CN115449743B - Alloy surface modification layer and preparation method thereof - Google Patents
Alloy surface modification layer and preparation method thereof Download PDFInfo
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- CN115449743B CN115449743B CN202211144240.XA CN202211144240A CN115449743B CN 115449743 B CN115449743 B CN 115449743B CN 202211144240 A CN202211144240 A CN 202211144240A CN 115449743 B CN115449743 B CN 115449743B
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 56
- 239000000956 alloy Substances 0.000 title claims abstract description 56
- 230000004048 modification Effects 0.000 title claims abstract description 56
- 238000012986 modification Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 86
- 239000010955 niobium Substances 0.000 claims abstract description 79
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 78
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 238000005516 engineering process Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 238000004880 explosion Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- 238000005474 detonation Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 12
- 239000012466 permeate Substances 0.000 abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010936 titanium Substances 0.000 abstract description 7
- 229910052719 titanium Inorganic materials 0.000 abstract description 7
- 229910001275 Niobium-titanium Inorganic materials 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000005728 strengthening Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 114
- 210000002381 plasma Anatomy 0.000 description 15
- 238000005299 abrasion Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000007788 roughening Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
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- 238000001704 evaporation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
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- 238000009826 distribution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000005542 laser surface treatment Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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Classifications
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
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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 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. According to the preparation method, a pulse explosion-plasma technology (PDT) is applied, the metal niobium is used for preparing the modified layer on the surface of the titanium alloy, so that the metal niobium permeates into the titanium alloy, the purity of the permeated metal niobium is up to more than 99 wt%, a multilayer 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 to more than 2 times as compared with that of a matrix, the wear resistance is improved by more than 30%, and the niobium is used as a 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 a workpiece made of metal materials, improve the material characteristics, endow the surface 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 prepared on the surface of the component. In order to improve the hardness and wear resistance of the coating, it is generally modified.
The laser surface treatment technology needs to pretreat the sample surface; the energy utilization rate is low; because of high energy, the treatment layer is easy to generate defects such as micro-crack bubbles and the like, and the performance is influenced; the laser equipment is high in cost, and subsequent maintenance and replacement of parts are also high in cost. Disadvantages of ion beam surface treatment techniques: the operation of the equipment requires extremely high energy, and meanwhile, the energy efficiency of the equipment is relatively low, so that the resource is extremely wasted; the radiation generated during the treatment process causes potential safety hazards and may damage the health of operators; the process has requirements on the shape of the workpiece, and can pollute the surface of the material and damage the workpiece. The strong current pulse electron beam surface treatment technology has strict environmental requirements, most of the requirements are carried out in a vacuum environment, and meanwhile, due to the high concentration degree of electron beams, a single treatment area is smaller, and a large-area sample is difficult to treat.
The need for the development of the aerospace industry has led to the development of the titanium industry at an average growth rate of about 8% per year. The annual output of titanium alloy processing materials in the world reaches 4 tens of thousands of tons, and the brand of titanium alloy is nearly 30. The titanium alloy is mainly used for manufacturing aircraft engine compressor components, and secondly structural components of rockets, missiles and high-speed aircraft. In the middle of the 60 s, titanium and its alloys have been used in general industries for manufacturing electrodes for the electrolytic industry, condensers for power stations, heaters for petroleum refining and sea water desalination, environmental pollution control devices, and the like. The titanium alloy has high strength, small density, good mechanical property, toughness and corrosion resistance, so that the titanium alloy meets industrial requirements. However, titanium alloys have poor processing properties, are difficult to cut, and are extremely likely to absorb impurities such as oxyhydrogen carbon during hot working. Also has poor wear resistance and complex production process. Therefore, there is an urgent need for a titanium alloy surface layer having high hardness and high wear resistance.
Disclosure of Invention
The object of the present application is to provide an alloy surface modification layer having 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 of the application is solved by adopting the following technical scheme.
In one aspect, embodiments herein provide 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.
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 matrix, and processing metal niobium into an electrode rod suitable for pulse explosion-plasma technical equipment to serve as an anode;
and adjusting the capacitance of pulse explosion-plasma technical equipment, and then placing the titanium alloy substrate on a processing table to obtain an alloy surface modification layer after pulse explosion processing.
Compared with the prior art, the embodiment of the application has at least the following advantages or beneficial effects:
the application adopts pulse explosion-plasma technology (PDT), adopts a composite method to increase the equipment voltage, gasifies the positive electrode niobium from the body to form plasma, utilizes a method of simultaneously adjusting gas explosion to enable the plasma containing niobium to act on the surface of the titanium alloy, and adopts a pulse mode to generate a current effect on an acting material to enable the niobium to permeate into the titanium alloy, and the purity of the permeated niobium is as high as 99wt.% or more, so that a multilayer layer structure of the titanium alloy-niobium-titanium alloy is formed on the surface of the titanium alloy, and a modified layer is prepared. The hardness and the wear resistance of the modified layer can be obviously improved, the hardness of the modified layer is improved to be more than 2 times higher than that of the matrix, the wear resistance is improved by more than 30%, and the niobium is used as a modified intermediate layer, so that the corrosion resistance of the material can be effectively improved. In addition, experiments of the inventor of the application find that only titanium alloy can be used as a substrate, niobium is permeated to form the modified layer structure, other metals cannot permeate niobium, and the modified layer structure of the type cannot be obtained.
The method adopts a pulse explosion-plasma technology (PDT) technology, which uses metallic niobium as an electrode material, adjusts different powers to treat a sample, uses a niobium electrode as a power anode, uses the sample as a power cathode, discharges a high-voltage power supply between the electrode and the sample, combines the energy of explosion gas explosion to impact the surface of the sample, and simultaneously, the electrode in the process generates melting and ion evaporation phenomena, the generated plasma and droplets impact the surface of the sample together under the drive of the explosion energy to form element infiltration phenomena, and the surface of the sample is modified under the combined action of electric energy, explosion energy, plasma and droplet impact to strengthen the surface performance. The operation is different from the traditional surface modification method of layer-by-layer superposition, the wear resistance and the strength of the modified layer can be effectively improved, the bonding strength is better, and the modified layer containing niobium is not added in a layer-by-layer superposition mode, but is permeated into the titanium alloy matrix, so that the modified layer containing niobium cannot have the problem of falling off, and the wrapping performance is excellent. The modified layer prepared by the method has high density, few defects and good strength. The method has the advantages of high energy conversion, green and pollution-free preparation process, little limitation 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 needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view 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 of example 3 of the present application;
FIG. 3 is an elemental distribution diagram of an alloy surface modification layer of example 3 of the present application;
FIG. 4 is a graph of hardness analysis at various depths of the alloy surface modification layer of example 3 of the present application;
FIG. 5 is a graph showing the analysis of the volumetric wear of the titanium alloy substrate of example 2 of the present application before and after treatment;
FIG. 6 is a scanning electron microscope image of the alloy surface modification layer of comparative example 1 of the present application;
fig. 7 is an elemental distribution diagram of an alloy surface-modified layer of comparative example 1 of the present application.
Icon: 1-titanium alloy matrix; 2-a modified layer comprising niobium; a 3-titanium alloy layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present application will be described in detail with reference to specific examples.
The embodiment provides an alloy surface modification layer, as shown in fig. 1, comprising a titanium alloy substrate 1, a niobium-containing modification layer 2 attached to the titanium alloy substrate 1, and a titanium alloy layer 3 attached to the niobium-containing modification layer 2. The application adopts pulse explosion-plasma technology (PDT), adopts a composite method to increase the equipment voltage, gasifies the positive electrode niobium from the body to form plasma, utilizes a method of simultaneously adjusting gas explosion to enable the plasma containing niobium to act on the surface of the titanium alloy, and adopts a pulse mode to generate a current effect on an acting material to enable the niobium to permeate into the titanium alloy, and the purity of the permeated niobium is as high as 99wt.% or more, so that a multilayer layer structure of the titanium alloy-niobium-titanium alloy is formed on the surface of the titanium alloy, and a modified layer is prepared. The hardness and the wear resistance of the modified layer can be obviously improved, the hardness of the modified layer is improved to be more than 2 times higher than that of the matrix, the wear resistance is improved by more than 30%, and the niobium is used as a modified intermediate layer, so that the corrosion resistance of the material can be effectively improved. In addition, experiments of the inventor of the application find that only titanium alloy can be used as a substrate, niobium is permeated to form the modified layer structure, other metals cannot permeate 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 described above has a thickness of 5-10 μm. By applying pulse explosion-plasma technology, niobium permeates into the titanium alloy to form a modified layer containing niobium with the thickness of 5-10 mu m, and the integral strength and the 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 15-25 μm. The titanium alloy layer is arranged on the outermost surface, and the thickness of the titanium alloy 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 substrate 1, and processing metal niobium into an electrode rod suitable for pulse explosion-plasma technical equipment to serve as an anode;
and (3) adjusting capacitance parameters of pulse explosion-plasma technical equipment, and then placing the titanium alloy substrate 1 on a processing table to obtain an alloy surface modification layer after pulse explosion processing. Polishing the surface can remove oxide on the surface, so that niobium is easier to permeate. The method adopts a pulse explosion-plasma technology (PDT) technology, wherein metal niobium is used as an electrode material, different powers are adjusted to treat a sample, the basic principle of the pulse explosion-plasma technology (PDT) technology is that a niobium electrode is used as a power anode, the sample is used as a power cathode, a high-voltage power supply generates a current effect under the action of plasma 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 droplets 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 droplet impact to strengthen the surface performance. The operation is different from the traditional surface modification method of layer-by-layer superposition, the wear resistance and the strength of the modified layer can be effectively improved, the bonding strength is better, and the modified layer containing niobium is not added in a layer-by-layer superposition mode, but is permeated into the titanium alloy matrix, so that the modified layer containing niobium cannot have the problem of falling off, and the wrapping performance is excellent. The modified layer prepared by the method has high density, few defects and good strength. The method has the advantages of high energy conversion, green and pollution-free preparation process, little limitation on environmental limiting 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 technology device described above has a capacitance of 300-2200 μf. The power of pulse explosion-plasma technical equipment is further adjusted by adjusting the capacitance to 300-2200 mu F, and the niobium penetration amount and depth are further adjusted, so that the thickness and depth of the niobium layer reach the requirements, and the whole modified layer has better strength and wear resistance.
In some embodiments of the present application, the voltage during the pulse detonation process is 5000-35000V. The voltage in the range can enable the positive electrode niobium to be gasified from the body to form plasma, so that the subsequent infiltration into the titanium alloy is facilitated, and the titanium alloy-niobium-titanium alloy multilayer structure is formed.
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 the volume ratio of oxygen, nitrogen and 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 to the nitrogen to the propane is 4:3:1. after the mixed gas is ejected from the explosion spray gun, niobium atoms are driven by the energy of explosion of the explosion gas to impact the surface of the titanium alloy, meanwhile, the process electrode is melted and evaporated, and generated plasmas and small molten drops impact the surface of the sample together under the driving of the explosion energy to form an element infiltration phenomenon, so that niobium infiltrates into the titanium alloy to form a surface modification layer. The mixed gas with the modified ratio 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. The flow rate of the mixed gas is too low, so that the energy generated during gas explosion can be reduced, the permeation effect of niobium is poor, and finally the hardness and the wear resistance of the whole modified layer are influenced; if the flow rate of the mixed gas is too high, the energy generated by the explosion of the gas is too large, which may cause damage to equipment, etc. When the flow is 130-160L/min, the permeation effect of niobium 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 impact frequency at the time of the pulse detonation treatment is 0.5-15 times/second.
In some embodiments of the present application, the electrode rod is greater than 5cm long and has a diameter of 0.5-1.5cm.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The preparation method of the alloy surface modification layer comprises the following steps:
polishing and roughening the surface of a titanium alloy substrate 1, and processing metal niobium into an electrode rod with the length of 6cm and the diameter of 0.5cm which is suitable for pulse explosion-plasma technical equipment, wherein the electrode rod is used as an anode;
the capacitance of the pulse explosion-plasma technical equipment is adjusted to 300 mu F, the voltage is set to 5000V, then the titanium alloy substrate 1 is placed on a processing table, and the volume ratio is 4:3:1, and carrying out pulse explosion treatment on the titanium alloy under the condition of the impact frequency of 10 times per second to obtain an alloy surface modification layer.
Example 2
The preparation method of the alloy surface modification layer comprises the following steps:
polishing and roughening the surface of a titanium alloy substrate 1, and processing metal niobium into an electrode rod with the length of 8cm and the diameter of 0.8cm which is suitable for pulse explosion-plasma technical equipment, wherein the electrode rod is used as an anode;
the capacitance of the pulse explosion-plasma technical equipment is adjusted to 800 muF, the voltage is set to 10000V, then the titanium alloy substrate 1 is placed on a processing table, and the volume ratio is 4:3:1, and carrying out pulse explosion treatment on the titanium alloy matrix 1 under the condition of the impact frequency of 6 times per second to obtain an alloy surface modification layer.
The volume abrasion loss of the titanium alloy substrate 1 before the pulse explosion treatment and the volume abrasion loss of the alloy surface modification layer after the pulse explosion treatment are shown in fig. 5. By observing fig. 5, the volume abrasion loss of the titanium alloy substrate 1 before pulse explosion treatment is 10.1729mm, and the volume abrasion loss of the alloy surface modification layer after 800 mu F capacitor Nb electrode treatment is 7.8334mm, and comparing the volume abrasion loss with the volume abrasion loss of the alloy surface modification layer after pulse explosion treatment, the volume abrasion loss is greatly reduced, and the hardness and the abrasion resistance of the modification layer are obviously improved due to the fact that the metal niobium permeates into the titanium alloy substrate 1.
