CN112301324B - Method for plating diamond film on steel substrate - Google Patents
Method for plating diamond film on steel substrate Download PDFInfo
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- CN112301324B CN112301324B CN202010995293.7A CN202010995293A CN112301324B CN 112301324 B CN112301324 B CN 112301324B CN 202010995293 A CN202010995293 A CN 202010995293A CN 112301324 B CN112301324 B CN 112301324B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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Abstract
The invention relates to a method for plating a diamond film on a steel substrate, which comprises the following steps: 1) Preparing a steel-based composite material containing nano diamond particles; 2) Plating a diamond film on the steel-based composite material containing the nano diamond particles; most of the diamond-plated films are formed by epitaxial growth on the nano diamond particles exposed on the surface of the steel substrate, a small part of the diamond films are formed by nucleation and growth on the rest part of the surface of the steel substrate, and the two types of films are mutually connected to form a film-plated structure with an anchoring function. After the method is adopted, the bonding strength between the diamond coating and the substrate is greatly improved, so that the anti-stripping and anti-scratching performances of the diamond coating (layer) are improved.
Description
Technical Field
The invention relates to the technical field of diamond coating, in particular to a method for coating a high-base-film bonding strength, anti-stripping and anti-scratching diamond film on a steel substrate.
Background
Diamond films and diamond-like films are gaining increasing attention for their highest hardness, thermal conductivity, thermal shock properties, as well as extremely high strength and excellent tribological properties. The preparation technology and application research of diamond coating are rapidly developed in the world, wherein the bonding strength between the diamond coating and a substrate is one of the core preparation technologies which are spotlighted in the world. The diamond film is easy to peel off and has poor scratch resistance under the action of heat or thermal stress due to large difference of thermal expansion coefficients of the steel matrix and the diamond film; in addition, the iron element has high carbon solubility and graphite phase tendency, and influences the bonding strength of the diamond coating and the matrix material and the performance of the coating. The base/film bonding strength has become the technical bottleneck of diamond coating of metal materials, especially steel materials. How to improve the bonding strength between the substrate and the plating layer has become a key technology for performing high-quality diamond plating on the surface of a steel substrate.
At present, the industrial diamond coating on common steel parts is a worldwide problem, 8 hundred million tons of steel are produced every year in China, more than one hundred million tons of mechanical parts made of steel are produced, and the number of the mechanical parts needing diamond coating on the surface is large, so that the realization of the high-quality diamond coating of steel materials is significant.
In order to improve the adhesive force between the diamond coating (layer) and the substrate (substrate) and overcome the problems of easy peeling off and low scratch resistance of the diamond coating, several representative process technologies adopted at home and abroad can be summarized as follows:
1. cleaning an enhanced substrate:
for example, the Chinese patent application with publication number CN108330443A discloses a "diamond-like coating method", which performs ion beam cleaning on the surface of a substrate to be coated and a graphite target before coating. Other cleaning means include ultrasonic cleaning, cleaning in an ultrasonic solution containing diamond particles, and the like.
2. Pre-coating a film on a substrate;
for example, a "diamond-like thin film coating method" disclosed in chinese patent publication No. CN100516286C, comprises coating Ti on a substrate, introducing nitrogen to prepare a TiN film, and coating a Ti-containing diamond-like thin film on the TiN film. At present, pre-plating Ni, cr and Cu on a substrate becomes a common method; the function of the pre-plated multilayer metal film is to balance the gradient difference of the coefficient of thermal expansion between the substrate and the diamond coating or to establish a stress buffer layer.
3. Eliminating or weakening the catalytic graphitization influence of the substrate material on the diamond;
such as: the acid-base two-step pretreatment after the ultrasonic vibration is introduced can effectively inhibit the adverse effect of cobalt on the diamond film by removing the Co catalytic graphitization effect on the surface of the hard alloy substrate, and plays a very important role in improving the adhesive force between the diamond film and the matrix.
For example, a CVD diamond film after B-impregnation on the surface of high-speed steel. In order to overcome the adverse effect of Fe element in high-speed steel on the growth of diamond, an intermediate layer of B and Fe compounds is firstly generated on the surface of the high-speed steel by using a boronizing technology, and then a CVD diamond film is prepared.
4. Doping diamond;
if silicon carbide is doped into the diamond coating, not only the fracture toughness of the coating can be improved, but also the adhesion between the film and the substrate can be improved. The composite film contains diamond, silicon carbide (beta-SiC), and may be doped with W, cr and Mo elements.
5. Preparing a matrix containing diamond particles by a powder metallurgy preparation method;
for example, the Chinese patent application with the publication number of CN1170776A discloses a method for manufacturing a diamond film coated hard alloy cutter, which provides that 150-600 meshes of diamond particles and WC-Co mixed materials are prepared into a substrate by a powder metallurgy method, and then diamond coating is carried out on the substrate, so as to realize diamond-impregnated coating on a hard alloy composite material containing 20-100 microns of diamond.
Although the bonding strength between the base films is improved to different degrees from different angles, the requirement of high-strength bonding performance between the substrate and the diamond coating is still difficult to meet, and the improvement of the anti-stripping and anti-scratching performance of the diamond coating (layer) is still a great obstacle for the industrial application of the diamond coating. In particular, high-performance diamond coatings are applied to steel substrates, such as engine cylinder liners (poor coating firmness due to large differences in linear expansion coefficients after heating), camshaft diamond coatings (large alternating impact force), and tool diamond coatings (poor coating firmness due to simultaneous heating and force), which are limited by cost, manufacturing process and performance, and hardly can be applied to the preparation of substrate materials by a powder metallurgy method containing diamond particles to enhance bonding force. Therefore, it is necessary to develop a new technology capable of greatly improving the bonding strength between the film (layer) and the substrate and having high cost performance.
Disclosure of Invention
The invention provides a method for plating a diamond film on a steel matrix, which is characterized in that the diamond film is plated on a steel matrix composite material containing nano diamond particles, the diamond film formed by the epitaxial growth of the nano diamond particles embedded in the matrix is rooted in the matrix, and the diamond film grown along with the surface of the matrix forms an integral film plating structure with an anchoring function; the bonding strength between the finally obtained diamond coating and the substrate is greatly improved, so that the anti-stripping and anti-scratching performances of the diamond coating (layer) are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for plating a diamond film on a steel substrate, comprising the steps of:
1) Preparing a steel-based composite material containing nano diamond particles;
2) Plating a diamond film on the steel-based composite material containing the nano diamond particles;
most of the diamond-plated films are formed by epitaxial growth on the nano diamond particles exposed on the surface of the steel substrate, a small part of the diamond films are formed by nucleation and growth on the rest part of the surface of the steel substrate, and the two types of films are mutually connected to form a film-plated structure with an anchoring function.
The nano-diamond particles comprise nano-scale diamond particles and micro-nano-scale diamond particles, and the particle size is not more than 1 micron.
The iron and steel based composite material containing the nano diamond particles is formed by infiltrating the pretreated nano diamond particles into an iron and steel matrix in an oxygen-free environment in a solid state thermal diffusion mode, wherein the temperature during the solid state thermal diffusion is 650-1350 ℃.
The iron and steel based composite material containing the nano diamond particles is prepared by performing diamond composite electroplating, diamond composite electroforming and diamond composite chemical plating on the surface of an iron and steel matrix, or is directly prepared by a diamond-containing powder metallurgy method and a diamond composite cast infiltration method.
The nano diamond particles are single nano diamond particles, or a mixture of the nano diamond particles and carbide, oxide and metal compound, or nano metal powder containing Ti/W/Mo/Cr/V which are uniformly mixed according to any proportion, and a compound formed by mechanical alloying and thermal diffusion.
The surface to be plated of the steel-based composite material containing the nano diamond particles is subjected to surface pretreatment before being plated with a diamond film.
The surface pretreatment is mechanical surface pretreatment, chemical surface pretreatment or mechanical-chemical surface pretreatment.
The steel-based composite material containing the nano diamond particles comprises a steel section, steel mechanical parts, tools, cutting tools and dies.
The diamond-like film and the nano-diamond film are coated on the diamond-like film.
Compared with the prior art, the invention has the beneficial effects that:
1) Realizing high-quality and high-performance anchoring diamond coating on a strategic base material, namely a steel material;
iron and steel materials are strategic basic materials all the time, and a large number of products in heavy equipment, high-performance mechanical parts, mechanical products and high-performance tools need to realize high-performance diamond coating on an iron and steel substrate; the anchoring diamond coating method breaks through the worldwide technical bottleneck of high-performance diamond coating by taking steel materials as matrixes, provides a practical technology for diamond coating of steel mechanical parts and mechanical products, and has great significance for improving the performance of the mechanical products, researching and developing new mechanical products and exploring new materials with composite functions.
2) The invention provides an anchoring diamond coating method, which improves the speed and quality of diamond coating;
at present, one of the research directions for the base/film bonding strength of diamond coating films of reinforced hard alloy substrates aims at the catalytic action of Co on diamond graphitization and a Co removal method. Research shows that the chemical corrosion cobalt-removing treatment can solve the problem of low nucleation rate of diamond coating, but is difficult to solve the problem of poor adhesion of high-cobalt hard alloy. After the dilute nitric acid chemical erosion decobalting pretreatment, the adhesion performance of the deposited diamond film is still not ideal.
The invention takes the high surface density nano diamond particles which are rooted in the steel substrate material and partially exposed on the surface of the substrate as the seed crystal or the crystal nucleus of the initial growth of the diamond film (layer), and the diamond film (layer) directly grows epitaxially on the nano diamond particles as the seed crystal or the crystal nucleus; together with the diamond film directly growing on the rest surface of the substrate, a diamond film plating structure with anchoring function is formed; the bonding strength between the anchored diamond coating and the substrate is greatly improved, thereby improving the anti-stripping and anti-scratching performances of the diamond coating (layer).
Experiments prove that the bonding strength between the diamond coating film generated by the anchoring method and the substrate is higher than that of the existing diamond coating film pretreated by pre-adhered diamond or impregnated diamond and is further higher than that of the diamond coating film pretreated by coating film. The mechanism is as follows: the nano or micro-nano diamond particles are rooted in the substrate, the surface energy of the nano or micro-nano diamond particles is higher than that of the micro diamond used by other technologies by several orders of magnitude, and the high surface energy 'crystal nucleus' accelerates the epitaxial growth of the diamond film; the volume density and the surface density of the nano diamond particles are more than 2 times higher than those of other technologies, and even if the volume fractions of the nano diamond particles are the same, the number of the nano diamond particles is much higher than that of micron-sized diamond particles, so that the diamond coating on the nano diamond particle reinforced steel-iron-based composite material has higher base/film bonding strength and higher growth speed. The steel material anchoring diamond coating product has excellent use performance.
3) The diamond particles diffused into the steel matrix are nano-scale or nano-micron-scale diamond particles, the surface energy is high, the surface density is large (about 40 percent of the surface area), a large number of nano diamond particles planted in the matrix are equivalent to diamond seed crystals with high density and high surface energy which are uniformly distributed and are pre-planted on the surface to be plated, the diamond film directly epitaxially grown by the seed crystals bridges the matrix and the plated film, and the firmest matrix/film non-interface connection is established. The higher the proportion of anchoring, bridging and direct epitaxial growth is, the higher the diamond coating speed and the bonding strength between the base and the film are.
Compared with the manufacturing method of the diamond film coated hard alloy cutter disclosed in the Chinese patent application with the publication number of CN1170776A, although the powder metallurgy method with the components not strictly limited is adopted, because the diamond powder with the bulk density of 20-30% and the granularity of 23-100 μm is used, the number of diamond particles exposed on the interface and the area ratio of diamond and non-diamond are far lower than the number and the occupied area ratio of nano diamond particles exposed on the interface in the composite material. The fact that the nano-diamond particles according to the present invention have a bulk density of up to 40% and a particle size of not more than 1 μm means that the number of nuclei or seeds available for direct epitaxial growth of diamond films is very different. The diamond film forming speed and the base/film binding force are far less than those of the nano diamond particles, and the high surface energy, the high quantity and the high occupied area ratio of the nano diamond particles determine that the epitaxial direct growth of the diamond film on the nano diamond particles is easier to occur and carry out, the film forming speed is higher, and the base/film binding force is stronger.
4) The nano diamond particles prepared by the thermal diffusion method enhance the heat conductivity, corrosion resistance, tribology performance and mechanical property of the steel-based composite material used as the matrix material of the diamond coating, provide a new approach for directly carrying out high-performance diamond coating on various alloy steel cutters, tools and moulds, and lay a technical foundation for the industrial production and practical application of high-performance steel mechanical parts of the diamond coating.
5) The method for preparing the diamond composite material by adopting the powder metallurgy method has high cost, and the thermal diffusion method is a better solution for realizing the industrial production of the nano diamond particle reinforced steel-iron-based composite material with high cost performance, and has low manufacturing cost and easy implementation. Particularly, the microstructure of the prepared steel-based composite material is a nano composite structure with ultrafine grain continuous gradient enhanced by nano diamond particles, the microstructure endows the composite material with mechanical and physical properties of high hardness, high strength, high toughness and high thermal conductivity, and the steel material often contains W/Mo/Cr/Ti/V alloy elements beneficial to diamond coating, so that a good foundation is laid for high-performance diamond coating on the steel material. The advantages are important feasibility basis for realizing high-performance and high-cost performance diamond coating on steel materials.
5) The method is suitable for high-wear-resistance high-heat-conductivity low-friction mechanical parts or mechanical products, cutting tools, dies, power transmission components, engine parts, extreme low-wear-resistance coupling parts, mechanical parts with ultra-long service life and ultra-corrosion-resistance and ultra-wear-resistance parts.
Drawings
FIG. 1 is a metallographic structure diagram of a steel-based composite material containing nano-diamond particles prepared by a thermal diffusion method according to the present invention.
Fig. 2 is a schematic diagram illustrating the principle of plating a diamond film on a steel-based composite material containing nano-diamond particles (prepared by a thermal diffusion method) according to the present invention.
Fig. 3 is a schematic diagram illustrating the principle of plating a diamond film on a steel-based composite material containing nano-diamond particles (a transition layer is prepared by a composite plating method) according to the present invention.
In the figure: 1. a steel matrix 11, a transition layer 2, nano diamond particles 3, a diamond film 4 formed by the epitaxial growth of the nano diamond particles exposed on the surface of the steel matrix, and a diamond film grown on the other surface of the steel matrix
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
the invention discloses a method for plating a diamond film on a steel substrate, which comprises the following steps:
1) Preparing a steel-based composite material containing the nano diamond particles (as shown in figure 1);
2) Plating a diamond film on the steel-based composite material containing the nano diamond particles;
as shown in fig. 2 and 3, most of the diamond-coated film is formed by epitaxial growth on the nano-diamond particles 2 exposed on the surface of the steel substrate 1 (as shown in fig. 2 and 3, reference numeral 3), and a small part of the diamond film (as shown in fig. 2 and 3, reference numeral 4) is formed by nucleation and growth on the rest of the surface of the steel substrate, and the two films are connected with each other to form a coating structure with an anchoring function.
The nano-diamond particles comprise nano-scale diamond particles and micro-nano-scale diamond particles, and the particle size is not more than 1 micron.
The iron and steel based composite material containing the nano diamond particles is formed by infiltrating the pretreated nano diamond particles into an iron and steel matrix in an oxygen-free environment in a solid state thermal diffusion mode, wherein the temperature during the solid state thermal diffusion is 650-1350 ℃.
The steel-based composite material containing the nano diamond particles is prepared by performing diamond composite electroplating, diamond composite electroforming and diamond composite chemical plating on the surface of a steel matrix, or is directly prepared by a diamond-containing powder metallurgy method and a diamond composite cast infiltration method.
The nano diamond particles are single nano diamond particles, or a mixture of the nano diamond particles and carbide, oxide and metal compound, or nano metal powder containing Ti/W/Mo/Cr/V which are uniformly mixed according to any proportion, and a compound formed by mechanical alloying and thermal diffusion.
The surface to be plated of the steel-based composite material containing the nano diamond particles is subjected to surface pretreatment before being plated with a diamond film.
The surface pretreatment is mechanical surface pretreatment, chemical surface pretreatment or mechanical-chemical surface pretreatment.
The steel-based composite material containing the nano diamond particles comprises steel profiles, steel mechanical parts, tools, cutting tools, dies and other steel mechanical products.
As shown in fig. 1, it is a metallographic structure diagram of a steel matrix composite material containing nano-diamond particles prepared by allowing nano-diamond particles to enter a steel matrix through a thermal diffusion manner. The figure shows that a large amount of nano-diamond particles with the granularity of less than 150nm are uniformly distributed in a steel matrix at high density.
As shown in fig. 2, which is a schematic diagram of the principle of plating a diamond film on a steel substrate containing nano-diamond particles according to the present invention, the diamond film is epitaxially grown on the nano-diamond particles 2 rooted on the steel substrate 1 and exposed on the surface of the steel substrate 1, the diamond film 4 grown on the remaining surface of the steel substrate 1 (between the nano-diamond particles 2) is directly nucleated and grown on the surface of the steel substrate 1, and the two types of films are concomitantly grown and connected to each other, thereby finally forming an integral diamond coating film with an anchoring function covering the surface of the steel substrate 1. The bonding strength between the diamond film rooted on the steel matrix and the steel matrix is greatly improved through the anchoring effect, so that the anti-stripping and anti-scratching performances of the diamond coating (layer) are improved.
In addition to the thermal diffusion method for preparing the steel-based composite material containing the nano-diamond particles, the method of coating the diamond composite material on the surface of the diamond film to be coated on the steel substrate can also be adopted to prepare the steel-based composite material containing the nano-diamond particles, i.e. the transition layer 11 is formed first, and the diamond film coating is carried out on the surface of the transition layer 11 to realize the strengthening of the film-substrate combination (as shown in figure 3).
The method for forming the transition layer 11 on the surface of the steel substrate by coating the diamond composite material can adopt one of the following methods: diamond composite electroplating, diamond composite electroforming and diamond composite chemical plating. The method of the invention is also applicable to non-ferrous metal substrates.
In addition, the steel-based composite material containing the nano diamond particles can also be prepared by adopting a method of casting and infiltrating the diamond particles on the surface layer, or carrying out high-energy beam melting on the diamond composite powder in an oxygen-free or vacuum environment, mixing the diamond particles and the metal powder according to a certain proportion, or sintering and molding through powder metallurgy, or carrying out hot extrusion molding, or carrying out sheath forging molding.
The purpose of pretreating the surface of the steel-based composite material containing the nano diamond particles to be coated is to activate and clean the nano diamond particles which are planted and exposed on the surface of the substrate material and the surface of the substrate. The selectable method comprises ultrasonic shot blasting, white corundum dry type sand blasting, glass bead dry type sand blasting, and surface cleaning after the shot blasting or the sand blasting, wherein the surface cleaning comprises the steps of ultrasonic acid solution cleaning, tap water rinsing → ultrasonic alkali solution cleaning, tap water rinsing → ultrasonic deionized water rinsing → drying and the like.
When diamond coating is carried out on the surface of the steel-based composite material containing the nano diamond particles, a conventional diamond coating method can be adopted, such as: CVD method, MPCVD method, arc ion plating, and the like.
The diamond film of the present invention includes diamond-like film, diamond-like film (DLC) and nano-diamond film. Because of the performance characteristics of high hardness, low friction coefficient, chemical inertness and the like, the diamond-like film is one of the main technical means for improving the wear-resisting service life of parts with relative contact motion to carry out surface treatment. However, diamond-like carbon (DLC) films have high internal stress and poor compatibility with metal materials, and thus it is difficult to plate a diamond-like carbon film having high adhesion and a thickness of 1 μm or more on a metal material. The current representative process is to plate a transition film, such as a TiC film or a Cr film, on the surface of high-speed steel in advance. However, the process is complex and high in cost, and the bonding force of the base film is still difficult to adapt to rough machining under heavy cutting and vibration (such as integral hard alloy for heavy cutting hobs); the diamond coating of diamond-containing high-speed steel prepared by using integral hard alloy and hard alloy diamond coating or powder metallurgy has high cost and low cost performance, and the invention can prepare the high-performance heavy-cutting hob by using the diamond coating after the nano diamond is infiltrated into the common high-speed steel, and the manufacturing cost is saved by more than 1/2.
As shown in fig. 1, the surface of the steel-based composite material containing nano-diamond particles is distributed with nano/micro-nano diamond particles with high surface density and rooted in the steel matrix 1, most of the diamond film is epitaxially grown on the surfaces of the nano-diamond particles 2 rooted in the steel matrix 1, and the rooted diamond film grows together with the diamond film 4 grown on the rest part of the surface of the steel matrix to form an anchoring coating structure. The anchoring structure greatly improves the binding force between the diamond coating and the steel substrate, so that the anti-stripping and anti-scratching performances of the diamond coating are obviously improved.
As shown in fig. 1, it is a metallographic structure diagram of a steel-based composite material containing nano-diamond particles prepared by a thermal diffusion method. As can be seen from fig. 1, the nano-diamond particles with an area density (bulk density) of about 40% are uniformly distributed in the steel matrix, the size of the nano-diamond particles diffused into the steel matrix is the same as the nominal size of the commercial nano-diamond, and the nano-diamond particles are normally distributed, and a large number of nano-diamond particles with smaller sizes can be identified only under higher resolution. Compared with the metal composite material containing micron-sized diamond, the larger the proportion of surface atoms is along with the reduction of the diamond particle size, the larger the specific surface area of the nano-diamond particles is, and the higher the surface energy is. On the surfaces of the nano diamond particles with higher surface energy and smaller granularity, the diamond film is easier to directly grow epitaxially. The high density of the nano diamond particles in the steel matrix accelerates the film forming speed of diamond coating and improves the coating quality. The diamond film nucleated and grown on the surface of the steel matrix without the nano-diamond particles is connected with the diamond film epitaxially grown on the adjacent nano-diamond particles to form a complete diamond film.
As shown in fig. 2, the nano-diamond particles 2 exposed on the surface of the steel substrate 1 serve as "seed crystals" for the epitaxial growth of the diamond film, which bridges the steel substrate 1 and the diamond film and becomes anchors for the plating film to root in the steel substrate 1. The diamond film (the part indicated by the serial number 4) growing on the exposed surface of the steel substrate without the nano diamond particles and the diamond film (the part indicated by the serial number 3) epitaxially growing by the nano diamond particles grow into a whole diamond coating. The nano-diamond with high surface density means high-density bridging points and more anchors and roots, namely, the anchoring function is stronger, the bonding strength between base films is higher, and the anti-stripping and anti-scratching performance of the coating film is higher.
As shown in fig. 3, a diamond composite coating film (layer) is firstly prepared on the surface of the steel substrate 1 as a transition layer 11 of the subsequent diamond coating film, then a diamond film is plated on the transition layer 11, and by preparing the transition layer 11 containing nano diamond particles, a high-quality diamond coating film with an anchoring structure can be realized by a common metal material.
The following embodiments are all provided to follow the technical scheme of the present invention, and detailed embodiments and specific operation procedures are provided, but the scope of the present invention is not limited to the following embodiments. The methods used in the following examples are conventional methods unless otherwise specified.
[ example 1 ]
In this embodiment, the method for plating the diamond film on the steel substrate specifically includes:
1) Preparing the steel-based composite material containing the nano diamond particles as a matrix of the diamond coating. The method comprises the following specific steps:
(1) activating and cleaning the surface to be plated: in this embodiment, the substrate to be plated with the diamond film is a steel mechanical part (hereinafter referred to as a workpiece), and the surface of the substrate is pretreated by a mechanical method or a mechanical-chemical method before plating, including one or more than two composite processes of shot blasting, supersonic shot blasting, screening, sanding, turning, milling, planing, grinding and the like;
(2) the method comprises the following steps of pretreating nano-scale or micro-nano-scale diamond particles with the particle size of 10-1000 nanometers: carrying out ball milling or sand grinding on the diamond particles to break and agglomerate, adding an active agent into the deagglomerated diamond particles, and carrying out ultrasonic dispersion in an oil-based solvent;
the pretreated nano diamond particles are in contact with the surface to be infiltrated of the workpiece in a slurry form directly or through a fluidized bed;
(3) establishment of anaerobic conditions: putting the workpiece to be plated with the diamond slurry into a container for vacuum pumping, wherein the vacuum degree is 10 -5 ～10 -2 pa or 10 -2 ～10 -1 pa。
(4) And (4) heating the container in the step (3) in a heating furnace to complete the thermal diffusion of the nano diamond particles into the steel matrix. The surface of the workpiece is provided with a steel-based composite material layer (surface diamond nano reconstruction for short) with nano diamond particle reinforced superfine crystal grain continuous gradient.
The thickness of the infiltration layer is determined by the thermal diffusion time, the temperature and the granularity of the nano diamond particles, the maximum thickness can reach 10mm, the diffusion speed is 0.5-1 mm, and the diffusion temperature range is 650-1350 ℃.
(5) And (4) cooling the container in the step (4) to 300-350 ℃ along with the furnace, discharging the container from the furnace, and cooling the container to room temperature in air.
(6) Taking out the workpiece and carrying out heat treatment according to a conventional method.
(7) And performing finish machining on the surface to be plated of the workpiece to the size, grinding and polishing the surface to be plated, and performing ultrasonic cleaning to expose the nano diamond particles in the composite permeable layer. The optimal pretreatment mode before plating can be adopted according to different working conditions and different requirements.
2) Diamond coating is carried out on the surface of the prepared steel-based composite material containing the nano diamond particles by adopting a conventional coating method (as shown in figure 2).
The embodiment is a new technology for carrying out high-strength diamond coating on a steel matrix, and the nano diamond is infiltrated into a steel material by a thermal diffusion method to prepare the steel matrix composite material containing nano diamond particles.
Carbon steel, alloy steel, tool steel die steel, bearing wheel steel, mechanical basic parts such as shaft parts, cylinder sleeves, oil-gas cylinder barrels, fluid mechanical pump parts and the like can refer to the process as long as the steel basic mechanical parts and mechanical products with high wear resistance and low friction or with the requirements of high surface hardness and long service life are required.
[ example 2 ] A method for producing a polycarbonate
In the embodiment, the method for diamond coating of the high-speed steel hob of the large-modulus turbine comprises the following specific steps:
(1) Performing semi-finishing on a hobbing cutter made of W6Mo5Cr4V2 (M2) high-speed steel, and performing oil and rust removal pretreatment;
(2) The nano diamond particles (with the granularity of 10 nm-500 nm) are subjected to sanding, ultrasonic deagglomeration and active agent dispersion pretreatment to prepare nano diamond slurry;
(3) Coating the tooth part of the hob with nano-diamond slurry in a sealable container, sealing the container, vacuumizing to a vacuum degree of 10 -5 ～10 -2 pa；
(4) Placing the container in the step (3) in a heating furnace, heating at the temperature of 800-1040 ℃, and performing thermal diffusion of the nano diamond particles into the steel matrix;
(5) The diffusion time is 4 to 5 hours, and the mixture is discharged from the furnace when the temperature is cooled to below 350 ℃;
(6) Carrying out thermal refining on the hob permeated with the nano diamond particles, then carrying out finish machining, reserving grinding allowance after quenching, carrying out surface quenching and low-temperature tempering, then carrying out fine grinding to reach the size (considering the diamond coating thickness), grinding the surface to be coated, and cleaning the surface of a workpiece to enable the surface to meet the diamond coating requirement;
(7) And (3) finishing diamond coating of the hob by adopting a vacuum evaporation ion beam assisted deposition technology/MPCVD/other coating methods.
Diamond coating of the tool provides the best performance for tools machined from non-ferrous metallic materials, and is an ideal coating for machining graphite, metal Matrix Composites (MMC), high silicon aluminum alloys, copper alloys, and many other highly abrasive materials. Heavy cutting of nonferrous metal, heavy cutting of ferrous metal at low cooling speed and discontinuous heavy cutting are suitable for diamond coating of high-speed steel matrix.
[ example 3 ]
In the embodiment, the method is adopted to carry out diamond coating on the section of the spiral groove for sealing the compressor.
The sealing element of the compressor is required to be free of maintenance for more than 3 years, the working environment is high pressure and high temperature, the fluid contains hard particles, the conventional wear-resistant part is made of hard alloy, the spiral groove is machined by laser, the machining cost is high, and the roughness is difficult to meet the use requirement. By adopting the anchoring method diamond film coating technology, the tool steel can be used for replacing hard alloy, and the qualified high-performance product can be manufactured at low cost only by using the common processes of turning, milling, grinding and the like. The preparation process comprises the following steps:
(1) Selecting a common tool steel material, and performing semi-finishing according to a drawing;
(2) Thermal diffusion of the nanodiamond particles into the matrix was performed in the same manner as in steps (2) to (5) of examples 1 and 2;
(3) Carrying out integral quenching and low-temperature tempering on the workpiece infiltrated with the nano diamond particles to ensure that the hardness of the workpiece reaches HRC62-64;
(4) And (4) finishing the workpiece to size, and finishing the section of the sealing element and the surface of the spiral groove on the sealing element.
(5) Cleaning the surface to meet the requirement of diamond coating
(6) The nano diamond coating is carried out, the film thickness is controlled to be 500 nm-5 mu m, and the DLC film thickness is 1 mu m.
The steel-based precision mechanical parts with high or extremely high requirements on corrosion resistance and wear resistance can adopt the process of the embodiment, such as various valves, hydraulic parts, surgical instruments, titanium alloy artificial bones, high-speed bearings in a corrosive environment, outer space self-lubricating wear-resistant parts, screw pump parts, extruder parts, melt-blown die spinnerets and the like of fluid machinery.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (1)
1. A method of plating a diamond film on a steel substrate comprising the steps of:
1) Preparing a steel-based composite material containing nano diamond particles; the microstructure of the prepared steel-based composite material is a nano composite structure with nano diamond particles enhanced ultra-fine crystal grain continuous gradient; the steel-based composite material containing the nano-diamond particles is formed by infiltrating the pre-treated nano-diamond particles into a steel matrix in an oxygen-free environment in a solid state thermal diffusion mode, wherein the temperature during solid state thermal diffusion is 650-1350 ℃; the pretreatment process comprises the following steps: adding an active agent into diamond particles subjected to ball milling or sand grinding agglomeration and ultrasonic deagglomeration, and performing ultrasonic dispersion in an oil-based solvent; the pretreated nano diamond particles are in contact with the surface to be infiltrated of the workpiece in a slurry form directly or through a fluidized bed;
2) Plating a diamond film on the steel-based composite material containing the nano diamond particles;
most of the diamond-plated film is formed by epitaxial growth on the nano diamond particles exposed on the surface of the steel substrate, a small part of the diamond film is formed by nucleation and growth on the rest part of the surface of the steel substrate, and the two types of films are mutually connected to form a film coating structure with an anchoring function;
the nano-diamond particles comprise nano-scale diamond particles and micro-nano-scale diamond particles, the granularity is not more than 1 micron, the volume density of the nano-diamond particles is 40 percent, the nano-diamond particles planted in the substrate are used as high surface energy crystal nuclei for epitaxial growth to form a diamond film, the substrate and the coating film are bridged by the uniformly distributed high-density high surface energy diamond crystal seeds, and the substrate/film non-interface connection is established;
the nano diamond particles are single nano diamond particles, or a mixture of nano diamond particles and carbide, oxide and metal compound, or nano metal powder containing Ti/W/Mo/Cr/V which are uniformly mixed according to any proportion;
the surface to be plated of the steel-based composite material containing the nano diamond particles is subjected to surface pretreatment before being plated with a diamond film; the surface pretreatment is mechanical surface pretreatment, chemical surface pretreatment or mechanical-chemical surface pretreatment;
the steel-based composite material containing the nano diamond particles comprises a steel section, steel mechanical parts, tools, cutting tools and a die; and the workpiece infiltrated with the nano diamond particles is integrally quenched and tempered at low temperature;
the diamond-like film and the nano-diamond film are coated on the diamond-like film.
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