And/or calcirm-fluoride (CaF2)。
In the present invention, the consumption of the fluoride molten salt is this area conventional amount used, can generally be submerged
The metal_based material.
In the present invention, the fluoride molten salt is preferably fluoride of the impurity content less than 500ppm and melted
Salt, is more preferably less than 200ppm fluoride molten salt for impurity content.It is described according to common sense in the field
Impurity generally refers to water, oxygen or impurity metal ion in fluoride molten salt etc..
In the present invention, fluoride molten salt can be heated to molten condition by this area usual manner, it is fully mixed
Uniform acquisition eutectic salts are closed, the fluoride molten salt is preferably heated to by molten condition using electric furnace.
In the present invention, the fluoride molten salt is preferably placed in the metal of the resistance to fluoride molten salt corrosion
Used in crucible.The metallic crucible is preferably stainless steel crucible or nickel crucible.
In the present invention, the temperature of the insulation reaction is preferably 500~1000 DEG C, more preferably for
750~950 DEG C.The time of the insulation reaction is preferably 1~100 hour, is more preferably 5~20 hours.
Present invention also offers a kind of Metal Substrate that carbide coating is covered with as made from above-mentioned preparation method
Material.
According to common sense in the field, of the invention is covered with carbide coating in the metal_based material of carbide coating
Thickness can be adjusted according to actual needs, its thickness is up to 3~20 μm.
On the basis of common sense in the field is met, above-mentioned each optimum condition can be combined, produce this hair
Bright each preferred embodiments.
The present invention is raw materials used commercially available.
The positive effect of the present invention is：
The preparation method technological process of the present invention is simple, to techniques such as batch mixing orders without considered critical；Raw material
Species is few, environment-friendly without the extra addition adjuvant such as reducing agent and activator；Salt bath component is stable,
Without frequently changing salt bath；Applicability extensively, has no special requirements to specimen shape and size, sample cleaning
Easily, sample multiplicating can be handled, still ensures that thicknesses of layers is uniform, reduce production cost,
Be conducive to industrialized production.
The present invention is controllable in carbide coating dense uniform, thickness made from metal_based material surface, with base
Firm metallurgical binding is formed between body, adhesion is strong, and film layer species is more, can meet different use need
Ask, significantly improve the surface property of matrix material, make a concerted effort with high rigidity, high-wearing feature, anti-bite,
The excellent properties such as high temperature oxidation resisting and environmental corrosion.Carbide coating significantly improves material surface performance,
With excellent properties such as high rigidity, high-wearing feature, resistance to high temperature oxidation and environmental corrosions, gold substantially prolongs
The service life of metal elements, has widened the industrial applicability of metal material.
Brief description of the drawings
Fig. 1 is the experimental provision schematic diagram that metal_based material surface in situ of the present invention prepares carbide coating；
Wherein, 1 is thermal insulation furnace body, and 2 be container crucible, and 3 be fused salt, and 4 be metal_based material, and 5 be metal
Sill stationary fixture, 6 be inert atmosphere or vacuum atmosphere, and 7 be sealed crucible lid, and 8 be closed system
Device.
Fig. 2 is gray iron sample scans electron microscope (SEM) shape that embodiment 1 is covered with vanadium carbide coating
Looks figure；Wherein, figure A be its surface SEM shape appearance figures, 1~4 represent grab sample point, figure B be
Vanadium (V) distribution diagram of element of cross section.
Fig. 3 is the gray iron sample analysis figure that embodiment 2 is covered with chromium carbide coating；Wherein, figure A is its table
Face Scanning Electron microscope SEM shape appearance figures, 1~4 represents grab sample point, and figure B sweeps for cross section
Element is retouched in electron microscope shape appearance figure and section with the distribution map apart from case depth.
Fig. 4 is the gray iron specimen cross section analysis chart that embodiment 3 is covered with chromium carbide coating；Wherein, figure A is
Product cross section Scanning Electron microscope SEM shape appearance figures, figure B is element in cross-sectional sample with distance
The distribution map of case depth.
