Method of applying nanostructurised wear-resistant electroconductive coverings

FIELD: chemistry.

SUBSTANCE: invention relates to methods of applying electroconductive nanostructurised coverings with high electroconductivity and wear-resistance. Method includes supply of powder composition with reinforcing particles from four measuring apparatuses into supersonic stream of heated gas and application of powder composition on product surface. First, from first measuring apparatus reinforcing ultra-dispersive particles of ZrO2 with fraction from 0.1 to 1.0 mcm are supplied and product surface is processed until juvenile surface is formed. Then powder composition based on Cu or Al is applied on product surface by supplying powder from four measuring apparatuses. From the first measuring apparatus reinforcing ultra-dispersive ZrO2 particles are supplied, from the second - Cu or Al powder, form the third - reinforcing nanoparticles of quasi-crystalline compound of system Al-Cu-Fe, and from the fourth measuring apparatus - reinforcing particles Y2O3. Rate of heterophase flow during application of composition based on Cu or Al is changed within the range from 450 to 750 m/sec.

EFFECT: reduction of porosity, increase of wear-resistance, adhesive and cohesive strength of covering preserving its high electroconductivity.

4 cl, 1 tbl, 1 ex

 

The invention relates to the field of electrically conductive nanostructured coatings with functionally graded properties, in particular coatings that provide high conductivity and wear resistance of the surface of the parts and components of the friction pairs, working in very hard conditions.

The problem of increasing the wear resistance of materials while maintaining their high conductivity always occurs during the production of competitive products. There are a number of methods to improve the wear resistance of surfaces of friction pairs of machine parts (detonation spraying, plasma spraying, etc.). As you know, are more durable metal and ceramic coatings, which allow a particularly high mechanical and protective properties of the products.

In the known methods of thermal spraying powder material on a substrate to obtain a high adhesion used high-temperature two-phase flows (e.g. plasma, the energy of the explosion, the heat energy of the combustion gases, electromagnetic beam). Properties thus determined by physico-chemical processes occurring during the interaction with the substrate molten or close to it sprayed material.

In the method of gazete the chemical deposition of metal coatings with temperature heterophase flow over 3000°C there are a number of specific effects, which limits its application. It is, above all, the formation of oxides, nitrides, carbides, structural changes, the appearance of high thermo-mechanical stresses caused by the difference of coefficients of thermal expansion of the substrate and the applied coating, these phenomena significantly reduce the quality of the coating and the adhesion strength of coating material to the substrate, and the cohesion of the applied layer.

Special difficulties arise when applying non-equilibrium, chemically active materials. At the temperature of (0,4-0,6) from the melting temperature metal or alloy degradation of the original structure, the occurrence of brittle phases, the formation of complex oxides. This leads to a noticeable reduction of technological and operational properties of coatings and products in General. Therefore, in recent years intensive search of low-temperature methods for the formation of functional coatings.

One such method is the method of high-speed cold gas-dynamic spraying (HGDN).

The essence of the method consists of applying to the surface of powders of metals or their mixtures transported using supersonic gas flow. Known technologies of powder material, which is a fine particle size of from 1 to 120 microns, is accelerated in a supersonic SOP the e flow of compressed gas, to speeds exceeding the speed of sound, and goes on to cover. The temperature of coating material, as a rule, does not exceed 100°C. by changing the mass flow of coating powder and the introduction of the plasticizer to achieve regulation of the chemical composition across the thickness. Method of cold gas-dynamic spraying allows the deposition of films and coatings with thickness from 10 microns to several millimeters.

When applying plastic materials such as Al, si, the coating process occurs when the particle velocity 400-500 m/s Such speeds can be achieved when using air as the working gas. To increase the gas flow rate 1.2-1.5 times, which is very effective in obtaining coatings with high adhesion, carry out heating of the working gas, for example air, by passing it through a special resistive heater located to the nozzle block. Typically, the temperature of the working gas does not exceed 250°C, the temperature of the particles in the stream is 80-100°C.

