CN112609180A - In-situ synthesized nano TiC particle reinforced gradient composite coating and preparation method thereof - Google Patents
In-situ synthesized nano TiC particle reinforced gradient composite coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000004372 laser cladding Methods 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 13
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010949 copper Substances 0.000 claims description 2
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- 206010067484 Adverse reaction Diseases 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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Abstract
The invention relates to an in-situ synthesized nano TiC particle reinforced gradient composite coating and a preparation method thereof, belonging to the technical field of laser cladding, wherein the in-situ synthesized nano TiC particle reinforced gradient composite coating is made of a metal material doped with in-situ synthesized nano TiC particles, the average particle size of the in-situ synthesized nano TiC particles is 30-80nm, and the content of the in-situ synthesized nano TiC particles is gradually enhanced from the bottom of the coating along the thickness direction of the coating. The composite coating prepared by the method has low TiC content at the bottom of the coating, the TiC content is gradually increased along the coating thickness direction, and the TiC content is increased to the gradient coating with high TiC content on the coating surface, so that the coating surface has high performance, and the coating has high compatibility with a matrix interface and has no interface combination problem.
Description
Technical Field
The invention belongs to the technical field of laser cladding, and particularly relates to an in-situ synthesized nano TiC particle reinforced gradient composite coating and a preparation method thereof.
Background
The preparation of the ceramic particle reinforced metal matrix composite material by laser cladding is an important research direction of the current wear-resistant cladding coating. The reinforced ceramic particles can be divided into external particle reinforcement and in-situ self-generated particle reinforcement according to different adding modes of the reinforced ceramic particles. In the past, a method of directly adding ceramic particles (such as WC, TiC, TiN, SiC and the like) is usually adopted, the method has the defects that the size of the added ceramic phase particles is larger, the difference of thermophysical parameters with a mother phase metal is large, the solidification shrinkage of a cladding layer is hindered by the mother phase metal, the compatibility is poor, the interface of a reinforcing phase and the mother phase metal is thermodynamically unstable, the interface combination is influenced and is often a crack source, in addition, adverse reactions and attachments can be formed on the interface of the ceramic and the mother phase metal, so that the interface is a weak interface with low strength and low toughness, the ceramic particles can strip the mother phase metal under the action of heavy load, and the integral strengthening effect is weakened.
By in situ autogenesis, it is meant the in situ formation of a ceramic reinforcing phase by an exothermic reaction between an element and an element or between an element and a compound under certain conditions. Due to the introduction specificity of the ceramic phase, the ceramic phase has the advantages of fine size, no pollution on the surface of particles, better wettability with a mother phase and high interface bonding strength. The two characteristics enable the in-situ synthesized particle reinforced composite material to have higher strength and modulus, and good high-temperature performance, fatigue resistance and wear resistance compared with the traditional externally added reinforced phase composite material. Therefore, laser cladding for preparing in-situ synthesized particle reinforced coating is a hot spot of research.
With the development of nanotechnology, the focus of nanomaterial research has gradually shifted from the preparation of single nanopowder to the development and application of nanobubbles and nanolayered coatings. The nano coating changes the form, chemical composition, tissue structure and stress state of the surface of the solid material by means of the surface effect and small-size effect of the nano particles, and endows the surface of the material with good functional performance and structural mechanical performance.
The TiC ceramic belongs to a face-centered cubic crystal form, has small density, high melting point, good heat conducting property, high hardness, good chemical stability and good high-temperature oxidation resistance, and is a common composite coating strengthening phase.
Based on the principle, the in-situ synthesized TiC particle reinforced gradient composite coating prepared by laser cladding and the preparation method thereof are provided.
Disclosure of Invention
The invention aims to fuse a laser cladding nano-particle reinforced composite coating, a laser cladding in-situ authigenic particle reinforced composite coating and a laser cladding gradient coating together, and realize laser cladding in-situ authigenic preparation of the nano TiC particle reinforced gradient composite coating by taking high-energy ball-milled pure titanium, graphite and mother-phase metal mixed powder as a cladding material and preforming the mixed powder on the surface of a pretreated matrix.
The invention realizes the purpose through the following technical scheme:
the invention provides an in-situ synthesized nano TiC particle reinforced gradient composite coating, which is prepared from a metal material doped with in-situ synthesized nano TiC particles, wherein the in-situ synthesized nano TiC particles are prepared by presetting Ti powder and graphite powder on a matrix by a tabletting presetting method in a mother phase metal powder environment, are generated in situ in a laser cladding mode, have an average particle size of 30-80nm, and gradually increase the content of the in-situ synthesized nano TiC particles from the bottom of the coating along the thickness direction of the coating.
