CN120136545A - Zirconia composite ceramic microbeads and preparation method thereof - Google Patents
Zirconia composite ceramic microbeads and preparation method thereof Download PDFInfo
- Publication number
- CN120136545A CN120136545A CN202510622057.3A CN202510622057A CN120136545A CN 120136545 A CN120136545 A CN 120136545A CN 202510622057 A CN202510622057 A CN 202510622057A CN 120136545 A CN120136545 A CN 120136545A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- powder
- zirconia
- type silicon
- ceramic microbeads
- 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
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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- 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
-
- 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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
-
- 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
- C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
-
- 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
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
-
- 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
- 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
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Composite Materials (AREA)
Abstract
The invention discloses zirconia composite ceramic microbeads and a preparation method thereof, and belongs to the technical field of zirconia ceramic microbeads. The zirconia composite ceramic microbeads are prepared from 80-90 parts by mass of yttrium-stabilized tetragonal zirconia powder, 5-10 parts by mass of alumina powder and 5-10 parts by mass of silicon carbide composite powder. The invention takes yttrium stable tetragonal phase zirconia as a base material, and is supplemented with alumina and polycrystalline silicon carbide composite powder with multiple granularities, the overall wear resistance and corrosion resistance of the composite ceramic microbeads are improved by utilizing high wear-resistant and high corrosion-resistant silicon carbide powder, the Vickers hardness and strength of the zirconia composite ceramic microbeads are obviously improved after the silicon carbide composite powder is added, the wear rate is greatly reduced, and the mass loss rate after the strong acid solution is soaked is greatly reduced. The zirconia composite ceramic microbeads prepared by the method disclosed by the invention have the advantages of excellent wear resistance, good corrosion resistance, wide raw material sources, simple preparation method and good market prospect.
Description
Technical Field
The invention relates to the technical field of zirconia ceramic microbeads, in particular to a zirconia composite ceramic microbead and a preparation method thereof.
Background
The superfine grinding device is widely used in the fields of new energy battery materials, paint, coating and the like, and materials are crushed through various complex motions such as mutual collision and extrusion of grinding media, and in the use of the superfine grinding device, the selection of the grinding media is a very important problem, and the cost and the crushing efficiency in the crushing process and the quality of crushed products are determined. Common grinding media in the market include glass balls, steel balls, alumina balls, zirconia balls and the like. The zirconia ceramic microbeads are distinguished from a plurality of ceramic grinding media by the outstanding advantages of high strength, high hardness, excellent wear resistance, corrosion resistance and the like, are favored by the ceramic industry as high-end grinding materials, but the zirconia has relatively low hardness and poor acid corrosion resistance, so that the zirconia ceramic microbeads limit the application of the zirconia ceramic microbeads in the fields of high-hardness material grinding and acid material grinding.
In order to improve the overall performance of zirconia, researchers have made improvements accordingly. For example, CN112500834a discloses a zirconia composite grinding ball for grinding high purity zirconia powder and a preparation method thereof, the zirconia composite grinding ball is made by mixing yttrium stable tetragonal zirconia powder, monoclinic zirconia powder, superfine alumina powder and graphite powder according to a mass ratio of 60:10-30:1-20:1-5, the hardness of ceramic microbeads is improved by doping alumina powder with higher hardness into zirconia powder, however, although the hardness of alumina is higher than that of zirconia, the overall hardness of zirconia microbeads is improved to a limited extent under a certain doping amount, and the abrasion resistance and acid resistance of alumina are poor. CN116217270a discloses a process for producing diamond film coated medium balls on the surfaces of zirconia balls, which comprises the steps of mixing diamond micro powder with a composite binder to obtain diamond film coated powder and wetting zirconia balls with a wetting agent, uniformly mixing to form zirconia balls coated with the diamond film, and sintering to obtain the composite medium balls. However, this method did not test the wear and hardness of the composite media ball, and the impact resistance of the diamond film coating may limit the application of the composite media ball. In addition, the diamond micropowder used in the patent has a particle diameter d50≤200 nm, and the diamond powder with small particle diameter is difficult to obtain and has high cost, which may limit the large-scale application.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a zirconia composite ceramic microbead and a preparation method thereof.
As one aspect of the present invention, there is provided a method for preparing zirconia composite ceramic microbeads, comprising,
Mixing yttrium-stabilized tetragonal phase zirconium oxide, aluminum oxide and silicon carbide composite powder with water, and grinding to obtain slurry, wherein the mass ratio of the yttrium-stabilized tetragonal phase zirconium oxide to the silicon carbide composite powder is (80-90) (5-10);
Spraying and granulating the obtained slurry to form spherical particles;
forming spherical green bodies by adopting a rolling ball forming mode and spherical particles and glue;
Sintering the spherical green body to obtain zirconia composite ceramic microbeads;
the silicon carbide composite powder is prepared from silicon carbide powder with a crystal form of an alpha hexagonal structure and a beta cubic structure, wherein the mass ratio of the silicon carbide powder to the silicon carbide powder is (20-25) (70-78).
Preferably, the silicon carbide composite powder is formed by compositing A-type silicon carbide, B-type silicon carbide and C-type silicon carbide, wherein the crystal form of the A-type silicon carbide is of an alpha hexagonal structure, the median particle size is 0.6-0.8 mu m, the mass of the crystal form of the B-type silicon carbide accounts for 20% -25% of the total weight of the silicon carbide composite powder, the crystal form of the B-type silicon carbide is of a beta cubic structure, the median particle size of the crystal form of the B-type silicon carbide accounts for 0.3-0.5 mu m, the mass of the crystal form of the C-type silicon carbide accounts for 65% -75% of the total weight of the silicon carbide composite powder, the crystal form of the C-type silicon carbide is of a beta cubic structure, the median particle size of the C-type silicon carbide accounts for 50-90 nm, and the mass of the crystal form of the C-type silicon carbide composite powder accounts for 5% -10% of the total weight of the silicon carbide composite powder.
Preferably, the preparation method of the silicon carbide composite powder comprises the following steps of dispersing powder of A-type silicon carbide, B-type silicon carbide and C-type silicon carbide in ethanol to prepare slurry with solid content of 50%, placing the slurry into a roller mixer for 50-100 rpm to stir 2-3 h, and drying to obtain the silicon carbide composite powder.
Preferably, the mass parts of the yttrium-stabilized tetragonal phase zirconium oxide and the aluminum oxide are respectively (80-90): 5-10.
Preferably, the median particle size of the yttrium-stabilized tetragonal phase zirconia powder is 0.2-0.6 μm, and the median particle size of the alumina powder is 0.3-0.8 μm.
Preferably, the median particle diameter of the slurry is less than 0.5 mu m, and the solid content is 40% -60%.
Preferably, spray granulation is performed at a rotational speed of 9000 to 10000 rpm, an inlet temperature of 200 to 250 ℃, and an outlet temperature of 100 to 120 ℃.
Preferably, the sintering is carried out at a temperature of 1520-1600 ℃ for 1-3 hours.
Preferably, a polishing operation is also included after sintering is completed.
The invention further provides zirconia composite ceramic microbeads, which are prepared from 80-90 parts by mass of yttrium-stabilized tetragonal zirconia powder, 5-10 parts by mass of alumina powder and 5-10 parts by mass of silicon carbide composite powder.
Zirconia has three crystal structures, namely a cubic phase, a tetragonal phase and a monoclinic phase, under normal pressure. Under normal pressure and temperature, the stable crystal of zirconia is monoclinic phase, however, when the temperature of monoclinic zirconia is raised to 1170 ℃, it is converted into tetragonal zirconia, and volume shrinkage is caused as the phase change process occurs. When the temperature of tetragonal zirconia drops to 950 ℃, it will be converted to monoclinic zirconia, which will produce a volume expansion. In order to prevent the zirconia ceramic from cracking during sintering, the zirconia needs to be stabilized, and common stabilizers are yttria, ceria, magnesia, calcia and the like, and can replace the zirconia to form a substitutional solid solution to prevent the transformation of the crystal form. The yttrium stable tetragonal phase zirconia has the characteristics of good high temperature resistance, chemical corrosion resistance, wear resistance, oxidation resistance, high hardness and the like, and simultaneously has larger thermal expansion coefficient, smaller heat capacity and heat conductivity, so the yttrium stable tetragonal phase zirconia is used as a base material. Alumina has the characteristics of high hardness, high temperature stability, chemical stability and the like, but has low fracture toughness and poor wear resistance, and is used as an auxiliary material.
Silicon carbide is commonly used in the related fields of wear-resistant parts such as abrasive materials, mechanochemical sealing and the like because of stable chemical property, high heat conductivity coefficient, small thermal expansion coefficient and good wear resistance. Silicon carbide has a very high hardness, on the mohs scale 9.5, next to the hardest diamond in the world (10 scale). The silicon carbide has at least 70 crystal forms, and compared with the common crystal forms, the alpha-type silicon carbide mainly has a hexagonal/rhombohedral structure and the beta-type silicon carbide has a cubic structure, the alpha-type silicon carbide has high hardness, high wear resistance and high corrosion resistance, is a thermodynamically stable phase at high temperature, has higher surface energy and higher sintering activity, is easy to form a compact body at low temperature, and can be converted into the alpha-type silicon carbide at high temperature. In addition, silicon carbide powder can be classified into micron-sized, submicron-sized and nano-sized according to particle size, the smaller the particle size of the silicon carbide powder, the higher the sintering activity, the easier the agglomeration and the increase in cost. The A, B and C-type silicon carbide used in the patent are submicron (0.6-0.8 mu m) alpha-type, submicron (0.3-0.5 mu m) beta-type and nano (50-90 nm) beta-type silicon carbide powder respectively, the submicron alpha-type silicon carbide powder and the submicron beta-type silicon carbide powder are used as matrix materials, a small amount of nano beta-type silicon carbide powder is used as auxiliary materials to further improve sintering activity, and on the premise of not affecting the overall dispersibility of the powder, the silicon carbide composite powder with good sintering activity is formed, so that the composite ceramic microbeads formed by sintering the silicon carbide composite powder, zirconium oxide and aluminum oxide powder after being mixed are guaranteed to have the characteristics of high hardness, wear resistance, corrosion resistance and the like.
Further, the preparation method of the silicon carbide composite powder comprises the steps of,
Mixing the A-type, B-type and C-type silicon carbide powder according to the mass ratio of 20-25:65-75:5-10, dispersing in ethanol to prepare slurry with the solid content of 50%, placing the slurry into a roller mixer, stirring for 2-3 h, and continuously placing the slurry into an oven with the temperature of 80 ℃ for drying to obtain the silicon carbide composite powder.
Further, the median particle diameter of the yttrium-stabilized tetragonal phase zirconium oxide is 0.2-0.6 mu m, and the median particle diameter of the aluminum oxide is 0.3-0.8 mu m;
The invention also provides a preparation method of the zirconia composite ceramic microbeads, which comprises,
Mixing yttrium stable tetragonal phase zirconium oxide, aluminum oxide and silicon carbide composite powder with water, and grinding to obtain slurry;
Granulating the slurry by spraying to form spherical particle powder;
mixing and rolling spherical powder and glue (adhesive) to prepare a spherical green body in a rolling forming mode;
and sintering the spherical green body to obtain the zirconia composite ceramic microbeads.
In the invention, after yttrium-stabilized tetragonal zirconia, alumina, silicon carbide composite powder and water are mixed, a certain proportion of dispersing agent can be added during grinding, which is the conventional operation in the field, the types of the dispersing agent are not strictly limited, sodium polyacrylate, ammonium polyacrylate and the like can be adopted, and the addition amount can be 0.1-0.5% of the total mass of the slurry.
Further, the median particle diameter of the slurry is lower than 0.5 mu m, and the solid content is 40% -60%.
Further, spray granulation is performed at a rotational speed of 9000 to 10000 rpm, an inlet temperature of 200 to 250 ℃ and an outlet temperature of 100 to 120 ℃.
Further, the sintering is kept at 1500-1600 ℃ for 1-5 hours.
Further, a polishing operation is included after the sintering is completed.
Compared with the prior art, the invention has the following technical invention points:
The silicon carbide powder and the zirconia powder are compounded, and the overall hardness, the wear resistance and the corrosion resistance of the zirconia composite ceramic microbeads are improved through the high hardness, the high wear resistance and the high corrosion resistance of the silicon carbide, so that the application of the zirconia composite ceramic microbeads in the fields of high-hardness material grinding and acid material grinding is widened.
The silicon carbide composite powder is prepared by compounding silicon carbide powder of different crystal forms, the alpha silicon carbide powder has good hardness and wear resistance, but has lower sintering activity, the beta silicon carbide powder has high sintering activity and can be converted into alpha phase at high temperature, and the two silicon carbide powder are mixed in a proper proportion, so that the zirconia composite ceramic microbeads sintered at 1500-1600 ℃ are compact and have high hardness and high wear resistance.
The silicon carbide composite powder is prepared by compositing silicon carbide powder with specific granularity, submicron silicon carbide powder has good sintering activity and is easy to obtain, and nanometer silicon carbide powder has higher sintering activity, higher cost and easy agglomeration.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a flow chart of a method for preparing zirconia composite ceramic microbeads of the present invention;
FIG. 2 is a photograph showing a physical object of the zirconia composite ceramic microbead prepared in example 1 of the present invention;
FIG. 3 is a SEM photograph of zirconia composite ceramic beads prepared according to example 1 of the present invention;
FIG. 4 shows SEM photograph of zirconia composite ceramic microbeads prepared in example 2 of the present invention;
Fig. 5 shows SEM photographs of zirconia composite ceramic microbeads prepared in example 3 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
The examples and comparative examples of the present invention are described below using some of the raw materials:
Yttrium stable tetragonal phase zirconium oxide with median grain size of 0.5 μm, the sum of mass fraction of yttrium oxide and zirconium oxide being more than 99.5%, yttrium oxide being 5.4+ -0.2%, zirconium oxide being 94.6+ -0.2%, and co-precipitation method being adopted in Zhejiang Jingao company;
Alumina with a median particle size of 0.7 μm and a content of more than 99.9% is purchased from Shandong first Chemie Co., ltd;
the A-type silicon carbide powder has a median particle diameter of 0.8 mu m and an alpha-type crystal form. The median grain diameter of the B type silicon carbide powder is 0.5 mu m, and the crystal form is beta type. C-type silicon carbide powder with median diameter of 80 nm and beta-type crystal form. The three types of silicon carbide powder are purchased from Shaoxing crystal color technology Co.
Other raw materials not mentioned are common in the art, the above is only to help illustrate the present invention, and should not be construed as a strict limitation of the present invention, and those skilled in the art can directly purchase or prepare the same/similar raw materials themselves. These will not be described in detail in the embodiments.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1, a method for preparing zirconia composite ceramic microbeads, the steps are as follows,
S1, proportioning, namely weighing 80 kg yttrium stable tetragonal zirconia, 10 kg alumina, 10 kg silicon carbide composite powder and 100 kg water;
S2, ball milling pulping, namely adding yttrium stable tetragonal zirconia, alumina, silicon carbide composite powder and water into a ball milling tank, and performing ball milling to obtain slurry with the median particle diameter of 0.4 mu m and the solid content of 50%;
s3, spray granulation, namely, feeding the slurry into a spray granulation dryer, granulating at an inlet temperature of 230 ℃ and an outlet temperature of 110 ℃ at the rotational speed of a granulating tower atomizer of 9500 rpm, and obtaining spherical particles with good fluidity and diameter of 50 mu m;
s4, ball forming, namely spraying spherical particles and glue into a ball forming machine, and adjusting rolling time to form spherical green bodies with the median particle size of 1mm, wherein the spherical green bodies are 0.9-1.1 mm;
s5, sintering at a high temperature, namely transferring the spherical green body into an 1580 ℃ automatic kiln for heat preservation of 2h to obtain coarse materials;
S6, polishing the surface of the coarse material to reduce the surface roughness.
The preparation method of the silicon carbide composite powder comprises the steps of mixing 2.5 kg of A-type silicon carbide powder, 6.5 kg of B-type silicon carbide powder, 1 kg of C-type silicon carbide powder and 10 kg of ethanol, putting the mixture into a roller mixer, stirring the mixture for 2h under 100 rpm, and continuously putting the mixture into an oven at 80 ℃ for drying to obtain the silicon carbide composite powder.
Example 2, a method for preparing zirconia composite ceramic microbeads, the steps are as follows,
S1, proportioning, namely weighing 84 kg yttrium stable tetragonal zirconia, 10 kg alumina, 6 kg silicon carbide composite powder and 100 kg water;
S2, ball milling pulping, namely adding yttrium stable tetragonal zirconia, alumina, silicon carbide composite powder and water into a ball milling tank, and performing ball milling to obtain slurry with the median particle diameter of 0.4 mu m and the solid content of 50%;
s3, spray granulation, namely, feeding the slurry into a spray granulation dryer, granulating at an inlet temperature of 230 ℃ and an outlet temperature of 110 ℃ at the rotational speed of a granulating tower atomizer of 9500 rpm, and obtaining spherical particles with good fluidity and diameter of 50 mu m;
S4, ball forming, namely spraying spherical particles and glue into a ball forming machine to form a spherical green body with the diameter of 1 mm;
S5, sintering at a high temperature, namely transferring the spherical green body into an automatic kiln at 1520 ℃ for heat preservation of 2h to obtain coarse materials;
s6, polishing the surface of the coarse material.
The preparation method of the silicon carbide composite powder comprises the steps of mixing 1.5 kg of A-type silicon carbide powder, 3.9 kg of B-type silicon carbide powder, 0.6 kg of C-type silicon carbide powder and 6 kg of ethanol, putting the mixture into a roller mixer, stirring the mixture for 2h under 100 rpm, and continuously putting the mixture into an oven at 80 ℃ for drying to obtain the silicon carbide composite powder.
Example 3, a method for preparing zirconia composite ceramic microbeads, the steps are as follows,
S1, proportioning, namely weighing 80 kg yttrium stable tetragonal zirconia, 10 kg alumina, 10 kg silicon carbide composite powder and 100 kg water;
S2, ball milling pulping, namely adding yttrium stable tetragonal zirconia, alumina, silicon carbide composite powder and water into a ball milling tank, and performing ball milling to obtain slurry with the median particle diameter of 0.4 mu m and the solid content of 50%;
s3, spray granulation, namely, feeding the slurry into a spray granulation dryer, granulating at an inlet temperature of 230 ℃ and an outlet temperature of 110 ℃ at the rotational speed of a granulating tower atomizer of 9500 rpm, and obtaining spherical particles with good fluidity and diameter of 50 mu m;
S4, ball forming, namely spraying spherical particles and glue into a ball forming machine to form a spherical green body with the diameter of 1 mm;
s5, sintering at a high temperature, namely transferring the spherical green body into an automatic kiln at 1600 ℃ for heat preservation of 2h to obtain coarse materials;
s6, polishing the surface of the coarse material.
