CN110372376B - High-strength refractory material and preparation method thereof - Google Patents

High-strength refractory material and preparation method thereof Download PDF

Info

Publication number
CN110372376B
CN110372376B CN201910826276.8A CN201910826276A CN110372376B CN 110372376 B CN110372376 B CN 110372376B CN 201910826276 A CN201910826276 A CN 201910826276A CN 110372376 B CN110372376 B CN 110372376B
Authority
CN
China
Prior art keywords
parts
powder
refractory material
oxide powder
particle size
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.)
Active
Application number
CN201910826276.8A
Other languages
Chinese (zh)
Other versions
CN110372376A (en
Inventor
袁武
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zibo Longcheng refractory Co.,Ltd.
Original Assignee
Zibo Longcheng Refractory Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zibo Longcheng Refractory Co ltd filed Critical Zibo Longcheng Refractory Co ltd
Priority to CN201910826276.8A priority Critical patent/CN110372376B/en
Publication of CN110372376A publication Critical patent/CN110372376A/en
Application granted granted Critical
Publication of CN110372376B publication Critical patent/CN110372376B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—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
    • C04B35/482—Refractories from grain sized mixtures
    • 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
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—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
    • C04B2235/3248—Zirconates or hafnates, e.g. zircon
    • 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
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3886—Refractory metal nitrides, e.g. vanadium nitride, tungsten nitride
    • 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
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Products (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention provides a high-strength refractory material and a preparation method thereof; the high-strength refractory material comprises the following components in parts by mass: 72-90 parts of zirconium oxide powder, 15-20 parts of zirconium nitride powder, 12-28 parts of hafnium oxide powder, 8-16 parts of barium hafnate powder, 6-9 parts of neodymium oxide powder, 24-48 parts of bauxite and 15-25 parts of a binding agent. The high-strength refractory material provided by the invention has excellent permeation resistance and corrosion resistance, and simultaneously shows good thermal shock resistance, particularly, the high-temperature rupture strength and compressive strength of the high-strength refractory material are obviously superior to those of a commercially available zirconia refractory material, so that the use requirements of the refractory material under various working conditions can be met, and the service life of the refractory material is greatly prolonged. In addition, the preparation method of the high-strength refractory material also has the advantages of low temperature required by heat treatment, short time consumption, easy operation and the like. Therefore, the high-strength refractory material and the preparation method thereof have wide application prospects.

Description

High-strength refractory material and preparation method thereof
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a high-strength refractory material and a preparation method thereof.
Background
Zirconium dioxide (i.e. zirconia, ZrO) is well known2) Odorless, tasteless, white heavy amorphous powder. The zirconium oxide is slightly soluble in hydrochloric acid and nitric acid, slowly soluble in hydrofluoric acid and almost insoluble in water; its relative density is 5.85, melting point 2680 deg.C, boiling point 4300 deg.C, and its hardness is inferior to diamond. Based on the above characteristics, zirconia is widely used for the production of various commercially available refractory materials.
However, the conventional zirconia-based refractory material often has defects such as low compressive strength and low flexural strength, and thus cannot achieve the universality of industrial application.
In the prior art, for example, chinese patent CN1294104C owned by saint gobain european design research center discloses a high zirconia content fused cast refractory material consisting of, on an oxide basis:
ZrO2greater than 92% by weight
SiO2: 2-8% by weight
Na2O: 0.12 to 1% by weight
Al2O3: 0.2 to 2% by weight
Y is not less than 0.5 wt%2O3CaO < 2.6 wt.%, provided that Y2O3: 0.3 to 2wt%, or with the proviso that CaO: 0.5-1.93 wt%.
As another example, chinese patent application CN109626993A provides a zirconia refractory material comprising the following components: 50-55% of electric melting monoclinic zirconia, 6-9% of dead burned magnesia fine powder, 8-12% of metal aluminum powder, 2-6% of yttrium oxide, 1-5% of barium oxide, 2-6% of phenolic-butyronitrile type thermoplastic phenolic resin and the balance of hexamethylenetetramine. Although the fracture toughness and the strength of the zirconia refractory provided by CN109626993A are improved, the fracture toughness and the strength of the zirconia refractory do not reach the standard of practical popularization and application.
Disclosure of Invention
In order to solve the above technical problems in the prior art, the inventors have developed and prepared a completely new zirconia-based refractory. The new zirconia refractory material is easy to prepare and mold, has the advantages of few appearance defects and high yield, and shows higher compressive strength and rupture strength, thereby having longer service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a high-strength refractory material, which comprises the following components in parts by mass:
72-90 parts of zirconium oxide powder
15-20 parts of zirconium nitride powder
12-28 parts of hafnium oxide powder
8-16 parts of barium hafnate powder
6-9 parts of neodymium oxide powder
24-48 parts of bauxite
15-25 parts of a binding agent.
Preferably, in the high-strength refractory material, the mass parts of the components are as follows:
76-85 parts of zirconium oxide powder
16-18 parts of zirconium nitride powder
17-24 parts of hafnium oxide powder
10-13 parts of barium hafnate powder
7-9 parts of neodymium oxide powder
30-44 parts of bauxite
18-21 parts of a binding agent.
It is worth supplementing and explaining that the zirconium nitride (NZr) powder has high purity, small particle size, large specific surface area and high surface activity; NZr is a refractory hard compound with high decomposition temperature and good chemical stability, soThe high-temperature resistance, corrosion resistance and wear resistance of the high-strength refractory material can be improved by adding the NZr, so that the NZr can be used as one of high-temperature structural raw materials in the technical scheme provided by the invention. Nanoscale hafnium oxide (HfO)2) The powder has three crystal structures of monoclinic, tetragonal and cubic, and is matched with the zirconia powder in the specific proportion, so that the finished product rate is unexpectedly improved, and appearance defects such as bubbles, cracks and the like in the material are reduced. The inventor surprisingly finds that the use of the nano-sized barium hafnate powder is beneficial to improving the compactness of the refractory material, so that the nano-sized barium hafnate powder is taken as one of the high-temperature structural raw materials in the technical scheme provided by the invention. In addition, a small amount of neodymium oxide (Nd)2O3) As a rare earth metal oxide, its addition promotes the high temperature resistance of the finished product and reduces the time consumed by heat treatment to some extent.
Preferably, in the high-strength refractory, the zirconia powder has an average particle size of 20 to 32 μm, the zirconium nitride powder has an average particle size of 40 to 60 μm, the hafnium oxide powder has an average particle size of 50 to 65nm, the barium hafnate powder has an average particle size of 70 to 80nm, and the neodymium oxide powder has an average particle size of 12 to 25 μm.
Preferably, in the above high-strength refractory, in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles having a particle size of less than 300 μm and not less than 160 μm, and 25-45 wt% of particles having a particle size of less than 160 μm and not less than 40 μm.
Preferably, in the high-strength refractory material, the binder is a thermosetting phenolic resin, and the carbon residue rate of the thermosetting phenolic resin is not less than 60%.
Further preferably, in the above high-strength refractory, the raw materials for preparing the thermosetting phenol resin include: o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde.
Still more preferably, in the high-strength refractory, a molar ratio of the o-phenylphenol, the o-ethylphenol, the p-ethylphenol, and the formaldehyde is (1 to 2): (4-5): (2-5): (9-18).
It is worth pointing out that the experiment proves that the use of the thermosetting phenolic resin as the binding agent not only is beneficial to the binding of the various powder raw materials, but also obviously reduces the temperature required by the heat treatment.
