CN115449743A - Alloy surface modification layer and preparation method thereof - Google Patents
Alloy surface modification layer and preparation method thereof Download PDFInfo
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- 238000012986 modification Methods 0.000 title claims abstract description 61
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- 238000002360 preparation method Methods 0.000 title abstract description 14
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 80
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 238000005516 engineering process Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
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- 239000012466 permeate Substances 0.000 abstract description 8
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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
- C23C10/06—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
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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
- C23C10/02—Pretreatment of the material to be coated
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Abstract
The application provides an alloy surface modification layer and a preparation method thereof, and relates to the technical field of surface strengthening. An alloy surface modification layer includes a titanium alloy substrate, a niobium-containing modification layer attached to the titanium alloy substrate, and a titanium alloy layer attached to the niobium-containing modification layer. The application applies pulse explosion-plasma technology (PDT), a modified layer is prepared on the surface of a titanium alloy by using metal niobium, the metal niobium permeates into the titanium alloy, the purity of the permeated metal niobium is up to more than 99wt.%, a multilayer layer structure of the titanium alloy-niobium-titanium alloy is formed on the surface of the titanium alloy, the hardness and the wear resistance of the modified layer can be obviously improved, the hardness of the modified layer is improved by more than 2 times than that of a base body, the wear resistance is improved by more than 30%, and the niobium is used as the modified intermediate layer, so that the corrosion resistance of the material can be effectively improved.
Description
Technical Field
The application relates to the technical field of surface strengthening, in particular to an alloy surface modification layer and a preparation method thereof.
Background
The surface modification strengthening technology is widely applied to mechanical parts, can strengthen the surface performance of workpieces made of metal materials, improves the material characteristics, endows the surfaces with new functions, and becomes an important material technology in the manufacturing industry. In order to enhance the hardness and wear resistance of the component, a coating is typically applied to the surface of the component. The coating is usually modified to improve its hardness and wear resistance.
The laser surface treatment technology needs to pretreat the surface of a sample; the energy utilization rate is low; because the energy is large, the processing layer is easy to generate defects such as microcrack bubbles and the like, and the performance is influenced; laser equipment is costly and the cost of subsequent maintenance and replacement of parts is also high. Disadvantages of ion beam surface treatment techniques: the operation of the equipment needs extremely high energy, and meanwhile, the energy efficiency of the equipment is low, so that the resource is greatly wasted; the radiation generated in the treatment process causes potential safety hazards and may damage the physical health of operators; this process requires the shape of the workpiece and can contaminate the surface of the material, damaging the workpiece. The high current pulse electron beam surface treatment technology has strict requirements on the environment, most of the high current pulse electron beam surface treatment technologies are required to be carried out in a vacuum environment, and simultaneously, the electron beam concentration degree is high, the single treatment area is small, and large-area samples are difficult to treat.
The need for the development of the aerospace industry has led the titanium industry to grow at an average annual growth rate of about 8%. The annual output of the world titanium alloy processing materials reaches more than 4 ten thousand tons, and the titanium alloy grades are nearly 30. The titanium alloy is mainly used for manufacturing parts of an air compressor of an aircraft engine, and is a structural part of rockets, missiles and high-speed airplanes. In the middle of the 60 s, titanium and its alloys have been used in general industries for making electrodes for the electrolysis industry, condensers for power stations, heaters for petroleum refining and seawater desalination, and environmental pollution control devices. The titanium alloy has high strength, small density, good mechanical property, good toughness and corrosion resistance, so that the titanium alloy meets the industrial requirement. However, titanium alloys have poor workability and are difficult to cut, and they are very likely to absorb impurities such as hydrogen, oxygen, nitrogen, and carbon during hot working. Also has poor abrasion resistance and complex production process. Therefore, a titanium alloy surface layer having high hardness and high wear resistance is urgently required.
Disclosure of Invention
The purpose of the application is to provide an alloy surface modification layer, and the alloy surface modification layer has the advantages of high hardness and high wear resistance.
Another object of the present application is to provide a method for preparing an alloy surface modification layer, so as to obtain the alloy surface modification layer.
The technical problem to be solved by the application is solved by adopting the following technical scheme.
In one aspect, embodiments of the present application provide an alloy surface modification layer, including a titanium alloy substrate, a niobium-containing modification layer attached to the titanium alloy substrate, and a titanium alloy layer attached to the niobium-containing modification layer.
On the other hand, the embodiment of the application provides a preparation method of an alloy surface modification layer, which comprises the following steps:
polishing the surface of a titanium alloy substrate, and processing niobium metal into an electrode bar suitable for pulse explosion-plasma technology equipment to serve as a positive electrode;
and adjusting the capacitance of pulse explosion-plasma technology equipment, placing the titanium alloy substrate on a treatment table, and performing pulse explosion treatment to obtain an alloy surface modified layer.
Compared with the prior art, the embodiment of the application has at least the following advantages or beneficial effects:
the method applies a pulse explosion-Plasma (PDT) technology, adopts a composite method to improve equipment voltage, gasifies niobium at a positive electrode from a body to form plasma, acts the plasma containing the niobium on the surface of the titanium alloy by utilizing a method of regulating gas explosion simultaneously, generates a current effect on an acting material in a pulse mode to ensure that the niobium permeates into the titanium alloy, the purity of the permeated niobium is up to more than 99 wt%, and forms a multilayer structure of the titanium alloy-niobium-titanium alloy on the surface of the titanium alloy to prepare a modified layer. The hardness and the wear resistance of the modified layer can be obviously improved, the hardness of the modified layer is improved by more than 2 times compared with that of the base body, the wear resistance is improved by more than 30%, and the niobium is used as the modified intermediate layer, so that the corrosion resistance of the material can be effectively improved. In addition, through experiments by the inventor of the present application, it was found that only titanium alloy can be used as a substrate to allow niobium to infiltrate to form the modified layer structure, and other metals cannot realize the infiltration of niobium, and the modified layer structure of the type cannot be obtained.
The method adopts a pulse explosion-plasma technology (PDT) technology, metal niobium is used as an electrode material, different powers are adjusted to process a sample, the pulse explosion-plasma technology (PDT) technology adopts the basic principle that a niobium electrode is used as a power supply anode, the sample is used as a power supply cathode, a high-voltage power supply discharges between the electrode and the sample, the surface of the sample is impacted by combining the energy of explosion gas explosion, meanwhile, the electrode in the process generates melting and ion evaporation phenomena, the generated plasma and small molten drops impact the surface of the sample together under the driving of the explosion energy to form an element infiltration phenomenon, and the surface of the sample is modified under the combined action of electric energy, explosion energy, the plasma and the molten drop impact, so that the surface performance is enhanced. The operation is different from the traditional surface modification method of stacking layer by layer, the wear resistance and the strength of the modified layer can be effectively improved, the bonding strength is better, and the niobium-containing modified layer is not added in a layer-by-layer stacking mode but permeates into the titanium alloy matrix, so that the niobium-containing modified layer cannot fall off, and the wrapping performance is excellent. The modified layer prepared by the method has the advantages of high density, few defects and good strength. The method has the advantages of high energy conversion, green and pollution-free preparation process, low limit on environmental limiting conditions, capability of being carried out in an atmospheric environment and high treatment rate.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a schematic structural diagram of an alloy surface modification layer according to an embodiment of the present application;
FIG. 2 is a scanning electron microscope image of an alloy surface modification layer according to example 3 of the present application;
FIG. 3 is a distribution diagram of elements of an alloy surface modification layer according to example 3 of the present application;
FIG. 4 is a graph of hardness analysis at different depths for the alloy surface modification layer of example 3 of the present application;
FIG. 5 is a graph showing the volumetric wear loss analysis of the titanium alloy substrate of example 2 of the present application before and after the treatment;
FIG. 6 is a scanning electron micrograph of an alloy surface modification layer of comparative example 1 of the present application;
FIG. 7 is an elemental distribution diagram of the alloy surface modification layer of comparative example 1 of the present application.
Icon: 1-a titanium alloy substrate; 2-a niobium containing modification layer; a 3-titanium alloy layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to specific examples.
The embodiment of the application provides an alloy surface modification layer, as shown in fig. 1, comprising a titanium alloy substrate 1, a niobium-containing modification layer 2 attached on the titanium alloy substrate 1, and a titanium alloy layer 3 attached on the niobium-containing modification layer 2. The method applies a pulse explosion-Plasma (PDT) technology, adopts a composite method to improve equipment voltage, gasifies niobium at a positive electrode from a body to form plasma, acts the plasma containing the niobium on the surface of the titanium alloy by utilizing a method of regulating gas explosion simultaneously, generates a current effect on an acting material in a pulse mode to ensure that the niobium permeates into the titanium alloy, the purity of the permeated niobium is up to more than 99 wt%, and forms a multilayer structure of the titanium alloy-niobium-titanium alloy on the surface of the titanium alloy to prepare a modified layer. The hardness and the wear resistance of the modified layer can be obviously improved, the hardness of the modified layer is improved by more than 2 times compared with that of the base body, the wear resistance is improved by more than 30%, and the niobium is used as the modified intermediate layer, so that the corrosion resistance of the material can be effectively improved. In addition, through experiments by the inventor of the present application, it was found that only titanium alloy can be used as a substrate to allow niobium to infiltrate to form the modified layer structure, and other metals cannot realize the infiltration of niobium, and the modified layer structure of the type cannot be obtained.
In some embodiments of the present application, the niobium-containing modified layer 2 has a thickness of 5 to 10 μm. By applying the pulse explosion-plasma technology, niobium is permeated into the titanium alloy to form a niobium-containing modified layer with the thickness of 5-10 mu m, so that the overall strength and wear resistance of the modified layer can be effectively improved.
In some embodiments of the present application, the titanium alloy layer 3 has a thickness of 15 to 25 μm. The outermost surface is a titanium alloy layer, and the thickness of the layer is 15-25 mu m, so that the niobium layer can be protected.
The embodiment of the application also provides a preparation method of the alloy surface modification layer, which comprises the following steps:
polishing the surface of a titanium alloy matrix 1, and processing metallic niobium into an electrode bar suitable for pulse explosion-plasma technology equipment to serve as a positive electrode;
and adjusting the capacitance parameter of pulse explosion-plasma technical equipment, placing the titanium alloy matrix 1 on a treatment table, and performing pulse explosion treatment to obtain an alloy surface modified layer. The surface of the niobium alloy is polished to remove oxides on the surface, so that niobium can penetrate more easily. The method adopts a pulse explosion-plasma technology (PDT) technology, metal niobium is used as an electrode material, different powers are adjusted to process a sample, the pulse explosion-plasma technology (PDT) technology has the basic principle that a niobium electrode is used as a power supply anode, the sample is used as a power supply cathode, a high-voltage power supply generates a current effect between the electrode and the sample under the action of plasma, the surface of the sample is impacted by combining the energy of explosion gas explosion, meanwhile, the electrode in the process generates melting and ion evaporation phenomena, the generated plasma and small molten drops impact the surface of the sample together under the driving of the explosion energy to form an element infiltration phenomenon, and the surface of the sample is modified under the combined action of electric energy, explosion energy, plasma and molten drop impact to enhance the surface performance. The operation is different from the traditional surface modification method of stacking layer by layer, the wear resistance and the strength of the modified layer can be effectively improved, the bonding strength is better, and the niobium-containing modified layer is not added in a layer-by-layer stacking mode but permeates into the titanium alloy matrix, so that the niobium-containing modified layer cannot fall off, and the wrapping performance is excellent. The modified layer prepared by the method has the advantages of high density, few defects and good strength. The method has the advantages of high energy conversion, green and pollution-free preparation process, low limit on environmental restriction conditions, capability of being carried out in an atmospheric environment and high treatment rate.
In some embodiments of the present application, the pulsed detonation-plasma technique apparatus described above has a capacitance of 300-2200 μ F. The capacitance is adjusted to 300-2200 muF, the power of pulse explosion-plasma technology equipment is adjusted, and the niobium infiltration amount and the niobium penetration depth are adjusted, so that the thickness and the depth of the niobium layer are required, and the whole modified layer has better strength and wear resistance.
In some embodiments of the present application, the voltage of the pulse explosion treatment is 5000-35000V. The voltage in the range can enable the anode niobium to be gasified from the body to form plasma, so that the anode niobium can be conveniently and subsequently infiltrated into the titanium alloy to form a multilayer structure of the titanium alloy-niobium-titanium alloy.
In some embodiments of the present application, the gas used in the pulse explosion treatment is a mixed gas of oxygen, nitrogen and propane, and a volume ratio of the oxygen, the nitrogen and the propane is 4:3:1. the gas used in the pulse explosion treatment is a mixed gas of oxygen, nitrogen and propane, and the volume ratio of the oxygen, the nitrogen and the propane is 4:3:1. after the mixed gas is ejected from the explosion spray gun, niobium atoms are driven by the explosion energy of the explosion gas to impact the surface of the titanium alloy, meanwhile, melting and ion evaporation phenomena occur on the process electrode, the generated plasma and small molten drops impact the surface of a sample under the drive of the explosion energy, an element infiltration phenomenon is formed, and niobium is infiltrated into the titanium alloy to form a surface modification layer. The mixed gas in the changed proportion has better explosion energy and can effectively promote the permeation of niobium.
In some embodiments of the present application, the flow rate of the mixed gas is 130-160L/min. If the flow rate of the mixed gas is too low, the energy generated during gas explosion can be reduced, so that the niobium permeation effect is poor, and the hardness and the wear resistance of the whole modified layer are affected; and if the flow rate of the mixed gas is too high, the energy generated by gas explosion is too large, and equipment damage and the like can be caused. When the flow is 130-160L/min, the niobium infiltration effect can be ensured, so that the finally obtained modified layer has high strength and good wear resistance.
In some embodiments of the present application, the impulse type explosion treatment has an impact frequency of 0.5 to 15 times/second.
In some embodiments of the present application, the electrode rod is processed to have a length of more than 5cm and a diameter of 0.5-1.5cm.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
A preparation method of an alloy surface modification layer comprises the following steps:
the surface of a titanium alloy matrix 1 is polished to be rough, and metal niobium is processed into an electrode rod which is suitable for pulse explosion-plasma technology equipment, wherein the length of the electrode rod is 6cm, and the diameter of the electrode rod is 0.5cm, and the electrode rod is used as a positive electrode;
adjusting the capacitance of pulse explosion-plasma technical equipment to be 300 muF, setting the voltage to be 5000V, then placing the titanium alloy substrate 1 on a treatment table, and carrying out treatment on the titanium alloy substrate in a volume ratio of 4:3:1, carrying out pulse type explosion treatment on the titanium alloy under the condition that the impact frequency is 10 times/second to obtain an alloy surface modification layer.
Example 2
A preparation method of an alloy surface modification layer comprises the following steps:
the surface of a titanium alloy matrix 1 is polished to be rough, and metal niobium is processed into an electrode rod which is suitable for pulse explosion-plasma technology equipment, wherein the length of the electrode rod is 8cm, and the diameter of the electrode rod is 0.8cm, and the electrode rod is used as a positive electrode;
adjusting the capacitance of pulse explosion-plasma technical equipment to 800 muF, setting the voltage to 10000V, then placing the titanium alloy substrate 1 on a processing table, and carrying out treatment on the titanium alloy substrate in a volume ratio of 4:3:1, carrying out pulse type explosion treatment on the titanium alloy matrix 1 under the condition that the impact frequency is 6 times/second to obtain an alloy surface modification layer by using mixed gas of oxygen, nitrogen and propane with the flow rate of 140L/min.
Fig. 5 shows the volume wear amount of the titanium alloy substrate 1 before the pulse explosion treatment and the volume wear amount of the alloy surface modification layer after the pulse explosion treatment. Observing fig. 5, the volume wear amount of the titanium alloy substrate 1 before pulse type explosion treatment is 10.1729mm, and the volume wear amount of the alloy surface modification layer after 800 muF capacitance Nb electrode treatment is 7.8334mm, and the comparison shows that the volume wear amount is greatly reduced after pulse type explosion treatment, because the metal niobium permeates into the titanium alloy substrate 1, the hardness and the wear resistance of the modification layer are obviously improved.
Example 3
A preparation method of an alloy surface modification layer comprises the following steps:
polishing the surface of a titanium alloy matrix 1 to be rough, and processing metallic niobium into an electrode rod which is suitable for pulse explosion-plasma technology equipment, wherein the length of the electrode rod is 10cm, and the diameter of the electrode rod is 1cm, and the electrode rod is used as a positive electrode;
adjusting the capacitance of the pulse explosion-plasma technical equipment to 1200 muF, setting the voltage to 15000V, then placing the titanium alloy substrate 1 on a treatment table, and carrying out the following steps of: 3:1, carrying out pulse type explosion treatment on the titanium alloy matrix 1 under the condition that the impact frequency is 1 time/second to obtain an alloy surface modification layer by using mixed gas of oxygen, nitrogen and propane with the flow rate of 140L/min.
The scanning electron microscope image of the alloy surface modified layer is shown in fig. 2, fig. 2-a shows that the bottom is a titanium alloy substrate, the upper surface is 2 layers of layers, fig. 2-b is an enlarged view of a selected frame part in fig. 2-a, and the structures of a titanium alloy matrix 1, a niobium-containing modified layer 2 and a titanium alloy layer 3 can be obviously seen.
The element distribution diagram of the alloy surface modification layer, and FIG. 3-a is a local scanning electron microscope image of the alloy surface modification layer; FIG. 3-b is the EDS surface scan of FIG. 3-a, showing that niobium is distributed between the titanium alloy substrate 1 and the titanium alloy layer 3; fig. 3-c is a point scan of each point in fig. 3-a, and it can be seen that the niobium content is different for each point, and the niobium content in the niobium-containing modified layer 2 can reach 99.16%.
The hardness analysis of the alloy surface modified layer is shown in fig. 4, it can be seen that the hardness of the alloy surface modified layer is higher at 0-20 μm, and is about 380HV at the most, and in combination with fig. 2, it can be seen that the modified layer 2 containing niobium and the titanium alloy layer 3 are at 0-20 μm, and in comparison with the hardness at 20-110 μm, it can be clearly seen that the hardness at deeper depth is lower, and is about 170HV at the least, at this time, in combination with fig. 2, it can be clearly seen that the titanium alloy substrate 1 is at 20-110 μm, which means that the hardness of the surface of the titanium alloy substrate 1 can be greatly improved by subjecting the titanium alloy substrate 1 to pulse explosion treatment with niobium.
Example 4
A preparation method of an alloy surface modification layer comprises the following steps:
polishing the surface of a titanium alloy matrix 1 to be rough, and processing metallic niobium into an electrode rod suitable for pulse explosion-plasma technical equipment, wherein the length of the electrode rod is 12cm, and the diameter of the electrode rod is 1.2cm, and the electrode rod is used as a positive electrode;
adjusting the capacitance of pulse explosion-plasma technical equipment to 1800 muF, setting the voltage to 2500V, then placing the titanium alloy substrate 1 on a treatment table, and carrying out treatment on the titanium alloy substrate at a volume ratio of 4:3:1, carrying out pulse type explosion treatment on the titanium alloy matrix 1 under the condition that the impact frequency is 7 times/second to obtain an alloy surface modification layer.
Example 5
A preparation method of an alloy surface modification layer comprises the following steps:
polishing the surface of a titanium alloy matrix 1 to be rough, and processing metallic niobium into an electrode rod which is suitable for pulse explosion-plasma technology equipment, wherein the length of the electrode rod is 15cm, and the diameter of the electrode rod is 1.5cm, and the electrode rod is used as a positive electrode;
adjusting the capacitance of the pulse explosion-plasma technical equipment to 2200 muF, setting the voltage to 35000V, then placing the titanium alloy substrate 1 on a processing table, and carrying out the following steps of: 3:1, carrying out pulse type explosion treatment on the titanium alloy matrix 1 under the condition that the impact frequency is 8 times/second to obtain an alloy surface modification layer by using mixed gas of oxygen, nitrogen and propane with the flow rate of 160L/min.
Comparative example 1
This comparative example is essentially identical to example 3, except that: metal niobium is replaced with metal tantalum.
The scanning electron microscope image of the alloy surface modification layer obtained by the comparative example 1 is shown in fig. 6, fig. 6-a shows that the bottom is a titanium alloy substrate, and 1 tantalum modification layer structure is arranged on the titanium alloy substrate, fig. 6-b is an enlarged view of a selected part in a frame in fig. 6-a, the structures of a titanium alloy substrate, a tantalum-containing modification layer and an insert (which is used for fixing the titanium alloy and is convenient for subsequent sample grinding) positioned above the modification layer can be obviously seen, and the structure of the uppermost layer is different from that of the substrate of the bottom layer, which indicates that the tantalum does not penetrate into the titanium alloy although the same treatment method is adopted.
The element distribution diagram of the alloy surface modification layer obtained by the present comparative example 1, and fig. 7-a is a local scanning electron microscope image of the alloy surface modification layer; FIG. 7-b is the EDS surface scan of FIG. 7-a showing that the tantalum element is not agglomerated, i.e., no tantalum penetration layer is formed; fig. 7-c is a point scan of the points in fig. 3-a, where it can be seen that each point has a very low tantalum content, up to only 2.23.
Comparing example 3 with comparative example 1, it can be seen that this modified layer structure can be obtained only by pulse explosion treatment of titanium alloy with niobium, and other metals cannot achieve infiltration of niobium, nor can a modified layer structure of this type be obtained. In summary, the present application applies pulse explosion-plasma technology (PDT), adopts a composite method to increase the equipment voltage, gasifies the niobium of the positive electrode from the bulk to form plasma, applies the plasma containing niobium to the surface of the titanium alloy by using a simultaneous regulated gas explosion method, and the pulse mode generates a current effect on the applied material to cause the niobium to permeate into the titanium alloy, wherein the purity of the permeated niobium is as high as more than 99wt.%, and a multilayer layer structure of titanium alloy-niobium-titanium alloy is formed on the surface of the titanium alloy to prepare the modified layer. The hardness and the wear resistance of the modified layer can be obviously improved, the hardness of the modified layer is improved by more than 2 times compared with that of a matrix, the wear resistance is improved by more than 30%, and the niobium is used as the modified intermediate layer, so that the corrosion resistance of the material can be effectively improved. In addition, through experiments by the inventor of the present application, it was found that only titanium alloy can be used as a substrate to allow niobium to infiltrate to form the modified layer structure, and other metals cannot realize the infiltration of niobium, and the modified layer structure of the type cannot be obtained.
The method adopts a pulse explosion-plasma technology (PDT) technology, metal niobium is used as an electrode material, different powers are adjusted to process a sample, the pulse explosion-plasma technology (PDT) technology adopts the basic principle that a niobium electrode is used as a power supply anode, the sample is used as a power supply cathode, a high-voltage power supply discharges between the electrode and the sample, the surface of the sample is impacted by combining the energy of explosion gas explosion, meanwhile, the electrode in the process generates melting and ion evaporation phenomena, the generated plasma and small molten drops impact the surface of the sample together under the driving of the explosion energy to form an element infiltration phenomenon, and the surface of the sample is modified under the combined action of electric energy, explosion energy, the plasma and the molten drop impact, so that the surface performance is enhanced. The operation is different from the traditional surface modification method of stacking layer by layer, the wear resistance and the strength of the modified layer can be effectively improved, the bonding strength is better, and the niobium-containing modified layer is not added in a layer-by-layer stacking mode but permeates into the titanium alloy matrix, so that the niobium-containing modified layer cannot fall off, and the wrapping performance is excellent. The modified layer prepared by the method has the advantages of high density, few defects and good strength. The method has the advantages of high energy conversion, green and pollution-free preparation process, low limit on environmental restriction conditions, capability of being carried out in an atmospheric environment and high treatment rate.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
Claims (10)
1. An alloy surface modification layer comprising a titanium alloy substrate, a niobium-containing modification layer attached to the titanium alloy substrate, and a titanium alloy layer attached to the niobium-containing modification layer.
2. The alloy surface modification layer according to claim 1, wherein the niobium-containing modification layer has a thickness of 5 to 10 μm.
3. The alloy surface modification layer according to claim 1, wherein the titanium alloy layer has a thickness of 15 to 25 μm.
4. A method for preparing the alloy surface modification layer according to any one of claims 1 to 3, comprising the steps of:
polishing the surface of a titanium alloy substrate, and processing niobium metal into an electrode bar suitable for pulse explosion-plasma technology equipment to serve as a positive electrode;
and adjusting the capacitance of pulse explosion-plasma technology equipment, placing the titanium alloy substrate on a treatment table, and performing pulse explosion treatment to obtain an alloy surface modified layer.
5. The method for preparing the alloy surface modification layer according to claim 4, wherein the capacitance of the pulsed detonation-plasma technology device is 300-2200 μ F.
6. The method for preparing the alloy surface modification layer according to claim 4, wherein the voltage during the pulse type explosion treatment is 5000-35000V.
7. The method for preparing the alloy surface modification layer according to claim 4, wherein the gas used in the pulse explosion treatment is a mixed gas of oxygen, nitrogen and propane, and the volume ratio of the oxygen, the nitrogen and the propane is 4:3:1.
8. the method for preparing the alloy surface modification layer according to claim 7, wherein the flow rate of the mixed gas is 130-160L/min.
9. The method for preparing the alloy surface modification layer according to claim 4, wherein the impulse type explosion treatment has an impact frequency of 0.5-15 times/second.
10. The method of claim 4, wherein the electrode rod has a processed length of more than 5cm and a diameter of 0.5-1.5cm.
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