The preparation method of the silicon carbide composite powder comprises the steps of mixing 2 kg of A-type silicon carbide powder, 7.5 of kg of B-type silicon carbide powder, 0.5 of kg of C-type silicon carbide powder and 10 kg of ethanol, putting the mixture into a roller mixer, stirring the mixture under 80 rpm for 1.5 of h, and continuously putting the mixture into an oven at 80 ℃ for drying to obtain the silicon carbide composite powder.
Example 4, a method for preparing zirconia composite ceramic microbeads, the steps are as follows,
S1, proportioning, namely weighing 82 kg yttrium stable tetragonal zirconia, 10 kg alumina, 8 kg silicon carbide composite powder and 100 kg water;
S2, ball milling pulping, namely adding yttrium stable tetragonal zirconia, alumina, silicon carbide composite powder and water into a ball milling tank, and performing ball milling to obtain slurry with the median particle diameter of 0.4 mu m and the solid content of 50%;
s3, spray granulation, namely, feeding the slurry into a spray granulation dryer, granulating at an inlet temperature of 230 ℃ and an outlet temperature of 110 ℃ at the rotational speed of a granulating tower atomizer of 9500 rpm, and obtaining spherical particles with good fluidity and diameter of 50 mu m;
S4, ball forming, namely spraying spherical particles and glue into a ball forming machine to form a spherical green body with the diameter of 1 mm;
s5, sintering at a high temperature, namely transferring the spherical green body into an automatic kiln at 1560 ℃ for heat preservation of 2h to obtain coarse materials;
s6, polishing the surface of the coarse material.
The preparation method of the silicon carbide composite powder comprises the steps of mixing 1.6 kg of A-type silicon carbide powder, 5.6 kg of B-type silicon carbide powder, 0.8 kg of C-type silicon carbide powder and 8 kg of ethanol, then placing the mixture into a roller mixer, stirring 1.5 h under 100 rpm, and continuously placing into an 80-DEG C oven for drying to obtain the silicon carbide composite powder.
Comparative example 1, a method for preparing zirconia composite ceramic microbeads, was substantially the same as example 1, except that the silicon carbide composite powder was prepared by the following method,
Mixing 2.5 kg of A-type silicon carbide powder, 7.5 of kg of B-type silicon carbide powder and 10 kg of ethanol, putting the mixture into a roller mixer, stirring the mixture under 100 rpm for 2h, and continuously putting the mixture into an 80 ℃ oven for drying to obtain the silicon carbide composite powder.
Comparative example 2, a method for preparing zirconia composite ceramic microbeads, was substantially the same as example 1, except that the silicon carbide composite powder was prepared by the following method,
Mixing 2.5 kg of A-type silicon carbide powder, 7.5 of kg of C-type silicon carbide powder and 10 kg of ethanol, putting the mixture into a roller mixer, stirring the mixture under 100 rpm for 2h, and continuously putting the mixture into an 80 ℃ oven for drying to obtain the silicon carbide composite powder.
Comparative example 3, a method for preparing zirconia composite ceramic microbeads, was basically the same as example 1, except that the method for preparing silicon carbide composite powder was,
Mixing 10 kg of A-type silicon carbide powder and 10 kg of ethanol, putting the mixture into a roller mixer, stirring the mixture under the condition of 100 rpm for 2h, and continuously putting the mixture into an 80 ℃ oven for drying to obtain the silicon carbide composite powder.
Comparative example 4, a method for preparing zirconia composite ceramic microbeads, was basically the same as example 1, except that the method for preparing silicon carbide composite powder was,
Mixing 9 kg type B silicon carbide powder, 1kg of C type silicon carbide powder and 10 kg ethanol, putting the mixture into a roller mixer, stirring for 2h under the condition of 100 rpm, and continuously putting into an 80 ℃ oven for drying to obtain the silicon carbide composite powder.
Comparative example 5, a method for preparing zirconia composite ceramic microbeads, the steps are as follows,
S1, proportioning, namely weighing 90 kg yttrium stable tetragonal phase zirconium oxide, 10 kg aluminum oxide and 100 kg water;
S2, ball milling pulping, namely adding yttrium stable tetragonal zirconia, alumina and water into a ball milling tank, and performing ball milling to obtain slurry with the median particle size of 0.4 mu m and the solid content of 50%;
s3, spray granulation, namely, feeding the slurry into a spray granulation dryer, granulating at an inlet temperature of 230 ℃ and an outlet temperature of 110 ℃ at the rotational speed of a granulating tower atomizer of 9500 rpm, and obtaining spherical particles with good fluidity and diameter of 50 mu m;
S4, ball forming, namely spraying spherical particles and glue into a ball forming machine to form a spherical green body with the diameter of 1 mm;
s5, sintering at a high temperature, namely transferring the spherical green body into a 1450 ℃ automatic kiln for heat preservation of 2h to obtain coarse materials;
s6, polishing the surface of the coarse material.