Meanwhile, a second aspect of the present invention provides a method for preparing the high-strength refractory material according to the first aspect, comprising the steps of:
s1: adding the zirconium oxide powder, the zirconium nitride powder, the hafnium oxide powder, the barium hafnate powder, the neodymium oxide powder and a first part of the binding agent into a mixing and grinding machine, and mixing and grinding for 5-10 minutes;
s2: adding the bauxite and the rest of the second part of the bonding agent into the mixing and grinding machine, and mixing and grinding for 15-30 minutes to obtain a mixture;
s3: pressing the mixture under the pressure of 90-120 MPa for molding, and drying at the temperature of 130-180 ℃ for 24-36 hours to obtain a dried blank;
s4: and (3) placing the dried blank in a sintering furnace, introducing nitrogen, performing heat treatment, and naturally cooling along with the furnace to obtain the high-strength refractory material.
Preferably, in the above preparation method, the mass ratio of the first part of the binding agent in S1 to the second part of the binding agent in S2 is 3: 2. experimental analysis proves that the batch addition of the binding agent is beneficial to full contact and mutual adhesion of various powder raw materials.
Preferably, in the above preparation method, the heat treatment in S4 is: preserving the heat for 5-7 hours at the temperature of 1150-1450 ℃.
Therefore, the preparation method has simple steps, is easy to operate and is suitable for large-scale industrial production.
In summary, compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
through detection, the high-strength refractory material disclosed by the invention has excellent permeation resistance and corrosion resistance, and simultaneously shows good thermal shock resistance, particularly, the high-temperature rupture strength and compressive strength of the high-strength refractory material are obviously superior to those of a commercially available zirconia refractory material, so that the use requirements of the refractory material under various working conditions can be met, and the service life of the refractory material is greatly prolonged. In addition, the preparation method of the high-strength refractory material also has the advantages of low temperature required by heat treatment, short time consumption, easy operation and the like.
Therefore, the high-strength refractory material and the preparation method thereof have wide application prospects.
Detailed Description
The high-strength refractory according to the first aspect of the present invention is composed of the following components in parts by mass:
76-85 parts of zirconium oxide powder
16-18 parts of zirconium nitride powder
17-24 parts of hafnium oxide powder
10-13 parts of barium hafnate powder
7-9 parts of neodymium oxide powder
30-44 parts of bauxite
18-21 parts of a binding agent.
In a preferred embodiment, the average particle size of the zirconium oxide powder is 20 to 32 μm, the average particle size of the zirconium nitride powder is 40 to 60 μm, the average particle size of the hafnium oxide powder is 50 to 65nm, the average particle size of the barium hafnate powder is 70 to 80nm, and the average particle size of the neodymium oxide powder is 12 to 25 μm.
In a preferred embodiment, in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles having a particle size of less than 300 μm and not less than 160 μm, and 25-45 wt% of particles having a particle size of less than 160 μm and not less than 40 μm.
In a preferred embodiment, the binding agent is thermosetting phenolic resin, and the residual carbon rate of the thermosetting phenolic resin is more than or equal to 60%.
In a further preferred embodiment, the raw materials for preparing the thermosetting phenolic resin comprise: o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde.
In a further preferred embodiment, the molar ratio of the o-phenylphenol, the o-ethylphenol, the p-ethylphenol and the formaldehyde is (1-2): (4-5): (2-5): (9-18).
The method for producing the high-strength refractory according to the second aspect of the present invention comprises the steps of:
s1: adding the zirconium oxide powder, the zirconium nitride powder, the hafnium oxide powder, the barium hafnate powder, the neodymium oxide powder and a first part of the binding agent into a mixing and grinding machine, and mixing and grinding for 5-10 minutes;
s2: adding the bauxite and the rest of the second part of the bonding agent into the mixing and grinding machine, and mixing and grinding for 15-30 minutes to obtain a mixture;
s3: pressing the mixture under the pressure of 90-120 MPa for molding, and drying at the temperature of 130-180 ℃ for 24-36 hours to obtain a dried blank;
s4: and (3) placing the dried blank in a sintering furnace, introducing nitrogen, performing heat treatment, and naturally cooling along with the furnace to obtain the high-strength refractory material.
In a preferred embodiment, the mass ratio of the first portion of the binding agent in S1 to the second portion of the binding agent in S2 is 3: 2.
in a preferred embodiment, the heat treatment in S4 is: preserving the heat for 5-7 hours at the temperature of 1150-1450 ℃.
The present invention will be described in detail and specifically with reference to the following examples so that the present invention may be better understood, but the following examples do not limit the scope of the present invention.
Example 1
The high-strength refractory material is prepared according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder, neodymium oxide powder and a first part of binding agent into a mixing and grinding machine, and mixing and grinding for 8 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 30 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under the pressure of 90MPa to form, and drying at the temperature of 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, keeping the temperature at 1400 ℃ for 7 hours, and naturally cooling along with the furnace to obtain the high-strength refractory material.
The raw materials comprise the following components in parts by mass:
72 parts of zirconium oxide powder
16 parts of zirconium nitride powder
14 parts of hafnium oxide powder
8 parts of barium hafnate powder
Neodymium oxide powder 6 parts
Bauxite 25 parts
17 parts of a binding agent;
the average particle size of the zirconium oxide powder is 25 micrometers, the average particle size of the zirconium nitride powder is 40 micrometers, the average particle size of the hafnium oxide powder is 50nm, the average particle size of the barium hafnate powder is 80nm, and the average particle size of the neodymium oxide powder is 25 micrometers; in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles with the particle size of less than 300 mu m and more than or equal to 160 mu m, and 25-45 wt% of particles with the particle size of less than 160 mu m and more than or equal to 40 mu m;
wherein the binding agent is thermosetting phenolic resin which is prepared from o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde (the molar ratio is 1: 4: 5: 16), and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60%.
Example 2
The high-strength refractory material is prepared according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder, neodymium oxide powder and a first part of binding agent into a mixing and grinding machine, and mixing and grinding for 8 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 30 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under the pressure of 90MPa to form, and drying at the temperature of 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, keeping the temperature at 1400 ℃ for 6 hours, and naturally cooling along with the furnace to obtain the high-strength refractory material.
The raw materials comprise the following components in parts by mass:
76 parts of zirconium oxide powder
16 parts of zirconium nitride powder
19 parts of hafnium oxide powder
10 parts of barium hafnate powder
Neodymium oxide powder 7 parts
Bauxite 33 parts
18 parts of a binding agent;
the average particle size of the zirconium oxide powder is 25 micrometers, the average particle size of the zirconium nitride powder is 40 micrometers, the average particle size of the hafnium oxide powder is 50nm, the average particle size of the barium hafnate powder is 80nm, and the average particle size of the neodymium oxide powder is 25 micrometers; in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles with the particle size of less than 300 mu m and more than or equal to 160 mu m, and 25-45 wt% of particles with the particle size of less than 160 mu m and more than or equal to 40 mu m;
wherein the binding agent is thermosetting phenolic resin which is prepared from o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde (the molar ratio is 1: 4: 5: 16), and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60%.
Example 3
The high-strength refractory material is prepared according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder, neodymium oxide powder and a first part of binding agent into a mixing and grinding machine, and mixing and grinding for 8 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 30 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under the pressure of 90MPa to form, and drying at the temperature of 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, keeping the temperature at 1400 ℃ for 6 hours, and naturally cooling along with the furnace to obtain the high-strength refractory material.
The raw materials comprise the following components in parts by mass:
80 parts of zirconia powder
18 parts of zirconium nitride powder
20 parts of hafnium oxide powder
11 parts of barium hafnate powder
Neodymium oxide powder 8 parts
Bauxite 36 parts
19 parts of a binding agent;
the average particle size of the zirconium oxide powder is 25 micrometers, the average particle size of the zirconium nitride powder is 40 micrometers, the average particle size of the hafnium oxide powder is 50nm, the average particle size of the barium hafnate powder is 80nm, and the average particle size of the neodymium oxide powder is 25 micrometers; in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles with the particle size of less than 300 mu m and more than or equal to 160 mu m, and 25-45 wt% of particles with the particle size of less than 160 mu m and more than or equal to 40 mu m;
wherein the binding agent is thermosetting phenolic resin which is prepared from o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde (the molar ratio is 1: 4: 5: 16), and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60%.
Example 4
The high-strength refractory material is prepared according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder, neodymium oxide powder and a first part of binding agent into a mixing and grinding machine, and mixing and grinding for 8 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 30 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under the pressure of 90MPa to form, and drying at the temperature of 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, keeping the temperature at 1400 ℃ for 6 hours, and naturally cooling along with the furnace to obtain the high-strength refractory material.
The raw materials comprise the following components in parts by mass:
84 parts of zirconium oxide powder
18 parts of zirconium nitride powder
24 parts of hafnium oxide powder
13 parts of barium hafnate powder
Neodymium oxide powder 9 parts
Bauxite 42 parts
21 parts of a binding agent;
the average particle size of the zirconium oxide powder is 25 micrometers, the average particle size of the zirconium nitride powder is 40 micrometers, the average particle size of the hafnium oxide powder is 50nm, the average particle size of the barium hafnate powder is 80nm, and the average particle size of the neodymium oxide powder is 25 micrometers; in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles with the particle size of less than 300 mu m and more than or equal to 160 mu m, and 25-45 wt% of particles with the particle size of less than 160 mu m and more than or equal to 40 mu m;
wherein the binding agent is thermosetting phenolic resin which is prepared from o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde (the molar ratio is 1: 4: 5: 16), and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60%.
Example 5
The high-strength refractory material is prepared according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder, neodymium oxide powder and a first part of binding agent into a mixing and grinding machine, and mixing and grinding for 10 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 25 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under 110MPa, and drying at 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, keeping the temperature at 1350 ℃ for 5 hours, and naturally cooling along with the furnace to obtain the high-strength refractory material.
The raw materials comprise the following components in parts by mass:
80 parts of zirconia powder
18 parts of zirconium nitride powder
20 parts of hafnium oxide powder
11 parts of barium hafnate powder
Neodymium oxide powder 8 parts
Bauxite 36 parts
19 parts of a binding agent;
the average particle size of the zirconium oxide powder is 25 micrometers, the average particle size of the zirconium nitride powder is 40 micrometers, the average particle size of the hafnium oxide powder is 50nm, the average particle size of the barium hafnate powder is 80nm, and the average particle size of the neodymium oxide powder is 25 micrometers; in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles with the particle size of less than 300 mu m and more than or equal to 160 mu m, and 25-45 wt% of particles with the particle size of less than 160 mu m and more than or equal to 40 mu m;
wherein the binding agent is thermosetting phenolic resin which is prepared from o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde (the molar ratio is 2: 4: 4: 13), and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60%.
Example 6
The high-strength refractory material is prepared according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder, neodymium oxide powder and a first part of binding agent into a mixing and grinding machine, and mixing and grinding for 10 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 25 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under 110MPa, and drying at 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, keeping the temperature at 1200 ℃ for 6 hours, and naturally cooling along with the furnace to obtain the high-strength refractory material.
The raw materials comprise the following components in parts by mass:
80 parts of zirconia powder
18 parts of zirconium nitride powder
20 parts of hafnium oxide powder
11 parts of barium hafnate powder
Neodymium oxide powder 8 parts
Bauxite 36 parts
19 parts of a binding agent;
the average particle size of the zirconium oxide powder is 25 micrometers, the average particle size of the zirconium nitride powder is 40 micrometers, the average particle size of the hafnium oxide powder is 50nm, the average particle size of the barium hafnate powder is 80nm, and the average particle size of the neodymium oxide powder is 25 micrometers; in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles with the particle size of less than 300 mu m and more than or equal to 160 mu m, and 25-45 wt% of particles with the particle size of less than 160 mu m and more than or equal to 40 mu m;
wherein the binding agent is thermosetting phenolic resin which is prepared from o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde (the molar ratio is 2: 5: 5: 16), and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60%.
Example 7
The high-strength refractory material is prepared according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder, neodymium oxide powder and a first part of binding agent into a mixing and grinding machine, and mixing and grinding for 10 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 25 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under 110MPa, and drying at 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, keeping the temperature at 1300 ℃ for 6 hours, and naturally cooling along with the furnace to obtain the high-strength refractory material.
The raw materials comprise the following components in parts by mass:
80 parts of zirconia powder
18 parts of zirconium nitride powder
20 parts of hafnium oxide powder
11 parts of barium hafnate powder
Neodymium oxide powder 8 parts
Bauxite 36 parts
19 parts of a binding agent;
the average particle size of the zirconium oxide powder is 25 micrometers, the average particle size of the zirconium nitride powder is 40 micrometers, the average particle size of the hafnium oxide powder is 50nm, the average particle size of the barium hafnate powder is 80nm, and the average particle size of the neodymium oxide powder is 25 micrometers; in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles with the particle size of less than 300 mu m and more than or equal to 160 mu m, and 25-45 wt% of particles with the particle size of less than 160 mu m and more than or equal to 40 mu m;
wherein the binding agent is thermosetting phenolic resin which is prepared from o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde (the molar ratio is 2: 5: 5: 18), and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60%.
Comparative example 1
In this comparative example, neodymium oxide (Nd) was not added2O3) Powder; the proportions, types, and specific parameters of the zirconia powder, the zirconium nitride powder, the hafnium oxide powder, the barium hafnate powder, the bauxite, and the binder were the same as in example 6;
