CN106676494A - Method capable of improving corrosion resistance of nickel-aluminium bronze - Google Patents
Method capable of improving corrosion resistance of nickel-aluminium bronze Download PDFInfo
- Publication number
- CN106676494A CN106676494A CN201710035967.7A CN201710035967A CN106676494A CN 106676494 A CN106676494 A CN 106676494A CN 201710035967 A CN201710035967 A CN 201710035967A CN 106676494 A CN106676494 A CN 106676494A
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- China
- Prior art keywords
- nickel
- corrosion
- aluminum bronze
- aluminium bronze
- corrosion resistance
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
Abstract
The invention provides a method capable of improving the corrosion resistance of nickel-aluminium bronze. The method comprises the following steps: carrying out surface polishing on the nickel-aluminium bronze, then cleaning, and carrying out ion implantation at a voltage of 30-40kV and a current of 1-2mA to form a corrosion-resistant layer on the surface of the nickel-aluminium bronze. Compared with the prior art, the method has the following beneficial effects: 1. a modification effect is obvious, and the phase-selection corrosion of the nickel-aluminium bronze can be effectively suppressed; 2. the surface material of the nickel-aluminium bronze is directly modified, the corrosion-resistant layer on the surface is combined with a matrix alloy by virtue of a chemical bond, and the problem of a bonding force has no need to be considered; 3. the types and contents of the implanted metal ions can be accurately controlled to realize regulation and control on the components and thickness of the corrosion-resistant layer; 4. high temperature is not needed during the ion implantation process, and the phase change of the internal structure of the nickel-aluminium bronze is avoided, so that the mechanical property is not sacrificed while the corrosion resistance is improved; and 5. the deformation of a workpiece and the change of the dimensions are avoided.
Description
Technical field
The present invention relates to a kind of method for improving nickel-aluminum bronze corrosion resistance, belongs to technical field of surface.
Background technology
Good decay resistance and high mechanical performance that nickel-aluminum bronze (NAB) alloy has because of it and extensively should
In for marine environment, such as seawater pipeline, naval vessel valve and offshore drilling platform equipment.As cast condition nickel-aluminum bronze tissue is more multiple
It is miscellaneous, mainly including thick copper-rich α phase, retained martensitic β ' phases and intermetallic compound κ phases (κ I, κ II, κ III, κ IV).By
In each difference in chemical composition and structure, cause the difference of each phase corrosion behavior, so as to sending out of causing phase selection to corrode
It is raw.Research finds, in neutral corrosive medium, α phases of the β ' mutually and in eutectoid structure α+κ III is corroded at first, causes material
The failure of material.Additionally, as cast condition nickel-aluminum bronze has the defects such as component segregation, coarse grains, tissue looseness, in high corrosion, height
The phenomenons such as corrosion fatigue and spot corrosion are susceptible under secondary alternate load marine environment, the service life of material is greatly reduced, are limited
Make the development of mankind's Activities of Ocean.
At present, the method for improving nickel-aluminum bronze material corrosion resisting property mainly has mixing yoghurt, thermal spraying, surface
Laser melting coating and heat treatment etc..But the above processing method is often existed, and treatment temperature is higher, residual stress is excessive, cannot
A series of problems, such as avoiding phase selection from corroding.
Cr is often added in various alloys as a kind of corrosion resistance element, but due to the difference of element fusing point, it is difficult to
During nickel-aluminum bronze material is added it in smelting process.Ion implantation technique is metal watch will to be injected into after acceleration of ions
Face, injects ion not by spreading and solid solubility is affected, it is possible to obtain excellent modified effect.The present invention adopts ion implanting
Technology forms method of the rich Cr anticorrosion layers to improve the corrosion resisting property of material on nickel-aluminum bronze surface, there is presently no report.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of method of raising nickel-aluminum bronze corrosion resistance.
The present invention is achieved by the following technical solutions：
The invention provides a kind of method for improving nickel-aluminum bronze corrosion resistance, it comprises the steps：
Nickel-aluminum bronze is carried out after the polishing of surface, to clean up, voltage in 30~40kV, is carried out under the electric current of 1~2mA
Ion implanting, on the surface of the nickel-aluminum bronze anti-corrosion layer is formed.
Preferably, the dosage of the ion implanting is every square centimeter 1 × 1016~5 × 1017。
Preferably, the nickel-aluminum bronze for vacuum melting cast alloy, composition be the aluminum of 9~12wt%, 2~
The nickel of 6wt%, the ferrum of 3~6wt%, the manganese of 1~2wt%, balance of copper.
Preferably, the thickness of the anti-corrosion layer is 40~100nm, and injection element is high in class in anti-corrosion layer
This distribution.
Preferably, the injection element is Cr.