The zirconia composite ceramic microbeads prepared in all examples and comparative examples were subjected to density, hardness and self-abrasion tests with reference to standard JC/T2136-2012 microcrystalline zirconia grinding media ball, used for grinding high-purity zirconia powder, detecting the zirconia content finally introduced by a belt mill, namely the abrasion loss, and tested for the crush strength by a crush strength tester. The quality loss rate of the zirconia composite ceramic microbeads prepared in all examples and comparative examples after being soaked in 10% sulfuric acid is tested by referring to national standard GB/T4738-2015 method for measuring acid and alkali resistance of domestic ceramic materials. The results are shown in Table 1,
TABLE 1 test results of zirconia composite ceramic microbeads
,
As can be seen from the test results in Table 1, the zirconia composite ceramic microbeads prepared in examples 1 to 4 of the present invention have suitable density, higher hardness and crush strength, lower self-abrasion and abrasion loss, and lower acid foam mass loss rate, and exhibit high hardness, high strength, high abrasion resistance and high corrosion resistance. In comparative example 1, the sintering activity of the composite silicon carbide ceramic powder is reduced without the auxiliary sintering of the C-type nano silicon carbide powder, and the sintering density of the ceramic microbeads is reduced, so that the density, the strength, the wear resistance and the corrosion resistance of the ceramic microbeads are reduced. In comparative example 2, too much C-type nano silicon carbide powder is used, the composite silicon carbide ceramic powder is agglomerated, and the sintering density of the ceramic microbeads and the dispersion uniformity of the silicon carbide phase in the composite ceramic microbeads are also affected, so that the overall wear resistance, hardness, strength and corrosion resistance of the composite ceramic microbeads are reduced. In comparative example 3, only the A-type silicon carbide powder is used, the A-type silicon carbide powder has higher hardness, but has poorer sintering activity, and the sintering density of the composite ceramic microbeads is reduced, but the influence of the hardness is smaller, and the overall density, the wear resistance, the strength and the corrosion resistance of the composite ceramic microbeads are reduced. Comparative example 4 used only type B and type C silicon carbide powders, which had relatively high sintering activity, but required complete conversion to the alpha phase at high temperature to exhibit corrosion resistance and wear resistance, and the sintering process used in this patent did not ensure complete conversion in order not to affect the sintering of zirconia, so that the hardness, wear resistance and corrosion resistance of the final composite ceramic microbead could not achieve the desired effects. Comparative example 5 was compounded without the addition of silicon carbide powder, and the alumina zirconia composite ceramic microbeads had higher density and acceptable wear resistance, but had very low hardness and poor corrosion resistance.
It should be noted that the foregoing description is only a preferred embodiment of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood that modifications, equivalents, improvements and modifications to the technical solution described in the foregoing embodiments may occur to those skilled in the art, and all modifications, equivalents, and improvements are intended to be included within the spirit and principle of the present invention.
Claims (9)
1.A method for preparing zirconia composite ceramic microbeads is characterized by comprising the following steps of,
Mixing yttrium-stabilized tetragonal phase zirconium oxide, aluminum oxide and silicon carbide composite powder with water, and grinding to obtain slurry, wherein the mass ratio of the yttrium-stabilized tetragonal phase zirconium oxide to the silicon carbide composite powder is (80-90) (5-10);
Spraying and granulating the obtained slurry to form spherical particles;
forming spherical green bodies by adopting a rolling ball forming mode and spherical particles and glue;
Sintering the spherical green body to obtain zirconia composite ceramic microbeads;
the silicon carbide composite powder is prepared from silicon carbide powder with a crystal form of an alpha hexagonal structure and a beta cubic structure, wherein the mass ratio of the silicon carbide powder to the silicon carbide powder is (20-25) (70-78).
2. The preparation method of the zirconia composite ceramic microbeads is characterized in that the silicon carbide composite powder is formed by compositing A-type silicon carbide, B-type silicon carbide and C-type silicon carbide, wherein the crystal form of the A-type silicon carbide is of an alpha hexagonal structure, the median particle size is 0.6-0.8 mu m, the mass of the crystal form of the B-type silicon carbide accounts for 20% -25% of the total weight of the silicon carbide composite powder, the crystal form of the B-type silicon carbide is of a beta cubic structure, the median particle size is 0.3-0.5 mu m, the mass of the crystal form of the C-type silicon carbide accounts for 65% -75% of the total weight of the silicon carbide composite powder, the crystal form of the C-type silicon carbide is of a beta cubic structure, the median particle size of the C-type silicon carbide is 50-90 nm, and the mass of the crystal form of the C-type silicon carbide composite powder accounts for 5% -10% of the total weight of the silicon carbide composite powder.