Fig. 5 is X-ray diffraction analysis (XRD) figure of the vanadium carbide coating of embodiment 1.
Fig. 6 is X-ray diffraction analysis (XRD) figure of the chromium carbide coating of embodiment 2.
Fig. 7 is that embodiment 2 is covered with the gray iron material of chromium carbide coating and the nano impress of original gray iron material
H between hardness H and compression distance h2- 1/h scatter charts.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but is not therefore limited the present invention to
Among described scope of embodiments.The experimental method of unreceipted actual conditions in the following example, according to normal
Rule method and condition, or selected according to catalogue.
In following embodiments, gray iron material (belonging to cast iron category) used is the commercially available HT250 trades mark
Metal (phosphorus content 3.16~3.3%), confession penetration enhancer pure vanadium powder and pure chromium powder used are commercially available pure metal powder,
Purity is more than 99.9%.Alloy crucible used is 316L stainless steel crucibles.Other assistant experiment materials are equal
It is commercially available.
Embodiment 1
Fig. 1 is the experimental provision schematic diagram that metal_based material surface in situ of the present invention prepares carbide coating；
Wherein, 1 is thermal insulation furnace body；2 be container crucible；3 be fused salt；4 be metal_based material；5 be metal
Sill stationary fixture；6 be inert atmosphere or vacuum；7 be sealed crucible lid；8 be closed system device.
The preparation method for being covered with the gray iron of vanadium carbide coating is as follows：
(1) gray iron material cuts into suitable dimension sample with wire electric discharge, then with abrasive paper for metallograph to table
Face carries out pre-grinding and polishing, until surfacing, similar to minute surface；By the grey ferroelectric sample nothing of pre- milled
Cold wind is dried up after water-ethanol cleaning；
(2) 316L stainless steel crucibles are cleaned with running water first, then carried out clearly with absolute ethyl alcohol
Wash, after cold wind drying, dehydrated in 120 DEG C of vacuum drying chamber 2 hours；
(3) by fluoride mixing eutectic fused salt LiF-NaF-KF, (mol ratio is 46.5：11.5：42),
The suitable little particle of size is broken into, is fitted into 316L stainless steel crucibles；Wherein, solid salt addition
So that fused salt liquid level is totally submerged on the basis of gray iron material after solid salt melting；Fluoride mixing eutectic fused salt
Impurity content be less than 500ppm；
(4) by metal vanadium powder simultaneously be placed in the 316L stainless steel crucibles equipped with fused salt, vanadium metal with
The mass ratio of fluoride fused salt mixt is 10%；
(5) ready 316L stainless steel crucibles are inserted in the high-temperature electric resistance furnace of closed argon gas atmosphere, plus
Heat to fluoride fused salt mixt is melted completely；
(6) fixture for being fixed with grey ferroelectric sample is put into fuse salt, is completely submerged in grey ferroelectric sample
In fuse salt, insulation reaction 10 hours, holding temperature is 850 DEG C；
(7) after completion of the reaction, power supply is closed, grey ferroelectric sample is taken out, is cleaned after cooling in room temperature water,
The fused salt of remained on surface is removed, obtains to surface and is covered with the grey ferroelectric sample of vanadium carbide coating；
(8) 316L stainless steel crucibles connect, are still placed in for penetration enhancer vanadium and fused salt in sealing device, remain
Reuse again.
Embodiment 2
The preparation process of the gray iron of chromium carbide coating is covered with to use such as the experimental provision of Fig. 1 in embodiment 1.
The preparation method for being covered with the gray iron of chromium carbide coating is as follows：
(1) gray iron material cuts into suitable dimension sample with wire electric discharge, then with abrasive paper for metallograph to table
Face carries out pre-grinding and polishing, until surfacing, similar to minute surface；By the grey ferroelectric sample nothing of pre- milled
Water-ethanol is cleaned, cold wind drying；
(2) 316L stainless steel crucibles are cleaned with running water first, then carried out clearly with absolute ethyl alcohol
Wash, after cold wind drying, dehydrated in 120 DEG C of vacuum drying chamber 2 hours or so；
(3) by fluoride mixing eutectic fused salt LiF-NaF-KF, (mol ratio is 46.5：11.5：42),
The suitable little particle of size is broken into, is fitted into 316L stainless steel crucibles；Wherein, solid salt addition
So that fused salt liquid level is totally submerged on the basis of gray iron material after solid salt melting；Fluoride mixing eutectic fused salt
Impurity content be less than 500ppm；
(4) by crome metal powder simultaneously be placed in the 316L stainless steel crucibles equipped with fused salt, crome metal with
The mass ratio of fluoride fused salt mixt is 7.5%.
(5) ready stainless steel crucible is inserted in the high-temperature electric resistance furnace of closed atmosphere, is heated to fluorination
Thing fused salt mixt is melted completely；
(6) fixture for being fixed with grey ferroelectric sample is put into fuse salt, is completely submerged in grey ferroelectric sample
In fuse salt, insulation reaction 5 hours, holding temperature is 950 DEG C；
(7) after completion of the reaction, power supply is closed, grey ferroelectric sample is taken out, is cleaned after cooling in room temperature water,
The fused salt of remained on surface is removed, obtains to surface and is covered with the grey ferroelectric sample of chromium carbide coating；
(8) 316L stainless steel crucibles, be still placed in sealing device for penetration enhancer chromium and fused salt, remain again
It is secondary to reuse.
Embodiment 3
The preparation process of the gray iron of chromium carbide coating is covered with to use such as the experimental provision of Fig. 1 in embodiment 1.
The preparation method for being covered with the gray iron of chromium carbide coating is as follows：
(1) gray iron material cuts into suitable dimension sample with wire electric discharge, then with abrasive paper for metallograph to table
Face carries out pre-grinding and polishing, until surfacing, similar to minute surface；By the grey ferroelectric sample nothing of pre- milled
Water-ethanol is cleaned, cold wind drying；
(2) 316L stainless steel crucibles are cleaned with running water first, then carried out clearly with absolute ethyl alcohol
Wash, after cold wind drying, dehydrated in 120 DEG C of vacuum drying chamber 2 hours or so；
(3) by fluoride mixing eutectic fused salt LiF-NaF-KF, (mol ratio is 46.5：11.5：42),
The suitable little particle of size is broken into, is fitted into 316L stainless steel crucibles；Wherein, solid salt addition
So that fused salt liquid level is totally submerged on the basis of gray iron material after solid salt melting；Fluoride mixing eutectic fused salt
Impurity content be less than 200ppm；
(4) by crome metal powder simultaneously be placed in the 316L stainless steel crucibles equipped with fused salt, crome metal with
The mass ratio of fluoride fused salt mixt is 15%.
(5) ready stainless steel crucible is inserted in the high-temperature electric resistance furnace of closed atmosphere, is heated to fluorination
Thing fused salt mixt is melted completely；
(6) fixture for being fixed with grey ferroelectric sample is put into fuse salt, is completely submerged in grey ferroelectric sample
In fuse salt, insulation reaction 20 hours, holding temperature is 750 DEG C；
(7) after completion of the reaction, power supply is closed, grey ferroelectric sample is taken out, is cleaned after cooling in room temperature water,
The fused salt of remained on surface is removed, obtains to surface and is covered with the grey ferroelectric sample of chromium carbide coating；
(8) 316L stainless steel crucibles, be still placed in sealing device for penetration enhancer chromium and fused salt, remain again
It is secondary to reuse.
Effect example 1
Electron microscope is scanned to the grey ferroelectric sample for being covered with carbide coating prepared by embodiment 1~3
(SEM) pattern and elemental composition power spectrum (EDS) analysis.
