CN104525859A - Crushing wall and rolling mortar wall, and respective production methods thereof - Google Patents

Crushing wall and rolling mortar wall, and respective production methods thereof Download PDF

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CN104525859A
CN104525859A CN201410657866.XA CN201410657866A CN104525859A CN 104525859 A CN104525859 A CN 104525859A CN 201410657866 A CN201410657866 A CN 201410657866A CN 104525859 A CN104525859 A CN 104525859A
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wall
rolled mortar
crushing
mould
mortar wall
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CN104525859B (en
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许云华
叶芳霞
燕映霖
梁淑华
钟黎声
赵娜娜
王娟
邹军涛
肖鹏
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Xian University of Technology
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Xian University of Technology
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Abstract

The invention aims to provide a crushing wall and a rolling mortar wall and respective production methods thereof. The tapered work surface of the combination of the crushing wall and the rolling mortar wall is provided with a carbide coating. The carbide coating includes a V2C dense ceramic layer, and further includes a micrometer V8C7 dense ceramic layer and a V8C7-substrate fusion layer. The V2C dense ceramic layer, the micrometer V8C7 dense ceramic layer and the V8C7-substrate fusion layer are sequentially distributed in a gradient manner. The coating and the substrate are metallurgically bonded, and the bonding force is strong, so the problems of non-metallurgical bonding between present hard particles and a metal substrate, weak bonding force and easy shedding of the particles are overcome, and the wear resistance of the surface of a crushing cavity between the crushing wall and the rolling mortar wall is greatly improved.

Description

Crushing wall and rolled mortar wall and preparation method thereof
Technical field
The present invention relates to a kind of composite breaking wall and composite rolled mortar wall and preparation method thereof with wear-resistant coating, particularly relate to a kind of composite breaking wall and composite rolled mortar wall and preparation method thereof with wear resistant carbide coating, be specifically related to a kind of composite breaking wall and composite rolled mortar wall and preparation method thereof that are applied to the wear resistant carbide coating on potassium steel surface.
Background technology
Gyratory crusher is widely used in broken and disintegrating apparatus in small, broken bits in the industrial trades such as coal, mine, metallurgy, building materials, the energy.The major wear item of gyratory crusher is that mantle crushing wall and quiet cone rolled mortar wall serve as a contrast body.Under gyratory crusher working condition, two lining bodies bear simultaneously the friction, impact, extruding etc. of material strong, high cycle, the effect of alternate stress repeatedly, the quality of its quality directly has influence on efficiency and the service life of equipment, also affects output and the technical-economic index of product simultaneously.At present, mainly there is following problem in the crushing wall used in gyratory crusher and rolled mortar wall abrasion-proof lining body:
(1) breaking wall of spindle breaker and rolled mortar wall mainly adopt single metal material to make, such as potassium steel ZGMn13 and polynary low potassium steel material, and composite mainly contains powder metallurgy composite, hard alloy overlay welding composite etc.The feature of various material is: potassium steel only realizes austenite under high load capacity and high impact stresses after work hardening, just can give full play to its wearability to martensitic solid-state phase changes.And in gyratory crusher, the material in crusher chamber is less to rolled mortar wall impact strength, work hardening is not obvious.And polynary low potassium steel macrohardness lower (about HRC40), can not resist press-in and the paddling of material, in use procedure, surface produces a large amount of cuttings and flow low-cycle fatigue.Visible, crushing wall and the rolled mortar wall wearability of single material are poor, and service life is shorter.The research that powder metallurgy process prepares composite is still immature, composite prepared by the method, and its alloying component is difficult to be uniformly distributed in the base, poor controllability, owing to the addition of surfactant, makes to occur the defects such as a large amount of pores in material structure.The hard alloy particle complex abrasion-proof lining body adopting overlaying method to prepare, be difficult to ensure hard alloy particle being uniformly distributed at metallic matrix, poor controllability, and motlten metal at high temperature produces a large amount of oxides, these oxide magazines rest in metallic matrix, thus have impact on wearability and the toughness of composite.
(2) owing to wearing no resistance, seriously, in use often do not reach the operating mode required by design, cause gyratory crusher hydraulic performance decline, crushed product size is bigger than normal for crushing wall and rolled mortar wall wear liner, and energy consumption increases, and operating cost improves.
But the hardness only improving crushing wall and rolled mortar wall matrix material is still not enough to the persistence that ensures that it is on active service, be therefore the economical and effective means of this problem of solution in its working position increase coating.It is the coating of carbide material that present stage uses more, and hardness is high, abrasion resistance properties is superior feature that it has, covers alloy base surperficial wearability and the life-span can improving the parts prepared by matrix material with coating way.Wherein VC pbe a kind of common coating material, it has following advantageous features:
(1) physical and chemical performance of the excellences such as density is low, intensity is high, elastic modelling quantity is high, anti-oxidant, wear-resisting, corrosion-resistant is possessed;
(2) tendency of growing up in sintering process is little, and particle is generally rounded, is a kind of ideal reinforcing material;
(3) vanadium resource enriches, and easily obtain, less expensive, vanadium carbide obtains and generally applies in metal-base composites;
(4) have very high heat endurance and the face-centred cubic structure of high rigidity, closely, this is convenient to be combined with steel substrate better for lattice paprmeter and lattice types and austenite;
(5) VC pstandard enthalpy of formation △ G 0be worth low, its synthetic reaction is easy to carry out;
(6) VC pthe steel-based composite material of coating except hardness is high, wearability well except, machinable, forging, welding, heat treatment reinforcement and be out of shape little, and there is the cold and hot working performance of common steel-smelting.Therefore, VC pcoating material is widely used as the wearing face of chipless cold/hot metal machining tool, cutting tool, various mould, antiwear heat resisting is anti-corrosion part.
The method preparing carbide coating at present has chemical vapour deposition technique, physical vaporous deposition, heat spraying method, hot plating method etc., but these methods, there is the deficiencies such as production equipment requirement is harsh, production efficiency is low, anchoring strength of coating is low.
Therefore how VC is obtained at the outer wall of crushing wall and the inwall of rolled mortar wall pcoating, and the preparation method selecting that a kind of production equipment is simple, technological process is short, obtain with good, the difficult drop-off of basal body binding force and the coating of mechanical property, anti-wear performance excellence is problem demanding prompt solution.
Summary of the invention
The defect existed for above-mentioned prior art and deficiency, the object of the present invention is to provide a kind of crushing wall and rolled mortar wall, and crusher chamber surface in-between has a kind of wear-resistant coating, and crushing wall and rolled mortar wall matrix are still potassium steel matrix, and this wear-resistant coating is V 2c dense ceramic layers, its chemical stability and wearability good, there is low-friction coefficient, high rigidity, low-surface-energy and low thermal conductiv-ity; And further, provide a kind of preparation method for obtaining above-mentioned composite breaking wall and rolled mortar wall.It is long that the method can prepare the life-span, the series of products of the composite breaking wall that operating cost is low and rolled mortar wall, and it is mutually mate on gyratory crusher.
Further, the present invention also provides a kind of crushing wall and rolled mortar wall, crusher chamber surface between its crushing wall and rolled mortar wall has a kind of gradient composite coating, it is preferably coated on the outer surface of crushing wall and the inner surface of rolled mortar wall, to improve wearability and the fracture toughness on its surface, particularly high-manganese steel-base surface, and a kind of preparation method for obtaining above-mentioned coating is provided.
Described crushing wall and rolled mortar wall, crusher chamber surface in-between has wear-resistant coating.Crushing wall involved in the present invention and rolled mortar wall model as follows: Mei Zhuo (Nordberg) GP series crushing wall, rolled mortar wall: GP100, GP200, GP300, GP330C; Mei Zhuo (Nordberg) HP series crushing wall, rolled mortar wall: HP200, HP300, HP400, HP500; Sandvik gyratory crusher series crushing wall, rolled mortar wall: H3800, H4800, H6800, H8800; S series is raised by China: S75B, S155B, S240B, S400B, S75D, S155D, S240D, S400D.Respectively there is wear-resistant coating at the outer wall of crushing wall and the inwall of rolled mortar wall, thus ensure that the crusher chamber surface between crushing wall and rolled mortar wall has very high hardness and good wearability, and its body portion has good toughness.
For realizing the object of the invention, present invention employs following technical scheme:
A kind of crushing wall and rolled mortar wall, crusher chamber surface in-between has wear-resistant coating, and this wear-resistant coating is V 2c dense ceramic layers; Preferably, V 2c dense ceramic layers is as the criterion monocrystalline phase, and described accurate monocrystalline refers to mutually, between polycrystalline phase and monocrystalline mutually between, compared to polycrystalline phase, uniform orientation is high, crystal boundary obviously reduces, and the microscopic structure that atomic arrangement is more orderly.