Compared with prior art, the present invention has following beneficial effect：
1st, modified effect substantially, can effectively suppress the generation of nickel-aluminum bronze phase selection corrosion；
2nd, directly nickel-aluminum bronze surfacing is modified, is chemical bonds between surface corrosion resistance layer and matrix alloy,
Adhesion problem need not be considered；
3rd, it is capable of the species and content of precise control injection metal ion, realizes the regulation and control to anti-corrosion composition of layer and thickness；
4th, without the need for high temperature in ion implantation process, the phase transformation of nickel-aluminum bronze interior tissue will not be caused, improves corrosion resisting property
While do not sacrifice its mechanical performance；
5th, the deformation of workpiece and the change of size are not result in.
Description of the drawings
The detailed description by reading non-limiting example made with reference to the following drawings, the further feature of the present invention,
Objects and advantages will become more apparent upon：
Fig. 1 is each element content inside the implanted layer of one embodiment of the invention with the change picture of injection depth；
Fig. 2 exists for the as cast condition nickel-aluminum bronze of the embodiment of the present invention with the nickel-aluminum bronze after injection various dose Cr ion
Polarization curve comparison diagram in 3.5%NaCl solution；
Fig. 3 exists for the as cast condition nickel-aluminum bronze of the embodiment of the present invention with the nickel-aluminum bronze after injection various dose Cr ion
Electrochemical impedance spectroscopy curve comparison figure in 3.5%NaCl solution；
Fig. 4 is the nickel-aluminum bronze salt fog reality after the as cast condition nickel-aluminum bronze and injection various dose Cr ion of the embodiment of the present invention
Test front and rear surfaces photomacrograph comparison diagram.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some deformations and improvement can also be made.These belong to the present invention
Protection domain.
Embodiment 1
This example is related to a kind of method that ion implanting improves nickel-aluminum bronze corrosion resisting property, and methods described includes following step
Suddenly：
Step one：As cast condition nickel-aluminum bronze surface successively Jing 400# -800# -1200# -2000# waterproof abrasive papers machinery is beaten
Mill, is then polished to minute surface with 0.5 μm of diamond paste.Sample is put in into ultrasound 15min in alcoholic solution, subsequently
Deionized water is rinsed well, and cold wind is standby after drying up；
Step 2：The nickel-aluminum bronze sample handled well is placed in ion implantation apparatuses vacuum chamber, with 40kV voltages, 1mA beams
By Cr ion implantings to specimen surface, implantation dosage is 1 × 10 to stream16ion/cm2。
Embodiment 2
This example is related to a kind of method that ion implanting improves nickel-aluminum bronze corrosion resisting property, and methods described includes following step
Suddenly：
Step one：As cast condition nickel-aluminum bronze surface successively Jing 400# -800# -1200# -2000# waterproof abrasive papers machinery is beaten
Mill, is then polished to minute surface with 0.5 μm of diamond paste.Sample is put in into ultrasound 15min in alcoholic solution, subsequently
Deionized water is rinsed well, and cold wind is standby after drying up；
Step 2：The nickel-aluminum bronze sample handled well is placed in ion implantation apparatuses vacuum chamber, with 30kV voltages, 2mA beams
By Cr ion implantings to specimen surface, implantation dosage is 5 × 10 to stream17ion/cm2。
Embodiment 2 provides the test data to the modified anticorrosion layer inner element distribution in surface.With Auger electron spectroscopy to resistance to
Erosion layer carries out depth profiling, and each element content is as shown in Figure 1 with the change of injection depth.Understand that injection depth is about 100nm,
Cr is in class Gaussian Profile, and peak value is reached at 40nm.
Using CHI660E electrochemical workstations, to as cast condition nickel-aluminum bronze and injected not respectively using standard three electrode system
(include Cr+, Cr with dosage Cr ions2+,Cr3+And Cr4+In one or more valence states) (1 × 1016ion/cm2；5×
1017ion/cm2) nickel-aluminum bronze material electrochemical corrosion performance test, polarization curve pair are carried out in 3.5wt%NaCl solution
Than result as shown in Fig. 2 electrochemical impedance spectroscopy comparing result is as shown in Figure 3.
Nickel-aluminum bronze sample after as cast condition nickel-aluminum bronze and injection Cr is put in the lump 12 days in salt fog cabinet, is observed and is recorded
Specimen surface situation of change, as shown in Figure 4.
(a-as cast condition NAB；B-injection 1 × 1016ion/cm2Cr；C-injection 5 × 1017ion/cm2Cr；Before i-1-salt fog
Initial pattern；I-2-salt fog pattern, i=a, b, c after 12 days)
As cast condition NAB, injection 1 × 1016ion/cm2The NAB of Cr and injection 5 × 1017ion/cm2Before the NAB salt fogs of Cr just
Primary state pattern is respectively as shown in Fig. 4 a-1,4b-1 and 4c-1.Understand that the change of NAB surfaces is little after injection Cr, color from yellow by
Fade to silvery white.Salt fog after 12 days surface topography respectively as shown in Fig. 4 a-2,4b-2 and 4c-2：After the salt air corrosion of as cast condition NAB
Surface covers one layer of yellow product, and has green corrosion thing to occur, and corrodes the most serious；Injection 1 × 1016ion/cm2The NAB of Cr
One layer of brown corrosion product of Surface Creation；And inject 5 × 1017ion/cm2The NAB surfaces of Cr still remain original silvery white
Color, only fragmentary yellow product occurs, and there occurs slight corrosion.As can be seen here, the corrosion resistance that Cr improves NAB is injected
Can, and implantation dosage is 5 × 1017ion/cm2NAB corrosion resisting properties it is best.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can within the scope of the claims make various modifications or modification, this not shadow
Ring the flesh and blood of the present invention.
