CN106835015B - The method that a kind of pair of metallic cerium surface is modified - Google Patents
The method that a kind of pair of metallic cerium surface is modified Download PDFInfo
- Publication number
- CN106835015B CN106835015B CN201710047335.2A CN201710047335A CN106835015B CN 106835015 B CN106835015 B CN 106835015B CN 201710047335 A CN201710047335 A CN 201710047335A CN 106835015 B CN106835015 B CN 106835015B
- Authority
- CN
- China
- Prior art keywords
- cerium
- coating
- metallic
- metallic cerium
- titanium nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- 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
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/46—Sputtering by ion beam produced by an external ion source
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
Abstract
The method that a kind of pair of metallic cerium surface is modified belongs to rare earth metal corrosion protection technology field.This method utilizes Dual ion beam sputtering deposition system, argon ion sputtering cleaning is carried out first on the metallic cerium surface of sanding and polishing, then it carries out nitridation reaction sputter process and generates cerium nitride coating, finally directly sputtered with ceramic target such as titanium nitride again, titanium nitride ceramic coating is generated, finally the double-deck coating compound in cerium surface formation cerium nitride and titanium nitride.By carrying out nitrogen treatment and cvd nitride titanium coating to metallic cerium, the anti-aging corrosive nature of metallic cerium is remarkably reinforced, shown by electrochemical tests test, metallic cerium corrosion electric current density can reduce about 5 times before and after the processing, cerium nitride and titanium nitride coating are golden yellow coating simultaneously, to increase the surface aesthetic effects of metallic cerium.
Description
Technical field
The method more particularly to a kind of metallic cerium being modified the present invention relates to a kind of pair of metallic cerium surface it is surfaces nitrided and
The method that coating film treatment improves its anti-aging corrosive nature belongs to rare earth metal corrosion protection technology field.
Background technique
Metallic cerium is commonly used for reducing agent, catalyst and alloy addition, in the modern times as a kind of important rare earth element
There is important and extensive purposes in industry.
But since metallic cerium chemical property is very active, it is easy to oxidation corrosion at room temperature, in atmospheric conditions very
It can tarnish and aging fastly, to influence its metallic character and appearance quality.It mainly takes at present and metallic cerium is carried out
The closed and mode stored in shady and cool or kerosene medium is passively to slow down the oxidation corrosion of metallic cerium, but these methods are to gas
Close property requires height, is easy to pollute metallic cerium, and storage effect is unsatisfactory, metallic cerium still can occur more serious
Oxidation corrosion.
Summary of the invention
The object of the present invention is to provide the methods that a kind of pair of metallic cerium surface is modified, by carrying out on metallic cerium surface
Nitridation and coating film treatment make it effectively improve the anti-aging corrosive nature of metallic cerium, and increase metallic cerium surface aesthetic effects, from
And further expansion its application range.
In order to achieve the above object, the technical solution adopted by the present invention is that:
The method that a kind of pair of metallic cerium surface is modified, it is characterised in that this method carries out as follows:
1) Dual ion beam sputtering deposition system is used, it is clear to carry out argon ion sputtering using metallic cerium surface of the auxiliary source to polishing
It washes, system operating pressure is 0.8 × 10-2Pa~1.0 × 10-2Pa;
2) main source and auxiliary source are opened simultaneously, and main source uses argon ion, and argon flow is 6sccm~8sccm, and auxiliary source uses nitrogen
Ion, nitrogen flow are 4sccm~5sccm, carry out reactive sputtering nitrogen treatment to the metallic cerium after cleaning, form one layer of nitridation
Cerium coating, system operating pressure are 1.0 × 10-2Pa~2.3 × 10-2Pa;
3) under conditions of double-ion beam system does not open vacuum chamber, automatic rotary target platform is to titanium nitride ceramic target
Operating pressure of uniting control is 1.0 × 10-2Pa~2.3 × 10-2Pa carries out titanium nitride coating sputtering sedimentation, makes on cerium nitride coating
Face re-forms one layer of titanium nitride coating, finally the double-deck coating compound in metallic cerium surface one layer of cerium nitride of formation and titanium nitride.
In above-mentioned technical proposal, when carrying out argon ion sputtering cleaning, argon ion energy is 500eV~700eV, ar-ion beam
Stream is 30mA~70mA.
Preferably, in reactive sputtering nitrogen treatment, main source argon ion energy is 2000eV~2700eV, line 60mA
~90mA, auxiliary source Nitrogen ion energy is 400eV~500eV, line is 25mA~45mA.
Preferably, the cerium nitride thickness of coating of generation is 0.8 μm~1 μ m, and titanium nitride coating is with a thickness of 200nm-
500nm。
The present invention has the following advantages that and the technical effect of high-lighting: by carrying out nitrogen treatment and deposition nitrogen to metallic cerium
Change titanium coating, the anti-aging corrosive nature of metallic cerium is remarkably reinforced, and shows metal before and after the processing by electrochemical tests test
Cerium corrosion electric current density can reduce about 5 times, while cerium nitride and titanium nitride coating are golden yellow coating, to increase metal
The surface aesthetic effects of cerium.
Detailed description of the invention
Fig. 1 is double-ion beam reactive sputtering cerium nitride and sputtering sedimentation titanium nitride system schematic.
In Fig. 1: the main source 1-;The auxiliary source 2-;3- sample;4- target platform
Fig. 2 is the cerium nitride coating XRD spectra that reactive sputtering of the present invention generates.
Fig. 3 is the titanium nitride coating XRD spectra that sputtering sedimentation of the present invention generates.
Fig. 4 a is the surface electromicroscopic photograph after the rigid sanding and polishing of metallic cerium;Fig. 4 b is same metallic cerium sample in big gas bar
Electromicroscopic photograph after being stored 5 days under part.
Fig. 5 is metallic cerium through inventive method electrochemical corrosion polarization curve spectrogram before and after the processing.
Curve (a) is treated sample in Fig. 5;Curve (b) is untreated metallic cerium.
Specific embodiment
The technical solutions of the present invention will be further described in the following with reference to the drawings and specific embodiments.
The method that a kind of pair of metallic cerium surface provided by the invention is modified is to utilize Dual ion beam sputtering deposition system
(as shown in Figure 1) carries out argon ion sputtering cleaning on the metallic cerium surface of sanding and polishing first, then carries out nitridation reaction sputtering
Processing generates cerium nitride coating, is finally directly sputtered with ceramic target such as titanium nitride again, generates titanium nitride ceramic coating, most
Cerium nitride/titanium nitride two-layer compound coating is formed on cerium surface eventually, to greatly improve the aging corrosive nature of metallic cerium.To
The method for improving metallic cerium corrosion resistance.
It specifically comprises the following steps:
1) Dual ion beam sputtering deposition system is used, it is clear to carry out argon ion sputtering using metallic cerium surface of the auxiliary source to polishing
It washes, system operating pressure is 0.8 × 10-2Pa~1.0 × 10-2Pa;When carrying out argon ion sputtering cleaning, argon ion energy is
500eV~700eV, argon ion line are 30mA~70mA;
2) main source and auxiliary source are opened simultaneously, and main source uses argon ion, and argon flow is 6sccm~8sccm, and auxiliary source uses nitrogen
Ion, nitrogen flow are 4sccm~5sccm, carry out reactive sputtering nitrogen treatment to the metallic cerium after cleaning, form one layer of nitridation
Cerium coating, system operating pressure are 1.0 × 10-2Pa~2.3 × 10-2Pa;The cerium nitride thickness of coating is preferably 0.8 μm~1 μm
Range, main source argon ion energy is generally 2000eV~2700eV, line is 60mA~90mA;Auxiliary source Nitrogen ion energy is generally
400eV~500eV, line are 25mA~45mA.
3) under conditions of double-ion beam system does not open vacuum chamber, automatic rotary target platform is to titanium nitride ceramic target
Operating pressure of uniting control is 1.0 × 10-2Pa~2.3 × 10-2Pa carries out titanium nitride coating sputtering sedimentation, makes on cerium nitride coating
Face re-forms one layer of titanium nitride coating, and titanium nitride coating thickness is preferably 200nm-500nm, is finally formed on metallic cerium surface
Cerium nitride and the compound double-deck coating of titanium nitride.
To make it is further understood that the present invention, will be described in detail by following embodiment.
Embodiment 1
1) polishing, polishing and the metallic cerium sample (10mm × 10mm × 3mm) being cleaned by ultrasonic are immediately placed on double ion
In the vacuum chamber of beam sputter-deposition system on chip bench, closes chamber and vacuumized;
2) base vacuum reaches 8.5 × 10-5After Pa, auxiliary source is passed through argon gas, flow 5sccm, and working gas pressure is 0.9
×10-2Pa, source ion energy 600eV (electron volts), line 35mA supplemented by running parameter carry out sputter clean to metallic cerium sample
15 minutes, stop auxiliary source later;
3) main source leads to argon gas, flow 7sccm, and working gas pressure is 1.5 × 10-2Pa, running parameter are argon ion energy
2500eV, line 80mA are measured, the high pure metal cerium target good to preparatory grinding and buffing carries out sputter clean, is that reactive sputtering is quasi-
Standby, cleaning stopped main source after 15 minutes;
4) auxiliary source leads to nitrogen, flow 5sccm, Nitrogen ion energy 500eV, line 35mA;Main source leads to argon gas, and flow is
7sccm, argon ion energy 2500eV, line 70mA, working gas pressure is 2.2 × 10-2Pa is carried out at reactive sputtering nitridation
Reason, forms certain thickness cerium nitride coating;
5) under conditions of not opening system vacuum chamber, the high-purity cerium target of automatic control type rotating is pressed to high purity silicon nitride titanium target
According to step
4) parameter is finally formed on metallic cerium surface again in the titanium nitride coating of cerium nitride surface sputtering sedimentation 200nm
Cerium nitride/
Titanium nitride two-layer compound coating.
Metallic cerium is not processed by the invention it can be seen from Fig. 4 a and 4b, stored in atmospheric conditions after polishing 1 hour and
5 days, cosmetic variation was obvious, the metallic cerium surface oxidation seriously corroded after 5 days.And it is treated by the present method after metallic cerium storage
5 days, corrosion phenomenon did not occurred for surface, and treated sample surfaces present golden yellow, increase the aesthetics of metallic cerium.
For the validity for further proving the invention, electrochemistry electrokinetic potential has been carried out before and after the processing through the invention to metallic cerium
Polarization curve test, as shown in figure 5, curve (a) is test result after metallic cerium is processed by the invention, it is (b) without the present invention
The metallic cerium test result of processing, it can be seen that by the present invention processing obvious polarization of post-etching current potential, obtain corruption through over-fitting
Erosion current density is shown in Table 1, and corrosion electric current density is reduced to 0.198 μ A by 0.986 μ A, is reduced about 5 times, is shown that its is anticorrosive
Performance greatly improves.
1 electrochemical tests fitting result of table
Claims (4)
1. the method that a kind of pair of metallic cerium surface is modified, it is characterised in that this method carries out as follows:
1) Dual ion beam sputtering deposition system is used, carries out argon ion sputtering cleaning using metallic cerium surface of the auxiliary source to polishing,
System operating pressure is 0.8 × 10-2Pa~1.0 × 10-2Pa;
2) main source and auxiliary source are opened simultaneously, main source uses argon ion, and argon flow is 6sccm~8sccm, auxiliary source using nitrogen from
Son, nitrogen flow are 4sccm~5sccm, carry out reactive sputtering nitrogen treatment to the metallic cerium after cleaning, form one layer of cerium nitride
Coating, system operating pressure are 1.0 × 10-2Pa~2.3 × 10-2Pa;
3) under conditions of double-ion beam system does not open vacuum chamber, automatic rotary target platform to titanium nitride ceramic target, system work
Make pressure control 1.0 × 10-2Pa~2.3 × 10-2Pa carries out titanium nitride coating sputtering sedimentation, makes above cerium nitride coating again
One layer of titanium nitride coating is formed, finally the double-deck coating compound in metallic cerium surface formation cerium nitride and titanium nitride.
2. the method that a kind of pair of metallic cerium surface according to claim 1 is modified, it is characterised in that: carry out argon ion
When sputter clean, argon ion energy is 500eV~700eV, and argon ion line is 30mA~70mA.