More preferably, along V 2c dense ceramic layers longitudinal profile, its thickness is 9-23 μm, is preferably 12-20 μm, is more preferably 15-20 μm; Preferably, wherein V 2the volume fraction of C is greater than 80%, is preferably greater than 90%; Preferably, V 2c crystallite dimension is 20-50 μm, is preferably 30-50 μm.
In addition, the present invention also provides a kind of crushing wall and rolled mortar wall, and crusher chamber surface in-between has gradient composite coating, and described gradient composite coating is carbide coating, comprises the V of distribution gradient successively 2c dense ceramic layers, micron V 8c 7dense ceramic layers, V 8c 7with the fused layer of matrix.
Preferably, V 2c dense ceramic layers is as the criterion monocrystalline phase, and described accurate monocrystalline refers to mutually, between polycrystalline phase and monocrystalline mutually between, compared to polycrystalline phase, uniform orientation is high, crystal boundary obviously reduces, and the microscopic structure that atomic arrangement is more orderly.
More preferably, along V 2c dense ceramic layers longitudinal profile, its thickness is 9-23 μm, is preferably 12-20 μm, is more preferably 15-20 μm; Preferably, wherein V 2the volume fraction of C is greater than 80%, is preferably greater than 90%; Preferably, V 2c crystallite dimension is 20-50 μm, is preferably 30-50 μm.
Further preferably, along micron V 8c 7dense ceramic layers longitudinal profile, its thickness is 17-88 μm, is preferably 40-80 μm, is more preferably 60-80 μm; Preferably, V 8c 7volume fraction be greater than 70%, be preferably greater than 75%; Preferably, V 8c 7crystallite dimension be 5-15 μm, be preferably 6-15 μm, be more preferably 8-15 μm.
Still more preferably, along V 8c 7with the fused layer longitudinal profile of matrix, its thickness is 122 μm-1069 μm, preferred 300-1060 μm; Preferably, wherein V 8c 7volume fraction be 20%-85%, be preferably 50%-85%; Preferably, V 8c 7crystallite dimension be 5-20 μm, be preferably 10-20 μm.
Preferably, gradient composite coating gross thickness is 148-1180 μm, preferably at 400-1180 μm.
More preferably, crushing wall and rolled mortar wall matrix obtain single austenite structure after water-tenacity treatment; Preferably, this gradient composite coating is applied in potassium steel surface.
The invention provides a kind of crusher chamber surface and there is the crushing wall of wear-resistant coating and the preparation method of rolled mortar wall, comprise the steps:
1) first prepare a vanadium plate, preferably, wherein the purity of vanadium should control at 99.7-99.9%; More preferably, the THICKNESS CONTROL of described vanadium plate is at 0.2-3mm; Preferably, described vanadium plate is first by addition surface treatment;
2) according to the size of crushing wall and rolled mortar wall, make crushing wall mould and rolled mortar wall mould respectively, groove is set respectively at the outer wall of crushing wall mould and the inwall of rolled mortar wall mould, difference fixed outer carbon source in groove, then vanadium plate is wound on respectively in the groove of crushing wall outer mold wall and rolled mortar wall mould inner wall, itself and external carbon source are combined closely; Preferably, crushing wall mould and rolled mortar wall mould is made respectively with polystyrene foam plastics;
3) make sand mold according to crushing wall and rolled mortar wall size, and crushing wall mould and rolled mortar wall mould are placed in sand mold die cavity respectively; Preferably, CO is used 2waterglass hardened sand, precoated sand, self-hardening resin sand or tide mould sand make sand mold;
4) potassium steel base material is smelted for molten steel; Preferably, temperature controls at 1500-1560 DEG C;
5), poured into by above-mentioned molten steel in the above-mentioned sand mold being placed with broken wall mould and rolled mortar wall mould, vanadium plate and external carbon source, after molten steel cooled and solidified, take out foundry goods, sand removal process, makes crushing wall outer wall and rolled mortar wall inwall be respectively the complex with vanadium plate; Preferably, evaporative pattern process for suction casting is adopted to be poured into by above-mentioned molten steel in the above-mentioned sand mold being placed with crushing wall mould and rolled mortar wall mould, vanadium plate and external carbon source; Preferably, cast temperature controls at 1500-1560 DEG C, and casting time is that 20-60 is advisable second; More preferably, molten steel room temperature cooling.
Preferably, the width dimensions at crushing wall outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall, and preferably, the width at compound position is generally the 1/2-4/5 of crusher chamber wall cone; More preferably, the compound position of crushing wall outer wall is even depth; Further preferably, depth dimensions is the 1/5-4/5 of crushing wall wall thickness.The hierarchy structure shape and size at rolled mortar wall inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall of same specification.Preferably, crushing wall outer wall compound position and rolled mortar wall inwall compound position are annular;
6) crushing wall obtained having cast and rolled mortar wall complex put into the holding furnace inside holding with protective atmosphere; finally cool to room temperature with the furnace; thus the crusher chamber surface between crushing wall and rolled mortar wall forms wear-resistant coating, and crushing wall and rolled mortar wall matrix are still potassium steel matrix.
Wherein, wear-resistant coating is V 2c dense ceramic layers.
Preferably, this V is obtained by control temperature retention time, holding temperature 2c dense ceramic layers; Preferably, V 2c dense ceramic layers is as the criterion monocrystalline phase, and described accurate monocrystalline refers to mutually, between polycrystalline phase and monocrystalline mutually between, compared to polycrystalline phase, uniform orientation is high, crystal boundary obviously reduces, and the microscopic structure that atomic arrangement is more orderly.
The present invention also provide a kind of crusher chamber surface have the crushing wall of gradient composite coating and rolled mortar wall preparation method, comprise the steps:
1) first prepare a vanadium plate, preferably, wherein the purity of vanadium should control at 99.7-99.9%; More preferably, the THICKNESS CONTROL of described vanadium plate is at 0.2-3mm; Preferably, described vanadium plate is first by addition surface treatment;
2) according to the size of crushing wall and rolled mortar wall, make crushing wall mould and rolled mortar wall mould respectively, groove is set respectively at the outer wall of crushing wall mould and the inwall of rolled mortar wall mould, difference fixed outer carbon source in groove, then vanadium plate is wound on respectively in the groove of crushing wall outer mold wall and rolled mortar wall mould inner wall, itself and external carbon source are combined closely; Preferably, crushing wall mould and rolled mortar wall mould is made respectively with polystyrene foam plastics;
3) make sand mold according to crushing wall and rolled mortar wall size, and crushing wall mould and rolled mortar wall mould are placed in sand mold die cavity respectively; Preferably, CO is used 2waterglass hardened sand, precoated sand, self-hardening resin sand or tide mould sand make sand mold;
4) steel substrate is smelted for molten steel; Preferably, temperature controls at 1500-1560 DEG C;
5) poured into by above-mentioned molten steel in the above-mentioned sand mold being placed with broken wall mould and rolled mortar wall mould, vanadium plate and external carbon source, after molten steel cooled and solidified, take out foundry goods, sand removal process, makes crushing wall outer wall and rolled mortar wall inwall be respectively the complex with vanadium plate.Preferably, evaporative pattern process for suction casting is adopted to be poured into by above-mentioned molten steel in the above-mentioned sand mold being placed with broken wall mould and rolled mortar wall mould, vanadium plate and external carbon source; Preferably, cast temperature controls at 1500-1560 DEG C, and casting time is that 20-60 is advisable second; More preferably, molten steel room temperature cooling.
Preferably, the width dimensions at crushing wall outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall, and preferably, the width at compound position is generally the 1/2-4/5 of crusher chamber wall cone; More preferably, the compound position of crushing wall outer wall is even depth; Further preferably, depth dimensions is the 1/5-4/5 of crushing wall wall thickness.The hierarchy structure shape and size at rolled mortar wall inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall of same specification.Preferably, crushing wall outer wall compound position and rolled mortar wall inwall compound position are annular;
6) crushing wall obtained having cast and rolled mortar wall put into the holding furnace inside holding with protective atmosphere, finally cool to room temperature with the furnace, thus the crusher chamber surface between crushing wall and rolled mortar wall forms gradient composite coating, and crushing wall and rolled mortar wall matrix are still steel matrix;
7) the crusher chamber surface of gained has crushing wall and the rolled mortar wall of gradient composite coating, obtains single austenite structure after water-tenacity treatment.
Preferably, vanadium plate thickness is 0.2-3mm; If be less than 0.2mm, then vanadium plate just complete reaction in cast recombination process, can not obtain V 2c organizes, and directly generates Dispersed precipitate V 8c 7; Then cause diffusion length to increase more than 3mm, reaction power is not enough.
Preferably, by strictly controlling above-mentioned steps 6) in holding temperature and the relation of time, obtain described accurate monocrystalline phase V 2c dense ceramic layers.This ceramic layer presents comparatively obvious accurate single crystal organization, and show as crystal boundary under light microscope and reduce, affect the dislocation also corresponding minimizing of fracture toughness, the sub boundary in generation increases, and effectively improves the anti-crack ability of this ceramic layer.
Preferably, by rate-determining steps 6) in temperature retention time, holding temperature obtain this gradient composite coating and carbide coating, described carbide coating comprises the accurate monocrystalline phase V of distribution gradient successively 2c dense ceramic layers, micron V 8c 7dense ceramic layers, V 8c 7with the fused layer of matrix.
More preferably, above-mentioned steps 6) in holding temperature, temperature retention time and the gross thickness of gradient composite coating that finally can obtain meet following formula,
L＝kTlogt1/2+b 0
Wherein:
The gross thickness (μm) of L---gradient composite coating,
K---be constant, value is 0-1, k ≠ 0,
T---holding temperature (K),
T---temperature retention time (s),
B 0---original depth (μm), the thickness of the composite bed formed after namely molten steel is poured into a mould and between vanadium plate.
To sum up, described gradient composite coating, comprises V 2c dense ceramic layers, hardness is high.Described V 2c dense ceramic layers is as the criterion monocrystalline phase, and described accurate monocrystalline refers to mutually, the arrangement of atom unlike monocrystalline there is identical lattice like that, but still there is strict order, present geometry arrangement; Uniform orientation is high, crystal boundary obviously reduces, and atomic arrangement is more orderly.Accurate monocrystalline is between polycrystalline phase with monocrystalline phase, and compared to polycrystalline phase, the crystal boundary of accurate monocrystalline phase obviously reduces, and dislocation density is low, has more sub boundary, and therefore hardness has obvious lifting; And than monocrystalline phase, it requires lower to preparation method, and organize more stable.
Preferably, in step 1) in, surface-treated step is as follows:
First step pickling, selects the hydrogen peroxide of the hydrochloric acid of 300ml/L or the phosphoric acid of 60ml/L or 120ml/L, rear running water;
Second step pickling, selects the hydrogen peroxide of the hydrofluoric acid of 300ml/L or the sulfuric acid of 200ml/L or 240ml/L, rear running water;
3rd step surface finish, selects 800-1200 object Al 2o 3sand paper, finally uses alcohol ultrasonic cleaning.
More preferably, step 2) in external carbon source be graphite paper or graphite powder; Preferably, described graphite paper is more than three grades, and purity is 85-99%, and thickness is 0.1-0.35mm; Preferably, described graphite powder selects granularity at 600-1000 order, and purity is 85-99%.
Preferably, step 6) in, be warming up to 1000-1160 DEG C, programming rate controls at 5-7 DEG C/min, and temperature retention time is 6.5-11.5h, preferred 8-10h.
Preferably, selected steel matrix is potassium steel.
Preferably, protection gas is argon gas or nitrogen, and gas flow is 5-8ml/min.
Wherein, holding temperature should be strict controlled in above-mentioned scope, and temperature is higher than 1160 DEG C, and the liquid phase in course of reaction is too much, and makes V 2c is transformed into V 8c 7, and accurate monocrystalline phase V can not be obtained 2c; But temperature is lower than 1000 DEG C, then the solubility of V is too low, and reaction cannot be carried out by forward.Same, temperature retention time also should keep one reasonably interval, the time more than 11.5h, nearly all V 2c can change V into 8c 7, and lower than 6.5h, then react the V of acquisition 2very little, coating layer thickness is difficult to ensure C, and best should remain on 8-10h.
More preferably, there is the composite breaking wall of carbide coating and rolled mortar wall by further heat treatment to obtain more suitably matrix: within 1 hour, be warmed up to 300-400 DEG C, then 1000-1050 DEG C is warmed up to by the speed of 50-80 per hour DEG C, potassium steel is made fully to carry out austenitizing, insulation 2-3 hour, carrying out the water-tenacity treatment total processing time in water of then being quenched is 13-14 hour.
Described crushing wall and rolled mortar wall take potassium steel as matrix, and selected potassium steel matrix is ZGMn13-1, ZGMn13-2, ZGMn13-3, ZGMn13-4 or ZGMn13-5, sees GB GB/T 5680-1998.Matrix obtains single austenite structure after water-tenacity treatment.
The present invention is by after the crushing wall casting especially evaporative pattern suction pouring and obtain potassium steel matrix+vanadium and rolled mortar wall complex, introduce external carbon source, directly carbide coating can be formed on the surface of crushing wall and rolled mortar wall in the mode adding thermal diffusion, it is metallurgical binding between carbide coating and matrix, adhesion is very strong, and overcome non-metallurgical binding between existing hard particles and metallic matrix, adhesion is very weak, particle holds caducous problem, has increased substantially the mechanical property of coating.And the method is simple to operate, without the need to complex device, crushing wall and the rolled mortar wall of acquisition are functional.Different heat treatment modes, makes crushing wall and rolled mortar wall have different mechanical properties, meets the requirement of actual production.Due to V 2the formation of C dense ceramic layers, this ceramic layer presents comparatively obvious accurate single crystal organization, and show as crystal boundary under light microscope and reduce, affect the dislocation also corresponding minimizing of fracture toughness, the sub boundary in generation increases, and effectively improves the anti-crack ability of this ceramic layer.Therefore surface has higher hardness HRC45-60, and its relative wear resistance is 6-10 times of potassium steel.Described relative wear resistance is defined as: take matrix material as standard specimen, in identical abrasive grain, same load, after disk rotates same number of turns with same rotational speed, tested coating produces the relative wear resistance that ratio that wear extent and standard specimen produce wear extent is called coating, therefore be several times of matrix also referred to as the relative wear resistance of coating, the examination criteria of following identical parameters is identical with it.
This is due to V wherein 2c dense ceramic layers is as the criterion single crystal organization, chemical stability and wearability good, there is low-friction coefficient, high rigidity, low-surface-energy and low thermal conductiv-ity.And micron V on the other side 8c 7the hardness of ceramic layer can only reach HRC42-50, and its relative wear resistance is 4-8 times of matrix.
Accompanying drawing explanation
Outer carbon source (graphite paper or graphite powder) and the layout drawing of vanadium plate in crushing wall outer mold wall groove before Fig. 1 casts;
Outer carbon source (graphite paper or graphite powder) and the layout drawing of vanadium plate in rolled mortar wall mould inner wall groove before Fig. 2 casts;
The partial enlarged drawing that composite breaking wall outer wall after Fig. 3 heat treatment and sample intercept;
The partial enlarged drawing that composite rolled mortar wall inwall after Fig. 4 heat treatment and sample intercept.
Detailed description of the invention
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Wherein, CO can be adopted when making sand mold 2any one in waterglass hardened sand, precoated sand, self-hardening resin sand or tide mould sand.
Embodiment 1: the preparation method of composite breaking wall and rolled mortar wall, comprises the steps:
1, first prepare a vanadium plate 1, wherein the purity of vanadium should control 99.7%.Described vanadium plate 1 should first by surface treatment in addition, and step is as follows:
First step pickling, selects the hydrochloric acid of 300ml/L, rear running water;
Second step pickling, selects the hydrofluoric acid of 300ml/L, rear running water;
3rd step surface finish, selects 800 object Al 2o 3sand paper, finally uses alcohol ultrasonic cleaning.The THICKNESS CONTROL of described vanadium plate 1 is at 0.2mm.
2, according to the size of crushing wall 2 with rolled mortar wall 3, crushing wall mould 4 and rolled mortar wall mould 5 is made respectively with polystyrene foam plastics, groove is set respectively at the outer wall of crushing wall mould 4 and the inwall of rolled mortar wall mould 5, respectively in groove internal fixtion external carbon source 6, external carbon source 6 is graphite paper, described graphite paper is more than three grades, and purity is 85%, and thickness is 0.1mm.Then vanadium plate is wound on respectively in the groove of crushing wall mould 4 outer wall and rolled mortar wall mould 5 inwall, itself and graphite paper are combined closely (as depicted in figs. 1 and 2).
3, according to crushing wall 2 and rolled mortar wall 3 size, CO is used 2waterglass hardened sand makes sand mold 7, and crushing wall mould 4 and rolled mortar wall mould 5 are placed in sand mold 7 die cavity respectively.
