CN116589294A - Preparation method of special-shaped ZTA ceramic particles - Google Patents
Preparation method of special-shaped ZTA ceramic particles Download PDFInfo
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- CN116589294A CN116589294A CN202310410478.0A CN202310410478A CN116589294A CN 116589294 A CN116589294 A CN 116589294A CN 202310410478 A CN202310410478 A CN 202310410478A CN 116589294 A CN116589294 A CN 116589294A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 196
- 239000002245 particle Substances 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 73
- 239000002002 slurry Substances 0.000 claims abstract description 60
- 239000008188 pellet Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000002270 dispersing agent Substances 0.000 claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 69
- 239000003349 gelling agent Substances 0.000 claims description 26
- 239000011324 bead Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 235000010413 sodium alginate Nutrition 0.000 claims description 16
- 239000000661 sodium alginate Substances 0.000 claims description 16
- 229940005550 sodium alginate Drugs 0.000 claims description 16
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 13
- 238000005054 agglomeration Methods 0.000 claims description 12
- 230000002776 aggregation Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 23
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 8
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 description 18
- 239000010431 corundum Substances 0.000 description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001272 pressureless sintering Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000010955 niobium Substances 0.000 description 10
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
Classifications
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
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- 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
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- 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
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- 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
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- 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
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- 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
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
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- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention relates to the technical field of composite materials, in particular to a preparation method of a special-shaped ZTA particle ceramic material. The method comprises the following steps: adding dispersant, gelatinizer, and ZTA ceramic powder obtained by co-precipitation, niobium oxide powder, and solvent into ball milling equipment, ball milling at ball milling rotation speed of 150-300 rpm for at least 7 hr to obtain ceramic slurry suspension for gel, and dripping the obtained slurry into CaCl of 0.3-0.8mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering out gel pellets, cleaning, and then treating the gel pellets with an acid solution; finally sintering at 1400-1450 ℃ to obtain the product. The invention obtains the special-shaped ZTA particle ceramic material particles with ultra-high hardnessThe particles and the surfaces of the obtained particles are provided with folds, which provides necessary conditions for the use of the particles as a high-quality reinforcement.
Description
Technical Field
The invention relates to the technical field of composite materials; in particular to a special-shaped ZTA particle ceramic material and a preparation method thereof, and the special-shaped ZTA particle ceramic material is used as a ceramic reinforcement of an iron-based composite wear-resistant material and is applied to crushing (reducing) equipment.
Background
The application and research of wear-resistant materials plays an important role in the current industrial development, such as mechanical equipment of cement, machinery, electric power, mine, metallurgy, ships, chemical industry and coal industry, grinding balls, grinding discs, grinding rollers and auxiliaries of various mills, as well as crushing walls, crushing plates, impact crusher plate hammers and the like of crushers; the parts of large dredging pump overflow parts, slurry pump parts, conveying pipelines and the like which are worn by impact corrosion and the industrial and mining are worn by hard abrasive materials in the production process and are in severe wearing environments such as corrosion, high-temperature oxidation, high impact and the like, so that rapid wear and failure are extremely easy to occur. Nowadays, single metal materials or alloy materials are more and more difficult to meet the actual production requirements under severe working conditions, and fatigue failure of a small number of parts can cause great loss which is difficult to estimate, so that the ceramic composite metal matrix composite wear-resistant materials are more and more applied to wear-resistant places on a large scale.
