CN103806034B - A kind of method of textile surface constant current electrodeposit metals copper - Google Patents

Abstract

The invention relates to a method for constant current electrodeposition of metallic copper on the surface of textiles, comprising: immersing the fabric in an inorganic acid solution of a nitrogen-containing polymer monomer, vibrating, and then spraying an ammonium persulfate oxidation solution on the fabric to obtain a conductive fabric ; The above-mentioned conductive fabric is subjected to constant current electrodeposition in an electrolyte solution, rinsed and dried. The preparation method of the present invention is simple, the composition of the solution is simple, safe and environment-friendly, and the cost is low, and the conductive metal layer with different microscopic shapes can be obtained by controlling the magnitude of the current density, and has broad application prospects in the field of intelligent textiles.

Description

A method for constant current electrodeposition of metal copper on the surface of textiles

technical field

The invention belongs to the field of preparation of conductive fabrics, in particular to a method for constant current electrodeposition of metal copper on the surface of textiles.

Background technique

The direct metal electrodeposition (direct electroplating) process on non-metallic surfaces began with the discussion of the plastic direct metal electrodeposition process. The traditional method of depositing metal films on the surface of non-conductive substrates is often achieved by electroless deposition (electroless plating), but the process involves Expensive noble metal salt catalysis, the use of formaldehyde as a reducing agent, and the generation of hydrogen gas during the electroless deposition process are likely to cause pinhole pitting in the coating, which affects the apparent quality of the coating. In view of the existence of the above problems, people began to explore the direct electrodeposition process of non-conductive substrates while continuing to carry out the research on the electroless deposition process. To achieve direct metal electrodeposition on the surface of a non-conductive substrate, a conductive prefabricated layer must first be formed on the surface. Usually, conductive polymer systems, Pd/Sn systems and carbon particle suspension systems are used as conductive substances. Among them, polypyrrole and polyaniline are mostly used in the conductive polymer system, and most of them are in the form of colloid or in-situ deposition. They not only act as a conductive prefabricated layer in the electrodeposition process but also build a conductive network together with the deposited metal. In actual use Gradually showing greater commercial application value.

At present, there are almost no reports on the direct electrodeposition on flexible substrates such as fibers or fabrics. However, there are precedents for electrochemical preparation methods applied to fiber substrates. From 2009 to 2011, F.Cases et al. continuously reported their research group The work carried out on the electrochemical preparation of polyaniline on the surface of the fabric deposited with polypyrrole film provides a reference for the fiber matrix as an electrochemical electrode. [MolinaJ,RioAI,BonastreJ,etal.Electrochemicalpolymerisationofanilineonconductingtextilesofpolyestercoveredwithpolypyrrole/AQSA[J].EuropeanPolymerJournal,2009,45(4):1302-1315.][MolinaJ,FernándezJ,RioAI,etal.Electrochemicalsynthesisofpolyanilineonconductingfabricsofpolyestercoveredwithpolypyrrole/PW ₁₂ O ₄₀ ^3- .Chemicalandelectrochemicalcharacterization[ J].Synthetic Metals,2011,161(11-12):953-963.]

There is no relevant report at home and abroad on the electrodeposition of metal Cu on the surface of textiles with a predetermined conductive polymer by constant current method. By controlling the current density and electroplating time, conductive textiles with different properties can be obtained to meet the needs of different fields, and have broad application prospects in smart textiles.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for constant current electrodeposition of metal copper on the surface of textiles. The preparation method of the present invention is simple, avoiding the use of expensive noble metal salts and toxic formaldehyde reducing agents when electroless deposition is used, and the composition of the electrolyte is simple. Safety and environmental protection, low cost, low performance requirements for equipment.

A method for constant current electrodeposition of metal copper on the surface of textiles of the present invention, comprising:

(1) Immerse the fabric in an aqueous solution composed of a nitrogen-containing polymer monomer and an inorganic acid, shake it, and then spray ammonium persulfate oxidation solution on the fabric to obtain a conductive fabric;

(2) Conduct constant current electrodeposition of the above-mentioned conductive fabric in the electrolyte, rinse and dry; the electrolyte is composed of copper sulfate, sodium citrate, and sodium sulfate.

The fabric in the step (1) is one of polyester cloth, nylon cloth and polyester nylon cloth.

In the step (1), the nitrogen-containing macromolecular monomer is polyaniline or polypyrrole; the inorganic acid is one of hydrochloric acid, nitric acid, and sulfuric acid.

In the step (1), the monomer concentration in the aqueous solution composed of the nitrogen-containing polymer monomer and the inorganic acid is 0.8-1.2 mol/L, and the ratio of the molar concentration of the monomer to the inorganic acid is 1:1.

The oscillation in the step (1) is at 70-90°C for 60-90min.

The concentration of the ammonium persulfate oxidizing solution in the step (1) is 0.4-0.6 mol/L; the temperature of the ammonium persulfate oxidizing solution is lower than 10° C., and the pH value is 3-4.

The electrolyte composition in the step (2) is that the concentration of copper sulfate is 0.6-0.8 mol/L, the concentration of sodium citrate is 0.04-0.08 mol/L, the concentration of sodium sulfate is 0.2-0.6 mol/L, and the pH value is 3-4 .

The constant current electrodeposition process in the step (2) is as follows: the conductive fabric is used as the cathode, the titanium metal electrode is used as the anode, and the saturated calomel electrode is used as the reference electrode.

The room temperature energized current density is 100-150mA/cm ² , and the energized time is 10-30s, and then reduced to a current density of 60-80A/cm ² , and energized for 90-120s.

Beneficial effect

(1) The preparation method of the present invention is simple, avoiding the use of expensive noble metal salts and toxic formaldehyde reducing agents when electroless deposition is used, the composition of the electrolyte is simple, safe and environmentally friendly, low cost, and low performance requirements for equipment;

(2) The conductive fabric obtained in the present invention has excellent conductive properties. By controlling the electroplating conditions, a conductive metal copper plating layer that is firmly combined with the textile matrix and interlaced with the polymer conductive layer can be obtained. The fabric is stable in nature and meets the development requirements. The needs of smart textiles have broad application prospects;

(3) The present invention controls the magnitude of the current density to obtain conductive metal layers with different microscopic shapes, and has broad application prospects in the field of smart textiles.

detailed description

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

This embodiment adopts polyester cloth

(1) Immerse the fabric in an aqueous solution composed of 1.0mol/L aniline and 1.0mol/L hydrochloric acid, shake it at 90°C for 60 minutes and take it out;

(2) Spray 0.5 mol/L ammonium persulfate oxidation solution with a pH value of 4 pre-cooled to 5°C on the fabric obtained in step (1) to obtain a conductive fabric;

(3) The above-mentioned conductive fabric is used as the cathode, the titanium metal electrode is used as the anode, and the saturated calomel electrode is used as the reference electrode. In an electrolyte solution with a pH value of mol/L of 4, energize at 120mA/cm ² for 30s at room temperature;

(4) Reduce the current to 60mA/cm ² and continue to energize for 120s before taking it out, rinsing and drying.

Tests show that the surface resistance of the fabric is 10±2mΩ/sq, and the fabric has excellent electrical conductivity, friction resistance and washability.

Example 2

This embodiment adopts polyester brocade cloth

(1) Immerse the fabric in an aqueous solution composed of 0.8mol/L aniline and 0.8mol/L hydrochloric acid, shake it at 80°C for 60 minutes and take it out;

(2) Spray 0.4 mol/L ammonium persulfate oxidation solution with a pH value of 4 pre-cooled to 5°C on the fabric obtained in step (1) to obtain a conductive fabric;

(3) The above-mentioned conductive fabric is used as the cathode, the titanium metal electrode is used as the anode, and the saturated calomel electrode is used as the reference electrode. In an electrolyte solution with a pH value of mol/L of 4, energize at 100mA/ ^cm2 for 20s at room temperature;

(4) Reduce the current to 80mA/cm ² and continue to energize for 100s, take it out, rinse and dry.

Tests show that the surface resistance of the fabric is 5±2mΩ/sq, and the fabric has excellent electrical conductivity, friction resistance and washability.

Example 3

This embodiment adopts nylon cloth

(1) Immerse the fabric in an aqueous solution composed of 0.6mol/L aniline and 0.6mol/L hydrochloric acid, shake it at 85°C for 60 minutes and take it out;

(2) Spray 0.3 mol/L ammonium persulfate oxidation solution with a pH value of 4 pre-cooled to 5°C on the fabric obtained in step (1) to obtain a conductive fabric;

(3) The above-mentioned conductive fabric is used as the cathode, the titanium metal electrode is used as the anode, and the saturated calomel electrode is used as the reference electrode. In an electrolyte solution with a pH value of mol/L of 4, energize at 80mA/ ^cm2 for 30s at room temperature;

(4) Reduce the current to 60mA/cm ² and continue to energize for 120s before taking it out, rinsing and drying.

Tests show that the surface resistance of the fabric is 20±2mΩ/sq, and the fabric has excellent electrical conductivity, friction resistance and washing resistance.

Example 4

This embodiment adopts polyester brocade cloth

(1) Immerse the fabric in an aqueous solution composed of 1.0mol/L aniline and 1.0mol/L hydrochloric acid, shake it at 80°C for 60 minutes and take it out;

(2) Spray 0.4 mol/L ammonium persulfate oxidation solution with a pH value of 4 pre-cooled to 5°C on the fabric obtained in step (1) to obtain a conductive fabric;

(3) The above-mentioned conductive fabric is used as the cathode, the titanium metal electrode is used as the anode, and the saturated calomel electrode is used as the reference electrode. In an electrolyte solution with a pH value of mol/L of 4, energize at 80mA/ ^cm2 for 30s at room temperature;

(4) Reduce the current to 60mA/cm ² and continue to energize for 100s, take it out, rinse and dry.

Tests show that the surface resistance of the fabric is 10±2mΩ/sq, and the fabric has excellent electrical conductivity, friction resistance and washability.

Claims (9)

1. a method for textile surface constant current electrodeposit metals copper, comprising:

(1) by textile impregnation in the aqueous solution of nitrogen containing polymer monomer and inorganic acid composition, vibration is then sprayed on fabricAmmonium persulfate oxidation solution, obtains conductive fabric;

(2) above-mentioned conductive fabric is carried out in electrolyte to constant current electro-deposition, rinsing is dried; Wherein electrolyte by copper sulphate,Natrium citricum, sodium sulphate composition.

2. the method for a kind of textile surface constant current electrodeposit metals copper according to claim 1, is characterized in that: instituteTo state fabric in step (1) be woven dacron, polyamide fabric, wash the one in bright and beautiful cloth.

3. the method for a kind of textile surface constant current electrodeposit metals copper according to claim 1, is characterized in that: instituteStating nitrogen containing polymer monomer in step (1) is polyaniline or polypyrrole; Inorganic acid is one in hydrochloric acid, nitric acid, sulfuric acidKind.

4. the method for a kind of textile surface constant current electrodeposit metals copper according to claim 1, is characterized in that: instituteStating monomer concentration in the aqueous solution of nitrogen containing polymer monomer and inorganic acid composition in step (1) is 0.8～1.2mol/L, singleBody is 1:1 with the ratio of the molar concentration of inorganic acid.

5. the method for a kind of textile surface constant current electrodeposit metals copper according to claim 1, is characterized in that: instituteStating vibration in step (1) is under 70-90 DEG C of condition, vibration 60-90min.

6. the method for a kind of textile surface constant current electrodeposit metals copper according to claim 1, is characterized in that: instituteThe concentration of stating ammonium persulfate oxidation solution in step (1) is 0.4-0.6mol/L; The temperature of ammonium persulfate oxidation solution is lower than 10DEG C, pH value 3-4.

7. the method for a kind of textile surface constant current electrodeposit metals copper according to claim 1, is characterized in that: instituteStating in step (2) electrolyte, to consist of concentration of copper sulfate be that 0.6-0.8mol/L, sodium citrate concentration are 0.04-0.08mol/L, sodium sulfate concentration are 0.2-0.6mol/L, pH value 3～4.

8. the method for a kind of textile surface constant current electrodeposit metals copper according to claim 1, is characterized in that: instituteStating constant current electrodeposition technology in step (2) is: conductive fabric is negative electrode, and titanium electrode is anode, saturated calomelElectrode is reference electrode, and room temperature energising, then reduces electric current energising.

9. the method for a kind of textile surface constant current electrodeposit metals copper according to claim 8, is characterized in that: instituteStating room temperature electrical current density is 100-150mA/cm², be 10-30s conduction time, is then decreased to current density to be60-80A/cm², energising 90-120s.