3. The method for preparing the zirconia composite ceramic microbeads according to claim 1 or 2, wherein the preparation method comprises the following steps of dispersing powder of A-type silicon carbide, B-type silicon carbide and C-type silicon carbide in ethanol to prepare slurry with the solid content of 50%, placing the slurry into a roller mixer, stirring for 2-3 h by 50-100 rpm, and drying to obtain the silicon carbide composite powder.
4. The method for preparing the zirconia composite ceramic microbeads according to claim 1 or 2, wherein the mass parts of yttrium-stabilized tetragonal zirconia and alumina are respectively (80-90): (5-10).
5. The method for preparing zirconia composite ceramic microbeads according to claim 1 or 2, wherein the median particle size of the yttrium-stabilized tetragonal zirconia powder is 0.2-0.6 μm, and the median particle size of the alumina powder is 0.3-0.8 μm.
6. The method for preparing zirconia composite ceramic microbeads according to claim 1, wherein the median particle size of the slurry is less than 0.5 μm, and the solid content is 40% -60%.
7. The method for preparing zirconia composite ceramic microbeads according to claim 1, wherein spray granulation is performed at a rotation speed of 9000-10000 rpm, an inlet temperature of 200-250 ℃ and an outlet temperature of 100-120 ℃.
8. The method for preparing the zirconia composite ceramic microbeads according to claim 1, wherein the sintering is carried out at 1520-1600 ℃ for 1-3 hours.
9. The method for preparing zirconia composite ceramic microbeads according to claim 1, further comprising a polishing operation after sintering is completed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510622057.3A CN120136545B (en) | 2025-05-15 | 2025-05-15 | Zirconia composite ceramic microbeads and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510622057.3A CN120136545B (en) | 2025-05-15 | 2025-05-15 | Zirconia composite ceramic microbeads and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN120136545A true CN120136545A (en) | 2025-06-13 |
| CN120136545B CN120136545B (en) | 2025-08-01 |
Family
ID=95959824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202510622057.3A Active CN120136545B (en) | 2025-05-15 | 2025-05-15 | Zirconia composite ceramic microbeads and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN120136545B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120463493A (en) * | 2025-07-09 | 2025-08-12 | 浙江金琨西立锆珠有限公司 | Composite rare earth oxide co-stabilized zirconia ceramic microbeads and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0263033A2 (en) * | 1986-10-02 | 1988-04-06 | Ceramiques Techniques Desmarquest, S.A. | Method of making composite articles containing a ceramic matrix reinforced by zirconia particles and optionally by monocrystalline silicon carbide fibres, and articles obtained thereby |
| US4891341A (en) * | 1985-09-20 | 1990-01-02 | Ceramatec, Inc. | Fine-grained ceramics and method for making the same |
| JPH03223158A (en) * | 1990-01-29 | 1991-10-02 | Tokai Carbon Co Ltd | Manufacturing method of high strength, high toughness silicon carbide reinforced alumina-zirconia ceramic material |
| US5851943A (en) * | 1994-06-03 | 1998-12-22 | Industrial Research Limited | Ceramic production process |
| WO2001098207A1 (en) * | 2000-06-19 | 2001-12-27 | Corning Incorporated | Plasticizable mixture and method of using |
| US20040023788A1 (en) * | 2002-07-30 | 2004-02-05 | Kennametal Inc. | Ceramic body reinforced with coarse silicon carbide whiskers and method for making the same |
| WO2021116348A1 (en) * | 2019-12-11 | 2021-06-17 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Ceramic sensor |
| CN113402263A (en) * | 2021-07-02 | 2021-09-17 | 海南大学 | Alumina-based composite ceramic and preparation method thereof |
| CN113683435A (en) * | 2021-10-08 | 2021-11-23 | 江西信达航科新材料科技有限公司 | Preparation method of multiphase composite reinforced silicon carbide ceramic |
| CN119683996A (en) * | 2025-01-06 | 2025-03-25 | 浙江金琨西立锆珠有限公司 | Composite zirconia ceramic microbead and preparation method thereof |
| CN119874371A (en) * | 2024-12-11 | 2025-04-25 | 襄阳五二五泵业有限公司 | Sintered ceramic material for industrial slurry pump and preparation method thereof |
-
2025
- 2025-05-15 CN CN202510622057.3A patent/CN120136545B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4891341A (en) * | 1985-09-20 | 1990-01-02 | Ceramatec, Inc. | Fine-grained ceramics and method for making the same |
| EP0263033A2 (en) * | 1986-10-02 | 1988-04-06 | Ceramiques Techniques Desmarquest, S.A. | Method of making composite articles containing a ceramic matrix reinforced by zirconia particles and optionally by monocrystalline silicon carbide fibres, and articles obtained thereby |
| JPH03223158A (en) * | 1990-01-29 | 1991-10-02 | Tokai Carbon Co Ltd | Manufacturing method of high strength, high toughness silicon carbide reinforced alumina-zirconia ceramic material |
| US5851943A (en) * | 1994-06-03 | 1998-12-22 | Industrial Research Limited | Ceramic production process |
| WO2001098207A1 (en) * | 2000-06-19 | 2001-12-27 | Corning Incorporated | Plasticizable mixture and method of using |
| US20040023788A1 (en) * | 2002-07-30 | 2004-02-05 | Kennametal Inc. | Ceramic body reinforced with coarse silicon carbide whiskers and method for making the same |
| WO2021116348A1 (en) * | 2019-12-11 | 2021-06-17 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Ceramic sensor |
| CN113402263A (en) * | 2021-07-02 | 2021-09-17 | 海南大学 | Alumina-based composite ceramic and preparation method thereof |
| CN113683435A (en) * | 2021-10-08 | 2021-11-23 | 江西信达航科新材料科技有限公司 | Preparation method of multiphase composite reinforced silicon carbide ceramic |
| CN119874371A (en) * | 2024-12-11 | 2025-04-25 | 襄阳五二五泵业有限公司 | Sintered ceramic material for industrial slurry pump and preparation method thereof |
| CN119683996A (en) * | 2025-01-06 | 2025-03-25 | 浙江金琨西立锆珠有限公司 | Composite zirconia ceramic microbead and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 柴建龙;郭亚威;朱亚滨;李淑芬;申铁龙;姚存峰;崔明焕;王志光;: "SiC含量对ZTA和ATZ复相陶瓷力学及热学性能的影响", 陶瓷学报, no. 02, 18 April 2019 (2019-04-18) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120463493A (en) * | 2025-07-09 | 2025-08-12 | 浙江金琨西立锆珠有限公司 | Composite rare earth oxide co-stabilized zirconia ceramic microbeads and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN120136545B (en) | 2025-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN120136545B (en) | Zirconia composite ceramic microbeads and preparation method thereof | |
| CN104829218B (en) | Bimodal active alumina micropowder and preparation method | |
| CN108546118B (en) | Yttria-stabilized zirconia powder, preparation method thereof and ceramic | |
| CN107459357A (en) | Silicon carbide composite powder body and its preparation method and application | |
| CN101117673A (en) | Preparation method of cemented carbide containing plate-like tungsten carbide grains | |
| CN109054452A (en) | Copper-chromium black pigment and preparation method thereof | |
| CN102311114A (en) | Preparation method of nanometer tungsten carbide | |
| CN106244970A (en) | Hot spray powder and preparation method thereof | |
| CN114988886A (en) | Preparation method of high-purity alpha-alumina powder capable of being sintered at low temperature | |
| CN112209419A (en) | Preparation method of spherical yttrium oxide powder for high apparent density thermal spraying | |
| CN113620328B (en) | Preparation method of nano alumina seed crystal and preparation method of high-purity alumina nanocrystalline | |
| CN105819833A (en) | Preparation method of self-sharpening microcrystalline alumina ceramic abrasive particles | |
| CN112723882A (en) | Gadolinium zirconate thermal barrier coating ceramic granulation powder for atmospheric plasma spraying and preparation method and application thereof | |
| CN101279840A (en) | A kind of preparation method of aluminum oxide-tungsten carbide titanium nanocomposite ceramic material | |
| CN112194491A (en) | Pressureless sintering boron carbide ceramic powder and preparation method and application thereof | |
| US11472743B2 (en) | Sintered zircon beads | |
| CN111072375A (en) | Preparation method of aluminum oxide grinding balls | |
| CN110078120B (en) | Preparation method of yttria-stabilized zirconia powder based on supercritical dispersion roasting | |
| CN119683996A (en) | Composite zirconia ceramic microbead and preparation method thereof | |
| CN114853021B (en) | Nanometer tungsten carbide powder and preparation method thereof | |
| CN100590097C (en) | Method for making low-cost zirconia ceramic grinding media | |
| CN108017388B (en) | Lanthanum zirconate-based ceramic granulated powder for atmospheric plasma spraying and preparation method thereof | |
| CN117845086B (en) | Binding phase-free superfine hard alloy and preparation method thereof | |
| CN111662578B (en) | Preparation process of spherical chromium oxide composite agglomerated powder and product prepared by preparation process | |
| CN118421113B (en) | A rare earth-doped alumina titanium spraying material, its coating and preparation method |
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 |