The composite material formed by adding the ceramic as the second reinforcing phase into the metal matrix not only has high hardness, high wear resistance, high heat resistance and high corrosion resistance of the ceramic, but also can exert good toughness, plasticity, heat conductivity and electric conductivity of the metal matrix. The composite material is widely studied and applied at present due to the good performance. The composition ratio of various ZTA ceramics and the sintering process are different, but the micro-hardness of the ZTA ceramics is not lower than 1500HV, and the ZTA ceramics has low price, the linear expansion coefficient is close to that of various iron and steel materials, and has no metallurgical reaction with molten iron at high temperature, thus being a ceramic second phase for preparing ceramic reinforced metal composite materials. At present, most ZTA ceramic preparation methods mainly comprise a series of processes of pulverizing, pressing, forming, sintering and crushing, wherein fine ZTA ceramic powder is generally prepared by precipitation copolymerization, and ZTA ceramic particles are prepared by the steps, and the microhardness of the ZTA ceramic particles is generally about 1500 HV; or mixing the nano-scale alumina and zirconia powder by high-energy ball milling to obtain ceramic slurry, and finally sintering to obtain the three-dimensional network ZTA ceramic, as described in a preparation method of a high-performance ceramic reinforced iron-based composite material in patent 2020111656217. However, both methods have corresponding limitations, the former has extremely high requirements on crushing equipment, and meanwhile, due to the existence of a large number of sharp edges and corners, a large number of stress concentrations are generated at the edges and corners in the subsequent preparation process of the iron-based composite material, so that the cracking failure tendency of the composite material is increased, and the wear resistance of the composite material is indirectly reduced; the latter has high requirements on raw materials, and meanwhile, the prepared three-dimensional network ceramic has a porous structure, so that the three-dimensional network ceramic has high brittleness, is not easy to transport, and has low yield. The raw materials selected by the patent 201580050007.7 ceramic particles and the manufacturing method thereof are a mixture of ceramic powder with single components, the component components and the mass ratio are uncertain, the components are complex, and the process flow is complex. The patent 201811620521.1 discloses a preparation method of a surface-treated ZTA particle reinforced steel-based composite wear-resistant part, which introduces a method for preparing a porous ZTA ceramic preform by using ZTA ceramic particles and a metal binder, thereby preparing a steel-based composite material. In obvious difference with the invention, the adopted porous ZTA ceramic preform adopts ZTA ceramic particles prepared by a crushing method, and the sharp edges and corners cause the tendency of stress concentration to be increased, so that the cracking tendency of the composite material is increased, and the abrasion process of the composite material is accelerated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of the special-shaped ZTA ceramic particle reinforced metal-based wear-resistant composite material, which controls the production cost, simplifies the production process, solves the component distribution of the material, the corresponding sintering process formulation and the preparation problem of the ZTA particle ceramic material, and solves the problem of large stress concentration on the ZTA ceramic surface. The special-shaped ZTA particle ceramic material with good friction resistance, high hardness and no sharp edges and corners and the corresponding composite wear-resistant material thereof are prepared.
The invention relates to a preparation method of special-shaped ZTA ceramic particles; the method comprises the following steps:
adding a dispersing agent, a gelatinizing agent, ZTA ceramic powder, niobium oxide powder and a solvent into ball milling equipment, and performing ball milling for at least 7 hours at a ball milling rotating speed of 150-300 rpm to obtain ceramic slurry suspension for gel; regulating the pH of the ceramic slurry suspension for the gel to 5.5-6.5, preferably 5.8-6.2; obtaining standby slurry; the ZTA ceramic raw material is obtained by a copolymerization precipitation method;
dripping the prepared standby slurry into CaCl of 0.3-0.8mol/L, preferably 0.3-0.55mol/L, more preferably 0.3-0.5mol/L 2 In the solution (of course, 0.3mol/L, 0.4mol/L and 0.5mol/L can obtain good effect, but the concentration of 0.3mol/L can obviously promote the hardness of the product by matching with the technological parameters before and after) to form gel pellets, and the gel pellets are added into CaCl 2 Soaking in the solution for at least 60min, filtering out gel pellets, cleaning, and then treating the gel pellets with an acid solution;
treating the gel pellets with an acid solution, drying and sintering to obtain a product; the sintering temperature is 1400-1450 ℃ (preferably 1430-1450 ℃), and the time is more than or equal to 20min, preferably 30-120min, and more preferably 45-75min. In the course of the development of the technology according to the invention, it has also been found that 0.1mol/LCaCl is employed 2 The hardness of the solution, resulting in a product, is not ideal.
The gelling agent is at least one selected from sodium alginate, oxalic acid, ammonium phosphate and sodium phosphate.
The dispersing agent is preferably at least one of polyacrylic acid, polyvinyl alcohol and ethylene glycol.
The solvent is at least one selected from deionized water, absolute ethyl alcohol and acetone.
In the invention, the mass ratio of the dispersing agent, the gelatinizing agent, the ZTA ceramic particles and the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 7-20:1.5-3.5:65-90:170-190. The adding amount of the niobium oxide powder is 0.2-0.5wt% of the ZTA ceramic powder.
