CN105274596A - Method for preparing nano-copper coating through electrodeposition - Google Patents
Method for preparing nano-copper coating through electrodeposition Download PDFInfo
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- CN105274596A CN105274596A CN201510718605.9A CN201510718605A CN105274596A CN 105274596 A CN105274596 A CN 105274596A CN 201510718605 A CN201510718605 A CN 201510718605A CN 105274596 A CN105274596 A CN 105274596A
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Abstract
The invention discloses a method for preparing a nano-copper coating through electrodeposition. The method includes the steps that after being subjected to ultrasonic cleaning through acetone and ultra-pure water, a stainless steel wire is soaked in a strong acid solution for etching; and after electrodeposition is conducted with the etched stainless steel wire as a working electrode, a platinum electrode as a counter electrode, a saturated calomel electrode as a reference electrode and a copper salt solution as an electrolyte, cleaning and drying are conducted, and then the nano-copper coating is obtained. The electron microscope surface scanning analysis proves that particles of the prepared nano-copper coating range from 80 nm to 150 nm, are of a porous structure and are evenly distributed; the nano-copper coating is large in specific surface area and high in adsorption capacity, is used for extracting phthalic acid esters (PAEs) in environmental samples, and is high in extraction efficiency, stability and acid and alkali resistance. The coating obtained through an extraction head in the solid phase microextraction technology is high in extraction efficiency, stability and acid and alkali resistance. In addition, the particle size and shape of the nano-copper coating are controlled by selecting voltages, the number of scanning turns and scanning rate. The preparation process is simple, cost is low, and operability is high.
Description
Technical field
The present invention relates to a kind of preparation of Nanometer Copper coating, particularly relate to a kind of method of electrodeposited nanocrystalline copper coating, be mainly used in the coating of extracting head in solid phase micro-extraction technique, belong to field of nanometer material technology and environmental analysis Material Field.
Background technology
Solid phase micro-extraction technique (SolidPhaseMicroextraction, SPME) is a kind of without the need to solvent, simple to operate, time saving and energy saving technology, extensively obtains the favor of environmental analysis investigator.Extracting head is the most important thing of SPME, and the performance of the coating of extracting head and extracting head has close relationship, and its coating determines the sensitivity of analytical procedure, the selectivity of extraction, the repeatability of mensuration.But the shortcomings such as price is high, kind is few, duration of service is short, poor stability that current solid-phase micro-extraction coating also exists, therefore, the coated material of development high efficiency low cost has very important significance and using value.Wherein copper nano material is especially because it has stable performance and special physicochemical property have bright development prospect.
Investigators' Nanometer Copper of pattern and configurations that used multiple method to prepare, these methods have its respective merits and demerits, and not all method is all suitable for preparing all types of nano material.Such as, although Gas condensation method has, prepared nano-particle surface is clean, relative density also comparatively advantages of higher, but still there is the shortcomings such as cost is higher, productivity is lower.And electrodip process is the alternative method of the many nanocrystalline materials of preparation, the nanocrystalline material formation time prepared with electrodip process is short, stable in properties, and therefore electrodip process has prepared one of the most promising method of fully dense nano material.
Summary of the invention
Object of the present invention provides a kind of method of electrodeposited nanocrystalline copper coating, and to reduce the preparation cost of Nanometer Copper coating, stability and the life-span of improving Nanometer Copper coating are short.
The method of electrodeposited nanocrystalline copper coating of the present invention is after Stainless Steel Wire being used successively acetone, ultrapure water ultrasonic cleaning, immerses in strong acid solution and etches; Then with etching Stainless Steel Wire for working electrode, platinum electrode is to electrode, and saturated calomel electrode is reference electrode, copper salt solution is electrolytic solution, and control voltage, the scanning number of turns, scanning speed carry out galvanic deposit, and taking-up ultrapure water cleans, isolated dry air, obtains Nanometer Copper coating.
The specification of described Stainless Steel Wire is Φ=0.25 ~ 0.45mm; Described strong acid solution is the sulfuric acid of mass concentration 20 ~ 40%, hydrochloric acid or hydrofluoric acid solution; The etching of Stainless Steel Wire in strong acid solution is carried out under the envrionment temperature of 30 DEG C ~ 50 DEG C, and etching time is 40 ~ 60min.
The electrolytic solution copper salt solution of described galvanic deposit is copper sulfate or the copper nitrate solution of 1 ~ 5mmol/L; The voltage control of galvanic deposit is at-1.0V ~ 1.0V, and the scanning number of turns is that 5 circle ~ 100 are enclosed, and sweep velocity is 10mv/s ~ 60mv/s.
Analyzed by electron-microscope scanning, show that the particle of Nanometer Copper coating prepared by the present invention is between 80 ~ 150nm, structure is vesicular structure, and is evenly distributed; Specific surface area is large, high adsorption capacity, and for extracting phthalate in environmental sample (PAEs), extraction efficiency is high, stability and acid and alkali-resistance strong.In addition, the particle diameter of nano coating of the present invention and pattern control by selecting voltage, the scanning number of turns and scanning speed, and preparation technology is simple, and cost is low, strong operability.
Accompanying drawing explanation
Fig. 1 is the Stainless Steel Wire and etching Stainless Steel Wire SEM figure that do not etch.
Fig. 2 is that example 1 galvanic deposit products therefrom SEM of the present invention schemes.
Fig. 3 is that example 2 galvanic deposit products therefrom SEM of the present invention schemes.
Fig. 4 is that example 3 galvanic deposit products therefrom SEM of the present invention schemes.
Fig. 5 is that example 4 galvanic deposit products therefrom SEM of the present invention schemes.
Fig. 6 is that example 4 galvanic deposit products therefrom EDS of the present invention schemes.
Embodiment
Be described further below by the method for specific embodiment to electrodeposited nanocrystalline copper coating of the present invention.
Embodiment 1
(1) first by Stainless Steel Wire (Φ=0.25mm) acetone ultrasonic cleaning 10min, then ultrapure water ultrasonic cleaning 10min is used;
(2) under the envrionment temperature of 35 DEG C, Stainless Steel Wire one end is immersed in the wang aqueous solution of mass concentration 30% and etch 60min; Take out, be placed in methanol solution and preserve; Fig. 1 is the Stainless Steel Wire and etching Stainless Steel Wire SEM figure that do not etch.As seen from Figure 1, the Stainless Steel Wire surface ratio after etching is more coarse, greatly increases the specific surface area of Stainless Steel Wire, can increase the intensity with melts combine further;
(3) CuSO of 5mmol/L is prepared
4solution is as electrolytic solution, and under three-electrode system, (Stainless Steel Wire of etching is working electrode, and platinum electrode is to electrode, saturated calomel electrode is reference electrode), control voltage is at-0.5V ~ 1.0V, and the scanning number of turns is 30 circles, sweep velocity is that 15mv/s carries out galvanic deposit, obtains Nanometer Copper fiber head; Taking-up ultrapure water cleans, dry under isolated air, obtains uniform nanometer copper particle.The SEM figure of product is shown in the left figure of accompanying drawing 2(to be magnification is the SEM figure of 10,000 times, the right figure SEM figure that to be magnification be under 50,000 times.）。Can show that the Nanometer Copper coating of preparation has good configuration of surface, structural porous by Fig. 2, coating is evenly distributed, and specific surface area is large.
Embodiment 2
(1) first by Stainless Steel Wire (Φ=0.25mm) acetone ultrasonic cleaning 10min, then ultrapure water ultrasonic cleaning 10min is used;
(2) under the envrionment temperature of 45 DEG C, Stainless Steel Wire one end of etching is immersed in the wang aqueous solution of mass concentration 30% and etch 50min; Take out, be placed in methanol solution and preserve;
(3) CuSO of 2mmol/L is prepared
4solution is as electrolytic solution, and under three-electrode system, (Stainless Steel Wire of etching is working electrode, and platinum electrode is to electrode, saturated calomel electrode is reference electrode), control voltage is at-0.2V ~ 0.4V, and the scanning number of turns is 20 circles, sweep velocity is that 40mv/s carries out galvanic deposit, obtains Nanometer Copper fiber head; Taking-up ultrapure water cleans, dry under isolated air, obtains uniform nanometer copper particle.The SEM figure of product is shown in the left figure of accompanying drawing 3(to be magnification is the SEM figure of 10,000 times, the right figure SEM figure that to be magnification be under 50,000 times.）。The Nanometer Copper coating can prepared by Fig. 3 has good configuration of surface, structural porous, and coating is evenly distributed, and specific surface area is large.
Embodiment 3
(1) first by Stainless Steel Wire (Φ=0.35mm) acetone ultrasonic cleaning 10min, then ultrapure water ultrasonic cleaning 10min is used;
(2) under the condition of 45 DEG C, Stainless Steel Wire one end of etching is immersed in the hydrofluoric acid solution of mass concentration 30% and etch 30min; Take out, be placed in methanol solution and preserve;
(3) Cu (NO of 3mmol/L is prepared
3)
2solution is as electrolytic solution, under three-electrode system, (Stainless Steel Wire of etching is working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode), between control voltage-0.5V ~ 0.2V, the scanning number of turns is 30 circles, and sweep velocity is for being 30mv/s, carry out galvanic deposit, obtain Nanometer Copper fiber head; Taking-up ultrapure water cleans, dry under isolated air, obtains uniform nanometer copper particle.The SEM figure of product is shown in the left figure of accompanying drawing 4(to be magnification is the SEM figure of 10,000 times, and right figure magnification is the SEM figure under 50,000 times.）。Can draw by Fig. 4 the configuration of surface that the Nanometer Copper coating of preparation has had, structural porous, coating is evenly distributed, and specific surface area is large.
Embodiment 4
(1) first by Stainless Steel Wire (Φ=0.35mm) acetone ultrasonic cleaning 10min, then ultrapure water ultrasonic cleaning 10min is used;
(2) at 40 DEG C, Stainless Steel Wire one end is immersed in the sulphuric acid soln of mass concentration 40% and etch 60min; Take out, be placed in methanol solution and preserve;
(3) Cu (NO of 1mmol/L is prepared
3)
2solution makes electrolytic solution, under three-electrode system, (Stainless Steel Wire of etching is working electrode, platinum electrode is to electrode, saturated calomel electrode is reference electrode), galvanic deposit Nanometer Copper, control voltage is between-0.5V ~ 0.5V, and the scanning number of turns is 20 circles, sweep velocity is that 20mv/s carries out galvanic deposit, obtains Nanometer Copper fiber head; Taking-up ultrapure water cleans, dry under isolated air, obtains uniform nanometer copper particle.The SEM figure of product is shown in the left figure of accompanying drawing 5(to be magnification is the SEM figure of 10,000 times, and right figure is the SEM figure under magnification 50,000 times.）。Can draw by Fig. 5 the configuration of surface that the Nanometer Copper coating of preparation has had, structural porous, coating is evenly distributed, and specific surface area is large.Fig. 6 is that galvanic deposit products therefrom EDS schemes.Institute's plating coating can be drawn mainly containing copper by Fig. 6, and have part ferro element, oxygen element.
Claims (7)
1. a method for electrodeposited nanocrystalline copper coating, after Stainless Steel Wire being used successively acetone, ultrapure water ultrasonic cleaning, immerses in strong acid solution and etches; Then with etching Stainless Steel Wire for working electrode, platinum electrode is to electrode, and saturated calomel electrode is reference electrode, copper salt solution is electrolytic solution, and control voltage, the scanning number of turns, scanning speed carry out galvanic deposit, and taking-up ultrapure water cleans, isolated dry air, obtains Nanometer Copper coating.
2. the method for electrodeposited nanocrystalline copper coating as claimed in claim 1, is characterized in that: the specification of described Stainless Steel Wire is Φ=0.25 ~ 0.45mm.
3. the method for electrodeposited nanocrystalline copper coating as claimed in claim 1 or 2, is characterized in that: described strong acid solution is the sulfuric acid of mass concentration 20 ~ 40%, hydrochloric acid or hydrofluoric acid solution.
4. the method for electrodeposited nanocrystalline copper coating as claimed in claim 3, is characterized in that: the etching time of described Stainless Steel Wire in strong acid solution is 40 ~ 60min.
5. the method for electrodeposited nanocrystalline copper coating as claimed in claim 3, is characterized in that: it is carry out under the envrionment temperature of 30 DEG C ~ 50 DEG C that described Stainless Steel Wire etches in strong acid solution.
6. the method for electrodeposited nanocrystalline copper coating as claimed in claim 1, is characterized in that: described copper salt solution is copper sulfate or the copper nitrate solution of 1 ~ 5mmol/L.
7. the method for electrodeposited nanocrystalline copper coating as claimed in claim 1, is characterized in that: described galvanic deposit is at voltage-1.0V ~ 1.0V, and the scanning number of turns is that 5 circle ~ 100 are enclosed, and sweep velocity is carry out under 10mv/s ~ 60mv/s.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803514A (en) * | 2016-03-25 | 2016-07-27 | 邵志松 | Electroplating method for specific surface area copper plating layer |
| CN107937943A (en) * | 2017-11-16 | 2018-04-20 | 中达电子(江苏)有限公司 | Porous wick structure and preparation method thereof |
| CN110117802A (en) * | 2019-05-06 | 2019-08-13 | 浙江大学 | A kind of preparation method of multistage three-dimensional microstructures |
| CN112295264A (en) * | 2020-11-30 | 2021-02-02 | 清华大学深圳国际研究生院 | Method for manufacturing solid phase micro-extraction probe |
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| CN101496958A (en) * | 2009-01-14 | 2009-08-05 | 南开大学 | Solid phase micro-extraction device and method for preparing fibre extraction head thereof |
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| CN101496958A (en) * | 2009-01-14 | 2009-08-05 | 南开大学 | Solid phase micro-extraction device and method for preparing fibre extraction head thereof |
| CN102489255A (en) * | 2011-11-24 | 2012-06-13 | 济南大学 | Preparation method for metal wire solid-phase micro-extraction fiber of noble metal nanometer material-ionic liquid composite functional coating |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803514A (en) * | 2016-03-25 | 2016-07-27 | 邵志松 | Electroplating method for specific surface area copper plating layer |
| CN107937943A (en) * | 2017-11-16 | 2018-04-20 | 中达电子(江苏)有限公司 | Porous wick structure and preparation method thereof |
| CN107937943B (en) * | 2017-11-16 | 2019-04-26 | 中达电子(江苏)有限公司 | Porous wick structure and preparation method thereof |
| CN110117802A (en) * | 2019-05-06 | 2019-08-13 | 浙江大学 | A kind of preparation method of multistage three-dimensional microstructures |
| CN112295264A (en) * | 2020-11-30 | 2021-02-02 | 清华大学深圳国际研究生院 | Method for manufacturing solid phase micro-extraction probe |
| CN112295264B (en) * | 2020-11-30 | 2022-04-12 | 清华大学深圳国际研究生院 | Method for manufacturing solid phase micro-extraction probe |
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Application publication date: 20160127 |