Fig. 2 is gray iron sample scans electron microscope (SEM) shape that embodiment 1 is covered with vanadium carbide coating
Looks figure；Wherein, figure A be its surface SEM shape appearance figures, 1~4 represent grab sample point, figure B be
Vanadium (V) distribution diagram of element of cross section.The element composition of 1~4 each point is as shown in table 1；Can by table 1
Know, gray iron specimen surface is completely covered in gray iron specimen surface richness vanadium, v element.From scheming B, in examination
There is the enriched layer of a thin layer vanadium in the outmost surface of sample, in the light tone of silvery white.
Table 1
Fig. 3 is the gray iron sample analysis figure that embodiment 2 is covered with chromium carbide coating；Wherein, figure A is its table
Face Scanning Electron microscope SEM shape appearance figures, 1~4 represents grab sample point, and figure B sweeps for cross section
Element is retouched in electron microscope shape appearance figure and section with the distribution map apart from case depth.The member of 1~4 each point
Element composition is as shown in table 2, and as shown in Table 2, gray iron specimen surface is chromium-rich, and gray iron is completely covered in chromium
Specimen surface；From scheming B, there is one layer of chromium-enriched layer, correspondence chromium carbide generation in sample outmost surface
Thickness, about 5.5 μm, lower section 4 curves parallel with baseline are represented in figure B, Na, Si, O and
The elements such as K are with the increase of depth, changes of contents very little.
Table 2
Fig. 4 is the gray iron specimen cross section analysis chart that embodiment 3 is covered with chromium carbide coating；Wherein, figure A is
Product cross section Scanning Electron microscope SEM shape appearance figures, figure B is element in cross-sectional sample with distance
The distribution map of case depth.From scheming A, there is one layer of silvery white thin layer in sample outmost surface, should be
The chromium carbide coating of generation；From scheming B, there is one layer of chromium-enriched layer, correspondence carbon in sample outmost surface
Change chromium generation thickness, about 5 μm.
Effect example 2
X-ray diffraction analysis are carried out to the grey ferroelectric sample for being covered with carbide coating prepared by embodiment 1~2
(XRD) structure and the phase composition of gray iron material carbide surface coating, are characterized.The analysis of embodiment 1
As a result such as Fig. 5, the analysis result of embodiment 2 is as shown in Figure 6.
As shown in Figure 5, after by the method processing in embodiment 1, gray iron surface species diffraction maximum is corresponding
Structure is vanadium carbide, illustrates to form carbonization vfanadium compound in grey iron surface.It will be appreciated from fig. 6 that by implementation
After method processing in example 2, the corresponding structure of gray iron surface species diffraction maximum is Cr23C6And Cr7C3,
Illustrate to form Cr in grey iron surface23C6And Cr7C3Two kinds of carbide.
The result of effect example 1 and effect example 2 shows, using the preparation method of the present invention in ash
Iron material surface deposited one layer of uniform vanadium carbide or chromium carbide coating.
Effect example 3
The carbide coating obtained to embodiment 1~3 carries out superficial film Thickness Analysis.
Exemplified by being covered with the grey ferroelectric sample of chromium carbide coating by the surface of embodiment 2, specific method of testing is as follows：
The chromium carbide thicknesses of layers that grey iron surface is covered with is measured using XRF calibrator (XRF).
The wavelength of XRF is feature to different elements, the fluorescence intensity come out according to Element release, is come
Enter the quantitative analysis of row element thickness distribution.Acquisition is surveyed after region element intensity, utilizes Survey Software
Thickness of coating is analyzed, by being contrasted with standard sample, thickness value is obtained.The measurement error of thickness
It can be controlled within 5%.
What 8 differences of the gray iron specimen surface for being covered with chromium carbide coating to the product of embodiment 2 were carried out
Thickness test result, it is as a result as shown in table 3 below.The thickness testing method of embodiment 1,3 is with above-mentioned reality
Apply example 2.As shown in Table 3, the grey iron surface even compact of embodiment 1 is coated with vanadium carbide coating,
Average thickness is 3.950 μm；The grey iron surface even compact of embodiment 2 is coated with chromium carbide coating,
5.494 μm of average thickness；The grey iron surface even compact of embodiment 3 is coated with chromium carbide coating, puts down
Equal thickness is 4.791 μm.
Table 3
Effect case study on implementation 4
Exemplified by being covered with the grey ferroelectric sample of chromium carbide coating by the surface of embodiment 2, case hardness measurement is carried out,
Specific method of testing is as follows：
Gray iron and the original grey ferroelectric sample progress surface for being covered with chromium carbide coating to the surface of embodiment 2 respectively are pre-
Polishing is ground, the surface of two kinds of samples is met certain flatness, follow-up hardness is convenient for and surveys
Amount.Respectively two samples are carried out with nano-indentation hardness measurements first, maximum compression distance 2000nm,
Poisson's ratio 0.25.Fig. 7 is the gray iron material and original gray iron material that embodiment 2 is covered with chromium carbide coating
H between nano-indentation hardness H and compression distance h2- 1/h scatter charts.Respectively to embodiment 2
Surface is covered with the gray iron of chromium carbide coating and the H of original grey ferroelectric sample2- 1/h curves are fitted rear extension,
It can be good at the Composite hardness H of reaction material with the intersection point of ordinate0.Understood according to Fig. 7, it is real
Apply the Composite hardness H that the surface of example 2 is covered with the gray iron of chromium carbide coating0For 20.5GPa (H0 2=422.2),
The Composite hardness H of original grey ferroelectric sample0For 3.5GPa (H0 2=12.1), it was demonstrated that surface coating carbonization
The hardness of gray iron matrix is set to improve about 6 times after chrome coating.
The gray iron of chromium carbide coating and original gray iron specimen surface grab sample 6 are covered with to the surface of embodiment 2
Individual point carries out micro-hardness measurement, and imposed load is 100gf during test, and guarantor's load time is 15s, as a result such as
Shown in table 4.It follows that the hardness of the original grey ferroelectric sample of embodiment 2 is about 310HV, coating carbonization
Hardness is about 2000HV after chrome coating, makes grey iron-based after further demonstrating surface coating chromium carbide coating
The hardness of body improves about 6 times.
Table 4
Claims (10)
1. a kind of preparation method for the metal_based material for being covered with carbide coating, it comprises the following steps：
Under inert atmosphere or vacuum atmosphere, metal_based material is added to the fluorine contained for penetration enhancer of molten condition
Compound fused salt, insulation reaction produces the metal_based material for being covered with carbide coating；Wherein, the confession penetration enhancer
For the one or more simple substance or its oxide in chromium, vanadium, niobium, titanium, silicon and zirconium.
2. preparation method as claimed in claim 1, it is characterised in that the confession penetration enhancer and the fluorine
The mass ratio of compound fused salt is 5~20%, preferably 7.5~15%；
And/or, the confession penetration enhancer is one or more simple substance in chromium, vanadium, niobium, titanium, silicon and zirconium,
Preferably simple substance chromium and/or elemental vanadium.
3. preparation method as claimed in claim 1, it is characterised in that the inert atmosphere is argon gas
Atmosphere and/or nitrogen atmosphere；
And/or, the metal_based material is the iron-based of iron-based material, preferably phosphorus content 0.014~6%
Material, the more preferably iron-based material for phosphorus content 3~6%, above-mentioned percentage is mass percent.
4. preparation method as claimed in claim 1, it is characterised in that the metal_based material is adding
Before entering, pretreating process is first passed through；The pretreating process is preferably carried out by operations described below：Polishing,
Solvent cleans and removed solvent；
Wherein, the polishing is preferably polished using sand paper；It is the preferred solvents anhydrous second
Alcohol；The mode for removing solvent is preferably using cold wind drying.
5. preparation method as claimed in claim 1, it is characterised in that the confession penetration enhancer before use,
By pretreating process；The pretreating process is preferably carried out at the drying of 1~2 hour in an oven
Reason；The temperature of the baking oven is preferably more than 100 DEG C.
6. preparation method as claimed in claim 1, it is characterised in that the fluoride molten salt is alkali
One or more in metal fluoride, alkali earth metal fluoride, zirconium fluoride and sodium fluoborate；
Described alkali metal fluoride is preferably the one or more in lithium fluoride, sodium fluoride and potassium fluoride；
Described alkali earth metal fluoride is preferably magnesium fluoride and/or calcirm-fluoride.
7. preparation method as claimed in claim 6, it is characterised in that the fluoride molten salt is fluorine
Change lithium-sodium fluoride fused salt, lithium fluoride-potassium fluoride fused salt, potassium fluoride-sodium fluoride fused salt, potassium fluoride-fluorination
Zirconium fused salt, lithium fluoride-sodium fluoride-potassium fluoride fused salt；Preferably lithium fluoride, sodium fluoride and potassium fluoride with
Mol ratio is 46.5：11.5：42 lithium fluoride-the sodium fluorides mixed-potassium fluoride eutectic fused salt.
8. preparation method as claimed in claim 1, it is characterised in that the fluoride molten salt is miscellaneous
Matter content is less than 500ppm fluoride molten salt, and preferably impurity content is less than 200ppm fluorination
Thing fused salt；
And/or, the fluoride molten salt is heated to by molten condition using electric furnace；
And/or, the fluoride molten salt is placed in the metallic crucible of the resistance to fluoride molten salt corrosion and carried out
Use；The metallic crucible is preferably stainless steel crucible or nickel crucible.
9. preparation method as claimed in claim 1, it is characterised in that the temperature of the insulation reaction
For 500~1000 DEG C, preferably 750~950 DEG C；
And/or, the time of the insulation reaction is 1~100 hour, preferably 5~20 hours.
10. it is covered with carbide coating made from a kind of preparation method as described in any one of claim 1~9
Metal_based material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107127334A (en) * | 2017-05-09 | 2017-09-05 | 东北大学 | A kind of nano particle of carbide metal core shell structure and preparation method thereof |
| CN108300960A (en) * | 2018-03-06 | 2018-07-20 | 中国科学院海洋研究所 | Penetration enhancer and its application are expanded in a kind of surface of not metal-containing powders |
| CN108624839A (en) * | 2018-06-22 | 2018-10-09 | 中国科学院上海应用物理研究所 | A kind of preparation method of stainless steel aluminized coating |
| CN111039291A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院金属研究所 | Method for preparing NbC and/or TaC powder in situ by molten salt disproportionation reaction |
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| US5769966A (en) * | 1994-05-11 | 1998-06-23 | The United States Of America As Represented By The Department Of Energy | Insulator coating for high temperature alloys method for producing insulator coating for high temperature alloys |
| CN1609272A (en) * | 2004-10-13 | 2005-04-27 | 昆明理工大学 | Process for producing metal carbonide hard face coating and application thereof |
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| US5769966A (en) * | 1994-05-11 | 1998-06-23 | The United States Of America As Represented By The Department Of Energy | Insulator coating for high temperature alloys method for producing insulator coating for high temperature alloys |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107127334A (en) * | 2017-05-09 | 2017-09-05 | 东北大学 | A kind of nano particle of carbide metal core shell structure and preparation method thereof |
| CN108300960A (en) * | 2018-03-06 | 2018-07-20 | 中国科学院海洋研究所 | Penetration enhancer and its application are expanded in a kind of surface of not metal-containing powders |
| CN108624839A (en) * | 2018-06-22 | 2018-10-09 | 中国科学院上海应用物理研究所 | A kind of preparation method of stainless steel aluminized coating |
| CN111039291A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院金属研究所 | Method for preparing NbC and/or TaC powder in situ by molten salt disproportionation reaction |
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