Claims (5)
1. it is a kind of improve nickel-aluminum bronze corrosion resistance method, it is characterised in that comprise the steps：
Nickel-aluminum bronze is carried out after the polishing of surface, to clean up, voltage in 30~40kV, ion is carried out under the electric current of 1~2mA
Injection, on the surface of the nickel-aluminum bronze anti-corrosion layer is formed.
2. the method for improving nickel-aluminum bronze corrosion resistance as claimed in claim 1, it is characterised in that the agent of the ion implanting
Measure as every square centimeter 1 × 1016~5 × 1017。
3. the method for improving nickel-aluminum bronze corrosion resistance as claimed in claim 1, it is characterised in that the nickel-aluminum bronze is true
The cast alloy of empty melting, composition is the aluminum of 9~12wt%, the nickel of 2~6wt%, the ferrum of 3~6wt%, the manganese of 1~2wt%,
Balance of copper.
4. the method for improving nickel-aluminum bronze corrosion resistance as claimed in claim 1, it is characterised in that the thickness of the anti-corrosion layer
Spend for 40~100nm, injection element is in class Gaussian Profile in anti-corrosion layer.
5. the as claimed in claim 4 method for improving nickel-aluminum bronze corrosion resistance, it is characterised in that the injection element is
Cr。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710035967.7A CN106676494A (en) | 2017-01-18 | 2017-01-18 | Method capable of improving corrosion resistance of nickel-aluminium bronze |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710035967.7A CN106676494A (en) | 2017-01-18 | 2017-01-18 | Method capable of improving corrosion resistance of nickel-aluminium bronze |
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| CN106676494A true CN106676494A (en) | 2017-05-17 |
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| CN201710035967.7A Pending CN106676494A (en) | 2017-01-18 | 2017-01-18 | Method capable of improving corrosion resistance of nickel-aluminium bronze |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396690A (en) * | 2019-08-08 | 2019-11-01 | 湘潭大学 | A kind of nickel-aluminum bronze surface laser cladding amorphous composite coating and preparation method thereof |
| CN111468817A (en) * | 2020-04-15 | 2020-07-31 | 河海大学常州校区 | Preparation method of high-manganese aluminum bronze surface friction stir processing modified layer |
| CN112518241A (en) * | 2020-11-19 | 2021-03-19 | 山东科技大学 | Preparation method and application of nickel-aluminum bronze/zinc-based nano composite material |
| CN113707526A (en) * | 2020-05-20 | 2021-11-26 | 中微半导体设备(上海)股份有限公司 | Component, method for forming plasma-resistant coating and plasma reaction device |
| CN114318196A (en) * | 2021-12-27 | 2022-04-12 | 清华大学深圳国际研究生院 | Method for improving cavitation corrosion resistance of nickel-aluminum bronze workpiece |
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| US4863810A (en) * | 1987-09-21 | 1989-09-05 | Universal Energy Systems, Inc. | Corrosion resistant amorphous metallic coatings |
| CN104357708A (en) * | 2014-11-12 | 2015-02-18 | 中船重工西安东仪科工集团有限公司 | Environment-friendly safe melting process method of high-performance nickel-aluminum bronze |
| CN104862522A (en) * | 2015-04-24 | 2015-08-26 | 中国科学院宁波材料技术与工程研究所 | Nickel-aluminum bronze alloy and preparation method thereof |
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2017
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| US4863810A (en) * | 1987-09-21 | 1989-09-05 | Universal Energy Systems, Inc. | Corrosion resistant amorphous metallic coatings |
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| CN104862522A (en) * | 2015-04-24 | 2015-08-26 | 中国科学院宁波材料技术与工程研究所 | Nickel-aluminum bronze alloy and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396690A (en) * | 2019-08-08 | 2019-11-01 | 湘潭大学 | A kind of nickel-aluminum bronze surface laser cladding amorphous composite coating and preparation method thereof |
| CN111468817A (en) * | 2020-04-15 | 2020-07-31 | 河海大学常州校区 | Preparation method of high-manganese aluminum bronze surface friction stir processing modified layer |
| CN113707526A (en) * | 2020-05-20 | 2021-11-26 | 中微半导体设备(上海)股份有限公司 | Component, method for forming plasma-resistant coating and plasma reaction device |
| CN112518241A (en) * | 2020-11-19 | 2021-03-19 | 山东科技大学 | Preparation method and application of nickel-aluminum bronze/zinc-based nano composite material |
| CN114318196A (en) * | 2021-12-27 | 2022-04-12 | 清华大学深圳国际研究生院 | Method for improving cavitation corrosion resistance of nickel-aluminum bronze workpiece |
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