CN107010931A - A kind of ceramic bull block has preparation method - Google Patents

A kind of ceramic bull block has preparation method Download PDF

Info

Publication number
CN107010931A
CN107010931A CN201710334547.9A CN201710334547A CN107010931A CN 107010931 A CN107010931 A CN 107010931A CN 201710334547 A CN201710334547 A CN 201710334547A CN 107010931 A CN107010931 A CN 107010931A
Authority
CN
China
Prior art keywords
ceramic
tzp
bull block
ceramic bull
10vol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710334547.9A
Other languages
Chinese (zh)
Other versions
CN107010931B (en
Inventor
陈利祥
石星军
许申鸿
陈欣言
孙光辉
葛晓辉
姜学军
武青
周旭波
李显辉
杜晓红
马军艳
刘华堂
徐韶鸿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao University
Original Assignee
Qingdao University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao University filed Critical Qingdao University
Priority to CN201710334547.9A priority Critical patent/CN107010931B/en
Publication of CN107010931A publication Critical patent/CN107010931A/en
Application granted granted Critical
Publication of CN107010931B publication Critical patent/CN107010931B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C3/00—Profiling tools for metal drawing; Combinations of dies and mandrels
    • B21C3/02—Dies; Selection of material therefor; Cleaning thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63444—Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Abstract

The invention belongs to new material mould preparing technical field, it is related to a kind of ceramic bull block tool preparation method, technical process is prepared including suspension, green compact are molded, normal sintering and microwave sintering totally four steps, using aluminum oxide and 3Y TZP micro mists as raw material, ceramic bull block tool is prepared using advanced isostatic pressed one-shaping technique and Microwave Sintering Techniques, only the surface polishing of ceramic bull block tool need to can be used after finishing for sintering, the wear-resisting crystal of ceramic die by solid phase binding mode combine closely ceramic grain-boundary bond strength increase, compactness extent is improved, ceramic, solid-phase is sintered, improve integral hardness, ceramic grain-boundary intensity and tough performance withstand the destruction of wire drawing compression and shearing, change the wear mechanism of wire drawing die, service life is 46 times of sintered carbide die, reduce the cost of manufacture of ceramic bull block tool, improving the performance indications of ceramic material, on the premise of product quality and production efficiency, reduce production link；Its scientific in principle is reasonable, high yield rate.

Description

A kind of ceramic bull block has preparation method
Technical field：
The invention belongs to new material mould preparing technical field, it is related to a kind of ceramic bull block tool preparation method, with two-phase Composite ceramic material ZTA (Zirconia reinforced alumina ceramic) is raw material, using gel injection-moulding+hydrostatic profile and normal sintering+ Microwave Sintering Techniques prepare ceramic bull block tool.
Background technology：
Metal drawing die material mainly has three kinds：Hard metal (WC-Co), glomerocryst (PCD), diamond (ND), hard are closed Gold and diamond are traditional mold materials, and since the forties, sintered carbide die is occupied an leading position in wire drawing with mould always, The characteristics of sintered carbide die is intensity and good toughness, high abrasion resistance, repair a die conveniently, be of relatively low cost, most specifications Mould be still so far using this kind of material, still, because hard alloy is to be formed by WC and Co through high temperature sintering, Co contents one As be 3-18 or so, in drawing process, metallic cobalt be easy to by bracing wire material some regions occur " microcosmic hot weld conjunction " and produce Plastic deformation occurs for raw adhesive wear, makes " netted tungsten carbide " or " island shape tungsten carbide " fracture damage, causes mould to grind Loss effect；Glomerocryst (PCD) is a kind of abrasion resistance material that the seventies grow up, and bonding gold is mixed by diamond microcrystals Category, is made by HTHP, good with the wire drawing die mechanical strength of glomerocryst, because diamond microcrystals are in forming process Random orientation overcome eccentric wear caused by monocrystal anisotropy, so, glomerocryst mould wearability is fabulous, is sintered carbide die 20-200 times, the using effect of glomerocryst mould is even better than diamond mould, but glomerocryst production cost is high, and equipment is complicated, investment Greatly, glomerocryst mould hardness height brings very big difficulty to repairing a die, and repairs a die the time and expense is much higher than sintered carbide die, general glomerocryst The cost of repairs of mould is about 1/3rd of its price；Diamond mould is only thin in part producing then due to costly, processing difficulties Applied on the finishing die of silk.
Ceramic material with metal phase ratio in terms of manufacturing wire drawing die the characteristics of having many excellent, also, cost of material is remote Less than hard alloy, glomerocryst and rough diamond；Though the hardness of ceramic die slightly above hard alloy, is significantly less than glomerocryst mould, examination Checking is real, is repaired the quality of ceramic die using the former hard alloy means that repair a die and is complied fully with requirement, moreover, for using ceramic die It need not add equipment and increase repairs a die cost；The reason for domestic enterprise does not use generally so far is that：Although making ceramics The cost of material of wire-drawing die is relatively low, but the manufacture craft for adopting sintered carbide die (is punched and ground after burning till Process) make ceramic bull block tool cost it is but very high, for ceramic material, burn till that rear material hardness is high, grinding is difficult, institute So that traditional processing method process costs are too high, it is difficult to promote the use of.Therefore, a kind of low cost, high reliability are researched and developed and is used The ceramic bull block tool preparation method of performance, prepares the ceramic bull block tool of substituted metal wire-drawing die, is conducive to ceramic wire drawing The mass of mould is promoted the use of, and the achievement in research that advances science is quickly converted to commodity, before good scale industrialization Scape.
The content of the invention：
It is an object of the invention to overcome the shortcoming that prior art is present, seek to design a kind of low cost, high reliability and The ceramic bull block tool preparation method of performance, prepares the ceramic bull block tool of substituted metal wire-drawing die, is conducive to ceramics The mass of wire-drawing die is promoted the use of.
To achieve these goals, the technical process of ceramic bull block tool preparation method of the present invention includes suspension Prepare, green compact shaping, normal sintering and microwave sintering totally four steps：
(1), prepared by suspension：By acrylamide monomer and N, N ' methylene-bisacrylamides are according to 17:1 mass ratio It is mixed with and obtains mixture, then by mixture and water according to 18：85 mass ratio, which is mixed with, obtains pre-mixing liquor, in pre-mixing liquor The middle dispersant for adding 0.5% mass fraction, purity are more than 99% and granularity is less than 0.5 μm of powdery 3Y-TZP and purity is 99% and granularity be 1 μm of powdery Al2O3It is 9.5 and suspended substance of the solid volume fraction more than 50% to be configured to pH value, will be suspended Body is placed in mixing in ball mill and the aqueous systems ceramic slurry suspension that viscosity is less than 300mPa.S is obtained after 12 hours, and mixture exists Mass percent in aqueous systems ceramic slurry suspension is 3%, completes the preparation of suspension；
