CN101070592A - Composite ion-injection surface modification method for copper and its alloy - Google Patents
Composite ion-injection surface modification method for copper and its alloy Download PDFInfo
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- CN101070592A CN101070592A CN 200710041967 CN200710041967A CN101070592A CN 101070592 A CN101070592 A CN 101070592A CN 200710041967 CN200710041967 CN 200710041967 CN 200710041967 A CN200710041967 A CN 200710041967A CN 101070592 A CN101070592 A CN 101070592A
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- copper
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Abstract
The invention relates to a surface modified method for composite ion infusion of copper and its alloy in the area of material technology. Firstly, the copper or the copper alloy surface is grinded, and is polished to 1200#-1500#. Then the deionized water and organic liquid are used to ablution the surface of sample, after drying spare. Composite ion infusion technology is adopted to infuse copper and its alloy into the equipment of ion implantation compound coating, which can realize simultaneously infusion the nonmetallic element and the metallic element to the surface of copper and its alloy. For high energy ion infusion into copper and its alloy surface at very high speed, causes its surface to have many point defects and line defects are yielded in the surface of copper and its alloy. These defects can strengthen the surface of material surface, enhance its degree of hardness, and improve its wear-resisting performance. It also can remarkably reduce adsorptive capacity of oxygen in the surface of copper and its alloy, or form a slice of compact oxidized protective film in its surface, and thus enhance the anti-oxygenic properties and the corrosion-resisting properties of copper and its alloy.
Description
Technical field
What the present invention relates to is a kind of method of metallic substance technical field, specifically is the method for the composite ion-injection surface modification of a kind of copper and alloy thereof.
Background technology
Copper is a kind of ancient and young nonferrous materials, and along with the superpower anti-microbial property of copper product is familiar with by people, and people improve with standard of living and enhanced health perception day by day, and the range of application of copper is also more extensive.At present existing a lot of bibliographical informations, copper and alloy thereof have extremely strong antibiotic, bacteria resistance function.Can reach 99.99% as bacteriostasis rate, outclass appliance water material commonly used streptococcus aureus, dust Xi Shi intestinal bacteria, Pseudomonas aeruginosa and Candida albicans etc.Copper and alloy thereof are except being extensive use of in traditional field such as electric power, cool-heat-exchanger, military project and artwork at present, and copper handle, copper lock, copper tap, water pipe, copper cooker etc. are also very universal in daily living article; For preventing that related productss such as copper antimicrobial laundry machine that " secondary pollution " research and develop and produce, inner tube of water bowl from also having begun to come into the market.But the wear resistance of most brass works is relatively poor, easy oxidation discoloration, and perishable in the environment that the nitric acid of ammonia, oxidisability and sulfuric acid exist, often be difficult to satisfy service requirements.With the red copper is example, although it is antibiotic, bacteriostasis is the strongest, its intensity, hardness are all very low, and perishable.
Through discovery to the prior art literature search; the Chinese invention patent publication number is: CN1616715A; contriver: people such as Xu Qunjie, Zhou Yang; patent name: " copper inhibitor "; this patent disclosure a kind of copper inhibitor; the erosion rate of copper is effectively controlled, and its mechanism is: inhibiter and copper acting in conjunction generate one deck passivation protection film on the surface of copper.But its defective is: although method that this patent proposed and reagent can slow down the corrosion of copper, can't obviously improve the hardness and the wear resistance on the surface of copper, and the low strength of copper has limited its broader applications to a great extent just.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the method for the composite ion-injection surface modification of a kind of copper and alloy thereof is provided.Employing is injected the method for other metals and non-metallic element at copper and alloy surface thereof, mechanical properties such as its intensity and hardness is significantly improved, and improves its corrosion resistance nature.
The present invention is achieved through the following technical solutions, and the present invention specifically comprises the steps:
Step 1: at first copper or copper alloy surface are ground, and be polished to 1200#-1500#, with deionized water and organic liquor sample surfaces is cleaned, the oven dry back is standby;
Step 2: adopt the compound ion injection technology, copper and alloy thereof are put into ion implantation composite coating equipment, be implemented in copper and alloy surface thereof and inject non-metallic element and metallic element simultaneously.
