Method of copper coating of polymer composition materials on basis of carbon fibers

FIELD: technological process.

SUBSTANCE: invention is related to methods of copper coating of plastics, in particular, polymer composition materials on the basis of carbon fibers and may be used in manufacture of furniture fittings, household appliances and utensils, in automobile and radio industries. Method includes preparation of polymer composition material surface - cleaning, degreasing, immersion and soaking of polymer composition material for 40 - 60 minutes in acid solution of electrolyte with the following composition, g/l: copper sulfate 195 - 235, concentrated sulfuric acid 50 - 60, sodium chloride 0.07 - 0.15 and electrochemical depositing of copper in the same electrolyte at temperature of 20 - 24°C, current density of 5.0 - 6.0 A/dm2 for 5-10 minutes, pH of electrolyte - 1.

EFFECT: allows to increase purity of productivity, to simplify copper coating process, to increase environmental safety and economic efficiency of production.

2 dwg, 2 tbl, 13 ex

 

The invention relates to a method of copper plating of plastics, in particular of polymer composite materials based on carbon fibers. Widespread metallized plastics obtained in the production of furniture accessories, household appliances, household items, automotive and electronic industries.

There is a method of copper plating of polymer composite materials, which includes cleaning, handling at room temperature in the activating solution, the following ratio of components, 10-3mol/l:

Chloride palladium1,0÷5,6
1.2 epoxypropoxyphenyl0,6÷2,0
Acetic acid3÷10
Before potassium3÷5
Neogenic lubricant0,4÷1,0

The heat treatment is carried out at a temperature of 200±20°C for 10-30 minutes

There is a method of copper plating of carbon materials, which are used primarily for polymer composites with highly dispersed carbon fibers, including treatment in an aqueous solution of copper sulfate with stirring and the periodic introduction of powdered zinc. Order to expedite the surveillance process and improved anti-friction properties of the coating solution further injected sulfuric acid and zinc sulfate in the following ratio of components, g/l:

Copper sulphate (CuSO4*5H2O)20-40
Zinc sulfateof 0.05-0.2
Concentrated sulphuric acid34-66

Powder zinc injected at 20°With portions of 1-2 g for 0.5-1.0 HR to content in the solution 15-46 g/l, and then continue processing for 0.5-1 h, and the process is conducted at a ratio of cover material and used a solution of 20 g:1 l

There is a method of metallization of polymer composite materials, taken as a prototype, which includes the following operations:

1) surface preparation of parts coated, which consists of:

- cleanup - remove surface dirt, dust, various foreign substances;

- degreasing, which is to be deleted from the coated surface of fats and oils, which reduce its wettability (organic solvents - acetone, gasoline, etc. or alkaline solutions with surfactant);

- etching occurring on the surface of polymer composite materials and accompanied by changes in its structure and physico-chemical properties, the composition of the solution, g/l:

To2Cr2O747
H2SO4 825,

- immersion of the product in the etching solution at 3-45 min at a temperature of 60-80°C;

- washing with water, then ammonia solution and again with water.

- sensibilizirovannoy - auxiliary operations when activated surface. It consists in depositing on the surface of the polymer composite material in the hydrolysis of salts of divalent tin, whereby recovering metal during the subsequent metallization. As sensitizers used acid solutions of composition, g/l:

SnCl2*H2O10-100
HCl10-50;

- enable processing of the sensitized surface with solutions of compounds of the active metals composition of the aqueous solution, g/l:

PdCl20,2-0,5
HCl1,1-3,3,

the essence of the process of activation is the deposition on the surface of the polymer composite material of catalytically active metal in the form of colloidal particles or low-solubility compounds, which starts the recovery of the precipitated metal;

- sensitised and activated surface is dried;

2) the reating a conductive layer on the surface by dipping the polymer composite material in the solution, containing, g/l:

CuSO4*5H2O5
KNaC4H4O625
NaOH7
formalin (40%)10

when the pH of 12.8;

3) electrochemical deposition of metal on the conductive layer polymer composite material by immersion in a galvanic bath with sulfate electrolyte, consisting, g/l:

Copper sulphate (CuSO4*5H2O)225-275
Concentrated sulphuric acid (H2SO4)50-75,

at a temperature of 27-28°and current density of 3 to 30 A/DM2.

Method of metallization of polymer composite materials is complex, multi-stage, labour input. Consequently, deterioration of ecological environment and increase economic production costs.

When creating a method of copper plating of polymer composite materials based on carbon fibers following objectives were set: to reduce the number of technological operations, increase safety, to simplify the process of copper plating, to improve environmental safety and production efficiency.

For R the solutions of the tasks in the way that the copper plating of polymer composite materials based on carbon fibers, includes surface preparation - cleaning, degreasing the surface of the polymer composite material based on carbon fibers and electrochemical copper deposition, electrochemical deposition of copper is conducted additionally immersion and restraint polymer composite material based on carbon fibers for 40÷60 minutes in an acidic electrolyte solution of the following composition, g/l;

Copper sulphate (CuSO4*5H2O)195÷235
Concentrated sulphuric acid (H2SO4)50÷60
Sodium chloride (NaCl)0,07÷0,15,

and electrochemical copper deposition is carried out on the surface of the polymer composite material in the same electrolyte at a temperature of 20÷24°C, current density of 5.0÷6,0 A/DM2for 5÷10 minutes, the pH of the electrolyte is 1.

The proposed method of copper plating of polymer composite materials based on carbon fibers is illustrated in figure 1, 2 and table 1, 2.

Figure 1 presents a graph of the dependence of the output copper current (t, %) on the composition of the acidic electrolyte solution during immersion and exposure of polymer composite material based on carbon fibers.

Figure 2 p is estaline micrograph of the surface of the copper coating on polymer composite material based on carbon fibers at current density:

a) 1.0 a/DM2×100;

b) a 5.0 A/DM2×100;

C) 5,5 A/DM2×100;

g) 6,0 A/DM2×100;

d) 8.0 a/DM2×100.

Table 1 Properties (the current output, hardness, surface resistivity) of copper coatings on polymer composite material based on carbon fibers from time of electrolysis at a current density of 5.5 A/DM2.

Table 2 Properties (the current output, adhesion, surface resistivity) of copper coatings on polymer composite material based on carbon fibers from the current density at the time of electrolysis 7 minutes

Method of copper plating of polymer composite materials based on carbon fibers were carried out in the electrochemical cell with a copper anode as an auxiliary electrode. As working electrodes used electrodes made of composite material, which was a polymer composite material has a cylindrical shape with the linear dimensions: outer diameter - 1.5 cm, an internal diameter of 0.9 cm, length 5.8 cm, consisting of carbon fibers based on polyacrylonitrile fibres and binder (pack brand-261), based on the epoxy resin composition grades up-612, the UE-610 and hardener - anilinopiperidine resin (WUT 2-292-68)obtained by the method of winding. Polymer compositions the ionic material was subjected to mechanical cleaning with sandpaper No. 2, followed by polishing to remove surface dirt, dust and various foreign substances. Degreasing spent organic solvents - toluene, acetone, benzine, alcohol, etc. To electrochemical deposition of copper additionally held immersion and restraint polymer composite material based on carbon fibers for 40÷60 minutes in an acidic electrolyte solution of the following composition, g/l:

Copper sulphate (CuSO4*5H2O)195÷235
Concentrated sulphuric acid (H2SO4)50÷60
Sodium chloride (NaCl)0,07÷0,15

Electrochemical deposition of copper was performed on the surface of the polymer composite material in the same electrolyte at a temperature of 20÷24°C, current density of 5.0÷6,0 A/DM2for 5÷10 minutes, the pH of the electrolyte is 1, the electrochemical cell with a copper anode as an auxiliary electrode.

Then the polymer composite material based on carbon fibers with copper coating was rinsed with water and dried at 60÷80°C for 15÷20 minutes

Example 1. In the above method of copper plating of polymer composite materials based on carbon fibers prior to electrochemical deposition of copper additionally check the Dili immersion and restraint polymer composite material based on carbon fibers for 40 minutes in an acidic electrolyte solution of the following composition, g/l:

Copper sulphate (CuSO4*5H2O)195
Concentrated sulphuric acid (H2SO4)50
Sodium chloride (NaCl)0,07,

electrochemical deposition of copper was performed on the surface of the polymer composite material in the same electrolyte at a temperature of 20°C, current density of 5.0 A/DM2within 5 minutes, the pH of the electrolyte is 1.

Example 2. In the above method of copper plating of polymer composite materials based on carbon fibers prior to electrochemical deposition of copper additionally held immersion and restraint polymer composite material based on carbon fibers for 60 minutes in an acidic electrolyte solution of the following composition, g/l:

Copper sulphate (CuSO4*5H2O)235
Concentrated sulphuric acid (H2SO4)60
Sodium chloride (NaCl)0,15,

electrochemical deposition of copper was performed on the surface of the polymer composite material in the same electrolyte at a temperature of 24°C, current density of 6.0 A/DM2within 10 minutes, the pH of the electrolyte is 1.

Example 3. In the above method of copper plating of polymer composite materials based on carbon fibers prior to electrochemical deposition of copper additionally held immersion and restraint polymer composite material based on carbon fibers for 50 minutes in an acidic electrolyte solution of the following composition, g/l:

Copper sulphate (CuSO4*5H2O)215
Concentrated sulphuric acid (H2SO4)55
Sodium chloride (NaCl)0,11,

electrochemical deposition of copper was performed on the surface of the polymer composite material in the same electrolyte at a temperature of 22°C, current density of 5.5 A/DM2within 7 minutes, the pH of the electrolyte is 1. When this was received fine-grained, homogeneous, solid, solid, shiny coat (pigv), the current output was 98.0% (Fig 1, 2).

Example cab copper plating of polymer composite materials based on carbon fibers were performed according to example 3, and electrochemical copper deposition was performed at a current density of 1.0 a/DM2. The coating in this case was thin, inhomogeneous (figa).

