CN116855941A - Marine environment corrosion-resistant diamond-like carbon coating and preparation method thereof - Google Patents
Marine environment corrosion-resistant diamond-like carbon coating and preparation method thereof Download PDFInfo
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- CN116855941A CN116855941A CN202310890721.3A CN202310890721A CN116855941A CN 116855941 A CN116855941 A CN 116855941A CN 202310890721 A CN202310890721 A CN 202310890721A CN 116855941 A CN116855941 A CN 116855941A
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- 238000000576 coating method Methods 0.000 title claims abstract description 86
- 239000011248 coating agent Substances 0.000 title claims abstract description 84
- 238000005260 corrosion Methods 0.000 title claims abstract description 63
- 230000007797 corrosion Effects 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052799 carbon Inorganic materials 0.000 title claims description 8
- 239000010410 layer Substances 0.000 claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 45
- 230000007704 transition Effects 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 39
- 239000011159 matrix material Substances 0.000 claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000002346 layers by function Substances 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims description 42
- 238000000151 deposition Methods 0.000 claims description 40
- 230000008021 deposition Effects 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 26
- 239000011651 chromium Substances 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000002344 surface layer Substances 0.000 claims description 13
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000009489 vacuum treatment Methods 0.000 claims description 4
- 239000013077 target material Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 239000007921 spray Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000006390 lc 2 Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001315 Tool steel Inorganic materials 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 101000686227 Homo sapiens Ras-related protein R-Ras2 Proteins 0.000 description 1
- 102100025003 Ras-related protein R-Ras2 Human genes 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
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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
- C23C14/06—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
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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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
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The embodiment of the application provides a marine environment corrosion-resistant diamond-like coating and a preparation method thereof, wherein the marine environment corrosion-resistant diamond-like coating comprises a nano metal bonding layer, a WC transition layer and a surface DLC functional layer which are alternately compounded by Cr-Ti, wherein the first surface of the nano metal bonding layer is in fit arrangement with the first surface of an alloy matrix, the second surface of the nano metal bonding layer is in fit arrangement with the first surface of the WC transition layer, and the second surface of the WC transition layer is in fit arrangement with the first surface of the surface DLC functional layer; the thickness range of the marine environment corrosion-resistant diamond-like coating is 3.0-6.0 mu m, so that the prepared marine environment corrosion-resistant diamond-like coating has higher corrosion resistance.
Description
Technical Field
The application relates to the technical field of coating preparation, in particular to a marine environment corrosion-resistant diamond-like coating and a preparation method thereof.
Background
With the continuous expansion of the development scale of the ocean, the ocean industry, including the offshore industry, the ocean channel, the artificial island and the wharf, the offshore oil platform, the submarine oil and gas transmission pipeline and the like, will be multiplied, and a large amount of metal and alloy materials are widely used. However, the marine environment is a very corrosive disaster environment, and corrosion of metal and alloy materials in the marine environment is unavoidable. In the prior art, the method for protecting the metal and alloy materials from corrosion in the marine environment generally adopts a common corrosion-resistant layer for protection, and the service lives of the metal and alloy materials are reduced because the common corrosion-resistant layer cannot permanently protect the metal and alloy materials.
Disclosure of Invention
The embodiment of the application provides a marine environment corrosion-resistant diamond-like coating and a preparation method thereof, which can enable the prepared marine environment corrosion-resistant diamond-like coating to have higher corrosion resistance.
A first aspect of an embodiment of the present application provides a marine corrosion-resistant diamond-like coating comprising a nano-metallic bond layer, a WC transition layer, and a surface DLC functional layer alternately composited of Cr-Ti, wherein,
the first surface of the nano metal bonding layer is in fit with the first surface of the alloy matrix, the second surface of the nano metal bonding layer is in fit with the first surface of the WC transition layer, and the second surface of the WC transition layer is in fit with the first surface of the surface DLC functional layer;
the thickness range of the marine environment corrosion-resistant diamond-like coating is 3.0-6.0 mu m.
In one possible implementation, the thickness of the nano metal bonding layer ranges from 0.5 μm to 1.5 μm, the nano metal bonding layer is formed by arranging nano columnar crystals, and the ratio of the Cr element content to the Ti element content in the nano metal bonding layer ranges from 1.0 to 1.5.
In one possible implementation, the thickness of the WC transition layer ranges from 2.0 μm to 4.5 μm, the WC transition layer is formed by arranging nano columnar crystals, and the ratio of the content of W element to the content of C element in the WC transition layer ranges from 0.90 to 1.05.
In one possible implementation, the thickness of the surface DLC functional layer is in the range of 0.5 to 1.5 μm, the porosity of the surface DLC functional layer being below 2%.
A second aspect of an embodiment of the present application provides a method for preparing a marine environment corrosion resistant diamond-like coating, for preparing a marine environment corrosion resistant diamond-like coating according to any one of the first aspects, the method comprising:
providing a first preparation mold;
placing an alloy matrix in a preparation space in the first preparation mold, and performing vacuum treatment on the preparation space;
alternately starting a chromium target and a titanium target in a first preparation mold, and depositing the chromium target and the titanium target on the surface of the oxidized alloy matrix to form a Cr-Ti alternately compounded nano metal bonding layer;
starting a WC target material in a first preparation mold to deposit on the surface layer of the nano metal bonding layer so as to form a WC transition layer;
acetylene is introduced into a preparation space of the first preparation mold, and a DLC functional layer is formed on the surface layer of the WC transition layer by deposition, so that the marine environment corrosion-resistant diamond-like coating is obtained.
In one possible implementation manner, the alternately opening chromium targets and titanium targets in the first preparation mold are deposited on the surface of the oxidized alloy matrix to form a Cr-Ti alternately compounded nano metal bonding layer, which comprises:
the ion source is turned on in the preparation space,
impact-removing oxidation treatment is carried out on the alloy matrix for 100-150 minutes by an ion source in the first preparation mould so as to obtain a deoxidized alloy matrix;
heating the temperature in the preparation space to 100-160 ℃ and controlling the temperature in the coating process not to exceed 200 ℃;
and alternately starting a chromium target and a titanium target in a first preparation mold to deposit on the surface of the oxidized alloy matrix to form a Cr-Ti alternately compounded nano metal bonding layer, wherein the sputtering time of the single chromium target or the titanium target is 10-30 minutes, the deposition is performed for 3-7 times alternately, the deposition bias voltage is 50-100V, and the target power is 4-10 KW.
In one possible implementation manner, the WC target is opened in the first preparation mold to deposit on the surface layer of the nano metal adhesive layer, so that the deposition bias voltage is 20-60V, the target power is 4-10 KW, and the sputtering time is 210-400 minutes when the WC transition layer is formed.
In one possible implementation, when acetylene is introduced into the preparation space of the first preparation mold and deposited on the surface layer of the WC transition layer to form the DLC functional layer, the flow rate of the acetylene is 100-350 sccm, and the deposition time is 180-240 minutes.
The embodiment of the application has at least the following beneficial effects:
the marine environment corrosion-resistant diamond-like coating comprises a nano metal bonding layer, a WC transition layer and a surface DLC functional layer which are alternately compounded by Cr-Ti, wherein the first surface of the nano metal bonding layer is adhered and adhered to the first surface of an alloy matrix, the second surface of the nano metal bonding layer is adhered and adhered to the first surface of the WC transition layer, the second surface of the WC transition layer is adhered and adhered to the first surface of the surface DLC functional layer, and the thickness range of the marine environment corrosion-resistant diamond-like coating is 3.0-6.0 mu m, so that the marine environment corrosion-resistant diamond-like coating comprises the Cr-Ti alternately compounded metal bonding layer, cr and Ti have low electrochemical level and are extremely easy to passivate, the excellent interface combination of the WC transition layer and the DLC functional layer with the alloy matrix can be ensured, and the marine corrosion-resistant performance is provided, so that the marine environment corrosion-resistant diamond-like coating has high binding force, wear resistance, self-lubrication, corrosion resistance and the like.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of a marine corrosion resistant diamond-like coating according to an embodiment of the present application;
FIG. 2 is a schematic flow chart of a method for preparing a marine corrosion-resistant diamond-like coating according to an embodiment of the application;
FIG. 3 is a schematic illustration of a marine corrosion resistant diamond-like coating surface according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The terms first, second and the like in the description and in the claims and in the above-described figures are used for distinguishing between different objects and not necessarily for describing a sequential or chronological order. Furthermore, the terms "comprise" and "have," as well as any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed steps or elements but may include other steps or elements not listed or inherent to such process, method, article, or apparatus.
Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the described embodiments of the application may be combined with other embodiments.
Referring to fig. 1, fig. 1 is a schematic view of a marine corrosion resistant diamond-like coating according to an embodiment of the present application. As shown in fig. 1, the marine environment corrosion-resistant diamond-like carbon coating comprises a nano metal bonding layer 1, a WC transition layer 2 and a surface DLC functional layer 3 which are alternately compounded by Cr-Ti, wherein,
the first surface of the nano metal bonding layer 1 is in fit with the first surface of the alloy matrix 4, the second surface of the nano metal bonding layer 1 is in fit with the first surface of the WC transition layer 2, and the second surface of the WC transition layer 2 is in fit with the first surface of the surface DLC functional layer 3;
the thickness range of the marine environment corrosion-resistant diamond-like coating is 3.0-6.0 mu m.
In one possible implementation manner, the thickness of the nano metal bonding layer 1 ranges from 0.5 μm to 1.5 μm, the nano metal bonding layer is formed by arranging nano columnar crystals, and the ratio of the content of Cr element to the content of Ti element in the nano metal bonding layer ranges from 1.0 to 1.5. Wherein, cr element is Cr element, ti element is Ti element. The surface DLC functional layer is a surface diamond functional layer.
In one possible implementation manner, the thickness of the WC transition layer 2 ranges from 2.0 μm to 4.5 μm, the WC transition layer is formed by arranging nano columnar crystals, and the ratio of the content of W element to the content of C element in the WC transition layer ranges from 0.90 to 1.05.
In one possible implementation, the thickness of the surface DLC functional layer 3 is in the range of 0.5 to 1.5 μm, the porosity of the surface DLC functional layer being below 2%.
Referring to fig. 2, fig. 2 is a schematic flow chart of a method for preparing a corrosion-resistant diamond-like coating in marine environment according to an embodiment of the application. As shown in fig. 2, a method for preparing a marine environment corrosion resistant diamond-like coating is used to prepare a marine environment corrosion resistant diamond-like coating according to any of the previous embodiments, the method comprising:
201. a first preparation mold is provided.
202. Placing the alloy matrix in a preparation space in the first preparation mold, and performing vacuum treatment on the preparation space.
203. And alternately starting a chromium target and a titanium target in the first preparation mold, and depositing the chromium target and the titanium target on the surface of the oxidized alloy matrix to form a Cr-Ti alternately compounded nano metal bonding layer.
204. And opening the WC target material in a first preparation mold to deposit on the surface layer of the nano metal bonding layer so as to form the WC transition layer.
205. Acetylene is introduced into a preparation space of the first preparation mold, and a DLC functional layer is formed on the surface layer of the WC transition layer by deposition, so that the marine environment corrosion-resistant diamond-like coating is obtained.
Wherein, the first preparation mold can be a preparation mold of vacuum vapor deposition technology, etc. The first preparation mold comprises an ion source and a preparation space, and the preparation space can be subjected to vacuum treatment and the like.
Because Cr targets and Ti targets are respectively introduced in the preparation process of the marine environment corrosion-resistant diamond-like carbon coating, the double-target magnetron sputtering deposition is used for preparing the Cr-Ti alternately compounded metal bonding layer, the equipment is not required to be greatly modified, and the operation is simple.
The marine environment corrosion-resistant diamond-like carbon coating has low internal stress, high bonding force with an alloy matrix and higher stripping resistance due to the special layered structure of the nano metal bonding layer, the WC transition layer and the surface DLC functional layer;
and the marine environment corrosion-resistant diamond-like carbon coating has low electrochemical level of Cr and Ti due to the nano-metal bonding layer, is extremely easy to passivate, can ensure good interface combination of the WC transition layer and the surface DLC functional layer with an alloy matrix, provides marine corrosion resistance, and ensures that the surface DLC functional layer has excellent comprehensive properties of high bonding force, wear resistance, self lubrication, marine corrosion resistance and the like.
Meanwhile, the marine environment corrosion-resistant diamond-like carbon coating has good adaptability to various metal materials such as stainless steel, titanium alloy, heat-resistant steel, high-strength steel, tool steel, high-temperature alloy and the like. The alloy matrix may include stainless steel matrix, titanium alloy matrix, heat resistant steel matrix, high strength steel matrix, tool steel matrix, superalloy matrix, etc.
In one possible implementation manner, the alternately opening chromium targets and titanium targets in the first preparation mold are deposited on the surface of the oxidized alloy matrix to form a Cr-Ti alternately compounded nano metal bonding layer, which comprises:
a1, starting an ion source in a preparation space,
a2, performing impact deoxidation treatment on the alloy matrix for 100-150 minutes by using an ion source in the first preparation mold to obtain a deoxidized alloy matrix;
a3, heating the temperature in the preparation space to 100-160 ℃, and controlling the temperature in the film coating process not to exceed 200 ℃;
a4, alternately starting a chromium target and a titanium target in the first preparation mold to deposit on the surface of the oxidized alloy matrix to form a Cr-Ti alternately compounded nano metal bonding layer, wherein the single sputtering time of the chromium target or the titanium target is 10-30 minutes, the deposition is performed for 3-7 times alternately, the deposition bias voltage is 50-100V, and the target power is 4-10 KW.
Wherein the ions in the ion source may be argon plasma.
In one possible implementation manner, the WC target is opened in the first preparation mold to deposit on the surface layer of the nano metal adhesive layer, so that the deposition bias voltage is 20-60V, the target power is 4-10 KW, and the sputtering time is 210-400 minutes when the WC transition layer is formed.
In one possible implementation, when acetylene is introduced into the preparation space of the first preparation mold and deposited on the surface layer of the WC transition layer to form the DLC functional layer, the flow rate of the acetylene is 100-350 sccm, and the deposition time is 180-240 minutes.
In a specific example, for example, in example 1, a Cr-Ti/WC/DLC coating was prepared on the surface of a PH13-8Mo martensitic precipitation-hardening stainless steel as an alloy substrate by the following process:
(1) And (3) carrying out pretreatment of deposition: vacuumizing to less than 10mPa, starting an ion source, starting the ion source, bombarding the surface of the alloy matrix with Ar+ plasma for 120min, removing an oxide layer and other free gas components on the surface of the alloy matrix, and heating the stainless steel of the alloy matrix at 150 ℃.
(2) The Ci-Ti alternate composite nano metal bonding layer is sputtered by double targets in a magnetron way, a chromium target and a titanium target are alternately started, the sputtering time of the single chromium target or the titanium target is 15 minutes, the deposition is alternately carried out for 5 times, the deposition bias voltage is 80V, and the power of the target is 6.5KW.
(3) Magnetron sputtering deposition WC transition layer: the WC target was turned on, the deposition bias was 40V, the target power was 6.5KW, and the sputtering time was 330 minutes.
(4) PE-CVD deposits a surface DLC functional layer: acetylene (C2H 2) was introduced and the flow of C2H2 was maintained at 250sccm for a deposition time of 210 minutes.
At the end of the deposition, the sample is removed. The surface of the prepared marine environment corrosion-resistant diamond-like coating is shown in figure 3, the surface of the marine environment corrosion-resistant diamond-like coating is smooth, and defects such as cracks and holes are not found. The coating thickness was measured by ball milling to be 4.8 μm.
Wherein, the friction coefficient of the coating is 0.101 (the counter-grinding auxiliary material is TB17 counter-grinding pin), the wear rate is 5.8x10 < -7 > mm3/Nm, the binding force Lc1= N, lc2 =37N by the scratch method has excellent wear-resistant self-lubricating performance, and the interface binding force of the coating and the alloy matrix is high. After the coating is corroded by salt fog for 240 hours, the surface appearance is perfect and smooth, and no corrosion trace is found.
Comparative example 1
The difference between comparative example 1 and example 1 is that the deposition parameters of the coating are changed, the deposition time of the DLC functional layer on the PE-CVD deposition surface is 300 minutes, the deposition time of the amorphous carbon film on the surface layer is too long, the thickness is over 1.5 mu m, the internal stress of the coating is large, lc1 is only 13N after the binding force test of a scratch method, and the capability of the coating for resisting cracking is poor.
Comparative example 2
Comparative example 1 differs from example 1 in that the coating deposition parameters were changed, the magnetron sputtering WC transition layer time was 180 minutes, the deposition time of the transition layer was too short, the thickness was less than 2.5 μm, the total thickness of the coating (3.2 μm) was required, but the transition layer thickness was too thin, the internal stress of the coating was large, the friction coefficient was 0.126 (TB 17 vs. pin for the grinding side material), the wear rate was 8.1x10-6 mm3/Nm, and the wear rate of the coating was increased by more than 10 times as compared with the DLC coating in example 1.
Comparative example 3
The difference between comparative example 1 and example 1 is that the coating deposition parameters are changed, the number of times of alternate deposition of the magnetron sputtering metal bonding layer is 2, the number of times of alternate deposition is small, the thickness of the bonding layer is less than 0.5 μm, the total thickness (4.1 μm) of the coating meets the requirement, but the thickness of the metal bonding layer is too thin, the interface bonding force is low, lc2 is only 25N after the bonding force test of a scratch method, and the capability of the coating for resisting interface peeling is poor.
Example 2
The difference from example 1 is that the DLC coating deposition substrate is selected as a100 alloy steel. The surface of the coating is perfect, the friction coefficient of the coating is 0.112 (the counter grinding auxiliary material is TB17 counter grinding pin), the wear rate is 4.1X10-7 mm3/Nm, the binding force Lc1= N, lc 2=38N of the scratch method is excellent in wear-resistant self-lubricating performance, and the interface binding force of the coating and the alloy matrix is high. After 240 hours of salt spray corrosion, the surface of the coating is perfect and smooth, and no corrosion trace is found.
Example 3
The difference from example 1 is that the DLC coating deposition substrate is selected to be 30CrMnSiNi2A ultra high strength alloy steel. The surface of the coating is perfect, the friction coefficient of the coating is 0.093 (the counter grinding auxiliary material is TB17 counter grinding pin), the abrasion rate is 2.1X10-7 mm3/Nm, and the binding force of the scratch method is Lc1= N, lc2 =31N. After the DLC coating is corroded by salt spray for 240 hours, the surface of the coating is still intact and smooth, no corrosion trace is seen, and the DLC coating has excellent marine salt spray corrosion resistance.
Example 4
The difference from example 1 is that the DLC coating deposition substrate is selected to be TC21 titanium alloy. The surface of the coating is perfect, the friction coefficient of the coating is 0.123, the abrasion rate is 5.1X10-7 mm3/Nm, and the bonding force of the scratch method is Lc1=29N, lc 2=41N. After the DLC coating is corroded by salt spray for 240 hours, the surface of the coating is still intact and smooth, no corrosion trace is seen, and the DLC coating has excellent marine salt spray corrosion resistance.
Example 5
The difference from example 1 is that the DLC coating deposition substrate is selected to be TC4 titanium alloy. The surface of the coating is perfect, the friction coefficient of the coating is 0.117 (the counter grinding auxiliary material is TB17 counter grinding pin), the abrasion rate is 6.1X10-7 mm3/Nm, and the binding force of the scratch method is Lc1= N, lc 2=39N. After the DLC coating is corroded by salt spray for 240 hours, the surface of the coating is still intact and smooth, no corrosion trace is seen, and the DLC coating has excellent marine salt spray corrosion resistance.
The foregoing has outlined rather broadly the more detailed description of embodiments of the application, wherein the principles and embodiments of the application are explained in detail using specific examples, the above examples being provided solely to facilitate the understanding of the method and core concepts of the application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Claims (8)
1. The marine environment corrosion-resistant diamond-like coating is characterized by comprising a nano metal bonding layer, a WC transition layer and a surface DLC functional layer which are alternately compounded by Cr-Ti,
the first surface of the nano metal bonding layer is in fit with the first surface of the alloy matrix, the second surface of the nano metal bonding layer is in fit with the first surface of the WC transition layer, and the second surface of the WC transition layer is in fit with the first surface of the surface DLC functional layer;
the thickness range of the marine environment corrosion-resistant diamond-like coating is 3.0-6.0 mu m.
2. The marine corrosion resistant diamond-like coating according to claim 1, wherein the thickness of the nano metal bonding layer ranges from 0.5 to 1.5 μm, the nano metal bonding layer is formed by arranging nano columnar crystals, and the ratio of the Cr element content to the Ti element content in the nano metal bonding layer ranges from 1.0 to 1.5.
3. The marine corrosion resistant diamond-like coating according to claim 2, wherein the WC transition layer has a thickness ranging from 2.0 to 4.5 μm, the WC transition layer is formed by arranging nano columnar crystals, and a ratio of the W element content to the C element content in the WC transition layer ranges from 0.90 to 1.05.
4. A marine corrosion resistant diamond-like coating according to claim 3, wherein the thickness of the surface DLC functional layer is in the range of 0.5 to 1.5 μm, and the porosity of the surface DLC functional layer is below 2%.
5. A method of preparing a marine corrosion resistant diamond-like coating according to any one of claims 1 to 4, the method comprising:
providing a first preparation mold;
placing an alloy matrix in a preparation space in the first preparation mold, and performing vacuum treatment on the preparation space;
alternately starting a chromium target and a titanium target in a first preparation mold, and depositing the chromium target and the titanium target on the surface of the oxidized alloy matrix to form a Cr-Ti alternately compounded nano metal bonding layer;
starting a WC target material in a first preparation mold to deposit on the surface layer of the nano metal bonding layer so as to form a WC transition layer;
acetylene is introduced into a preparation space of the first preparation mold, and a DLC functional layer is formed on the surface layer of the WC transition layer by deposition, so that the marine environment corrosion-resistant diamond-like coating is obtained.
6. The method for preparing a marine corrosion resistant diamond-like coating according to claim 5, wherein alternately opening the chromium target and the titanium target in the first preparation mold and depositing the chromium target and the titanium target on the surface of the oxidized alloy substrate to form a Cr-Ti alternately compounded nano-metal bonding layer comprises:
the ion source is turned on in the preparation space,
impact-removing oxidation treatment is carried out on the alloy matrix for 100-150 minutes by an ion source in the first preparation mould so as to obtain a deoxidized alloy matrix;
heating the temperature in the preparation space to 100-160 ℃ and controlling the temperature in the coating process not to exceed 200 ℃;
and alternately starting a chromium target and a titanium target in a first preparation mold to deposit on the surface of the oxidized alloy matrix to form a Cr-Ti alternately compounded nano metal bonding layer, wherein the sputtering time of the single chromium target or the titanium target is 10-30 minutes, the deposition is performed for 3-7 times alternately, the deposition bias voltage is 50-100V, and the target power is 4-10 KW.
7. The method for preparing a marine corrosion resistant diamond-like coating according to claim 5, wherein the first preparation mold is opened to deposit a WC target on the surface layer of the nano metal bonding layer, so that the deposition bias voltage is 20-60V, the target power is 4-10 KW, and the sputtering time is 210-400 minutes when the WC transition layer is formed.
8. The method for preparing a marine corrosion resistant diamond-like carbon coating according to claim 5, wherein when acetylene is introduced into the preparation space of the first preparation mold and deposited on the surface layer of the WC transition layer to form the surface DLC functional layer, the flow rate of the acetylene is 100-350 sccm, and the deposition time is 180-240 minutes.
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