In the step 1, described organic liquor is meant: dehydrated alcohol or anhydrous propanone.
In the step 2, described compound ion injection technology, be meant: the steam of gas or metallic element is carried out ionization, and through high-voltage electric field be accelerated into have several ten thousand in addition millions of electron-volts of energy carry beam, inject workpiece surface, after with atom in the top layer nuclear collision, electronic impact and charge-exchange taking place constantly, its energy constantly reduces, and finally rests in the workpiece surface.The element kind, component proportions and even the weave construction that cause material surface after ion implantation change, and then aspect performances such as its physics, chemistry, mechanics and biomedicine are changed, thereby reach the purpose of material surface modifying.
Described compound ion injection technology, concrete steps are:
1). the vacuum chamber that copper after step 1 handled or copper alloy are put into ion implantation composite coating equipment, make up with mechanical pump and molecular pump that to pump it to vacuum tightness be 1 * 10
-3Pa～5 * 10
-3Pa;
2). the setting acceleration voltage is 30kV～70kV, and beam current density is 20 μ A/cm
2～40 μ A/cm
2
3). copper and alloy substrate thereof are carried out ion implantation, make implantation dosage be controlled at following scope: 1 * 10
17～6 * 10
17Ions/cm
2(number of ions/centimetre
2).
In the step 2, described injection non-metallic element is meant: N or B; Described injected with metallic elements is meant: Zn, Al or Ti metallic element.
Ion implantation composite coating equipment described in the step 2 of the present invention is the Chinese patent of CN1206386C referring to notification number.Its constructional feature is: gas ion source, metal ion source, magnetically controlled DC sputtering target source, six shared vacuum chambers in source such as middle frequency pulsed magnetron sputtering target source and two cover DC magnetic filtering arc ion plating sources, and be fixed on the shell of composite film coating machine, gas ion source vertically is positioned at the center on vacuum chamber top, metal ion source is positioned at a side of gas ion source, oblique cutting is in vacuum chamber top, magnetically controlled DC sputtering target source and medium frequency magnetron sputtering target source, two DC magnetic filtering arc ion plating sources then are distributed on two diagonal lines, and be positioned at position on the upper side, vacuum chamber both sides, the medullary ray in six sources converges in many with on the sample table workpiece, and vacuum-pumping system is connected with vacuum chamber.Its function: this equipment integrates the different materials process for modifying surface, except that can be used to material carry out ion implantation, also can be used for magnetron sputtering, also can be used for multi-arc ion plating film.
The present invention adopts ion-implanted surface-modified technology, inject element and other ion implantation technology parameters by optimized choice, under the prerequisite of the original anti-microbial property that guarantees copper and alloy thereof, both improved surface strength, hardness and the wear resistance of copper and alloy thereof, improve its corrosion resistance nature again.Among the present invention, the selection of ion implantation dosage and other injection technology parameters is very crucial, and this is because must significantly improve its intensity, hardness and antioxidant property under the prerequisite of the anti-microbial property that guarantees copper and alloy thereof.Among the present invention, inject ion and cause the lattice distortion on copper and copper alloy matrix surface, injecting ion and dislocation interacts, dislocation motion is obstructed, so can improve mechanical properties such as the intensity of copper and its metal and hardness on the other hand, inject element and can reduce the oxygen adsorptive capacity of copper and alloy surface thereof or form the oxide film of one deck densification on its surface, thus the further oxidation of copper and alloy thereof or the intrusion of corrosive medium can be hindered, thus improve its antioxidant property and corrosion resistance nature.
The present invention is by injecting N or B nonmetallic ion and Zn, Al or Ti metal ion at copper and alloy surface compound ion thereof, success realizes both having improved intensity, hardness and other mechanical property of copper and alloy thereof, improves the anti-oxidant and corrosion resistance nature of copper and alloy thereof again to a certain extent.Inject multiple element simultaneously at copper and alloy surface thereof, under the prerequisite of the excellent antibacterial that guarantees not reduce substantially copper and alloy thereof, bacteriostasis, improve its wear-resisting, anti-corrosion and antioxidant property effectively.Ion implantation is a kind of purified non-harmful material surface modifying new technology, compares with other sufacing, and its advantage richly endowed by nature aspect the feature of environmental protection is particularly attracted attention.Copper and alloy thereof after intermediate ion of the present invention injects mainly can be applicable to household appliances such as air-conditioning and washing machine, hygiene medical treatment industry and toy industry; For promoting copper anti-biotic material great significance.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
Present embodiment 1 is implemented under following implementation condition and technical requirements condition:
With purity is that 99.9% red copper is a matrix, injects nitrogen, zinc and titanium ion on its surface, and step is as follows:
(1) the red copper sample surfaces is polished to 1500# with SiC sand paper, cleans up with deionized water and dehydrated alcohol then, oven dry;
(2) the red copper matrix is put into the vacuum chamber of ion implanter, carried out nitrogen, zinc and titanium ion compound ion to its surface and inject, injection be injection zinc and titanium ion earlier in proper order, and the nitrogen ion reinjects.Its injection parameter is: vacuum tightness is 1 * 10
-3Pa;
The acceleration voltage of Zn and Ti is 30kV, and the Zn implantation dosage is 3 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density 35 μ A/cm
2, about 200 ℃ of target temperature; The Ti implantation dosage is 1 * 10
17Ions/cm
2, beam current density 35 μ A/cm
2, about 250 ℃ of target temperature;
The acceleration voltage of N is 65kV, and implantation dosage is 3 * 10
17Ions/cm
2, beam current density is 25 μ A/cm
2, about 300 ℃ of target temperature.
The control injection length makes the implantation dosage that reaches required, will inject sample then and keep 40min in vacuum chamber, takes out sample and gets final product.
Inject and improve about 3～5 times before back red copper hardness is injected; The wear resistance and the corrosion resisting property of sample all are significantly increased; Injecting the back is 95% to the Candida albicans sterilizing rate.
Embodiment 2:
Present embodiment 2 is implemented under following implementation condition and technical requirements condition:
With purity is that 99.9% red copper is a matrix, injects boron, aluminium and titanium ion on its surface, and step is as follows:
(1) the red copper sample surfaces is polished to 1500# with SiC sand paper, cleans up with deionized water and dehydrated alcohol then, oven dry;
(2) the red copper matrix is put into the vacuum chamber of ion implanter, carried out boron, aluminium and titanium ion compound ion to its surface and inject, injection be injection aluminium and titanium ion earlier in proper order, and the boron ion reinjects.Its injection parameter is: vacuum tightness is 5 * 10
-3Pa;
The acceleration voltage of Al and Ti is 45kV, and the Al implantation dosage is 6 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density 5 μ A/cm
2, about 250 ℃ of target temperature; The Ti implantation dosage is 2 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density 40 μ A/cm
2, about 250 ℃ of target temperature;
The acceleration voltage of B is 70kV, and implantation dosage is 1 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density is 25 μ A/cm
2, about 320 ℃ of target temperature.
The control injection length makes the implantation dosage that reaches required, will inject sample then and keep 30min in vacuum chamber, takes out sample and gets final product.
Inject and improve whole 5～8 times before back red copper hardness is injected, the wear resistance and the corrosion resistance nature of sample obviously improve; Inject the back streptococcus aureus, dust Xi Shi intestinal bacteria bacteriostasis rate are reached 96%.
Embodiment 3:
Present embodiment 3 is implemented under following implementation condition and technical requirements condition:
With H70 brass is matrix, injects nitrogen, aluminium and titanium ion on its surface, and step is as follows:
(1) the brass sample surfaces is polished to 1200# with SiC sand paper, cleans up with deionized water and acetone then, oven dry;
(2) brass base is put into the vacuum chamber of ion implanter, carried out nitrogen, aluminium and titanium compound ion to its surface and inject, injection is in proper order: inject aluminium and titanium ion earlier, the nitrogen ion reinjects.Its injection parameter is: vacuum tightness is 1 * 10
-3Pa;
The acceleration voltage of Ti and Al is 40kV, and the Al implantation dosage is 3 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density 25 μ A/cm
2, about 250 ℃ of target temperature; The Ti implantation dosage is 1 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density 35 μ A/cm
2, about 250 ℃ of target temperature;
The acceleration voltage of N is 65kV, and implantation dosage is 1 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density is 30 μ A/cm
2, about 350 ℃ of target temperature.
The control injection length makes the implantation dosage that reaches required, will inject sample then and keep 30min in vacuum chamber, takes out sample and gets final product.
Inject back brass hardness and improve 3～5 times before the injection, the wear resistance and the corrosion resistance nature of sample significantly improve, owing to inject the oxygen absorbed that the passivation layer of aluminium and titanium formation greatly reduces brass, so its antioxidant property obviously strengthens; Inject the back sample streptococcus aureus, dust Xi Shi intestinal bacteria bacteriostasis rate are reached 93%.
Embodiment 4:
Present embodiment 4 is implemented under following implementation condition and technical requirements condition:
With H70 brass is matrix, injects boron, aluminium and titanium ion on its surface, and step is as follows:
(1) the brass sample surfaces is polished to 1300# with SiC sand paper, cleans up with deionized water and acetone then, oven dry;
(2) brass base is put into the vacuum chamber of ion implanter, carried out boron, aluminium and titanium compound ion to its surface and inject, injection is in proper order: inject aluminium and titanium ion earlier, the boron ion reinjects.Its injection parameter is: vacuum tightness is 3 * 10
-3Pa;
The acceleration voltage of Ti and Al is 45kV, and the Al implantation dosage is 2 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density 35 μ A/cm
2, about 250 ℃ of target temperature; The implantation dosage of Ti is 1 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density 35 μ A/cm
2, about 250 ℃ of target temperature;
The acceleration voltage of B is 70kV, and implantation dosage is 3 * 10
17Ions/cm
2(number of ions/centimetre
2), beam current density is 35 μ A/cm
2, about 350 ℃ of target temperature.
The control injection length makes the implantation dosage that reaches required, will inject sample then and keep 30min in vacuum chamber, takes out sample and gets final product.
Inject and improve 3～5 times before back brass hardness is injected.Because the passivation layer that injects aluminium formation greatly reduces the oxygen absorbed of brass, so its antioxidant property obviously strengthens, the corrosion resistance nature of sample significantly improves.
Claims (7)
1. the method for the composite ion-injection surface modification of copper and alloy thereof is characterized in that, specifically comprises the steps:
Step 1: at first copper or copper alloy surface are ground, polish, with deionized water and organic liquor sample surfaces is cleaned, the oven dry back is standby;
Step 2: adopt the compound ion injection technology, copper and alloy thereof are put into ion implantation composite coating equipment, be implemented in copper and alloy surface thereof and inject non-metallic element and metallic element simultaneously.
2. the method for the composite ion-injection surface modification of copper as claimed in claim 1 and alloy thereof is characterized in that, in the step 1, described organic liquor is meant: dehydrated alcohol or anhydrous propanone.
3. the method for the composite ion-injection surface modification of copper as claimed in claim 1 and alloy thereof is characterized in that, in the step 1, described polishing is to 1200#-1500#.
4. the method for the composite ion-injection surface modification of copper as claimed in claim 1 and alloy thereof, it is characterized in that, in the step 2, described ion implantation technology is meant: the steam of gas or metallic element is carried out ionization, and be accelerated into a year beam through high-voltage electric field, inject workpiece surface, after atom generation nuclear collision, electronic impact and charge-exchange in the top layer, its energy constantly reduces, and finally rests in the workpiece surface.
5. as the method for the composite ion-injection surface modification of claim 1 or 4 described copper and alloy thereof, it is characterized in that, described compound ion injection technology, concrete steps are:
1). the vacuum chamber that copper after step 1 handled or copper alloy are put into ion implantation composite coating equipment, make up with mechanical pump and molecular pump that to pump it to vacuum tightness be 1 * 10
-3Pa～5 * 10
-3Pa;
2). the setting acceleration voltage is 30 kV～70kV, and beam current density is 20 μ A/cm
2～40 μ A/cm
2
3). copper and alloy substrate thereof are carried out ion implantation, make implantation dosage be controlled at 1 * 10
17Number of ions/centimetre
2～6 * 10
1Number of ions/centimetre
2In the scope.
6. the method for the composite ion-injection surface modification of copper as claimed in claim 1 and alloy thereof is characterized in that, in the step 2, described non-metallic element is meant: N or B.
7. the method for the composite ion-injection surface modification of copper as claimed in claim 1 and alloy thereof is characterized in that, in the step 2, described metallic element is meant: Zn, Al or Ti.
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|---|---|---|---|
| CN200710041967A CN101070592B (en) | 2007-06-14 | 2007-06-14 | Composite ion-injection surface modification method for copper and its alloy |
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|---|---|---|---|
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| CN102477526A (en) * | 2010-11-22 | 2012-05-30 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacture method thereof |
| CN103031523A (en) * | 2011-09-30 | 2013-04-10 | 先健科技(深圳)有限公司 | Preparation method of copper-bearing compound coating on metal component of medical device and medical device |
| CN103682366A (en) * | 2012-08-31 | 2014-03-26 | 海洋王照明科技股份有限公司 | Aluminum foil/carbon composite current collector, preparation method of current collector and lithium ion battery |
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| CN104342627A (en) * | 2014-09-25 | 2015-02-11 | 昆明理工大学 | Surface strengthening treatment method for pure copper material |
| CN114927632A (en) * | 2022-05-16 | 2022-08-19 | 湘潭大学 | Modified zinc metal sheet and preparation method and application thereof |
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Family Cites Families (3)
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| US6281127B1 (en) * | 1999-04-15 | 2001-08-28 | Taiwan Semiconductor Manufacturing Company | Self-passivation procedure for a copper damascene structure |
| CN1288072A (en) * | 1999-09-10 | 2001-03-21 | 北京辐射中心 | Technology for mfg. ion implantation by electrical contact metallic vapor cacuum arc source |
| CN1865493A (en) * | 2006-06-22 | 2006-11-22 | 武汉科技大学 | Process for preparing antibacterial stainless steel by using binary ion-implantation method |
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| CN102477526A (en) * | 2010-11-22 | 2012-05-30 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacture method thereof |
| CN102477526B (en) * | 2010-11-22 | 2015-02-04 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacture method thereof |
| CN103031523A (en) * | 2011-09-30 | 2013-04-10 | 先健科技(深圳)有限公司 | Preparation method of copper-bearing compound coating on metal component of medical device and medical device |
| CN103682366A (en) * | 2012-08-31 | 2014-03-26 | 海洋王照明科技股份有限公司 | Aluminum foil/carbon composite current collector, preparation method of current collector and lithium ion battery |
| CN103682366B (en) * | 2012-08-31 | 2016-12-21 | 海洋王照明科技股份有限公司 | Aluminium foil/carbon composite current collector, its preparation method and lithium ion battery |
| CN103928393A (en) * | 2013-01-10 | 2014-07-16 | 中芯国际集成电路制造(上海)有限公司 | Connecting piece and manufacturing method thereof |
| CN103928393B (en) * | 2013-01-10 | 2018-02-16 | 中芯国际集成电路制造(上海)有限公司 | Connector and its manufacture method |
| CN104342627A (en) * | 2014-09-25 | 2015-02-11 | 昆明理工大学 | Surface strengthening treatment method for pure copper material |
| CN114927632A (en) * | 2022-05-16 | 2022-08-19 | 湘潭大学 | Modified zinc metal sheet and preparation method and application thereof |
| CN114927632B (en) * | 2022-05-16 | 2024-01-26 | 湘潭大学 | Modified zinc metal sheet and preparation method and application thereof |
| CN115261812A (en) * | 2022-07-29 | 2022-11-01 | 北京科技大学 | Ion implantation surface modification method for Zn-Cu-Li ternary zinc alloy material |
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