Example 3
The preparation method of the alloy surface modification layer comprises the following steps:
polishing and roughening the surface of a titanium alloy substrate 1, and processing metal niobium into an electrode rod with the length of 10cm and the diameter of 1cm which is suitable for pulse explosion-plasma technical equipment, wherein the electrode rod is used as an anode;
the capacitance of the pulse explosion-plasma technical equipment is adjusted to 1200 muF, the voltage is set to 15000V, then the titanium alloy substrate 1 is placed on a processing table, and the volume ratio is 4:3:1, and carrying out pulse explosion treatment on the titanium alloy matrix 1 under the condition of the impact frequency of 1 time per second to obtain an alloy surface modification layer.
The scanning electron microscope image of the alloy surface modified layer is shown in fig. 2, the bottom of the alloy surface modified layer is a titanium alloy substrate, a 2-layer structure is arranged on the alloy surface modified layer, and fig. 2-b is an enlarged view of a frame selected part in fig. 2-a, so that the structures of the titanium alloy substrate 1, the niobium-containing modified layer 2 and the titanium alloy layer 3 can be obviously seen.
FIG. 3-a is a partial scanning electron microscope image of the alloy surface modification layer; FIG. 3-b is a scan of the EDS surface of FIG. 3-a, showing that niobium is distributed between the titanium alloy substrate 1 and the titanium alloy layer 3; FIG. 3-c shows the results of a spot scan for each spot in FIG. 3-a, and it was found that the niobium content was different for each spot and the niobium content in the niobium-containing modified layer 2 was 99.16%.
As shown in FIG. 4, the hardness analysis of the alloy surface modified layer showed that the alloy surface modified layer had a higher hardness of about 380HV at 0-20. Mu.m, while in combination with FIG. 2, it was found that the modified layer 2 and the titanium alloy layer 3 containing niobium at 0-20. Mu.m, and the hardness at the deeper position of 20-110. Mu.m was significantly lower, and the hardness at the lowest was about 170HV, and in combination with FIG. 2, it was found that the titanium alloy substrate 1 at 20-110. Mu.m was found, which means that the surface hardness of the titanium alloy substrate 1 could be greatly improved by subjecting the titanium alloy substrate 1 to pulse explosion treatment with niobium.
Example 4
The preparation method of the alloy surface modification layer comprises the following steps:
polishing and roughening the surface of a titanium alloy substrate 1, and processing metal niobium into an electrode rod with the length of 12cm and the diameter of 1.2cm which is suitable for pulse explosion-plasma technical equipment, wherein the electrode rod is used as an anode;
the capacitance of the pulse explosion-plasma technical equipment is adjusted to 1800 mu F, the voltage is set to 2500V, then the titanium alloy substrate 1 is placed on a processing table, and the volume ratio is 4:3:1, and carrying out pulse explosion treatment on the titanium alloy matrix 1 under the condition of the impact frequency of 7 times per second to obtain an alloy surface modification layer.
Example 5
The preparation method of the alloy surface modification layer comprises the following steps:
polishing and roughening the surface of a titanium alloy substrate 1, and processing metal niobium into an electrode rod with the length of 15cm and the diameter of 1.5cm which is suitable for pulse explosion-plasma technical equipment, wherein the electrode rod is used as an anode;
the capacitance of the pulse explosion-plasma technical equipment is adjusted to 2200 mu F, the voltage is set to 35000V, then the titanium alloy substrate 1 is placed on a processing table, and the volume ratio is 4:3:1, and carrying out pulse explosion treatment on the titanium alloy matrix 1 under the condition of the impact frequency of 8 times per second to obtain an alloy surface modification layer.
Comparative example 1
This comparative example is substantially identical to example 3, except that: the metallic niobium is replaced with metallic tantalum.
The scanning electron microscope image of the alloy surface modification layer obtained in this comparative example 1 is shown in fig. 6, and fig. 6-a shows that the bottom is a titanium alloy substrate, and there is 1 layer of tantalum modification layer structure on the substrate, and fig. 6-b shows an enlarged view of the frame-selected part in fig. 6-a, and it can be seen that the titanium alloy substrate, the tantalum-containing modification layer and the mosaic material (which is used for fixing the titanium alloy and facilitates subsequent sample grinding) located above the modification layer have structures, and it can be seen that the uppermost layer structure is different from the structure of the substrate of the bottom layer, which indicates that tantalum does not infiltrate into the titanium alloy although the same treatment method is adopted.
FIG. 7-a is a partial scanning electron microscope image of the alloy surface-modified layer obtained by the present comparative example 1; FIG. 7-b is a view of the EDS surface scan of FIG. 7-a, showing that the tantalum element is free of agglomeration, i.e., no tantalum penetration layer is formed; fig. 7-c shows the results of a spot scan of the spots in fig. 3-a, where each spot has a very low tantalum content, which is only 2.23 at the highest.
In comparative examples 3 and 1, it can be seen that this modified layer structure could be formed only by subjecting the titanium alloy to pulse explosion treatment using niobium, and that other metals could not achieve infiltration of niobium, nor could it obtain this type of modified layer structure. In summary, the present application applies pulse explosion-plasma technology (PDT), adopts a composite method to increase the voltage of the device, gasifies the positive electrode niobium from the body to form plasma, and simultaneously adjusts the gas explosion method to apply the plasma containing niobium to the surface of the titanium alloy, and the pulse mode generates a current effect on the acting material to make the niobium permeate into the titanium alloy, and the purity of the permeated niobium is as high as 99wt.% or more, so as to form a multilayer structure of the titanium alloy-niobium-titanium alloy on the surface of the titanium alloy, and 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 to be more than 2 times higher than that of the matrix, the wear resistance is improved by more than 30%, and the niobium is used as a modified intermediate layer, so that the corrosion resistance of the material can be effectively improved. In addition, experiments of the inventor of the application find that only titanium alloy can be used as a substrate, niobium is permeated to form the modified layer structure, other metals cannot permeate niobium, and the modified layer structure of the type cannot be obtained.
The method adopts a pulse explosion-plasma technology (PDT) technology, which uses metallic niobium as an electrode material, adjusts different powers to treat a sample, uses a niobium electrode as a power anode, uses the sample as a power cathode, discharges a high-voltage power supply between the electrode and the sample, combines the energy of explosion gas explosion to impact the surface of the sample, and simultaneously, the electrode in the process generates melting and ion evaporation phenomena, the generated plasma and droplets impact the surface of the sample together under the drive of the explosion energy to form element infiltration phenomena, and the surface of the sample is modified under the combined action of electric energy, explosion energy, plasma and droplet impact to strengthen the surface performance. The operation is different from the traditional surface modification method of layer-by-layer superposition, the wear resistance and the strength of the modified layer can be effectively improved, the bonding strength is better, and the modified layer containing niobium is not added in a layer-by-layer superposition mode, but is permeated into the titanium alloy matrix, so that the modified layer containing niobium cannot have the problem of falling off, and the wrapping performance is excellent. The modified layer prepared by the method has high density, few defects and good strength. The method has the advantages of high energy conversion, green and pollution-free preparation process, little limitation on environmental limiting conditions, capability of being carried out in an atmospheric environment and high treatment rate.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
Claims (7)
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;
the preparation method of the alloy surface modification layer comprises the following steps:
polishing the surface of a titanium alloy matrix, and processing metal niobium into an electrode rod suitable for pulse explosion-plasma technical equipment to serve as an anode;
adjusting the capacitance of pulse explosion-plasma technical equipment, then placing a titanium alloy substrate on a treatment table, and obtaining an alloy surface modification layer after pulse explosion treatment;
the gas used in the pulse explosion treatment is a mixed gas of oxygen, nitrogen and propane, and the volume ratio of the oxygen to the nitrogen to the propane is 4:3:1, a step of;
the flow rate of the mixed gas is 130-160L/min.
2. An alloy surface modification layer according to claim 1, wherein said niobium-containing modification layer has a thickness of 5-10 μm.
3. An alloy surface modification layer according to claim 1, wherein the titanium alloy layer has a thickness of 15-25 μm.
4. An alloy surface modification layer according to claim 1, wherein the pulsed explosion-plasma technology device has a capacitance of 300-2200 μf.
5. An alloy surface modifying layer as claimed in claim 1 wherein the pulsed detonation treatment voltage is in the range 5000V to 35000V.
6. An alloy surface modifying layer as claimed in claim 1 wherein the impact frequency upon the pulsed detonation process is in the range of 0.5 to 15 times/sec.
7. The alloy surface modification layer according to claim 1, wherein the electrode rod has a length of greater than 5cm and a diameter of 0.5-1.5cm after processing.
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