(2), green compact are molded：It is poured into mould, puts after the initiator that 1% mass fraction is added in suspension Enter in baking oven and the temperature of baking oven is set as that 60 DEG C make suspension pension gelation be gelinite, then 250MPa is carried out to gelinite Isostatic cool pressing pressurize 8-15 minutes, forms the green compact of ceramic bull block；
(3), normal sintering：Green compact are placed in the normal sintering equipment that heating rate is 150 DEG C/h and rise to 900 DEG C, guarantor Temperature 1 hour, completes normal sintering；
(4), microwave sintering：Green compact are placed in the microwave sintering device that heating rate is 15 DEG C/h again and rise to 1500 DEG C, Insulation 30 minutes, completes microwave sintering.
Dispersant of the present invention is the ammonium polymethacrylate solution that mass percent concentration is 5%；Initiator is Mass percent concentration is 5% ammonium persulfate aqueous solution.
3Y-TZP percents by volume in ceramic bull block tool prepared by the present invention are respectively 5%vol, 10%vol, 15% Vol and 20%vol.
The agent structure of microwave sintering device of the present invention include magnetron, microwave power supply, circulator, water load, Four tuners, heating chamber, load, antenna array, swinging mounting and pallet；It is provided with the microwave power supply and circulator of magnetron Left end duct type is connected, and the lower end of circulator is provided with the left end duct type of water load, the right-hand member of circulator and four tuners Connection, the right-hand member of four tuners is connected with the heating chamber duct type right angle of hollow type rectangular configuration, is provided with load heating chamber Top be provided with antenna array, the bottom of heating chamber is provided with swinging mounting, and the top of swinging mounting is provided with circular plate-like shape knot The pallet of structure；The microwave frequency of magnetron is 2.45GHZ；The peak power output of microwave power supply is 5KW；Circulator is used for The back wave of load is sent into water load, it is returned to magnetron, to protect magnetron；Water load is used to absorb circulator The back wave of feeding；The back wave that four tuners are used to control heating chamber to make load is minimum；The material of heating chamber is stainless steel； Antenna array is used for converging microwave and microwave is smoothly entered heating chamber；Swinging mounting is used to rotate and support pallet, pallet is existed Moved in a circle under the drive of swinging mounting；Pallet is used to carry the article being sintered.
Microwave sintering of the present invention is the extremely high frequency that the electric dipole moment for being sintered material internal is encouraged by microwave energy The vibration of rate produces fuel factor, belongs to the uniform heating of globality, simultaneously as being sintered response time of the material to electromagnetic field Extremely short, firing rate is fast, and directly the inside for being sintered material is heated by electromagnetic field, makes the thermograde for being sintered material Small, homogeneous heating suppresses the undue of crystal grain and grown up, further improves the performance indications for being sintered material, energy-conserving and environment-protective.
The experimentation of ceramic bull block tool of the present invention is the technique mistake for having preparation method according to ceramic bull block Journey prepares the ceramic bull block tool that 3Y-TZP contents are respectively 5,10,15 and 20Vol%, using conventional experimental method and equipment Test relative density, hardness, bending strength and the fracture toughness of ceramic bull block tool；When 3Y-TZP content is more than 10vol%, The relative density of ceramic bull block tool reaches more than 99%, and hereafter the relative density increasing degree of ceramic bull block tool diminishes；3Y- The influence for the bending strength that TZP changes of contents has to ceramic bull block is not obvious；When 3Y-TZP content is more than 10vol%, The hardness of ceramic bull block tool declines, and reason is that 3Y-TZP hardness itself is relatively low；When 3Y-TZP content is less than 10Vol%, pottery The fracture toughness increase of porcelain wire-drawing die is obvious, when 3Y-TZP content is more than 10Vol%, the fracture toughness of ceramic bull block tool Increase is not obvious, reason be 3Y-TZP content it is big when, the relative density of ceramic bull block tool is also big, because modulus of elasticity is big Al2O3Constraint to 3Y-TZP, in the presence of applied stress, can phase transformation cubic phase volume fraction not containing with 3Y-TZP The increase of amount and increase, therefore, when density is higher, bending strength change is little, though fracture toughness has increase, amplitude is also little； In addition, microwave sintering has a significant impact to the attriting performance that ceramic bull block has, the resistance to of ceramic bull block tool can be significantly improved Mill property, accordingly, it is determined that using 10Vol%3Y-TZP-Al2O3The raw material having for ceramic bull block, and according to sintered carbide wire drawing die Technical standard, devise can one-shot forming go out ceramic bull block tool nib and various pieces workspace mould, With microwave sintering method, the ceramic bull block tool suitable for wire drawing copper and aluminium wire is fired into respectively, totally 6 series, is respectively： 10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 1.13,10Vol%3Y-TZP-Al2O3Material, sizing area is a diameter of 1.16,10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 2.79,10Vol%3Y-TZP-Al2O3Material, sizing area is straight Footpath is 2.82,10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 3.15 and 10Vol%3Y-TZP-Al2O3Material, it is fixed Footpath area a diameter of 3.18.
