阅读说明：本技术 一种碳纤维织物电镀液的配制方法 (Preparation method of carbon fiber fabric electroplating solution ) 是由 张丽 马晓飞 张志成 于 2021-08-03 设计创作，主要内容包括：本发明公开了一种碳纤维织物电镀液的配制方法,涉及织物电镀技术领域,本发明采用可溶性镍盐、可溶性铁盐作为主盐,在碳纤维织物表面形成致密、均匀且光亮的镀镍层、镀铁层或镀镍铁层,通过具有PTC效应的金属镍、铁的镀覆来改善碳纤维织物的导电性,降低电阻率,并使电阻率随碳纤维织物自身温度的升高而增大,同时利用金属镍、铁的磁性能来提高碳纤维织物的电磁屏蔽性能,从而制得兼具电致发热和电磁屏蔽功能的高性能纺织品。(The invention discloses a preparation method of a carbon fiber fabric electroplating solution, which relates to the technical field of fabric electroplating, wherein soluble nickel salt and soluble ferric salt are used as main salts, a compact, uniform and bright nickel plating layer, iron plating layer or nickel-iron plating layer is formed on the surface of a carbon fiber fabric, the conductivity of the carbon fiber fabric is improved by plating metal nickel and iron with PTC effect, the resistivity is reduced, the resistivity is increased along with the increase of the temperature of the carbon fiber fabric, and the electromagnetic shielding performance of the carbon fiber fabric is improved by utilizing the magnetic performance of the metal nickel and iron, so that a high-performance textile with both electrothermal and electromagnetic shielding functions is prepared.)

1. A preparation method of carbon fiber fabric electroplating solution is characterized by comprising the following steps: adding main salt, conductive salt, complexing agent, buffering agent and additive into deionized water at room temperature, stirring for dissolving, and uniformly mixing to obtain electroplating solution;

the main salt is one or a mixture of two of soluble nickel salt and soluble iron salt;

the conductive salt is one or more of sodium chloride, potassium chloride and potassium nitrate;

the complexing agent is one or more of citric acid, lactic acid, tartaric acid and glycine;

the buffer is one or more of boric acid, acetic acid, tartaric acid and salts thereof;

the additives include stress relief agents, wetting agents, and brighteners.

2. The method for preparing a carbon fiber fabric electroplating solution as set forth in claim 1, wherein: the concentration of each component in the electroplating solution is 300g/L of main salt 100-.

3. The method for preparing a carbon fiber fabric electroplating solution as set forth in claim 1, wherein: the soluble nickel salt is nickel sulfate or nickel chloride.

4. The method for preparing a carbon fiber fabric electroplating solution as set forth in claim 1, wherein: the soluble ferric salt is ferrous sulfate, ferrous chloride or ferric nitrate.

5. The method for preparing a carbon fiber fabric electroplating solution as set forth in claim 1, wherein: the pH value of the electroplating solution is 5-7.

6. The method for preparing a carbon fiber fabric electroplating solution as set forth in claim 1, wherein: the stress relieving agent is one or more of coumarin and o-benzoyl sulfonyl imide.

7. The method for preparing a carbon fiber fabric electroplating solution as set forth in claim 1, wherein: the wetting agent is one or more of sodium dodecyl sulfate and sodium phenyl sulfonate.

8. The method for preparing a carbon fiber fabric electroplating solution as set forth in claim 1, wherein: the brightener is one or more of saccharin and propiolic alcohol ethoxylate.

The technical field is as follows:

the invention relates to the technical field of fabric electroplating, in particular to a preparation method of carbon fiber fabric electroplating solution.

Background art:

the carbon fiber has the excellent characteristics of high strength, light weight, high temperature resistance, corrosion resistance and high electric heat conversion rate, and has the softness and the processability of textile fiber, and the carbon fiber and the textile thereof become indispensable strategic new materials for national economy and national defense construction. The consumption of carbon fiber fabrics in China is increasing day by day, the market demand is vigorous, and the productivity of the carbon fiber industry is continuously expanded along with the increasing downstream demand. The carbon fiber has excellent electrical conductivity and thermal conductivity, strong dielectric loss and adjustable impedance, is an ideal raw material for preparing high-performance electric heating fabrics and electromagnetic shielding fabrics, and has wide application in civil and military fields.

However, the carbon fiber has a low temperature coefficient of resistance, and is difficult to realize adaptive temperature adjustment; meanwhile, the carbon fiber has high electromagnetic reflectivity, is easy to cause secondary electromagnetic radiation damage to the environment, and has low magnetic conductivity and narrow absorption frequency band. The defects of the body structure of the carbon fiber are further overcome, the overall performance of the electro-heating and electromagnetic shielding fabric is improved, and the carbon fiber electro-heating and electromagnetic shielding fabric plays a key role in promoting product upgrading, technical progress and industrial structure adjustment in the field of electro-heating and electromagnetic shielding in China.

The invention aims to provide a carbon fiber fabric electroplating solution, which takes soluble nickel salt and/or soluble iron salt as main salt, plates nickel and/or iron on the surface of carbon fiber, improves the conductivity by utilizing the PTC (positive temperature coefficient) characteristic of the carbon fiber fabric, increases the resistivity of the carbon fiber fabric along with the self temperature rise, and further meets the use requirement of an electro-heating textile.

The invention content is as follows:

the technical problem to be solved by the invention is to provide a preparation method of the carbon fiber fabric electroplating solution, which can form a compact, uniform and bright nickel plating layer, iron plating layer or nickel-iron plating layer on the surface of the carbon fiber fabric by screening and optimizing the composition and the proportion of the electroplating solution, control the cost and simplify the preparation operation.

The invention aims to provide a preparation method of a carbon fiber fabric electroplating solution.

The main salt is one or the mixture of two of soluble nickel salt and soluble iron salt. Under the action of electroplating, a nickel-plated layer, an iron-plated layer or a nickel-plated iron layer is deposited on the carbon fiber fabric.

The conductive salt is one or more of sodium chloride, potassium chloride and potassium nitrate. The conductive salt is used for improving the conductivity of the electroplating solution, reducing the voltage of the tank and improving the deep plating capacity of the electroplating solution.

The complexing agent is one or more of citric acid, lactic acid and glycine. The complexing agent can increase the polarization of the cathode in addition to complexing the metal ions.

The buffer is one or more of boric acid, acetic acid, tartaric acid and salts thereof. The buffer is used to control the pH of the plating solution, particularly near the cathode.

The additives include stress relief agents, wetting agents, and brighteners. Although the additives are present in the plating bath in low amounts, they can significantly affect the performance of the plating process and the application properties of the coating.

The concentration of each component in the electroplating solution is 300g/L of main salt 100-.

The soluble nickel salt is nickel sulfate or nickel chloride.

The soluble ferric salt is ferrous sulfate, ferrous chloride or ferric nitrate.

The pH value of the electroplating solution is 5-7.

The mass ratio of the stress relieving agent, the wetting agent and the brightening agent contained in the additive is (5-10): (0.5-2): 0.5-2).

The stress relieving agent is one or a mixture of two of coumarin and o-benzoyl sulfonyl imide. The stress relieving agent can reduce the internal stress of the coating, improve the binding force of the coating and the carbon fiber fabric, and prevent the coating from generating bubbles and even falling off.

The wetting agent is one or more of sodium dodecyl sulfate and sodium phenyl sulfonate. The wetting agent can reduce the interfacial tension between the electroplating solution and the cathode, so that bubbles are easy to separate from the surface of the cathode, and pinholes are prevented from being generated in the plating layer.

The brightener is one or more of saccharin and propiolic alcohol ethoxylate. The addition of the brightener can enable the plating layer to become flat and smooth, thereby achieving the bright visual effect.

The invention also aims to provide application of the stress relieving agent in preparation of the carbon fiber fabric electroplating solution.

The stress relieving agent is 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-diketone.

The 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-diketone is prepared by substitution reaction of piperazine-2, 3-diketone and (3-bromopropoxy) trimethylsilane.

The inventor successfully synthesizes 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-diketone aiming at the existing stress relieving agent in the field and combining molecular design with the assistance of organic synthesizers, and tests show that the compound can be used as the stress relieving agent, and has obviously stronger effect of relieving the internal stress of a plating layer than coumarin and o-benzoyl sulfimide.

The invention has the beneficial effects that: the invention adopts soluble nickel salt and soluble ferric salt as main salts to form a compact, uniform and bright nickel plating layer, iron plating layer or nickel-iron plating layer on the surface of the carbon fiber fabric, improves the conductivity of the carbon fiber fabric by plating metal nickel and iron with PTC effect, reduces the resistivity, increases the resistivity along with the increase of the temperature of the carbon fiber fabric, and simultaneously improves the electromagnetic shielding performance of the carbon fiber fabric by utilizing the magnetic performance of the metal nickel and iron, thereby preparing the high-performance textile with the functions of electric heating and electromagnetic shielding.

The specific implementation mode is as follows:

in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.

