CN115595580B - Material for forming tantalum/tantalum-iron gradient layer on carbon steel surface and preparation method thereof - Google Patents

Material for forming tantalum/tantalum-iron gradient layer on carbon steel surface and preparation method thereof Download PDF

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CN115595580B
CN115595580B CN202211316953.XA CN202211316953A CN115595580B CN 115595580 B CN115595580 B CN 115595580B CN 202211316953 A CN202211316953 A CN 202211316953A CN 115595580 B CN115595580 B CN 115595580B
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tantalum
carbon steel
voltage
substrate
temperature
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CN115595580A (en
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吴红艳
倪瑞安
江凡
仇延钊
于露
杨丹宁
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Nanjing University of Information Science and Technology
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Nanjing University of Information Science and Technology
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • 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
    • C23C10/06—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases
    • C23C10/08—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases only one element being 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
    • 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
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • C23C14/34—Sputtering
    • 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
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/542—Controlling the film thickness or evaporation rate
    • 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
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer

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Abstract

The invention discloses a material for forming a tantalum/tantalum-iron gradient layer on the surface of carbon steel and a preparation method thereof, wherein the material adopts a double glow plasma surface metallurgy heat treatment method and comprises the following steps: (1) Cleaning the surfaces of the target material and the metal substrate, removing air and introducing protective gas; (2) pre-bombardment treatment; (3) gradient heating, constant temperature diffusion and rapid deposition; (4) annealing and cooling. The method has the advantages of simple and easy process, good controllability of the thickness of the tantalum layer, low cost and no pollution. The self-diffusion enhances the combination of a surface coating and a matrix, and the tantalum/tantalum-iron gradient layer obtained on the surface of the carbon steel can meet the performance use requirements under the general condition without subsequent high-temperature diffusion annealing. Has great significance for replacing high-cost tantalum materials with low-cost materials and reducing energy consumption.

Description

Material for forming tantalum/tantalum-iron gradient layer on carbon steel surface and preparation method thereof
Technical Field
The invention relates to a material for forming a coating on the surface of steel and a preparation method thereof, in particular to a material for forming a tantalum/tantalum-iron gradient layer on the surface of carbon steel and a preparation method thereof.
Background
The ordinary carbon steel has the advantages of simple smelting process, low cost, good pressure processing performance, good cutting processing performance and good comprehensive mechanical property, is the earliest basic material used in modern industry and has the largest dosage, and is widely applied to building, bridge, railway, vehicle, ship and various mechanical manufacturing industries, and simultaneously is also applied to almost aspects of petrochemical industry, aerospace, food processing, biological medicine manufacturing and the like. However, fatigue damage or corrosive wear and the like are still extremely easy to occur in a complex and harsh working environment, and the surface modification is a good choice.
Tantalum has a series of excellent properties such as high melting point, low vapor pressure, good cold processing performance, high chemical stability, strong liquid metal corrosion resistance, large dielectric constant of a surface oxide film and the like. However, due to the high cost of tantalum wire, plate, ingot, etc., a large economic burden is often brought about, and to avoid these problems, chemical vapor deposition diffusion (CVD), physical sputter deposition diffusion (PVD), etc. techniques are often used for the surface treatment of plain carbon steel.
The CVD deposition diffusion method and the rapid condensation method are one of the current methods for modifying the surface of plain carbon steel, which has industrial production, but still have some problems: if the edge is easy to crack, even broken, the yield is low, the pollution in the reaction process is large, the surface of the sample is not smooth, the roughness is large, and the like. In the PVD preparation process, methods such as magnetron sputtering, vacuum evaporation sputtering, multi-arc ion plating and the like are adopted, and tantalum layers can be infiltrated on the surface of the common carbon steel. Although the film obtained by the PVD process is uniform and compact, the preparation efficiency is low, the treatment area is small, the cost is high, the preparation conditions are not easy to control, and particularly the surface film is thin.
The preparation process for obtaining the tantalum layer is to directly heat and sputter and deposit on the surface of the substrate, so that the tantalum element is directly attached to the surface of the substrate. However, from the current technology, there is a great progress space in terms of preparation efficiency, cost, controllability, binding force between the tantalum layer and the substrate, thickness of the tantalum layer, and the like. And the most critical is that the tantalum layer prepared by the technology is too thin to replace pure tantalum consumables in various fields, and the technology is improved in order to obtain low-cost materials to replace high-cost tantalum materials and reduce energy consumption.
Disclosure of Invention
The invention aims to: the invention aims to provide a material for forming a tantalum/tantalum-iron gradient layer on the surface of carbon steel with good bonding force between a matrix and the surface and controllable composition or thickness;
a second object of the present invention is to provide a method for preparing the material for forming a tantalum/tantalum-iron gradient layer on the surface of carbon steel.
The technical scheme is as follows: the material for forming the tantalum/tantalum-iron gradient layer on the surface of the carbon steel comprises a carbon steel substrate, a tantalum layer, a tantalum-iron diffusion transition layer with the thickness of 1-10 mu m at the interface of the carbon steel substrate and a tantalum deposition layer with the thickness of 0-100 mu m outside the tantalum-iron diffusion transition layer.
Wherein, tantalum and iron respectively account for the mass percent of the transition layer in the tantalum-iron diffusion transition layer: tantalum: 100-0wt% of iron: 0-40wt%.
The preparation method of the material for forming the tantalum/tantalum-iron gradient layer on the surface of the carbon steel comprises the following steps:
(1) Placing the tantalum target material, the carbon steel base material and the low-carbon steel workpiece with the surfaces cleaned in a furnace, and introducing vacuum inert gas for protection;
(2) Respectively applying voltage to the tantalum target material, the carbon steel base material and the low-carbon steel workpiece, and heating to perform pre-bombardment purification treatment;
(3) Carrying out gradient heating, constant temperature diffusion and rapid deposition treatment, and comprising the following steps:
(3.1) utilizing the double glow cross-linking discharge phenomenon to alternately change and adjust the voltage and current of the tantalum target material and the carbon steel base material, so that the temperature gradient of the carbon steel base material is increased to a preset temperature for activation;
(3.2) reducing the voltage of the carbon steel substrate, increasing the voltage of the tantalum target, properly increasing the temperature of the carbon steel substrate to a preset temperature, and uniformly diffusing the tantalum element on the surface of the substrate at constant temperature;
(3.3) reducing the voltage of the carbon steel substrate, properly increasing the voltage of the tantalum target, enabling the sputtering rate of the tantalum element to be larger than the reverse sputtering rate and rapidly depositing on the surface of the carbon steel substrate;
(4) In the cooling process, firstly, the voltage of the tantalum target material and the carbon steel substrate is alternately and slowly reduced until the temperature is reduced to a preset value, and then stress relief annealing and heat preservation are carried out; the tantalum target and carbon steel substrate voltages are then alternately slowly reduced again.
Wherein, the interval between the tantalum target material and the carbon steel base material is kept between 10mm and 50 mm. Too large distance, low plasma concentration of target elements, inability to form a high-thickness surface layer on the metal substrate and insufficient diffusion depth; too small a distance, the target element will generate strong reverse sputtering phenomenon on the surface of the metal substrate, and the target element cannot diffuse into the metal substrate.
Wherein, the step (1) comprises the following steps: cleaning the surface of a target material and a metal substrate: cleaning and removing greasy dirt, dust, oxide layer and impurities on the surface of a pure tantalum target, a carbon steel matrix or a low carbon steel workpiece, and placing the cleaned pure tantalum target, carbon steel matrix or low carbon steel workpiece in a furnace or a protective cover in the furnace; wherein, pure tantalum target material, carbon steel matrix or low carbon steel workpiece are respectively cleaned by acetone and absolute ethyl alcohol by ultrasonic.
Exhausting air and introducing protective gas: after the air in the furnace body is exhausted, inert gas which does not react with the pure tantalum target material, the carbon steel matrix or the low carbon steel workpiece is introduced into the furnace until the air pressure in the furnace reaches a set value.
The step (2) is a pre-bombardment treatment stage, wherein voltages are respectively applied to a pure tantalum target material, a carbon steel matrix or a low-carbon steel workpiece, adsorbates and oxide layers on the surfaces are cleaned, and the carbon steel matrix is heated to a set temperature; in the step (2), the substrate voltage in the carbon steel substrate surface activation stage is 200V-500V, the gas pressure in the furnace is 10Pa-25Pa, the sputtering and purifying voltage of the tantalum target is 200V-500V, the gas pressure in the furnace is 10Pa-25Pa, and the pre-bombardment treatment time is 10min-30min.
Wherein, the step (3) is a stage of gradient heating, constant temperature diffusion and rapid deposition; in the step (3), the voltage of the carbon steel substrate workpiece and the voltage of the pure tantalum target are increased, so that the surface of the carbon steel substrate is heated in a gradient way and fully activated (namely, the surface of the carbon steel substrate is heated in a gradient way and activated); then reducing the voltage of the base material, increasing the voltage of a pure tantalum target material to generate tantalum element plasma in the furnace, and continuously preserving the heat of the base material for more than 0.5h to enable the tantalum element to diffuse into the metal base material (namely, the constant-temperature diffusion stage of the target material element) to form a surface tantalum-penetrating diffusion layer; then, the voltage of the carbon steel matrix or the low-carbon steel workpiece is reduced again, the voltage of the pure tantalum target material is properly increased, the reverse sputtering rate is reduced, and the thickness of the original film layer is further increased (namely, the rapid deposition stage of the target material element);
Further, the air pressure in the furnace in the step (3) is larger than the air pressure in the furnace in the step (2); further, the air pressure in the furnace in the carbon steel substrate surface pre-bombardment stage is 10Pa-25Pa; in the step (3), the air pressure in the furnace in the sputtering, activating, diffusing and heat preserving stages is 25Pa-40Pa.
In the step (3.1), the voltage of the carbon steel substrate is increased to 550V-700V, and the voltage of the tantalum target is unchanged, so that the temperature of the substrate reaches 700-750 ℃ and is kept for 30-40 min.
In the step (3.2), after the surface of the base material is activated, the voltage of the carbon steel base material is gradually reduced to 420V-450V, and meanwhile, the voltage of the tantalum target material is gradually increased to 800V-900V, so that the temperature of the carbon steel base material is increased to 750-800 ℃ and maintained for 50-60 min; so that the tantalum element can be well diffused on the surface of the substrate.
In the step (3.3), the terminal voltage of the carbon steel substrate is reduced to 390V-420V, the terminal voltage of the tantalum target is increased to 900V-1000V, the temperature of the carbon steel substrate is maintained at 650-1000 ℃ for 1-5h, and the reverse sputtering rate is reduced. Deposition is performed under preset conditions. Generating plasma of target elements in the furnace to obtain a sample after the target elements diffuse to the surface of the metal substrate; the heat preservation time at the preset temperature is generally more than 1h according to the thickness requirement of the tantalum layer on the surface.
Wherein, the step (4) is an annealing cooling stage; in the step (4), the voltage of the target material and the substrate is firstly and slowly reduced until the temperature is reduced to a preset value, and then the stress is removed, annealed and kept for a period of time, so that the stress concentration is eliminated. Then slowly reducing the target voltage and the substrate voltage until the power supply is turned off, then turning off the protective gas source, stopping vacuumizing, and taking out the product after cooling to room temperature.
In the step (4), the cathode voltage of the target material is firstly reduced by 10V-50V/min, the carbon steel substrate is reduced to 450-500 ℃ and is subjected to stress relief annealing for 30-45min, then the cathode voltage of the target material and the substrate is alternately reduced by 30V-60V/min until the power supply is turned off, then the protection air source is turned off, the vacuumizing is stopped, and the sample is taken out after being cooled to room temperature along with the furnace. Because the difference of the thermal expansion coefficients of the base material and the tantalum element is large, the temperature reduction speed is too high, so that the tantalum element segregation is not uniform and the internal stress crack is generated, and a seepage layer is cracked or falls off.
The principle of the invention: the invention provides an improvement of the heat treatment process on the basis of adopting the double glow plasma surface metallurgy technology to realize the modification treatment of the surface of the metal substrate, and simultaneously avoids the technical problems.
The double glow plasma surface metallurgical heat treatment process is to set vacuum container or independent electrode inside the vacuum cavity as anode and two cathodes: one is a high content target that provides the target element, and the other is a workpiece and a metal substrate. And a voltage-adjustable direct current power supply is respectively arranged between the two cathodes. After the protective gas is filled as the working gas, two direct current power supplies are started, and a double glow discharge phenomenon is formed around the two cathodes. And a high-voltage target cathode glow discharge for generating ion bombardment, and depositing the sputtered target elements on the surface of the substrate. And the other high-voltage workpiece is subjected to cathode glow discharge to heat the metal substrate, so that the target material element deposited on the surface diffuses into the substrate to form the metal material with high target material element.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable effects: (1) The double glow plasma surface metallurgical heat treatment process is utilized, so that the metal surface modification process is simple and easy to implement, the tantalum layer or thickness is good in controllability, the cost is low, no pollution is caused, the binding force between the substrate and the surface is good, and the method is suitable for large-scale industrialized production; (2) The surface tantalum-doped carbon steel with a tantalum layer or controllable thickness is prepared by controlling and adjusting cathode voltage, current, the distance between a target material and a base material and reaction time, and the obtained carbon steel can meet performance use requirements under general conditions without subsequent high-temperature diffusion annealing. Has great significance for replacing high-cost tantalum materials with low-cost materials and reducing energy consumption; (3) The tantalum-doped/tantalum-iron stainless steel material with controllable thickness is obtained through the change of parameters, and is flexibly adjusted according to the actual situation requirement, so that the actual use requirement is met.
Drawings
FIG. 1 is a cross-sectional profile of a sample prepared in example 1 of the present invention;
FIG. 2 shows the content distribution of iron, tantalum and iron elements in the depth direction of a sample prepared in example 1 of the present invention in the cross-sectional morphology;
FIG. 3 is a cross-sectional profile of a sample prepared in example 2 of the present invention;
Fig. 4 shows the content distribution of iron, tantalum, and iron elements in the depth direction in the cross-sectional morphology of the sample prepared in example 2 of the present invention.
Detailed Description
The present invention is described in further detail below.
Example 1
The method takes 316L stainless steel as a base material, has the thickness of 3mm, takes 99.99% pure Ta as a target material, and realizes the uniform diffusion of tantalum element in the 316L stainless steel by means of the actions of two cathodes on the pre-sputtering, heating, diffusion, deposition and the like of the base material and the target material respectively, wherein the technical process and the steps are as follows:
(1) And (3) putting 99.99% pure Ta which is wiped by absolute ethyl alcohol as a target material on a source electrode sample holder, placing a 316L stainless steel substrate which is ultrasonically cleaned by acetone and absolute ethyl alcohol on a workpiece cathode object table below, covering the periphery of a sample by a low-carbon steel plate heat preservation sleeve for heat preservation, and keeping the distance between the sample and the target material at 15mm.
(2) Starting a vacuum pumping device in the double glow plasma surface metallurgy technology, pumping the gas pressure to 5Pa by using a mechanical pump, further pumping the gas pressure of a furnace body to 6 multiplied by 10 -4 Pa by using a molecular pump, keeping the furnace in a full high vacuum state, filling argon into the furnace, pumping the gas again to the above-mentioned extreme vacuum degree, repeating for 3 times to discharge the air in the furnace, and keeping the temperature for 25 minutes.
(3) Closing the molecular pump, keeping the mechanical pump working, introducing argon gas to enable the air pressure in the furnace body to reach 20Pa, carrying out pre-bombardment treatment on the base material and the target, keeping the voltage of the base material at 400V at the moment, keeping the voltage of the target at 400V, and carrying out pre-bombardment cleaning on the sample and the target for 10 minutes to remove adsorbed substances on the surface.
(4) After pre-bombardment, adjusting the working pressure of argon to 40Pa, increasing the voltage of the base material to 650V, keeping the voltage of the target material unchanged, activating the surface of the base material after the temperature of the base material is increased to 750 ℃, and preheating and working for 30 minutes; then reducing the voltage of the base material to 450V, increasing the voltage of the target material to 850V, adjusting the working pressure of argon to 35Pa, keeping the temperature at 800 ℃, preserving the heat for 60 minutes, and carrying out diffusion homogenization treatment; then, the voltage of the base material is reduced to 400V again, the voltage of the target material is properly increased to 950V, the reverse sputtering rate is reduced, the thickness of the film layer is further increased, and the temperature is kept at 700 ℃ for 4 hours for deposition.
(5) Cooling: firstly, reducing the cathode voltage of a target material at 30V/min, maintaining double glow for 20min when the cathode voltage is reduced to be the same as the cathode voltage of a substrate at 400V, then properly reducing the voltage of two poles to 300-350V again to enable the temperature to be controlled at 500 ℃ for stress relief annealing for 30min, finally, alternately reducing the cathode voltage of the target material and the substrate at 50V/min until the power supply is closed, then pumping the vacuum furnace to the vacuum degree of 2X 10 -4 Pa, cooling to the room temperature, discharging and taking out.
The thickness of the surface film layer obtained by the process reaches 55 mu m, the surface is of a typical sheet structure, the surface film layer is compact and uniform, and a tantalum/tantalum-iron gradient layer which takes tantalum as a deposition layer and tantalum-iron is formed along the thickness direction as shown in fig. 1 and 2.
Example 2
The method takes 316L stainless steel as a base material, has the thickness of 3mm, takes 99.99% pure Ta as a target material, and realizes the uniform diffusion of tantalum element in the 316L stainless steel by means of the actions of two cathodes on the pre-sputtering, heating, diffusion, deposition and the like of the base material and the target material respectively, wherein the technical process and the steps are as follows:
(1) And (3) putting 99.99% pure Ta which is wiped by absolute ethyl alcohol as a target material on a source electrode sample holder, placing a 316L stainless steel substrate which is ultrasonically cleaned by acetone and absolute ethyl alcohol on a workpiece cathode object table below, covering the periphery of a sample by a low-carbon steel plate heat preservation sleeve for heat preservation, and keeping the distance between the sample and the target material at 30mm.
(2) Firstly, starting a vacuum pumping device in the double glow plasma surface metallurgical technology, pumping the gas pressure to 5Pa by using a mechanical pump, further pumping the gas pressure of a furnace body to 6X 10 -4 Pa by using a molecular pump, keeping the furnace in a full high vacuum state, filling argon into the furnace, pumping the furnace again to the above-mentioned extreme vacuum degree, repeating for 3 times to discharge the air in the furnace, and keeping the furnace for 10 minutes.
(3) Closing the molecular pump, keeping the mechanical pump working, introducing argon gas to enable the air pressure in the furnace body to reach 20Pa, carrying out pre-bombardment treatment on the base material and the target, keeping the voltage of the base material at 400V at the moment, keeping the voltage of the target at 400V, and carrying out pre-bombardment cleaning on the sample and the target for 30 minutes to remove adsorbed substances on the surface.
(4) After pre-bombardment, adjusting the working pressure of argon to 35Pa, increasing the voltage of a substrate to 600V, increasing the voltage of a target to 570V, activating the surface of the substrate after the temperature of the substrate is increased to 750 ℃, preheating, and working for 30 minutes; then reducing the voltage of the base material to 440V, increasing the voltage of the target material to 900V, adjusting the working pressure of argon to 36Pa, keeping the temperature at 800 ℃, preserving the heat for 1h, and carrying out diffusion homogenization treatment; then the voltage of the base material is reduced to 400V again, the voltage of the target material is kept at 900V, the reverse sputtering rate is reduced, the thickness of the film layer is further improved, and the deposition is carried out after 3h of heat preservation.
(5) And cooling, namely firstly reducing the cathode voltage of the target material at 30V/min, maintaining the double glow for 20min when the cathode voltage is reduced to be the same as the cathode voltage of the substrate at 400V, then properly reducing the voltage of two poles to 300-350V again to enable the temperature to be controlled at 500 ℃ for stress relief annealing for 30min, finally reducing the cathode voltage of the target material and the substrate at 50V/min alternately until the power supply is closed, then pumping the vacuum furnace to the vacuum degree of 2X 10 -4 Pa, cooling to the room temperature, and taking out from the furnace.
The thickness of the surface film layer obtained by the process reaches 35 mu m, the surface is of a typical sheet structure, the surface is compact and uniform, and a tantalum/tantalum-iron gradient alloying layer which takes tantalum as a deposition layer and a tantalum-iron diffusion layer is formed along the thickness direction as shown in fig. 3 and 4.

Claims (6)

1. A material for forming a tantalum/tantalum-iron gradient layer on the surface of carbon steel, which is characterized by comprising a carbon steel substrate, a tantalum layer, a tantalum-iron diffusion transition layer with the thickness of 1-10 mu m at the interface of the carbon steel substrate, and a tantalum deposition layer with the thickness of 0-100 mu m outside the tantalum-iron diffusion transition layer;
The preparation method of the material for forming the tantalum/tantalum-iron gradient layer on the surface of the carbon steel comprises the following steps:
(1) Placing the tantalum target material, the carbon steel base material and the low-carbon steel workpiece with the surfaces cleaned in a furnace, and introducing vacuum inert gas for protection;
(2) Respectively applying voltage to the tantalum target material, the carbon steel base material and the low-carbon steel workpiece, and heating to perform pre-bombardment purification treatment;
(3) Carrying out gradient heating, constant temperature diffusion and rapid deposition treatment, and comprising the following steps:
(3.1) utilizing the double glow cross-linking discharge phenomenon to alternately change and adjust the voltage and current of the tantalum target material and the carbon steel base material, so that the temperature gradient of the carbon steel base material is increased to a preset temperature for activation; firstly, increasing the voltage of a carbon steel substrate to 550-700V, keeping the voltage of a tantalum target constant, enabling the temperature of the substrate to reach 700-750 ℃ and keeping for 30-40 min;
(3.2) reducing the voltage of the carbon steel substrate, increasing the voltage of the tantalum target, properly increasing the temperature of the carbon steel substrate to a preset temperature, and uniformly diffusing the tantalum element on the surface of the substrate at constant temperature; after the surface of the base material is activated, the voltage of the carbon steel base material is gradually reduced to 420V-450V, and meanwhile, the voltage of the tantalum target material is gradually increased to 800V-900V, so that the temperature of the carbon steel base material is increased to 750-800 ℃ and maintained for 50-60 min;
(3.3) reducing the voltage of the carbon steel substrate, properly increasing the voltage of the tantalum target, enabling the sputtering rate of the tantalum element to be larger than the reverse sputtering rate and rapidly depositing on the surface of the carbon steel substrate; reducing the terminal voltage of the carbon steel substrate to 390V-420V, improving the terminal voltage of the tantalum target to 900V-1000V, keeping the temperature of the carbon steel substrate at 650-1000 ℃ for 1-5h, and reducing the reverse sputtering rate;
In the step (3), the air pressure in the furnace is 25Pa-40Pa;
(4) In the cooling process, firstly, the voltage of the tantalum target material and the carbon steel substrate is alternately and slowly reduced until the temperature is reduced to a preset value, and then stress relief annealing and heat preservation are carried out; the tantalum target and carbon steel substrate voltages are then alternately slowly reduced again.
2. The material for forming a tantalum/tantalum-iron gradient layer on the surface of carbon steel according to claim 1, wherein the tantalum and iron in the tantalum-iron diffusion transition layer respectively account for the mass percent of the transition layer: tantalum: 100-0wt% of iron: 0-40wt%.
3. A method of preparing a material for forming a tantalum/tantalum-iron gradient layer on a carbon steel surface as claimed in claim 1, comprising the steps of:
(1) Placing the tantalum target material, the carbon steel base material and the low-carbon steel workpiece with the surfaces cleaned in a furnace, and introducing vacuum inert gas for protection;
(2) Respectively applying voltage to the tantalum target material, the carbon steel base material and the low-carbon steel workpiece, and heating to perform pre-bombardment purification treatment;
(3) Carrying out gradient heating, constant temperature diffusion and rapid deposition treatment, and comprising the following steps:
(3.1) utilizing the double glow cross-linking discharge phenomenon to alternately change and adjust the voltage and current of the tantalum target material and the carbon steel base material, so that the temperature gradient of the carbon steel base material is increased to a preset temperature for activation; firstly, increasing the voltage of a carbon steel substrate to 550-700V, keeping the voltage of a tantalum target constant, enabling the temperature of the substrate to reach 700-750 ℃ and keeping for 30-40 min;
(3.2) reducing the voltage of the carbon steel substrate, increasing the voltage of the tantalum target, properly increasing the temperature of the carbon steel substrate to a preset temperature, and uniformly diffusing the tantalum element on the surface of the substrate at constant temperature; after the surface of the base material is activated, the voltage of the carbon steel base material is gradually reduced to 420V-450V, and meanwhile, the voltage of the tantalum target material is gradually increased to 800V-900V, so that the temperature of the carbon steel base material is increased to 750-800 ℃ and maintained for 50-60 min;
(3.3) reducing the voltage of the carbon steel substrate, properly increasing the voltage of the tantalum target, enabling the sputtering rate of the tantalum element to be larger than the reverse sputtering rate and rapidly depositing on the surface of the carbon steel substrate; reducing the terminal voltage of the carbon steel substrate to 390V-420V, improving the terminal voltage of the tantalum target to 900V-1000V, keeping the temperature of the carbon steel substrate at 650-1000 ℃ for 1-5h, and reducing the reverse sputtering rate;
In the step (3), the air pressure in the furnace is 25Pa-40Pa;
(4) In the cooling process, firstly, the voltage of the tantalum target material and the carbon steel substrate is alternately and slowly reduced until the temperature is reduced to a preset value, and then stress relief annealing and heat preservation are carried out; the tantalum target and carbon steel substrate voltages are then alternately slowly reduced again.
4. A method of producing a material for forming a tantalum/tantalum-iron gradient layer on a carbon steel surface according to claim 3, wherein the distance between said tantalum target and said carbon steel substrate is 10mm to 50mm.
5. The method for producing a material for forming a tantalum/tantalum-iron gradient layer on a carbon steel surface according to claim 3, wherein in the step (2), the substrate voltage in the carbon steel substrate surface activation stage is 200V-500V, the in-furnace gas pressure is10 Pa-25Pa, the tantalum target sputter-cleaning voltage is 200V-500V, the in-furnace gas pressure is10 Pa-25Pa, and the pre-bombardment treatment time is10 min-30min.
6. The method of claim 3, wherein in step (4), the cathode voltage of the target is reduced by 10V-50V/min, the carbon steel substrate is reduced to 450-500 ℃ and annealed for 30-45min, and then the cathode voltage of the target and the substrate are alternately reduced to power off by 30V-60V/min.
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