Compared with prior art, using ultra-fine aluminum oxide and 3Y-TZP micro mists as raw material, microscopic structure is uniform to the present invention Fine grain 3Y-TZP-Al2O3, metastable tetragonal zirconia phase zircite (t-ZrO2) particle dispersion is in alumina substrate, raw material has strong Degree is high, wearability is good, and preferably, coefficient of friction is small for polishability, the characteristics of corrosion resistance is high, self-lubricating property is good, using advanced Isostatic pressed one-shaping technique and Microwave Sintering Techniques preparation elevated temperature strength are big, thermal shock resistance is good, wear-resistant, corrosion-resistant, size is steady Only the surface polishing of ceramic bull block tool need to can be used after finishing qualitative good ceramic bull block tool, sintering, it is to avoid sinter Attrition process process afterwards, the wear-resisting crystal of ceramic die is increased by solid phase binding mode ceramic grain-boundary bond strength of combining closely Plus, compactness extent is improved, ceramic, solid-phase sintering, it is to avoid the presence of metal adhesive phase, the wear-resisting crystalline phase of per stroke is compared hard Alloy is substantially more, improves integral hardness, and ceramic grain-boundary intensity and tough performance withstand the destruction of wire drawing compression and shearing, changed Become the wear mechanism of wire drawing die, so as to effectively improve the service life of ceramic bull block tool, service life is sintered carbide die 4-6 times, greatly reduce the cost of manufacture of ceramic bull block tool, improve the performance indications of ceramic material, product quality and On the premise of production efficiency, production link is reduced, in favor of promoting the use of；Its scientific in principle rationally, strong operability, energy consumption is low, High yield rate, cost are low, and use environment is friendly, there is good prospects for commercial application.
Brief description of the drawings：
Fig. 1 is process flow diagram of the invention.
Fig. 2 is the agent structure principle schematic of microwave sintering device of the present invention.
The relative density corresponding relation line chart that Fig. 3 has for 3Y-TZP of the present invention content with ceramic bull block.
The bending strength corresponding relation line chart that Fig. 4 has for 3Y-TZP of the present invention content with ceramic bull block.
The hardness corresponding relation line chart that Fig. 5 has for 3Y-TZP of the present invention content with ceramic bull block.
The fracture toughness corresponding relation line chart that Fig. 6 has for 3Y-TZP of the present invention content with ceramic bull block.
Fig. 7 is the experimentation schematic diagram that ceramic bull block of the present invention has.
Embodiment：
Below by embodiment and the invention will be further described with reference to accompanying drawing.
Embodiment 1：
The technical process for the ceramic bull block tool preparation method that the present embodiment is related to is prepared including suspension, green compact are molded, Normal sintering and microwave sintering totally four steps：
(1), prepared by suspension：By acrylamide monomer and N, N ' methylene-bisacrylamides are according to 17:1 mass ratio It is mixed with and obtains mixture, then by mixture and water according to 18：85 mass ratio, which is mixed with, obtains pre-mixing liquor, in pre-mixing liquor The middle dispersant for adding 0.5% mass fraction, purity are more than 99% and granularity is less than 0.5 μm of powdery 3Y-TZP and purity is 99% and granularity be 1 μm of powdery Al2O3It is 9.5 and suspended substance of the solid volume fraction more than 50% to be configured to pH value, will be suspended Body is placed in crushing in ball mill and the aqueous systems ceramic slurry suspension that viscosity is less than 300mPa.S is obtained after 12 hours, and mixture exists Mass percent in aqueous systems ceramic slurry suspension is 3%, completes the preparation of suspension；
(2), green compact are molded：It is poured into mould, puts after the initiator that 1% mass fraction is added in suspension Enter in baking oven and the temperature of baking oven is set as that 60 DEG C make suspension pension gelation be gelinite, then 250MPa is carried out to gelinite Isostatic cool pressing pressurize 8-15 minutes, forms the green compact of ceramic bull block；
(3), normal sintering：Green compact are placed in the normal sintering equipment that heating rate is 150 DEG C/h and rise to 900 DEG C, guarantor Temperature 1 hour, completes normal sintering；
(4), microwave sintering：Green compact are placed in the microwave sintering device that heating rate is 15 DEG C/h again and rise to 1500 DEG C, Insulation 30 minutes, completes microwave sintering.