and, preparing a refractory material according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder and a first part of binding agent into a mixing and grinding machine, and mixing and grinding for 10 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 25 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under 110MPa, and drying at 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, preserving the heat for 10 hours at the temperature of 1200 ℃, and naturally cooling along with the furnace to obtain the refractory material.
Comparative example 2
In this comparative example, the thermosetting phenol resin according to the present invention was not used as a binder; the proportions, types, and specific parameters of the zirconia powder, the zirconium nitride powder, the hafnium oxide powder, the barium hafnate powder, the neodymium oxide powder, and the bauxite powder were the same as in example 6;
and, preparing a refractory material according to the following steps:
adding zirconium oxide powder, zirconium nitride powder, hafnium oxide powder, barium hafnate powder and neodymium oxide powder into a mixing and grinding machine, and mixing and grinding for 10 minutes; adding the bauxite into the mixing and grinding machine, and mixing and grinding for 25 minutes to obtain a mixture; pressing the mixture under 110MPa, and drying at 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, preserving the heat for 6 hours at the temperature of 1850 ℃, and naturally cooling along with the furnace to obtain the refractory material.
Comparative example 3
The refractory material is prepared according to the following steps:
adding the zirconium oxide powder, the zirconium nitride powder, the neodymium oxide powder and the first part of the binding agent into a mixing and grinding machine, and mixing and grinding for 10 minutes; adding the bauxite and the rest of the second part of the binding agent into the mixing and grinding machine, and mixing and grinding for 25 minutes to obtain a mixture; wherein the mass ratio of the first part of binding agent to the second part of binding agent is 3: 2; pressing the mixture under 110MPa, and drying at 150 ℃ for 36 hours to obtain a dried blank; and (3) placing the dried blank in a sintering furnace, introducing nitrogen, keeping the temperature at 1200 ℃ for 6 hours, and naturally cooling along with the furnace to obtain the refractory material.
The raw materials comprise the following components in parts by mass:
111 parts of zirconium oxide powder
18 parts of zirconium nitride powder
Hafnium oxide powder 0 part
0 part of barium hafnate powder
Neodymium oxide powder 8 parts
Bauxite 36 parts
19 parts of a binding agent;
wherein the average grain diameter of the zirconia powder is 25 μm, the average grain diameter of the zirconium nitride powder is 40 μm, and the average grain diameter of the neodymium oxide powder is 25 μm; in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles with the particle size of less than 300 mu m and more than or equal to 160 mu m, and 25-45 wt% of particles with the particle size of less than 160 mu m and more than or equal to 40 mu m;
wherein the binding agent is thermosetting phenolic resin which is prepared from o-phenylphenol, o-ethylphenol, p-ethylphenol and formaldehyde (the molar ratio is 2: 5: 5: 16), and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60%.
Although refractory materials were prepared in example 6, comparative example 1 and comparative example 2, the duration and temperature of the heat treatment required in the preparation process were different, as shown in table 1 below:
TABLE 1 comparison of Heat treatment conditions
Conditions of heat treatment Example 6 Comparative example 1 Comparative example 2
Temperature of heat treatment 1200℃ 1200℃ 1850℃
Duration of the heat treatment 6 hours 10 hours 6 hours
It was found by analysis that the only difference between example 6 and comparative example 1 was the addition of a suitable amount of neodymium oxide powder, whereas the addition of neodymium oxide powder was omitted from comparative example 1, with the result that the heat treatment time required during the preparation of the high-strength refractory described in example 6 was significantly shorter; the only difference between example 6 and comparative example 2 is that a specific thermosetting phenolic resin is used as a binder, whereas comparative example 2 does not use a binder at all, with the result that the heat treatment temperature required during the preparation of the high strength refractory described in example 6 is significantly lower.
Therefore, in fact, the preparation method of the high-strength refractory material has the advantages of low temperature required by heat treatment, short time consumption, easy product forming, easy operation and the like.
In addition, the inventor respectively carries out the measurement on the key indexes of the examples 1 to 7 and the comparative examples 1 to 3 according to GB/T2997-2015 test method for bulk density, apparent porosity and true porosity of the densely-shaped refractory product, GB/T30873-2014 test method for thermal shock resistance of refractory material, GB/T3002-2017 test method for high-temperature breaking strength of refractory material and GB/T5072-2008 test method for normal-temperature compressive strength of refractory material, and the specific measurement results are shown in the following table 2:
TABLE 2 test results of main properties of refractory
Figure 987652DEST_PATH_IMAGE002
Therefore, the high-strength refractory material prepared by the method provided by the invention is more compact, and the key indexes of the high-strength refractory material, such as compression strength, breaking strength, thermal shock resistance and the like, are obviously superior to those of a comparative example.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (5)

1. The high-strength refractory material is characterized by comprising the following components in parts by mass:
Figure FDA0002385507640000011
the average particle size of the zirconium oxide powder is 20-32 microns, the average particle size of the zirconium nitride powder is 40-60 microns, the average particle size of the hafnium oxide powder is 50-65 nm, the average particle size of the barium hafnate powder is 70-80 nm, and the average particle size of the neodymium oxide powder is 12-25 microns;
wherein the binding agent is thermosetting phenolic resin, and the carbon residue rate of the thermosetting phenolic resin is more than or equal to 60 percent; the raw materials for preparing the thermosetting phenolic resin comprise: o-phenylphenol, o-ethylphenol, p-ethylphenol, formaldehyde; the molar ratio of the o-phenylphenol to the o-ethylphenol to the p-ethylphenol to the formaldehyde is (1-2): (4-5): (2-5): (9-18).
2. The high strength refractory of claim 1, wherein in the bauxite: al (Al)2O3More than 80wt%, Fe2O3The content is less than 2 wt%; and the bauxite has a grain composition of: 55-75 wt% of particles having a particle size of less than 300 μm and not less than 160 μm, and 25-45 wt% of particles having a particle size of less than 160 μm and not less than 40 μm.
3. The method of preparing a high strength refractory according to claim 1, comprising the steps of:
s1: adding the zirconium oxide powder, the zirconium nitride powder, the hafnium oxide powder, the barium hafnate powder, the neodymium oxide powder and a first part of the binding agent into a mixing and grinding machine, and mixing and grinding for 5-10 minutes;
s2: adding the bauxite and the rest of the second part of the bonding agent into the mixing and grinding machine, and mixing and grinding for 15-30 minutes to obtain a mixture;
s3: pressing the mixture under the pressure of 90-120 MPa for molding, and drying at the temperature of 130-180 ℃ for 24-36 hours to obtain a dried blank;
s4: and (3) placing the dried blank in a sintering furnace, introducing nitrogen, performing heat treatment, and naturally cooling along with the furnace to obtain the high-strength refractory material.
4. The method of claim 3, wherein the mass ratio of the first portion of the binding agent in S1 to the second portion of the binding agent in S2 is 3: 2.
5. the production method according to claim 3, wherein the heat treatment in S4 is: preserving the heat for 5-7 hours at the temperature of 1150-1450 ℃.
CN201910826276.8A 2019-09-03 2019-09-03 High-strength refractory material and preparation method thereof Active CN110372376B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910826276.8A CN110372376B (en) 2019-09-03 2019-09-03 High-strength refractory material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910826276.8A CN110372376B (en) 2019-09-03 2019-09-03 High-strength refractory material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110372376A CN110372376A (en) 2019-10-25
CN110372376B true CN110372376B (en) 2020-06-30

Family

ID=68261418

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910826276.8A Active CN110372376B (en) 2019-09-03 2019-09-03 High-strength refractory material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110372376B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111943692B (en) * 2020-06-30 2022-05-10 辽宁东和新材料股份有限公司 High-performance magnesia-calcium brick and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107922274B (en) * 2016-05-27 2021-08-27 住友电气工业株式会社 Sintered material and cutting tool comprising the same
CN106927819A (en) * 2017-03-14 2017-07-07 南京云启金锐新材料有限公司 Hot pressed sintering high-purity zirconia composite ceramics and preparation method thereof

Also Published As

Publication number Publication date
CN110372376A (en) 2019-10-25

Similar Documents

Publication Publication Date Title
CN106995308B (en) Ceramic riving knife material and preparation method thereof
CN110511035A (en) A kind of high entropy ceramics of high-ductility high wear-resistant and its preparation method and application
CN106673626B (en) Low-cost alumina powder material for producing self-toughening alumina wear-resistant ceramic
CN107245621B (en) A kind of wear-and corrosion-resistant molybdenum alloy and preparation method thereof
CN107522485B (en) Spinel fiber reinforced zirconia refractory material and preparation process thereof
CN106977185A (en) A kind of aluminium oxide ceramics and preparation method thereof
CN105254283A (en) Preparation method for alumina ceramic matrix material
CN112028637A (en) Preparation method of high-reliability long-life silicon nitride ceramic ball for aviation bearing
CN106145958B (en) Si3N4/TiC/ graphene composite ceramic tool material with Anisotropy and preparation method thereof
CN110372376B (en) High-strength refractory material and preparation method thereof
CN105819833A (en) Preparation method of self-sharpening microcrystalline alumina ceramic abrasive particles
CN112250442A (en) Preparation method of high-toughness binderless nanocrystalline hard alloy
CN104552032A (en) Metal nano material composite binder and composite binder diamond grinding wheel
CN111995403B (en) Corrosion-resistant silicon nitride ceramic and preparation method thereof
CN107500776B (en) Polycrystalline cubic boron nitride cutter material and preparation method thereof
CN109265179A (en) A kind of silicon nitride material
CN109384464B (en) Nano ceramic container and preparation method thereof
CN107900920A (en) A kind of porous surface diamond abrasive for high efficient grinding and preparation method thereof
CN1552664A (en) Producing method for composite carbide ceramic material by liquid-phase sintering and ceramic products
CN114804843B (en) High-strength ultrathin rock plate and preparation method thereof
JPS6259565A (en) High density alumina/zirconia sintered body and its production
CN105252433A (en) Magnesium borate whisker reinforced nano ceramic binding agent diamond grinding wheel and manufacturing method thereof
CN114380606A (en) Preparation process of machined high-strength refractory material
CN104355601B (en) A kind of self lubricity nozzle pottery and its preparation method
CN113045295A (en) High-strength ceramic sectional material and preparation method thereof

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
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20200605

Address after: No. 666, Quanwang Road, Wangcun Town, Zhoucun District, Zibo City, Shandong Province

Applicant after: Zibo Longcheng refractory Co.,Ltd.

Address before: 410006 no.459, lushong Road, Changsha high tech Development Zone, Yuelu District, Changsha City, Hunan Province

Applicant before: Changsha Huamai New Material Co.,Ltd.

GR01 Patent grant
GR01 Patent grant