CN105728716A - Core-shell type metal graphite composite powder material and preparation method thereof - Google Patents
Core-shell type metal graphite composite powder material and preparation method thereof Download PDFInfo
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- CN105728716A CN105728716A CN201610143960.2A CN201610143960A CN105728716A CN 105728716 A CN105728716 A CN 105728716A CN 201610143960 A CN201610143960 A CN 201610143960A CN 105728716 A CN105728716 A CN 105728716A
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- 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
- B22F1/17—Metallic particles coated with metal
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- 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
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Abstract
The invention discloses a core-shell metal graphite composite powder material and a preparation method thereof, wherein graphite particles subjected to shaping and activation pretreatment are dispersed into a prepared ammonium solution, metal salt to be coated is selected to be dissolved in the ammonium solution, metal is reduced from the solution under a certain pressure and a certain temperature and deposited on the surfaces of the graphite particles to form compact coating layers, and the thickness and the density of the metal coating layers on the surfaces can be accurately controlled according to requirements. The preparation method has the advantages of good economy and easy application and popularization; the core-shell metal graphite composite powder material prepared by the invention has the advantage of uniform components, and the performance of a part or a coating prepared by the core-shell metal graphite composite powder material is more excellent. The core-shell metal graphite composite powder material prepared by the invention is particularly suitable for preparing mechanical parts operating at high temperature and self-lubricating antifriction coatings thereof, and abradable seal coatings between turbine engine compressor blades and a casing.
Description
Technical field
The present invention relates to composite and increase material manufacture, powder metallurgical technology, particularly relating to a kind of hud typed metallic graphite carbon composite powder material and preparation method and application.
Background technology
Graphite is a kind of important non-renewable resources, is widely used in the fields such as metallurgy, chemical industry, machinery, electronics, Aero-Space, defence and military.China is graphite resource big country, and explored reserves are the 72% of world saving.But China's graphite industry lacks intensive processing.Graphite is carried out intensive processing, it is achieved the lifting of graphite products performance so that it is become high value added product, be the effective way of graphite industry of running business big and strong.
The features such as metallic graphite carbon composite powder material is that one progressively business-like graphite efficiently rises in value mode, and its preparation method generally requires have technical maturity, good economy performance, cladding is complete, covering amount is accurately controlled simultaneously and production scale is flexible.But current domestic metal graphite composite material is frequently with simple mechanical mixing or electroless plating method, its performance or production efficiency are difficult to fully meet the instructions for use of high-end product.
Metallic graphite carbon is for one of common used material preparing ceramic-metal composite, mix by metal dust and powdered graphite direct mechanical, there is the shortcoming that mixing is uneven, adopting hud typed powder is raw material, can consistent ceramic phase and metal phase to greatest extent, metal just can be made with a small amount of metal to become the microstructure of network mutually, give full play to the premium properties of pottery.Meanwhile, with hud typed powder preparation composite, it is possible to save mixing procedure, and third phase element can be made to be prone to add.
Development along with the new and high technology such as Aeronautics and Astronautics, nuclear energy, the requirement of lubriation material has been surmounted the operating limit of lubricating oil or fat, traditional soft metal and other solid lubrication micropowder are as anti-attrition cover layer, and intensity is low, wear no resistance, and can not meet the composite request of performance.In this case, solid self-lubricating composite material arises at the historic moment.Lubricity and abradability due to the existing graphite of metallic graphite carbon powder, there is again metal as the binding agent between coating self, coating and component, thus one of it is the conventional antifriction material of the increasing material manufacturing technology such as thermal spraying, laser melting coating, for preparing the self-lubricant anti-friction coating between the mechanical component worked under the harsh conditions such as high load capacity, high speed, and the abradable seal coating between turbine engine compressor blade and casing.According to the powder preparation coatings that metal and graphite direct mechanical mix, owing to powder body and wetting metal are generally poor, segregation easily occurs, and coating structure is uneven, and porosity is high, binding ability is poor, it is easily generated local and falls the problems such as block, adopt nuclear-shell structure type powder, owing to graphite granule Surface coating has uniform metal level, metal is good with the wettability of metal, effectively raises the binding ability between granule and between granule and parent metal.
Summary of the invention
The technical problem to be solved is to provide a kind of hud typed metallic graphite carbon composite powder material and preparation method thereof for above-mentioned prior art, and it is in powder metallurgy, the application increasing material manufacture field.The hud typed metallic graphite carbon composite powder of gained has that technology is simple, with low cost, purity is high, the thickness of clad and density controllable precise and the feature such as production scale is flexible, is with a wide range of applications.
The present invention proposes to solve the technological approaches of the problems referred to above, hud typed metallic graphite carbon composite powder material, it is the powdered graphite of metallic cover, for adopting following steps products therefrom: (1) by carrying out shaping, screening, cleaning, sucking filtration, drying to powdered graphite surface, it is ensured that the integral coating rate of metallic graphite carbon powder；(2) stir by the powdered graphite after cleaning is put in the weak solution of activator, filter after certain time, washing, dry, it is ensured that, it is ensured that the uniformity of metallic cover layer thickness and cladding integrity；(3) configuration ammonium salt solution, prepares into suspension by surface treated powdered graphite, ammonium salt solution, slaine, catalyst etc. according to certain ratio, it is ensured that reaction rate；(4) then the solution prepared is injected in autoclave, is designed by mechanical agitation and autoclave inner-wall so that graphite nuclei granule suspends in the solution all the time, it is ensured that the integral coating rate of powder；(6) reacting with under reducing atmosphere under uniform temperature and pressure, until the metal salt component in ammonium salt solution reacts completely, required metal component is all deposited on core granule surface.(7) powder is separated with solution after terminating by reaction by filtration, is washed out and dries, it is thus achieved that required composite powder.
Metal graphite composite material of the present invention adopts flake graphite or spherical graphite as core granule, and core granule can be coarse granule, it is also possible to be fine powder, and grain size intervals is preferably at 1～200 μm.
Metal carbonyl coat element used by metal graphite composite material of the present invention includes the metallic element of IB, IIB, VIII transition arrowheads such as gold, platinum, silver, copper, stannum, nickel, cobalt, and coating thickness is between 1～200 μm.
Powdered graphite of the present invention, before being dispersed to ammonium salt solution, its surface needs through physics Shape correction and activating pretreatment.Difference according to cladding metal, the activator of employing includes Fe2+、Mn2+、Cr2+Phosphorous acid hydrogen salt, bisulfites, phosphite, nitrite, sulphite, sulfide compound and hydrazine, formaldehyde.
Metallic graphite carbon powder of the present invention, is produced by Hydrothermal Pressure Hydrogen Reduction method, and the catalyst added in ammonium salt solution is anthraquinone or class anthraquinone.
The present invention compared with prior art has following major advantage:
1, the preparation method of the present invention according to the difference of purposes, can be adopted to obtain the metallic graphite carbon powder that metallic cover layer thickness is controlled；
2, the preparation method of the present invention is compared with traditional chemical plating method, and economy is better, the hud typed metallic graphite carbon composite powder that preparation metallic cover layer thickness preferably is bigger, it is easy to application；
3, hud typed metallic graphite carbon composite powder material prepared by the present invention, compared with traditional metallic graphite carbon mixed-powder, evenly, the performance adopting its parts prepared or coating is also more excellent for composition；
4, hud typed metallic graphite carbon composite powder material prepared by the present invention, is particularly useful for making mechanical part and the self-lubricant anti-friction coating thereof of operation under high temperature and the abradable seal coating between turbine engine compressor blade and casing.
Accompanying drawing explanation
Fig. 1 is the SEM pattern photo of flake graphite before Shape correction；
Fig. 2 is the SEM pattern photo of flake graphite after Shape correction；
Fig. 3 is the SEM pattern photo of the hud typed nickel bag graphite composite powder of embodiment 1 synthesis；
Fig. 4 is the SEM cross sectional photograph of the hud typed nickel bag graphite composite powder of embodiment 1 synthesis；
Fig. 5 is the SEM pattern photo of the hud typed Cu-cladding Al Rod composite powder of the 2-in-1 one-tenth of embodiment；
Fig. 6 is the SEM cross sectional photograph of the hud typed Cu-cladding Al Rod composite powder of the 2-in-1 one-tenth of embodiment.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention will be further described.
Embodiment 1: nickel bag flake graphite composite powder
Pre-treatment: flake graphite (as shown in Figure 1) is put into and carried out Shape correction 20min in particle shaping system, screened, cleaning, sucking filtration, dry, it is thus achieved that grain size intervals is 200～300 orders, mellow and full graphite granule (as shown in Figure 2)；
Pretreatment: the graphite granule through pre-treatment is at room temperature immersed in (20%FeSO in copperas solution4·7H2O)15min.Then pass through and filter to isolate graphite granule, be injected in autoclave together with ammonium nickel sulfate solution.
Dispensing: Ni2+: 60g/L；NH3Ni=2.5 1；Graphite: 50g/L
Liquid feeding closes the logical hydrogen displaced air of still and is heated to 140 DEG C of addition hydrogen to the about 15min of 3MPa, and nickel ion concentration is reduced to 1g/L from 60g/L.
Through washing and dry, it is thus achieved that the hud typed nickel bag graphite composite powder shown in Fig. 3 and Fig. 4.
Embodiment 2: copper-clad lamellar graphite composite powder
Pre-treatment: flake graphite is put into and carried out Shape correction 20min in particle shaping system, screened, cleaning, sucking filtration, dry, it is thus achieved that grain size intervals is 200～300 orders, mellow and full graphite granule；
Pretreatment: the graphite granule through pre-treatment is at room temperature immersed in (20%FeSO in copperas solution4·7H2O)15min.Then pass through and filter to isolate graphite granule, be injected in autoclave together with ammonium copper sulfate solution.
Dispensing: Cu2+: 40g/L；NH3Cu=2 1；Graphite: 50g/L
Liquid feeding closes the logical hydrogen displaced air of still and is heated to 140 DEG C of addition hydrogen to the about 15min of 3MPa, and copper ion concentration is reduced to 0.8g/L from 50g/L.
Through washing and dry, it is thus achieved that the hud typed Cu-cladding Al Rod composite powder shown in Fig. 5 and Fig. 6.
Claims (10)
1. a hud typed metallic graphite carbon composite powder material, it is the powdered graphite of metallic cover, it is characterized in that, graphite granule through pretreatment is distributed in the ammonium salt solution configured, the slaine that selection to be coated with, it is dissolved in ammonium salt solution, under the reducing atmosphere of certain pressure, uniform temperature, metal is restored constantly from above-mentioned solution, and it is deposited on graphite granule surface, form compact clad, it is possible to the accurately thickness of control core particle surface metal carbonyl coat and density according to demand.
2. hud typed metallic graphite carbon composite powder material according to claim 1, it is characterised in that described composite adopts flake graphite or spherical graphite as core granule；For flake graphite, need to carry out Shape correction before cladding.
3. hud typed metallic graphite carbon composite powder material according to claim 1, it is characterised in that described composite grain size intervals is at 1～200 μm.
4. hud typed metallic graphite carbon composite powder material according to claim 1, it is characterized in that, described metal is the metal that can restore from ammonium salt solution at high temperature and pressure, the metallic element of IB, IIB, VIII such as including gold, platinum, silver, copper, stannum, nickel, cobalt.
5. the preparation method of the hud typed metallic graphite carbon composite powder material according to claim 1-4 any claim, it is characterised in that comprise the following steps:
(1) configuration ammonium salt solution；
(2) surface treated powdered graphite, ammonium salt solution, slaine, catalyst etc. are prepared into suspension according to certain ratio；
(3) solution prepared is injected in autoclave, by mechanical agitation, core granule is suspended in the solution all the time；
(4) reacting with under reducing atmosphere under uniform temperature and pressure, until the metal salt component in ammonium salt solution reacts completely, required metal component is all deposited on core granule surface.
(5) powder is separated with solution after terminating by reaction by filtration, is washed out and dries, it is thus achieved that required composite powder.
6. preparation method according to claim 5, it is characterised in that the surface treatment described in step is:
(1) powdered graphite surface is carried out shaping, screening, cleaning, sucking filtration, dries；
(2) powdered graphite after cleaning is put in the weak solution of activator and stir, filter after certain time, wash, dry.
7. preparation method according to claim 6, it is characterised in that described activator is selected from Fe2+、Mn2+、Cr2+Phosphorous acid hydrogen salt, bisulfites, phosphite, nitrite, sulphite, one or more in sulfide compound and hydrazine, formaldehyde.
8. preparation method according to claim 5, it is characterised in that described catalyst is anthraquinone or class anthraquinone.
9. preparation method according to claim 5, it is characterised in that the ammonium salt solution described in step (1) is made up of water, ammonia and ammonium sulfate；High temperature described in step (4) is 100～200 DEG C；Reducing atmosphere described in step (4) is hydrogen, and pressure is 1～10MPa.
10. the hud typed metallic graphite carbon composite powder material according to claim 1-4 any claim is in the purposes of powder metallurgy or Surface Engineering, powder metallurgy is used for preparing the needs such as tool tip, wire-drawing die are high temperature resistant, self-lubricating, erosion-resisting parts, be used for adopting the technique such as thermal spraying, laser melting coating to need high temperature resistant, self-lubricating, anticorrosive or seal coating in the preparation of mechanical part surface in Surface Engineering.
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Cited By (5)
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| CN107695345A (en) * | 2017-10-27 | 2018-02-16 | 北京理工大学 | A kind of composite granule of refractory metal cladding zirconium diboride carborundum |
| CN111705231A (en) * | 2020-07-03 | 2020-09-25 | 毛金昌 | Nickel-based copper-clad graphite self-lubricating composite material and sintering method thereof |
| CN113540464A (en) * | 2021-07-16 | 2021-10-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of metal nanoparticle modified graphite material and three-dimensional graphite skeleton pole piece |
| CN114890413A (en) * | 2022-04-15 | 2022-08-12 | 中南大学 | Graphite @ Ti 2 SnC powder particles and preparation method thereof |
| CN115870493A (en) * | 2023-03-01 | 2023-03-31 | 矿冶科技集团有限公司 | Low-burning-loss composite powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107695345A (en) * | 2017-10-27 | 2018-02-16 | 北京理工大学 | A kind of composite granule of refractory metal cladding zirconium diboride carborundum |
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| CN113540464A (en) * | 2021-07-16 | 2021-10-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of metal nanoparticle modified graphite material and three-dimensional graphite skeleton pole piece |
| CN114890413A (en) * | 2022-04-15 | 2022-08-12 | 中南大学 | Graphite @ Ti 2 SnC powder particles and preparation method thereof |
| CN114890413B (en) * | 2022-04-15 | 2023-09-01 | 中南大学 | Graphite @ Ti 2 SnC powder particles and preparation method thereof |
| CN115870493A (en) * | 2023-03-01 | 2023-03-31 | 矿冶科技集团有限公司 | Low-burning-loss composite powder and preparation method thereof |
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Application publication date: 20160706 |