The dispersant that the present embodiment is related to is the ammonium polymethacrylate solution (PMAA- that mass percent concentration is 5% NH4)；Initiator is the ammonium persulfate aqueous solution that mass percent concentration is 5%.
In ceramic bull block manufactured in the present embodiment tool 3Y-TZP (3%mol yittrium oxide as stabilizer Tetragonal two Zirconia ceramics) percent by volume is respectively 5%vol, 10%vol, 15%vol and 20%vol.
The agent structure for the microwave sintering device that the present embodiment is related to includes magnetron 1, microwave power supply 2, circulator 3, water Load 4, four tuners 5, heating chamber 6, load 7, antenna array 8, swinging mounting 9 and pallet 10；It is provided with the microwave of magnetron 1 Power supply 2 is connected with the left end duct type of circulator 3, and the lower end of circulator 3 is provided with water load 4, the right-hand member of circulator 3 and four The left end duct type connection of tuner 5, the right-hand member of four tuners 5 and the duct type right angle of heating chamber 6 of hollow type rectangular configuration Connection, the top for being provided with 7 heating chambers 6 of load is provided with antenna array 8, and the bottom of heating chamber 6 is provided with swinging mounting 9, rotates The top of support 9 is provided with the pallet 10 of circular plate-like shape structure；The microwave frequency that magnetron 1 is launched is 2.45GHZ；Microwave power supply 2 peak power output is 5KW；Circulator 3 is used to the back wave for loading 7 sending into water load 4, it is returned to magnetron 1, to protect magnetron 1；Water load 4 is used for the back wave for absorbing the feeding of circulator 3；Four tuners 5 are used to control heating chamber 6 Make the back wave of load 7 minimum；The material of heating chamber 6 is stainless steel；Antenna array 8 is used for converging microwave and microwave is smoothly entered Heating chamber 6；Swinging mounting 9 is used to rotate and support pallet 10, pallet 10 is moved in a circle under the drive of swinging mounting 9； Pallet 10 is used to carry the article being sintered.
The microwave sintering that the present embodiment is related to be by microwave energy encourage be sintered material internal electric dipole moment it is high The vibration of frequency produces fuel factor, belongs to the uniform heating of globality, simultaneously as when being sintered material to the response of electromagnetic field Between it is extremely short, firing rate is fast, and directly the inside for being sintered material is heated by electromagnetic field, makes the thermograde for being sintered material Small, homogeneous heating suppresses the undue of crystal grain and grown up, further improves the performance indications for being sintered material, energy-conserving and environment-protective.
The experimentation for the ceramic bull block tool that the present embodiment is related to is the technique for having preparation method according to ceramic bull block Process prepares the Zirconia reinforced alumina ceramic wire-drawing die that 3Y-TZP contents are respectively 5,10,15 and 20Vol%, using normal Relative density, hardness, bending strength and the fracture toughness of experimental method and equipment the test ceramic bull block tool of rule, experimental result As shown in drawings：In Fig. 3, when 3Y-TZP content is more than 10vol%, the relative density of ceramic bull block tool reach 99% with On, hereafter the relative density increasing degree of ceramic bull block tool diminishes；In Fig. 4,3Y-TZP changes of contents is to ceramic bull block The influence of the bending strength of tool is not obvious；In Fig. 5, when 3Y-TZP content is more than 10vol%, under the hardness of ceramic bull block tool Drop, reason is that 3Y-TZP hardness itself is relatively low；In Fig. 6, when 3Y-TZP content is less than 10Vol%, it is disconnected that ceramic bull block has Split toughness increase obvious, when 3Y-TZP content is more than 10Vol%, the fracture toughness increase of ceramic bull block tool is not obvious, former Because be 3Y-TZP content it is big when, ceramic bull block tool relative density it is also big, due to the big Al of modulus of elasticity2O3To 3Y-TZP Constraint, in the presence of applied stress, can the cubic phase volume fraction of phase transformation do not increase with the increase of 3Y-TZP content Plus, therefore, when density is higher, bending strength change is little, though fracture toughness has increase, amplitude is also little.In addition, microwave sintering The attriting performance that ceramic bull block has is had a significant impact, the wearability of ceramic bull block tool can be significantly improved, accordingly, it is determined that Use 10Vol%3Y-TZP-Al2O3The raw material having for ceramic bull block, and according to the technical standard of sintered carbide wire drawing die, if Counted can one-shot forming go out ceramic bull block tool nib and various pieces workspace mould, use microwave sintering side Method, is fired into the ceramic bull block tool suitable for wire drawing copper and aluminium wire, totally 6 series, is respectively respectively：10Vol%3Y- TZP-Al2O3Material, sizing area a diameter of 1.13,10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 1.16, 10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 2.79,10Vol%3Y-TZP-Al2O3Material, sizing area is a diameter of 2.82,10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 3.15 and 10Vol%3Y-TZP-Al2O3Material, sizing area A diameter of 3.18.

Claims (6)

1. a kind of ceramic bull block has preparation method, it is characterised in that technical process includes suspension preparation, green compact shaping, routine Sintering and microwave sintering totally four steps：
(1), prepared by suspension：By acrylamide monomer and N, N ' methylene-bisacrylamides are according to 17:1 mass ratio mixing Mixture is prepared, then by mixture and water according to 18：85 mass ratio, which is mixed with, obtains pre-mixing liquor, adds in pre-mixing liquor Enter the dispersant of 0.5% mass fraction, purity be more than 99% and granularity be less than 0.5 μm of powdery 3Y-TZP and purity for 99% and Granularity is 1 μm of powdery Al2O3It is 9.5 and suspended substance of the solid volume fraction more than 50% to be configured to pH value, and suspended substance is placed in The aqueous systems ceramic slurry suspension that viscosity is less than 300mPa.S is obtained after being mixed 12 hours in ball mill, mixture is in aqueous systems Mass percent in ceramic slurry suspension is 3%, completes the preparation of suspension；
(2), green compact are molded：It is poured into after the initiator that 1% mass fraction is added in suspension in mould, is put into baking The temperature of baking oven is set as that 60 DEG C make suspension pension gelation be gelinite in case, then the cold etc. of 250MPa is carried out to gelinite Static pressure pressurize 8-15 minutes, forms the green compact of ceramic bull block；
(3), normal sintering：Green compact are placed in the normal sintering equipment that heating rate is 150 DEG C/h and rise to 900 DEG C, insulation 1 Hour, complete normal sintering；
(4), microwave sintering：Green compact are placed in the microwave sintering device that heating rate is 15 DEG C/h again and rise to 1500 DEG C, insulation 30 minutes, complete microwave sintering.
2. ceramic bull block according to claim 1 has preparation method, it is characterised in that the dispersant is quality percentage Specific concentration is 5% ammonium polymethacrylate solution；Initiator is the ammonium persulfate aqueous solution that mass percent concentration is 5%.
3. ceramic bull block according to claim 1 has preparation method, it is characterised in that in the ceramic bull block tool of preparation 3Y-TZP percents by volume be respectively 5%vol, 10%vol, 15%vol and 20%vol.
4. ceramic bull block according to claim 1 has preparation method, it is characterised in that the master of the microwave sintering device Body structure includes magnetron, microwave power supply, circulator, water load, four tuners, heating chamber, load, antenna array, rotation branch Frame and pallet；The left end duct type of the microwave power supply and circulator that are provided with magnetron is connected, and the lower end of circulator is provided with water Load, the right-hand member of circulator is connected with the left end duct type of four tuners, right-hand member and the hollow type rectangle knot of four tuners The heating chamber duct type right angle connection of structure, the top for being provided with load heating chamber is provided with antenna array, and the bottom of heating chamber is set There is swinging mounting, the top of swinging mounting is provided with the pallet of circular plate-like shape structure；The microwave frequency of magnetron is 2.45GHZ；The peak power output of microwave power supply is 5KW；Circulator is used to the back wave of load sending into water load, makes it not Cause to return to magnetron, to protect magnetron；Water load is used for the back wave for absorbing circulator feeding；Four tuners are used to control Heating chamber makes the back wave of load minimum；The material of heating chamber is stainless steel；Antenna array is used for converging microwave and makes microwave smooth Into heating chamber；Swinging mounting is used to rotate and support pallet, pallet is moved in a circle under the drive of swinging mounting；Pallet For carrying the article being sintered.
5. ceramic bull block according to claim 1 has preparation method, it is characterised in that the microwave sintering is by micro- The vibration that wave energy excitation is sintered the extremely high frequency of the electric dipole moment of material internal produces fuel factor, belongs to the uniform of globality and adds Heat, simultaneously as the response time for being sintered material to electromagnetic field is extremely short, firing rate is fast, by electromagnetic field directly to being sintered The inside heating of material, makes the thermograde for being sintered material small, homogeneous heating, suppresses the undue of crystal grain and grows up, further carries Height is sintered the performance indications of material, energy-conserving and environment-protective.
6. ceramic bull block according to claim 1 has preparation method, it is characterised in that the experiment of ceramic bull block tool Journey is respectively 5,10,15 and 20Vol% to have the technical process of preparation method according to ceramic bull block to prepare 3Y-TZP contents Ceramic bull block has, using relative density, hardness, the bending strength of conventional experimental method and equipment test ceramic bull block tool And fracture toughness；When 3Y-TZP content is more than 10vol%, the relative density of ceramic bull block tool reaches more than 99%, hereafter The relative density increasing degree of ceramic bull block tool diminishes；The bending strength that 3Y-TZP changes of contents has to ceramic bull block Influence is not obvious；3Y-TZP content be more than 10vol% when, ceramic bull block tool hardness decline, reason be 3Y-TZP in itself Hardness is relatively low；When 3Y-TZP content is less than 10Vol%, the fracture toughness increase of ceramic bull block tool is obvious, and 3Y-TZP's contains Amount be more than 10Vol% when, ceramic bull block tool fracture toughness increase it is unobvious, reason be 3Y-TZP content it is big when, ceramics The relative density of wire-drawing die is also big, due to the big Al of modulus of elasticity2O3Constraint to 3Y-TZP, in the presence of applied stress, Can the cubic phase volume fraction of phase transformation do not increase with the increase of 3Y-TZP content, therefore, when density is higher, bending strength Change is little, though fracture toughness has increase, amplitude is also little；In addition, microwave sintering has to the attriting performance that ceramic bull block has Significantly affect, the wearability of ceramic bull block tool can be significantly improved, accordingly, it is determined that using 10Vol%3Y-TZP-Al2O3For pottery The raw material of porcelain wire-drawing die, and according to the technical standard of sintered carbide wire drawing die, devise can one-shot forming go out ceramic wire drawing The nib of mould and the mould of various pieces workspace, with microwave sintering method, be fired into respectively suitable for wire drawing copper and The ceramic bull block of aluminium wire has, totally 6 series, is respectively：10Vol%3Y-TZP-Al2O3Material, sizing area is a diameter of 1.13,10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 1.16,10Vol%3Y-TZP-Al2O3Material, sizing area are straight Footpath is 2.79,10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 2.82,10Vol%3Y-TZP-Al2O3Material, sizing Area a diameter of 3.15 and 10Vol%3Y-TZP-Al2O3Material, sizing area a diameter of 3.18.
CN201710334547.9A 2017-05-12 2017-05-12 Preparation method of ceramic wire drawing die Active CN107010931B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710334547.9A CN107010931B (en) 2017-05-12 2017-05-12 Preparation method of ceramic wire drawing die