4, smelt potassium steel base material for molten steel, temperature controls at 1500 DEG C, and selected potassium steel matrix is ZGMn13-1.
5, evaporative pattern process for suction casting is adopted, above-mentioned molten steel is poured in the above-mentioned sand mold 7 being placed with broken wall mould 4 and rolled mortar wall mould 5, vanadium plate 1 and graphite paper, cast temperature controls at 1500 DEG C, casting time is be advisable for 20 seconds, after molten metal room temperature cooled and solidified, take out foundry goods, sand removal process, makes crushing wall 2 outer wall and rolled mortar wall 3 inwall be respectively the complex with vanadium plate.The width dimensions at crushing wall 2 outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall 2, and the width at compound position is generally 1/2 of crusher chamber cone, and the compound position of crushing wall 2 outer wall is even depth, and depth dimensions is 1/5 of crushing wall 2 wall thickness.The hierarchy structure shape and size at rolled mortar wall 3 inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall 2 of same specification.Crushing wall 2 outer wall compound position and rolled mortar wall 3 inwall compound position are annular.
6, the crushing wall 2 and rolled mortar wall 3 complex that have obtained having cast put into the holding furnace inside holding with protective atmosphere; be warming up to 1000 DEG C; programming rate controls at 5 DEG C/min; temperature retention time is 6.5h; finally cool to room temperature with the furnace; thus the crusher chamber surface between crushing wall 2 and rolled mortar wall 3 forms gradient composite coating, and crushing wall and rolled mortar wall matrix are still ZGMn13-1.Described protection gas is argon gas, and gas flow is 5ml/min.
7, the crusher chamber surface of gained has crushing wall 2 and the rolled mortar wall 3 of gradient composite coating, single austenite structure is obtained after water-tenacity treatment, heat treatment step is: within 1 hour, be warmed up to 300 DEG C, then 1000 DEG C are warmed up to by the speed of 50 DEG C per hour, potassium steel is made fully to carry out austenitizing, be incubated 2 hours, carrying out the water-tenacity treatment total processing time in water of then being quenched is 13 hours.
As Fig. 3 and Fig. 4, gained gradient composite coating comprises V 2c dense ceramic layers 8, be as the criterion monocrystalline phase, and its crystallite dimension is 20 μm; Along coating longitudinal profile, its thickness is 9 μm, wherein V 2the volume fraction of C is 90%.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2micron V under C dense ceramic layers 8 8c 7dense ceramic layers 9, along coating longitudinal profile, its thickness is 17 μm, V 8c 7volume fraction be 75%, its crystallite dimension is 5 μm.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2c dense ceramic layers 8 and micron V 8c 7v under dense ceramic layers 9 8c 7with the fused layer 10 of matrix, along coating longitudinal profile, its thickness is 122 μm, wherein V 8c 7volume fraction be 20%, its crystallite dimension is 5 μm.Now, described carbide coating is composite coating, by described accurate monocrystalline V 2c dense ceramic layers 8, micron V 8c 7dense ceramic layers 9 and V 8c 7form with the fused layer 10 of matrix, and distribution gradient successively, its gross thickness is 148 μm.Described crushing wall and rolled mortar wall matrix are austenite.Crushing wall outer wall and rolled mortar wall inwall have higher hardness HRC45, and its relative wear resistance is 6 times of matrix.
Embodiment 2: the preparation method of composite breaking wall and rolled mortar wall, comprises the steps:
1, first prepare a vanadium plate 1, wherein the purity of vanadium should control 99.8%.Described vanadium plate 1 should first by surface treatment in addition, and step is as follows:
First step pickling, the phosphoric acid of 60ml/L, rear running water;
Second step pickling, the sulfuric acid of 200ml/L, rear running water;
3rd step surface finish, selects 1000 object Al 2o 3sand paper, finally uses alcohol ultrasonic cleaning.The THICKNESS CONTROL of described vanadium plate 1 is at 1mm.
2, according to the size of crushing wall 2 with rolled mortar wall 3, crushing wall mould 4 and rolled mortar wall mould 5 is made respectively with polystyrene foam plastics, groove is set respectively at the outer wall of crushing wall mould 4 and the inwall of rolled mortar wall mould 5, respectively in groove internal fixtion external carbon source 6, external carbon source 6 is graphite paper, described graphite paper is more than three grades, and purity is 99%, and thickness is 0.2mm.Then vanadium plate 1 is wound on respectively in the groove of crushing wall mould 4 outer wall and rolled mortar wall mould 5 inwall, itself and graphite paper are combined closely (as depicted in figs. 1 and 2).
3, according to crushing wall 2 and rolled mortar wall 3 size, make sand mold 7 with precoated sand, and crushing wall mould 4 and rolled mortar wall mould 5 are placed in sand mold 7 die cavity respectively.
4, smelt potassium steel base material for molten steel, temperature controls at 1510 DEG C, and selected potassium steel matrix is ZGMn13-2.
5, evaporative pattern process for suction casting is adopted, above-mentioned molten steel is poured in the above-mentioned sand mold 7 being placed with broken wall mould 4 and rolled mortar wall mould 5, vanadium plate 1 and graphite paper, cast temperature controls at 1510 DEG C, casting time is be advisable for 30 seconds, after molten metal room temperature cooled and solidified, take out foundry goods, sand removal process, makes crushing wall 2 outer wall and rolled mortar wall 3 inwall be respectively the complex with vanadium plate 1.The width dimensions at crushing wall 2 outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall 2, and the width at compound position is generally 3/5 of crusher chamber cone, and the compound position of crushing wall 2 outer wall is even depth, and depth dimensions is 2/5 of crushing wall 2 wall thickness.The hierarchy structure shape and size at rolled mortar wall 3 inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall 2 of same specification.Crushing wall 2 outer wall compound position and rolled mortar wall 3 inwall compound position are annular.
6, the crushing wall 2 and rolled mortar wall 3 complex that have obtained having cast put into the holding furnace inside holding with protective atmosphere; be warming up to 1050 DEG C; programming rate controls at 6 DEG C/min; temperature retention time is 7.5h; finally cool to room temperature with the furnace; thus the crusher chamber surface between crushing wall 2 and rolled mortar wall 3 forms gradient composite coating, and crushing wall and rolled mortar wall matrix are still ZGMn13-2.Described protection gas is nitrogen, and gas flow is 5ml/min.
7, the crusher chamber surface of gained has crushing wall 2 and the rolled mortar wall 3 of gradient composite coating, single austenite structure is obtained after water-tenacity treatment, heat treatment step is: within 1 hour, be warmed up to 350 DEG C, then 1020 DEG C are warmed up to by the speed of 60 DEG C per hour, potassium steel is made fully to carry out austenitizing, be incubated 3 hours, carrying out the water-tenacity treatment total processing time in water of then being quenched is 14 hours.
Described gradient composite coating comprises V 2c dense ceramic layers 8, be as the criterion monocrystalline phase, and its crystallite dimension is 22 μm; Along coating longitudinal profile, its thickness is 12 μm; Wherein V 2the volume fraction of C is 80%.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2micron V under C dense ceramic layers 8 8c 7dense ceramic layers 9, along coating longitudinal profile, its thickness is 52 μm, V 8c 7volume fraction be 78%, its crystallite dimension is 7 μm.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2c dense ceramic layers 8 and micron V 8c 7v under dense ceramic layers 9 8c 7with the fused layer 10 of matrix, along coating longitudinal profile, its thickness is 397 μm, wherein V 8c 7volume fraction be 60%, its crystallite dimension is 15 μm.Now, described carbide coating is composite coating, by described accurate monocrystalline V 2c dense ceramic layers 8, micron V 8c 7dense ceramic layers 9 and V 8c 7form with the fused layer 10 of matrix, and distribution gradient successively, its gross thickness is 461 μm.Described crushing wall and rolled mortar wall matrix are austenite.Crushing wall outer wall and rolled mortar wall inwall have higher hardness HRC52, and its relative wear resistance is 7 times of matrix.
Embodiment 3: the preparation method of composite breaking wall and rolled mortar wall, comprises the steps:
1, first prepare a vanadium plate 1, wherein the purity of vanadium should control 99.8%.Described vanadium plate 1 should first by surface treatment in addition, and step is as follows:
First step pickling, the hydrogen peroxide of 120ml/L, rear running water;
Second step pickling, the hydrogen peroxide of 240ml/L, rear running water;
3rd step surface finish, selects 1000 object Al 2o 3sand paper, finally uses alcohol ultrasonic cleaning.The THICKNESS CONTROL of described vanadium plate 1 is at 0.35mm.
2, according to the size of crushing wall 2 with rolled mortar wall 3, crushing wall mould 4 and rolled mortar wall mould 5 is made respectively with polystyrene foam plastics, groove is set respectively at the outer wall of crushing wall mould 4 and the inwall of rolled mortar wall mould 5, respectively in groove internal fixtion external carbon source 6, external carbon source 6 is graphite paper, described graphite paper is more than three grades, and purity is 95%, and thickness is 0.35mm.Then vanadium plate 1 is wound on respectively in the groove of crushing wall mould 4 outer wall and rolled mortar wall mould 5 inwall, itself and graphite paper are combined closely (as depicted in figs. 1 and 2).
3, according to crushing wall 2 and rolled mortar wall 3 size, make sand mold 7 with self-hardening resin sand, and crushing wall mould 4 and rolled mortar wall mould 5 are placed in sand mold 7 die cavity respectively.
4, smelt potassium steel base material for molten steel, temperature controls at 1520 DEG C, and selected potassium steel matrix is ZGMn13-3.
5, evaporative pattern process for suction casting is adopted, above-mentioned molten steel is poured in the above-mentioned sand mold 7 being placed with broken wall mould 4 and rolled mortar wall mould 5, vanadium plate 1 and graphite paper, cast temperature controls at 1520 DEG C, casting time is be advisable for 40 seconds, after molten metal room temperature cooled and solidified, take out foundry goods, sand removal process, makes crushing wall 2 outer wall and rolled mortar wall 3 inwall be respectively the complex with vanadium plate 1.The width dimensions at crushing wall 2 outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall 2, and the width at compound position is generally 7/10 of crusher chamber cone, and the compound position of crushing wall 2 outer wall is even depth, and depth dimensions is 3/5 of crushing wall 2 wall thickness.The hierarchy structure shape and size at rolled mortar wall 3 inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall 2 of same specification.Crushing wall 2 outer wall compound position and rolled mortar wall 3 inwall compound position are annular.
6, the crushing wall 2 and rolled mortar wall 3 complex that have obtained having cast put into the holding furnace inside holding with protective atmosphere; be warming up to 1080 DEG C; programming rate controls at 7 DEG C/min; temperature retention time is 9.5h; finally cool to room temperature with the furnace; thus the crusher chamber surface between crushing wall 2 and rolled mortar wall 3 forms gradient composite coating, and crushing wall and rolled mortar wall matrix are still ZGMn13-3.Described protection gas is argon gas, and gas flow is 5ml/min.
7, the crusher chamber surface of gained has crushing wall 2 and the rolled mortar wall 3 of gradient composite coating, single austenite structure is obtained after water-tenacity treatment, heat treatment step is: within 1 hour, be warmed up to 400 DEG C, then 1050 DEG C are warmed up to by the speed of 80 DEG C per hour, potassium steel is made fully to carry out austenitizing, be incubated 3 hours, carrying out the water-tenacity treatment total processing time in water of then being quenched is 14 hours.
Described gradient composite coating comprises V 2c dense ceramic layers 8, be as the criterion monocrystalline phase, and its crystallite dimension is 25 μm; Along coating longitudinal profile, its thickness is 14 μm; Wherein V 2the volume fraction of C is 95%.
Further, comprise and be positioned at above-mentioned accurate monocrystalline V 2micron V under C dense ceramic layers 8 8c 7dense ceramic layers 9, along coating longitudinal profile, its thickness is 57 μm, V 8c 7volume fraction be 80%, its crystallite dimension is 10 μm.
Further, can also comprise and be positioned at above-mentioned accurate monocrystalline V 2c dense ceramic layers 8 and micron V 8c 7v under dense ceramic layers 9 8c 7with the fused layer 10 of matrix, along coating longitudinal profile, its thickness is 667 μm, wherein V 8c 7volume fraction be 75%, its crystallite dimension is 15 μm.Now, described carbide coating is composite coating, by described accurate monocrystalline V 2c dense ceramic layers 8, micron V 8c 7dense ceramic layers 9 and V 8c 7form with the fused layer 10 of matrix, and distribution gradient successively, its gross thickness is 738 μm.Described crushing wall and rolled mortar wall matrix are austenite.Crushing wall outer wall and rolled mortar wall inwall have higher hardness HRC56, and its relative wear resistance is 9 times of matrix.
Embodiment 4: the preparation method of composite breaking wall and rolled mortar wall, comprises the steps:
1, first prepare a vanadium plate 1, wherein the purity of vanadium should control 99.9%.Described vanadium plate 1 should first by surface treatment in addition, and step is as follows:
First step pickling, selects the phosphoric acid of 60ml/L, rear running water;
Second step pickling, the sulfuric acid of 200ml/L, rear running water;
3rd step surface finish, selects 1200 object Al 2o 3sand paper, finally uses alcohol ultrasonic cleaning.The THICKNESS CONTROL of described vanadium plate 1 is at 3mm.
2, according to the size of crushing wall 2 with rolled mortar wall 3, crushing wall mould 4 and rolled mortar wall mould 5 is made respectively with polystyrene foam plastics, groove is set respectively at the outer wall of crushing wall mould 4 and the inwall of rolled mortar wall mould 5, respectively in groove internal fixtion external carbon source 6, external carbon source 6 is graphite powder, described graphite powder selects granularity at 600 orders, and purity is 85%.Then vanadium plate 1 is wound on respectively in the groove of crushing wall mould 4 outer wall and rolled mortar wall mould 5 inwall, itself and graphite powder are combined closely (as depicted in figs. 1 and 2).
3, according to crushing wall 2 and rolled mortar wall 3 size, make sand 7 type with tide mould sand, and crushing wall mould 4 and rolled mortar wall mould 5 are placed in sand mold 7 die cavity respectively.
4, smelt potassium steel base material for molten steel, temperature controls at 1530 DEG C, and selected potassium steel matrix is ZGMn13-4.
5, evaporative pattern process for suction casting is adopted, above-mentioned molten steel is poured in the above-mentioned sand mold 7 being placed with broken wall mould 4 and rolled mortar wall mould 5, vanadium plate 1 and graphite powder, cast temperature controls at 1530 DEG C, casting time is be advisable for 50 seconds, after molten metal room temperature cooled and solidified, take out foundry goods, sand removal process, makes crushing wall 2 outer wall and rolled mortar wall 3 inwall be respectively the complex with vanadium plate 1.The width dimensions at crushing wall 2 outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall 2, and the width at compound position is generally 1/2 of crusher chamber cone, and the compound position of crushing wall 2 outer wall is even depth, and depth dimensions is 4/5 of crushing wall 2 wall thickness.The hierarchy structure shape and size at rolled mortar wall 3 inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall 2 of same specification.Crushing wall 2 outer wall compound position and rolled mortar wall 3 inwall compound position are annular.
6, the crushing wall 2 and rolled mortar wall 3 complex that have obtained having cast put into the holding furnace inside holding with protective atmosphere; be warming up to 1160 DEG C; programming rate controls at 7 DEG C/min; temperature retention time is 11.5h; finally cool to room temperature with the furnace; thus the crusher chamber surface between crushing wall 2 and rolled mortar wall 3 forms gradient composite coating, and crushing wall and rolled mortar wall matrix are still ZGMn13-4.Described protection gas is argon gas, and gas flow is 6ml/min.
7, the crusher chamber surface of gained has crushing wall 2 and the rolled mortar wall 3 of gradient composite coating, single austenite structure is obtained after water-tenacity treatment, heat treatment step is: within 1 hour, be warmed up to 300-400 DEG C, then 1030 DEG C are warmed up to by the speed of 60 DEG C per hour, potassium steel is made fully to carry out austenitizing, be incubated 2.5 hours, carrying out the water-tenacity treatment total processing time in water of then being quenched is 13.5 hours.
Described gradient composite coating comprises V 2c dense ceramic layers 8, be as the criterion monocrystalline phase, and its crystallite dimension is 50 μm, and along coating longitudinal profile, its thickness is 23 μm, wherein V 2the volume fraction of C is 95%.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2micron V under C dense ceramic layers 8 8c 7dense ceramic layers 9, along coating longitudinal profile, its thickness is 88 μm, V 8c 7volume fraction be 80%, its crystallite dimension is 15 μm.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2c dense ceramic layers 8 and micron V 8c 7v under dense ceramic layers 9 8c 7with the fused layer 10 of matrix, along coating longitudinal profile, its thickness is 1069 μm, wherein V 8c 7volume fraction be 55%, its crystallite dimension is 20 μm.Now, described carbide coating is composite coating, by described accurate monocrystalline V 2c dense ceramic layers 8, micron V 8c 7dense ceramic layers 9 and V 8c 7form with the fused layer 10 of matrix, and distribution gradient successively, its gross thickness is 1180 μm.Described crushing wall and rolled mortar wall matrix are austenite.Crushing wall outer wall and rolled mortar wall inwall have higher hardness HRC60, and its relative wear resistance is 10 times of matrix.
Embodiment 5: the preparation method of composite breaking wall and rolled mortar wall, comprises the steps:
1, first prepare a vanadium plate 1, wherein the purity of vanadium should control 99.7%.Described vanadium plate 1 should first by surface treatment in addition, and step is as follows:
First step pickling, selects the hydrochloric acid of 300ml/L, rear running water;
Second step pickling, the hydrogen peroxide of 240ml/L, rear running water;
3rd step surface finish, selects 800 object Al 2o 3sand paper, finally uses alcohol ultrasonic cleaning.The THICKNESS CONTROL of described vanadium plate 1 is at 0.2mm.
2, according to the size of crushing wall 2 with rolled mortar wall 3, crushing wall mould 4 and rolled mortar wall mould 5 is made respectively with polystyrene foam plastics, groove is set respectively at the outer wall of crushing wall mould 4 and the inwall of rolled mortar wall mould 5, respectively in groove internal fixtion external carbon source 6, external carbon source 6 is graphite powder, described graphite powder selects granularity at 800 orders, and purity is 89%.Then vanadium plate 1 is wound on respectively in the groove of broken wall mould 4 outer wall and rolled mortar wall mould 5 inwall, itself and graphite powder are combined closely (as depicted in figs. 1 and 2).
3, according to crushing wall 2 and rolled mortar wall 3 size, CO is used 2waterglass hardened sand makes sand mold 7, and crushing wall mould 4 and rolled mortar wall mould 5 are placed in sand mold 7 die cavity respectively.
4, smelt potassium steel base material for molten steel, temperature controls at 1540 DEG C, and selected potassium steel matrix is ZGMn13-5.
5, evaporative pattern process for suction casting is adopted, above-mentioned molten steel is poured in the above-mentioned sand mold 7 being placed with broken wall mould 4 and rolled mortar wall mould 5, vanadium plate 1 and graphite powder, cast temperature controls at 1540 DEG C, casting time is be advisable for 60 seconds, after molten metal room temperature cooled and solidified, take out foundry goods, sand removal process, makes crushing wall 2 outer wall and rolled mortar wall 3 inwall be respectively the complex with vanadium plate 1.The width dimensions at crushing wall 2 outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall 2, and the width at compound position is generally 3/5 of crusher chamber cone, and the compound position of crushing wall 2 outer wall is even depth, and depth dimensions is 1/5 of crushing wall 2 wall thickness.The hierarchy structure shape and size at rolled mortar wall 3 inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall 2 of same specification.Crushing wall 2 outer wall compound position and rolled mortar wall 3 inwall compound position are annular.
6, the crushing wall 2 and rolled mortar wall 3 complex that have obtained having cast put into the holding furnace inside holding with protective atmosphere; be warming up to 1150 DEG C; programming rate controls at 7 DEG C/min; temperature retention time is 8.5h; finally cool to room temperature with the furnace; thus the crusher chamber surface between crushing wall 2 and rolled mortar wall 3 forms gradient composite coating, and crushing wall and rolled mortar wall matrix are still ZGMn13-5.Described protection gas is nitrogen, and gas flow is 7ml/min.
7, the crusher chamber surface of gained has crushing wall 2 and the rolled mortar wall 3 of gradient composite coating, single austenite structure is obtained after water-tenacity treatment, heat treatment step is: within 1 hour, be warmed up to 370 DEG C, then 1010 DEG C are warmed up to by the speed of 55 DEG C per hour, potassium steel is made fully to carry out austenitizing, be incubated 3 hours, carrying out the water-tenacity treatment total processing time in water of then being quenched is 13 hours.
Described gradient composite coating comprises V 2c dense ceramic layers 8, be as the criterion monocrystalline phase, and crystallite dimension is 42 μm; Along coating longitudinal profile, its thickness is 22 μm; Wherein V 2the volume fraction of C is 80%.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2micron V under C dense ceramic layers 8 8c 7fine and close close ceramic layer 9, along coating longitudinal profile, its thickness is 77 μm, V 8c 7volume fraction be 78%, its crystallite dimension is 14 μm.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2c dense ceramic layers 8 and micron V 8c 7v under dense ceramic layers 9 8c 7with the fused layer 10 of matrix, along coating longitudinal profile, its thickness is 1005 μm, wherein V 8c 7volume fraction be 60%, its crystallite dimension is 15 μm.Now, described carbide coating is composite coating, by described accurate monocrystalline V 2c dense ceramic layers 8, micron V 8c 7dense ceramic layers 9 and V 8c 7form with the fused layer 10 of matrix, and distribution gradient successively, its gross thickness is 1104 μm.Described crushing wall and rolled mortar wall matrix are austenite.Crushing wall outer wall and rolled mortar wall inwall have higher hardness HRC47, and its relative wear resistance is 6.5 times of matrix.
Embodiment 6: the preparation method of composite breaking wall and rolled mortar wall, comprises the steps:
1, first prepare a vanadium plate 1, wherein the purity of vanadium should control 99.9%.Described vanadium plate 1 should first by surface treatment in addition, and step is as follows:
First step pickling, selects the hydrogen peroxide of 120ml/L, rear running water;
Second step pickling, the hydrogen peroxide of 240ml/L, rear running water;
3rd step surface finish, selects 1200 object Al 2o 3sand paper, finally uses alcohol ultrasonic cleaning.The THICKNESS CONTROL of described vanadium plate 1 is at 1.5mm.
2, according to the size of crushing wall 2 with rolled mortar wall 3, crushing wall mould 4 and rolled mortar wall mould 5 is made respectively with polystyrene foam plastics, groove is set respectively at the outer wall of crushing wall mould 4 and the inwall of rolled mortar wall mould 5, respectively in groove internal fixtion external carbon source 6, external carbon source 6 is graphite powder, described graphite powder selects granularity at 1000 orders, and purity is 99%.Then vanadium plate 1 is wound on respectively in the groove of crushing wall outer mold wall 4 and rolled mortar wall mould 5 inwall, itself and graphite powder are combined closely.
3, according to crushing wall 2 and rolled mortar wall 3 size, make sand mold 7 with precoated sand, and crushing wall mould 4 and rolled mortar wall mould 5 are placed in sand mold 7 die cavity respectively.
4, smelt potassium steel base material for molten steel, temperature controls at 1560 DEG C, and selected potassium steel matrix is ZGMn13-1.
5, evaporative pattern process for suction casting is adopted, above-mentioned molten steel is poured in the above-mentioned sand mold 7 being placed with broken wall mould 4 and rolled mortar wall mould 5, vanadium plate 1 and graphite powder, cast temperature controls at 1560 DEG C, casting time is be advisable for 20 seconds, after molten metal room temperature cooled and solidified, take out foundry goods, sand removal process, makes crushing wall 2 outer wall and rolled mortar wall 3 inwall be respectively the complex with vanadium plate 1.The width dimensions at crushing wall 2 outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall 2, and the width at compound position is generally 4/5 of crusher chamber cone, and the compound position of crushing wall 2 outer wall is even depth, and depth dimensions is 2/5 of crushing wall 2 wall thickness.The hierarchy structure shape and size at rolled mortar wall 3 inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall 2 of same specification.Crushing wall 2 outer wall compound position and rolled mortar wall 3 inwall compound position are annular.
6, the crushing wall 2 and rolled mortar wall 3 complex that have obtained having cast put into the holding furnace inside holding with protective atmosphere; be warming up to 1100 DEG C; programming rate controls at 7 DEG C/min; temperature retention time is 10.5h; finally cool to room temperature with the furnace; thus the crusher chamber surface between crushing wall 2 and rolled mortar wall 3 forms gradient composite coating, and crushing wall and rolled mortar wall matrix are still ZGMn13-1.Described protection gas is nitrogen, and gas flow is 8ml/min.
7, the crusher chamber surface of gained has crushing wall 2 and the rolled mortar wall 3 of gradient composite coating, single austenite structure is obtained after water-tenacity treatment, heat treatment step is: within 1 hour, be warmed up to 400 DEG C, then 1050 DEG C are warmed up to by the speed of 80 DEG C per hour, potassium steel is made fully to carry out austenitizing, be incubated 3 hours, carrying out the water-tenacity treatment total processing time in water of then being quenched is 14 hours.
Described gradient composite coating comprises V 2c dense ceramic layers 8, be as the criterion monocrystalline phase, and its crystallite dimension is 36 μm; Along coating longitudinal profile, its thickness is 20 μm; Wherein V 2the volume fraction of C is 95%.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2micron V under C dense ceramic layers 8 8c 7dense ceramic layers 9, along coating longitudinal profile, its thickness is 72 μm, V 8c 7volume fraction be 90%, its crystallite dimension is 12 μm.
Further, also comprise and be positioned at above-mentioned accurate monocrystalline V 2c dense ceramic layers 8 and micron V 8c 7v under dense ceramic layers 9 8c 7with the fused layer 10 of matrix, along coating longitudinal profile, its thickness is 993 μm, wherein V 8c 7volume fraction be 85%, its crystallite dimension is 15 μm.Now, described carbide coating is composite coating, by described accurate monocrystalline V 2c dense ceramic layers 8, micron V 8c 7dense ceramic layers 9 and V 8c 7form with the fused layer 10 of matrix, and distribution gradient successively, its gross thickness is 1085 μm.Described crushing wall and rolled mortar wall matrix are austenite.Crushing wall outer wall and rolled mortar wall inwall have higher hardness HRC50, and its relative wear resistance is 7 times of matrix.
Comparative example 1, its preparation method is as follows: with laser cladding directly by V 8c 7the cladding of vanadium carbide particle is in the taper work face of crushing wall outer wall and rolled mortar wall inwall, and obtain carbide coating, thickness is 30 μm, and volume fraction is 80%, and the hardness of working face is HRC42, and relative wear resistance is 3.6 times of matrix.
In comparative example, Laser Surface Modification Technology production cost is high, and production efficiency is low, and technological parameter is wayward, and uses bonding agent will cause pore and slag inclusion in use procedure; And in composite bed, there is not accurate monocrystalline V 2c dense ceramic layers and micron V 8c 7dense ceramic layers, composite bed thickness and V 8c 7content is less, V 8c 7crystallite dimension is larger; Simultaneously, recombination process is only externally add the intergranular gap of hard vanadium carbide to carry out casting and blend and carry out melting, sintering to additional particle, non-metallurgical binding between hard vanadium carbide particle and metallic matrix, adhesion is very weak, particle easily comes off or there is oxidation, Inclusion Problem, therefore, its mechanical property is poor.
Last it is noted that the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (21)

1. crushing wall and a rolled mortar wall, crusher chamber surface in-between has wear-resistant coating, it is characterized in that: described wear-resistant coating is V 2c dense ceramic layers.
2. crushing wall as claimed in claim 1 and rolled mortar wall, is characterized in that: V 2c dense ceramic layers is as the criterion monocrystalline phase, and described accurate monocrystalline refers to mutually, between polycrystalline phase and monocrystalline mutually between, compared to polycrystalline phase, uniform orientation is high, crystal boundary obviously reduces, and the microscopic structure that atomic arrangement is more orderly.
3. crushing wall as claimed in claim 1 or 2 and rolled mortar wall, is characterized in that: along V 2c dense ceramic layers longitudinal profile, its thickness is 9-23 μm, is preferably 12-20 μm, is more preferably 15-20 μm; Preferably, wherein V 2the volume fraction of C is greater than 80%, is preferably greater than 90%; Preferably, V 2c crystallite dimension is 20-50 μm, is preferably 30-50 μm.
4. crushing wall and a rolled mortar wall, crusher chamber surface in-between has gradient composite coating, it is characterized in that: described gradient composite coating is carbide coating, comprises the V of distribution gradient successively 2c dense ceramic layers, micron V 8c 7dense ceramic layers, V 8c 7with the fused layer of matrix.
5. crushing wall as claimed in claim 4 and rolled mortar wall, is characterized in that: V 2c dense ceramic layers is as the criterion monocrystalline phase, and described accurate monocrystalline refers to mutually, between polycrystalline phase and monocrystalline mutually between, compared to polycrystalline phase, uniform orientation is high, crystal boundary obviously reduces, and the microscopic structure that atomic arrangement is more orderly.
6. the crushing wall as described in claim 4 or 5 and rolled mortar wall, is characterized in that: along V 2c dense ceramic layers longitudinal profile, its thickness is 9-23 μm, is preferably 12-20 μm, is more preferably 15-20 μm; Preferably, wherein V 2the volume fraction of C is greater than 80%, is preferably greater than 90%; Preferably, V 2c crystallite dimension is 20-50 μm, is preferably 30-50 μm.
7. the crushing wall as described in one of claim 4-6 and rolled mortar wall, is characterized in that: along micron V 8c 7dense ceramic layers longitudinal profile, its thickness is 17-88 μm, is preferably 40-80 μm, is more preferably 60-80 μm; Preferably, V 8c 7volume fraction be greater than 70%, be preferably greater than 75%; Preferably, V 8c 7crystallite dimension be 5-15 μm, be preferably 6-15 μm, be more preferably 8-15 μm.
8. the crushing wall as described in one of claim 4-7 and rolled mortar wall, is characterized in that: along V 8c 7with the fused layer longitudinal profile of matrix, its thickness is 122 μm-1069 μm, preferred 300-1060 μm; Preferably, wherein V 8c 7volume fraction be 20%-85%, be preferably 50%-85%; Preferably, V 8c 7crystallite dimension be 5-20 μm, be preferably 10-20 μm.
9. the crushing wall as described in one of claim 4-8 and rolled mortar wall, is characterized in that: gradient composite coating gross thickness is 148-1180 μm, preferably at 400-1180 μm.
10. the crushing wall as described in one of claim 4-9 and rolled mortar wall, is characterized in that: matrix obtains single austenite structure after water-tenacity treatment; Preferably, this gradient composite coating is applied in potassium steel surface.
The preparation method of 11. 1 kinds of crushing wall and rolled mortar walls as described in one of claim 1-3, is characterized in that, the crusher chamber surface between crushing wall and rolled mortar wall has wear-resistant coating, comprises the steps:
1) first prepare a vanadium plate, preferably, wherein the purity of vanadium should control at 99.7-99.9%; More preferably, the THICKNESS CONTROL of described vanadium plate is at 0.2-3mm; Preferably, described vanadium plate is first by addition surface treatment;
2) according to the size of crushing wall and rolled mortar wall, make crushing wall mould and rolled mortar wall mould respectively, groove is set respectively at the outer wall of crushing wall mould and the inwall of rolled mortar wall mould, difference fixed outer carbon source in groove, then vanadium plate is wound on respectively in the groove of crushing wall outer mold wall and rolled mortar wall mould inner wall, itself and external carbon source are combined closely; Preferably, crushing wall mould and rolled mortar wall mould is made respectively with polystyrene foam plastics;
3) make sand mold according to crushing wall and rolled mortar wall size, and crushing wall mould and rolled mortar wall mould are placed in sand mold die cavity respectively; Preferably, CO is used 2waterglass hardened sand, precoated sand, self-hardening resin sand or tide mould sand make sand mold;
4) potassium steel base material is smelted for molten steel; Preferably, temperature controls at 1500-1560 DEG C;
5) poured into by above-mentioned molten steel in the above-mentioned sand mold being placed with broken wall mould and rolled mortar wall mould, vanadium plate and external carbon source, after molten steel cooled and solidified, take out foundry goods, sand removal process, makes crushing wall outer wall and rolled mortar wall inwall be respectively the complex with vanadium plate; Preferably, evaporative pattern process for suction casting is adopted to be poured into by above-mentioned molten steel in the above-mentioned sand mold being placed with broken wall mould and rolled mortar wall mould, vanadium plate and external carbon source; Preferably, cast temperature controls at 1500-1560 DEG C, and casting time is that 20-60 is advisable second; More preferably, molten steel room temperature cooling;
Preferably, the width dimensions at crushing wall outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall; Preferably, the width at compound position is generally the 1/2-4/5 of crusher chamber wall cone; More preferably, the compound position of crushing wall outer wall is even depth; Further preferably, depth dimensions is the 1/5-4/5 of crushing wall wall thickness.The hierarchy structure shape and size at rolled mortar wall inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall of same specification; Preferably, crushing wall outer wall compound position and rolled mortar wall inwall compound position are annular;
6) crushing wall obtained having cast and rolled mortar wall complex put into the holding furnace inside holding with protective atmosphere, finally cool to room temperature with the furnace, thus the crusher chamber surface between crushing wall and rolled mortar wall forms wear-resistant coating, and crushing wall and rolled mortar wall matrix are still potassium steel matrix;
Wherein, wear-resistant coating is V 2c dense ceramic layers.
The preparation method of 12. crushing walls as claimed in claim 11 and rolled mortar wall, is characterized in that: V 2c dense ceramic layers is as the criterion monocrystalline phase, and described accurate monocrystalline refers to mutually, between polycrystalline phase and monocrystalline mutually between, compared to polycrystalline phase, uniform orientation is high, crystal boundary obviously reduces, and the microscopic structure that atomic arrangement is more orderly; Preferably, by rate-determining steps 6) in temperature retention time, holding temperature obtain this V 2c dense ceramic layers.
The preparation method of 13. 1 kinds of crushing wall and rolled mortar walls as described in one of claim 4-10, is characterized in that, the crusher chamber surface between crushing wall and rolled mortar wall has gradient composite coating, comprises the steps:
1) first prepare a vanadium plate, preferably, wherein the purity of vanadium should control at 99.7-99.9%; More preferably, the THICKNESS CONTROL of described vanadium plate is at 0.2-3mm; Preferably, described vanadium plate is first by addition surface treatment;
2) according to the size of crushing wall and rolled mortar wall, make crushing wall mould and rolled mortar wall mould respectively, groove is set respectively at the outer wall of crushing wall mould and the inwall of rolled mortar wall mould, difference fixed outer carbon source in groove, then vanadium plate is wound on respectively in the groove of crushing wall outer mold wall and rolled mortar wall mould inner wall, itself and external carbon source are combined closely; Preferably, crushing wall mould and rolled mortar wall mould is made respectively with polystyrene foam plastics;
3) make sand mold according to crushing wall and rolled mortar wall size, and crushing wall mould and rolled mortar wall mould are placed in sand mold die cavity respectively; Preferably, CO is used 2waterglass hardened sand, precoated sand, self-hardening resin sand or tide mould sand make sand mold;
4) steel substrate is smelted for molten steel; Preferably, temperature controls at 1500-1560 DEG C;
5) poured into by above-mentioned molten steel in the above-mentioned sand mold being placed with broken wall mould and rolled mortar wall mould, vanadium plate and external carbon source, after molten steel cooled and solidified, take out foundry goods, sand removal process, makes crushing wall outer wall and rolled mortar wall inwall be respectively the complex with vanadium plate; Preferably, evaporative pattern process for suction casting is adopted to be poured into by above-mentioned molten steel in the above-mentioned sand mold being placed with broken wall mould and rolled mortar wall mould, vanadium plate and external carbon source; Preferably, cast temperature controls at 1500-1560 DEG C, and casting time is that 20-60 is advisable second; More preferably, molten steel room temperature cooling;
Preferably, the width dimensions at crushing wall outer wall compound position is substantially identical with the crusher chamber length dimension of crushing wall, and preferably, the width at compound position is generally the 1/2-4/5 of crusher chamber wall cone; More preferably, the compound position of crushing wall outer wall is even depth; Further preferably, depth dimensions is the 1/5-4/5 of crushing wall wall thickness.The hierarchy structure shape and size at rolled mortar wall inwall compound position are identical with the hierarchy structure shape and size at the compound position of another crushing wall of same specification; Preferably, crushing wall outer wall compound position and rolled mortar wall inwall compound position are annular;
6) crushing wall obtained having cast and rolled mortar wall complex put into the holding furnace inside holding with protective atmosphere, finally cool to room temperature with the furnace, thus the crusher chamber surface between crushing wall and rolled mortar wall forms gradient composite coating, and crushing wall and rolled mortar wall matrix are still steel matrix;
7) the crusher chamber surface of gained has crushing wall and the rolled mortar wall of gradient composite coating, obtains single austenite structure after water-tenacity treatment.
The preparation method of 14. crushing walls as claimed in claim 13 and rolled mortar wall, it is characterized in that: by rate-determining steps 6) in temperature retention time, holding temperature obtain this gradient composite coating and carbide coating, described carbide coating comprises the accurate monocrystalline phase V of distribution gradient successively 2c dense ceramic layers, micron V 8c 7dense ceramic layers V 8c 7with the fused layer of matrix.
The preparation method of 15. crushing walls as claimed in claim 14 and rolled mortar wall, is characterized in that: in step 6) in holding temperature, temperature retention time and the gross thickness of gradient composite coating that finally can obtain meet following formula,
L＝kTlogt 1/2+b 0
Wherein:
The gross thickness (μm) of L---gradient composite coating,
K---be constant, value is 0-1, k ≠ 0,
T---holding temperature (K),
T---temperature retention time (s),
B 0---original depth (μm), the thickness of the composite bed formed after namely molten steel is poured into a mould and between vanadium plate.
The preparation method of 16. crushing walls as described in one of claim 13-15 and rolled mortar wall, is characterized in that: described step 1) in, surface-treated step is as follows:
First step pickling, selects the hydrogen peroxide of the hydrochloric acid of 300ml/L or the phosphoric acid of 60ml/L or 120ml/L, rear running water;
Second step pickling, selects the hydrogen peroxide of the hydrofluoric acid of 300ml/L or the sulfuric acid of 200ml/L or 240ml/L, rear running water;
3rd step surface finish, selects 800-1200 object Al 2o 3sand paper, finally uses alcohol ultrasonic cleaning.
The preparation method of 17. crushing walls as described in one of claim 13-16 and rolled mortar wall, is characterized in that: described step 2) in external carbon source be graphite paper or graphite powder; Preferably, described graphite paper is more than three grades, and purity is 85-99%, and thickness is 0.1-0.35mm; Preferably, described graphite powder selects granularity at 600-1000 order, and purity is 85-99%.
The preparation method of 18. crushing walls as described in one of claim 13-17 and rolled mortar wall, is characterized in that: described step 6) in, be warming up to 1000-1160 DEG C, programming rate controls at 5-7 DEG C/min, and temperature retention time is 6.5-11.5h, preferred 8-10h.
The preparation method of 19. crushing walls as described in one of claim 13-18 and rolled mortar wall, is characterized in that: selected steel matrix is potassium steel.
The preparation method of 20. crushing walls as described in one of claim 13-19 and rolled mortar wall, it is characterized in that: described protection gas is argon gas or nitrogen, gas flow is 5-8ml/min.
The preparation method of 21. crushing walls as described in one of claim 13-20 and rolled mortar wall, it is characterized in that: described step 7) in heat treatment step be warmed up to 300-400 DEG C in 1 hour, then 1000-1050 DEG C is warmed up to by the speed of 50-80 per hour DEG C, potassium steel is made fully to carry out austenitizing, insulation 2-3 hour, carrying out the water-tenacity treatment total processing time in water of then being quenched is 13-14 hour.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111496415A (en) * 2020-05-19 2020-08-07 大连华锐重工特种备件制造有限公司 High-performance movable and fixed cone in cone crusher and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102848546A (en) * 2012-09-12 2013-01-02 章鹏 Cylinder used in double-screw extruder, and manufacturing method thereof
CN203004081U (en) * 2012-11-07 2013-06-19 山东日能超硬材料有限公司 Gang saw tool bit for cutting granite
CN203355781U (en) * 2013-06-18 2013-12-25 浙江裕融实业有限公司 High manganese steel rolled mortar wall structure
CN103615514A (en) * 2013-11-26 2014-03-05 无锡格莱德科技有限公司 Automobile transmission gear
CN203525759U (en) * 2013-06-18 2014-04-09 浙江裕融实业有限公司 High manganese steel crushing wall structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102848546A (en) * 2012-09-12 2013-01-02 章鹏 Cylinder used in double-screw extruder, and manufacturing method thereof
CN203004081U (en) * 2012-11-07 2013-06-19 山东日能超硬材料有限公司 Gang saw tool bit for cutting granite
CN203355781U (en) * 2013-06-18 2013-12-25 浙江裕融实业有限公司 High manganese steel rolled mortar wall structure
CN203525759U (en) * 2013-06-18 2014-04-09 浙江裕融实业有限公司 High manganese steel crushing wall structure
CN103615514A (en) * 2013-11-26 2014-03-05 无锡格莱德科技有限公司 Automobile transmission gear

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
材产: "特殊准单晶物质", 《军民两用技术与产品》 *
韩杰才等: "金属/陶瓷梯度涂层工艺现状", 《材料工程》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111496415A (en) * 2020-05-19 2020-08-07 大连华锐重工特种备件制造有限公司 High-performance movable and fixed cone in cone crusher and preparation method thereof
CN111496415B (en) * 2020-05-19 2024-04-12 大连华锐重工特种备件制造有限公司 High-performance dynamic fixed cone in cone crusher and preparation method thereof

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