CN105948761B - Shaft-like β-the Si such as a kind of3N4+ TiN+O '-Sialon diphase ceramic materials and preparation method thereof - Google Patents

Shaft-like β-the Si such as a kind of3N4+ TiN+O '-Sialon diphase ceramic materials and preparation method thereof Download PDF

Info

Publication number
CN105948761B
CN105948761B CN201610279603.9A CN201610279603A CN105948761B CN 105948761 B CN105948761 B CN 105948761B CN 201610279603 A CN201610279603 A CN 201610279603A CN 105948761 B CN105948761 B CN 105948761B
Authority
CN
China
Prior art keywords
sio
tin
sialon
shaft
tio
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
CN201610279603.9A
Other languages
Chinese (zh)
Other versions
CN105948761A (en
Inventor
郭伟明
于俊杰
林华泰
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.)
JILIN CHANGYU TETAO NEW MATERIAL TECHNOLOGY Co.,Ltd.
Original Assignee
Guangdong University of Technology
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 Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN201610279603.9A priority Critical patent/CN105948761B/en
Publication of CN105948761A publication Critical patent/CN105948761A/en
Application granted granted Critical
Publication of CN105948761B publication Critical patent/CN105948761B/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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/591—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by reaction sintering
    • 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
    • C04B35/64—Burning or sintering processes
    • C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
    • 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
    • C04B2235/3224—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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides 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
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • 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
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron

Abstract

The invention discloses the shaft-like β Si such as a kind of3N4+ TiN+O'Sialon diphase ceramic materials and preparation method thereof are to introduce TiO2Colloidal sol introduces Re as Si powder nitrided catalysts, in-situ preparation nano TiN reinforced phase2O3‑Al2O3‑SiO2Sintering aid promotes Si3N4Sintering densification, the shaft-like β Si such as formation3N4Crystal grain, and generate O'Sialon.The β Si of the present invention3N4+ TiN+O'Sialon diphase ceramic materials have excellent mechanical property, high-temperature behavior, anti-oxidant and corrosion resistance.

