CN104768900A - Silicon nitride sintered body and sliding member using same - Google Patents

Silicon nitride sintered body and sliding member using same Download PDF

Info

Publication number
CN104768900A
CN104768900A CN201380057709.9A CN201380057709A CN104768900A CN 104768900 A CN104768900 A CN 104768900A CN 201380057709 A CN201380057709 A CN 201380057709A CN 104768900 A CN104768900 A CN 104768900A
Authority
CN
China
Prior art keywords
silicon nitride
nitride sinter
crystallization
addition
phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201380057709.9A
Other languages
Chinese (zh)
Other versions
CN104768900B (en
Inventor
青木克之
小松通泰
船木开
山口晴彦
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.)
Toshiba Corp
Toshiba Materials Co Ltd
Original Assignee
Toshiba Corp
Toshiba Materials 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 Toshiba Corp, Toshiba Materials Co Ltd filed Critical Toshiba Corp
Publication of CN104768900A publication Critical patent/CN104768900A/en
Application granted granted Critical
Publication of CN104768900B publication Critical patent/CN104768900B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/30—Parts of ball or roller bearings
    • F16C33/32—Balls
    • 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
    • C04B35/597—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 oxynitride, e.g. SIALONS
    • 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
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—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
    • C04B2235/32—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
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • 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
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • 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
    • C04B2235/3258—Tungsten oxides, tungstates, 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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal carbides
    • C04B2235/3847—Tungsten carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—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
    • C04B2235/3865—Aluminium nitrides
    • 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
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
    • C04B2235/3878—Alpha silicon nitrides
    • 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
    • C04B2235/3895—Non-oxides with a defined oxygen content, e.g. SiOC, TiON
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • 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
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C04B2235/85—Intergranular or grain boundary phases
    • 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
    • C04B2235/963—Surface properties, e.g. surface roughness
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2240/00—Specified values or numerical ranges of parameters; Relations between them
    • F16C2240/40—Linear dimensions, e.g. length, radius, thickness, gap
    • F16C2240/54—Surface roughness

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Products (AREA)
  • Rolling Contact Bearings (AREA)

Abstract

This silicon nitride sintered body is characterized in that, during XRD analysis, when the strongest peak intensities detected at 29.6+-0.3 DEG and 31.0+-0.3 DEG corresponding to a hexagonal [alpha]-SiAlON crystal are I29.6 DEG and I31.0 DEG and the strongest peak intensities detected at 33.6+-0.3 DEG and 36.1+-0.3 DEG corresponding to a [beta]-Si3N4 crystal are I33.6 DEG and I36.1 DEG , these strongest peak intensities fulfill the relation (I29.6 DEG + I31.0 DEG ) / (I33.6 DEG + I36.1 DEG ) = 0.10 to 0.30 ... (1), the area ratio of the grain boundary phase per 100[mu]m100[mu]m unit area in an arbitrary cross section of the silicon nitride sintered body is 25-40%, and the machinable coefficient is 0.100-0.120. By means of the present invention, it is possible to provide a silicon nitride sintered body optimal for sliding members having sliding characteristics that remain stable for a long time, and to provide a sliding member using the same.

Description

Silicon nitride sinter and use the sliding component of this silicon nitride sinter
Technical field
Embodiments of the present invention relate to silicon nitride sinter and use the sliding component of this silicon nitride sinter.
Background technology
Silicon nitride sinter is widely used as the structured material of the sliding component such as bearing ball, roller.Such as former, as bearing (bearing) component of supporting rotating shaft, particularly as the structured material of bearing ball, usually use the metallic substance such as bearing steel.But the metallic substance such as bearing steel are insufficient due to wear resistance, so the deviation that there is bearing life increases, thus stably cannot to obtain the problem that the high high speed rotating of reliability drives.
As a kind of means solved the problem, in recent years, use silicon nitride sinter as the structured material of bearing ball.Silicon nitride sinter sliding properties in pottery is also excellent, so under the using state of a part, wear resistance is sufficient, even if can confirm when carrying out high speed rotating, within the time limit to a certain degree, also can realize the high rotary actuation of reliability.
Sintering as former silicon nitride sinter forms, and known has silicon nitride-rare-earth oxide-alumina series, silicon nitride-silicon oxide yttrium-aluminum oxide-aluminium nitride-titanium system etc.Yttrium oxide (Y in above-mentioned sintering composition 2o 3) etc. the sintering aids such as rare-earth oxide all the time usually used as sintering aid use, in order to improve coking property, make sintered compact densification thus realize high strength and add.Such as, open in Japanese Unexamined Patent Publication 2006-36554 publication (patent documentation 1).
In addition, in Japanese Unexamined Patent Publication 2002-326875 publication (patent documentation 2), disclosing when implementing the cut resistance test of regulation, demonstrating the long-life silicon nitride sintered compact of more than 400 hours.
On the other hand, for the sliding component such as bearing ball using silicon nitride sinter, require more than 400 hours and then long lifetime of 800 hours.By carrying out the long lifetime of bearing ball, non-maintainingization of the sliding parts such as bearing can be realized.
The product that the sliding components such as bearing are used in lathe, electronics, automobile, aircraft also have the various fields such as wind-power electricity generation.If realize the long lifetime of sliding component, then can realize the long lifetime of various product, and then realize non-maintainingization.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-36554 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-326875 publication
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is: provide sliding properties can possess the silicon nitride sinter of long-term reliability more and use the sliding component of this silicon nitride sinter.
For solving the means of problem
According to an embodiment of the invention, a kind of silicon nitride sinter can be obtained, it is characterized in that: when carrying out XRD analysis to silicon nitride sinter, when will be I corresponding to the strongest intensity settings that 29.6 ± 0.3 ° of hexagonal system α-SiAlON crystallization and 31.0 ± 0.3 ° of places detect 29.6 °, I 31.0 °, on the other hand will correspond to β-Si 3n 4the strongest intensity settings that 33.6 ± 0.3 °, 36.1 ± 0.3 ° places of crystallization detect is I 33.6 °, I 36.1 °time, each strongest intensity meets following relational expression:
(I 29.6°+I 31.0°)/(I 33.6°+I 36.1°)＝0.10～0.30 (1)
In the arbitrary cross-section of described silicon nitride sinter, the area ratio of the Grain-Boundary Phase that per unit area is 100 μm × 100 μm is 25 ~ 40%, and can process coefficient (machinable coefficients) is 0.100 ~ 0.120.
In addition, when carrying out XRD analysis to silicon nitride sinter, corresponding to Y 4si 2o 7n 2the strongest intensity I that 39.5 ± 0.3 ° of places of (J phase) detect 39.5 °preferably meet following relational expression:
(I 39.5°)/(I 33.6°+I 36.1°)＝0.03～0.10 (2)
In addition, when carrying out XRD analysis to silicon nitride sinter, corresponding to Y 2si 3o 12n (H phase), YSiO 2n (K phase) or Y 2si 3o 3n 4in the strongest intensity I that detects of any one 31.9 ± 0.3 ° of above place 31.9 °preferably meet following relational expression:
(I 31.9°)/(I 33.6°+I 36.1°)＝0.05～0.15 (3)
In addition, XRD analysis is preferably carried out at the arbitrary cross-section of silicon nitride sinter.
In addition, the Grain-Boundary Phase comprising the crystallization of Hf-Y-O based compound and the amorphous phase containing Y-Al-O is preferably possessed.In addition, the particle such as carbide, oxide compound, nitride that median size is less than 2 μm is preferably possessed.In addition, preferred described particle is the particle of molybdenum compound.In addition, preferably in the Al of oxide compound scaled value containing 5 ~ 10 quality %, more than any one in the rare earth element of oxide compound scaled value containing 1 ~ 10 quality %, more than any one in 4A, 5A, 6A element of oxide compound scaled value containing 1 ~ 5 quality %, and the mol (mole) of preferably Al and rare earth element is than being A1 (mo1) ﹕ rare earth element (mol)=1 ﹕ 1 ~ 8 ﹕ 1.In addition, preferred Vickers' hardness (Hv) is more than 1500, Fracture Toughness (K 1C) be 6.0MPam 1/2above, and preferably 3 flexural strengths are preferably more than 900MPa.
In addition, the feature of the sliding component of embodiment is the silicon nitride sinter employing described embodiment.In addition, preferred sliding component is bearing ball.In addition, slipping plane preferably surfaceness (Ra) be the abrasive surface of less than 0.5 μm.
The effect of invention
Present embodiment can provide a kind of silicon nitride sinter can giving long-term reliability for sliding properties.In addition, coefficient can be processed owing to have adjusted, even if so carried out surface grinding processing, also due to threshing can be reduced, so easily obtain smooth slipping plane.For this reason, even if for the sliding component employing this sintered compact, also long-term reliability can be obtained.
Accompanying drawing explanation
Fig. 1 is the stereographic map of an embodiment of the sliding component representing use silicon nitride sinter of the present invention and formed.
Embodiment
Below, be described with regard to embodiment.
(the first embodiment)
First embodiment relates to a kind of silicon nitride sinter, it is characterized in that: when carrying out XRD analysis to silicon nitride sinter, when will be I corresponding to the strongest intensity settings that 29.6 ± 0.3 ° of hexagonal system α-SiAlON crystallization and 31.0 ± 0.3 ° of places detect 29.6 °, I 31.0 °, on the other hand will correspond to β-Si 3n 4the strongest intensity settings that 33.6 ± 0.3 °, 36.1 ± 0.3 ° places of crystallization detect is I 33.6 °, I 36.1 °time, each strongest intensity meets following relational expression:
(I 29.6°+I 31.0°)/(I 33.6°+I 36.1°)＝0.10～0.30 (1)
In the arbitrary cross-section of described silicon nitride sinter, the area ratio of the Grain-Boundary Phase that per unit area is 100 μm × 100 μm is 25 ~ 40%, and can process coefficient is 0.100 ~ 0.120.
First, the condition with regard to implementing XRD analysis is described.Measuring surface is arbitrary surfaces or the arbitrary cross-section of sintered compact, is set as that surface roughness Ra is milled to the abrasive surface of less than 1 μm.XRD analysis is set as carrying out under Cu target (Cu-K α), tube voltage 40kV, tube current 40mA, sweep velocity 2.0 °/min, slit (RS) 0.15mm, sweep limit (2 θ) 10 ° ~ 60 °.In addition, sweep limit (2 θ), if comprise 10 ° ~ 60 °, also can be regarded as and carry out broad scope.Particularly preferably be the section of sintered compact.If analyzed with section, then also can as the face of area ratio obtaining Grain-Boundary Phase.
First embodiment when carrying out XRD analysis, when will be I corresponding to the strongest intensity settings that 29.6 ± 0.3 ° of hexagonal system α-SiAlON crystallization and 31.0 ± 0.3 ° of places detect 29.6 °, I 31.0 °, on the other hand will correspond to β-Si 3n 4the strongest intensity settings that 33.6 ± 0.3 °, 36.1 ± 0.3 ° places of crystallization detect is I 33.6 °, I 36.1 °time, each strongest intensity meets following relational expression: (I 29.6 °+ I 31.0 °)/(I 33.6 °+ I 36.1 °)=0.10 ~ 0.30.The peak position of carrying out XRD analysis determined by the lattice parameter of respective crystallization.
If there is hexagonal system α-SiAlON crystallization, then detect peak value at 29.6 ± 0.3 ° and 31.0 ± 0.3 ° of places.In other words, if detect peak value at 29.6 ± 0.3 ° and 31.0 ± 0.3 ° of places, just mean to there is hexagonal system α-SiAlON crystallization.In addition, I is used 29.6 °and I 31.0 °the reason of two peak strengths is the impacts in order to relax the change that peak strength is caused by crystalline orientation.
In addition, if there is β-Si 3n 4crystallization, then detect peak value at 33.6 ± 0.3 ° and 36.1 ± 0.3 ° of places.In other words, if detect peak value at 33.6 ± 0.3 ° and 36.1 ± 0.3 ° of places, just mean to there is β-Si 3n 4crystallization.In addition, I is used 33.6 °and I 36.1 °the reason of two peak strengths is the impacts in order to relax the change that peak strength is caused by crystalline orientation.
In the first embodiment, (I is met 29.6 °+ I 31.0 °)/(I 33.6 °+ I 36.1 °)=0.10 ~ 0.30.The size of peak strength decides according to the amount of respective crystallization.So-called (hexagonal crystal α-SiAlON crystallization/β-Si 3n 4crystallization) peak strength than i.e. (I 29.6 °+ I 31.0 °)/(I 33.6 °+ I 36.1 °) be 0.10 ~ 0.30, refer to relative to β-Si 3n 4, there is the hexagonal system α-SiAlON crystallization of specified amount in crystallization.
In addition, if there is hexagonal crystal α-SiAlON crystallization, then near 34.4 °, 35.1 °, also peak value is detected.In addition, if there is β-Si 3n 4crystallization, then also detect peak value near 23.4 °, 27.1 °.The presence or absence of the peak value detected near this, also may be used for holding hexagonal crystal α-SiAlON crystallization and β-Si 3n 4the presence or absence of the existence of crystallization.In addition, overlapping with other crystalline peak described later and when being difficult to distinguish, also can combine with various qualitative analysis.
Hexagonal system α-SiAlON crystallization and β-Si is become by there is hexagonal system α-SiAlON crystallization 3n 4the tissue that crystallized mixed exists, there is deviation in that can reduce Grain-Boundary Phase, thus can strengthen Grain-Boundary Phase.For this reason, hardness, toughness etc. as sintered compact are improved, thus also can improve wear resistance.Hexagonal system α-SiAlON crystallization also can have both spherical shape or columnar shape.
Especially, hexagonal crystal α-SiAlON crystallization preferably aspect ratio be less than 2.β-Si 3n 4crystallization to be aspect ratio be more than 2 long column shape shape.The silicon nitride sinter of patent documentation 1 and patent documentation 2 is by making β-Si 3n 4the intricate ground of crystallization is wound around mutually and forms hardness and the high silicon nitride sinter of toughness.On the other hand, due to β-Si 3n 4crystallization is long column shape shape, so β-Si 3n 4the deviation of crystallization grain boundary size is each other comparatively large, thus is formed locally the many positions of Grain-Boundary Phase and the few position of Grain-Boundary Phase.For this reason, the reduction of the long term life of sliding properties can be seen.
In the first embodiment, due to the β-Si of long column shape shape 3n 4crystallization and hexagonal crystal α-SiAlON crystallized mixed that is spherical or column exist, and thus become hexagonal crystal α-SiAlON crystallization and enter β-Si 3n 4the structure in crystallization gap each other, thus the ratio that exists of Grain-Boundary Phase can be made to stablize.
At (hexagonal crystal α-SiAlON crystallization/β-Si 3n 4crystallization) peak strength than lower than 0.10 time, hexagonal crystal α-SiAlON crystallization is very few, thus Grain-Boundary Phase exist ratio deviation increase.On the other hand, at (hexagonal crystal α-SiAlON crystallization/β-Si 3n 4crystallization) peak strength larger and more than 0.30 time, β-Si 3n 4the ratio of crystallization reduces, β-Si 3n 4the tissue that the intricate ground of crystallization is wound around mutually reduces, thus sliding properties reduces.
In addition, the area ratio of the Grain-Boundary Phase of the per unit area 100 μm × 100 μm of the arbitrary cross-section of silicon nitride sinter being set as 25 ~ 40%, there is deviation in what easily control Grain-Boundary Phase thus.In the first embodiment, to remove β-Si 3n 4crystallization be Grain-Boundary Phase mutually beyond hexagonal crystal α-SiAlON crystallization.Even if the silicon nitride sinter of the first embodiment is measured arbitrary cross-section, namely whichever section, the area ratio of the Grain-Boundary Phase that per unit area is 100 μm × 100 μm is also in the scope of 25 ~ 40%.Owing to controlling in the ratio of unit surface 100 μm × 100 μm these tiny areas to Grain-Boundary Phase, so not only the hardness of sintered compact and fracture toughness property are improved, and the long-term reliability of sliding properties can be obtained.
In addition, the measuring method of the area ratio of Grain-Boundary Phase is as described below.First, the arbitrary cross-section of silicon nitride sinter is obtained.Attrition process is implemented to this section, makes its surface roughness Ra be less than 1 μm.For clear and definite β-Si 3n 4the region of crystallization and hexagonal crystal α-SiAlON crystallization and Grain-Boundary Phase, carries out plasma etch process to the abrasive surface obtained.
If enforcement plasma etch process, then due to β-Si 3n 4crystallization is different from the etch-rate of Grain-Boundary Phase with hexagonal crystal α-SiAlON crystallization, so one party can be pruned more.Such as, at use CF 4plasma etching in, β-Si 3n 4crystallization and hexagonal crystal α-SiAlON crystallization due to etch-rate comparatively large (easily being etched), so β-Si 3n 4crystallization and hexagonal crystal α-SiAlON crystallization become recess, and Grain-Boundary Phase becomes protuberance.
In addition, etch processes also can be the chemical milling using bronsted lowry acids and bases bronsted lowry.SEM image taking (magnifications of more than 1000 times) is carried out to the minute surface after etch processes.In SEM photo, β-Si can be distinguished by the difference of contrast gradient 3n 4crystallization and hexagonal crystal α-SiAlON crystallization and Grain-Boundary Phase.Usually, Grain-Boundary Phase seems in white.By carrying out etch processes, the difference of contrast gradient can be made clearly.
By carrying out image analysis to SEM photo, the area ratio of the Grain-Boundary Phase of per unit area can be measured.In addition, in image analysis, chromoscan Grain-Boundary Phase part and the method for carrying out image analysis is effective.In addition, when a visual field is less than unit surface 100 μm × 100 μm, also repeatedly can take, make it add up to unit surface 100 μm × 100 μm.
In addition, the coefficient processed of the silicon nitride sinter of the first embodiment is 0.100-0.120.
The above-mentioned coefficient Mc that processes is the value calculated from following formula (4).
Mc＝Fn 9/8/(K 1c 1/2·Hv 5/8) (4)
In formula (4), Fn is loading of pressing in, in this case 20kgf.The loading of pressing in Fn of 20kgf is suitable numerical value in the hardness measuring silicon nitride sinter and toughness.Vickers' hardness (Hv) is measured according to JIS-R-1610.Fracture Toughness (K 1C) measure according to the pressing in method (IF method, Indentation Fracture method) of JIS-R-1607.When the calculating of Fracture Toughness, use newly former formula.About bearing ball described later, its section is used to measure.
Coefficient Mc can be processed represent to employ loading of pressing in (Fn), Vickers' hardness (Hv) and Fracture Toughness (K 1C) the coefficient of processibility.This is the relational expression of transverse crack fracture model, Mc represent the amount removed by 1 abrasive particle.Mean that can to process coefficient Mc larger, the amount once can processed is larger.
So-called transverse crack fracture model, refers to as material removing mechanism during ground finish, the model proposed by EvansShi and MarshallShi.In this model, 1 grinding abrasive particle by the amount of substance (Δ V) that is removed during material surface at power Fn, Vickers' hardness (Hv) and Fracture Toughness (K that abrasive particle is pressed into along the vertical direction of material 1C) relation aspect, be represented as and [Fn 9/8/ (K 1c 1/2hv 5/8)] value be directly proportional.At this, Δ V is replaced into and can processes coefficient Mc.
Processing is roughly distinguished, and can be divided into brittle mode and ductility pattern.Brittle mode is equivalent to so-called roughing, and ductility pattern is equivalent to so-called precision work.So-called abrasion, it is generally acknowledged and be equivalent to ductility pattern, think the requirement performance meeting wear resistance component, importantly do not reduce the processibility of ductility pattern and improve the processibility of brittle mode.In addition, as one of abrasion model, the mechanism it is generally acknowledged is: produce small pre-crackle (precrack) at crystal boundary, because it is propagated until material surface destroys, thus produces abrasion.
Represent that the parameter Sc.m of the severe of the mechanical contact of abrasion model is according to coefficientoffrictionμ, most dahe sesame stress Pmax, the crystallization particle diameter d of material, Fracture Toughness K 1crepresent with following formula.
Sc.m＝[(1+10·μ)·Pmax·(d 1/2)]/K 1c
When this means that parameter Sc.m is larger, abrasion are just large, and when parameter Sc.m is less, abrasion are just little.It can thus be appreciated that: by reducing the crystallization particle diameter d of material or strengthening Fracture Toughness K 1c, abrasion can be suppressed.
When considering in these, can process coefficient Mc preferably 0.100 ~ 0.120 scope.When can process coefficient Mc lower than 0.100, the attrition process amount caused by abrasive particle is less, thus silicon nitride sinter the attrition process time increase.If can process coefficient Mc more than 0.120, then the attrition process quantitative change that caused by abrasive particle of silicon nitride sinter is too much.If attrition process amount is comparatively large, then processibility is improved, but reduces as the weather resistance of sliding component.
Coefficient Mc can be processed and be in the silicon nitride sinter of 0.100 ~ 0.120 scope on the basis making as sintered compact hardness and fracture toughness property be improved, can also sliding properties be improved.In addition, due to threshing vestige when carrying out attrition process to slipping plane can be reduced, so easily to obtain surface roughness Ra be less than 0.5 μm and then be the tabular surface of less than 0.1 μm.If consideration processibility, then can process coefficient Mc preferably 0.110 ~ 0.120 scope.
In addition, when carrying out XRD analysis to silicon nitride sinter, corresponding to Y 4si 2o 7n 2the strongest intensity I that 39.5 ± 0.3 ° of places of (J phase) detect 39.5 °preferably meet relational expression: (I 39.5 °)/(I 33.6 °+ I 36.1 °)=0.03 ~ 0.10.
Y 4si 2o 7n 2(J phase) is for being present in the crystallization phases of Grain-Boundary Phase.What is called detects peak value at 39.5 ± 0.3 ° of places, refers to there is Y 4si 2o 7n 2(J phase).By by Y 4si 2o 7n 2peak strength ratio (the I of (J phase) 39.5 °)/(I 33.6 °+ I 36.1 °) be set in 0.03 ~ 0.10 scope, can Grain-Boundary Phase be strengthened.By strengthening Grain-Boundary Phase, the long-term reliability of sliding properties can be improved further.
In addition, if there is Y 4si 2o 7n 2(J phase), then near 31.0 °, 34.4 °, 36.1 °, 39.5 °, 44.5 °, (± 0.3 °) place also can detect peak value.Why select I 39.5 °, be because represent that the possibility of strongest is higher in the peak value corresponding to J phase.
In addition, when carrying out XRD analysis to silicon nitride sinter, corresponding to Y 2si 3o 12n (H phase), YSiO 2n (K phase) or Y 2si 3o 3n 4in the strongest intensity I that detects of any one 31.9 ± 0.3 ° of above place 31.9 °preferably meet (I 31.9 °)/(I 33.6 °+ I 36.1 °)=0.05 ~ 0.15.
Y 2si 3o 12n (H phase), YSiO 2n (K phase) or Y 2si 3o 3n 4in any one be the crystallization phases being present in Grain-Boundary Phase.What is called detects peak value at 31.9 ± 0.3 ° of places, refers to there is Y 2si 3o 12n (H phase), YSiO 2n (K phase) or Y 2si 3o 3n 4in any one above crystallization phases.
By by peak strength ratio (I 31.9 °)/(I 33.6 °+ I 36.1 °) be set in 0.05 ~ 0.15 scope, can Grain-Boundary Phase be strengthened.By strengthening Grain-Boundary Phase, the long-term reliability of sliding properties can be improved further.In addition, about selection I 31.9 °reason, be because it be correspond to Y 2si 3o 12n (H phase), YSiO 2n (K phase) or Y 2si 3o 3n 4in any one above peak value in one of highest peak.
In addition, the Grain-Boundary Phase comprising the crystallization of Hf-Y-O based compound and the amorphous phase containing Y-Al-O is preferably possessed.The crystallization of Hf-Y-O based compound is the compound crystal containing hafnium, yttrium and oxygen.In addition, the amorphous phase containing Y-Al-O is the amorphous phase at least containing yttrium, aluminium and oxygen.
Hafnium is activeconstituents, reacts with yttrium and oxygen and forms the crystallization of Hf-Y-O based compound, promotes Si 3n 4growth response.At this moment, it is generally acknowledged and also contribute to Y 4si 2o 7n 2(J phase), Y 2si 3o 12n (H phase), YSiO 2n (K phase) or Y 2si 3o 3n 4in the formation of more than a kind.
In addition, by amorphous phase (glassy phase) will be set as mutually containing Y-Al-O, then the homogeneous distribution easily controlling Grain-Boundary Phase is become.In addition, the presence or absence of the existence of the crystallization of Hf-Y-O based compound and the amorphous phase containing Y-Al-O can be confirmed by tem analysis.
In addition, the particle such as carbide, oxide compound, nitride that median size is less than 2 μm is preferably possessed.As above-mentioned particle, be preferably selected from the particle at least a kind among silicon (Si), the vanadium (V) of 5A race, niobium (Nb), tantalum (Ta), the chromium (Cr) of 6A race, molybdenum (Mo), tungsten (W).
Above-mentioned particle, by being present in Grain-Boundary Phase, contributes to the strengthening of Grain-Boundary Phase.In addition, in order to realize the strengthening of Grain-Boundary Phase, preferred median size is less than 2 μm, more preferably less than 1.5 μm.If median size is comparatively large and more than 2 μm, then hinder the continuous distribution of crystal boundary, likely become the cause of textural defect.
In addition, above-mentioned particle is preferably molybdenum compound particle.Molybdenum compound particle owing to having oilness, so by being present in slipping plane (surface of silicon nitride sinter), the sliding properties of slipping plane can be improved.In addition, in molybdenum compound particle, molybdenum carbide (Mo 2c) oilness of particle is excellent.
In addition, at β-Si 3n 4in crystallization, preferably major axis is more than 2 μm, and maximum aspect ratio is less than 7.In addition, in hexagonal crystal α-SiAlON crystallization, no matter be spherical shape or columnar shape, its median size is all preferably less than 2 μm.In addition, the median size of spherical shape, columnar shape (aspect ratio is less than 2) is set as particle diameter by using the circular diameter of equal value of major axis, and is obtained by the mean value of 100.
In addition, preferably in the Al of oxide compound scaled value containing 5 ~ 10 quality (wt) %, more than any one in the rare earth element of oxide compound scaled value containing 1 ~ 10 quality %, more than any one in 4A, 5A, 6A element of oxide compound scaled value containing 1 ~ 5 quality %, and the mol of preferably Al and rare earth element is than being Al (mol) ﹕ rare earth element (mo1)=1 ﹕ 1 ~ 8 ﹕ 1.
A1 (aluminium) is the composition improving coking property, and is form hexagonal crystal α-SiAlON crystallization and the necessary composition of Y-Al-O based compound amorphous phase.In addition, when adding as sintering aid, preferably A1 2o 3(aluminum oxide), A1N (aluminium nitride).If Al converts lower than 5 quality % in oxide compound, then likely make the ratio of Grain-Boundary Phase reduce, and likely make the formation of various crystallised component and amorphousness composition not enough.On the other hand, if more than 10 quality %, then Grain-Boundary Phase is likely made too to increase.
Preferably among Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), Lu (lutetium) more than at least a kind of rare earth element.In addition, when adding as sintering aid, preferably add as rare-earth oxide.In addition, if any one in rare earth element above in oxide compound scaled value lower than 1 quality %, more than 10 quality %, then the ratio of Grain-Boundary Phase is likely in outside the scope of embodiment, and becomes difficulty with the adjustment of the mol ratio of Al element.
In addition, in rare earth element, yttrium is preferred.If yttrium, then as being formed containing Y 4si 2o 7n 2(J phase), Y 2si 3o 12n (H phase), YSiO 2n (K phase), Y 2si 3o 3n 4, the crystallization of Hf-Y-O based compound, Y-Al-O amorphous phase composition and play a role.In addition, the generation of α-SiAlON crystallization is also promoted.
In addition, preferably in more than any one in 4A, 5A, 6A element of oxide compound scaled value containing 1 ~ 5 quality %.4A race element is Ti (titanium), Zr (zirconium), Hf (hafnium).In addition, 5A race element is V (vanadium), Nb (niobium), Ta (tantalum).In addition, 6A race element is Cr (chromium), Mo (molybdenum), W (tungsten).It is use TiO that the oxide compound of 4A race element converts 2, ZrO 2, HfO 2convert.In addition, the oxide compound of 5A race element converts is use V 2o 5, Nb 2o 5, Ta 2o 5convert.In addition, the oxide compound of 6A race element converts is use Cr 2o 3, MoO 3, WO 3convert.
In addition, when adding as sintering aid, preferably more than any one in oxide compound, carbide, nitride to add.In addition, 4A race element preferably adds in the form of the oxide, and 5A race element and 6A race element preferably add with the form of carbide.In addition, 4A race element is preferably Hf, and 6A race element is preferably Mo.Hf as previously mentioned, plays a role as the composition forming the crystallization of Hf-Y-O based compound.In addition, preferably by Mo with molybdenum carbide (Mo 2c) form of particle is added.As previously mentioned, molybdenum compound particle becomes Grain-Boundary Phase strengthening composition, simultaneously as improve slipping plane oilness composition and play a role.The particle of 5A race element and 6A race element has oilness, but wherein molybdenum compound has the most excellent oilness.
In addition, as composition other than the above, the silicon carbide (SiC) as carbide particle can be listed.When adding silicon carbide, preferably in the scope of 1 ~ 5wt%.
In addition, the mol of Al and rare earth element is than being preferably Al (mol) ﹕ rare earth element (mol)=1 ﹕ 1 ~ 8 ﹕ 1.By making Al measure with 1 ~ 8 of rare earth element amount times of existence, hexagonal crystal α-SiAlON crystallization becomes easy formation.In addition, preferably at Al (in the scope of mol) ﹕ rare earth element (mol)=1.4 ﹕ 1 ~ 7.0 ﹕ 1.
In addition, when being added as sintering aid by above-mentioned each composition, when alpha-silicon nitride powders amount is set as 100 mass parts, the total oxygen amount of sintering aid is preferably in the scope of 1.20 ~ 2.50 mass parts.As the interpolation form of various sintering aid, the ratio of being added with the form of nitride or carbide by allotment, just can be set as above-mentioned scope using the amount of adding as oxide compound.Such as, can list with AlN interpolation Al composition, use Mo 2c etc. add the method for Mo composition.By reducing the total oxygen amount of sintering aid, increasing nitride, also easily forming hexagonal crystal α-SiAlON crystallization.In addition, oxide sintering aid contributes to the formation of the equal Grain-Boundary Phase of amorphousness containing Y-Al-O.For this reason, by making the total oxygen amount of sintering aid in above-mentioned scope, the area ratio of Grain-Boundary Phase can also be controlled.
In addition, if be above-mentioned silicon nitride sinter, then can demonstrate excellent characteristic, its Vickers' hardness (Hv) is more than 1500, Fracture Toughness (K 1c) be 6.0MPam 1/2above, 3 flexural strengths are more than 900MPa.
In addition, Vickers' hardness (Hv) is measured according to JIS-R-1610.Fracture Toughness (K 1C) measure according to the pressing in method (IF method) of JIS-R-1607.In addition, in the calculating of Fracture Toughness, use newly former formula.In addition, 3 bending intensity are measured according to JIS-R-1601.
(the second embodiment)
Second embodiment is the sliding component of the silicon nitride sinter employing the first embodiment.As sliding component, bearing ball, roller, check ball, wear-resistant pad, plunger, roller etc. can be listed.These sliding components slide with the counter-element be made up of hardware and pottery etc.In order to improve the weather resistance of slipping plane, be preferably designed for surfaceness (Ra) attrition process become less than 0.5 μm so that be less than 0.1 μm, be more preferably the abrasive surface of less than 0.05 μm.By making slipping plane become smooth, the weather resistance of silicon nitride sinter can be improved, reducing the aggressiveness for counter-element simultaneously.By reducing the aggressiveness for counter-element, due to the consumption of counter-element can be reduced, so the weather resistance of the device enrolling sliding component can be improved.
As the device enrolling sliding component, lathe can be listed, product that electronics, automobile, aircraft also have the various fields such as wind-power electricity generation.
Fig. 1 shows bearing ball as an example of sliding component and revolving member.In FIG, symbol 1 is bearing ball.Bearing ball 1 is the spheroid of proper sphere shape.In general, configure multiple bearing ball and form bearing.Bearing ball makes whole surface become slipping plane.In addition, when forming bearing, owing to using multiple bearing ball, so also require the homogeneity of shape.The silicon nitride sinter of the first embodiment is owing to being adjusted to 25 ~ 40% by the area ratio of Grain-Boundary Phase, and coefficient Mc can be processed be adjusted to 0.100 ~ 0.120, even if so implement the attrition process that surfaceness (Ra) is less than 0.5 μm, its threshing is also few, thus threshing vestige is also little.For this reason, when carrying out the attrition process employing diamond abrasive grain, the few and tabular surface of cleaning of threshing vestige can be obtained.
In addition, by control per unit area 100 μm × 100 μm Grain-Boundary Phase area ratio, crystallize into and grade, sliding properties stabilization chronically can be made.Such as, when former bearing ball, there is when running continuously the weather resistance of 400 ~ 500 hours, and the present invention can obtain the weather resistance of more than 700 hours and then more than 800 hours.Therefore, not only can maintain the long-term reliability of sliding component, and the effect such as long-term reliability or non-maintainingization of the device enrolling bearing ball of the present invention can be obtained.
(manufacture method of the silicon nitride sinter of the first embodiment)
Be described with regard to manufacture method below.As long as the silicon nitride sinter of the first embodiment has above-mentioned formation, just there is no particular limitation for manufacture method, but as being used for the method effectively obtaining this silicon nitride sinter, can list following method.
First, alpha-silicon nitride powders is prepared.Alpha-silicon nitride powders is preferably: oxygen level is below 1.7 quality %, the α facies pattern silicon nitride (α-Si containing more than 85 quality % 3n 4), median size is less than 1.0 μm, and then is less than 0.8 μm.By making α-Si in sintering circuit 3n 4powder grain is grown to β-Si 3n 4crystallization, can obtain the silicon nitride sinter that sliding properties is excellent.
Secondly, sintering aid powder is prepared.As sintering aid, with Al composition and rare earth element composition for neccessary composition.In addition, as required, more than at least a kind and silicon carbide being selected among 4A race elemental composition, 5A race elemental composition and 6A race elemental composition is added.
In addition, as previously mentioned, preferably add, to make the mol of Al and rare earth element than being Al (mol) ﹕ rare earth element (mol)=1 ﹕ 1 ~ 8 ﹕ 1.In addition, when adding sintering aid, when alpha-silicon nitride powders amount is set as 100 mass parts, the total oxygen amount of preferred sintering aid is the scope of 1.20 ~ 2.50 mass parts.In order to control the oxygen amount of the composition added as sintering aid, preferably Al composition being added with the form of AlN, 5A race elemental composition and 6A race elemental composition are added with the form of carbide.Especially, AlN together with rare earth element with α-Si 3n 4reacting and forming hexagonal crystal α-SiAlON crystallization aspect is effective sintering aid.
Then, above-mentioned alpha-silicon nitride powders and sintering aid powder is mixed.Mixed processes uses ballmillmixer etc. and mixes, thus becomes Homogeneous phase mixing state.Especially, by making α-Si 3n 4the dispersion state of powder and AlN powder and rare-earth compounds becomes Homogeneous phase mixing, and hexagonal crystal α-SiAlON crystallization is just easily formed uniformly.In addition, in order to Homogeneous phase mixing, preferably will the mixed processes of ballmillmixer etc. be used to implement more than 50 hours.In addition, be set as that the wet-mix process carrying out mixed processes in the solution is also effective to Homogeneous phase mixing.
In addition, with in the operation of wet-format allotment raw mixture, preferably in advance Al based compound and rare-earth compounds are deployed into the slip of favorable dispersity, are then mixed in the slip as the alpha-silicon nitride powders of main raw material.The index of dispersiveness at this moment preferably uses following thixotropy index (TI value) to manage.If improve velocity of shear a, b continuously in rotational viscosimeter, then have in coherent fluid, viscosity can reduce usually.Now, the ratio of the viscosity number η under velocity of shear a and b becomes TI value.
TI value=η b/ η a
The not special regulation of the numerical value of velocity of shear a, b, but to be set as that the value that TI value gets more than 1 is advisable.TI value, more close to 1, more close to the behavior of Newtonian fuid, implies that this is the slip not having to condense or condense very weak high dispersive.In the present case, carry out adjusting thus make TI value when setting a=6 (1/s), b=60 (1/s) get the numerical value of 1.0 ~ 2.0.In addition, s represents second.By using such hybrid mode, the uniform grain growing of hexagonal crystal α-SiAlON crystallization when can effectively sinter.
Then, in raw mixture alpha-silicon nitride powders and sintering aid powder mixed, binding agent is added.The mixing of raw mixture and binding agent is carried out pulverizing and granulation on one side as required, uses ball mill etc. to be implemented.Raw mixture is configured as desired shape.Forming process is by enforcements such as moulding press and cold isostatic presses (CIP).Compacting pressure is preferably more than 100MPa.Then, degreasing is carried out to the molding obtained in forming process.Degreasing process is preferably implemented at the temperature of the scope of 300 ~ 600 DEG C.Degreasing process is implemented in an atmosphere or in non-oxidizing atmosphere, and there is no particular limitation for atmosphere.
Then, at the temperature of 1600 ~ 1900 DEG C of scopes, sinter the degreasing body obtained in degreasing process.If sintering temperature is lower than 1600 DEG C, then the grain growing of crystalline silicon nitride particle likely becomes insufficient.That is, from α-Si 3n 4to β-Si 3n 4reaction and insufficient, likely cannot obtain fine and close tissue of sintered body.In this case, silicon nitride sinter reduces as reliability of material.If sintering temperature is more than 1900 DEG C, then crystalline silicon nitride particle too carries out grain growing, likely causes intensity to reduce, or likely makes the ratio of Grain-Boundary Phase be in outside scope.
In above-mentioned sintering circuit, can be implemented by any one in normal pressure-sintered and pressure sintering.Sintering circuit is preferably implemented in non-oxidizing atmosphere.As non-oxidizing atmosphere, nitrogen atmosphere and argon atmospher can be listed.
After sintering circuit, in non-oxidizing atmosphere, preferably implement hot isostatic pressing (HIP) process of more than 30MPa.As non-oxidizing atmosphere, nitrogen atmosphere and argon atmospher can be listed.HIP treatment temp is preferably the scope of 1500 ~ 1900 DEG C.By implementing HIP process, the pore in silicon nitride sinter can be eliminated.If HIP processing pressure is lower than 30MPa, then cannot obtain such effect fully.
For the silicon nitride sinter manufactured like this, implement attrition process at the position of necessity and make sliding component.Attrition process is preferably implemented with diamond abrasive grain.Silicon nitride sinter due to embodiment has good processibility, so can reduce by tooling cost during silicon nitride sinter making sliding component.In addition, can to obtain surfaceness (Ra) be less than 0.5 μm and then be the tabular surface of less than 0.1 μm, less than 0.05 μm.
(embodiment 1)
(embodiment 1 ~ 13 and comparative example 1 ~ 2)
As alpha-silicon nitride powders, preparation oxygen level is 1.2 quality %, median size is 0.7 μm, α-Si 3n 4ratio be the powder of 99 quality %.Then, as sintering aid, the sintering aid that table 1 represents is prepared.In addition, sintering aid powder all uses median size to be the powder of less than 1.3 μm.
Table 1
Then, coordinate above-mentioned alpha-silicon nitride powders and sintering aid powder, carried out the wet mixing of 50 hours by ball mill.Carry out mixing thus make TI value at this moment be 1.0 ~ 2.0.Then, take out from solution and after drying, mix with binding agent, carried out the mixed processes of 20 hours by ball mill, thus mix mixing raw material powder respectively.
Then, by moulding press, each raw mixture is formed, then carry out degreasing at 460 DEG C.Then, littlely at present degreasing body to be sintered in 1700 ~ 1800 DEG C × 4 ~ 6 in nitrogen atmosphere.
Then HIP process is implemented to the sintered compact obtained.HIP process is implemented under the pressure of 100MPa, under the condition of 1600 DEG C × l ~ 2 hour.Just the silicon nitride sinter of embodiment 1 ~ 13 and comparative example 1 ~ 2 is produced thus.In addition, the size that 3 flexural strength measurement test portions (silicon nitride sinter) are processed into 3mm × 4mm × 50mm uses.
For the test portion (silicon nitride sinter) of embodiment 1 ~ 13 and comparative example 1 ~ 2, surfaceness (Ra) is ground to form less than 0.1 μm.Afterwards, Vickers' hardness (Hv), Fracture Toughness (K is measured 1C), 3 flexural strengths, coefficient Mc can be processed.Vickers' hardness (Hv), with the loading of pressing in of 20kgf, adopts and measures according to the method for JIS-R-1610.Fracture Toughness, with the loading of pressing in of 20kgf, is measured according to the pressing in method (IF method) of JIS-R-1607, and is obtained by newly former formula.In addition, 3 flexural strengths adopt and measure according to the method for JIS-R-1601.Its result is as shown in table 2.
Table 2
Shown by the result shown in above-mentioned each table 1 ~ 2: in the silicon nitride sinter of each embodiment, Vickers' hardness (Hv) is more than 1500, Fracture Toughness (K 1c) be 6.0MPam 1/2above, 3 flexural strengths are more than 900MPa, can process coefficient Mc in the scope of 0.100 ~ 0.120.As the calculated example of Mc, the coefficient processed of embodiment 1 is with loading of pressing in Fn=20kgf, Vickers' hardness Hv=1592, Fracture Toughness K 1c=6.6MPam 1/2, pass through Mc=20 9/8/ (6.6 1/21592 5/8) value that calculates.
In addition, use the abrasive surface of section, obtained the peak strength ratio of each crystallization by XRD analysis.Its result is as shown in table 3.
Table 3
Then, use the SEM photo of the abrasive surface of section, obtain the area ratio of the Grain-Boundary Phase of per unit area 100 μm × 100 μm.The area ratio of Grain-Boundary Phase measures 5 place's unit surface 100 μm × 100 μm, records its upper and lower bound.In addition, according to tem analysis, investigate in Grain-Boundary Phase with or without " crystallization of Hf-Y-O based compound " and " Y-Al-O based compound amorphous phase ".Its result as described in Table 4.
Table 4
Shown by the result shown in above-mentioned table 4: in the silicon nitride sinter of each embodiment, the area ratio of Grain-Boundary Phase is in the scope of 25 ~ 40%.
(embodiment 1B ~ 13B and comparative example 1B ~ 2B)
With the bearing ball of the manufacture method manufacture same with embodiment 1 ~ 13 and comparative example 1 ~ 2 as sliding component.Carry out grinding and make the diameter of bearing ball be 9.525mm, surfaceness (Ra) is 0.01 μm.
About attrition process, preparation surface roughness (Ra) attrition process becomes test portion before 0.01 μm as test portion, compares surfaceness when using ciamond grinder (#120) to carry out attrition process.About attrition process condition, make the working (finishing) area of test portion constant, load is set as 40N, is that 300rpm processes by the speed setting of grinding disc, measures and carries out processing until surfaceness (Ra) after not having the time of the change of surfaceness (Ra).Threshing state can be measured by this attrition process.Threshing state and surfaceness have dependency, and numerical value is larger, mean and more easily produce threshing, thus it is contemplated that the reliability in rolling longevity test is in the tendency of reduction.
In addition, the change of roll life-span and the crushing strength before and after the life-span of rolling is measured.When carrying out the measurement in rolling life-span and crushing strength, using to have and the bearing ball that surfaceness (Ra) is the polished surface of 0.01 μm is processed in bearing ball surface grinding.
In addition, the life-span of rolling is the bearing ball of preparation 3 each embodiments, at the diameter being set in bearing steel SUJ2 upper surface be 40mm track on configure 3 above-mentioned bearing balls at equal intervals.Under the oil bath lubrication condition of turbine oil, at applied load thus under the state making the Max.contact stress of 5.9GPa act on bearing ball, with under rotating speed 1200rpm until there is the time measurement of the peeling off rolling life-span in bearing ball surface.In addition, the measurement in life-span is rolled with continuous 800 hours for the upper limit and carrying out.
In addition, about the crushing strength before and after rolling test, 2 ball crush method are adopted to obtain the load of bearing ball generation destruction.Its result is as shown in table 5.
Table 5
Shown by the result shown in above-mentioned table 5: the bearing ball of each embodiment demonstrates the excellent sliding properties of more than 700 hours.Distinguish and particularly possessed the crystallization of Hf-Y-O based compound and add Mo 2c, as the embodiment 1 ~ 6 of sintering aid, is still maintaining excellent characteristic after reaching 800 hours.
Bearing ball uses the whole surface of sintered compact as the sliding component of slipping plane.Therefore, if as the characteristic good of bearing ball, be then namely used in other sliding component, show excellent characteristic too.Therefore, the silicon nitride sinter of embodiment goes for sliding component miscellaneous.
In addition, above just several embodiment of the present invention is illustrated, but these embodiments are pointed out as an example, and it does not seek to limit scope of invention.The embodiment of these novelties can be implemented in other various mode, in the scope not departing from invention main idea, can carry out various omissions, displacement and change.These embodiments and distortion thereof are included in scope of invention and main idea, and comprise in the scope of invention and the substitute equivalents thereof recorded in detail in the claims.
Utilizability in industry
According to silicon nitride sinter of the present invention and the sliding component using this silicon nitride sinter, about sliding properties, the silicon nitride sinter can giving long-term reliability can be provided.In addition, coefficient can be processed owing to have adjusted, even if so carry out surface grinding processing, also due to threshing can be reduced, so easily obtain smooth slipping plane.Therefore, about the sliding component using this sintered compact, also long-term reliability can be obtained.
Nomenclature:
1 bearing ball (silicon nitride sinter, sliding component)

Claims (12)

1. a silicon nitride sinter, is characterized in that: when carrying out XRD analysis to silicon nitride sinter, when will be I corresponding to the strongest intensity settings that 29.6 ± 0.3 ° of hexagonal system α-SiAlON crystallization and 31.0 ± 0.3 ° of places detect 29.6 °, I 31.0 °, on the other hand will correspond to β-Si 3n 4the strongest intensity settings that 33.6 ± 0.3 °, 36.1 ± 0.3 ° places of crystallization detect is I 33.6 °, I 36.1 °time, each strongest intensity meets following relational expression:
(I 29.6°+I 31.0°)/(I 33.6°+I 36.1°)＝0.10～0.30 (1)
In the arbitrary cross-section of described silicon nitride sinter, the area ratio of the Grain-Boundary Phase that per unit area is 100 μm × 100 μm is 25 ~ 40%, and can process coefficient is 0.100 ~ 0.120.
2. silicon nitride sinter according to claim 1, is characterized in that: when carrying out XRD analysis to silicon nitride sinter, is corresponding to Y 4si 2o 7n 2the i.e. strongest intensity I that detects of 39.5 ± 0.3 ° of places of J phase 39.5 °meet following relational expression:
(I 39.5°)/(I 33.6°+I 36.1°)＝0.03～0.10 (2)。
3. silicon nitride sinter according to claim 1 and 2, is characterized in that: when carrying out XRD analysis to silicon nitride sinter, is corresponding to Y 2si 3o 12n and H phase, YSiO 2n and K phase or Y 2si 3o 3n 4in the strongest intensity I that detects of any one 31.9 ± 0.3 ° of above place 31.9 °meet following relational expression:
(I 31.9°)/(I 33.6°+I 36.1°)＝0.05～0.15 (3)。
4. the silicon nitride sinter according to any one of claims 1 to 3, is characterized in that: XRD analysis is carried out at the arbitrary cross-section of silicon nitride sinter.
5. the silicon nitride sinter according to any one of Claims 1 to 4, is characterized in that: possess the Grain-Boundary Phase comprising the crystallization of Hf-Y-O based compound and the amorphous phase containing Y-Al-O.
6. the silicon nitride sinter according to any one of Claims 1 to 5, is characterized in that: possess oxide compound, carbide, any one above particle in nitride that median size is less than 2 μm.
7. silicon nitride sinter according to claim 6, is characterized in that: described particle is molybdenum compound particle.
8. the silicon nitride sinter according to any one of claim 1 ~ 7, it is characterized in that: in the Al of oxide compound scaled value containing 5 ~ 10 quality %, more than any one in the rare earth element of oxide compound scaled value containing 1 ~ 10 quality %, more than any one in 4A, 5A, 6A element of oxide compound scaled value containing 1 ~ 5 quality %, and the mol of Al and rare earth element is than being A1 (mo1) ﹕ rare earth element (mol)=1 ﹕ 1 ~ 8 ﹕ 1.
9. the silicon nitride sinter according to any one of claim 1 ~ 8, is characterized in that: Vickers' hardness Hv is more than 1500, Fracture Toughness K 1Cfor 6.0MPam 1/2above, and 3 bending intensity be more than 900MPa.
10. a sliding component, is characterized in that: it use the silicon nitride sinter according to any one of claim 1 ~ 9.
11. sliding components according to claim 10, is characterized in that: sliding component is bearing ball.
12. sliding components according to claim 10 or 11, is characterized in that: slipping plane to be surface roughness Ra the be abrasive surface of less than 0.5 μm.
CN201380057709.9A 2012-12-14 2013-12-06 Silicon nitride sinter and use the sliding component of this silicon nitride sinter Active CN104768900B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012273964 2012-12-14
JP2012-273964 2012-12-14
PCT/JP2013/082858 WO2014092021A1 (en) 2012-12-14 2013-12-06 Silicon nitride sintered body and sliding member using same

Publications (2)

Publication Number Publication Date
CN104768900A true CN104768900A (en) 2015-07-08
CN104768900B CN104768900B (en) 2016-05-25

Family

ID=50934312

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380057709.9A Active CN104768900B (en) 2012-12-14 2013-12-06 Silicon nitride sinter and use the sliding component of this silicon nitride sinter

Country Status (3)

Country Link
JP (1) JP6334413B2 (en)
CN (1) CN104768900B (en)
WO (1) WO2014092021A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108840687A (en) * 2018-07-26 2018-11-20 深圳市东川技术研究有限公司 A kind of high-intensitive sintering process for matching grand new material
CN117083256A (en) * 2022-03-16 2023-11-17 株式会社东芝 Silicon nitride sintered body and abrasion resistant member using same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106715032B (en) * 2014-09-25 2020-07-28 株式会社东芝 Silicon nitride sintered body friction stir welding tool member and friction stir welding apparatus using same
CN107207366B (en) 2015-01-23 2020-11-24 株式会社东芝 High thermal conductivity silicon nitride sintered body, silicon nitride substrate and silicon nitride circuit substrate using same, and semiconductor device
JP2017209716A (en) * 2016-05-27 2017-11-30 日本特殊陶業株式会社 Friction agitation joining tool
WO2023162746A1 (en) * 2022-02-25 2023-08-31 京セラ株式会社 Silicon nitride sintered body

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413972A (en) * 1993-12-23 1995-05-09 The Dow Chemical Company SiAlON composites and method of preparing the same
JP2007130700A (en) * 2005-11-08 2007-05-31 Ngk Spark Plug Co Ltd Sialon cutting tool, and tool equipped with the same
JP2010241616A (en) * 2009-04-01 2010-10-28 Toshiba Corp Impact resistant member and method for manufacturing the same
CN102791406A (en) * 2010-03-11 2012-11-21 钴碳化钨硬质合金公司 Coated ceramic cutting insert and method of making the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59182276A (en) * 1983-03-31 1984-10-17 株式会社東芝 Silicon nitride sintered body
SE451581B (en) * 1984-04-06 1987-10-19 Sandvik Ab CERAMIC MATERIAL MAINLY BASED ON SILICON NITRIDE, ALUMINUM NITRIDE AND ALUMINUM OXIDE
JPS62275071A (en) * 1986-05-22 1987-11-30 日立金属株式会社 Tough sialon
JP2736386B2 (en) * 1988-04-07 1998-04-02 株式会社豊田中央研究所 Silicon nitride sintered body
JPH04209764A (en) * 1990-11-30 1992-07-31 Toyota Central Res & Dev Lab Inc Silicon nitride sintered material and its production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413972A (en) * 1993-12-23 1995-05-09 The Dow Chemical Company SiAlON composites and method of preparing the same
JP2007130700A (en) * 2005-11-08 2007-05-31 Ngk Spark Plug Co Ltd Sialon cutting tool, and tool equipped with the same
JP2010241616A (en) * 2009-04-01 2010-10-28 Toshiba Corp Impact resistant member and method for manufacturing the same
CN102791406A (en) * 2010-03-11 2012-11-21 钴碳化钨硬质合金公司 Coated ceramic cutting insert and method of making the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108840687A (en) * 2018-07-26 2018-11-20 深圳市东川技术研究有限公司 A kind of high-intensitive sintering process for matching grand new material
CN117083256A (en) * 2022-03-16 2023-11-17 株式会社东芝 Silicon nitride sintered body and abrasion resistant member using same

Also Published As

Publication number Publication date
CN104768900B (en) 2016-05-25
WO2014092021A1 (en) 2014-06-19
JP6334413B2 (en) 2018-05-30
JPWO2014092021A1 (en) 2017-01-12

Similar Documents

Publication Publication Date Title
EP2915793B1 (en) Wear resistant member
CN104768900A (en) Silicon nitride sintered body and sliding member using same
JP5732037B2 (en) Wear-resistant member and method for manufacturing the same
JP5886337B2 (en) Wear-resistant member and wear-resistant device using the same
CN103764596B (en) Silicon nitride sinter and manufacture method thereof and use its wear parts and bearing
US9663407B2 (en) Silicon nitride wear resistant member and method for producing silicon nitride sintered compact
JP6491964B2 (en) Silicon nitride sintered body and wear-resistant member using the same
JP4723127B2 (en) Alumina ceramic sintered body, method for producing the same, and cutting tool
JP4693374B2 (en) Manufacturing method of sintered silicon nitride
JPWO2008032427A1 (en) Sliding member and bearing using the same
US20230093291A1 (en) Silicon nitride sintered body, wear-resistant member using the same, and method for producing silicon nitride sintered body
JP7353820B2 (en) Silicon nitride sintered body and wear-resistant parts using the same
JP5349525B2 (en) Rolling element
JP2007326745A (en) Wear resistant member, wear resistant equipment and method of manufacturing wear resistant member
JP2006036553A (en) Silicon nitride sintered compact and its manufacturing method
JP2008230922A (en) Silicon nitride sintered compact and sliding member using the same
JPH10194841A (en) Highly tough silicon nitride sintered compact and its production

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant