CN111197176A - Electrochemical treatment method of copper foil and composite copper foil material - Google Patents
Electrochemical treatment method of copper foil and composite copper foil material Download PDFInfo
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- CN111197176A CN111197176A CN201911389912.1A CN201911389912A CN111197176A CN 111197176 A CN111197176 A CN 111197176A CN 201911389912 A CN201911389912 A CN 201911389912A CN 111197176 A CN111197176 A CN 111197176A
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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Abstract
The invention discloses an electrochemical treatment method of a copper foil and a composite copper foil material. The electrochemical treatment method comprises the following steps: at least enabling the copper foil subjected to the plasma surface treatment as a cathode, an anode and electrolyte to jointly construct an electrochemical reaction system; electrifying the electrochemical reaction system to perform electrochemical reaction, thereby forming a silane polymer film layer on the surface of the copper foil through polycondensation; the electrolyte comprises a mixed solution of sodium sulfate, dodecyl trimethoxy silane and an acid solution. The plasma surface treatment and electrochemical alkylation reaction provided by the invention have the advantages of rapid reaction and controllable process, and can meet the requirement of rapid surface passivation treatment in the actual production of copper foil; meanwhile, a silane polymer film generated by treating the copper foil in two steps has high stability and good oxidation resistance; meanwhile, compared with the traditional chromium-containing passivation technology, the technology has the advantages of being green and pollution-free.
Description
Technical Field
The invention belongs to the technical field of copper foil surface treatment, and particularly relates to an electrochemical treatment method of a copper foil and a composite copper foil material.
Background
The fresh surface of the copper foil produced by electrolysis is easy to oxidize in the air under the condition of no surface protection. The copper foil surface treatment process can effectively improve the oxidation resistance of the copper foil, improve the storage time of the copper foil, reduce the requirement of the copper foil on a storage place, and ensure that the quality of the copper foil can meet the standard when in use.
The existing copper foil anticorrosion and oxidation resistant surface treatment process can be divided into two types from raw material sources, namely a chromium passivation process and a chromium-free passivation process. Among them, the chromium passivation process has the most extensive application and the most obvious defects because of its good oxidation resistance. The raw materials adopted by chromium passivation are mostly dichromate, a chromium oxide layer is generated on the surface of the copper foil by adopting a chemical or electrochemical method, and the chromium oxide has good corrosion resistance and high temperature resistance and can play a good role in corrosion resistance and oxidation resistance. Meanwhile, hexavalent chromium ions present in dichromate have toxicity and carcinogenicity, and may adversely affect the human body and the surrounding environment during handling and discharge. In order to avoid the damage of hexavalent chromium to the environment and human bodies and reduce the environmental protection pressure of enterprises, many enterprises begin to research the passivation process of chromium-free copper foil, such as the passivation process mainly comprising tin, phytic acid or chitosan, and the like, which have more or less defects in some aspects, or cannot achieve the same level of anticorrosion and antioxidation effects as the chromium-containing passivation, or the formula composition is too complex, the components of the copper foil are difficult to stably control in the actual production, or the reaction speed is too slow, so that the requirement of performing rapid passivation treatment on the surface in the actual production of the copper foil is difficult to meet.
Disclosure of Invention
The invention mainly aims to provide an electrochemical treatment method of a copper foil and a composite copper foil material, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an electrochemical treatment method of a copper foil, which comprises the following steps:
carrying out plasma surface treatment on the copper foil;
at least enabling the copper foil subjected to plasma surface treatment as a cathode, an anode and electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte comprises a mixed solution of sodium sulfate, dodecyl trimethoxy silane and an acid solution;
and electrifying the electrochemical reaction system to perform electrochemical reaction, thereby forming a silane polymer film layer on the surface of the copper foil through polycondensation.
The embodiment of the invention also provides a composite copper foil material obtained by the method, and the composite copper foil material comprises a copper foil and a silane polymer film layer formed on the surface of the copper foil.
Compared with the prior art, the invention has the beneficial effects that: the method comprises the steps of firstly carrying out plasma surface treatment on a copper foil, and then carrying out electrochemical alkylation treatment on the surface of the copper foil by taking hydrolyzed dodecyl trimethoxy silane as a raw material to obtain a silane polymer film layer. Compared with the traditional chemical method, the process firstly uses plasma to treat the surface of the copper foil to generate a large amount of hydroxyl on the surface of the copper foil, then uses the copper foil subjected to plasma surface treatment as a cathode to carry out electrochemical alkylation reaction, and silane can form firm chemical bonding with the surface of the copper foil through the hydroxyl to form a silane polymer film layer; meanwhile, compared with the traditional chromium-containing passivation technology, the technology has the advantages of being green and pollution-free.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic view of an electrochemical treatment process for copper foil according to an exemplary embodiment of the present invention;
FIGS. 2a to 2c are SEM images of the surface of a copper foil obtained after the surface treatment in example 1 of the present invention;
FIG. 3 is an EDS chart of the surface of a copper foil obtained after surface treatment of example 1 of the present invention;
FIG. 4 is a Fourier infrared spectrum of the surface of a copper foil obtained after the surface treatment in example 1 of the present invention;
FIG. 5 is a surface Raman spectrum of the copper foil obtained after the surface treatment of example 1 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made extensive research and practice to provide the technical scheme of the present invention, the process comprises the steps of firstly treating the surface of the copper foil by using plasma to generate hydroxyl on the surface of the copper foil, then taking the treated copper foil as a cathode, adopting hydrolyzed dodecyl trimethoxy silane as a raw material, and carrying out electrodeposition in an acidic aqueous solution, wherein silane can form firm chemical bonding with the surface of the copper foil through the hydroxyl, and a silane polymer film layer is generated on the surface of the copper foil, so that the process is a good copper foil surface treatment process.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a method for electrochemically treating a copper foil, including:
carrying out plasma surface treatment on the copper foil;
at least enabling the copper foil subjected to plasma surface treatment as a cathode, an anode and electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte comprises a mixed solution of sodium sulfate, dodecyl trimethoxy silane and an acid solution;
and electrifying the electrochemical reaction system to perform electrochemical reaction, thereby forming a silane polymer film layer on the surface of the copper foil through polycondensation.
In the invention, the electrochemical treatment process of the copper foil can realize continuous production through the transmission device.
In some more specific embodiments, the plasma surface treatment is performed by low-voltage capacitive coupling discharge and parallel plate discharge, wherein the power supply frequency is 3-134Hz and the power is 10-400W.
In some more specific embodiments, the surface treatment method comprises: and (2) uniformly mixing the dodecyl trimethoxy silane and the acid solution, hydrolyzing at 5-60 ℃ for 1-48h, and then adding sodium sulfate into the hydrolyzed solution to obtain the electrolyte.
Furthermore, the volume ratio of the dodecyl trimethoxy silane to the electrolyte is 12-90: 100.
Further, the acid solution includes any one or a combination of two or more of a hydrochloric acid solution, a sulfuric acid solution, an acetic acid solution, and an oxalic acid solution, and is not limited thereto.
Further, the concentration of the acid solution in the electrolyte is 0.05-2 mol/L.
Further, the concentration of sodium sulfate in the electrolyte is 0.1-15 g/L.
Further, the pH value of the electrolyte is 3.0-5.0.
Further, the method comprises: when the electrochemical reaction is carried out, the current density is 2-60A/m2The temperature of the electrolyte is 20-70 ℃.
Further, the copper foil is formed by electrolysis.
Further, the anode includes a titanium plate, and is not limited thereto.
Further, the surface of the titanium plate is coated with a protective coating.
In some more specific embodiments, the electrochemical treatment further comprises: after the electrochemical reaction is finished, washing, drying and foil rolling treatment are carried out on the obtained copper foil;
in some more specific embodiments, the electrochemical treatment comprises (as shown with reference to fig. 1):
(1) carrying out plasma surface treatment on the copper foil;
(2) mixing dodecyl trimethoxy silane and an acid solution, wherein the volume ratio of the dodecyl trimethoxy silane to the mixed solution is 12-90:100, the concentration of the acid solution is 0.05-2mol/L, hydrolyzing at 5-60 ℃ for 1-48h, and then adding sodium sulfate and mixing uniformly to obtain the electrolyte; during the hydrolysis process of the dodecyl trimethoxy silane, Si-O-C bonds are broken, and-CH in molecules3Will be substituted by an H atom, or by a hydrogen atom,C12H25Si(OCH3)3molecular structure changed to C12H25Si(OH)3Three hydroxyl groups are present in the molecular structure;
(3) using the electrolyte obtained in the step (2), taking the copper foil subjected to plasma surface treatment as a cathode, taking a metal titanium plate covered with a coating on the surface as an anode, and electrolyzing at a current density of 2-60A/m2The temperature of the electrolyte is 20-70 ℃, hydrogen evolution reaction is continuously generated on the surface of the copper foil cathode in the electrolytic process, and OH is generated at the same time-Enriched in these OH groups near the cathode-Has the promotion of C12H25Si(OH)3The action of dehydration condensation, because the surface of the copper foil is subjected to plasma surface treatment, a large number of hydroxyl groups exist, and condensed silane and the hydroxyl groups are chemically bonded to generate a firm silane polymer film layer with the corrosion and oxidation resistance on the surface of the copper foil;
(4) and washing, drying and rolling the copper foil with the silane polymer film layer to obtain a finished product.
The invention also provides a composite copper foil material obtained by the method, which comprises a copper foil and a silane polymer film layer formed on the surface of the copper foil.
Further, the thickness of the silane polymer film layer is 2nm-10 μm.
The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Carrying out plasma surface treatment on the copper foil, wherein the discharge mode is low-voltage capacitive coupling discharge, the operation mode is parallel plate discharge, the copper foil generated by electrodeposition passes through the parallel plates, and hydroxyl is generated on the surface; the power supply frequency was set at 3Hz and the power was 10W.Uniformly mixing dodecyl trimethoxy silane with a sulfuric acid solution and an acetic acid solution, and hydrolyzing at 5 ℃ for 48 hours, wherein the volume ratio of the dodecyl trimethoxy silane to the mixed solution is 12: 100; then, adding sodium sulfate into the hydrolyzed solution to obtain the electrolyte, wherein the acid concentration in the electrolyte is 0.05mol/L, and the sodium sulfate concentration in the electrolyte is 0.1 g/L; in the passivation tank, the electrolyte is used, a metal titanium plate with a protective coating covered on the surface is used as an anode, and the electrolytic current density is 2A/m2The temperature of bath solution is 70 ℃, the copper foil subjected to plasma surface treatment enters a passivation bath through a transmission device to be used as a cathode of the electrochemical reaction, after the copper foil is subjected to the electrochemical treatment and leaves the passivation bath through the transmission device, a silane polymer film layer is formed on the surface of the copper foil, and a finished product is obtained after washing, drying and foil rolling, and the surface of the finished product has good corrosion resistance and oxidation resistance through detection.
FIGS. 2a-2c are SEM images of the surface of the copper foil after electrodeposition treatment in this example; FIG. 3 is an EDS chart of the surface of the copper foil after electrodeposition treatment in this example, showing that: the undulation structure generated after the surface treatment of the copper foil is distributed more uniformly, and the specific surface area of the surface of the copper foil is obviously increased; fig. 4 and 5 are a fourier infrared spectrogram and a raman spectrogram of the surface of the copper foil product, respectively.
Example 2
Carrying out plasma surface treatment on the copper foil, wherein the discharge mode is low-voltage capacitive coupling discharge, the operation mode is parallel plate discharge, the copper foil generated by electrodeposition passes through the parallel plates, hydroxyl is generated on the surface, the power frequency is set at 134Hz, and the power is 400W. Uniformly mixing dodecyl trimethoxy silane with a hydrochloric acid solution and an acetic acid solution, and hydrolyzing at 60 ℃ for 1h, wherein the volume ratio of the dodecyl trimethoxy silane to the mixed solution is 90: 100; then, adding sodium sulfate into the hydrolyzed solution to obtain the electrolyte, wherein the acid concentration in the electrolyte is 2mol/L, and the sodium sulfate concentration in the electrolyte is 15 g/L; in the passivation tank, the electrolyte is used, a metal titanium plate with a protective coating covered on the surface is used as an anode, and the electrolytic current density is 60A/m2The temperature of the bath solution is 20 ℃, and the bath solution is subjected to plasma surface treatmentThe copper foil enters the passivation tank through a transmission device and is used as a cathode of the electrochemical reaction. After electrochemical treatment, after the copper foil leaves the passivation tank through a transmission device, a silane polymer film layer is formed on the surface of the copper foil, and a finished product is obtained after washing, drying and foil rolling, wherein the surface of the finished product has good corrosion resistance and oxidation resistance through detection.
Example 3
Carrying out plasma surface treatment on the copper foil, wherein the discharge mode is low-voltage capacitive coupling discharge, the operation mode is parallel plate discharge, the copper foil generated by electrodeposition passes through the parallel plates, hydroxyl is generated on the surface, the power frequency is set at 80Hz, and the power is 240W. Uniformly mixing dodecyl trimethoxy silane with a nitric acid solution and an acetic acid solution, and hydrolyzing at 25 ℃ for 12h, wherein the volume ratio of the dodecyl trimethoxy silane to the mixed solution is 20: 100; then, adding sodium sulfate into the hydrolyzed solution to obtain the electrolyte, wherein the acid concentration in the electrolyte is 0.5mol/L, and the sodium sulfate concentration in the electrolyte is 7 g/L; in the passivation tank, the electrolyte is used, a metal titanium plate with a protective coating covered on the surface is used as an anode, and the electrolytic current density is 10A/m2The temperature of bath solution is 50 ℃, the copper foil after plasma surface treatment enters a passivation bath through a transmission device to be used as a cathode of the electrochemical reaction, after the copper foil is subjected to the electrochemical treatment and leaves the passivation bath through the transmission device, a silane polymer film layer is already formed on the surface of the copper foil, and a finished product is obtained after washing, drying and foil rolling, and the surface of the finished product has good corrosion resistance and oxidation resistance through detection.
Example 4
Carrying out plasma surface treatment on the copper foil, wherein the discharge mode is low-voltage capacitive coupling discharge, the operation mode is parallel plate discharge, the copper foil generated by electrodeposition passes through the parallel plates, hydroxyl is generated on the surface, the power frequency is set at 20Hz, and the power is 60W. Uniformly mixing dodecyl trimethoxy silane with a nitric acid solution and an oxalic acid solution, and hydrolyzing at 35 ℃ for 10 hours, wherein the volume ratio of the dodecyl trimethoxy silane to the mixed solution is 50: 100; then adding sodium sulfate into the hydrolyzed solution to obtain the electrolyte, wherein the acid concentration in the electrolyte is 0.9mol/L, wherein the concentration of sodium sulfate in the electrolyte is 10 g/L; in the passivation tank, the electrolyte is used, a metal titanium plate with a protective coating covered on the surface is used as an anode, and the electrolytic current density is 30A/m2The temperature of bath solution is 30 ℃, the copper foil after plasma surface treatment enters a passivation bath through a transmission device to be used as a cathode of the electrochemical reaction, after the copper foil is subjected to the electrochemical treatment and leaves the passivation bath through the transmission device, a silane polymer film layer is already formed on the surface of the copper foil, and a finished product is obtained after washing, drying and foil rolling, and the surface of the finished product has good corrosion resistance and oxidation resistance through detection.
Comparative example 1
Mixing dodecyl trimethoxy silane with nitric acid solution and oxalic acid solution, and hydrolyzing at 35 deg.C for 10 hr, wherein the volume ratio of dodecyl trimethoxy silane to the mixture is 50: 100; then adding sodium sulfate into the hydrolyzed solution to obtain the mixed solution; wherein the acid concentration in the mixed solution is 0.9mol/L, the sodium sulfate concentration in the mixed solution is 10g/L, and the temperature of the mixed solution is 30 ℃; the copper foil is soaked in the mixed solution for the same time as that of the example 4, because the plasma treatment and the electrochemical deposition are not carried out, the soaking treatment is only carried out, the reaction speed is slow, the silane polymer film layer cannot be well deposited, the bonding force between the silane polymer film layer and the copper foil base is not strong, and the corrosion resistance and the oxidation resistance of the obtained copper foil product are far lower than those of the copper foil prepared in the example 4.
Comparative example 2
Uniformly mixing dodecyl trimethoxy silane with a nitric acid solution and an oxalic acid solution, and hydrolyzing at 35 ℃ for 10 hours, wherein the volume ratio of the dodecyl trimethoxy silane to the mixed solution is 50: 100; then, adding sodium sulfate into the hydrolyzed solution to obtain the electrolyte, wherein the acid concentration in the electrolyte is 0.9mol/L, and the sodium sulfate concentration in the electrolyte is 10 g/L; in the passivation tank, the electrolyte is used, a metal titanium plate with a protective coating covered on the surface is used as an anode, and the electrolytic current density is 30A/m2The temperature of the bath solution is 30 ℃, the copper foil without plasma surface treatment enters a passivation bath through a transmission device to be used as a cathode of the electrochemical reaction, and the copper foil passes throughAfter electrochemical treatment, the copper foil leaves the passivation tank through a transmission device, and then is washed, dried and rolled to obtain a finished product, because the copper foil is not subjected to plasma treatment, the bonding force between the silane polymer film layer and the copper foil base is not strong, and the corrosion resistance and oxidation resistance of the obtained copper foil product are far lower than those of the copper foil prepared in the embodiment 4.
Comparative example 3
Carrying out plasma surface treatment on the copper foil, wherein the discharge mode is low-voltage capacitive coupling discharge, the operation mode is parallel plate discharge, the copper foil generated by electrodeposition passes through the parallel plates, hydroxyl is generated on the surface, the power frequency is set at 20Hz, and the power is 60W. Mixing dodecyl trimethoxy silane with nitric acid solution and oxalic acid solution, and hydrolyzing at 35 deg.C for 10 hr, wherein the volume ratio of dodecyl trimethoxy silane to the mixture is 50: 100; then adding sodium sulfate into the hydrolyzed solution to obtain the mixed solution; wherein the acid concentration in the mixed solution is 0.9mol/L, the sodium sulfate concentration in the mixed solution is 10g/L, and the temperature of the mixed solution is 30 ℃; the copper foil subjected to the plasma surface treatment is soaked in the mixed solution for the same time as in example 4, and since the electrochemical deposition treatment is not carried out and only the dipping treatment is carried out, the reaction speed is slow, the silane polymer film layer cannot be well deposited, and the corrosion resistance and oxidation resistance of the obtained copper foil product are far lower than those of the copper foil prepared in example 4.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for electrochemically treating a copper foil, characterized by comprising:
carrying out plasma surface treatment on the copper foil;
at least enabling the copper foil subjected to plasma surface treatment as a cathode, an anode and electrolyte to jointly construct an electrochemical reaction system, wherein the electrolyte comprises a mixed solution of sodium sulfate, dodecyl trimethoxy silane and an acid solution;
and electrifying the electrochemical reaction system to perform electrochemical reaction, thereby forming a silane polymer film layer on the surface of the copper foil through polycondensation.
2. A surface treatment method according to claim 1, characterized in that: the plasma surface treatment adopts a low-voltage capacitive coupling discharge mode and a parallel plate discharge mode as an operation mode, wherein the power frequency is 3-134Hz, and the power is 10-400W.
3. A surface treatment method according to claim 1, characterized by comprising: and (2) uniformly mixing the dodecyl trimethoxy silane and the acid solution, hydrolyzing at 5-60 ℃ for 1-48h, and then adding sodium sulfate to obtain the electrolyte.
4. The electrochemical treatment method according to claim 1, characterized in that: the volume ratio of the dodecyl trimethoxy silane to the electrolyte is 12-90: 100.
5. The electrochemical treatment method according to claim 1, characterized in that: the acid solution comprises any one or the combination of more than two of hydrochloric acid solution, sulfuric acid solution, acetic acid solution and oxalic acid solution; preferably, the concentration of the acid solution in the electrolyte is 0.05-2 mol/L.
6. The electrochemical treatment method according to claim 1, characterized in that: the concentration of sodium sulfate in the electrolyte is 0.1-15 g/L;
and/or the pH value of the electrolyte is 3.0-5.0.
7. The electrochemical treatment method according to claim 1, characterized by comprising: when the electrochemical reaction is carried out, the current density is 2-60A/m2The temperature of the electrolyte is 20-70 ℃.
8. The electrochemical processing method of claim 1, wherein the anode comprises a titanium plate; preferably, the surface of the titanium plate is coated with a protective coating.
9. The electrochemical treatment method according to claim 1, wherein the copper foil is formed by electrolysis.
10. A composite copper foil material obtained by the method of any one of claims 1 to 9, comprising a copper foil, and a silane polymer film layer formed on a surface of the copper foil;
preferably, the thickness of the silane polymer film layer is 2nm-10 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112888149A (en) * | 2021-01-12 | 2021-06-01 | 深圳市鑫诺诚科技有限公司 | Conductive, shielding and heat-dissipating composite material |
| CN113122894A (en) * | 2021-04-16 | 2021-07-16 | 江西富鸿金属有限公司 | Tinned copper wire of 5G signal data power cable |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4980196A (en) * | 1990-02-14 | 1990-12-25 | E. I. Du Pont De Nemours And Company | Method of coating steel substrate using low temperature plasma processes and priming |
| US5093154A (en) * | 1988-09-05 | 1992-03-03 | Matsushita Electric Industrial Co., Ltd. | Process for preparing a monomolecular built-up film |
| US20030113479A1 (en) * | 2001-08-23 | 2003-06-19 | Konica Corporation | Atmospheric pressure plasma treatmet apparatus and atmospheric pressure plasma treatment method |
| US20030166342A1 (en) * | 2001-05-07 | 2003-09-04 | Applied Materials, Inc. | Integrated method for release and passivation of MEMS structures |
| CN101914797A (en) * | 2010-08-11 | 2010-12-15 | 西北农林科技大学 | Method for preparing composite nano film on metal surface |
| CN102230203A (en) * | 2011-07-06 | 2011-11-02 | 浙江大学 | Electro-deposition preparation method and application of silane film |
| CN102358946A (en) * | 2011-08-05 | 2012-02-22 | 华南理工大学 | Preparation method for metal material surface antifriction and antiwear nano-composite film |
| CN102632031A (en) * | 2012-04-16 | 2012-08-15 | 浙江大学 | Method for preparing superhydrophobic surface |
| CN103556171A (en) * | 2013-10-30 | 2014-02-05 | 中国科学院青海盐湖研究所 | Method for producing sodium dichromate through cationic membrane electrolysis |
| CN103882495A (en) * | 2014-04-16 | 2014-06-25 | 山东理工大学 | Method for preparing aluminum alloy anti-adhesive surface by electrolyzing plasma |
| US8962097B1 (en) * | 2007-09-07 | 2015-02-24 | Edward Maxwell Yokley | Surface properties of polymeric materials with nanoscale functional coating |
| CN104451807A (en) * | 2014-12-25 | 2015-03-25 | 哈尔滨工程大学 | Method of preparing silicane film on metal surface by electro-deposition |
| CN104878434A (en) * | 2015-06-09 | 2015-09-02 | 中国科学院青海盐湖研究所 | Method for preparing nanometer thin film on copper or copper alloy surface |
| CN108525970A (en) * | 2018-03-13 | 2018-09-14 | 上海交通大学 | The preparation method of noble metal super-double-hydrophobic surface |
| CN108543686A (en) * | 2018-03-13 | 2018-09-18 | 上海交通大学 | The preparation method of iron group metal super-double-hydrophobic surface |
| CN111410921A (en) * | 2020-05-02 | 2020-07-14 | 冯亿生 | Composite protective film |
-
2019
- 2019-12-30 CN CN201911389912.1A patent/CN111197176B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5093154A (en) * | 1988-09-05 | 1992-03-03 | Matsushita Electric Industrial Co., Ltd. | Process for preparing a monomolecular built-up film |
| US4980196A (en) * | 1990-02-14 | 1990-12-25 | E. I. Du Pont De Nemours And Company | Method of coating steel substrate using low temperature plasma processes and priming |
| US20030166342A1 (en) * | 2001-05-07 | 2003-09-04 | Applied Materials, Inc. | Integrated method for release and passivation of MEMS structures |
| US20030113479A1 (en) * | 2001-08-23 | 2003-06-19 | Konica Corporation | Atmospheric pressure plasma treatmet apparatus and atmospheric pressure plasma treatment method |
| US8962097B1 (en) * | 2007-09-07 | 2015-02-24 | Edward Maxwell Yokley | Surface properties of polymeric materials with nanoscale functional coating |
| CN101914797A (en) * | 2010-08-11 | 2010-12-15 | 西北农林科技大学 | Method for preparing composite nano film on metal surface |
| CN102230203A (en) * | 2011-07-06 | 2011-11-02 | 浙江大学 | Electro-deposition preparation method and application of silane film |
| CN102358946A (en) * | 2011-08-05 | 2012-02-22 | 华南理工大学 | Preparation method for metal material surface antifriction and antiwear nano-composite film |
| CN102632031A (en) * | 2012-04-16 | 2012-08-15 | 浙江大学 | Method for preparing superhydrophobic surface |
| CN103556171A (en) * | 2013-10-30 | 2014-02-05 | 中国科学院青海盐湖研究所 | Method for producing sodium dichromate through cationic membrane electrolysis |
| CN103882495A (en) * | 2014-04-16 | 2014-06-25 | 山东理工大学 | Method for preparing aluminum alloy anti-adhesive surface by electrolyzing plasma |
| CN104451807A (en) * | 2014-12-25 | 2015-03-25 | 哈尔滨工程大学 | Method of preparing silicane film on metal surface by electro-deposition |
| CN104878434A (en) * | 2015-06-09 | 2015-09-02 | 中国科学院青海盐湖研究所 | Method for preparing nanometer thin film on copper or copper alloy surface |
| CN108525970A (en) * | 2018-03-13 | 2018-09-14 | 上海交通大学 | The preparation method of noble metal super-double-hydrophobic surface |
| CN108543686A (en) * | 2018-03-13 | 2018-09-18 | 上海交通大学 | The preparation method of iron group metal super-double-hydrophobic surface |
| CN111410921A (en) * | 2020-05-02 | 2020-07-14 | 冯亿生 | Composite protective film |
Non-Patent Citations (2)
| Title |
|---|
| MOSTOFI SARKARI, NAVID 等: ""Assessing effects of (3-aminopropyl) trimethoxysilane self-assembled layers on surface characteristics of organosilane-grafted moisture-crosslinked polyethylene substrate: A comparative study between chemical vapor deposition and plasma-facilitated"", 《APPLIED SURFACE SCIENCE》 * |
| 屈钧娥 等: ""铝及铝合金表面自组装功能膜的研究进展"", 《材料导报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112888149A (en) * | 2021-01-12 | 2021-06-01 | 深圳市鑫诺诚科技有限公司 | Conductive, shielding and heat-dissipating composite material |
| CN113122894A (en) * | 2021-04-16 | 2021-07-16 | 江西富鸿金属有限公司 | Tinned copper wire of 5G signal data power cable |
| CN113122894B (en) * | 2021-04-16 | 2022-05-20 | 江西富鸿金属有限公司 | Tinned copper wire of 5G signal data power cable |
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