As a further optimization scheme of the invention, the mass percentage of the Ti powder, the graphite powder and the mother phase metal powder is 4x: x (100-5x), wherein x is 1-6.
The invention also provides a preparation method of the in-situ synthesized nano TiC particle reinforced gradient composite coating, which comprises the following steps:
step S1: carrying out ball milling on Ti powder, graphite powder and mother phase metal powder, and uniformly mixing to obtain mixed powder;
step S2: pretreating a substrate, and presetting mixed powder on the surface of the pretreated substrate by adopting a tabletting presetting method to obtain preset powder;
step S3: performing laser cladding on the preset powder to obtain an in-situ self-generated nano TiC particle reinforced gradient composite coating, wherein the laser cladding process parameters are as follows: the laser power is 1000-2000W, the spot diameter is 2-4mm, the laser scanning speed is 3-6mm/s, argon is adopted to carry out gas protection on a molten pool, and the gas carrying amount is 3-8L/min;
in the laser cladding process under the parameters, Ti in the mixed powder reacts with graphite in situ in a molten pool to generate TiC reinforced particles under the action of a high-energy-density laser beam, most of the TiC reinforced particles in the coating are nano particles smaller than 100nm, the average particle size is 30-80nm, and meanwhile, the TiC reinforced particles with small density are in a floating effect in the molten pool, so that the low TiC content at the bottom of the coating is obtained, and the TiC content is gradually reinforced along the coating thickness direction; to a gradient coating with a high TiC content on the surface of the coating and the more to the surface of the coating there is a relatively higher proportion of TiC particles in the nano agglomerates and TiC particles growing up to submicron dimensions.
As a further optimization scheme of the invention, in the step S1, the original average particle sizes of the Ti powder, the graphite powder and the mother phase metal powder are respectively 10-50 μm, 1-5 μm and 30-60 μm.
As a further optimized scheme of the present invention, in step S1, the ball milling process parameters are: the protective gas is Ar gas, the ball milling medium is stainless steel balls or zirconia ceramic balls, the ball-material ratio is 5-20:1, the rotating speed is 300-500r/min, the ball milling time is 20-40h, and the average particle size of the fine mixed powder after ball milling is 0.2-1 mu m.
As a further optimized solution of the present invention, in step S1, the parent-phase metal powder is one of a nickel-based alloy, a cobalt-based alloy, an iron-based alloy, and a copper-based alloy powder.
As a further optimized solution of the present invention, in step S2, the method for preprocessing the substrate includes: and sequentially carrying out sand paper polishing, oil removal and drying treatment on the surface of the matrix.
As a further optimization scheme of the invention, in the step S2, the thickness of the pre-pressed mixed powder coating is 0.2-2 mm.
The invention has the beneficial effects that:
(1) the cladding material is mixed powder of Ti, graphite and parent phase metal, the Ti and the graphite react in situ to generate TiC reinforced particles in the cladding process, the TiC reinforced particle composite coating is in-situ synthesized TiC reinforced particle composite coating, compared with an external particle reinforced composite coating, the TiC reinforced particle composite coating has the advantages of small size of a reinforced phase, no pollution on the surface of the reinforced particle, better wettability with the parent phase metal, high interface bonding strength and the like, and the coating has higher strength and modulus, and good high-temperature performance, fatigue resistance and wear resistance.
(2) The invention obtains the mixed powder with uniform mixing and fine particles by carrying out long-time high-energy ball milling on the original Ti, graphite and the parent-phase metal powder, thereby generating nano-scale TiC reinforced particles in the laser cladding process, and a plurality of high-melting-point nano TiC reinforced particles are firstly solidified in a molten pool, so that the nucleation rate in the whole molten pool solidification process is greatly increased, and the parent-phase crystal grains are prevented from growing, thereby the parent-phase crystal grains in the coating are finer, and under the double actions of nano-particle reinforcing effect and parent-phase fine-grain reinforcing, compared with the conventional larger-size TiC particle reinforced composite coating, the hardness and wear resistance of the coating can be further improved, and the coating can keep higher toughness.
(3) Based on the floating effect of the low-density TiC reinforced particles in the laser molten pool, the service life of the molten pool is controlled by controlling laser cladding process parameters, so that the TiC reinforced particles obtain moderate floating time, the low TiC content at the bottom of the coating is obtained, the TiC content is gradually increased along the thickness direction of the coating, and the TiC content reaches the gradient coating with high TiC content on the surface of the coating, so that the surface of the coating has high performance, and the coating has high compatibility with a substrate interface and has no interface combination problem.
(4) The invention adopts a tabletting method to preset laser cladding mixed powder, and compared with the current commonly used thermal spraying method and bonding method preset process, the invention not only avoids the problems of advanced oxidation of partial powder and consumption of a large amount of fuel caused by the thermal spraying method, but also eliminates the problem of impurity pollution caused by a bonding agent in the powder bonding method, and can realize green presetting of the powder.
(5) The cladding object of the invention contains a certain proportion of graphite, and the powder has high light absorption and high laser utilization rate.
(6) The invention combines the in-situ synthesized particle reinforced composite coating, the nano particle reinforced composite coating and the gradient coating together, prepares the in-situ synthesized nano particle reinforced gradient composite coating through laser cladding, and can integrate the advantages of the three coatings into a whole, thereby greatly improving the comprehensive performance of the prepared coating.
Drawings
FIG. 1 is a schematic view of a laser-clad in-situ synthesized nano TiC particle-reinforced gradient composite coating of the present invention;
in the figure: 1. a parent phase metal powder; 2. graphite powder; 3. ti powder; 4. parent phase metal (liquid); 5. ti (liquid); 6. TiC reinforcing particles; 7. mother phase metal (solid)
Detailed Description
The present application is described in further detail below, and it should be noted that the following detailed description is provided for illustrative purposes only, and is not intended to limit the scope of the present application, which is defined by the appended claims.
As shown in fig. 1, the preparation process of the in-situ synthesized nano TiC particle reinforced gradient composite coating of the present invention comprises the following steps:
step S1: introducing protective gas Ar gas into a high-energy ball mill, adopting stainless steel balls or zirconia ceramic balls as ball milling media, putting Ti powder 3, graphite powder 2 and mother-phase metal powder 1 with the mass percentage of 4x: x (100-5x) (wherein x is 1-6) into the high-energy ball mill according to the proportion of ball material ratio of 5-20:1, and ball milling for 20-40h under the condition of the rotation speed of 300 plus materials of 500r/min to obtain mixed powder which is uniformly mixed and has fine particles, wherein the average particle size of the mixed powder is 0.2-1 mu m;
the original Ti powder is irregular with the purity of 99.9 percent, the average particle size is 10-50 mu m, the graphite powder is flocculent with the purity of 99.5 percent, the average particle size is 1-5 mu m, the parent-phase metal powder is spherical Ni powder with the purity of 99.9 percent, and the average particle size is 30-60 mu m;
step S2: sequentially carrying out sand paper polishing, oil removal and drying treatment on the matrix; green presetting of the mixed powder is realized on the surface of the matrix by adopting a tabletting presetting method, the mixed powder is pressed and formed on a press machine through a die, and the thickness of the coating of the tabletting preset mixed powder is 0.2-2 mm;
step S4: laser cladding: putting the base body with the preset powder into a laser processing machine tool, introducing argon with the gas carrying capacity of 3-8L/min to carry out gas protection on a molten pool, and controlling laser cladding technological parameters as follows: the laser power is 1000-.
Under the action of a high-energy-density laser beam in the laser cladding process, Ti in the mixed powder and graphite react in situ in a molten pool to generate TiC reinforced particles, and the average size of the TiC reinforced particles is 30-80 nm.
The laser cladding in-situ synthesized nano TiC particle reinforced gradient composite coating is a gradient coating which is obtained based on the floating effect of low-density TiC reinforced particles in a molten pool, wherein the volume percentage of TiC at the bottom of the coating is less than 5%, the TiC content is gradually enhanced along the coating thickness direction, and the volume percentage of TiC on the surface of the coating is more than 25%.
Most of the TiC reinforced particles in the coating are nano particles with the particle size less than 100nm, and the higher the TiC reinforced particles are, and the TiC particles with the particle size reaching submicron size are.
Example 1
In order to verify the performance of the coating prepared by the invention, the embodiment is provided, and the in-situ synthesized nano TiC particle reinforced gradient composite coating is prepared by the method, and the specific parameters and steps are as follows:
step S1: introducing protective gas Ar gas into a ball mill by using a high-energy ball mill with the model of Pulverisette 6 of Germany Fritsch company, adopting zirconia ceramic balls as a ball milling medium, and putting Ti powder 3, graphite powder 2 and mother-phase metal powder 1 with the mass percentage of 16:4:80 into the high-energy ball mill according to the proportion of ball material ratio of 10:1 to ball mill for 30 hours at the rotating speed of 400r/min to obtain mixed powder which is uniformly mixed and has fine particles, wherein the average particle size of the mixed powder is 0.2-1 mu m;
step S2: selecting the size of 100 multiplied by 30 multiplied by 10mm3The 42CrMo alloy structural steel is used as a matrix, and the surface of the matrix is sequentially subjected to sand paper polishing, oil removal and drying treatment; the green presetting of mixed powder is realized on the surface of a matrix by adopting a tabletting presetting method, the matrix is pressed and formed on a press machine through a mould, and the tabletting presetting mixed powder coatingThe layer thickness is 1 mm;
step S3: laser cladding: selecting SLCF-X12 × 25 model of Shanghai Boehringer-Marek laser Equipment Co., Ltd2The laser processing machine tool is used for placing a base body with preset powder into the laser processing machine tool, introducing argon with the gas carrying capacity of 5L/min to carry out gas protection on a molten pool, and controlling laser cladding technological parameters to be: the laser power is 1500W, the diameter of a light spot is 3mm, the laser scanning speed is 5mm/s, and the in-situ self-generated nano TiC particle 6 reinforced gradient composite coating is obtained by carrying out laser cladding on the preset powder.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (8)
1. The in-situ synthesized nano TiC particle reinforced gradient composite coating is characterized in that the coating is made of a metal material doped with in-situ synthesized nano TiC particles, the in-situ synthesized nano TiC particles are prepared by presetting Ti powder and graphite powder on a matrix by a tabletting presetting method in a mother phase metal powder environment, and are generated in situ in a laser cladding mode, the average particle size is 30-80nm, and the content of the in-situ synthesized nano TiC particles is gradually enhanced from the bottom of the coating along the thickness direction of the coating.
2. The in-situ synthesized nano TiC particle reinforced gradient composite coating of claim 1, wherein the mass percentage of the Ti powder, the graphite powder and the parent phase metal powder is 4x: x (100-5x), wherein x is 1-6.
3. A method for preparing in-situ synthesized nano TiC particle reinforced gradient composite coating as claimed in any one of claims 1 to 2, comprising the following steps:
step S1: carrying out ball milling on Ti powder, graphite powder and mother phase metal powder, and uniformly mixing to obtain mixed powder;
step S2: pretreating a substrate, and presetting mixed powder on the surface of the pretreated substrate by adopting a tabletting presetting method to obtain preset powder;
step S3: performing laser cladding on the preset powder to obtain an in-situ self-generated nano TiC particle reinforced gradient composite coating, wherein the laser cladding process parameters are as follows: the laser power is 1000-2000W, the spot diameter is 2-4mm, the laser scanning speed is 3-6mm/s, argon is adopted to carry out gas protection on a molten pool, and the gas carrying amount is 3-8L/min.
4. The method for preparing in-situ synthesized nano TiC particle reinforced gradient composite coating according to claim 3, wherein the method comprises the following steps: in the step S1, the Ti powder, the graphite powder, and the matrix metal powder have primary average particle sizes of 10 to 50 μm, 1 to 5 μm, and 30 to 60 μm, respectively.
5. The method for preparing in-situ synthesized nano TiC particle reinforced gradient composite coating according to claim 3, wherein the method comprises the following steps: in the step S1, the ball milling process parameters are as follows: the protective gas is Ar gas, the ball milling medium is stainless steel balls or zirconia ceramic balls, the ball-material ratio is 5-20:1, the rotating speed is 300-500r/min, the ball milling time is 20-40h, and the average particle size of the fine mixed powder after ball milling is 0.2-1 mu m.
6. The method for preparing in-situ synthesized nano TiC particle reinforced gradient composite coating according to claim 3, wherein the method comprises the following steps: in the step S1, the parent-phase metal powder is one of nickel-based alloy, cobalt-based alloy, iron-based alloy, and copper-based alloy powder.
7. The method for preparing in-situ synthesized nano TiC particle reinforced gradient composite coating according to claim 3, wherein the method comprises the following steps: in step S2, the method for preprocessing the substrate includes: and sequentially carrying out sand paper polishing, oil removal and drying treatment on the surface of the matrix.
8. The method for preparing in-situ synthesized nano TiC particle reinforced gradient composite coating according to claim 3, wherein the method comprises the following steps: in the step S2, the thickness of the pre-pressed mixed powder coating is 0.2-2 mm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113337815A (en) * | 2021-06-24 | 2021-09-03 | 西安文理学院 | Method for preparing double-scale iron-based composite gradient coating based on high-speed laser cladding method |
| CN117418143A (en) * | 2023-12-19 | 2024-01-19 | 汕头大学 | Ceramic reinforced metal matrix composite gradient coating and preparation method and application thereof |
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