As a further preferable aspect, in the present invention, the mass ratio of the dispersant, the gelling agent, the ZTA ceramic particles, and the solvent is; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:170-190.
In order to further improve the effect of the product, 0.2 to 0.3 percent, preferably 0.25 percent of the mass of the ZTA ceramic particles is additionally introduced in the process of proportioningNb 2 O 5 And (3) powder. The study shows that only a proper amount of Nb is introduced 2 O 5 The powder can be sintered at 1400-1450 ℃ to obtain a high-quality product.
The concentration ratio of the sodium alginate in the ceramic slurry is 0.3-2.0wt%, preferably 0.8-1.2wt%, and more preferably 1wt%.
The invention relates to a preparation method of special-shaped ZTA ceramic particles, wherein the ZTA ceramic raw material is powder with particle size not higher than 80 mu m, and the component is 80wt% of Al 2 O 3 And 20wt% Yttrium Stabilized Zirconia (YSZ).
The invention relates to a preparation method of special-shaped ZTA ceramic particles, which comprises the steps of ball milling ceramic slurry for 8-30 hours, preferably 8-12 hours, and further preferably 11-12 hours.
According to the preparation method of the special-shaped ZTA ceramic particles, the suspension is obtained by ball milling, in order to keep the suspension relatively stable, the pH value is regulated to about 6 by using acetic acid, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained, and the standby slurry is obtained.
The invention relates to a preparation method of special-shaped ZTA ceramic particles, wherein liquid drops of slurry are obtained by a syringe or an extrusion impact device, and the liquid gelation reaction medium is calcium chloride solution.
The invention relates to a preparation method of special-shaped ZTA ceramic particles, which comprises the steps of filtering gel pellets, cleaning the gel pellets with organic substances, preferably alcohols, and then treating the gel pellets with acid solution. In industrial applications, ethanol is preferred for washing. The gel beads are treated with 0.4 to 0.6mol/L, preferably 0.5mol/L, of acetic acid solution for at least 15min.
The invention relates to a preparation method of special-shaped ZTA ceramic particles, which comprises the steps of treating gel pellets with acid solution, drying and sintering, wherein the drying temperature is 75-85 ℃ and the time is 20-28h.
The invention relates to a preparation method of special-shaped ZTA ceramic particles, which is characterized in that the dried ceramic particles are heated to 1440-1450 ℃ for sintering at a heating rate of 1-10 ℃/min in an oxygen-containing atmosphere to prepare the special-shaped ZTA ceramic particles.
Preferably, the preparation method of the special-shaped ZTA ceramic particles comprises the steps of carrying out pressureless sintering on the dried ceramic particles in an air atmosphere, carrying out pressureless sintering on the dried ceramic particles in the air atmosphere, firstly raising the temperature to 500 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 1 hour, raising the temperature to 800 ℃ at the heating rate of 2 ℃/min, raising the temperature to the target temperature at the heating rate of 5 ℃/min, preserving heat for 1 hour, and cooling along with a furnace to obtain spherical ZTA ceramic particles.
The invention achieves a product with macroscopic dimensions, at least one dimension being in the order of millimeters or more. Preferably, the size is 2-2.5mm.
The product obtained by the invention is special-shaped ZTA ceramic particles; the special-shaped ZTA ceramic particles are spherical or ellipsoidal, have no sharp edges and corners, and have hardness close to that of the ZTA ceramic particles prepared by a pressing-forming-sintering-crushing method. After optimization, the surface of the product is also provided with folds.
In the ZTA particle ceramic material prepared by the invention, the obtained special-shaped ZTA ceramic particles have macroscopic sharp edges and corners, and the Vickers microhardness HV 0.1 1700-1920HV (1740-1920 HV is optimized), and folds are formed on the surface, so that the tight combination of the molten metal and the product after casting is facilitated. The preparation process is relatively simple, the raw materials are cheap and easy to obtain, and the parameters are controllable. The invention has the wrinkled spherical or ellipsoidal particles, not only has the high hardness and strength of ZTA ceramic particles, but also reduces casting stress through the specific non-angular structure, reduces cracking tendency of the composite material, and indirectly improves the wear resistance of the related composite material.
As a further preferable scheme, the preparation method of the special-shaped ZTA ceramic particles comprises the following steps:
step one
Weighing 1% sodium alginate solution, and 0.25% Nb 2 O 5 Powder with deionized water, dispersant and Nb 2 O 5 Placing the yttrium-stabilized zirconia (YSZ) grinding balls subjected to powder treatment in a ball mill, wherein the rotating speed is 200rpm, and the ball milling time is 12 hours, so as to obtain a ceramic slurry suspension which is preliminarily used for gel; in the suspension, dispersing agent, gelatinizer, ZTA ceramic particles and solvent areThe quantitative ratio is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:180; wherein is used
The ZTA granulating powder is obtained by copolymerization precipitation method, and has particle diameter smaller than 74 μm, nb 2 O 5 The consumption of the powder is 0.25% relative to the mass of the ZTA granulated powder micro powder, and the dispersing agent is polyacrylic acid;
step two
In order to keep the suspension relatively stable, acetic acid is used for adjusting the pH value to about 6, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained;
step three
Dropping the ceramic slurry into CaCl of 0.3mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering out gel pellets, washing with alcohol twice, and then treating the gel pellets with 0.5mol/L acetic acid solution for 15min;
step four
Drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to 1450 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles. The maximum hardness of the product obtained by the scheme breaks through 1900HV for the first time 0.1 The method comprises the steps of carrying out a first treatment on the surface of the Far better than the results of other exploratory experiments.
The preparation process of the ZTA ceramic slurry is strictly controlled, so that the ZTA ceramic slurry with good fluidity and good adhesiveness can be prepared.
According to the invention, sodium alginate is used as a gelling agent, ZTA granulated powder is used as a raw material, so that the ageing reaction step is omitted, the cost is saved, and nitric acid and other reactants are not used, so that the method is more environment-friendly.
The invention uses sodium alginate as a gelling agent and uses an extrusion device to successfully prepare the profiled ZTA ceramic particle blank.
The special-shaped ZTA ceramic particles with controllable particle size and shape are prepared by strictly controlling the ZTA ceramic sintering process and adopting a sol-gel method.
The invention designs a brand-new sol-gel sintering process, and successfully solves the problem that the ZTA edges and corners prepared by a crushing method are sharp and the modification needs high requirements on wear-resistant equipment by using sodium alginate as a gelling agent, and prepares the special-shaped ZTA ceramic particles without sharp edges and corners.
The special-shaped ZTA ceramic particles designed by the invention have the hardness which is relatively equal to that of the ZTA prepared by the crushing method, and the strength of the ceramic particles obtained under partial conditions is even slightly improved, so that the special-shaped ZTA ceramic particles are used as a reinforcing body of the composite material, the casting internal stress and the quenching internal stress of the composite material are reduced, and the cracking and failure tendency of the composite material in the use process are effectively reduced.
Drawings
FIG. 1 is a graph of the macro morphology of the shaped ZTA ceramic particles obtained in example 1;
FIG. 2 is a scanning electron microscope image of the shaped ZTA ceramic particles obtained in example 1 after sintering;
FIG. 3 is a graph of cross-section and macroscopic morphology of the shaped ZTA ceramic particles obtained in example 3 after sintering;
FIG. 4 is a schematic cross-sectional macroscopic view of the cast special-shaped ZTA ceramic particle reinforced metal-based wear-resistant composite material of the embodiment 1;
FIG. 5 is a graph of the macroscopic morphology of the shaped ZTA ceramic particles obtained in comparative example 1;
FIG. 6 is a schematic diagram of the macroscopic dimensions of the shaped ZTA ceramic particles obtained in comparative example 1;
FIG. 7 is a scanning electron microscope image of the shaped ZTA ceramic particles obtained in comparative example 1 after sintering;
FIG. 8 is a graph of the macro morphology of the shaped ZTA ceramic particles obtained in comparative example 2;
FIG. 9 is a schematic diagram of macroscopic dimensions of the shaped ZTA ceramic particles obtained in comparative example 2;
it can be seen from fig. 1 that the shaped ZTA ceramic particles have a rounded shape without sharp corners.
As can be seen from figure 2, the special-shaped ZTA ceramic particles have low porosity after sintering and uniform surface structure distribution.