Example 1

Preparing an electroplating solution: adding 120g/L nickel sulfate, 50g/L ferrous sulfate, 30g/L sodium chloride, 40g/L citric acid, 25g/L boric acid and 10g/L additive (coumarin, sodium dodecyl sulfate and saccharin in a mass ratio of 8:0.5: 1) into deionized water at room temperature, stirring for dissolving, and uniformly mixing to obtain an electroplating solution with the pH value of 5.

Example 2

Preparing an electroplating solution: at room temperature, 200g/L ferrous sulfate, 40g/L potassium chloride, 30g/L citric acid, 20g/L lactic acid, 30g/L boric acid and 15g/L additive (coumarin, sodium phenylsulfonate and saccharin in a mass ratio of 10:1: 1) are added into deionized water, stirred and dissolved, and uniformly mixed to obtain the electroplating solution with the pH value of 5.

Example 3

Preparing an electroplating solution: adding 150g/L nickel sulfate, 25g/L sodium chloride, 40g/L citric acid, 20g/L boric acid, 20g/L sodium tartrate and 10g/L additive (the mass ratio of the o-benzoylsulfimide to the sodium dodecyl sulfate to the propiolic alcohol ethoxylate is 8:0.5: 0.5) into deionized water at room temperature, stirring for dissolving, and uniformly mixing to obtain the electroplating solution with the pH value of 6.

Example 4

Preparing an electroplating solution: adding 100g/L nickel sulfate, 80g/L ferrous sulfate, 35g/L sodium chloride, 50g/L citric acid, 35g/L boric acid and 12g/L additive (coumarin, sodium dodecyl sulfate and saccharin in a mass ratio of 10:0.5: 1) into deionized water at room temperature, stirring for dissolving, and uniformly mixing to obtain an electroplating solution with the pH value of 6.

Example 5

Example 5 was carried out in exactly the same manner as in example 1 except that the coumarin in example 1 was replaced with 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-dione of equivalent mass.

The 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-dione is prepared by substitution reaction of piperazine-2, 3-dione and (3-bromopropoxy) trimethylsilane in a molar ratio of 1: 1.

Synthesis of 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-dione: adding piperazine-2, 3-dione, (3-bromopropoxy) trimethylsilane and triethylamine in a molar ratio of 1:1:1 into ethanol, heating to reflux, carrying out heat preservation reaction, monitoring the reaction by TLC, stopping the reaction after the reaction is completed, carrying out reduced pressure distillation to remove ethanol, washing the concentrate, drying in an oven at 80 ℃ to obtain a white solid, and carrying out column chromatography separation (an eluent is ethyl acetate-petroleum ether) to obtain 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-dione with the yield of 98.6%.¹H NMR(DMSO-d6,400MHz),δ:8.68(s,1H),3.74(t,2H),3.34-3.25(m,4H),2.94(t,2H),1.78(m,2H),0.23(s,9H)；ESI-MS:m/z＝245.12[M+1]⁺.

Example 6

Pretreating a carbon fiber fabric by adopting the pretreatment method of embodiment 1 in patent CN 112144272A, taking the pretreated carbon fiber fabric as a cathode, taking a platinum sheet with the same size as a counter electrode, respectively pouring the electroplating solutions prepared in embodiments 1-5 into an electroplating bath, heating the electroplating solutions in a water bath to control the temperature of the electroplating solutions to be 50 +/-1 ℃, and stirring to ensure the uniformity of the electroplating solutions; adjusting the pulse power parameter, t_on＝0.5ms，t_off2ms, current density 2A/dm²Fixing an electrode, starting a power supply, and beginning to perform metal plating on the carbon fiber fabric, wherein the plating time is controlled to be 15 min; and (4) turning off the power supply, taking out the carbon fiber fabric, washing with deionized water, and drying in a vacuum oven.

The internal stress of the plating layers formed using the plating solutions prepared in examples 1 to 5, respectively, was measured by X-ray diffraction method as mentioned in the background of patent CN 201510393963.7, and the results are shown in the following table.

	Internal stress/MPa of plating layer
		Example 1	21.5
Example 2	24.7
		Example 3	23.8
Example 4	22.4
		Example 5	15.6

As can be seen from the above table, in example 5, compared with examples 1 to 4, the internal stress of the plating layer can be significantly reduced by using 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-dione as a stress relieving agent, thereby illustrating that 1- (3- ((trimethylsilyl) oxy) propyl) piperazine-2, 3-dione can be used as a stress relieving agent for preparing a carbon fiber fabric electroplating solution, and the reduction of the internal stress of the plating layer is beneficial to the improvement of the adhesion and application performance of the plating layer.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.