CN114875355A - Preparation process of composite protective coating on surface of mold - Google Patents
Preparation process of composite protective coating on surface of mold Download PDFInfo
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- CN114875355A CN114875355A CN202210417962.1A CN202210417962A CN114875355A CN 114875355 A CN114875355 A CN 114875355A CN 202210417962 A CN202210417962 A CN 202210417962A CN 114875355 A CN114875355 A CN 114875355A
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
- C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
- C23C10/22—Metal melt containing the element to be diffused
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
Abstract
The invention relates to the technical field of metal surface strengthening modification, in particular to a preparation process of a composite protective coating on the surface of a die; the method comprises the steps of cleaning and drying the die, then embedding the cleaned die into the mixed molten liquid for heat preservation and permeation treatment, wherein the obtained lanthanum-containing organic matter can effectively improve the permeability and permeation speed of tungsten powder; the sodium borate, the sodium chloride, the potassium chloride and the yttrium oxide cooperate with each other, so that the temperature required by tungsten infiltration can be effectively reduced, and the infiltration efficiency and the infiltration quality of metal tungsten can be effectively improved; then the processed mould is placed in an atmosphere furnace to remove impurities and purify the mould, and then the mould is subjected to infiltration treatment to form a composite coating with excellent wear resistance and oxidation resistance on the surface of the mould; and finally, depositing a tantalum coating on the die, so that the hardness and the toughness of the die are improved, the cracking probability of the die is reduced, the fatigue resistance of the die is improved, and the quality of the die is improved.
Description
Technical Field
The invention relates to the technical field of metal surface strengthening modification, in particular to a preparation process of a composite protective coating on the surface of a mold.
Background
The die is basic technological equipment in the manufacturing industry, products produced by the die are high in precision, high in efficiency, good in consistency and low in energy consumption, and the die is widely applied to various fields of the manufacturing industry, such as automobiles, energy sources, machinery, aerospace, national defense industry and the like. When the mold without any treatment is applied, the mold can be cracked and failed quickly, so that the surface treatment of the mold is basically carried out, and the surface treatment mainly comprises three main types: firstly, the surface of the mould is infiltrated to optimize the performance; secondly, the improvement is carried out by high-energy beam surface treatment; and thirdly, surface coating. The carburized layer is typically subjected to ion nitriding, carbonitriding and the like at present, so that the toughness, strength and wear resistance of the surface of the die are improved.
However, nitriding treatment of the die can generate a catalytic phase, so that the die can crack and the like while the hardness and the strength of the die are improved, and the service life of the die is shortened. And the hardness and toughness of the nitrided die are relatively poor, and further improvement is needed.
Disclosure of Invention
Aiming at the technical problems in the background art, the invention provides a preparation process of a composite protective coating on the surface of a mold, and the treated mold has excellent wear resistance and oxidation resistance; the hardness and the toughness of the die are also improved, the probability of cracking of the die is reduced, the fatigue resistance of the die is improved, and the quality of the die is improved.
Technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation process of a composite protective coating on the surface of a mold comprises the following steps:
step one, preparing an internal coating on the surface of a mold;
I. selecting a mold made of H13 (4 Cr5MoSiV 1), cleaning the surface of the mold with clean water, cleaning liquid and absolute ethyl alcohol in sequence, putting the mold into ultrasonic cleaning equipment for ultrasonic cleaning for 30-40 min, taking out the mold after cleaning is finished, and drying the mold with hot air;
II. Dehydrating the compound permeation promoter at the temperature of 450-600 ℃ for 70-100 min, and melting the compound permeation promoter at the temperature of 870-980 ℃; then adding a proper amount of tungsten-containing powder, a reducing agent and an activating agent into the compound permeation promoter; after uniform mixing, embedding a mould into the obtained mixed solution, carrying out heat preservation treatment for 3-6 h, taking out the mould after the tungsten infiltration process is finished, soaking the mould in a sodium hydroxide solution with the temperature of 50-60 ℃ and the concentration of 4-7% for 20-40 min, cleaning the surface of the mould with clean water, and drying the mould;
III, placing the dried mould in an atmosphere furnace, heating the furnace to 900-1300 ℃ at the speed of 8-12 ℃/min in the ammonia gas atmosphere with the flow rate of 100-450 mL/min, and carrying out heat preservation treatment for 10-25 h at the temperature; after the furnace temperature is cooled to room temperature, taking out the mold, cleaning the mold by ultrasonic waves for 5-10 min, and then drying the mold;
IV, embedding the mould treated in the step III into a modifier, then transferring one of the moulds into a heating furnace, heating the furnace to 800-1400 ℃ at a heating speed of 10-15 ℃/min under the protection of nitrogen atmosphere, and carrying out heat preservation treatment for 8-24 h at the temperature; after the heat preservation treatment is finished, naturally cooling the furnace temperature to room temperature; then taking out the die, sequentially cleaning the die by using deionized water and absolute ethyl alcohol, and drying the die by using hot air;
step two, preparing an external coating on the surface of the die;
placing the mould processed in the step one in a vacuum chamber, and introducing a proper amount of argon into the vacuum chamber to keep the pressure in the chamber within the range of 0.2-0.6 Pa; then, a power supply is started, a high-purity tantalum target with the purity higher than 99.96% is selected as a target material, and the tantalum coating deposition is carried out on the die; after the deposition is finished, the pulse bias power supply and the arc source are closed, argon gas input is stopped, the high vacuum valve is closed, the air release valve is started after the temperature of the mold is naturally cooled to be below 80 ℃, the vacuum chamber is opened, the mold is taken out, and then the mold is processed.
Furthermore, the compound permeation promoter in the step II is prepared by compounding 75-90 parts by weight of sodium borate, 6-10 parts by weight of sodium chloride, 4-8 parts by weight of potassium chloride, 5-8 parts by weight of yttrium oxide and 8-15 parts by weight of the permeation promoter.
Furthermore, the preparation method of the penetration enhancer comprises the following steps:
under the protection of inert gas, adding a proper amount of lanthanum chloride into a proper amount of 1, 4-epoxybutane according to a solid-liquid ratio of 1.0-1.3 mol/L, adding organic sodium salt with the molar weight 2.5-3.5 times that of the lanthanum chloride into the obtained mixture while stirring, and stirring and reacting for 25-30 h at room temperature; and after the reaction is finished, sequentially carrying out centrifugal separation and concentration treatment on the obtained product components to obtain a coarse product of the permeation enhancer, then respectively cleaning the coarse product of the permeation enhancer for 2-3 times by using ethoxyethane and n-hexane, and then carrying out vacuum concentration treatment to obtain a finished product of the permeation enhancer.
Further, the preparation method of the organic sodium salt comprises the following steps:
i. adding a proper amount of cyclopentadiene and 1, 4-epoxybutane into a reaction device according to the volume ratio of 1: 2-4, and then adding metal sodium with the same molar quantity as the cyclopentadiene into the reaction device; under the ice-water bath state, adding bromocyclopentane with the molar weight equal to that of the sodium metal into the reaction equipment while stirring, and reacting for 50-70 min under the ice-water bath state by stirring; after the reaction is finished, centrifugally separating the biological components, distilling the obtained filtrate at normal pressure to recover 1, 4-epoxybutane, then distilling under reduced pressure at the temperature of 63-66 ℃ under the condition of 1.0-1.4 kPa, and collecting the obtained distillate;
ii. And (e) mixing the fraction obtained in the step (i) with 1, 4-epoxybutane according to a volume ratio of 1: 4-6, adding 6-10% by mass of metal sodium into the mixture under the atmosphere of dry nitrogen, and reacting for 20-30 hours at the temperature of 20-30 ℃, wherein the finally obtained solid matter is the finished product of the organic sodium salt.
Furthermore, the tungsten powder in the step II is tungsten oxide, tungsten powder or ferrotungsten powder, and the dosage of the tungsten powder is 8-16% of the compound permeation promoter.
Furthermore, the reducing agent in the step II is any one of aluminum powder, silicon powder and titanium powder, and the dosage of the reducing agent is 5-9% of the compound permeation promoter.
Furthermore, the activating agent in the step II is any one of sodium fluoride and potassium fluoride, and the dosage of the activating agent is 3-6% of the compound permeation-aid agent.
Further, the modifier used in the step IV is prepared by the following method: mixing 20-55 parts by weight of silicon powder, 3-7 parts by weight of potassium fluoride and 45-90 parts by weight of aluminum oxide, ball-milling until the particle size of the mixed raw material is 1-3 mu m, and drying in a vacuum environment to obtain a finished modifier.
Furthermore, in the deposition process of the tantalum coating, the current intensity of an arc source is 180-250A, the pulse negative bias is 250-360V, the duty ratio is 75-90%, and the deposition time is 30-60 min.
Advantageous effects
Compared with the known public technology, the technical scheme provided by the invention has the following beneficial effects:
1. the invention firstly cleans and dries the mould, then embeds the cleaned mould into the mixed solution composed of the compound permeation-aid agent, the tungsten powder, the reducing agent and the activating agent to carry out the heat preservation and permeation treatment. In the method, lanthanum chloride and organic sodium salt are used as raw materials and are subjected to chemical reaction in 1, 4-epoxybutane to finally prepare the lanthanum-containing organic matter. The obtained lanthanum-containing organic matter can effectively improve the permeability and the permeation speed of the tungsten powder. The sodium borate, the sodium chloride, the potassium chloride and the yttrium oxide cooperate with each other, so that the temperature required by tungsten infiltration can be effectively reduced, and the infiltration efficiency and the infiltration quality of metal tungsten can be effectively improved. Then the processed mould is placed in an atmosphere furnace to remove impurities and purify the mould, then the purified mould is embedded into a modifier, and silicon powder, potassium fluoride and aluminum oxide in the modifier act on the surface of the mould under the high-temperature condition to form a composite coating with excellent wear resistance and oxidation resistance, so that the quality of the mould is effectively improved.
2. And placing the die containing the internal coating in a vacuum chamber, and performing tantalum coating deposition on the die by taking a high-purity tantalum target as a target material, so as to deposit a uniform, flat and compact tantalum coating on the outer surface of the die. The hardness and toughness of the die are effectively improved, the probability of cracking of the die is reduced, the service life of the die is prolonged, the number of times of grinding of the die is saved, and the production cost is saved. In addition, the fatigue resistance of the die can be effectively improved, and the quality of the die is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be further described with reference to the following examples.
Example 1
A preparation process of a composite protective coating on the surface of a mold comprises the following steps:
step one, preparing an internal coating on the surface of a mold;
I. selecting a mold made of H13 (4 Cr5MoSiV 1), cleaning the surface of the mold with clean water, cleaning liquid and absolute ethyl alcohol in sequence, putting the mold into ultrasonic cleaning equipment for ultrasonic cleaning for 30min, taking out the mold after cleaning is finished, and drying the mold with hot air;
II. Dehydrating the compound permeation promoter at 450 ℃ for 70min, and melting the compound permeation promoter at 870 ℃; then adding a proper amount of tungsten-containing powder, a reducing agent and an activating agent into the compound permeation promoter; after uniform mixing, embedding a mould into the obtained mixed molten liquid for heat preservation treatment for 3h, taking out the mould after the tungsten infiltration process is finished, soaking the mould in a sodium hydroxide solution with the temperature of 50 ℃ and the concentration of 4% for 20min, cleaning the surface of the mould with clean water, and drying the mould;
III, placing the dried mould in an atmosphere furnace, heating the furnace to 900 ℃ at the speed of 8 ℃/min under the ammonia gas atmosphere with the flow rate of 100mL/min, and carrying out heat preservation treatment for 10 hours at the temperature; after the furnace temperature is cooled to room temperature, taking out the mold, cleaning the mold for 5min by using ultrasonic waves, and then drying the mold;
IV, embedding the mould processed in the step III into a modifier, then transferring one of the moulds into a heating furnace, heating the furnace to 800 ℃ at a heating speed of 10 ℃/min under the protection of nitrogen atmosphere, and carrying out heat preservation treatment for 8 hours at the temperature; after the heat preservation treatment is finished, naturally cooling the furnace temperature to room temperature; then taking out the die, sequentially cleaning the die by using deionized water and absolute ethyl alcohol, and drying the die by using hot air;
step two, preparing an external coating on the surface of the die;
placing the mould processed in the step one in a vacuum chamber, and introducing a proper amount of argon into the vacuum chamber to keep the pressure in the chamber within the range of 0.2 Pa; then, a power supply is started, a high-purity tantalum target with the purity higher than 99.96% is selected as a target material, and the tantalum coating deposition is carried out on the die; after the deposition is finished, the pulse bias power supply and the arc source are closed, argon gas input is stopped, the high vacuum valve is closed, the air release valve is started when the temperature of the mold is naturally cooled to be below 80 ℃, the vacuum chamber is opened, and the mold is taken out, so that the treatment of the mold is finished.
And step II, compounding the compound permeation enhancer by 75 parts of sodium borate, 6 parts of sodium chloride, 4 parts of potassium chloride, 5 parts of yttrium oxide and 8 parts of the permeation enhancer in parts by weight.
The preparation method of the penetration enhancer comprises the following steps: under the protection of inert gas, adding a proper amount of lanthanum chloride into a proper amount of 1, 4-epoxybutane according to a solid-liquid ratio of 1.0mol/L, adding organic sodium salt with the molar weight 2.5 times that of the lanthanum chloride into the obtained mixture while stirring, and stirring and reacting for 25 hours at room temperature; after the reaction is finished, the obtained product components are sequentially subjected to centrifugal separation and concentration treatment to obtain a permeation enhancer crude product, then the permeation enhancer crude product is respectively cleaned for 2 times by using ethoxyethane and n-hexane, and then the permeation enhancer crude product is subjected to vacuum concentration treatment to obtain a permeation enhancer finished product.
The preparation method of the organic sodium salt comprises the following steps:
i. adding a proper amount of cyclopentadiene and 1, 4-epoxybutane into a reaction device according to the volume ratio of 1: 2, and then adding metal sodium with the same molar quantity as the cyclopentadiene into the reaction device; under the ice-water bath state, adding bromocyclopentane with the molar weight equal to that of the sodium metal into the reaction equipment while stirring, and stirring and reacting for 50min under the ice-water bath state; after the reaction is finished, centrifugally separating the biological components, distilling the obtained filtrate at normal pressure to recover 1, 4-epoxybutane, then distilling under reduced pressure at the conditions of 1.0kPa and 63 ℃ and collecting the obtained distillate;
ii. And (3) mixing the fraction obtained in the step (i) with 1, 4-epoxybutane according to the volume ratio of 1: 4, adding metal sodium with the mass of 1, 4-epoxybutane being 6% in the atmosphere of dry nitrogen, and reacting for 20 hours at the temperature of 20 ℃, wherein the finally obtained solid matter is the finished product of the organic sodium salt.
And (3) selecting tungsten oxide powder as the tungsten powder in the step (II), wherein the dosage of the tungsten oxide powder is 8% of the compound permeation promoter.
And (3) selecting aluminum powder as a reducing agent in the step (II), wherein the dosage of the aluminum powder is 5% of that of the compound permeation promoter.
And (3) selecting sodium fluoride as an activating agent in the step (II), wherein the dosage of the sodium fluoride is 3% of that of the compound permeation promoter.
The preparation method of the modifier used in the step IV comprises the following steps: mixing 20 parts by weight of silicon powder, 3 parts by weight of potassium fluoride and 45 parts by weight of aluminum oxide, ball-milling until the particle size of the mixed raw material is 1 mu m, and then drying under a vacuum environment to obtain a finished modifier.
In the deposition process of the tantalum coating, the current intensity of an arc source is 180A, the pulse negative bias is 250V, the duty ratio is 75%, and the deposition time is 30 min.
Example 2
This example is different from example 1 in that: the specific proportion of each component in the compound penetration enhancer is different, and specifically comprises the following components: 75-90 parts of sodium borate, 6-10 parts of sodium chloride, 4-8 parts of potassium chloride, 5-8 parts of yttrium oxide and 8-15 parts of a permeation promoter.
Example 3
This example is different from example 1 in that: the specific proportion of each component in the compound penetration enhancer is different, and specifically comprises the following components: 75-90 parts of sodium borate, 6-10 parts of sodium chloride, 4-8 parts of potassium chloride, 5-8 parts of yttrium oxide and 8-15 parts of a permeation promoter.
Comparative example 1: nitriding the die by only adopting a traditional process (the nitriding process adopts a patent document with the patent application number of CN 201611231273.2);
comparative example 2: the difference from the embodiment 1 is that: tungsten infiltration treatment is not carried out on the die;
comparative example 3: the difference from the embodiment 1 is that: the mould is not embedded into the modifier for infiltration treatment;
comparative example 4: the difference from the embodiment 1 is that: the surface of the die was not subjected to tantalum coating deposition;
comparative example 5: the difference from the embodiment 1 is that: no permeation promoter is used in the tungsten infiltration process;
performance testing
The mold products provided in examples 1 to 3 and comparative examples 1 to 5 of the present invention were respectively referred to as experimental examples 1 to 3 and comparative examples 1 to 5, and the following performance tests were performed on each group of mold products, and the obtained data were recorded in tables 1 and 2:
table 1:
table 2:
note: 1. and (3) testing the wear resistance: testing the wear resistance of the outer protection layer of the die product by adopting an MG2000 high-temperature friction wear testing machine; wherein the temperature of the test environment is 25 ℃ and 200 ℃, the load is 20N, the speed is 0.4m/s, and the sliding distance is 300 m.
2. The fatigue test conditions for each mold product sample were: the stress ratio R is 0.2, the span L is 1.0m, the frequency f is 317 times/min, and the test load Pmin/Pmax is 94kN/470 kN.
By comparing and analyzing the relevant data in the tables 1 and 2, the processed die of the invention has excellent wear resistance and oxidation resistance; the hardness and the toughness of the die are also improved, the probability of cracking of the die is reduced, the fatigue resistance of the die is improved, and the quality of the die is improved. Therefore, the mold surface treatment process provided by the invention has wider market prospect and is more suitable for popularization.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (9)
1. A preparation process of a composite protective coating on the surface of a mold is characterized by comprising the following steps:
step one, preparing an internal coating on the surface of a mold;
I. selecting a mold made of H13 (4 Cr5MoSiV 1), cleaning the surface of the mold with clean water, cleaning liquid and absolute ethyl alcohol in sequence, putting the mold into ultrasonic cleaning equipment for ultrasonic cleaning for 30-40 min, taking out the mold after cleaning is finished, and drying the mold with hot air;
II. Dehydrating the compound permeation promoter at the temperature of 450-600 ℃ for 70-100 min, and melting the compound permeation promoter at the temperature of 870-980 ℃; then adding a proper amount of tungsten-containing powder, a reducing agent and an activating agent into the compound permeation promoter; after uniform mixing, embedding a mould into the obtained mixed solution, carrying out heat preservation treatment for 3-6 h, taking out the mould after the tungsten infiltration process is finished, soaking the mould in a sodium hydroxide solution with the temperature of 50-60 ℃ and the concentration of 4-7% for 20-40 min, cleaning the surface of the mould with clean water, and drying the mould;
III, placing the dried mould in an atmosphere furnace, heating the furnace to 900-1300 ℃ at the speed of 8-12 ℃/min in the ammonia gas atmosphere with the flow rate of 100-450 mL/min, and carrying out heat preservation treatment for 10-25 h at the temperature; after the furnace temperature is cooled to room temperature, taking out the mold, cleaning the mold by ultrasonic waves for 5-10 min, and then drying the mold;
IV, embedding the mould treated in the step III into a modifier, then transferring one of the moulds into a heating furnace, heating the furnace to 800-1400 ℃ at a heating speed of 10-15 ℃/min under the protection of nitrogen atmosphere, and carrying out heat preservation treatment for 8-24 h at the temperature; after the heat preservation treatment is finished, naturally cooling the furnace temperature to room temperature; then taking out the die, sequentially cleaning the die by using deionized water and absolute ethyl alcohol, and drying the die by using hot air;
step two, preparing an external coating on the surface of the die;
placing the mould processed in the step one in a vacuum chamber, and introducing a proper amount of argon into the vacuum chamber to keep the pressure in the chamber within the range of 0.2-0.6 Pa; then, a power supply is started, a high-purity tantalum target with the purity higher than 99.96% is selected as a target material, and the tantalum coating deposition is carried out on the die; after the deposition is finished, the pulse bias power supply and the arc source are closed, argon gas input is stopped, the high vacuum valve is closed, the air release valve is started after the temperature of the mold is naturally cooled to be below 80 ℃, the vacuum chamber is opened, the mold is taken out, and then the mold is processed.
2. The preparation process of the composite protective coating on the surface of the mold according to claim 1, characterized in that: and the compound permeation promoter in the step II is prepared by compounding 75-90 parts by weight of sodium borate, 6-10 parts by weight of sodium chloride, 4-8 parts by weight of potassium chloride, 5-8 parts by weight of yttrium oxide and 8-15 parts by weight of the permeation promoter.
3. The preparation process of the composite protective coating on the surface of the mold according to claim 2, wherein the permeation promoter is prepared by the following steps:
under the protection of inert gas, adding a proper amount of lanthanum chloride into a proper amount of 1, 4-epoxybutane according to a solid-liquid ratio of 1.0-1.3 mol/L, adding organic sodium salt with the molar weight 2.5-3.5 times that of the lanthanum chloride into the obtained mixture while stirring, and stirring and reacting for 25-30 h at room temperature; and after the reaction is finished, sequentially carrying out centrifugal separation and concentration treatment on the obtained product components to obtain a coarse product of the permeation enhancer, then respectively cleaning the coarse product of the permeation enhancer for 2-3 times by using ethoxyethane and n-hexane, and then carrying out vacuum concentration treatment to obtain a finished product of the permeation enhancer.
4. The process for preparing the composite protective coating on the surface of the mold according to claim 3, wherein the preparation method of the organic sodium salt comprises the following steps:
i. adding a proper amount of cyclopentadiene and 1, 4-epoxybutane into a reaction device according to the volume ratio of 1: 2-4, and then adding metal sodium with the same molar quantity as the cyclopentadiene into the reaction device; under the ice-water bath state, adding bromocyclopentane with the molar weight equal to that of the sodium metal into the reaction equipment while stirring, and reacting for 50-70 min under the ice-water bath state by stirring; after the reaction is finished, centrifugally separating the biological components, distilling the obtained filtrate at normal pressure to recover 1, 4-epoxybutane, then distilling under reduced pressure at the temperature of 63-66 ℃ under the condition of 1.0-1.4 kPa, and collecting the obtained distillate;
ii. And (e) mixing the fraction obtained in the step (i) with 1, 4-epoxybutane according to a volume ratio of 1: 4-6, adding 6-10% by mass of metal sodium into the mixture under the atmosphere of dry nitrogen, and reacting for 20-30 hours at the temperature of 20-30 ℃, wherein the finally obtained solid matter is the finished product of the organic sodium salt.
5. The preparation process of the composite protective coating on the surface of the mold according to claim 1, characterized in that: and the tungsten powder in the step II is tungsten oxide, tungsten powder or ferrotungsten powder, and the dosage of the tungsten powder is 8-16% of the compound permeation promoter.
6. The preparation process of the composite protective coating on the surface of the mold according to claim 1, characterized in that: and the reducing agent in the step II is any one of aluminum powder, silicon powder and titanium powder, and the dosage of the reducing agent is 5-9% of the compound permeation promoter.
7. The preparation process of the composite protective coating on the surface of the mold according to claim 1, characterized in that: and the activating agent in the step II is any one of sodium fluoride and potassium fluoride, and the dosage of the activating agent is 3-6% of the compound permeation promoter.
8. The process for preparing the composite protective coating on the surface of the mold according to claim 1, wherein the modifier used in the step IV is prepared by a method comprising the following steps: mixing 20-55 parts by weight of silicon powder, 3-7 parts by weight of potassium fluoride and 45-90 parts by weight of aluminum oxide, ball-milling until the particle size of the mixed raw material is 1-3 mu m, and drying in a vacuum environment to obtain a finished modifier.
9. The preparation process of the composite protective coating on the surface of the mold according to claim 1, characterized in that: in the deposition process of the tantalum coating, the current intensity of an arc source is 180-250A, the pulse negative bias is 250-360V, the duty ratio is 75-90%, and the deposition time is 30-60 min.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3784412A (en) * | 1971-02-22 | 1974-01-08 | Siemens Ag | Method for the manufacture of powdered tungsten containing electrode material |
| US4855188A (en) * | 1988-02-08 | 1989-08-08 | Air Products And Chemicals, Inc. | Highly erosive and abrasive wear resistant composite coating system |
| JPH048409A (en) * | 1990-04-26 | 1992-01-13 | Nippon Steel Corp | Coated cemented carbide tool excellent in shock resistance |
| US20030106270A1 (en) * | 2000-06-30 | 2003-06-12 | Baldoni J. Gary | Article of superabrasive coated with metal |
| CN1817507A (en) * | 2006-03-14 | 2006-08-16 | 河南科技大学 | Cast exudation of investment casting mould |
| CN101597739A (en) * | 2009-06-30 | 2009-12-09 | 北京科技大学 | A kind of borax salt bath tungstenized coating on steel matrix surface preparation method |
| CN103469150A (en) * | 2013-08-23 | 2013-12-25 | 杨树桐 | Method for permeating diamond into iron steel material by taking nano-structured carbon as permeation-promoter |
| CN105714243A (en) * | 2016-04-28 | 2016-06-29 | 厦门理工学院 | Method for preparing tungsten functional coating on tantalum surface at low temperature |
| CN108179377A (en) * | 2017-12-27 | 2018-06-19 | 厦门虹鹭钨钼工业有限公司 | A kind of complex gradient coating and preparation method thereof |
| CN109468581A (en) * | 2018-11-26 | 2019-03-15 | 广东省新材料研究所 | A kind of solid powder multiple elements design penetration enhancer and compound cementation process |
| CN112593180A (en) * | 2020-11-26 | 2021-04-02 | 苏州统明机械有限公司 | Manufacturing method of wear-resistant alloy coating of automobile brake disc |
| CN113025951A (en) * | 2021-03-02 | 2021-06-25 | 南昌大学 | Molybdenum alloy containing antioxidant composite coating and preparation method thereof |
| CN113699491A (en) * | 2021-08-31 | 2021-11-26 | 江西省科学院应用物理研究所 | Method for preparing tungsten-infiltrated composite coating |
-
2022
- 2022-04-20 CN CN202210417962.1A patent/CN114875355B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3784412A (en) * | 1971-02-22 | 1974-01-08 | Siemens Ag | Method for the manufacture of powdered tungsten containing electrode material |
| US4855188A (en) * | 1988-02-08 | 1989-08-08 | Air Products And Chemicals, Inc. | Highly erosive and abrasive wear resistant composite coating system |
| JPH048409A (en) * | 1990-04-26 | 1992-01-13 | Nippon Steel Corp | Coated cemented carbide tool excellent in shock resistance |
| US20030106270A1 (en) * | 2000-06-30 | 2003-06-12 | Baldoni J. Gary | Article of superabrasive coated with metal |
| CN1817507A (en) * | 2006-03-14 | 2006-08-16 | 河南科技大学 | Cast exudation of investment casting mould |
| CN101597739A (en) * | 2009-06-30 | 2009-12-09 | 北京科技大学 | A kind of borax salt bath tungstenized coating on steel matrix surface preparation method |
| CN103469150A (en) * | 2013-08-23 | 2013-12-25 | 杨树桐 | Method for permeating diamond into iron steel material by taking nano-structured carbon as permeation-promoter |
| CN105714243A (en) * | 2016-04-28 | 2016-06-29 | 厦门理工学院 | Method for preparing tungsten functional coating on tantalum surface at low temperature |
| CN108179377A (en) * | 2017-12-27 | 2018-06-19 | 厦门虹鹭钨钼工业有限公司 | A kind of complex gradient coating and preparation method thereof |
| CN109468581A (en) * | 2018-11-26 | 2019-03-15 | 广东省新材料研究所 | A kind of solid powder multiple elements design penetration enhancer and compound cementation process |
| CN112593180A (en) * | 2020-11-26 | 2021-04-02 | 苏州统明机械有限公司 | Manufacturing method of wear-resistant alloy coating of automobile brake disc |
| CN113025951A (en) * | 2021-03-02 | 2021-06-25 | 南昌大学 | Molybdenum alloy containing antioxidant composite coating and preparation method thereof |
| CN113699491A (en) * | 2021-08-31 | 2021-11-26 | 江西省科学院应用物理研究所 | Method for preparing tungsten-infiltrated composite coating |
Non-Patent Citations (2)
| Title |
|---|
| PIZANA, C等: "The role of dynamic recrystallization in [001] single-crystal W and W-Ta alloy ballistic rod penetration into steel targets", 《JOURNAL OF MATERIALS SCIENCE》, vol. 40, no. 18, pages 4849 - 4857, XP019210718, DOI: 10.1007/s10853-005-2021-9 * |
| 郭长庆等: "用钨铁粉和碳粉对45钢进行表面合金化", 《金属热处理》, vol. 36, no. 6, pages 33 - 36 * |
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