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710334547.9A CN107010931B (en) 2017-05-12 2017-05-12 Preparation method of ceramic wire drawing die

Publications (2)

Publication Number Publication Date
CN107010931A true CN107010931A (en) 2017-08-04
CN107010931B CN107010931B (en) 2020-03-31

Family

ID=59449164

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710334547.9A Active CN107010931B (en) 2017-05-12 2017-05-12 Preparation method of ceramic wire drawing die

Country Status (1)

Country Link
CN (1) CN107010931B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110904401A (en) * 2019-12-30 2020-03-24 江苏山峰铜业科技有限公司 Bare copper tinning process
CN111136589A (en) * 2019-12-30 2020-05-12 宁波大学 Abrasive grain boundary bonding and fixing grinding tool and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050272591A1 (en) * 2004-03-23 2005-12-08 Masahiro Nawa ZrO2-Al2O3 composite ceramic material and production method therefor
CN1978385A (en) * 2005-12-09 2007-06-13 中国科学院兰州化学物理研究所 Nano ceramic water-base gel casting method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050272591A1 (en) * 2004-03-23 2005-12-08 Masahiro Nawa ZrO2-Al2O3 composite ceramic material and production method therefor
CN1978385A (en) * 2005-12-09 2007-06-13 中国科学院兰州化学物理研究所 Nano ceramic water-base gel casting method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
庄哲峰等: "《工程材料及其应用》", 31 August 2013, 华中科技大学出版社 *
张琳等: "《航空工程材料及应用》", 30 September 2013, 国防工业出版社 *
肖奇等: "《无机材料热工基础》", 31 January 2010, 冶金工业出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110904401A (en) * 2019-12-30 2020-03-24 江苏山峰铜业科技有限公司 Bare copper tinning process
CN111136589A (en) * 2019-12-30 2020-05-12 宁波大学 Abrasive grain boundary bonding and fixing grinding tool and preparation method thereof
CN110904401B (en) * 2019-12-30 2021-11-30 江苏山峰铜业科技有限公司 Bare copper tinning process

Also Published As

Publication number Publication date
CN107010931B (en) 2020-03-31

Similar Documents

Publication Publication Date Title
CN101892411B (en) Novel WC-based hard alloy material and preparation method thereof
CN103572087B (en) The preparation method of boron carbide particles reinforced aluminum matrix composites
CN103521132B (en) Synthesis technique of high-grade self-sharpening polycrystalline diamond
CN106891272B (en) A kind of vitrified bond high-performance CBN grinding wheel and preparation method thereof based on strong electromagnetic
CN107385303A (en) A kind of high fine and close and high tenacity metal material and preparation method thereof
CN107010931A (en) A kind of ceramic bull block has preparation method
CN104073665B (en) A kind of preparation method of WC-Co-cBN composite
CN110273092A (en) A kind of CoCrNi particle reinforced magnesium base compound material and preparation method thereof
CN101857438A (en) Method for preparing aluminum oxide-titanium carbide-zirconium oxide nanocomposite ceramic material
CN112266251A (en) Preparation method of silicon nitride/titanium carbide ceramic material based on spark plasma sintering
CN103586296A (en) Mosaic ceramic drawing die and making method thereof
CN108411137B (en) Preparation method of ultra-fine grain tungsten carbide-based hard alloy
CN110818395B (en) SiC whisker and silicon nitride particle reinforced alumina-based ceramic cutter material and preparation process thereof
CN110202131A (en) A kind of preparation method of diamond composition
CN104073750A (en) TiC short fiber reinforced titanium-based composite material and preparation method thereof
CN107140995A (en) A kind of refractory ceramics crawler belt preparation method
CN110499442A (en) A kind of high-strength corrosion-resistant Cr3C2Base light-weight metal ceramal and preparation method thereof
CN102094131A (en) Preparation process and equipment of powder metallurgic multicomponent rare-earth alloy giant-magnetostrictive material
CN103204687A (en) Steel-casting brick for producing high-grade special alloy steel and production method thereof
CN102719695A (en) Cu-Al-Mn memory alloy prepared by powder metallurgy method
CN102731071A (en) Preparation method of Al-Ti-B and rare metal synergistically-toughened alumina
CN102775135A (en) Novel ceramic corundum abrasive
CN106518090B (en) A kind of Sialon ceramics friction welding (FW) stirring-head and preparation method thereof
CN105218100A (en) A kind of low-temperature growth Ti 2the method of AlC stupalith
CN110948407B (en) Preparation method of grinding tool

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant