CN112322942B - High-strength high-toughness oxidation-resistant metal-based self-lubricating composite material and preparation method thereof - Google Patents
High-strength high-toughness oxidation-resistant metal-based self-lubricating composite material and preparation method thereof Download PDFInfo
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- 230000003647 oxidation Effects 0.000 title claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 44
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 35
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- 238000000034 method Methods 0.000 claims abstract description 4
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- 239000000843 powder Substances 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000002490 spark plasma sintering Methods 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 7
- 230000004584 weight gain Effects 0.000 claims description 6
- 235000019786 weight gain Nutrition 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005551 mechanical alloying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 4
- 229910052582 BN Inorganic materials 0.000 abstract description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 9
- 210000003298 dental enamel Anatomy 0.000 description 8
- 239000010952 cobalt-chrome Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical class [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 3
- 229910001632 barium fluoride Inorganic materials 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
Abstract
The invention relates to the field of high-temperature self-lubricating and composite materials, in particular to a high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material and a preparation method thereof. Wherein, according to the weight percentage, the cobalt alloy is 70-85%, the silver is 8-15%, and the nano particles are 6-20%. According to the invention, the high-temperature strength of the alloy is improved by adding the nano cobalt or cobalt alloy particles, a compact glaze layer with a self-lubricating function is induced to be formed during high-temperature friction and wear, and the defect that the toughness of the composite material is reduced by adding self-lubricating ceramics such as fluoride, boron nitride, molybdenum disulfide and the like in the traditional method is avoided, so that the composite material has the comprehensive properties of high strength, high toughness, oxidation resistance and high-temperature self-lubricating, and can be used for producing oxidation resistance, high temperature resistance and motion and transmission parts under high load impact.
Description
Technical Field
The invention relates to the field of high-temperature self-lubricating and composite materials, in particular to a high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material and a preparation method thereof.
Background
With the rapid development of national defense construction and national economy in China, the damage of key component materials is accelerated by the coupling of multiple factors caused by increasingly harsh service environments in high-tech industries such as aviation, aerospace, deep sea, nuclear power and the like, and particularly, the cooperative coupling of high-temperature corrosion and frictional wear is used as a main damage mode of materials for high-temperature bearings, bushings and other transmission components serving in high-temperature environments in power systems, so that the key factors influencing the reliability and the service life of the whole system are formed. In view of such circumstances, the research and development of novel high temperature corrosion resistant self-lubricating composite materials are imminent.
In order to meet the requirements of high temperature resistance and self-lubrication of solid self-lubricating composite materials, heat-resistant alloy is generally used as a matrix of the composite material, and fluoride (such as eutectic compound of calcium fluoride and barium fluoride), boron nitride, molybdenum disulfide, barium sulfate and the like are used as high-temperature self-lubricating phases. For example, the iron-based alloy self-lubricating composite material disclosed in chinese patent CN200710307295.7, namely molybdenum disulfide and tungsten dioxide are added as self-lubricating phases; CN201410081277.1 discloses an iron-based alloy-based self-lubricating composite material, which is reinforced by alumina and silicon carbide ceramics, and calcium fluoride and barium fluoride are high-temperature self-lubricating phases; CN201610592419.X discloses a nickel-based alloy-based high-temperature self-lubricating composite material, which uses dihydrated tungsten as a high-temperature self-lubricating phase; CN201610592445.2 discloses a nickel-based alloy-based self-lubricating composite material, which takes an eutectic compound of calcium fluoride and barium fluoride as a high-temperature self-lubricating phase; CN201610443672.9 discloses a high-entropy alloy-based self-lubricating composite material, which takes fluoride, molybdenum disulfide and graphite as self-lubricating phases. The PM200 series high temperature self-lubricating composite material disclosed in US5034187 and the PS304 self-lubricating coating reported by NASA also contain a substantial amount of ceramic reinforcing phase, and a fluoride self-lubricant. The composite materials have excellent wide-temperature-range self-lubricating performance, but the fracture toughness of the composite materials is greatly reduced due to excessive ceramic phase, and the composite materials are limited in application in high-load impact environments.
According to the service requirements of national defense construction and industrial development of China on high-temperature moving parts, a novel high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material needs to be developed urgently to prepare moving parts capable of being impacted at high temperature and high load, such as: shafts, bushings, bearings, etc.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-strength high-toughness antioxidant metal-based self-lubricating composite material and a preparation method thereof, solves the problem that the self-lubricating composite material in the prior art cannot completely combine oxidation resistance, self-lubrication and high toughness, and can be used for producing oxidation-resistant, high-temperature-resistant and high-load-impact-resistant moving and transmission parts.
The specific technical scheme is as follows:
the high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material comprises the following components in percentage by weight:
70-85% of micron cobalt alloy;
8-15% of silver particles;
6-20% of nano cobalt or cobalt alloy particles.
The micron cobalt alloy is a cobalt-based high-temperature alloy or a high-entropy alloy, the mass fraction of cobalt is not less than 20%, the mass fraction of chromium is not less than 13%, and the granularity of original powder is 10-100 mu m; the silver particles are less than 100 μm; the particle of the nano cobalt or the cobalt alloy is less than 100 nm.
A preparation method of a high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material takes cobalt alloy as a matrix, silver as a low-temperature self-lubricating agent, and added nano cobalt or cobalt alloy particles are chemically combined with an interface of a metal/oxide/metal sandwich structure formed by the cobalt alloy matrix during sintering due to pre-oxidation treatment of the nano particles, so that the alloy strength is improved, and the preparation method specifically comprises the following steps:
(1) pre-oxidizing nano particles: pre-oxidizing the nano cobalt or cobalt alloy particles at the temperature of 600-900 ℃ for 5-30 min, and passivating the surfaces of the powder particles to form an oxide film;
(2) mechanical alloying of powder: mixing cobalt alloy, silver, nano cobalt or cobalt alloy particles in a composite material composition ratio by planetary ball milling, taking n-heptane with the mass fraction of 2-3% as a ball milling aid, rotating at 300-400 r/min, and drying after ball milling for 20-50 hours to obtain uniformly mixed alloying powder;
(3) spark plasma sintering: and (3) sintering the composite powder obtained in the step (2) by using discharge plasma, and cooling along with a furnace to obtain the composite material.
The technological parameters of the spark plasma sintering are as follows:
vacuum degree < 1 × 10-2atm；
Sintering temperature: 1050-1250 ℃;
temperature rise rate: 50-100 ℃/min;
sintering pressure: 25-50 MPa;
and keeping the temperature for 5-20 min.
The performance indexes of the composite material are as follows:
the density is more than or equal to 99 percent, the yield strength is more than or equal to 700MPa, the compressive strength is more than or equal to 1300MPa,
the friction is carried out at the temperature of 200-800 ℃, the average friction coefficient is 0.20-0.39, and the abrasion loss is less than 4.0 multiplied by 10-5mm3/(Nm); the oxidation resistance grade of the composite material is a complete oxidation resistance grade within a temperature range of 200-800 ℃, and after the composite material is oxidized for 100 hours, the oxidation weight gain is less than or equal to 0.4mg/cm2。
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the invention takes cobalt alloy as a matrix, silver as a low-temperature self-lubricating agent, and added nano cobalt or cobalt alloy particles can form interface chemical combination with a metal/oxide/metal sandwich structure with the cobalt alloy matrix during sintering due to the pre-oxidation treatment of the nano particles, thereby improving the alloy strength; in addition, when the ceramic material is abraded by high-temperature friction, a composite product layer rich in cobalt oxide and chromium oxide is formed on the surface of the ceramic material, and the ceramic material can be quickly converted into a compact enamel layer with a self-lubricating function under the condition of high-load rolling, so that the composite effect of oxidation resistance and self-lubricating is achieved.
(2) The invention takes the cobalt-based alloy as a matrix, can be a cobalt-based high-temperature alloy or a cobalt-containing high-entropy alloy, has the comprehensive advantages of high strength and high toughness, and ensures that an oxide film rich in cobalt oxide and chromium oxide and a transformed enamel layer are formed when the alloy is subjected to high-temperature friction and wear due to high cobalt and high chromium content. The cobalt oxide and the chromium oxide have better high-temperature sintering performance and tribological performance (low friction coefficient and wear rate), and lay a foundation for realizing high-temperature self-lubrication of the composite material. The high toughness of the cobalt-based alloy is substantially retained due to the absence of excess ceramic reinforcing phase and ceramic self-lubricant in the composite material
(3) According to the invention, nano cobalt or cobalt alloy particles (which are subjected to 600-900 ℃ pre-oxidation treatment to form a semi-continuous oxide spherical shell) are added into the composite material, and form a metal/oxide/metal sandwich type interface with an alloy matrix during sintering, so that the alloy strength can be greatly improved. Meanwhile, the components and the content of the particles are changed, the content of cobalt oxide in the oxidation product on the surface of the grinding mark can be regulated and controlled, the high-temperature sintering of an oxidation product film and the formation of an enamel layer are accelerated, and the high strength and the high-temperature self-lubricating performance of the composite material are further ensured.
(4) The spark plasma sintering of the invention can prepare high-density nano composite material by sintering, and the metal-based self-lubricating composite material prepared by the sintering method can inhibit the high-temperature growth of crystal grains to the maximum extent and realize the optimization of mechanical property and frictional wear property.
(5) The high-strength high-toughness metal-based self-lubricating composite material can be processed into high-temperature motion and transmission parts in various shapes, such as: the bearing, the bush, the shaft and the like realize the high temperature resistance, oxidation resistance, impact resistance and self-lubricating function of the component, and improve the service life of the component.
Drawings
FIG. 1 shows the appearance of grinding marks of a small amount of nano cobalt-chromium alloy particle-reinforced high-entropy alloy after friction at 400 ℃, a continuous enamel layer is not formed, and the alloy is ground into granular oxides;
FIG. 2 shows the appearance of a wear scar of a high-entropy alloy reinforced by a proper amount of nano cobalt particles after friction at 400 ℃ to form a continuous enamel layer.
Detailed Description
The present invention is described in detail below with reference to the drawings and examples, but the scope of the present invention is not limited by the drawings and examples.
Example 1:
in the embodiment, cobalt-based high-temperature alloy Co-27Cr-8W (wt.%) is used as an alloy matrix, the granularity is 15-53 μm, and the composite material is prepared by mixing silver (the granularity is about 40 μm) and nano cobalt particles (the particle size is about 50nm after pre-oxidation at 600 ℃ for 10 min), wherein the specific preparation parameters are as follows:
(1) powder mixing: the composite material comprises 80 wt% of cobalt-based alloy, 10 wt% of silver and 10 wt% of nano cobalt particles, and is prepared by ball-milling and mixing the components through a planetary ball mill at the rotating speed of 320 rpm for 24 hours to obtain composite powder.
(3) Spark plasma sintering: putting the ball-milled mixed composite powder into a graphite die, compacting, and sintering by a discharge plasma system:
vacuum degree: 1X 10-3atm；
Sintering temperature: 1100 ℃;
temperature rise rate: 50 ℃/min, preserving the temperature at the final sintering temperature for 15min, and then naturally cooling;
sintering pressure: 50 MPa.
The density of the sintered composite material is 99.5 percent, the yield strength is 1080MPa, the compressive strength is more than or equal to 1350MPa (without fracturing), and the fracture toughness is 40MPa √ m. The friction and wear test conditions are that a silicon nitride counter-grinding ball with the load of 10N and the diameter of 10mm is subjected to reciprocating friction for 30min, the linear velocity is 0.1m/s, the friction coefficient of the composite material is 0.23-0.37 at 200-800 ℃, and the wear rate is 0.6-3.5 multiplied by 10-5mm3/(Nm), oxidation at 800 ℃ for 100 hours with an oxidative weight gain of 0.16mg/cm2。
Comparative example 1
The difference from the embodiment 1 is that: the sintering mode of the composite material is common vacuum hot-pressing sintering.
Vacuum degree: 1X 10-3atm；
Sintering temperature: 1100 ℃;
temperature rise rate: 50 ℃/min, preserving the temperature at the final sintering temperature for 15min, and then naturally cooling;
sintering pressure: 50 MPa.
The density of the sintered composite material is 96.5 percent, the density is lower than that of a spark plasma sintering material, and the wear rate at 200-800 ℃ is 3.0-15.0 multiplied by 10-5mm3/(Nm)。
Comparative example 2
The difference from the embodiment 1 is that: the composite material comprises 88 wt% of cobalt-based alloy, 8 wt% of silver and 5 wt% of nano cobalt particles.
The friction coefficient of the sintered composite material is 0.30-0.55 at 200-800 ℃, and the wear rate is 3-10 multiplied by 10-5mm3/(Nm)。
Comparative example 3
The difference from the embodiment 1 is that: the composite material comprises 79 wt% of cobalt-based alloy, 6 wt% of silver and 25 wt% of nano cobalt-chromium (CoCr) alloy particles.
The yield strength of the sintered composite material is 1179MPa, and the fracture toughness is 19MPa √ m
Example 2
In the embodiment, cobalt-based high-temperature alloy Co-20Ni-17Cr-8W-8Mo (wt.%) is used as an alloy matrix, the granularity is 30-50 μm, and the composite material is prepared by mixing silver (granularity is about 40 μm) and nano cobalt chromium (CoCr) alloy particles (the granularity is about 50nm after pre-oxidation at 800 ℃ for 10 min), and the specific preparation parameters are as follows:
(1) powder mixing: the composite material comprises 77 wt% of cobalt-based high-temperature alloy, 12 wt% of silver and 15 wt% of nano cobalt-chromium particles, and is subjected to ball milling and mixing by a planetary ball mill at the rotating speed of 300 revolutions per minute for 30 hours to obtain composite powder.
(3) Spark plasma sintering: putting the ball-milled mixed composite powder into a graphite die, compacting, and sintering by a discharge plasma system:
vacuum degree: 1X 10-3atm；
Sintering temperature: 1200 ℃;
temperature rise rate: 55 ℃/min, preserving the temperature for 10min at the final sintering temperature, and then naturally cooling;
sintering pressure: 50 MPa.
The density of the sintered composite material is 99.3 percent, the yield strength is 1100MPa, the compressive strength is more than or equal to 1450MPa (without fracturing), and the fracture toughness is 33MPa √ m. The friction and wear test conditions are that a silicon nitride pair grinding ball with the load of 10N and the diameter of 10mm is subjected to reciprocating friction for 30min, the friction coefficient of the composite material is 0.20-0.33 at 200-800 ℃, and the wear rate is 0.5-3.1 multiplied by 10-5mm3/(Nm), oxidation at 800 ℃ for 100 hours, weight gain by oxidation of 0.19mg/cm2。
Example 3
In the embodiment, cobalt-containing high-entropy alloy (CoFeNiCr) is used as a matrix, the granularity is 30-50 μm, and the composite material is prepared by silver (the granularity is about 40 μm) and nano cobalt-chromium particles (the particle size is about 50nm after pre-oxidation at 900 ℃ for 10 min), wherein the specific preparation parameters are as follows:
(1) powder mixing: compound medicineThe composite material is prepared from cobalt-containing high-entropy alloy (CoFeNiCr)0.5)77 wt%, silver 10 wt% and nano cobalt chromium (CoCr) particles 15 wt%, and ball milling and mixing by a planetary ball mill at the rotating speed of 300 r/min for 40 hours to obtain the composite powder.
(3) Spark plasma sintering: putting the ball-milled mixed composite powder into a graphite die, compacting, and sintering by a discharge plasma system:
vacuum degree: 1X 10-3atm；
Sintering temperature: 1100 ℃;
temperature rise rate: 55 ℃/min, preserving the heat at the final sintering temperature for 8min, and then naturally cooling;
sintering pressure: 50 MPa.
The density of the sintered composite material is 99.2 percent, the yield strength is 820MPa, the compressive strength is more than or equal to 1380MPa (without fracturing), and the fracture toughness is 31MPa √ m. The friction and wear test conditions are that a silicon nitride pair grinding ball with the load of 10N and the diameter of 10mm is subjected to reciprocating friction for 30min, the friction coefficient of the composite material is 0.25-0.34 at 200-800 ℃, and the wear rate is 1.0-4.0 multiplied by 10-5mm3/(Nm), oxidation at 800 ℃ for 100 hours with an oxidative weight gain of 0.25mg/cm2。
Comparative example 1
The difference from the embodiment 3 is that: the composite material comprises cobalt-containing high-entropy alloy (CoFeNiCr)0.5)86 wt%, silver 10 wt%, and nano cobalt chromium (CoCr) particles 4 wt%.
The friction coefficient of the sintered composite material is 0.32-0.68 at 200-800 ℃, the appearance of grinding marks at 400 ℃ is shown in figure 1, a continuous enamel layer is not formed on the surface, and most of grinding is oxide particles.
Example 4
In this example, a cobalt-containing high entropy alloy (CoFeNiCr)0.5) The particle size of the composite material is 30-50 mu m, and the composite material is prepared by using the composite material as a matrix, silver (the particle size is about 40 mu m) and nano cobalt particles (the particle size is about 50nm after pre-oxidation at 700 ℃ for 20 min), wherein the specific preparation parameters are as follows:
(1) powder mixing: the composite material comprises cobalt-containing high-entropy alloy (CoFeNiCr)0.5)77 wt% of silver and 10 wt% of silver,And (3) ball-milling and mixing 12 wt% of nano cobalt particles by a planetary ball mill at the rotating speed of 300 r/min for 50 hours to obtain composite powder.
(3) Spark plasma sintering: putting the ball-milled mixed composite powder into a graphite die, compacting, and sintering by a discharge plasma system:
vacuum degree: 1X 10-3atm；
Sintering temperature: 1100 ℃;
temperature rise rate: 55 ℃/min, preserving the heat at the final sintering temperature for 8min, and then naturally cooling;
sintering pressure: 50 MPa.
The density of the sintered composite material is 99.6 percent, the yield strength is 740MPa, the compressive strength is more than or equal to 1410MPa (without fracturing), and the fracture toughness is 35MPa √ m. The friction and wear test conditions are that a silicon nitride pair grinding ball with the load of 10N and the diameter of 10mm is subjected to reciprocating friction for 30min, the friction coefficient of the composite material is 0.21-0.35 at 200-800 ℃, and the wear rate is 0.8-3.6 multiplied by 10-5mm3(Nm), wherein the grinding mark appearance at 400 ℃ is shown in figure 2, and a continuous enamel layer is formed on the surface and mainly comprises cobalt oxide and cobalt chromium spinel; oxidizing for 100 hours at 800 ℃, and increasing the weight by 0.31mg/cm2。
The results of the examples and the comparative examples show that the invention takes cobalt-based alloy as a base, silver is added as a self-lubricating phase, partially oxidized nano cobalt or cobalt alloy particles are strengthened, and an enamel layer with self-lubricating function is induced and formed on the friction surface, and the effects of self-lubricating and high-temperature oxidation resistance are achieved; the density of the composite material can be improved, the growth of nano crystals (particles) can be inhibited and the high-temperature mechanical property can be ensured by a special sintering preparation process; in addition, the composite material is not added with excessive ceramic reinforcing phase and ceramic self-lubricating agent, so that the composite material has excellent comprehensive properties of high strength, high toughness, oxidation resistance, self-lubrication and the like.
Claims (4)
1. The high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material is characterized in that: the composite material comprises the following components in percentage by weight:
70-85% of micron cobalt alloy;
8-15% of silver particles;
6-20% of nano cobalt or cobalt alloy particles;
the micron cobalt alloy is a cobalt-based high-temperature alloy or a high-entropy alloy, the mass fraction of cobalt is not less than 20%, the mass fraction of chromium is not less than 13%, and the granularity of original powder is 10-100 mu m; the silver particles are less than 100 μm; the particle size of the nano cobalt or cobalt alloy is less than 100nm, and the nano cobalt or cobalt alloy is subjected to preoxidation treatment at 600-900 ℃ for 5-30 min;
the composite material takes cobalt alloy as a matrix, silver as a low-temperature self-lubricating agent, and added nano cobalt or cobalt alloy particles form interface chemical bonding with a metal/oxide/metal sandwich structure with the cobalt alloy matrix during sintering due to pre-oxidation treatment of the nano particles, so that the alloy strength is improved, and the preparation method comprises the following steps:
(1) pre-oxidizing nano particles: pre-oxidizing the nano cobalt or cobalt alloy particles at the temperature of 600-900 ℃ for 5-30 min, and passivating the surfaces of the powder particles to form an oxide film;
(2) mechanical alloying of powder: mixing cobalt alloy, silver, nano cobalt or cobalt alloy particles in a composite material composition ratio by planetary ball milling, taking n-heptane with the mass fraction of 2-3% as a ball milling aid, rotating at 300-400 r/min, and drying after ball milling for 20-50 hours to obtain uniformly mixed alloying powder;
(3) spark plasma sintering: after the composite powder obtained in the step (2) is subjected to spark plasma sintering, the technological parameters are as follows: vacuum degree < 1 × 10-2atm; sintering temperature: 1050-1250 ℃; temperature rise rate: 50-100 ℃/min; sintering pressure: 25-50 MPa; keeping the temperature for 5-20 min; cooling along with the furnace to obtain a composite material;
the performance indexes of the composite material are as follows: the density is more than or equal to 99 percent, the yield strength is more than or equal to 700MPa, the compressive strength is more than or equal to 1300MPa, and the fracture toughness is more than or equal to 22 MPa
(ii) a The friction is carried out at the temperature of 200-800 ℃, the average friction coefficient is 0.20-0.39, and the abrasion loss is less than 4.0 multiplied by 10-5mm3/(Nm); at a temperature of 200-800 deg.CThe composite material has complete oxidation resistance level, and after oxidation for 100h, the oxidation weight gain is less than or equal to 0.4mg/cm2。
2. The preparation method of the high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material as claimed in claim 1, wherein the cobalt alloy is used as a matrix, silver is used as a low-temperature self-lubricating agent, and the added nano cobalt or cobalt alloy particles are subjected to pre-oxidation treatment and are chemically combined with the cobalt alloy matrix to form an interface of a metal/oxide/metal sandwich structure during sintering, so that the alloy strength is improved, and the preparation method specifically comprises the following steps:
(1) pre-oxidizing nano particles: pre-oxidizing the nano cobalt or cobalt alloy particles at the temperature of 600-900 ℃ for 5-30 min, and passivating the surfaces of the powder particles to form an oxide film;
(2) mechanical alloying of powder: mixing cobalt alloy, silver, nano cobalt or cobalt alloy particles in a composite material composition ratio by planetary ball milling, taking n-heptane with the mass fraction of 2-3% as a ball milling aid, rotating at 300-400 r/min, and drying after ball milling for 20-50 hours to obtain uniformly mixed alloying powder;
(3) spark plasma sintering: and (3) sintering the composite powder obtained in the step (2) by using discharge plasma, and cooling along with a furnace to obtain the composite material.
3. The method for preparing the high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material as claimed in claim 2, wherein the method comprises the following steps: the technological parameters of the spark plasma sintering are as follows:
vacuum degree < 1 × 10-2atm；
Sintering temperature: 1050-1250 ℃;
temperature rise rate: 50-100 ℃/min;
sintering pressure: 25-50 MPa;
and keeping the temperature for 5-20 min.
4. The preparation method of the high-strength high-toughness oxidation-resistant metal-based self-lubricating composite material according to claim 2, wherein the performance indexes of the composite material are as follows:
the density is more than or equal to 99 percent, the yield strength is more than or equal to 700MPa, the compressive strength is more than or equal to 1300MPa, and the fracture toughness is more than or equal to 22 MPa
(ii) a The friction is carried out at the temperature of 200-800 ℃, the average friction coefficient is 0.20-0.39, and the abrasion loss is less than 4.0 multiplied by 10-5mm3/(Nm); the oxidation resistance grade of the composite material is a complete oxidation resistance grade within a temperature range of 200-800 ℃, and after the composite material is oxidized for 100 hours, the oxidation weight gain is less than or equal to 0.4mg/cm2。
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