CN110156476A - A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application - Google Patents

A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application Download PDF

Info

Publication number
CN110156476A
CN110156476A CN201910344861.4A CN201910344861A CN110156476A CN 110156476 A CN110156476 A CN 110156476A CN 201910344861 A CN201910344861 A CN 201910344861A CN 110156476 A CN110156476 A CN 110156476A
Authority
CN
China
Prior art keywords
powder
nitride
rate
ductility
silicon
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.)
Pending
Application number
CN201910344861.4A
Other languages
Chinese (zh)
Inventor
郭伟明
谭大旺
陈志伟
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.)
Guangdong University of Technology
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 CN201910344861.4A priority Critical patent/CN110156476A/en
Publication of CN110156476A publication Critical patent/CN110156476A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/0006—Cutting members therefor
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/806—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/0006—Cutting members therefor
    • B26D2001/002—Materials or surface treatments therefor, e.g. composite materials
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Forests & Forestry (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Products (AREA)

Abstract

The invention belongs to ceramic cutter field, a kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application is disclosed.The silicon nitride ceramics is by Si3N4Powder and sintering aid Al2O3‑Re2O3Mixing is carried out, using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, and ball milling mixing is dried to obtain Si3N4‑Al2O3‑Re2O3Mixed powder, then by Si3N4‑Al2O3‑Re2O3Mixed powder is warming up to 700~900 DEG C, then under the protection of nitrogen, and axial pressure is to be warming up to 1600~1800 DEG C under 25~50MPa and keep the temperature, and is made through discharge plasma sintering.The present invention realizes its densification before α type is changed into β type, and matrix has high rigidity, while it is constant to retain long rodlike β type, so that β type crystal grain has strong toughening effect.Ceramics of the invention have preferable high hard high tenacity, can be applied in cutting tool field.

Description

A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application
Technical field
The invention belongs to ceramic cutter technical fields, nitrogenize silicon substrate more particularly, to a kind of high hard high-ductility (Si3N4) ceramics and its preparation method and application.
Background technique
Si3N4Ceramics are a kind of liquid phase sintered materials, usually with the phase transformation of α → β, α-during sintering densification Si3N4Belong to low-temperature stabilization crystal form, have etc. shaft-like crystal morphology, hardness is higher, and wearability is good；β-Si3N4It is brilliant to belong to high-temperature stable Type has long column shape or acicular crystal pattern, and the usual intensity, toughness of silicon nitride ceramics with this microstructure is higher, but Hardness is low.Common Si3N4Components are substantially β-Si3N4, there is excellent mechanical property and high-temperature stability, but it is hard Degree is often lower, therefore its application range is also restrained, and especially in cutting tool field, cutter life is lower.
Currently, related high hard, high-ductility Si3N4The research of ceramics is concentrated mainly on through refinement crystal grain, control sintering process The methods of (low temperature and pressure, air pressure) is realized.But on the one hand the silicon nitride cutting tool of these methods preparation is needed using superfine powder With the final size that crystal grain when mitigating crystal transfer is grown up, higher cost, on the other hand control sintering process preparation contains β- Si3N4The material of crystal grain is difficult to control β-Si3N4, content so that α-Si3N4, β-Si3N4The control coexisted is relatively difficult, hard It is difficult to spend toughness control, limits its using effect for processing certain materials, such as processing hardening is inclined to serious metal.And lead to Cross control addition β-Si3N4, seed feedstock and sintering process can at low temperature, α-Si3N4To β-Si3N4It is real before transformation completely Its existing densification, matrix have high rigidity, while retaining long rodlike β type Si3N4It is constant, so that β type Si3N4Crystal grain has strong increase The preparation of high hard high-ductility Si3N4 sintex is realized in tough effect.At present with the high hard high-ductility silicon-nitride-based ceramic material of technology preparation Expect and its is not reported in the application in cutter field.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art and disadvantage, it is an object of that present invention to provide a kind of hard high-ductilities to nitrogenize Silicon substrate (Si3N4) ceramics.
Another object of the present invention is to provide a kind of preparation methods of above-mentioned high hard high-ductility silicon-nitride-based ceramic.This method By with Al2O3Powder and rare earth oxide Re2O3Powder is sintering aid, is realized by low temperature discharge plasma agglomeration (SPS) High hard high-ductility Si3N4The preparation of Stupalox.
A further object of the present invention is to provide a kind of above-mentioned high hard high-ductility silicon-nitride-based ceramics in cutting tool field Using.
The purpose of the present invention is realized by following technical proposals:
A kind of high hard high-ductility silicon-nitride-based ceramic, the silicon nitride ceramics is by Si3N4Powder and sintering aid Al2O3-Re2O3 Mixing is carried out, using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, and ball milling mixing is dried to obtain Si3N4-Al2O3-Re2O3It is mixed Powder is closed, then by Si3N4-Al2O3-Re2O3Mixed powder is warming up to 700~900 DEG C in a vacuum with rate I, then in nitrogen Under protection, axial pressure is to be warming up to 1600~1800 DEG C under 25~50MPa with rate II and keep the temperature 1~15min, through discharging Plasma agglomeration is made；The Si3N4Including by α-Si3N4With β-Si3N4, wherein α-Si3N4With β-Si3N4Volume ratio be (5 ~8): (2~5).
Preferably, the relative density of the silicon nitride ceramics is 98~100%, and hardness is 18~21GPa, and fracture toughness is 6~10MPam1/2, bending strength is 600~1200MPa.
Preferably, the Si3N4: Al2O3-Re2O3Volume ratio be (45~47): (3~5).
Preferably, the Al2O3-Re2O3Middle Al2O3: Re2O3Volume ratio be (1~4): (1~4).
Preferably, the middle Re2O3Middle Re is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb Or Lu.
Preferably, the Si3N4The purity of powder is 98~100wt.%, wherein ɑ-Si3N4Partial size < 2 μm, β-Si3N4It is long Diameter ratio is 2~10, β-Si3N4Partial size be < 3 μm；The Al2O3The purity of powder is 99.8~99.99wt.%, the Al2O3Powder Partial size be < 500nm；The Re2O3The purity of powder is 99~99.9wt.%, the Re2O3The partial size of powder is < 1 μm.
Preferably, the rate I is 150~300 DEG C/min, and the rate II is 100~150 DEG C/min.
The preparation method of the hard high-ductility silicon-nitride-based ceramic of the height, comprises the following specific steps that:
S1. by Si3N4Powder and sintering aid Al2O3-Re2O3Mixing obtains Si after dry3N4-Al2O3-Re2O3Mixed powder Body；
S2. by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 700~900 DEG C are warming up to rate I, is then charged with 1atm nitrogen, in interior axial pressure to 30 ~50MPa, and 1600~1800 DEG C are warming up to rate II while inflating beginning, 1~15min is kept the temperature, hereafter with rate III is cooled to 700~900 DEG C, axial release, and furnace cooling, and the Si of high hard high-ductility is made3N4Ceramics.
Preferably, the rate I is 150~300 DEG C/min, and the rate II is 100~150 DEG C/min, the rate III is 80~150 DEG C/min.
Hard application of the high-ductility silicon-nitride-based ceramic in cutting tool field of the height.
Compared with prior art, the invention has the following advantages:
1. silicon nitride ceramics of the invention has the performance of high rigidity and high-ductility, this is because in the premise for guaranteeing consistency Under, by limiting α-Si3N4Crystal transfer, while retaining long rodlike β-Si3N4It is constant, so that β-Si3N4Crystal grain has strong increase Tough effect.
2. the present invention is low compared with nominal sintering temperatures using the temperature of discharge plasma sintering, the time is compared with conventional sintering process It is short, save cost.
3. the present invention is due to Si3N4Ceramics are in the interior realization densification of low-temperature short-time, and crystallite dimension is smaller, can be into one Step improves hardness, therefore, with preferable wearability and cutting ability, high-performance Si3N4Ceramics can be applied to bite Tool.
Detailed description of the invention
Fig. 1 is the hard high-ductility Silicon Nitride Ceramic Cutter green body microstructure photo of height prepared by embodiment 1.
Fig. 2 is that comparative example 1 does not add β-Si3N4Si is prepared in powder3N4Ceramic body microstructure photo.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.
Embodiment 1
1. preparation:
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: β-Si3N4: Al2O3: Yb2O3Volume ratio be 54.6:36.4:4.5:4.5 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, after planetary ball mill mixing 8h, obtains uniformly mixed Si3N4-Al2O3-Yb2O3Powder.
(2) by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 800 DEG C are warming up to the rate of 200 DEG C/min, 1atm nitrogen is then filled in 1min, is filled After the completion of gas, 35MPa is axially forced into 2min, and be warming up to while inflating beginning with the rate of 100 DEG C/min 1680 DEG C, 5min is kept the temperature, is hereafter cooled to 800 DEG C with the rate of temperature fall of 120 DEG C/min, axial release, and furnace cooling, it takes out It is processed after sample through subsequent mechanical and obtains high hard high-ductility Si3N4Base ceramic cutting tool.
2. performance test: the resulting Si of the present embodiment3N4The relative density of ceramics is 99.5%, hardness 20.5GPa, is broken Splitting toughness is 7.1MPam1/2, bending strength 880MPa.
Comparative example 1
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: Al2O3: Yb2O3Volume ratio be 91:4.5:4.5 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball is ball milling Jie Matter obtains uniformly mixed Si after planetary ball mill mixing 8h3N4-Al2O3-Yb2O3Powder.
(2) by α-Si3N4: Al2O3: Yb2O3Mixed powder is put into hot pressing furnace graphite jig, in the vacuum for being less than 1mbar Under the conditions of degree, 800 DEG C are warming up to the rate of 20 DEG C/min, 1atm nitrogen is then filled in 1min, after the completion of inflation, It is axially forced into 30MPa in 15min, and is warming up to 1680 DEG C while inflating beginning with the rate of 10 DEG C/min, keeps the temperature 1h, Hereafter 800 DEG C are cooled to the rate of temperature fall of 20 DEG C/min, axial release, and furnace cooling is taken out after sample through subsequent mechanical Processing obtains Si3N4Sintex.
2. performance test: the resulting Si of this comparative example3N4The relative density of ceramics is 99.8%, hardness 19.5GPa, is broken Splitting toughness is 5.5MPam1/2, bending strength 690MPa.Intensity, hardness and toughness is all compared with comparative example 1, in embodiment 1 It is able to maintain in higher level.Therefore, by way of discharge plasma sintering between low-temperature short-time, high hard high-ductility Si is realized3N4Pottery The preparation of porcelain cutter.
Fig. 1 is the microstructure photo of silicon nitride ceramics made from embodiment 1.As can be known from Fig. 1, sample crystal grain is tiny Etc. shaft-like and the rodlike combination of coarse length.Fig. 2 is Si made from comparative example 13N4The microstructure photo of ceramics.As can be known from Fig. 2, Si3N4Ceramics crystal grain be short cylinder and etc. shaft-like combine.In conjunction with the embodiments 1 with comparative example 1 in performance test it will be evident that In embodiment 1 by way of discharge plasma sintering between low-temperature short-time, fine grain, high hard high-ductility Si are realized3N4The system of ceramics It is standby.
Embodiment 2
1. preparation:
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: β-Si3N4: Al2O3: Yb2O3Volume ratio be 75.2:18.8:4:2 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, after planetary ball mill mixing 8h, obtains uniformly mixed Si3N4-Al2O3-Yb2O3Powder.
(2) by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 800 DEG C are warming up to the rate of 200 DEG C/min, 1atm nitrogen is then filled in 1min, is filled After the completion of gas, 50MPa is axially forced into 2min, and be warming up to while inflating beginning with the rate of 100 DEG C/min 1600 DEG C, 1min is kept the temperature, is hereafter cooled to 800 DEG C with the rate of temperature fall of 120 DEG C/min, axial release, and furnace cooling, it takes out It is processed after sample through subsequent mechanical and obtains high hard high-ductility Si3N4Sintex.
2. performance test: the resulting Si of the present embodiment3N4The relative density of ceramics is 98.3%, hardness 21.8GPa, is broken Splitting toughness is 6.2MPam1/2, bending strength 711MPa.
Embodiment 3
1. preparation:
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: β-Si3N4: Al2O3: Yb2O3Volume ratio be 45:45:3:7 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball Uniformly mixed Si is obtained after planetary ball mill mixing 8h for ball-milling medium3N4-Al2O3-Yb2O3Powder.
(2) by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 800 DEG C are warming up to the rate of 200 DEG C/min, 1atm nitrogen is then filled in 1min, is filled After the completion of gas, 30MPa is axially forced into 2min, and be warming up to while inflating beginning with the rate of 100 DEG C/min 1780 DEG C, 15min is kept the temperature, is hereafter cooled to 800 DEG C with the rate of temperature fall of 120 DEG C/min, axial release, and furnace cooling, it takes It is processed after sample through subsequent mechanical out and obtains high hard high-ductility Si3N4 sintex.
2. performance test: the resulting Si of the present embodiment3N4The relative density of ceramics is 100%, hardness 19.2GPa, fracture Toughness is 8.7MPam1/2, bending strength 989MPa.
Embodiment 4
1. preparation:
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: β-Si3N4: Al2O3: Yb2O3Volume ratio be 64.4:27.6:4:4 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, after planetary ball mill mixing 8h, obtains uniformly mixed Si3N4-Al2O3-Yb2O3Powder.
(2) by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 800 DEG C are warming up to the rate of 200 DEG C/min, 1atm nitrogen is then filled in 1min, is filled After the completion of gas, 40MPa is axially forced into 2min, and be warming up to while inflating beginning with the rate of 100 DEG C/min 1700 DEG C, 1min is kept the temperature, is hereafter cooled to 800 DEG C with the rate of temperature fall of 120 DEG C/min, axial release, and furnace cooling, it takes out It is processed after sample through subsequent mechanical and obtains high hard high-ductility Si3N4 sintex.
2. performance test: the resulting Si of the present embodiment3N4The relative density of ceramics is 99.4%, hardness 20.9GPa, is broken Splitting toughness is 6.8MPam1/2, bending strength 750MPa.
Embodiment 5
1. preparation:
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: β-Si3N4: Al2O3: Yb2O3Volume ratio be 60:30:2:8 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball Uniformly mixed Si is obtained after planetary ball mill mixing 8h for ball-milling medium3N4-Al2O3-Yb2O3Powder.
(2) by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 800 DEG C are warming up to the rate of 200 DEG C/min, 1atm nitrogen is then filled in 1min, is filled After the completion of gas, 40MPa is axially forced into 2min, and be warming up to while inflating beginning with the rate of 100 DEG C/min 1600 DEG C, 15min is kept the temperature, is hereafter cooled to 800 DEG C with the rate of temperature fall of 120 DEG C/min, axial release, and furnace cooling, it takes It is processed after sample through subsequent mechanical out and obtains high hard high-ductility Si3N4 sintex.
2. performance test: the resulting Si of the present embodiment3N4The relative density of ceramics is 99.9%, hardness 20.1GPa, is broken Splitting toughness is 6.9MPam1/2, bending strength 665MPa.
Embodiment 6
1. preparation:
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: β-Si3N4: Al2O3: Yb2O3Volume ratio be 69:23:6:2 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball Uniformly mixed Si is obtained after planetary ball mill mixing 8h for ball-milling medium3N4-Al2O3-Yb2O3Powder.
(2) by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 800 DEG C are warming up to the rate of 200 DEG C/min, 1atm nitrogen is then filled in 1min, is filled After the completion of gas, 38MPa is axially forced into 2min, and be warming up to while inflating beginning with the rate of 100 DEG C/min 1700 DEG C, 8min is kept the temperature, is hereafter cooled to 800 DEG C with the rate of temperature fall of 120 DEG C/min, axial release, and furnace cooling, it takes out It is processed after sample through subsequent mechanical and obtains high hard high-ductility Si3N4 sintex.
2. performance test: the resulting Si of the present embodiment3N4The relative density of ceramics is 99.5%, hardness 20.5GPa, is broken Splitting toughness is 6.6MPam1/2, bending strength 740MPa.
Embodiment 7
1. preparation:
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: β-Si3N4: Al2O3: Yb2O3Volume ratio be 64.3:25.7:2:8 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, after planetary ball mill mixing 8h, obtains uniformly mixed Si3N4-Al2O3-Yb2O3Powder.
(2) by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 800 DEG C are warming up to the rate of 200 DEG C/min, 1atm nitrogen is then filled in 1min, is filled After the completion of gas, 38MPa is axially forced into 2min, and be warming up to while inflating beginning with the rate of 100 DEG C/min 1800 DEG C, 8min is kept the temperature, is hereafter cooled to 800 DEG C with the rate of temperature fall of 120 DEG C/min, axial release, and furnace cooling, it takes out It is processed after sample through subsequent mechanical and obtains high hard high-ductility Si3N4 sintex.
2. performance test: the resulting Si of the present embodiment3N4The relative density of ceramics is 99.8%, hardness 18.2GPa, is broken Splitting toughness is 9.7MPam1/2, bending strength 1174MPa.
Embodiment 8
1. preparation:
(1) with Si3N4Powder is matrix material, with Al2O3Powder (purity 99.9%), Yb2O3(purity 99.99%), is pressed According to α-Si3N4: β-Si3N4: Al2O3: Yb2O3Volume ratio be 45:45:3:7 carry out ingredient, using ethyl alcohol as solvent, with Si3N4Ball Uniformly mixed Si is obtained after planetary ball mill mixing 8h for ball-milling medium3N4-Al2O3-Yb2O3Powder.
(2) by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, is being less than Under the vacuum degree condition of 1mbar, 800 DEG C are warming up to the rate of 200 DEG C/min, 1atm nitrogen is then filled in 1min, is filled After the completion of gas, 35MPa is axially forced into 2min, and be warming up to while inflating beginning with the rate of 100 DEG C/min 1600 DEG C, 10min is kept the temperature, is hereafter cooled to 800 DEG C with the rate of temperature fall of 120 DEG C/min, axial release, and furnace cooling, it takes It is processed after sample through subsequent mechanical out and obtains high hard high-ductility Si3N4 sintex.
2. performance test: the resulting Si of the present embodiment3N4The relative density of ceramics is 99.2%, hardness 19.0GPa, is broken Splitting toughness is 9.0MPam1/2, bending strength 913MPa.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of high hard high-ductility silicon-nitride-based ceramic, which is characterized in that the silicon nitride ceramics is by Si3N4Powder and sintering aid Al2O3-Re2O3Mixing is carried out, using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, and ball milling mixing is dried to obtain Si3N4- Al2O3-Re2O3Mixed powder, then by Si3N4-Al2O3-Re2O3Mixed powder, 700 are warming up in a vacuum with rate I~ 900 DEG C, then under the protection of nitrogen, axial pressure is to be warming up to 1600~1800 DEG C under 25~50MPa with rate II and keep the temperature 1~15min is made through discharge plasma sintering；The Si3N4Including by α-Si3N4With β-Si3N4, wherein α-Si3N4With β- Si3N4Volume ratio be (5~8): (2~5).
2. high hard high-ductility silicon-nitride-based ceramic according to claim 1, which is characterized in that the silicon nitride ceramics it is opposite Density is 98~100%, and hardness is 18~21GPa, and fracture toughness is 6~10MPam1/2, bending strength be 600~ 1200MPa。
3. high hard high-ductility silicon-nitride-based ceramic according to claim 1, which is characterized in that the Si3N4: Al2O3-Re2O3 Volume ratio be (45~47): (3~5).
4. high hard high-ductility silicon-nitride-based ceramic according to claim 2, which is characterized in that the Al2O3-Re2O3In Al2O3: Re2O3Volume ratio be (1~4): (1~4).
5. high hard high-ductility silicon-nitride-based ceramic according to claim 1, which is characterized in that the middle Re2O3Middle Re be Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
6. high hard high-ductility silicon-nitride-based ceramic according to claim 1, which is characterized in that the Si3N4The purity of powder is 98 ~100wt.%, wherein ɑ-Si3N40.3~2 μm of partial size, β-Si3N4Major diameter ratio is β-Si3N4Partial size be 0.3~3 μ m；The Al2O3The purity of powder is 99.8~99.99wt.%, the Al2O3The partial size of powder is 100~500nm；The Re2O3Powder Purity be 99~99.9wt.%, the Re2O3The partial size of powder is 0.2~1 μm.
7. high hard high-ductility silicon-nitride-based ceramic according to claim 1, which is characterized in that the rate I is 150~300 DEG C/min, the rate II is 100~150 DEG C/min.
8. the preparation method of high hard high-ductility silicon-nitride-based ceramic according to claim 1-7, which is characterized in that packet Include following specific steps:
S1. by Si3N4Powder and sintering aid Al2O3-Re2O3Mixing obtains Si after dry3N4-Al2O3-Re2O3Mixed powder；
S2. by Si3N4-Al2O3-Re2O3Mixed powder is put into discharge plasma sintering furnace graphite jig, less than 1mbar's Under vacuum degree condition, be warming up to 700~900 DEG C with rate I, be then charged with 1atm nitrogen, interior axial pressure to 30~ 50MPa, and 1600~1800 DEG C are warming up to rate II while inflating beginning, 1~15min is kept the temperature, hereafter with rate III It is cooled to 700~900 DEG C, axial release, and furnace cooling, the Si of high hard high-ductility is made3N4Ceramics.
9. the preparation method of high hard high-ductility silicon-nitride-based ceramic according to claim 8, which is characterized in that the rate I For 150~300 DEG C/min, the rate II is 100~150 DEG C/min, and the rate III is 80~150 DEG C/min.
10. application of the described in any item high hard high-ductility silicon-nitride-based ceramics of claim 1-7 in cutting tool field.
CN201910344861.4A 2019-04-26 2019-04-26 A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application Pending CN110156476A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910344861.4A CN110156476A (en) 2019-04-26 2019-04-26 A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910344861.4A CN110156476A (en) 2019-04-26 2019-04-26 A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application

Publications (1)

Publication Number Publication Date
CN110156476A true CN110156476A (en) 2019-08-23

Family

ID=67638736

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910344861.4A Pending CN110156476A (en) 2019-04-26 2019-04-26 A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application

Country Status (1)

Country Link
CN (1) CN110156476A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620715A (en) * 2021-08-12 2021-11-09 石家庄铁道大学 Preparation method of high-toughness high-lubrication silicon nitride ceramic skate
CN113880592A (en) * 2021-11-08 2022-01-04 北京理工大学 Preparation process of high-hardness high-toughness silicon nitride ceramic complex structural member
CN114436667A (en) * 2021-12-20 2022-05-06 辽宁伊菲科技股份有限公司 Preparation method for increasing toughness of silicon nitride
CN115448730A (en) * 2022-08-23 2022-12-09 衡阳凯新特种材料科技有限公司 High-strength high-heat-conductivity silicon nitride ceramic cutter and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1727307A (en) * 2005-07-27 2006-02-01 清华大学 Ceramics of silicon nitride with high antioxygenic property and preparation method
CN104926317A (en) * 2015-06-01 2015-09-23 广东工业大学 High-toughness Si3N4 ceramic preparation method
CN105016738A (en) * 2014-04-30 2015-11-04 广东工业大学 Silicon nitride ceramic and preparation method thereof
CN109160816A (en) * 2018-08-27 2019-01-08 广东工业大学 A kind of symmetrical and consecutive variations tough silicon nitride graded ceramics of table hard-core and its preparation method and application
CN109320259A (en) * 2018-11-16 2019-02-12 广东工业大学 A kind of silicon nitride base diamond composite material and preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1727307A (en) * 2005-07-27 2006-02-01 清华大学 Ceramics of silicon nitride with high antioxygenic property and preparation method
CN105016738A (en) * 2014-04-30 2015-11-04 广东工业大学 Silicon nitride ceramic and preparation method thereof
CN104926317A (en) * 2015-06-01 2015-09-23 广东工业大学 High-toughness Si3N4 ceramic preparation method
CN109160816A (en) * 2018-08-27 2019-01-08 广东工业大学 A kind of symmetrical and consecutive variations tough silicon nitride graded ceramics of table hard-core and its preparation method and application
CN109320259A (en) * 2018-11-16 2019-02-12 广东工业大学 A kind of silicon nitride base diamond composite material and preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PENG GUI-HUA，ET AL.: "Spark plasma sintered high hardness α/β Si3N4 composites with MgSiN2 as additives", 《SCRIPTA MATERIALIA》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620715A (en) * 2021-08-12 2021-11-09 石家庄铁道大学 Preparation method of high-toughness high-lubrication silicon nitride ceramic skate
CN113880592A (en) * 2021-11-08 2022-01-04 北京理工大学 Preparation process of high-hardness high-toughness silicon nitride ceramic complex structural member
CN113880592B (en) * 2021-11-08 2022-07-05 北京理工大学 Preparation process of high-hardness high-toughness silicon nitride ceramic complex structural member
CN114436667A (en) * 2021-12-20 2022-05-06 辽宁伊菲科技股份有限公司 Preparation method for increasing toughness of silicon nitride
CN115448730A (en) * 2022-08-23 2022-12-09 衡阳凯新特种材料科技有限公司 High-strength high-heat-conductivity silicon nitride ceramic cutter and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN110156476A (en) A kind of high hard high-ductility silicon-nitride-based ceramic and its preparation method and application
CN111253162B (en) Method for preparing high-strength high-toughness high-thermal-conductivity silicon nitride ceramic
CN109206141A (en) A kind of high hard high-ductility silicon nitride ceramics and its preparation method and application
CN109879669B (en) High-entropy ceramic composite material with high strength and preparation method and application thereof
JP3624219B2 (en) Polycrystalline SiC molded body, manufacturing method thereof and applied product comprising the same
CN105016738B (en) Silicon nitride ceramics and preparation method thereof
CN110218096A (en) A kind of high hard high abrasion silicon nitride ceramics and its preparation method and application
Kim et al. Microstructure control of in‐situ‐toughened α‐SiAlON Ceramics
EP0780351B1 (en) Aluminum nitride sintered body and method for manufacturing the same
Kim et al. Novel two‐step sintering process to obtain a bimodal microstructure in silicon nitride
CN109305816A (en) A kind of normal pressure-sintered method for preparing high heat conductivity silicon nitride ceramics
CN109694253A (en) A method of normal pressure-sintered silicon nitride ceramics thermal conductivity is improved by carbon doping
US5908798A (en) In-situ toughened alpha prime-sialon-based ceramics
CN109160816A (en) A kind of symmetrical and consecutive variations tough silicon nitride graded ceramics of table hard-core and its preparation method and application
CN114538931A (en) High-performance AlON transparent ceramic and low-temperature rapid preparation method thereof
CN108610055A (en) A kind of method that low-temp liquid-phase sintering prepares compact silicon nitride ceramics
CN112299861A (en) AlON transparent ceramic pseudo-sintering agent and application thereof, and preparation method of transparent ceramic
CN109942310B (en) Preparation method of high-performance silicon nitride porous ceramic
Lee et al. Effect of raw-Si particle size on the properties of sintered reaction-bonded silicon nitride
CN107651964A (en) A kind of AlN base composite ceramics and preparation method thereof
CN111302809A (en) High-thermal-conductivity and high-strength silicon nitride ceramic material and preparation method thereof
CN108314455B (en) Silicon carbide ceramic and preparation method and application thereof
Kim et al. Characterization of porous sintered reaction-bonded silicon nitride containing three different rare-earth oxides
Rhee et al. Effect of α-Si3N4 initial powder size on the microstructural evolution and phase transformation during sintering of Si3N4 ceramics
EP0658218B1 (en) Cermet or ceramic/glass composites including self-reinforced beta-silicon nitride, and method of making same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20190823

RJ01 Rejection of invention patent application after publication