CN103073268B - Alumina ceramic self-lubricating composite material and preparation method thereof - Google Patents
Alumina ceramic self-lubricating composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103073268B CN103073268B CN201110327284.1A CN201110327284A CN103073268B CN 103073268 B CN103073268 B CN 103073268B CN 201110327284 A CN201110327284 A CN 201110327284A CN 103073268 B CN103073268 B CN 103073268B
- Authority
- CN
- China
- Prior art keywords
- layer
- alumina
- oxide
- zirconium
- lubricant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses an alumina ceramic self-lubricating composite material and a preparation method thereof. The composite material is prepared from alumina, zirconia and a composite lubricant; the surface layer of the material is an alumina layer, and a spacing layer is an alumina-zirconia layer; and the material is prepared by using the process of ply stacking-cold pressing-hot pressing. The alumina ceramic self-lubricating composite material prepared in the invention has excellent mechanical and tribological properties and a wide adaptive temperature range (from room temperature to 1000 DEG C) and can be used as a lubricating and sealing material in an extremely severe environment (high temperature, corrosion, special atmosphere, etc.).
Description
Technical field
The present invention relates to a kind of high-performance ceramic matrix material and preparation method, be specially a kind of hot pressed sintering and prepare stratiform-gradient composite structure high-performance alumina-ceramic self-lubricating composite and preparation method thereof.
Background technology
Pottery self-lubricating composite is development along with modern military industrial technologies such as aerospace, is the lubricating requirement adapted under harsh working condition and the Novel lubricating material that develops rapidly.This kind of lubricant has significant advantage in high-low temperature resistant, environmental compatibility etc.And from the development in future, high-temperature structural ceramics uniquely can work long hours more than 1000 DEG C, has the low density lubricant of high strength and corrosion resistance nature simultaneously.But in research and practical application, pottery self-lubricating composite shows a series of deficiency, be mainly reflected in the oxidation of solid lubricant in high-temperature sintering process, decomposition and volatilization and the successional destruction of matrix understood to the intensity, toughness and the wear resistance that significantly reduce matrix material, thus reduce the reliability and stability of material itself, limit its practical application.Therefore, design preparation has the ceramic self-lubricating composite of excellent mechanical and tribological property concurrently, and to promotion, it has great importance in the application in the fields such as China's Aeronautics and Astronautics.
Summary of the invention
One is the object of the present invention is to provide to have stratiform-gradient composite structure, there is high strength, high tenacity, and in room temperature to 1000 DEG C of temperature ranges, there is self-lubricating property, preparation technology is simple, sintering temperature is low alumina-ceramic self-lubricating composite and preparation method thereof.
Technical scheme of the present invention is as follows:
A kind of alumina-ceramic self-lubricating composite, it is characterized in that material is made up of aluminum oxide, zirconium white and compounded lubricant, top layer is alumina layer, and wall is alumina-silica zirconium layer; Described alumina layer is made up of aluminum oxide (40 ~ 100wt%), sintering aid (0 ~ 10wt%) [(0 ~ 5wt%) cupric oxide+(0 ~ 5wt%) titanium dioxide], compounded lubricant (0 ~ 50wt%); Alumina-silica zirconium layer is made up of aluminium oxide-zirconium oxide (40 ~ 100wt%), sintering aid (0 ~ 10wt%) [(0 ~ 5wt%) cupric oxide+(0 ~ 5wt%) titanium dioxide], compounded lubricant (0 ~ 50wt%).
In its lamination, from inside to outside, compounded lubricant composition grows out of nothing, many by reducing, and form gradient, it accounts for each layer mass percent is 0% ~ 50%.
Described compounded lubricant is by graphite (0 ~ 10wt%), barium sulfate (0 ~ 10wt%) and Calcium Fluoride (Fluorspan)] (0 ~ 80wt%) form.
In described alumina-silica zirconium layer, the content of zirconium white (containing 2 ~ 3mol% yttrium oxide) is 8 ~ 12wt%.
The Thickness ratio of described alumina layer and alumina-silica zirconium layer is 1: 1.
A kind of preparation method of alumina-ceramic self-lubricating composite, it is characterized in that with commercialization aluminum oxide, zirconium white, cupric oxide, titanium oxide, yttrium oxide, graphite, barium sulfate and Calcium Fluoride (Fluorspan) powder for raw material, through physical mechanical method in proportion ball milling obtain the aluminum oxide that mixes and aluminium oxide-zirconium oxide initial powder; In steel die, the aluminum oxide mixed and aluminium oxide-zirconium oxide initial powder are replaced laying, carries out coldmoulding subsequently, forming pressure is 20 ~ 200MPa; The stratiform base substrate of coldmoulding is put into the hot pressing furnace sintering being connected with protective atmosphere (high pure nitrogen, argon gas or helium); temperature rise rate is 5 ~ 20 DEG C/min; sintering temperature is 1200 ~ 1350 DEG C, and sintering pressure is 20 ~ 30MPa, and sintering time is 30 ~ 60 minutes.
Principle of design of the present invention is as follows:
Material is by heterogeneous hard layer Al
2o
3and Al
2o
3-ZrO
2(3Y) form alternately, form the bionic laminar structure of strong interfacial bond, at hard layer Al
2o
3and Al
2o
3-ZrO
2(3Y) be evenly distributed with the solid lubrication constituent element of some amount in layer, and the content of lubricant component forms the structure of graded inwards from top layer.This structure due to middle mechanics supporting region be laminate structure, unrelieved stress and ZrO in laminate structure
2transformation toughening acts synergistically, and makes material have higher-strength and toughness; In addition, equally distributed solid lubrication constituent element is utilized to improve the contact condition of frictional interface the dragging deposited formation lubricant film of friction surface, to meet in certain temperature range continuous lubrication or lubricate at a certain temperature, achieving the structure/lubricating function integrated design of stupalith.
Advantage of the present invention is:
1, excellent mechanical property (high tenacity, high bending strength) and tribological property (possessing self-lubricating property in room temperature in 1000 DEG C of temperature ranges) is had concurrently.Aluminum oxide self-lubricating composite of the present invention, has stratiform-gradient composite structure feature.This structure makes material have excellent mechanics and tribological property concurrently, and in the temperature range of room temperature to 1000 DEG C, the frictional coefficient of material, far below mono-layer oxidized aluminium pottery, presents excellent self-lubricating property; The toughness of material, flexural strength and mono-layer oxidized aluminium ceramic phase are worked as, much larger than mono-layer oxidized aluminium pottery self-lubricating composite.With Al
2o
3layer and Al
2o
3-10wt%ZrO
2(3Y) Thickness ratio of layer be 1: 1, thickness be 82 μm for example: Al
2o
3/ Al
2o
3-ZrO
2(3Y) flexural strength of self-lubricating composite can reach 350MPa, and mono-layer oxidized aluminium ceramic phase is worked as, and is more than 5 times of self-lubricating composite of mono-layer oxidized aluminium pottery; Its frictional coefficient far below mono-layer oxidized aluminium pottery, in the temperature range of room temperature to 1000 DEG C with zirconia ceramics to when grinding, the frictional coefficient of material, all lower than 0.5, is about the half of mono-layer oxidized aluminium pottery.Meanwhile, the flexural strength of matrix material, tribological property and gradient index, thickness and composite lubricated agent content have obvious relation, show that the performance of this matrix material can be controlled by adjustment thickness, gradient index and lubricant content.
2, preparation technology is simple.The present invention adopts simple laying and heat pressing process finally to prepare high-performance Al
2o
3pottery self-lubricating stratified composite, technique is simple, workable, reproducible.Meanwhile, in order to obtain the matrix material of different volumes, only need by the number of plies of adjustment die size and matrix material, for satisfied different working condition provides convenience.In addition, introduce complex sintering aids, the sintering temperature of material is controlled, at about 1300 DEG C, decrease the oxidation of solid lubricant, decomposition and volatilization, thus ensure that effective performance of lubricant, optimize the performance of material.
Embodiment
Embodiment 1
Be that 50 grams, 100 ~ 200 object aluminum oxide, zirconium white 5 grams, titanium oxide 2 grams and cupric oxide 0.5 gram ball milling in alcohol medium obtains aluminium oxide-zirconium oxide mixed powder in 24 hours by particle size range; 50 grams, 100 ~ 200 object aluminum oxide, titanium oxide 2 grams and cupric oxide 0.5 gram ball milling in alcohol medium is obtained aluminum oxide mixed powder in 24 hours; 70 grams, 100 ~ 200 object Calcium Fluoride (Fluorspan), 10 grams, graphite, 10 grams, barium sulfate ball milling in alcohol medium is obtained composite solid lubricating agent in 12 hours; Be 5,15,25,35,45% to join composite solid lubricating agent good for above-mentioned ball milling in aluminum oxide and aluminium oxide-zirconium oxide mixed powder by massfraction, obtain aluminum oxide/lubricant and the aluminium oxide-zirconium oxide/lubricant composite granule of different lubricant content; In steel die, the aluminum oxide prepared and aluminium oxide-zirconium oxide and aluminum oxide/lubricant and aluminium oxide-zirconium oxide/lubricant composite granule are replaced laying, thickness is 0.5mm, by showing inwards, composite lubricated agent content successively decreases, the complete premolding of colding pressing under 100MPa pressure of laying.Finally, put into hot pressing furnace and sinter, temperature rise rate is 10 DEG C/min, and sintering temperature is 1300 DEG C, and sintering pressure is 20MPa, and sintering time is 50 minutes, and whole sintering process is all carry out under argon shield.The sintered sample of final acquisition is known by analysis, and stratiform-gradient-structure is obvious, and the mean thickness of every layer is about 85 μm.
Embodiment 2
Be that 50 grams, 100 ~ 200 object aluminum oxide, zirconium white 5 grams, titanium oxide 2 grams and cupric oxide 0.5 gram ball milling in alcohol medium obtains aluminium oxide-zirconium oxide mixed powder in 24 hours by particle size range; 50 grams, 100 ~ 200 object aluminum oxide, titanium oxide 2 grams and cupric oxide 0.5 gram ball milling in alcohol medium is obtained aluminum oxide mixed powder in 24 hours; 70 grams, 100 ~ 200 object Calcium Fluoride (Fluorspan), 10 grams, graphite, 10 grams, barium sulfate ball milling in alcohol medium is obtained composite solid lubricating agent in 12 hours; Be 5,15,25,35,45% to join composite solid lubricating agent good for above-mentioned ball milling in aluminum oxide and aluminium oxide-zirconium oxide mixed powder by massfraction, obtain aluminum oxide/lubricant and the aluminium oxide-zirconium oxide/lubricant composite granule of different lubricant content; In steel die, the aluminum oxide prepared and aluminium oxide-zirconium oxide and aluminum oxide/lubricant and aluminium oxide-zirconium oxide/lubricant composite granule are replaced laying, thickness is 2mm, by showing inwards, composite lubricated agent content successively decreases, the complete premolding of colding pressing under 120MPa pressure of laying.Finally, put into hot pressing furnace and sinter, temperature rise rate is 10 DEG C/min, and sintering temperature is 1350 DEG C, and sintering pressure is 20MPa, and sintering time is 50 minutes, and whole sintering process is all carry out under argon shield.The sintered sample of final acquisition is known by analysis, and stratiform-gradient-structure is obvious, and the mean thickness of every layer is about 315 μm.
Embodiment 3
Be that 50 grams, 100 ~ 200 object aluminum oxide, zirconium white 5 grams, titanium oxide 2 grams and cupric oxide 0.5 gram ball milling in alcohol medium obtains aluminium oxide-zirconium oxide mixed powder in 24 hours by particle size range; 50 grams, 100 ~ 200 object aluminum oxide, titanium oxide 2 grams and cupric oxide 0.5 gram ball milling in alcohol medium is obtained aluminum oxide mixed powder in 24 hours; 70 grams, 100 ~ 200 object Calcium Fluoride (Fluorspan), 10 grams, graphite, 10 grams, barium sulfate ball milling in alcohol medium is obtained composite solid lubricating agent in 12 hours; Be 5,20,35,50% to join composite solid lubricating agent good for above-mentioned ball milling in aluminum oxide and aluminium oxide-zirconium oxide mixed powder by massfraction, obtain aluminum oxide/lubricant and the aluminium oxide-zirconium oxide/lubricant composite granule of different lubricant content; In steel die, the aluminum oxide prepared and aluminium oxide-zirconium oxide and aluminum oxide/lubricant and aluminium oxide-zirconium oxide/lubricant composite granule are replaced laying, thickness is 0.5mm, by showing inwards, composite lubricated agent content successively decreases, the complete premolding of colding pressing under 100MPa pressure of laying.Finally, put into hot pressing furnace and sinter, temperature rise rate is 10 DEG C/min, and sintering temperature is 1350 DEG C, and sintering pressure is 20MPa, and sintering time is 50 minutes, and whole sintering process is all carry out under argon shield.The sintered sample of final acquisition is known by analysis, and stratiform-gradient-structure is obvious, and the mean thickness of every layer is about 85 μm.
Embodiment 4
Be that 50 grams, 100 ~ 200 object aluminum oxide, zirconium white 5 grams, titanium oxide 2 grams and cupric oxide 0.5 gram ball milling in alcohol medium obtains aluminium oxide-zirconium oxide mixed powder in 24 hours by particle size range; 50 grams, 100 ~ 200 object aluminum oxide, titanium oxide 2 grams and cupric oxide 0.5 gram ball milling in alcohol medium is obtained aluminum oxide mixed powder in 24 hours; 70 grams, 100 ~ 200 object Calcium Fluoride (Fluorspan), 10 grams, graphite, 10 grams, barium sulfate ball milling in alcohol medium is obtained composite solid lubricating agent in 12 hours; Be 5,10,20,30,40,50% to join composite solid lubricating agent good for above-mentioned ball milling in aluminum oxide and aluminium oxide-zirconium oxide mixed powder by massfraction, obtain aluminum oxide/lubricant and the aluminium oxide-zirconium oxide/lubricant composite granule of different lubricant content; In steel die, the aluminum oxide prepared and aluminium oxide-zirconium oxide and aluminum oxide/lubricant and aluminium oxide-zirconium oxide/lubricant composite granule are replaced laying, thickness is 0.5mm, by showing inwards, composite lubricated agent content successively decreases, the complete premolding of colding pressing under 100MPa pressure of laying.Finally, put into hot pressing furnace and sinter, temperature rise rate is 10 DEG C/min, and sintering temperature is 1350 DEG C, and sintering pressure is 20MPa, and sintering time is 50 minutes, and whole sintering process is all carry out under argon shield.The sintered sample of final acquisition is known by analysis, and stratiform-gradient-structure is obvious, and the mean thickness of every layer is about 85 μm.
Comparative example
Adopt the technique identical with embodiment 4 and fill a prescription the to prepare ceramic self-lubricating composite of mono-layer oxidized aluminium that mono-layer oxidized aluminium pottery and composite solid lubricating agent content are 45% massfraction.The sintered sample of final acquisition is tested known through mechanical property and tribological property: mono-layer oxidized aluminium ceramic phase composition is mainly Alpha-alumina, exist without other impurity phase, the density of material is 98.5%, flexural strength is 380MPa, is respectively 0.83,0.91 and 0.89 in room temperature, at 500 DEG C and 800 DEG C with zirconia ceramics to frictional coefficient when grinding; The density of mono-layer oxidized aluminium pottery self-lubricating composite is 97.5%, flexural strength is 67MPa, is respectively 0.42,0.53 and 0.51 in room temperature, at 500 DEG C and 800 DEG C with zirconia ceramics to frictional coefficient when grinding.
The Al of gained in described embodiment 1,2,3,4
2o
3/ Al
2o
3-ZrO
2(3Y) density of stratiform self-lubricating composite is all greater than 98%, and flexural strength, fracture toughness property and mono-layer oxidized aluminium ceramic phase are worked as, and flexural strength is all greater than 300MPa, fracture toughness property is all greater than 3MPam
1/2; With zirconia ceramics, 0.43,0.54 and 0.52 is respectively to frictional coefficient when grinding in room temperature, at 500 DEG C and 800 DEG C, suitable with mono-layer oxidized aluminium pottery self-lubricating composite.
From embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example, stratiform-gradient-structure alumina-ceramic self-lubricating composite prepared by present method has the features such as high mechanical property, use temperature wide ranges and excellent lubricating properties.
Claims (3)
1. an alumina-ceramic self-lubricating composite, is characterized in that material is made up of aluminum oxide, zirconium white and compounded lubricant, and top layer is alumina layer, and wall is alumina-silica zirconium layer; Described alumina layer is made up of aluminum oxide 47.6 ~ 90.5wt%, sintering aid 2.4 ~ 4.5wt%, compounded lubricant 5 ~ 50wt%; Alumina-silica zirconium layer is made up of aluminium oxide-zirconium oxide 47.8 ~ 90.9wt%, sintering aid 2.2 ~ 4.1wt%, compounded lubricant 5 ~ 50wt%; Compounded lubricant is made up of graphite 0 ~ 10wt%, barium sulfate 0 ~ 10wt% and its surplus Calcium Fluoride (Fluorspan); In material laminate, compounded lubricant composition is many by reducing from inside to outside, and form gradient, it accounts for each layer mass percent is 5% ~ 50%; Described sintering aid by mass ratio be 1: 4 cupric oxide and titanium dioxide form.
2. material as claimed in claim 1, is characterized in that in alumina-silica zirconium layer, and containing 2 ~ 3mol% yttrium oxide in zirconium white, the zirconic content containing 2 ~ 3mol% yttrium oxide is 8 ~ 12wt%.
3. material as claimed in claim 1, is characterized in that the Thickness ratio of alumina layer and alumina-silica zirconium layer is 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110327284.1A CN103073268B (en) | 2011-10-25 | 2011-10-25 | Alumina ceramic self-lubricating composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110327284.1A CN103073268B (en) | 2011-10-25 | 2011-10-25 | Alumina ceramic self-lubricating composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103073268A CN103073268A (en) | 2013-05-01 |
| CN103073268B true CN103073268B (en) | 2015-04-22 |
Family
ID=48149992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110327284.1A Active CN103073268B (en) | 2011-10-25 | 2011-10-25 | Alumina ceramic self-lubricating composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073268B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106244885B (en) * | 2016-07-28 | 2018-02-27 | 中国科学院兰州化学物理研究所 | A kind of sandwich construction aluminum oxide self-lubricating composite ceramic and preparation method thereof |
| CN107867857A (en) * | 2017-10-24 | 2018-04-03 | 陕西科技大学 | One kind oxidation zirconium base graded ceramicses cutter and preparation method thereof |
| CN108218407A (en) * | 2018-01-24 | 2018-06-29 | 烟台金泰美林科技股份有限公司 | A kind of valve alumina composite ceramic and preparation method thereof |
| CN108975933A (en) * | 2018-09-18 | 2018-12-11 | 广东蓝狮医疗科技有限公司 | Wear-resistant aluminium oxide-zirconium oxide composite ceramics of a kind of graphite enhancing and preparation method thereof |
| CN113564574B (en) * | 2021-07-05 | 2022-12-06 | 常州大学 | Nickel-coated graphite enhanced wear-resistant antifriction corrosion-resistant ceramic coating material, coating, and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02161612A (en) * | 1988-12-14 | 1990-06-21 | Fujitsu Ltd | Magnetic disk medium |
| CN1059416C (en) * | 1995-12-28 | 2000-12-13 | 中国科学院兰州化学物理研究所 | Composite self-lubricating zircite-graphite material |
| CN102092164B (en) * | 2009-12-09 | 2014-04-16 | 中国科学院兰州化学物理研究所 | Self-lubricating ceramic composite material with biomimetic structure and preparation method thereof |
| CN102094143A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院兰州化学物理研究所 | High-temperature self-lubricating nano composite ceramic material with toughness and preparation method thereof |
-
2011
- 2011-10-25 CN CN201110327284.1A patent/CN103073268B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Al2O3/Al2O3–ZrO2(3Y)层状纳米陶瓷复合材料的显微结构及弯曲强度;齐亚娥 等;《硅酸盐学报》;20110215;第 39 卷(第2 期);第229页左栏倒数第1段-右栏第1段，图1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103073268A (en) | 2013-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073268B (en) | Alumina ceramic self-lubricating composite material and preparation method thereof | |
| CN110483085A (en) | A kind of whisker reinforcement alumina composite ceramic and the preparation method and application thereof | |
| Qi et al. | Design and preparation of high-performance alumina functional graded self-lubricated ceramic composites | |
| Askari et al. | Fabrication and mechanical properties of Al2O3/SiC/ZrO2 functionally graded material by electrophoretic deposition | |
| Qi et al. | High-temperature self-lubricated properties of Al2O3/Mo laminated composites | |
| Fang et al. | Influence of structural parameters on the tribological properties of Al2O3/Mo laminated nanocomposites | |
| Xu et al. | Al2O3/(W, Ti) C/CaF2 multi-component graded self-lubricating ceramic cutting tool material | |
| Zhang et al. | Lubrication behavior of Y-TZP/Al2O3/Mo nanocomposites at high temperature | |
| RU2744543C1 (en) | Method for producing ceramic composite material based on silicon carbide, reinforced with silicon carbide fibers | |
| Fang et al. | Design and fabrication of laminated–graded zirconia self-lubricating composites | |
| Song et al. | Influence of structural parameters and transition interface on the fracture property of Al2O3/Mo laminated composites | |
| KR20120025396A (en) | Setter for firing | |
| Wang et al. | Effects of ZrO2 coating on the strength improvement of 2.5 D SiCf/SiO2 composites | |
| Li et al. | Improving the surface hardness of zirconia toughened alumina (ZTA) composites by surface treatment with a boehmite sol | |
| CN108640672A (en) | A kind of preparation method of light-weight magnesite-alumina spinel refractories | |
| CN103158295B (en) | There is the Al of biomimetic features 2o 3ceramic composite and preparation method | |
| CN103072325B (en) | Composite construction aluminium oxide/aluminium oxide-zirconium oxide laminar composite and preparation method | |
| Xia et al. | Effect of solid loading on properties of zirconia ceramic by direct ink writing | |
| Su et al. | Influence of fiber diameters on fracture and tribological properties of Al2O3/MoS2 fibrous monolithic ceramic | |
| Liu et al. | Bonding mechanisms and shear properties of alumina ceramic/stainless steel brazed joint | |
| Liu et al. | Tribological properties of NiCr–ZrO2 (Y2O3)–SrSO4 composites at elevated temperatures | |
| CN107867857A (en) | One kind oxidation zirconium base graded ceramicses cutter and preparation method thereof | |
| Li et al. | Tribological properties of spark-plasma-sintered ZrO 2 (Y 2 O 3)–Al 2 O 3–Ba x Sr 1− x SO 4 (x= 0.25, 0.5, 0.75) composites at elevated temperature | |
| JP4122431B2 (en) | Aluminum oxide wear-resistant member having a layered structure and method for producing the same | |
| CN109734452A (en) | A kind of pressureless sintering prepares high-densit Ti2The method of AlN ceramic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |