CN1966779A - Process for making Ni-Cu-Ag multilayer film - Google Patents
Process for making Ni-Cu-Ag multilayer film Download PDFInfo
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- CN1966779A CN1966779A CN 200510125524 CN200510125524A CN1966779A CN 1966779 A CN1966779 A CN 1966779A CN 200510125524 CN200510125524 CN 200510125524 CN 200510125524 A CN200510125524 A CN 200510125524A CN 1966779 A CN1966779 A CN 1966779A
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Abstract
The invention discloses a method for preparing Ni-Cu-Ag multilayer film. The invention adopts copper sulfate, niekel sulfate and argent nitrate as raw material to prepare solution for depositing the multilayer film, and prepares soft/hard commutative Ni-Cu-Ag multilayer film through electrochemistry deposition method. The characteristics of the method are: simple equipment and process, and low deposition temperature. The invention avoids the thermal stress and interlaminar thermal diffusion introduced to the material interior through physical method at high temperature. It is shown by experiments that: the Ni-Cu-Ag multilayer film has good tribology performance under vacuum conditions, and may solves the problems of material protection and lubrication in space environment.
Description
Technical field
The present invention relates to a kind of preparation method of metallized multilayer film, narrated a kind of preparation method of Ni/Cu/Ag multilayer film especially.
Background technology
Practice and result of study show that the multilayer film that high-modulus and low modulus alternate often provide surface property more fully than the single thin film that one-component forms.Because multilayer film not only has high intensity and high anti-flow performance, and can improve ground and Bond Strength of Coating, reduce the space in the coating system, can change the distribution of thin layer internal stress and crackle, improve YIELD STRENGTH and tribological property.And when the thickness in monolayer of multilayer film reached nano-scale, it often demonstrated the peculiar character of obvious different and the single thin film material of forming them at aspects such as mechanics, electricity, magnetics and optics.
In order to adapt to the particular requirement to material surface of aerospace, microelectronics (comprising magnetic recording material), biological and medical field, the tribology coating is just towards structure direction development ultra-thin, multiple stratification.Soft metal Ag film is owing to its good fluidity, and the part of breaking of film can be recovered oilness through adhering to again, has certain self-reparing capability.The Ag film also has stronger chemical stability and oxidation-resistance, and the frictional coefficient in vacuum environment is low and stable, so the Ag film is subjected to paying close attention to widely in space flight and tribological field.But aspect tribology, use the Ag film merely,,, be unfavorable for improving the overall performance of material, therefore, generally select the form of multiple stratification or compoundization to improve its resistance to abrasion to such an extent as to its abrasion resistance is relatively poor because of its lower hardness.The Young's modulus of Ni and Ag is respectively 201GPa and 70.7GPa, that is to say that the Young's modulus between Ag and the Ni exists than big-difference, if preparation soft or hard alternating N i/Ag multilayer film, this can make and produce big stress in Ag and the Ni interfacial layer.Therefore and the Young's modulus of Cu is 100GPa, adds Cu and relaxes that Young's modulus between Ag and the Ni is crossed big-difference and the stress that causes as the middle layer, and can improve Ag film and high base strength, improves the tribological property of multilayer film.The method for preparing metallized multilayer film with ion sputtering, physical vapor deposition, magnetron sputtering, molecular beam epitaxial growth etc. is compared, electro-deposition method equipment and technological process are simple, Production Time short, size and dimension to ground requires lower, depositing temperature is lower, so avoided material internal is introduced under the high temperature thermal stresses and interlayer thermodiffusion.Therefore electro-deposition method is one of effective way of preparation multilayer film.
Summary of the invention
The objective of the invention is to avoid the physical deposition method to prepare the deficiency of multilayer film, adopt electrodip process to prepare the Ni/Cu/Ag multilayer film.Thereby it is simple to have formed a kind of equipment and technological process, and cost is lower, the size and dimension of ground is required the preparation method of lower multilayer film.
A kind of preparation method of Ni-Cu-Ag multilayer film, the method for employing galvanic deposit, counter electrode is a platinum electrode, and working electrode is tinsel or conductive glass, and reference electrode is a saturated calomel electrode, it is characterized in that this method comprises following two steps successively:
The preparation of A, Ni/Cu film:
With copper sulfate, single nickel salt, boric acid, trisodium citrate and sodium lauryl sulphate are dissolved in the distilled water, and the Ph value is 2.0～3.0, are made into the solution of deposit N i/Cu film, keep 40 ℃～45 ℃ of depositing temperatures, electromotive force-0.05V～-0.4V between deposited copper, electromotive force≤-the 0.8V scope in nickel deposited; To make face and clean up, immerse in the electrolytic solution of handling through deoxygenation then, under the mode of deposition that sets in advance, carry out the preparation of Ni/Cu film.
The preparation of B, Ni/Cu film surfaces A g film
With Silver Nitrate, sulphosalicylic acid, imidazoles and potassium acetate are dissolved in the distilled water, and the pH value is 7.5～8.5, is made into the solution of galvanic deposit Ag film, and keeping depositing temperature is 20～30 ℃, and current density is 10～40mA/cm
2The Ni/Cu film that makes is immersed in the silver nitrate solution for preparing, under the mode of deposition that sets in advance, carry out the preparation of Ag film, promptly obtain the Ni/Cu/Ag multilayer film.
In steps A, the concentration of copper sulfate is 0.005～0.03molL
-1, the concentration of single nickel salt is 0.8～1.5molL
-1, the concentration of boric acid is 0.4～0.5molL
-1, the concentration of trisodium citrate is 0.15～0.25molL
-1, the concentration of sodium lauryl sulphate is 1.5 * 10
-4～2.5 * 10
-4MolL
-1
In step B, the concentration of Silver Nitrate is 0.1～0.2molL
-1, the concentration of sulphosalicylic acid is 0.6～0.8molL
-1, the concentration of imidazoles is 2.0～2.5molL
-1, the concentration of potassium acetate is 0.45～0.55molL
-1
The addition of the used imidazoles of the present invention is 3.0～4.0 times of sulphosalicylic acid mole number.
Ni/Cu/Ag multilayer film involved in the present invention has good tribological property, can be used as the antifriction antiwear protective coating.The experimental technique that adopts is as follows:
Adopt CZM type vacuum sphere-dish frictional testing machines to investigate the tribological property of Ni/Cu/Ag multilayer film, steel ball is the 9Cr18 of the back polishing of quenching, and diameter is 8mm.During test, steel ball fixedly sample rotates, and rotating speed is 300r/min and 500r/min.Test vacuum tightness is 5 * 10
-3Pa, load is 3N and 5N.Friction and wear test results shows, 9Cr18 steel ball and clean Stainless Steel Watch frictional coefficient when rubbing is higher, is about about 0.70.
With the piece of stainless steel is ground, monofilm thickness is 50nm, the test-results that total thickness is the Ni/Cu/Ag multilayer film of 2 μ m and 9Cr18 steel ball when rubbing shows: under 3N load and 300r/min rotating speed, frictional coefficient is initiated with 0.12, and reduce along with the increase of friction number of times, be reduced to 0.05 to rubbing after 18000 times; When rotating speed and friction number of times are constant, when load increased to 5N, its frictional coefficient was reduced to 0.11 gradually from initial 0.17; When load is 3N and rotating speed when being 500r/min, the frictional coefficient of Ni/Cu/Ag multilayer film is initiated with 0.17, along with steel ball the increase of the number of times that rubs being reduced, is reduced to 0.06 after friction 30000 times; And when load be 5N, when rotating speed is constant, presenting with its frictional coefficient of increase to the number of times that rubs increases earlier the phenomenon that afterwards reduces, and is 0.09 rubbing after 30000 times.
Above coefficient of friction data shows that Ni/Cu/Ag multilayer film involved in the present invention has good tribological property in vacuum environment, can be used as antifriction, wear-resistant protective coating.
Preparation method of the present invention compares with the method that ion sputtering, physical vapor deposition, magnetron sputtering, molecular beam epitaxial growth etc. prepare multilayer film, equipment and technological process are simple, Production Time short, size and dimension requirement to ground is lower, and depositing temperature is lower.The multilayer film of this method preparation has good tribological property in vacuum environment.
Embodiment
Embodiment 1:
The Ni/Cu/Ag multilayer film utilizes electrochemical workstation to carry out galvanic deposit in two steps.Adopt three-electrode system, reference electrode is a saturated calomel electrode, and counter electrode is a platinum electrode, and working electrode (substrate) (is of a size of 45 * 8.0mm) for stainless steel.Before deposition, the system face of substrate is cleaned up, feed high pure nitrogen in the electrolytic solution to remove the oxygen in the solution.Agents useful for same is analytical pure, and solution all adopts distilled water formulated.
The solution of (1) preparation deposition Ni/Cu film, concrete composition and mode of deposition are as follows: the concentration of copper sulfate is 0.005molL
-1, the concentration of single nickel salt is 1.2molL
-1, the concentration of boric acid is 0.45molL
-1, the concentration of trisodium citrate is 0.22molL
-1, the concentration of sodium lauryl sulphate is 1.6 * 10
-4MolL
-1Adjust pH is about 2.5, and temperature remains on 45 ℃.Select electromotive force-50mV (vs SCE) to come deposited copper coating, selection-1.1V (vs SCE) comes deposited nickel layer.By the depositing time of control single metal, preparation individual layer thickness is the Ni/Cu film of 50nm.
The solution of (2) preparation deposition Ag film, concrete composition and mode of deposition are as follows: the concentration of Silver Nitrate is 0.1molL
-1, the concentration of sulphosalicylic acid is 0.65molL
-1, the concentration of imidazoles is 2.0molL
-1, the concentration of potassium acetate is 0.5molL
-1, current density is 20mA/cm
2, temperature is 30 ℃.At the Ni/Cu film surface of preparation galvanostatic deposition Ag film, and the control depositing time to make the individual layer thickness be 50nm, can make the Ni/Cu/Ag multilayer film.
Claims (4)
1, a kind of preparation method of Ni-Cu-Ag multilayer film, the method for employing galvanic deposit, counter electrode is a platinum electrode, and working electrode is tinsel or conductive glass, and reference electrode is a saturated calomel electrode, it is characterized in that this method comprises following two steps successively:
The preparation of A, Ni/Cu film:
With copper sulfate, single nickel salt, boric acid, trisodium citrate and sodium lauryl sulphate are dissolved in the distilled water, and the Ph value is 2.0～3.0, are made into the solution of deposit N i/Cu film, keep 40 ℃～45 ℃ of depositing temperatures, electromotive force-0.05V～-0.4V between deposited copper, electromotive force≤-the 0.8V scope in nickel deposited; To make face and clean up, immerse in the electrolytic solution of handling through deoxygenation then, under the mode of deposition that sets in advance, carry out the preparation of Ni/Cu film.
The preparation of B, Ni/Cu film surfaces A g film
With Silver Nitrate, sulphosalicylic acid, imidazoles and potassium acetate are dissolved in the distilled water, and the pH value is 7.5～8.5, is made into the solution of galvanic deposit Ag film, and keeping depositing temperature is 20～30 ℃, and current density is 10～40mA/cm
2The Ni/Cu film that makes is immersed in the silver nitrate solution for preparing, under the mode of deposition that sets in advance, carry out the preparation of Ag film, promptly obtain the Ni/Cu/Ag multilayer film.
As the said method of claim 1, it is characterized in that in steps A that 2, the concentration of copper sulfate is 0.005～0.03molL
-1, the concentration of single nickel salt is 0.8～1.5molL
-1, the concentration of boric acid is 0.4～0.5molL
-1, the concentration of trisodium citrate is 0.15～0.25mo1L
-1, the concentration of sodium lauryl sulphate is 1.5 * 10
-4～2.5 * 10
-4MolL
-1
3,, it is characterized in that in step B the concentration of Silver Nitrate is 0.1～0.2molL as the said method of claim 1
-1, the concentration of sulphosalicylic acid is 0.6～0.8molL
-1, the concentration of imidazoles is 2.0～2.5molL
-1, the concentration of potassium acetate is 0.45～0.55molL
-1
4, as the said method of claim 1, the addition that it is characterized in that imidazoles is 3.0～4.0 times of sulphosalicylic acid mole number.
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| CN 200510125524 CN1966779A (en) | 2005-11-17 | 2005-11-17 | Process for making Ni-Cu-Ag multilayer film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102393409A (en) * | 2011-07-14 | 2012-03-28 | 徐志花 | Novel and high-efficiency NiCu/Cu electrochemical sensor for detecting nitrobenzene and preparation method thereof |
| CN104616728A (en) * | 2015-01-26 | 2015-05-13 | 河南大学 | Nanometer cable transparent conducting thin film with copper inner core and preparation method thereof |
| CN108336346A (en) * | 2018-02-07 | 2018-07-27 | 吉林师范大学 | A kind of application of germanium gallium nano wire as lithium ion battery electrode material |
| CN112410840A (en) * | 2020-09-22 | 2021-02-26 | 南昌航空大学 | Method for rapidly preparing Cu/Ni reactive nano multilayer film |
| CN115445615A (en) * | 2022-09-13 | 2022-12-09 | 中南大学 | Preparation method of nano metal core-shell structure |
-
2005
- 2005-11-17 CN CN 200510125524 patent/CN1966779A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102393409A (en) * | 2011-07-14 | 2012-03-28 | 徐志花 | Novel and high-efficiency NiCu/Cu electrochemical sensor for detecting nitrobenzene and preparation method thereof |
| CN104616728A (en) * | 2015-01-26 | 2015-05-13 | 河南大学 | Nanometer cable transparent conducting thin film with copper inner core and preparation method thereof |
| CN104616728B (en) * | 2015-01-26 | 2016-09-14 | 河南大学 | A kind of nano-cable transparent conductive film with copper as inner core and preparation method thereof |
| CN108336346A (en) * | 2018-02-07 | 2018-07-27 | 吉林师范大学 | A kind of application of germanium gallium nano wire as lithium ion battery electrode material |
| CN112410840A (en) * | 2020-09-22 | 2021-02-26 | 南昌航空大学 | Method for rapidly preparing Cu/Ni reactive nano multilayer film |
| CN115445615A (en) * | 2022-09-13 | 2022-12-09 | 中南大学 | Preparation method of nano metal core-shell structure |
| CN115445615B (en) * | 2022-09-13 | 2023-06-13 | 中南大学 | Preparation method of nano metal core-shell structure |
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