3. the method that a kind of pair of metallic cerium surface according to claim 1 or 2 is modified, it is characterised in that: main source argon
Ion energy is 2000eV~2700eV, line is 60mA~90mA, and auxiliary source Nitrogen ion energy is 400eV~500eV, line is
25mA~45mA.
4. the method that a kind of pair of metallic cerium surface according to claim 3 is modified, it is characterised in that: the nitridation of generation
Cerium thickness of coating is 0.8 μm~1 μ m, and titanium nitride coating is with a thickness of 200nm-500nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710047335.2A CN106835015B (en) | 2017-01-22 | 2017-01-22 | The method that a kind of pair of metallic cerium surface is modified |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710047335.2A CN106835015B (en) | 2017-01-22 | 2017-01-22 | The method that a kind of pair of metallic cerium surface is modified |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106835015A CN106835015A (en) | 2017-06-13 |
CN106835015B true CN106835015B (en) | 2019-07-12 |
Family
ID=59119362
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710047335.2A Active CN106835015B (en) | 2017-01-22 | 2017-01-22 | The method that a kind of pair of metallic cerium surface is modified |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106835015B (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104087902A (en) * | 2014-07-09 | 2014-10-08 | 南京信息工程大学 | Insulating coating on surface of metal material and preparation method of insulating coating |
-
2017
- 2017-01-22 CN CN201710047335.2A patent/CN106835015B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104087902A (en) * | 2014-07-09 | 2014-10-08 | 南京信息工程大学 | Insulating coating on surface of metal material and preparation method of insulating coating |
Non-Patent Citations (1)
Title |
---|
Compressibility and structural stability of CeN from experiment and theory. The;J. Staun Olsena等;《Journal of Alloys and Compounds》;20120417(第533期);第29-32页 |
Also Published As
Publication number | Publication date |
---|---|
CN106835015A (en) | 2017-06-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4685364B2 (en) | Method for depositing a crystalline α-Al 2 O 3 layer | |
CN103014599B (en) | Treatment process of composite surface of austenitic stainless steel | |
CN111441025B (en) | Corrosion-resistant high-entropy alloy film, preparation method and application thereof in seawater environment | |
CN103522627A (en) | Composite coating on surface of valve sealing piece and preparation method for composite coating | |
CN111647851A (en) | Zr-B-N nano composite coating with high hardness and high toughness and preparation method thereof | |
TW201239120A (en) | Housing and method for making same | |
CN106835015B (en) | The method that a kind of pair of metallic cerium surface is modified | |
CN113046703B (en) | High-hardness nano composite coating and preparation method and application thereof | |
CN110257771A (en) | A kind of c-CrAlSiN hard coat of high Al content and preparation method thereof | |
CN101800178A (en) | Preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric | |
CN104087902A (en) | Insulating coating on surface of metal material and preparation method of insulating coating | |
CN105970170B (en) | The method of hafnium/silicon nitride conduction and anti-corrosion multilayered structure coating is prepared on magnesium alloy | |
CN110714182A (en) | Chromium nitride coating, preparation method and application thereof | |
CN101445906A (en) | Method for preparing platinum coating layers on the surfaces of titanium and titanium alloy | |
CN111471973A (en) | Process for preparing Zr-B-N nano composite coating in reducing atmosphere | |
CN102400097A (en) | Shell and manufacturing method thereof | |
CN106011763A (en) | Method for preparing hafnium/silicon nitride conductive and anti-corrosion nano-composite coating on magnesium alloy | |
CN112301400B (en) | Preparation method of hard protection micro-arc oxidation film layer on surface of titanium alloy ball valve | |
JP5327534B2 (en) | Surface coated cutting tool with excellent chipping resistance and peeling resistance of hard coating layer | |
CN110886001A (en) | Method for effectively improving stress corrosion resistance of titanium alloy | |
CN111500990A (en) | Zr-Ti-B-N nano composite coating and preparation method thereof | |
CN111235570B (en) | Preparing Si/Si-containing on the surface of a substrate x N y Gradient modified membranes and methods | |
CN116145077B (en) | Ion nitriding method for PVD (physical vapor deposition) pre-precipitation and composite coating | |
US11339464B2 (en) | Plasma nitriding with PECVD coatings using hollow cathode ion immersion technology | |
CN110257789B (en) | high-Al-content c-TiAlSiN hard coating and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |