CN1502714A - Ternary boride base metal ceramic covering layer material and preparation technology thereof - Google Patents
Ternary boride base metal ceramic covering layer material and preparation technology thereof Download PDFInfo
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Abstract
The present invention relates to an engineering material and its preparation process, in particular, it is a ternary boride base metal ceramic hard covering layer material and its preparation process. Said invention uses the easily available metal and alloy powder as raw material, and adopts the slurry preparation process, blank body forming process and liquid phase sintering process to prepare ternary boride base metal ceramic covering layer material on the surface of metal base. Said invention utilizes the regulation of iron base adhesive phase composition so as to make the covering layer material retain high wear resistance, at the same time raise its corrosion resistance.
Description
(1) technical field
The present invention relates to engineering materials and preparation technology thereof, especially ternary boride-based metal ceramic hard clad material and preparation technology thereof.
(2) background technology
The material property of mechanical means component as wear-resistant, corrosion-resistant, withstand voltage, shock resistance, performance such as high temperature resistant, anti-oxidant, directly has influence on work-ing life and work reliability by its mechanized equipment of forming.The destruction of component is often from the surface beginning, and the local failure on surface will cause whole part to lose efficacy, and then causes the inefficacy of entire equipment.Therefore, by the composition that changes the metal parts top layer, the physical and chemical performance that structure is improved material surface, significant for the performance of the mechanized equipment that improves metal parts and formed.
For many years, aspect the physical and chemical performance of exploring raising metal parts top layer, people have invented a lot of novel materials and novel process.Adopt more metal material surface reinforcing process to have, thermospray (comprising flame plating, plasma spraying and electric arc spraying etc.), vapour deposition (PVD, CVD, PCVD, PACVD etc.), composite deposite, sol-gel, the deposited coating of SHS, focused beam surface strengthening, laser melting coating, built-up welding etc.These technologies by preparation coating efficient hardening the hardness of metal base surface, wear resistance and erosion resistance, but exist weak point respectively at aspects such as simplification, starting material system range of choice and the coating quality of processing unit and technological process, material property increase rates.
In recent years, inventing the multiple working method for preparing the metal base surface coating with cermet material aspect hardness that improves the metal base surface coating and wear-resisting, the corrosion resisting property, as self-fluxing alloy slurry process pre-coated vacuum sintering coating technology, can obtain the metal/ceramic compound coating of wear-resisting erosion resistance in the metallic surface; Application number 95103970, publication number 1133902, a name are called the Chinese patent of " a kind of preparation method of ceramic coat on surface of steel sheet ", adopt stacked batching and preheating pressing technology, can form the thick chromium carbide based metal ceramic coating of 2～3mm at steel plate or steel workpiece plane surface; Application number 96107025, publication number 1151354, a name are called the Japanese Patent of " coating material ", by weld seam clinkering combination, can be that metallic substrate surface prepares the corrosion-proof and high-strength clad material that Ni is MULTILAYER COMPOSITE such as metal level, metal stratum reticulare, corrosion resistant metal coating at Fe; Application number 98109698, publication number 1208085, a name are called the United States Patent (USP) of " goods that have coating ", adopt sedimentary method, on metallic matrix, prepare multilayered structure (comprising nickel dam, Pd-Ni alloy layer, high melting metal layer and refractory metal compound layer) and have the color of polishing brass and the clad material goods of wear-resisting erosion resistance performance; Application number 99806262, publication number 1301204, name be called " two metal plates,, Australian Patent, the another kind of metal of casting utilizes the overheated of institute casting metal on metallic matrix, makes to produce diffusion-bonded between the double layer of metal, makes clad material; Application number 00119494, publication number 1280213, a name are called the Chinese patent of " a kind of production technique of copper-clad panel ", on the plain carbon stool plate, adopt the method for flash to carry out Alloying Treatment, obtain anti-corrosion, wear-resisting and have the clad material of decoration function.
Above-mentioned metal ceramic coating material and preparation technology have improved wear-resisting, the corrosion resisting property of metallic matrix greatly, but the problem of several aspects below existing:
1, complex technical process;
2, used device structure complexity, cost height;
3, used starting material range of choice is little, and mostly is the noble metal material;
4, the performance variation of prepared coating is few, and to the bad adaptability of base material structure, the integrated performance index of material is low, range of application is limited bigger.
(3) summary of the invention
The purpose of this invention is to provide that a kind of material choice scope is big, the source is wide, be easy to get, high abrasion, high anti-corrosion cermet cladding material cheaply, and the clad material preparation technology that technological process is simple, easy to operate, processing quality is fit to multiple metallic matrix reliably.
The present invention includes the preparation technology of clad material and clad material.It is conceived substantially and utilizes the multiple metal that obtains easily, powdered alloy raw material, adopts liquid sintering technology to prepare ternary boride base metal ceramic covering layer material at metal base surface.By adjusting the composition of iron-based bonding phase, can make clad material when keeping high-wearing feature, increase substantially erosion resistance.In the liquid phase sintering process, utilize the in-situ chemical reaction between the raw material powder to form ternary boride ceramic hard phase, thereby increase substantially the wear resistance of material; Formed eutectic liquid phase in the coating, wetting with metallic matrix on the one hand, and make the firm metallurgical binding of generation between coating and the metallic matrix after the cooling, make by capillary force action on the other hand and the abundant densification of clad material form fine and close, hard, wear-resistant, corrosion resistant surface hard coating after the cooling.
The raw material of clad material consists of (weight ratio): Mo 35～55%, and B 4～10%, and C 0～1.5%, and Cr 0～15%, and Ni 0～10%, and Ti 0～10%, and Cu 0～10%, and all the other are Fe;
The optimum feed stock of clad material consists of: Mo 48%, and B 6%, and C 0.8%, and Cr 5%, and Ni 2%, and Ti 2%, and Cu 2%, and all the other are Fe.
The preparation technology of clad material comprises slip preparation technology, body formation technology and liquid sintering technology.
1, slip preparation technology
The employed slip of coating body formation is by cermet cladding material and additive processing and preparing;
The composition proportioning of slip additive is (weight ratio): binding agent 2～5%, and softening agent 0～3%, levelling agent 0～10%, all the other are organic solvent.
Organic solvent is: the mixed system of ethanol or ethanol and butanone (butanone);
Binding agent is: the polymkeric substance that polyvinyl butyral acetal (PVB), ethyl cellulose, polyvinyl acetate (PVAc), methyl esters (PMMA), vinyl acetate (PEMA) etc. dissolve in organic non-polar solvent selects one of them or its combined system;
Softening agent is: dinoctyl phthalate (DOP), glycerine, dibutyl phthalate (DBP), fourth (base) benzyl (base) phthalic ester select one of them or its combined system;
Levelling agent is: pimelinketone.
Clad material in the slip (metal, powdered alloy) is 1: 0.6～1.5 with the ratio (weight ratio) that cooperates of slip additive.
During the preparation slip, with clad material raw material (metal, powdered alloy) and slip additive (comprising: organic solvent, binding agent, softening agent, levelling agent) proportion the back in ball grinder ball milling mixed 24～48 hours, slip is crossed 400 mesh sieves, vacuum stripping again is the slip of shaping usefulness.
2, the forming technology of clad material base substrate
Before carrying out the shaping operation of coating base substrate on the metallic matrix, must eliminate rust to metallic matrix, surface cleaning such as cleaning handles.
2-1 curtain coating forming technology
Be applicable to the coating preparation on the metallic matrix of surfacing.The curtain coating of thin layer base substrate is shaped and adopts the curtain coating forming mill of all size, model, perhaps adopts easy slip to cast casting method.The mold base that slip is cast casting method adopts 3～5mm float glass sheet, above open and flat paving one deck PE film.It is the frame type that will quadrature that four limits of substrate glasses sheet surround internal range with the glass lath, is used for controlling the curtain coating scope of slip, thus the area of control thin layer base substrate.Utilize that the curtain coating moulding method can prepare that thickness is controlled at 30～2000 μ m, area controlled amount, whole even compact, apparent size is stable, surfacing is bright and clean, have the snappiness of appropriateness and the layer material base substrate of tensile strength.
2-2 application forming technology
Be applicable to the coating preparation of arbitrary shape metal base surface, mainly comprise: aerial spraying, airless spraying, electrostatic spraying, showering, dip-coating, powder coating, rotation application, brushing.
When the coating that utilizes application techniques to carry out the clad material base substrate was shaped, it is unsuitable excessive that formed overlay thickness is operated in an application, with slip can be smooth, smooth, evenly, stably stick to matrix surface and be advisable.For the matrix plane surface of horizontal direction, each is operated formed overlay thickness all over application and is advisable with 100～500 microns; For non-horizontal matrix surface, when particularly the matrix surface angle of inclination is big, each is operated formed overlay thickness all over application and should suitably reduce, as application for vertical matrix surface, should be advisable with 30～150 microns, when the formed overlay thickness of an application is excessive, form the slip drip easily.The used slip of reply does not stir off and in the application operation, to prevent slip generation segregation sedimentation.When coating green body layer that needs are shaped thicker, can after last time overlay drying, repeat the application shaping operation, reach desired thickness until the coating green body layer.
3, the liquid sintering technology of clad material
The thin slice base substrate that curtain coating is shaped through cutting, cutting back paving, be laminated on the flat surface of metallic matrix, covers above again and presses the alumina-ceramic flat board that can cover any surface finish of base substrate, inserts in the vacuum oven (inversion also can) then and carries out liquid phase sintering; Adopt coating process to carry out the workpiece of coating body formation, can directly place on the alumina-ceramic flat board of any surface finish, insert vacuum oven again and carry out liquid phase sintering.Vacuum tightness during sintering is 1.0Pa～1.0 * 10
-3Pa.The sintering temperature system is: with 5～15 ℃ of/minute rate of heating, be warming up to 400～450 ℃ from room temperature, be incubated 20～40 minutes; With 10～20 ℃ of/minute rate of heating, be warming up to 1000～1100 ℃ from 400～450 ℃, be incubated 20～40 minutes; With 5～15 ℃ of/minute rate of heating, be warming up to 1060～1300 ℃ of firing temperatures from 1000～1100 ℃, be incubated 10～40 minutes; Furnace cooling is reduced to room temperature from firing temperature then.According to the composition difference of clad material, firing temperature is selected in 1060～1300 ℃.
The present invention adopts slip application or curtain coating forming technology and liquid sintering technology to prepare ternary boride-based metal ceramic hard clad material at metal base surface.The ceramic hard that is formed by in-situ chemical reaction in the coating makes material have good wear resistance mutually, regulates material and forms the erosion resistance that can also significantly improve material.The used variety of raw material of this technology is many, the source is wide, and with low cost, technology is simple, and is easy to operate, the product practicality, and the ratio of performance to price is reasonable, and is strong to the adaptability of metal matrix material, the good processability of prepared clad material or component, its novel uniqueness.
(4) embodiment
Embodiment 1:
The raw material of the coating of table 1 embodiment 1 is formed
Raw material Mo powder B-Fe alloy powder C powder (graphite) Cr powder Ni powder Ti powder Cu powder iron powder
Content (weight ratio) 48% 30% 0.3% 2% 1% 00 surpluses
The raw material of the slip additive of each embodiment of table 2 is formed
Material polyethylene butyral (PVB) dinoctyl phthalate (DOP)+glycerine pimelinketone ethanol+butanone
Content (weight ratio) 1.6% 2.5% 6% surpluses
Function binding agent softening agent levelling agent organic solvent
The salient features of table 3 embodiment 1 clad material
The erosion resistance of the wear resistance coating of project coating hardness coating and high base strength coating
10～15 times of index HRA88 ± 2 350 ± 10MPa Q235 steel are better, and suitable coating raw material composition with stainless steel sees Table 1.The raw material composition of shaping slip additive sees Table 2.Each raw material is proportioned back the adding in the ball grinder, mixing and ball milling 24～48 hours, filter the final vacuum degasification with 400 mesh sieves, being prepared into thickness with casting method is 500 microns thin slice base substrate, after the cutting with 3 stacked metallic matrix (Q235) flat surfaces that place after the purification, carry out sintering by the sintering temperature system in vacuum oven, firing temperature is 1240 ℃, and material cools to room temperature with the furnace.The salient features of prepared clad material sees Table 3.
Embodiment 2:
The raw material of the coating of table 4 embodiment 2 is formed
Raw material Mo powder B-Fe alloy powder C powder (graphite) Cr powder Ni powder Ti powder Cu powder iron powder
Content (weight ratio) 48% 30% 0.8% 5% 2% 2% 2% surpluses
The salient features of table 5 embodiment 2 clad materials
The erosion resistance of the wear resistance coating of project coating hardness coating and high base strength coating
10～20 times of index HRA89 ± 2 360 ± 10MPa Q235 steel are good, and are suitable with the high-quality stainless steel
Coating raw material composition sees Table 4.The raw material composition of shaping slip additive sees Table 2.Each raw material is proportioned back the adding in the ball grinder, mixing and ball milling 24～48 hours, filter the final vacuum degasification with 400 orders, adopt air spray finishing spray formation on the surface that metallic matrix (Q235) has purified, every is 100 microns all over the green body layer thickness that is shaped, and carries out 12 times spray formation operations altogether; Carry out sintering by the sintering temperature system in vacuum oven, sintering temperature is 1210 ℃, cools to room temperature with the furnace.The salient features of prepared clad material sees Table 5.
Embodiment 3:
The raw material of the coating of table 6 embodiment 3 is formed
Raw material Mo powder B-Fe alloy powder C powder (graphite) Cr powder Ni powder Ti powder Cu powder iron powder
Content (weight ratio) 48% 30% 1.2% 10% 5% 4% 4% surpluses
The salient features of table 7 embodiment 3 clad materials
The erosion resistance of the wear resistance coating of project coating hardness coating and high base strength coating
12～16 times of index HRA90 ± 2 360 ± 10MPa Q235 steel are good, and are suitable with the high-quality stainless steel
Coating raw material composition sees Table 6.The raw material composition of shaping slip additive sees Table 2.The preparation of shaping slip is identical with embodiment 2 with coating blank forming technology.Carry out sintering by the sintering temperature system in vacuum oven, sintering temperature is 1200 ℃, cools to room temperature with the furnace.The salient features of prepared clad material sees Table 7.
Claims (7)
1, ternary boride base metal ceramic covering layer material is characterized by described cramic coat material composition and is (weight ratio):
Mo 35～55%, and B 4～10%, and C 0～1.5%, and Cr 0～15%, and Ni 0～10%, and Ti 0～10%, and Cu 0～10%, and all the other are Fe.
2, ternary boride base metal ceramic covering layer material according to claim 1 is characterized by optimum feed stock and forms (weight ratio):
Mo 48%, and B 6%, and C 0.8%, and Cr 5%, and Ni 2%, and Ti 2%, and Cu 2%, and all the other are Fe.
3, the preparation technology of ternary boride base metal ceramic covering layer material is characterized by this technology and comprises slip preparation technology, coating body formation technology and clad material liquid sintering technology.
4, the preparation technology of ternary boride base metal ceramic covering layer material according to claim 3 is characterized by described slip preparation technology and is: the employed slip of coating body formation, by cermet cladding material and additive processing and preparing;
The composition proportioning of slip additive is (weight ratio): organic solvent 75～95%, binding agent 2～5%, softening agent 0～3%, levelling agent 0～10%;
The cooperation ratio (weight ratio) of cermet cladding material and additive is 1: 0.6～1.5;
During the preparation slip, after cermet cladding material (metal, powdered alloy) and additive (solvent, binding agent, softening agent, levelling agent) proportioned, ball milling mixed 24～48 hours in ball grinder, and slip is crossed 400 mesh sieves, vacuum stripping again is the slip of shaping usefulness.
5, the preparation technology of ternary boride base metal ceramic covering layer material according to claim 3 is characterized by described coating body formation technology and comprises casting molding processes and application forming technology:
5-1, casting molding processes
Adopt the curtain coating forming mill, perhaps adopt easy slip to cast casting method; Easy slip is cast in the casting method, and mold base adopts the flat glass film of 3～5mm, above open and flat paving one deck PE film, it is the frame type that will quadrature that four limits of substrate glasses sheet surround internal range with the glass lath; Adopt this technology can prepare the base substrate that thickness is 30～2000 μ m, through cutting, the cutting after paving on metallic matrix, laminate, carry out liquid phase sintering then;
5-2, application forming technology
Comprise aerial spraying, airless spraying, electrostatic spraying, showering, dip-coating, powder coating, rotation application, brushing;
Metallic matrix must at first eliminate rust, surface cleaning such as cleaning handles before coating.
6, the preparation technology of ternary boride base metal ceramic covering layer material according to claim 3 is characterized by described clad material liquid sintering technology and is: adopt vacuum liquid-phase sintering technology, the vacuum tightness during sintering is 1.0 Pa～1.0 * 10
-3Pa, the sintering temperature system is: with 5～15 ℃ of/minute rate of heating, be warming up to 400～450 ℃ from room temperature, be incubated 20～40 minutes; With 10～20 ℃ of/minute rate of heating, be warming up to 1000～1100 ℃ from 400～450 ℃, be incubated 20～40 minutes; With 5～15 ℃ of/minute rate of heating, be warming up to 1060～1300 ℃ of firing temperatures from 1000～1100 ℃, be incubated 10～40 minutes; Furnace cooling is reduced to room temperature from firing temperature then; According to the composition difference of clad material, firing temperature is selected in 1060～1300 ℃.
7, the slip preparation technology of ternary boride base metal ceramic covering layer material according to claim 4 is characterized by described slip additive, comprising:
Organic solvent: the mixed system of ethanol or ethanol and butanone (butanone);
Binding agent: polyvinyl butyral acetal (PVB), ethyl cellulose, polyvinyl acetate (PVAc), methyl esters (PMMA), vinyl acetate (PEMA) etc. dissolve in the polymkeric substance of organic non-polar solvent, select one of them or its combined system;
Softening agent: dinoctyl phthalate (DOP), glycerine, dibutyl phthalate (DBP), fourth (base) benzyl (base) phthalic ester, select one of them or its combined system;
Levelling agent: pimelinketone.
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| CN102268671A (en) * | 2011-07-12 | 2011-12-07 | 华北电力大学 | Powder material of cladding layer with high temperature resistance and erosion resistance and preparation method of cladding layer |
| CN103468994A (en) * | 2013-09-17 | 2013-12-25 | 北京科技大学 | Method for preparing molybdenum nickel chromium boron multivariant boride metal ceramic |
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| CN105215365A (en) * | 2014-06-05 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | A kind of metal-cermic coating and preparation method thereof |
| WO2016101156A1 (en) * | 2014-12-23 | 2016-06-30 | 湖北宝德隆商贸有限公司 | Ceramic steel material and preparation method thereof |
| CN106868377A (en) * | 2017-03-08 | 2017-06-20 | 广东博杰特新材料科技有限公司 | High-strength Mo nickel boron ternary boride material and its making preparation method |
| CN109023345A (en) * | 2018-08-08 | 2018-12-18 | 天津德天助非晶纳米科技有限公司 | Ternary boride reinforced iron-base wear-resistant coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102268671B (en) * | 2011-07-12 | 2012-08-29 | 华北电力大学 | Powder material of cladding layer with high temperature resistance and erosion resistance and preparation method of cladding layer |
| CN102268671A (en) * | 2011-07-12 | 2011-12-07 | 华北电力大学 | Powder material of cladding layer with high temperature resistance and erosion resistance and preparation method of cladding layer |
| CN103468994A (en) * | 2013-09-17 | 2013-12-25 | 北京科技大学 | Method for preparing molybdenum nickel chromium boron multivariant boride metal ceramic |
| CN103468994B (en) * | 2013-09-17 | 2015-04-08 | 北京科技大学 | Method for preparing molybdenum nickel chromium boron multivariant boride metal ceramic |
| CN105215365A (en) * | 2014-06-05 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | A kind of metal-cermic coating and preparation method thereof |
| CN104233157B (en) * | 2014-09-11 | 2017-02-01 | 芜湖鼎瀚再制造技术有限公司 | Re-manufacturing process of bottom polar plate for LCD |
| CN104233157A (en) * | 2014-09-11 | 2014-12-24 | 芜湖鼎瀚再制造技术有限公司 | Re-manufacturing process of bottom polar plate for LCD |
| WO2016101156A1 (en) * | 2014-12-23 | 2016-06-30 | 湖北宝德隆商贸有限公司 | Ceramic steel material and preparation method thereof |
| CN106868377A (en) * | 2017-03-08 | 2017-06-20 | 广东博杰特新材料科技有限公司 | High-strength Mo nickel boron ternary boride material and its making preparation method |
| CN109023345A (en) * | 2018-08-08 | 2018-12-18 | 天津德天助非晶纳米科技有限公司 | Ternary boride reinforced iron-base wear-resistant coating and preparation method thereof |
| CN109852950A (en) * | 2019-02-28 | 2019-06-07 | 常州西夏墅东方工具有限公司 | A kind of preparation method of high mating type corrosion resistant metal ceramic coating material |
| CN111979464A (en) * | 2020-08-28 | 2020-11-24 | 南京航空航天大学 | Mo with dual-scale dual-form hard phase crystal grains2FeB2Base cermet and method for preparing same |
| CN111979464B (en) * | 2020-08-28 | 2021-11-05 | 南京航空航天大学 | Mo with dual-scale dual-form hard phase crystal grains2FeB2Base cermet and method for preparing same |
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