As can be seen from the figure 3, the ball milling time is 12 hours, the concentration of the reaction solution is 0.5mol/L, the cross-section holes made of the special-shaped ZTA ceramic particles after sintering at 1450 ℃ are very few, the structure is very uniform, and the surface has folds.
From figure 4, it can be seen that the majority of the shaped ZTA ceramic particles of the shaped ZTA ceramic particle reinforced metal-based wear-resistant composite material are well combined, and the interface is round.
As can be seen from fig. 5, the special-shaped ZTA ceramic particles prepared by directly mixing and ball milling alumina and zirconia powder have round shape and no sharp edges and corners.
As can be seen from fig. 6, the special-shaped ZTA ceramic particle size prepared by directly mixing and ball milling alumina and zirconia powder is about 2-2.5mm.
As can be seen from figure 7, the special-shaped ZTA ceramic particles prepared by directly mixing and ball milling alumina and zirconia powder have high porosity after sintering, uneven surface structure distribution and agglomeration.
From fig. 8, it can be seen that the shaped ZTA ceramic sintered by directly mixing and ball milling alumina and zirconia powder without adding dispersant does not form particles, and the macroscopic morphology is in the shape of tadpole.
From figure 9, it can be seen that the special-shaped ZTA ceramic prepared by directly mixing and ball milling alumina and zirconia powder and sintering the special-shaped ZTA ceramic without adding a dispersing agent has a size of about 3-4 mm.
The present invention will be described in further detail with reference to examples.
Detailed Description
The ZTA ceramic raw material used in the examples was a powder having a particle size of not more than 80 μm obtained by a coprecipitation method and a composition of 80wt% of Al 2 O 3 And 20wt% Yttrium Stabilized Zirconia (YSZ).
In the examples and comparative examples of the present invention, the hardness was Vickers microhardness HV 0.1 。
A preparation method of the special-shaped ZTA ceramic particles comprises the following steps:
example 1:
1. sodium alginate solution with mass fraction of 1% and weighed ZTA granulating powderMicro powder (obtained by co-precipitation method, particle diameter smaller than 74 μm), 0.25% Nb by mass 2 O 5 Powder (Nb) 2 O 5 The amount of the powder was 0.25% relative to the mass of the ZTA granulated powder micropowder, with deionized water, dispersant (polyacrylic acid), and Nb 2 O 5 The powder-treated Yttrium Stabilized Zirconia (YSZ) balls were placed in a ball mill at 200rpm for 10 hours to obtain a ceramic slurry suspension primarily used for gel. In the suspension, the mass ratio of the dispersing agent to the gelling agent to the ZTA ceramic powder to the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:180
2. In order to keep the suspension relatively stable, the pH value is regulated to about 6 by acetic acid, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained.
3. Dropwise adding the ceramic slurry into CaCl of 0.5mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering to obtain gel beads, washing with alcohol twice, and treating gel beads with 0.5mol/L acetic acid solution for 15min.
4. Drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to 1400 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles.
The hardness of the ceramic powder is tested by using a Vickers hardness tester (5 points are tested), and when the ceramic powder is sintered at 1400 ℃, the hardness reaches 1740HV at the highest, and exceeds the hardness of ZTA ceramic particles prepared by a crushing method, the sintering pores are less, the compactness is high, and the performance is excellent. See fig. 1 and 2.
Comparative example 1
1. Sodium alginate solution with mass fraction of 1% is prepared according to mass ratio of 4:1 weighed alumina and yttrium-stabilized zirconia (YSZ) powder (average particle size of the powder is less than 74 μm), 0.25 mass percent of Nb 2 O 5 Powder (Nb) 2 O 5 The amount of powder used was 0.25% relative to the total weight of alumina and Yttrium Stabilized Zirconia (YSZ) powder with deionized water, dispersant (polyacrylic acid), and Nb 2 O 5 The powder-treated Yttrium Stabilized Zirconia (YSZ) balls were placed in a ball mill at 200rpm for 10 hours to obtain a preliminary ceramic slurry suspension for gelation. In the suspension, the mass ratio of the dispersing agent to the gelling agent to the ZTA ceramic particles to the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:180;
2. in order to keep the suspension relatively stable, the pH is regulated to about 6 by acetic acid or hydrochloric acid, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained.
3. Dropwise adding the ceramic slurry into CaCl of 0.5mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering to obtain gel beads, washing with alcohol twice, and treating gel beads with 0.5mol/L acetic acid solution for 15min.
4. Drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to 1400 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles.
Hardness was tested using a vickers hardness tester (5 points tested) and after sintering the hardness was only 450HV, which was far lower than that of ZTA ceramic particles produced by crushing. Meanwhile, after sintering at 1400 ℃, the porous ceramic material has more pores and low density, a large number of agglomeration phenomena exist, and the performance is poor. See fig. 5, 6 and 7.
Comparative example 2
1. Sodium alginate solution with mass fraction of 1% is prepared according to mass ratio of 4:1 weighed alumina and yttrium-stabilized zirconia (YSZ) powder (average particle size of the powder is less than 74 μm), 0.25 mass percent of Nb 2 O 5 Powder (Nb) 2 O 5 The amount of powder used was 0.25% relative to the total weight of alumina and Yttrium Stabilized Zirconia (YSZ) powder and deionized water, and Nb 2 O 5 The powder-treated Yttrium Stabilized Zirconia (YSZ) balls were placed in a ball mill at 200rpm for 10 hours to obtain a preliminary ceramic slurry suspension for gelation. In the suspension, the mass ratio of the gelatinizer to the ZTA ceramic particles to the solvent is as follows; gelling agent: ZTA ceramic particles: solvent = 2:75:180;
2. in order to keep the suspension relatively stable, the pH is adjusted to about 6 with acetic acid or hydrochloric acid, and finally a ceramic slurry is obtained.
3. Dropwise adding the ceramic slurry into CaCl of 0.5mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering to obtain gel beads, washing with alcohol twice, and treating gel beads with 0.5mol/L acetic acid solution for 15min.
4. Drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to a target temperature of 1400 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles.
It can be seen that the ZTA ceramic particles cannot form an ellipsoidal abnormal shape due to no effect of the dispersing agent, have strong viscosity, and exhibit tadpole-like ZTA ceramic particles. See fig. 8 and 9
Example 2
1. Weighing 1% sodium alginate solution, and 0.25% Nb 2 O 5 Powder (Nb) 2 O 5 The amount of the powder was 0.25% relative to the mass of the ZTA granulated powder micropowder, with deionized water, dispersant (polyacrylic acid), and Nb 2 O 5 Placing the powder-treated Yttrium Stabilized Zirconia (YSZ) grinding balls in a ball mill at 200rpm for 12 hours to obtain a ceramic which is preliminarily used for gelSlurry suspension. In the suspension, the mass ratio of the dispersing agent to the gelling agent to the ZTA ceramic particles to the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:180;
2. in order to keep the suspension relatively stable, the pH value is regulated to about 6 by acetic acid, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained.
3. Dropwise adding the ceramic slurry into CaCl of 0.5mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering to obtain gel beads, washing with alcohol twice, and treating gel beads with 0.5mol/L acetic acid solution for 15min.
4. Drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to 1400 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles.
Hardness was tested using a vickers hardness tester (5 points tested) and the highest hardness of the product was 1710HV when sintered at 1400 ℃.
Example 3
1. Weighing 1% sodium alginate solution, and 0.25% Nb 2 O 5 Powder (Nb) 2 O 5 The amount of the powder was 0.25% relative to the mass of the ZTA granulated powder micropowder, with deionized water, dispersant (polyacrylic acid), and Nb 2 O 5 The powder-treated Yttrium Stabilized Zirconia (YSZ) balls were placed in a ball mill at 200rpm for 12 hours to obtain a ceramic slurry suspension primarily used for gel. In the suspension, the mass ratio of the dispersing agent to the gelling agent to the ZTA ceramic particles to the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:180;
2. in order to keep the suspension relatively stable, the pH value is regulated to about 6 by acetic acid, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained.
3. Dropping the ceramic slurry into CaCl of 0.3mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering to obtain gel beads, washing with alcohol twice, and treating gel beads with 0.5mol/L acetic acid solution for 15min.
4. Drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to 1450 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles.
Hardness was measured using a vickers hardness tester (5 points tested) and the highest hardness of the resulting product was 1920HV when sintered at 1450 ℃.
Comparative example 3
1. Weighing 1% sodium alginate solution, and 0.25% Nb 2 O 5 Powder (Nb) 2 O 5 The amount of the powder was 0.25% relative to the mass of the ZTA granulated powder micropowder, with deionized water, dispersant (polyacrylic acid), and Nb 2 O 5 The powder-treated Yttrium Stabilized Zirconia (YSZ) balls were placed in a ball mill at 200rpm for 10 hours to obtain a preliminary ceramic slurry suspension for gelation. In the suspension, the mass ratio of the dispersing agent to the gelling agent to the ZTA ceramic particles to the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:180;
2. in order to keep the suspension relatively stable, the pH value is regulated to about 6 by acetic acid, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained.
3. Dropping the ceramic slurry into CaCl of 0.3mol/L 2 In the form of solutionGel pellets were formed, after which the gel pellets were rapidly filtered, washed twice with alcohol, and then treated with 0.5mol/L acetic acid solution for 15min.
4. Drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to a target temperature of 1400 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles.
Due to its absence in CaCl 2 The solution is fully soaked, so that the inside and outside of the ceramic are subjected to ion exchange reaction comprehensively, most gel pellets are crushed and broken, and ellipsoidal ZTA ceramic particles cannot be formed.
Comparative example 4
1. Weighing 1% sodium alginate solution, and 0.25% Nb 2 O 5 Powder (Nb) 2 O 5 The amount of the powder was 0.25% relative to the mass of the ZTA granulated powder micropowder, with deionized water, dispersant (polyacrylic acid), and Nb 2 O 5 The powder-treated Yttrium Stabilized Zirconia (YSZ) balls were placed in a ball mill at 200rpm for 10 hours to obtain a ceramic slurry suspension primarily used for gel. In the suspension, the mass ratio of the dispersing agent to the gelling agent to the ZTA ceramic particles to the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:180;
2. in order to keep the suspension relatively stable, the pH value is regulated to about 6 by acetic acid, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained.
3. Dropwise adding the ceramic slurry into CaCl of 0.1mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering to obtain gel beads, washing with alcohol twice, and treating gel beads with 0.5mol/L acetic acid solution for 15min.
4. Drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to 1400 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles.
Hardness was measured using a vickers hardness tester (5 points were measured), and when sintered at 1400 ℃, the highest hardness was 950HV, indicating that the density was low and the sintered pores were large due to complete unreacted reaction in the low concentration reaction solution.
Comparative example 5
1. Weighing 1% sodium alginate solution, and 0.25% Nb 2 O 5 Powder (Nb) 2 O 5 The amount of the powder was 0.25% relative to the mass of the ZTA granulated powder micropowder, with deionized water, dispersant (polyacrylic acid), and Nb 2 O 5 The powder-treated Yttrium Stabilized Zirconia (YSZ) balls were placed in a ball mill at 200rpm for 12 hours to obtain a ceramic slurry suspension primarily used for gel. In the suspension, the mass ratio of the dispersing agent to the gelling agent to the ZTA ceramic particles to the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic particles: solvent = 10:2:75:180;
2. in order to keep the suspension relatively stable, the pH value is regulated to about 6 by acetic acid, so that the ceramic slurry does not generate suspended particles and has no agglomeration phenomenon, and finally, the ceramic slurry with good fluidity is obtained.
3. Dropping the ceramic slurry into CaCl of 0.3mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering to obtain gel beads, washing with alcohol twice, and treating gel beads with 0.5mol/L acetic acid solution for 15min.
4. And (3) drying the acid-treated pellets in an oven at 80 ℃ for 24 hours, placing the acid-washed gel pellets in a corundum crucible, then placing the corundum crucible in a muffle furnace, performing pressureless sintering under an air atmosphere, firstly raising the temperature to 550 ℃ at a heating rate of 1.5 ℃/min for 1 hour, then raising the temperature to 850 ℃ at a speed of 2 ℃/min, then raising the temperature to 1350 ℃ at a speed of 5 ℃/min for 1 hour, and cooling along with the furnace to obtain spherical ZTA ceramic particles.
Hardness was measured using a vickers hardness tester (5 points tested) and was found to be 960HV at maximum when sintered at 1350 ℃.
Claims (10)
1. A preparation method of special-shaped ZTA ceramic particles; the method is characterized in that; the method comprises the following steps:
adding a dispersing agent, a gelatinizing agent, ZTA ceramic powder, niobium oxide powder and a solvent into ball milling equipment, and performing ball milling for at least 7 hours at a ball milling rotating speed of 150-300 rpm to obtain ceramic slurry suspension for gel; regulating the pH of the ceramic slurry suspension for the gel to 5.5-6.5, preferably 5.8-6.2; obtaining standby slurry; the ZTA ceramic raw material is obtained by a copolymerization precipitation method;
dripping the prepared standby slurry into CaCl of 0.3-0.8mol/L, preferably 0.3-0.55mol/L, more preferably 0.3-0.5mol/L 2 Forming gel pellets in the solution and adding CaCl 2 Soaking in the solution for at least 60min, filtering out gel pellets, cleaning, and then treating the gel pellets with an acid solution;
treating the gel pellets with an acid solution, drying and sintering to obtain a product; the sintering temperature is 1400-1450 ℃ for 20min or longer, preferably 30-120min, and more preferably 45-75min;
the gelling agent is at least one selected from sodium alginate, oxalic acid, ammonium phosphate and sodium phosphate;
the dispersing agent is preferably at least one of polyacrylic acid, polyvinyl alcohol and ethylene glycol;
the solvent is at least one selected from deionized water, absolute ethyl alcohol and acetone;
the mass ratio of the dispersing agent to the gelling agent to the ZTA ceramic powder to the solvent is as follows; dispersing agent: gelling agent: ZTA ceramic powder: solvent = 7-20:1.5-3.5:65-90:170-190; the adding amount of the niobium oxide powder is 0.2-0.5wt% of the ZTA ceramic powder.
2. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: during the batching, nb is additionally introduced in an amount of 0.2-0.3%, preferably 0.25% of the mass of the ZTA ceramic particles 2 O 5 And (3) powder.
3. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: the concentration ratio of the sodium alginate in the ceramic slurry is 0.3-2.0wt%, preferably 0.8-1.2wt%, and more preferably 1wt%.
4. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: the ZTA ceramic raw material is powder with particle size not higher than 80 μm obtained by coprecipitation method, and contains 80wt% of Al 2 O 3 And 20wt% yttrium stabilized zirconia.
5. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: the ball milling of the ceramic slurry is carried out for 8-30 hours, preferably 8-12 hours, and more preferably 11-12 hours.
6. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: ball milling to obtain suspension, adjusting pH to 5.5-6.5 with acetic acid to make ceramic slurry have no suspended particles and no agglomeration phenomenon, and finally obtaining ceramic slurry with good fluidity to obtain standby slurry.
7. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: the liquid drops of the slurry are obtained by a syringe or extrusion ram, and the liquid gelling-reaction medium is a calcium chloride solution.
8. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: after filtering out the gel beads, the gel beads are washed with organic substances, preferably alcohols, and then treated with an acid solution. For industrial applications, ethanol is preferred for washing; treating the gel beads with 0.4-0.6mol/L acetic acid solution, preferably 0.5mol/L acetic acid solution for at least 15min;
the gel pellets are treated with an acid solution and sintered after drying, wherein the drying temperature is 75-85 ℃ and the drying time is 20-28h.
9. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: heating the dried ceramic particles to 1440-1450 ℃ at a heating rate of 1-10 ℃/min under the oxygen-containing atmosphere, and sintering to obtain the special-shaped ZTA particle ceramic;
preferably, the dried ceramic particles are sintered under air atmosphere in a pressureless way, and the ceramic particles are sintered under air atmosphere, wherein the ceramic particles are heated to 500 ℃ at a heating rate of 1.5 ℃/min for 1 hour, heated to 800 ℃ at a heating rate of 2 ℃/min, heated to a target temperature at a heating rate of 5 ℃/min for 1 hour, and cooled along with a furnace to obtain spherical ZTA ceramic particles.
10. The method for preparing the special-shaped ZTA ceramic particles according to claim 1, wherein the method comprises the following steps: the product is obtained in macroscopic dimensions, the dimensions of at least one dimension being in the order of millimeters or more. Preferably, the size is 2-2.5mm; the obtained special-shaped ZTA ceramic particles have no sharp macroscopic edges and corners, and the microhardness is 1700-1920HV.
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