The method is very promising when applied to homogeneous materials, i.e., when the substrate material and the material layer are close to each other on the crystallographic structure and the coefficients of thermal expansion.

In the well-known inventions is not regulirovanie the wear resistance while maintaining the high conductivity of the coating, which reduces the service life of the friction pairs. Difficulties arise when the pre-treatment of the surface of the product and bringing it to the surface to juvenile status. The optimum combination of processes of creation of the juvenile product surface and deposition of nanostructured functionally graded coatings with adjustable wear resistance and electrical conductivity in thickness.

There are several variants of the method HGDN and methods of applying metallic materials. In particular, in the presented prototype No. of patent RU 2285746 published 20.10.2006. presents a method of applying functional coatings of dissimilar materials, including:

1. The method of applying functional coatings of dissimilar materials, including the supply of powder in a supersonic flow of heated working gas (e.g. air) and applying it on a metal surface, characterized in that for the exception of interphase boundaries, and ensuring that changes in the chemical composition of the applied coating material on linear or logarithmic feed powders are produced simultaneously from two or more Autonomous working of the dispensers, and the density of the mass flow of powder from the dosing device 1 increases from 0.01 to 2 g/cm·cm2and the density of the mass flow of powder from the dispenser 2 respectively reduce in linear or logarithmic from 2 to 0.01 g/cm·cm 2thereby changing the chemical composition across the thickness of the applied coating.

2. The method according to claim 1, characterized in that for increasing the adhesion strength of the inner layers of the coating sprayed at speeds not less than 600 m/s, with maximum speeds of deposition corresponds to the minimum density of the mass flow of the powder is not more than 0.1 g/cm·cm2.

3. The method according to claim 1, characterized in that for increasing the adhesion and cohesive strength of coatings obtained powder material dispenser 1 further added "plasticizer", selected from Pb, Cu, Zn, Al, Ni, Co, Ti in an amount of from 1 to 50%.

4. The method according to claim 1, characterized in that the dosing device 2, to reduce the difference between the coefficients of thermal expansion of the sprayed material and the substrate material, sprayed powder, chemical composition corresponding to the chemical composition of the substrate.

The prototype disadvantages are that:

1. unable to provide for the regulation of the hardness thickness, which reduces wear, so as not introduced into the coating composition hardening component (reinforcing particles);

2. not provided pre-cleaning the substrate from oxides and other non-metallic inclusions, resulting in reduced adhesion and cohesion of the coating;

3. not solve the task of providing a low porosity, substantially in eUSA to wear.

The technical result of the present invention is to provide an efficient method of applying nanostructured wear-resistant electrically conductive coating providing higher wear resistance (measured wear less than 3.5·10-9mm/km) and low porosity (about 0.5%), as well as adhesion to the substrate and cohesion of the coating while maintaining the high conductivity of the order of 10-8Ohm·m

For this method of application of nanostructured wear-resistant electrically conductive coating comprising a supply of the powder composition with a reinforcing particles of the four dispensers in the supersonic flow of the heated gas with the formation of heterophase stream and applying the powder composition on the surface of the product, in this first from the first dispenser in a supersonic stream of heated gas is injected reinforcing ultrafine particles ZrO2a grain size of 0.1 to 1.0 μm and spend processing the surface of the product to the formation of the juvenile surface, then the surface is applied powder composition based on si or Al with pre-selected ratio of the components, by filing a powder of the four dispensers, from the first dispenser serves reinforcing ultrafine particles ZrO2from the second dispenser powder si or Al, from the third dispenser - reinforcing nanoparticles is quasi-connection system Al-Cu-Fe, and from the fourth dispenser - reinforcing particles Y2O3and the speed heterophase flow during the application of the composition based on si or Al change in the range from 450 to 750 m/S.

The speed heterophase flow of heated gas with a reinforcing ultrafine particles Zr2change in the range from 320 to 450 m/S.

The mass flow rate of powder from the dosing is chosen in the range from 5% to 80%, while the total mass flow rate of reinforcing particles with respect to the powder of si or Al is not less than 20% and does not exceed 80%.

Also, from the first, third and fourth dispenser serves a powder consisting of particles with the following ratio of fractions, volume. %:

with a particle diameter of 5-50 μm in an amount of from 50 to 99%,

with a particle diameter of 50-800 μm in an amount of from 1 to 50%.

In the first stage of application is pre-injected into a supersonic stream of heated gas (e.g. air) non-metallic ultrafine particles,

ZrO2, a grain size of 0.1 to 1.0 μm from the dispenser 1, and spend processing the surface of the sprayed product to the formation of the juvenile surface speed heterophase flow in this case is 320 to 450 m/s, after which the dispenser 1 is turned off. In the second stage, at speeds heterophase flow 450 to 750 m/s, juvenile surface of the sprayed product from the dispenser 2, 3 and 4 is applied, the powder is first composition with a pre-selected ratio of the components, on the basis of si or Al (filler 2) using the quasi-crystalline nanoparticles connection system Al-Cu-Fe (dispenser 3) and metal oxide ZrO2(dispenser 1), Y2About3(dispenser 4) to obtain nanostructured wear-resistant electrically conductive coating.

When the flow velocity (the second stage) is less than 450 m/s the kinetic energy of the incident particle flux is insufficient for the formation of nanostructured coatings. At a flow rate of more than 750 m/s is observed elastic collision and "rebound" sputtered particles from the substrate surface.

To obtain nanostructured coatings with adjustable wear resistance while maintaining high conductivity 2,2-2,8·10-8Ohm·m, the mass flow rate of powder from any dispenser varies from 5 to 80%, while the total mass flow rate of reinforcement nanostructured powders of the system Al-Cu-Fe and metal oxide ZrO2, Y2About3with respect to the powder foundations shall not be less than 20% and can exceed 80%. With increasing mass flow rate of reinforcement powders above 80% there is a sharp decrease of the conductivity of the coating. Lower consumption of reinforcing powders below 20% does not increase the wear resistance of the sprayed coating.

To reduce the porosity of the resulting coating are introduced nano-sized particles on isimage powder, that allows you to ensure the most dense packaging. The introduction of nano-sized particles in the composition of the powder composition is provided by the following technique. It is that preparing a powder composition for each of the reinforcing powders consisting of a mechanical mixture of reinforcing powders with a grain size of 5-50 μm and 50-800 nm, which then are loaded into dispensers 2, 3, 4 and fed into the gas stream together with powder foundations (si or Al) in the following sequence: at the beginning of turns on the dispenser 1 (ZrO2), the processing surface of the sprayed product to the formation of the juvenile surface, after which the dispenser 1 is turned off, then included all four of the dispenser, put the powder composition with a pre-selected ratio of the components, based on si or Al (filler 2) using the quasi-crystalline nanoparticles connection system Al-Cu-Fe (dispenser 3) and metal oxide ZrO2(dispenser 1), Y2About3(dispenser 4) to obtain nanostructured wear-resistant electrically conductive coating.

The result is a wear-resistant conductive coating with adjustable wear resistance while maintaining high conductivity 2,2-2,8·10-8Ohm·m, and the phase boundary layer is absent due to controlling the flow of powder from the offline rabotaushi the dispensers, in addition, the introduction of ultrafine particles of different fractions in a predetermined ratio allows to obtain coatings more dense packing, which reduces the number of pores (porosity about 0.5%). Snootiest is determined by the wear of the product in the installation type "disk to disk" with steel counterbody 40, which is (1.5÷3.5)·10-9mm/km for coatings obtained by different modes.

The development of the proposed method using a laser Doppler velocity meter based on the spherical interferometer Fabry-Perrot found that at speeds of 600 m/s and more there has been a significant increase in the turbulence of the flow. This increases the energy of the meeting dispersed particles with a barrier, and therefore increases the adhesion and cohesive strength of the coating and increases the utilization rate of the powder, However, this effect is mitigated by using a powder of a large fraction of more than 50 microns.

When used as a powder Foundation material, corresponding to the chemical composition of the surface of the sprayed product, provided the minimum change in the coefficient of thermal expansion in the resulting gradient layers coating that provides high adhesion strength caused dispersed material.

An EXAMPLE IMPLEMENTATION of the PROPOSED METHOD about titsa using as a reinforcing component nanoparticles quasicrystalline connection system Al-Cu-Fe and metal oxide ZrO 2, Y2O3with the dispersion of 5-50 μm and 50-800 nm and copper powder brands-01-01 with the dispersion of 5-25 microns.

As the carrier (substrate) used copper.

The coating was produced by the proposed method and by a known method.

Turns on the dispenser 1, which is placed in a powder ZrO2the fraction of 5-50 μm. Processing the surface to juvenile status, dispenser 1 is turned off. Together with the dispenser 1 includes dispensers 2, 3 and 4, which are mechanical mixtures of reinforcing powders of the system Al-Cu-Fe and metal oxide ZrO2, Y2About3different fractions, containing 50% fraction 20-32 μm, 20% fraction of 5-10 microns, 30% fraction of 0.2-0.6 μm and is coated nanostructured wear-resistant electrically conductive coating.

The results obtained are summarized in table. In the graph, the wear resistance is the ratio of the amounts of wear for the prototype and the proposed method. When you implement this process was used to install the type DIMET-403.

Technical and economic effect of the application of the proposed method of application of nanostructured wear-resistant electrically conductive coating will result in increasing the reliability of nodes, due to the increase of wear resistance, continuity, and enhance the cohesion and adhesion of the coating to a surface is STU parts while maintaining high conductivity.

From the table it is seen that the claimed technical effect (increasing the wear resistance of the coating while maintaining the high conductivity and the possibility of its regulation) is achieved only when specified in the tables technological parameters (speed heterophase flow, fraction size and content of the fraction in the powder compositions).

1. The method of application of nanostructured wear-resistant electrically conductive coating comprising a supply of the powder composition with a reinforcing particles of the four dispensers in the supersonic flow of the heated gas with the formation of heterophase stream and applying the powder composition on the surface of the product, wherein the first from the first dispenser in a supersonic stream of heated gas is injected reinforcing ultrafine particles ZrO2a grain size of 0.1 to 1.0 μm and spend processing the surface of the product to the formation of the juvenile surface, then the surface is applied powder composition based on si or Al with pre-selected ratio of the components by powder feeder of the four dispensers, from the first dispenser serves reinforcing ultrafine particles ZrO2from the second dispenser powder si or Al, from the third dispenser - reinforcing nanoparticles quasicrystalline the th connection system Al-Cu-Fe, and from the fourth dispenser - reinforcing particles Y2About3and the speed heterophase flow during the application of the composition based on si or Al change in the range from 450 to 750 m/S.

2. The method according to claim 1, characterized in that the speed of heterophase flow of heated gas with a reinforcing ultrafine particles ZrO2change in the range from 320 to 450 m/S.

3. The method according to claim 1, characterized in that the mass flow rate of powder from the dosing is chosen in the range from 5 to 80%, while the total mass flow rate of reinforcing particles with respect to the powder of si or Al is not less than 20% and does not exceed 80%.

4. The method according to claim 1, characterized in that the first, third and fourth dispenser serves a powder consisting of particles with the following ratio of fractions,%:
with a particle diameter of 5-50 μm in an amount of from 50 to 99%, with a particle diameter of 50-800 μm in an amount of from 1 to 50%.



 

Same patents:

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SUBSTANCE: method involves supplying powder composition from at least two dispensers into supersonic preheated gas flow and applying the powder composition onto the surface of a product. With using the first dispenser, reinforcing nonmetallic superdispersed Al2O3 particles of fraction 0.1 to 1.0 mcm are introduced into the supersonic preheated gas flow that is followed with processing the product surface to form a juvenile surface. Then with the second dispenser, an interlayer of powder from one or several metals of group: Al, Cu, Ni, Zn, Sn, Ti, Pb, Co and/or related alloys. Then functional-gradient coating layer is applied simultaneously from two dispensers to produce a coating of Al2O3 content increasing from said interlayer to the surface within 0.1 to 30 vl %.

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4 cl, 3 dwg, 1 tbl, 1 ex

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3 cl, 1 dwg

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3 cl, 2 tbl

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3 dwg, 1 tbl

FIELD: chemistry; photographic industry.

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1 cl, 1 tbl, 14 ex

FIELD: nanotechnology.

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11 dwg

FIELD: production processes.

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EFFECT: increase of adhesion, wear resistance and temperature stability of diamond-type coating.

11 cl, 1 dwg, 5 ex

FIELD: metallurgy.

SUBSTANCE: invention relates to metallurgy field and can be used for manufacturing of high-duty cast iron with globular graphite. For receiving of magnesium-bearing nano- modifying agent is blended with water solution of polyvinyl alcohol, chloride of magnesium and iron in molar correlation (10-5):1:1, agreeably, it is evaporated specified mixture before gel formation after what it is implemented carbonation at temperature 350-500°C in atmosphere of inert gas with formation of carbon nanotube, filled by chloride of magnesium and iron.

EFFECT: invention decrease magnesium losses 1,5-2 times with introduction of nano- modifying agents into the cast iron.

6 ex, 1 tbl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention can be used at production of finishing compositions, film coatings, radiation-resistant materials. The diamond-carbon material contains the carbon in the form of diamond cubic modification and the X-ray amorphous phase in the mass ratio (40-80):(60-20) respectively; the content of said material is as follows (wt %): carbon 89.1-95.2; hydrogen 1.2-5.0; nitrogen 2.1-4.8; oxygen 0.1-4.7; non-combustible admixtures 1.4-4.8. This material is obtained in enclosed volume, in the gas phase inert to carbon by the detonation of carbon-containing explosive with oxygen deficiency placed into the shell of deoxidant-containing condensed phase with deoxidant/carbon-containing explosive mass ratio not less than 0.01:1. The samples of the obtained diamond-carbon material are prepared for elemental analysis by exposition at 120-140°C under vacuum 0.01-10.0 Pa during 3-5 hrs and following treatment at 1050-1200°C by the oxygen flow with the rate providing their combustion during 40-50 s.

EFFECT: invention allows to obtain the product with high carbon content, predictable properties and ultimate composition in the desired phase state.

4 cl, 1 tbl, 25 ex

FIELD: carbon materials.

SUBSTANCE: weighed quantity of diamonds with average particle size 4 nm are placed into press mold and compacted into tablet. Tablet is then placed into vacuum chamber as target. The latter is evacuated and after introduction of cushion gas, target is cooled to -100оС and kept until its mass increases by a factor of 2-4. Direct voltage is then applied to electrodes of vacuum chamber and target is exposed to pulse laser emission with power providing heating of particles not higher than 900оС. Atomized target material form microfibers between electrodes. In order to reduce fragility of microfibers, vapors of nonionic-type polymer, e.g. polyvinyl alcohol, polyvinylbutyral or polyacrylamide, are added into chamber to pressure 10-2 to 10-4 gauge atm immediately after laser irradiation. Resulting microfibers have diamond structure and content of non-diamond phase therein does not exceed 6.22%.

EFFECT: increased proportion of diamond structure in product and increased its storage stability.

2 cl

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