Example 5. Method of copper plating of polymer composite materials on the basis of operon the x fibers were performed according to example 3, and electrochemical copper deposition was performed at a current density of 8.0 a/DM2. When this has been porous, coarse floor with a shattering of grains due to low adhesion (figd).

Example 6. Method of copper plating of polymer composite materials based on carbon fibers was carried out according to example 3, but electrochemical copper deposition was carried out for 2 minutes.

Example 7. Method of copper plating of polymer composite materials based on carbon fibers was carried out according to example 3, but electrochemical copper deposition was carried out for 30 minutes.

Example. 8 Method of copper plating of polymer composite materials based on carbon fibers was carried out according to example 3, however, before the electrochemical deposition of copper advanced immersion and restraint polymer composite material based on carbon fibers did not. In this case, the current output was low values of 60.8% out of 100% (Fig 1, 1).

Example 9. Method of copper plating of polymer composite materials based on carbon fibers was carried out according to example 3, but before the electrochemical deposition of copper additionally held immersion and restraint polymer composite material based on carbon fibers for 50 minutes in an acidic electrolyte solution of the following composition is a, g/l:

Concentrated sulphuric acid (H2SO4)55

The current output amounted to 70.8% (Fig 1, 3).

Example 10. Method of copper plating of polymer composite materials based on carbon fibers was carried out according to example 3, but before the electrochemical deposition of copper additionally held immersion and restraint polymer composite material based on carbon fibers for 50 minutes in an acidic electrolyte solution of the following composition, g/l:

Concentrated sulphuric acid (H2SO4)55
Sodium chloride (NaCl)0,11

The output of copper current - 77% (Fig 1, 4).

Example 11. Method of copper plating of polymer composite materials based on carbon fibers was carried out according to example 3, but before the electrochemical deposition of copper additionally held immersion and restraint polymer composite material based on carbon fibers for 50 minutes in an acidic electrolyte solution of the following composition, g/l:

Copper sulphate (CuSO4*5H2O)215
Concentrated sulphuric acid (H2SO4) 55

The current output is 82% (Fig 1, 5).

Example 12. Method of copper plating of polymer composite materials based on carbon fibers was carried out according to example 3, but before the electrochemical deposition of copper additionally held immersion and restraint polymer composite material based on carbon fibers for 50 minutes in an acidic electrolyte solution of the following composition, g/l:

Copper sulphate (CuSO4*5H2O)215

The current output is to 72.6%. (1, 6).

Thus, it was found that all the components of the acidic electrolyte, which further held immersion and restraint polymer composite material based on carbon fibers exposed on its surface.

Example 13. Method of copper plating of polymer composite materials based on carbon fibers was carried out according to example 3, but before the electrochemical deposition of copper additionally held immersion and restraint polymer composite material based on carbon fibers for 50 minutes in a solution of the following composition, g/l:

Hydrochloric acid (HCl)25

The current output - 69,2% (1, 7). This suggests that the best solution immersion and exposure of polymer composite material based on carbon fibers is claimed acidic electrolyte solution.

All properties of the copper coating polymer composite material based on carbon fibers are shown in table 1-2.

The advantages of the proposed method of copper plating of polymer composite materials based on carbon fibers lie in reducing the number of technological operations, such as etching, washing with water and ammonia with water again, sensibilizirovannoi, activation, application of a conductive layer. Increases the purity of the production due to the lack of wash water after etching and chemical copper plating. The proposed method of copper plating of polymer composite materials based on carbon fibers makes it possible to improve the environmental safety and economic efficiency of this production.

Table 1
Method of copper plating of polymer composite materials based on carbon fibers
# exampleThe time of electrolysis, minThe current output, %The hardness of the coating, kg/mm2Surface resistivity, 10-2Ohm*m
6297,0a 7.623,6
-497,59,88 2,17
1597,710,31,8
3798,010,60,93
210of 98.210,00,65
-1598,69,070,24
-20the 98.98,940,17
-2099,08,700,09
73099,28,100,09

Table 2
# exampleThe current density, A/DM2The current output, %Adhesion, MPaSurface resistivity, 10-2Ohm*m
41,043,025,384,4
-2,0of 60.539,97the 3.8
-3,090,342,42,6
-4,0for 95.245,81,5
15,096,746,20,098
35,598,050,60,09
26,0of 98.230,60,09
-7,098,417,460,09
58,099,010,20,09

Method of copper plating of polymer composite materials based on carbon fibers, including the preparation of the surface of the polymer composite material - cleaning, degreasing and electrochemical deposition of copper, wherein the electrochemical deposition of copper is conducted additionally immersion and restraint polymer composite material within 40-60 min in an acidic electrolyte solution of the following composition, g/l:

copper sulphate (CuSO4·5H2O)195-235
concentrated sulphuric acid (H2SO4)50-60
sodium chloride (NaCl)0,07-0,15,

and electrochemical copper deposition is carried out in the same electrolyte at a temperature of 20-24°C, current density of 5.0-6.0 A/DM2within 5-10 min, the pH of the electrolyte is 1.



 

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