Description

Shaft-like β-the Si such as a kind of3N4+ TiN+O '-Sialon diphase ceramic materials and its preparation Method
Technical field
The present invention relates to ceramic material field, more particularly to a kind of etc. shaft-like β-Si3N4+ TiN+O'-Sialon complex phase ceramics Material and preparation method thereof.
Background technology
Si3N4Powder there are two types of crystal form, etc. shaft-like α-Si3N4With the β-Si of long column shape3N4Crystal form.Have been generally acknowledged that α-Si3N4Belong to Low-temperature stabilization crystal form, β-Si3N4Belong to high-temperature stable crystal form.α-Si3N4To β-Si3N4Phase transformation category structural remodeling, about 1420 It DEG C undergoes phase transition.Due to β-Si3N4The through-hole structure of distinctive ABAB accumulations, this β phases have long column shape or acicular crystal shape Looks.Lange etc. (J.Am.Ceram.Soc., 62,1979,428-430) is put forward for the first time long column shape β-Si3N4Crystal grain is in tiny crystalline substance Grain α-Si3N4The bending strength and fracture toughness of material can be improved by being precipitated in matrix.β Phase Proportions are higher, and fracture toughness is better, But intensity has maximum value, the β-Si of high length-diameter ratio3N4The presence of crystal grain can improve intensity and toughness, but β-Si3N4Grain aspect Than being greatly different growth very much, it is unfavorable for material mechanical performance raising.
Invention content
It is an object of the invention to overcome disadvantage existing in the prior art, provide a kind of intensity is high, abrasion resistance properties are good, High temperature resistant and antioxygenic property it is good etc. shaft-like β-Si3N4+ TiN+O'-Sialon diphase ceramic materials.
Another object of the present invention is to provide the shaft-like β-Si such as above-mentioned3N4+ TiN+O'-Sialon diphase ceramic materials Preparation method.
The purpose of the invention is achieved by the following technical solution：
Shaft-like β-the Si such as a kind of3N4The preparation method of+TiN+O'-Sialon diphase ceramic materials is to introduce TiO2Colloidal sol is made For Si powder nitrided catalysts, in-situ preparation nano TiN reinforced phase introduces Re2O3-Al2O3-SiO2Sintering aid promotes Si3N4It burns Knot densification, the shaft-like β-Si such as formation3N4Crystal grain, and O'-Sialon is generated, specifically include following step：
(1) using Si powder as raw material, with TiO2Colloidal sol, Re2O3-Al2O3-SiO2For sintering aid, according to Si：TiO2： Re2O3-Al2O3-SiO2Mass fraction ratio is 60~98%：1~10%：1~30% proportioning obtains after batch mixing, drying Si-TiO2-Re2O3-Al2O3-SiO2Mixed powder, wherein Re be Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Any one of Ho, Er, Tm, Yb or Lu, the Re2O3-Al2O3-SiO2In Re2O3：Al2O3：SiO2Mass fraction ratio is 1 ~98%：1~98%：1~98%；
(2) by Si-TiO2-Re2O3-Al2O3-SiO2Mixed powder be put into mold carry out it is dry-pressing formed after, by cold etc. Hydrostatic profile obtains Si-TiO2-Re2O3-Al2O3-SiO2Green body；
(3) by Si-TiO2-Re2O3-Al2O3-SiO2Green body passes through the shaft-like β-Si such as gas pressure sintered reaction preparation3N4+TiN+ O'-Sialon diphase ceramic materials.
In step (1), by Si powder, TiO2Colloidal sol and Re2O3-Al2O3-SiO2By the mass fraction than carrying out dispensing, with Ethyl alcohol is solvent, with Si3N4Ball is ball-milling medium, and 4~20h is mixed on ball mill, Si-TiO is obtained after dry2-Re2O3- Al2O3-SiO2Mixed powder.
In step (1), ball mill is planetary ball mill, and 10h is mixed on planetary ball mill.
In step (1), Si：TiO2：Re2O3-Al2O3-SiO2Mass fraction than preferably 74.5%：4%：21.5%, Wherein Re=Y；The Re2O3-Al2O3-SiO2In Re2O3：Al2O3：SiO2Mass fraction ratio be 35%：35%：30%.
In step (2), 100~300MPa of pressure of cold isostatic compaction, the dwell time is 1~10min.
In step (2), the pressure preferred 200MPa, dwell time 5min of cold isostatic compaction.
In step (3), gas pressure sintered reaction is：By Si-TiO2-Re2O3-Al2O3-SiO2Green body is put into boron nitride crucible, Temperature is risen to 1000~1250 DEG C with the heating rate of 20 DEG C/min, then is risen to temperature with the heating rate of 10 DEG C/min 1300~1600 DEG C, and 1~4h is kept the temperature, insulating process nitrogen pressure is 0.1~5MPa, then with the heating rate of 5 DEG C/min Temperature is risen to 1600~2000 DEG C, and keeps the temperature 1~4h, insulating process nitrogen pressure is 0.1~5MPa, is reacted by air pressure Shaft-like β-the Si such as sintering acquisition3N4+ TiN+O'-Sialon diphase ceramic materials.
In step (3), gas pressure sintered reaction is preferably：By Si-TiO2-Re2O3-Al2O3-SiO2Green body is put into boron nitride earthenware Temperature is raised to 1200 DEG C with the heating rate of 20 DEG C/min, then temperature is raised to 1400 with the heating rate of 10 DEG C/min by crucible DEG C, and 2h is kept the temperature, insulating process nitrogen pressure is 0.5MPa, and temperature is then raised to 1850 DEG C with the heating rate of 5 DEG C/min, And 1h is kept the temperature, insulating process nitrogen pressure is 3.0MPa, passes through the shaft-like β-Si such as gas pressure sintered reaction acquisition3N4+TiN+O'- Sialon diphase ceramic materials.
Using the above method be prepared etc. shaft-like β-Si3N4+ TiN+O'-Sialon diphase ceramic materials, it is relatively close Degree is higher than 95%, and hardness is 10~22GPa, and fracture toughness is 3~8MPam1/2, bending strength is 600~1200MPa, TiN Grain size is 100~1000nm, β-Si3N4The average diameter of crystal grain is 1.33~2.58um.
Preferably, the present invention be prepared etc. shaft-like β-Si3N4+ TiN+O'-Sialon diphase ceramic materials are opposite Density is 99%, hardness 14GPa, fracture toughness 4.5MPam1/2, bending strength 1000MPa, TiN grain size is 500nm, β-Si3N4The average diameter of crystal grain is 1.90 ± 0.51um.
In the present invention, TiO2Colloidal sol at high temperature with Si3N4Reaction generates TiN reinforced phases, as shown in reaction equation (1)； Part SiO in sample2With Re2O3、Al2O3Reaction forms glass phase, improves densification, extra SiO2With Si3N4、Al2O3Occur Solid solution reaction forms O'-Sialon phases, as shown in reaction equation (2):
6TiO2(s)+2Si3N4(s)→6TiN(s)+6SiO2(s or l)+N2(g) (1)
0.49Si3N4(s)+0.49SiO2(s)+0.02Al2O3(s)→Si1.96Al0.04O1.04N1.96(s) (2)
The present invention has the following advantages that compared with prior art and effect：
(1) present invention prepare etc. shaft-like β-Si3N4+ TiN+O'-Sialon diphase ceramic materials, be with etc. shaft-like β- Si3N4For main phase, using TiN+O'-Sialon as the phase constitution structure of reinforced phase, which has more preferable, closer Crystal structure.
(2) present invention introduces TiO2Colloidal sol is as Si powder nitrided catalyst and in-situ preparation nano TiN reinforced phase, further The intensity and abrasion resistance properties of ceramic material are improved, Al is introduced2O3-Re2O3-SiO2Sintering aid promotes Si3N4Sintering densification, Shaft-like β-the Si such as formation3N4Crystal grain, and in-situ preparation O'-Sialon further increase the high-temperature behavior of ceramic material and anti-oxidant Performance.
(3) the TiN grain sizes that material in situ of the present invention generates are 100~1000nm, have superior mechanical property, high temperature Performance, anti-oxidant and corrosion resistance.
Description of the drawings
Fig. 1 be the present invention prepare etc. shaft-like β-Si3N4The XRD of+TiN+O'-Sialon diphase ceramic materials schemes.
Fig. 2 be the present invention prepare etc. shaft-like β-Si3N4The SEM of+TiN+O'-Sialon diphase ceramic materials schemes.
Specific implementation mode
Further detailed description is done to the present invention with reference to embodiment, embodiments of the present invention are not limited thereto. Be the existing conventional method of the art if experimental methods are without specified otherwise used in following, used dispensing or Material is unless otherwise specified by the available dispensing of commercial sources or material.
Embodiment 1
(1) using Si powder as raw material, with TiO2Colloidal sol, Y2O3-Al2O3-SiO2For sintering aid, gross mass is accounted for according to Si powder Mass fraction be 74.5%, TiO2Mass fraction is 4%, Y2O3-Al2O3-SiO2Mass fraction is 21.5% progress dispensing, Middle Y2O3：Al2O3：SiO2Mass fraction ratio is 35%：35%：30%, using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, 10h is mixed on planetary ball mill, and Si-TiO is obtained after dry2-Y2O3-Al2O3-SiO2Mixed powder.
(2) by Si-TiO2-Y2O3-Al2O3-SiO2Mixed powder is put into mold cold etc. quiet by carrying out after dry-pressing formed Pressure obtains Si-TiO2-Y2O3-Al2O3-SiO2Green body, cold isostatic compaction pressure 200MPa, dwell time 5min.
(3) by Si-TiO2-Y2O3-Al2O3-SiO2Green body is put into boron nitride crucible, will be warm with the heating rate of 20 DEG C/min Degree is raised to 1200 DEG C, then temperature is raised to 1400 DEG C with the heating rate of 10 DEG C/min, and keeps the temperature 2h, insulating process nitrogen pressure Power is 0.5MPa, temperature is then raised to 1850 DEG C with the heating rate of 5 DEG C/min, and keep the temperature 1h, insulating process nitrogen pressure For 3.0MPa, pass through the shaft-like β-Si such as gas pressure sintered reaction acquisition3N4+ TiN+O'-Sialon diphase ceramic materials.
The relative density of ceramic material manufactured in the present embodiment is 99%, hardness 14GPa, and fracture toughness is 4.5MPa·m1/2, bending strength 1000MPa, TiN grain size position 500nm, β-Si3N4The average diameter of crystal grain be 1.90 ± 0.51um。
Fig. 1 be etc. shaft-like β-Si3N4The XRD spectrum of+TiN+O'-Sialon diphase ceramic materials.From Fig. 1 as can be seen that For sample after gas pressure sintered reaction, Si powder is completely converted into β-Si3N。
Fig. 2 be etc. shaft-like β-Si3N4The SEM of+TiN+O'-Sialon diphase ceramic materials schemes.Figure it is seen that β- Si3N4Crystal grain is the shaft-like crystal grain such as uniform, and average diameter is 1.90 ± 0.51um.
Embodiment 2
It is 71%, TiO according to Si mass fractions2Mass fraction is 4%, Y2O3-Al2O3-SiO2Mass fraction be 25% into Row dispensing, wherein Y2O3：Al2O3：SiO2Mass fraction ratio is 30%：30%：40%, prepare Si- according to 1 method of embodiment TiO2-Y2O3-Al2O3-SiO2Then temperature is raised to 1200 DEG C by green body with the heating rate of 20 DEG C/min, then with 10 DEG C/min Heating rate temperature is raised to 1400 DEG C, and keep the temperature 2h, insulating process nitrogen pressure is 0.5MPa, then with 5 DEG C/min's Temperature is raised to 1700 DEG C by heating rate, keeps the temperature 1h, and insulating process nitrogen pressure is 3.0MPa, is obtained by gas pressure sintered reaction Etc. shaft-like β-Si3N4+ TiN+O'-Sialon diphase ceramic materials.
The relative density of ceramic material manufactured in the present embodiment is 99%, hardness 13.5GPa, fracture toughness 4MPa m1/2, bending strength 950MPa, TiN grain size is 450nm, β-Si3N4The average diameter of crystal grain is 1.46 ± 0.26um.
Embodiment 3
It is 81%, TiO according to Si mass fractions2Mass fraction is 4%, Y2O3-Al2O3-SiO2Mass fraction be 15% into Row dispensing, wherein Y2O3：Al2O3：SiO2Mass fraction ratio is 33.3%：33.3%：33.3%, it is prepared according to 1 method of embodiment Si-TiO2-Y2O3-Al2O3-SiO2Then temperature is raised to 1200 DEG C, then with 10 by green body with the heating rate of 20 DEG C/min DEG C/temperature is raised to 1400 DEG C, and keeps the temperature 2h by the heating rate of min, insulating process nitrogen pressure is 0.5MPa, then with 5 DEG C/ Temperature is raised to 1750 DEG C by the heating rate of min, and keeps the temperature 1h, and insulating process nitrogen pressure is 3.0MPa, is reacted by air pressure Shaft-like β-the Si such as sintering acquisition3N4+ TiN+O'-Sialon diphase ceramic materials.
The relative density of ceramic material manufactured in the present embodiment is 99%, hardness 14GPa, and fracture toughness is 3.5MPa·m1/2, bending strength 850MPa, TiN grain size is 500nm, β-Si3N4The average diameter of crystal grain be 1.53 ± 0.32um。
Embodiment 4
It is 77.5%, TiO according to Si powder mass fractions2Mass fraction is 4%, Y2O3-Al2O3-SiO2Mass fraction is 18.5% carries out dispensing, wherein Y2O3：Al2O3：SiO2Mass fraction ratio is 27%：27%：46%, according to 1 method system of embodiment Standby Si-TiO2-Y2O3-Al2O3-SiO2Then temperature is raised to 1200 DEG C by green body with the heating rate of 20 DEG C/min, then with Temperature is raised to 1400 DEG C by the heating rate of 10 DEG C/min, and keeps the temperature 2h, and insulating process nitrogen pressure is 0.5MPa, then with 5 DEG C/temperature is raised to 1800 DEG C, and keeps the temperature 1h by the heating rate of min, insulating process nitrogen pressure is 3.0MPa, anti-by air pressure Shaft-like β-the Si such as acquisition should be sintered3N4+ TiN+O'-Sialon diphase ceramic materials.
The relative density of ceramic material manufactured in the present embodiment is 98.5%, hardness 14.5GPa, and fracture toughness is 4MPa·m1/2, bending strength 950MPa, TiN grain size is 550nm, β-Si3N4The average diameter of crystal grain is 1.73 ± 0.45um.

Claims (8)

1. the shaft-like β-Si such as a kind of3N4The preparation method of+TiN+O'-Sialon diphase ceramic materials, it is characterised in that including following Step：
(1) using Si powder as raw material, with TiO2Colloidal sol, Re2O3-Al2O3-SiO2For sintering aid, according to Si：TiO2：Re2O3- Al2O3-SiO2Mass fraction ratio is 60~98%：1~10%：1~30% proportioning obtains Si- after batch mixing, drying TiO2-Re2O3-Al2O3-SiO2Mixed powder, wherein Re be Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Any one of Tm, Yb or Lu, the Re2O3-Al2O3-SiO2In Re2O3：Al2O3：SiO2Mass fraction ratio is 1~98%： 1~98%：1~98%；
(2) by Si-TiO2-Re2O3-Al2O3-SiO2Mixed powder be put into mold carry out it is dry-pressing formed after, pass through isostatic cool pressing Molding obtains Si-TiO2-Re2O3-Al2O3-SiO2Green body；
(3) by Si-TiO2-Re2O3-Al2O3-SiO2Green body passes through the shaft-like β-Si such as gas pressure sintered reaction preparation3N4+TiN+O'- Sialon diphase ceramic materials；The gas pressure sintered reaction is：By Si-TiO2-Re2O3-Al2O3-SiO2Green body is put into boron nitride Temperature is risen to 1000~1250 DEG C by crucible with the heating rate of 20 DEG C/min, then with the heating rate of 10 DEG C/min by temperature 1300~1600 DEG C are risen to, and keeps the temperature 1~4h, insulating process nitrogen pressure is 0.1~5MPa, then with the heating of 5 DEG C/min Temperature is risen to 1600~2000 DEG C by rate, and keeps the temperature 1~4h, and insulating process nitrogen pressure is 0.1~5MPa, anti-by air pressure Shaft-like β-the Si such as acquisition should be sintered3N4+ TiN+O'-Sialon diphase ceramic materials.
2. the shaft-like β-Si such as according to claim 13N4The preparation method of+TiN+O'-Sialon diphase ceramic materials, It is characterized in that：In step (1), by Si powder, TiO2Colloidal sol and Re2O3-Al2O3-SiO2By the mass fraction than carrying out dispensing, with Ethyl alcohol is solvent, with Si3N4Ball is ball-milling medium, and 4~20h is mixed on ball mill, Si-TiO is obtained after dry2-Re2O3- Al2O3-SiO2Mixed powder.
3. the shaft-like β-Si such as according to claim 23N4The preparation method of+TiN+O'-Sialon diphase ceramic materials, It is characterized in that：In step (1), ball mill is planetary ball mill, and 10h is mixed on planetary ball mill.
4. the shaft-like β-Si such as according to claim 13N4The preparation method of+TiN+O'-Sialon diphase ceramic materials, It is characterized in that：In step (1), Si：TiO2：Re2O3-Al2O3-SiO2Mass fraction ratio be 74.5%：4%：21.5%, wherein Re is Y；The Re2O3-Al2O3-SiO2In Re2O3：Al2O3：SiO2Mass fraction ratio be 35%：35%：30%.
5. the shaft-like β-Si such as according to claim 13N4The preparation method of+TiN+O'-Sialon diphase ceramic materials, It is characterized in that：In step (2), 100~300MPa of pressure of cold isostatic compaction, the dwell time is 1~10min.
6. the shaft-like β-Si such as according to claim 13N4The preparation method of+TiN+O'-Sialon diphase ceramic materials, It is characterized in that：In step (3), gas pressure sintered reaction is：By Si-TiO2-Re2O3-Al2O3-SiO2Green body is put into boron nitride crucible, Temperature is raised to 1200 DEG C with the heating rate of 20 DEG C/min, then temperature is raised to 1400 DEG C with the heating rate of 10 DEG C/min, And 2h is kept the temperature, insulating process nitrogen pressure is 0.5MPa, and temperature is then raised to 1850 DEG C with the heating rate of 5 DEG C/min, and 1h is kept the temperature, insulating process nitrogen pressure is 3.0MPa, passes through the shaft-like β-Si such as gas pressure sintered reaction acquisition3N4+TiN+O'- Sialon diphase ceramic materials.
7. it is a kind of using any one of claim 1~6 the method be prepared etc. shaft-like β-Si3N4+TiN+O'-Sialon Diphase ceramic material, it is characterised in that：Relative density is higher than 95%, and hardness is 10~22GPa, and fracture toughness is 3~8MPa m1/2, bending strength is 600~1200MPa, and TiN grain sizes are 100~1000nm, β-Si3N4The average diameter of crystal grain be 1.33~ 2.58μ m 。
8. the shaft-like β-Si such as according to claim 73N4+ TiN+O'-Sialon diphase ceramic materials, it is characterised in that：Phase It is 99% to density, hardness 14GPa, fracture toughness 4.5MPam1/2, bending strength 1000MPa, TiN grain size is 500nm, β-Si3N4The average diameter of crystal grain is 1.90 ± 0.51 μm.
CN201610279603.9A 2016-04-29 2016-04-29 Shaft-like β-the Si such as a kind of3N4+ TiN+O '-Sialon diphase ceramic materials and preparation method thereof Active CN105948761B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610279603.9A CN105948761B (en) 2016-04-29 2016-04-29 Shaft-like β-the Si such as a kind of3N4+ TiN+O '-Sialon diphase ceramic materials and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610279603.9A CN105948761B (en) 2016-04-29 2016-04-29 Shaft-like β-the Si such as a kind of3N4+ TiN+O '-Sialon diphase ceramic materials and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105948761A CN105948761A (en) 2016-09-21
CN105948761B true CN105948761B (en) 2018-09-07

Family

ID=56916489

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610279603.9A Active CN105948761B (en) 2016-04-29 2016-04-29 Shaft-like β-the Si such as a kind of3N4+ TiN+O '-Sialon diphase ceramic materials and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105948761B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108863396B (en) * 2018-06-14 2021-04-06 广东工业大学 Silicon nitride-based continuous functional gradient ceramic ball and preparation method and application thereof
CN113929471A (en) * 2021-11-08 2022-01-14 西安交通大学 High-temperature-resistant oxidized Si3N4O' -sialon composite ceramic and preparation method thereof
CN115611636B (en) * 2022-09-30 2023-07-28 广东工业大学 Surface modified cubic boron nitride powder and preparation method and application thereof
CN116693303A (en) * 2023-03-31 2023-09-05 江苏东浦精细陶瓷科技股份有限公司 TiN-Si 3 N 4 Near net shape forming method for composite material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103833370A (en) * 2014-01-08 2014-06-04 西北工业大学 Near shape preparation method of multiphase ceramic Si3N4-SiC
CN104926317A (en) * 2015-06-01 2015-09-23 广东工业大学 High-toughness Si3N4 ceramic preparation method
CN105254307A (en) * 2015-10-21 2016-01-20 广东工业大学 Method for preparing Si3N4- O'-Sialon-TiN ceramic ball material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103833370A (en) * 2014-01-08 2014-06-04 西北工业大学 Near shape preparation method of multiphase ceramic Si3N4-SiC
CN104926317A (en) * 2015-06-01 2015-09-23 广东工业大学 High-toughness Si3N4 ceramic preparation method
CN105254307A (en) * 2015-10-21 2016-01-20 广东工业大学 Method for preparing Si3N4- O'-Sialon-TiN ceramic ball material

Also Published As

Publication number Publication date
CN105948761A (en) 2016-09-21

Similar Documents

Publication Publication Date Title
CN105948761B (en) Shaft-like β-the Si such as a kind of3N4+ TiN+O '-Sialon diphase ceramic materials and preparation method thereof
Suehiro et al. Powder synthesis of Ca-α ‘-SiAlON as a host material for phosphors
CN104909765B (en) A kind of low cost, quick preparation high-performance Si3N4The method of Ceramic Balls
CN109206141A (en) A kind of high hard high-ductility silicon nitride ceramics and its preparation method and application
KR20170061755A (en) Alumina complex ceramics composition and manufacturing method thereof
JP5836522B2 (en) Method for manufacturing silicon nitride substrate
Suehiro et al. Powder synthesis of Y-α-SiAlON and its potential as a phosphor host
CN103130508A (en) Method for preparing texturing boride super-high-temperature ceramic
Al Malki et al. Effect of Al metal precursor on the phase formation and mechanical properties of fine-grained SiAlON ceramics prepared by spark plasma sintering
CN104926317A (en) High-toughness Si3N4 ceramic preparation method
CN110218096A (en) A kind of high hard high abrasion silicon nitride ceramics and its preparation method and application
Nekouee et al. Sintering behavior and mechanical properties of spark plasma sintered β–SiAlON/TiN nanocomposites
JP5046221B2 (en) Manufacturing method of highly reliable silicon nitride ceramics with high reliability
CN110156476A (en) A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application
CN105254307B (en) One kind prepares Si3N4The method of O ' Sialon TiN ceramics ball materials
CN101734920B (en) Titanium nitride porous ceramics and preparation method thereof
CN107651964A (en) A kind of AlN base composite ceramics and preparation method thereof
CN109942310A (en) A kind of preparation method of high-performance porous SiN ceramic
Sun et al. Effect of LiYO2 on the synthesis and pressureless sintering of Y2SiO5
Zabelina et al. SiC composites containing carbon nanotubes and oxide additives based on organoelementoxanes. Preparation by spark plasma sintering
CN108863395A (en) A kind of high heat conductance, high strength silicon nitride ceramic material and preparation method thereof
CN109970454A (en) A kind of transition metal oxide inhibit silicon nitride phase transformation method and its silicon nitride ceramics obtained
CN104609864B (en) A kind of method utilizing ferro-silicon nitride powder to prepare block body ceramic material
Tatli et al. Low temperature densification of silicon nitride using Li2O-based surface coatings
CN109400176A (en) A kind of high-performance silicon nitride ceramics and its preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20210922

Address after: 130000 building F2, phase 2-1, Beihu science and Technology Industrial Park, Beihu science and Technology Development Zone, Changchun City, Jilin Province

Patentee after: JILIN CHANGYU TETAO NEW MATERIAL TECHNOLOGY Co.,Ltd.

Address before: 510062 Dongfeng East Road, Yuexiu District, Guangzhou, Guangdong 729

Patentee before: GUANGDONG University OF TECHNOLOGY

TR01 Transfer of patent right