CN111576038A - Preparation method of super-hydrophobic oil-water separation fabric based on electroless copper plating - Google Patents

Abstract

The invention discloses a preparation method of super-hydrophobic oil-water separation fabric based on chemical copper plating. treatment; immersing in a copper-plating solution for copper-plating treatment to obtain a copper-plating fabric; immersing the copper-plating fabric in a corrosive zinc salt solution, and then immersing it in a dodecanoic acid ethanol solution after cleaning. The contact angle of the superhydrophobic oil-water separation fabric prepared by the invention can reach 159°, the separation efficiency of the mixed solution of dichloromethane and water can reach 99%, and the separation efficiency can still reach 96% after 60 times.

Description

A preparation method of superhydrophobic oil-water separation fabric based on electroless copper plating

technical field

The invention belongs to the technical field of super-hydrophobic materials, and in particular relates to a preparation method of a super-hydrophobic oil-water separation fabric based on chemical copper plating.

Background technique

In recent years, with the continuous improvement of living standards, a large amount of industrial wastewater and domestic sewage have been produced. In addition, the offshore oil exploration industry is prone to marine pollution events such as oil spills, and the oil-contaminated water has caused serious damage to the environment. It requires a large investment of human, material and financial resources, but the effect is very small. Therefore, how to effectively separate oil-water from oil-contaminated water has received more and more attention. According to the inspiration of superhydrophobic phenomena in nature, such as lotus leaf effect and rose effect, researchers have used various methods to prepare different types of oil-water separation materials, which are generally divided into two categories: superhydrophobic and lipophilic and oleophobic and hydrophilic. type. Oil-water separation is not only a key issue of current research, but also an important measure to effectively solve the ecological environment pollution caused by oily sewage. Oil-water separation can not only control environmental pollution problems, but also enable resource recycling.

Large-scale oil spills have a catastrophic impact on the ecological environment, and there is an urgent need to develop efficient and selective oil-water separation materials. The use of new oil-water separation materials can not only alleviate the harm of oil and organic matter to the ecological environment, but also bring considerable economic benefits to the recovery of a large number of oil spills. Although superhydrophobic filtration and adsorption materials have shown great potential in the selectivity of oil-water separation, there are still some problems and challenges:

(1) Nowadays, there are many preparation methods for superhydrophobic materials, but most of them face various defects. For example, the template method uses a special mold to copy the surface structure of the lotus leaf to obtain the same superhydrophobic structure as the lotus leaf. However, this method is limited and can only prepare materials of specific shapes, and cannot be used for large-scale production. Although some methods are very effective, they face problems such as high cost.

(2) At present, most of the oil in the oil-water mixture is light oil, which has a lower density than water, and often floats on the water surface in the oil-water mixture. This is detrimental for superhydrophobic and lipophilic materials, because the first contact with water is due to gravity, so the oil cannot be separated out. This is also the biggest problem for superhydrophobic and lipophilic materials used for oil-water separation.

(3) When superhydrophobic and lipophilic materials are used for oil-water separation, due to the viscosity of oil and not easy volatility, the efficiency of repeated use is often not high. Oil contamination degrades the superhydrophobic properties of the material and quickly loses oil-water separation.

(4) The key role in superhydrophobic materials is the hydrophobic group on the surface. Covering or corroding a layer of material with hydrophobic groups on the surface of the material will produce superhydrophobic properties. However, this layer of material or hydrophobic groups It is not strong and will lose its effectiveness after repeated use or friction and reduce the separation efficiency.

There are not many reports on the industrial application of oil-water separation materials. This is because although the stability of oil-water separation materials obtained under laboratory conditions at this stage is relatively good, from the perspective of preparation methods, deposition, coating and other methods are used. The constructed micro-nano rough structure, its effect in practical application is not yet clear. In fact, there are often solid particles, inorganic salts and other organic molecules in oil-water mixtures, and their components are complex and changeable, and how these components affect the stability of the material and the separation effect requires further exploration and research.

Therefore, it is very urgent to study a durable and efficient oil-water separation material and preparation method.

SUMMARY OF THE INVENTION

The purpose of this section is to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of the application to avoid obscuring the purpose of this section, abstract and title, and such simplifications or omissions may not be used to limit the scope of the invention.

The present invention has been made in view of the above and/or problems existing in the prior art.

Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art, and provide a preparation method of superhydrophobic oil-water separation fabric based on electroless copper plating.

In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions: a method for preparing a super-hydrophobic oil-water separation fabric based on chemical copper plating, comprising,

The fabric is copper-plated to obtain copper-plated fabric;

The copper-plated fabric is immersed in a corrosion solution, and then immersed in a dodecanoic acid ethanol solution after cleaning.

As a preferred solution of the present invention, wherein: the immersion in the corrosion solution is immersed in a corrosion solution with a concentration of 0.01-0.05mol/L at a temperature of 20-80°C for 2-4h, washed with distilled water, and dried at 60°C. Dry.

As a preferred solution of the present invention, wherein: the corrosion solution is one of zinc nitrate, antimony chloride and tin chloride.

As a preferred solution of the present invention, wherein: the immersion in dodecanoic acid ethanol solution is immersed in a dodecanoic acid ethanol solution with a concentration of 0.05-0.2 mol/L for 10 minutes at room temperature, and dried at 60°C.

As a preferred solution of the present invention, wherein: the copper plating treatment includes,

Treat fabrics with sodium alginate;

Immerse in nickel salt solution for nickel absorption treatment, then immerse in sodium borohydride solution for activation treatment after cleaning;

Immerse in copper plating solution for copper plating.

As a preferred solution of the present invention, wherein: for the treatment with sodium alginate, the fabric is soaked in a sodium alginate solution with a concentration of 0.25-0.75g/L for 3-5 minutes, taken out, rolled, and repeated for 3 ～5 times, drying at 50～70℃.

As a preferred solution of the present invention, wherein: in the nickel absorption treatment, the fabric treated with sodium alginate is soaked in a nickel salt solution with a concentration of 60g/L at room temperature for 1 hour, washed with distilled water, and dried at 60°C. .

As a preferred solution of the present invention, wherein: in the activation treatment, the fabric after the nickel absorption treatment is soaked in a sodium borohydride solution with a concentration of 10g/L for 40min at room temperature, and the pH value is adjusted with a 20% NaOH solution 10.5, washed with distilled water, and dried at 60°C.

As a preferred solution of the present invention, wherein: the immersion in the copper plating solution, the activated fabric is soaked in the copper plating solution at a temperature of 30-50 ℃ for 1-3 hours, washed with distilled water, dried at 50-70 ℃ Dry.

As a preferred solution of the present invention, wherein: in terms of mass concentration, the copper plating solution includes the following components:

As a preferred solution of the present invention, wherein: the accelerator is nickel sulfate or zinc bromide, the complexing agent is citric acid, the buffering agent is boric acid, and the reducing agent is sodium hypophosphite , one of dimethylamine borane, glyoxylic acid, ethylenediamine cobalt, potassium ferrocyanide and calcium dipotassium ferrocyanide.

As a preferred solution of the present invention, wherein: in the preparation method of the copper plating solution, copper sulfate and accelerator are added into distilled water to dissolve, and then a complexing agent and buffer are added to dissolve, and then a reducing agent is added to dissolve; Adjust pH to 8.5-9.5 with Na ₂ CO ₃ solution or NaOH solution.

Beneficial effects of the present invention:

(1) electroless copper plating traditionally uses precious metal palladium as the activation center, and the present invention adopts sodium alginate, which is natural, has low cost, is pollution-free, and realizes metal-free palladium electroless plating; sodium alginate encounters copper Such transition metal ions will condense and will not fall off from the fabric, with high bonding fastness and wide adaptability.

(2) Zinc nitrate is acidic, corrodes the metal copper coating, and produces zinc oxide in the process, forming a micro-nano structure with a certain roughness on the surface of the fabric. The carboxyl groups of dodecanoic acid react to form a superhydrophobic surface.

(3) The contact angle of the super-hydrophobic oil-water separation fabric prepared by the invention can reach 159°, and the separation efficiency of the mixed liquid of dichloromethane and water can reach 99%, and the separation efficiency can still reach 96% after 60 times.

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort. in:

Fig. 1 is the influence diagram of sodium alginate concentration on copper plating effect in the embodiment of the present invention 1.

FIG. 2 is an observation diagram of the surface morphology of the original polyester fabric and the copper-plated fabric in Example 2 of the present invention.

Fig. 3 is the XRD detection diagram of the fabric in Example 2 of the present invention.

FIG. 4 is a graph showing the test results of the resistance of the copper-plated fabric changing with the number of frictions in Example 2 of the present invention.

FIG. 5 is a graph showing the resistance test results of the resistance of the copper-coated fabric in Example 2 of the present invention as a function of the number of days placed in the air.

FIG. 6 is a graph showing the influence of the soaking temperature of the etching solution on the contact angle of the oil-water separation fabric in Example 5 of the present invention.

7 is an image of the maximum contact angle tested in Example 5 of the present invention.

8 is a graph showing the influence of the concentration of the corrosive solution on the contact angle of the oil-water separation fabric in Example 6 of the present invention.

9 is an image of the maximum contact angle tested in Example 6 of the present invention.

FIG. 10 is a graph showing the influence of the soaking time of the etching solution on the contact angle of the oil-water separation fabric in Example 7 of the present invention.

11 is an image of the maximum contact angle tested in Example 7 of the present invention.

FIG. 12 is a graph showing the effect of dodecanoic acid concentration on the contact angle of oil-water separation fabrics in Example 8 of the present invention.

13 is an image of the maximum contact angle tested in Example 8 of the present invention.

FIG. 14 is a physical view of the fabric after each step in each experimental process in Example 9 of the present invention.

FIG. 15 is a diagram of the oil-water separation experiment performed by the superhydrophobic oil-water separation fabric on the mixture of dichloromethane/water in Example 9 of the present invention.

16 is a graph of the experimental results of the relationship between the separation efficiency of dichloromethane/water and the number of cycles of the superhydrophobic oil-water separation fabric in Example 9 of the present invention.

Detailed ways

In order to make the above objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention will be described in detail below with reference to the embodiments of the specification.

Many specific details are set forth in the following description to facilitate a full understanding of the present invention, but the present invention can also be implemented in other ways different from those described herein, and those skilled in the art can do so without departing from the connotation of the present invention. Similar promotion, therefore, the present invention is not limited by the specific embodiments disclosed below.

Second, reference herein to "one embodiment" or "an embodiment" refers to a particular feature, structure, or characteristic that may be included in at least one implementation of the present invention. The appearances of "in one embodiment" in various places in this specification are not all referring to the same embodiment, nor are they separate or selectively mutually exclusive from other embodiments.

The reagents, medicines and materials used in each embodiment of the present invention are shown in Table 1;

Table 1

The experimental instruments used in each embodiment of the present invention are shown in Table 2.

Table 2

In order to remove oil stains and impurities on the surface of the fabric, the fabric was soaked in acetone, ultrasonically oscillated for 1 h, washed with distilled water, and dried at room temperature.

In order to roughen the surface of the fabric fiber, the HB-1B plasma modification treatment instrument is used to treat the fabric. On the one hand, the surface of the material can be modified, and on the other hand, the surface of the fabric can be corroded by roughening the fabric, and the surface of the fiber can be roughened. The parameters for fabric treatment are set as: the gas is oxygen; the treatment time is 1min; the working pressure is 100Pa; the RF power source is 150w.

Electroless copper plating experiments were carried out on the pretreated fabrics, and the following examples were carried out.

Example 1

Polyester fabrics were selected for electroless copper plating experiments.

(1) Treat fabric with sodium alginate;

Different concentrations of sodium alginate solutions of 0.25g/L, 0.5g/L, 0.75g/L, 3g/L, 5g/L, 10g/L and 15g/L were prepared respectively, and the degreasing treated fabrics were put into Soak in sodium alginate solution for 3 to 5 minutes, the liquor ratio is 1:100, and then use a small rolling mill to squeeze out the excess solution, do more immersion and more rolling, and repeat this step 3 to 5 times. After the fabric is taken out, it is placed in an oven and dried at 60°C.

(2) immersing in nickel salt solution to carry out nickel absorption treatment;

Prepare a nickel sulfate solution with a concentration of 60g/L, soak the fabric treated with sodium alginate in the nickel sulfate solution, the bath ratio is 1:50, soak it at room temperature for 1 hour, and stir and turn from time to time to make the fabric fully contact the solution. Absorb, then take out the fabric, do not wash, put it directly into the oven to dry at 60°C.

(3) immersing in sodium borohydride solution after cleaning to carry out activation treatment;

Prepare a sodium borohydride solution with a concentration of 10g/L, soak the dried fabric after the nickel absorption treatment in the sodium borohydride solution for 40min at room temperature, the bath ratio is 1:150, and adjust the pH value with 20% NaOH solution. 10.5, stirring from time to time to make it fully react to reduce the nickel; after washing the fabric, put it in a 60°C oven to dry.

(4) The copper plating treatment is performed by immersing in the copper plating solution.

The components in the copper plating solution, in terms of mass concentration, include: 9.6 g/L copper sulfate, 1.08 g/L nickel sulfate, 20 g/L citric acid, 30 g/L boric acid, and 40 g/L sodium hypophosphite.

Among them, copper sulfate and nickel sulfate are first dissolved in distilled water, then citric acid and boric acid are added to dissolve, and finally the reducing agent sodium hypophosphite is dissolved again. The copper plating solution is stirred with a timed two-way magnetic constant temperature stirrer, so that the solution can be fully dissolved , the liquor ratio is 1:150, and the pH value is adjusted to 9 with 20% NaOH solution.

The activated fabric is soaked in a copper plating solution at a temperature of 30-50 DEG C for 1-3 hours, washed with distilled water, and dried at 50-70 DEG C to obtain a copper-plated fabric.

The effect of sodium alginate concentration on the copper plating effect is shown in Figure 1, (a) is the original fabric, (b), (c), (d), (e), (f), (g), (h) It is the actual picture of the fabric after treatment with different concentrations of sodium alginate solution and then copper plating; (b), (c), (d), (e), (f), (g), (h) correspond to seaweed respectively The concentration of sodium solution is 3g/L, 5g/L, 10g/L, 15g/L, 0.25g/L, 0.5g/L, 0.75g/L.

It can be seen from the figure that the copper plating effect of (b), (c), (d) and (e) is poor, and the copper layer is distributed unevenly on the fabric, or even not plated. After analysis, it is speculated that the concentration of sodium alginate solution may be too high, and the solution does not evenly soak into the fabric, resulting in uneven copper plating and copper not adhering to the fabric. By comparison, it can be clearly seen that the coatings of (f), (g), (h) are much thicker than those of (b), (c), (d), and (e), and the coating distribution is relatively uniform, which confirms that guess. It can be seen from Figure 1 that when the concentration of sodium alginate solution is 0.5g/L, the plating layer on the fabric is the thickest.

Example 2

Polyester fabrics were selected for electroless copper plating experiments.

(1) Treat fabric with sodium alginate;

Prepare a sodium alginate solution with a concentration of 0.5g/L, put the degreasing treated fabrics into the sodium alginate solution and soak for 3-5min, the liquor ratio is 1:100, and then use a small rolling mill to press out the excess solution , more dipping and more rolling, repeat this step 3 to 5 times. After the fabric is taken out, it is placed in an oven and dried at 60°C.

(2) immersing in nickel salt solution to carry out nickel absorption treatment;

Prepare a nickel sulfate solution with a concentration of 60g/L, soak the fabric treated with sodium alginate in the nickel sulfate solution, the bath ratio is 1:50, soak it at room temperature for 1 hour, and stir and turn from time to time to make the fabric fully contact the solution. Absorb, then take out the fabric, do not wash, put it directly into the oven to dry at 60°C.

(3) immersing in sodium borohydride solution after cleaning to carry out activation treatment;

Prepare a sodium borohydride solution with a concentration of 10g/L, soak the dried fabric after the nickel absorption treatment in the sodium borohydride solution for 40min at room temperature, the bath ratio is 1:150, and adjust the pH value with 20% NaOH solution. 10.5, stirring from time to time to make it fully react to reduce the nickel; after washing the fabric, put it in a 60°C oven to dry.

(4) The copper plating treatment is performed by immersing in the copper plating solution.

The components in the copper plating solution, in terms of mass concentration, include: 9.6 g/L copper sulfate, 1.08 g/L nickel sulfate, 20 g/L citric acid, 30 g/L boric acid, and 40 g/L sodium hypophosphite.

Among them, copper sulfate and nickel sulfate are first dissolved in distilled water, then citric acid and boric acid are added to dissolve, and finally the reducing agent sodium hypophosphite is dissolved again. The copper plating solution is stirred with a timed two-way magnetic constant temperature stirrer, so that the solution can be fully dissolved , the liquor ratio is 1:150, and the pH value is adjusted to 9 with 20% NaOH solution.

The activated fabric is soaked in a copper plating solution at a temperature of 30-50 DEG C for 1-3 hours, washed with distilled water, and dried at 50-70 DEG C to obtain a copper-plated fabric.

The weight gain test of copper-coated polyester fabric was carried out by weighing method. According to the weight of the activated fabric and the weight of the copper-coated fabric, the weight gain rate was calculated by formula (1). The higher the weight gain rate, the more copper is plated, and the better the copper plating effect is.

δ=(W ₂ -W ₁ )/W ₁ ×100% (1)

In the formula: δ is the weight gain rate, %; W ₁ is the weight of the activated fabric, g; W ₂ is the weight of the copper-plated fabric, g.

The weight gain rate test results are shown in Table 3.

table 3

According to Table 3, the weight of the fabric increased after copper plating, and the weight gain rate reached more than 30%, indicating that more copper was plated, and the copper plating effect was better.

In order to study the change of surface morphology of polyester fabric after copper plating, the surface morphology of polyester original fabric and copper-plated fabric was observed by scanning electron microscope (SEM), as shown in Figure 2. According to (a) in Figure 2, the surface of the original fabric is smooth and has almost no rough structure; (b) in Figure 2 is the SEM image of the copper-plated fabric, it can be clearly seen that the surface of the fabric is covered with a dense copper layer, which is granular . It can be seen from the figure that the copper layer on the surface of the fabric is uniform, indicating that the copper plating effect is good.

In order to study the physical shape and structure of copper-plated fabrics, X-ray diffractometer was used to study the fabrics, and XRD detection was carried out. The detection results are shown in Figure 3. A is the diffraction curve of the original polyester fabric, and B is the diffraction curve of the copper-plated fabric. The wave crests of A polyester original fabric are located at 17.7826°, 22.5468°, and 26.9574° respectively. A copper-plated fabric is compared with a copper card (03-065-9743), the two diffraction angles are located at 43.4568° (111) and 50.5745° (200), respectively, corresponding to the copper standard sample card. The half-peak widths are 0.2558 and 0.2814, respectively, indicating a higher degree of crystallization.

The wear resistance of copper-plated fabrics was studied, and the YG401C Martindale automatic fabric flat rub was used to test, and the fabric was rubbed with the flat rub. With the increase of rubbing times, the test resistance changed with the increase of rubbing times. . The test results of the resistance of the copper-plated fabric as a function of the number of frictions are shown in Figure 4. According to Figure 4, after 100, 200, 300, 400 and 500 rubbing times, the surface specific resistance and volume specific resistance of the copper-plated fabric increased with the increase of rubbing times, but the resistance did not change very much. It can be seen that the resistance change is small and the electrical conductivity is good despite the friction, indicating that the copper-plated fabric has good wear resistance.

The copper-coated fabric was placed in the air, and the resistance was tested every two days. The oxidation resistance of the copper-coated fabric was represented by the change in resistance. The resistance of the copper-coated fabric changed with the number of days in the air. The resistance test results are as follows shown in Figure 5. As can be seen from Figure 5, as the copper-coated fabric is placed in the air for a longer time, the resistance increases significantly and the conductivity decreases. During this period, it can be observed that the fabric gradually turns black. According to the experimental results, it can be concluded that the oxidation resistance of the copper-plated fabric is poor.

Example 3

Polyester fabrics were selected for electroless copper plating experiments.

(1) Treat fabric with sodium alginate;

Prepare a sodium alginate solution with a concentration of 0.5g/L, put the degreasing treated fabrics into the sodium alginate solution and soak for 3-5min, the liquor ratio is 1:100, and then use a small rolling mill to press out the excess solution , more dipping and more rolling, repeat this step 3 to 5 times. After the fabric is taken out, it is placed in an oven and dried at 60°C.

(2) immersing in nickel salt solution to carry out nickel absorption treatment;

Prepare a nickel sulfate solution with a concentration of 60g/L, soak the fabric treated with sodium alginate in the nickel sulfate solution, the bath ratio is 1:50, soak it at room temperature for 1 hour, and stir and turn from time to time to make the fabric fully contact the solution. Absorb, then take out the fabric, do not wash, put it directly into the oven to dry at 60°C.

(3) immersing in sodium borohydride solution after cleaning to carry out activation treatment;

Prepare a sodium borohydride solution with a concentration of 10g/L, soak the dried fabric after the nickel absorption treatment in the sodium borohydride solution for 40min at room temperature, the bath ratio is 1:150, and adjust the pH value with 20% NaOH solution. 10.5, stirring from time to time to make it fully react to reduce the nickel; after washing the fabric, put it in a 60°C oven to dry.

(4) The copper plating treatment is performed by immersing in the copper plating solution.

The components in the copper plating solution, in terms of mass concentration, include: 9.6g/L copper sulfate, 1.08g/L zinc bromide, 20g/L citric acid, 30g/L boric acid, 40g/L ferrocyanide Potassium.

Among them, copper sulfate and nickel sulfate are first added to distilled water to dissolve, then citric acid and boric acid are added to dissolve, and finally sodium hypophosphite, a reducing agent, is dissolved again. The copper plating solution is stirred with a timed two-way magnetic constant temperature stirrer to make the solution fully dissolved. , the liquor ratio was 1:150, and the pH was adjusted to 9 with 20% Na ₂ CO ₃ solution.

The activated fabric is soaked in a copper plating solution at a temperature of 30-50 DEG C for 1-3 hours, washed with distilled water, and dried at 50-70 DEG C to obtain a copper-plated fabric.

The deposition rates of electroless copper plating in Example 2 and Example 3 were compared, and the deposition rate of electroless copper plating was represented by the thickness of the copper plating layer deposited per unit time (μm/h). Assuming that the coating density is 8.92 g/cm ³ and the thickness is uniform, it is calculated from the mass change before and after electroless plating. The results are shown in Table 4.

Table 4

It can be seen from Table 4 that, compared with Example 2, the addition of potassium ferrocyanide in Example 3 can lead to a decrease in the deposition rate, because potassium ferrocyanide can be adsorbed on the surface of the coating. influence diminished. Adding water, sodium carbonate and zinc bromide, the three work together can promote the free treatment of cyano groups from potassium ferrocyanide, adjust the ion balance in the solution, and reduce ferrous cyanide ions and copper ions, citric acid and citric acid. The amount of complexes formed by ions, etc., can reduce the adsorption strength of potassium ferrocyanide on the surface of the coating, prolong the time to reach saturation, and continuously reduce the deposition rate of copper plating.

Example 4

Cotton, polyester, polypropylene, polyester-cotton fabrics were selected for chemical copper plating experiments.

(1) Treat fabric with sodium alginate;

Prepare a sodium alginate solution with a concentration of 0.5g/L, put the degreasing treated fabrics into the sodium alginate solution and soak for 3-5min, the liquor ratio is 1:100, and then use a small rolling mill to press out the excess solution , more dipping and more rolling, repeat this step 3 to 5 times. After the fabric is taken out, it is placed in an oven and dried at 60°C.

(2) immersing in nickel salt solution to carry out nickel absorption treatment;

Prepare a nickel sulfate solution with a concentration of 60g/L, soak the fabric treated with sodium alginate in the nickel sulfate solution, the bath ratio is 1:50, soak it at room temperature for 1 hour, and stir and turn from time to time to make the fabric fully contact the solution. Absorb, then take out the fabric, do not wash, put it directly into the oven to dry at 60°C.

(3) immersing in sodium borohydride solution after cleaning to carry out activation treatment;

Prepare a sodium borohydride solution with a concentration of 10g/L, soak the dried fabric after the nickel absorption treatment in the sodium borohydride solution for 40min at room temperature, the bath ratio is 1:150, and adjust the pH value with 20% NaOH solution. 10.5, stirring from time to time to make it fully react to reduce the nickel; after washing the fabric, put it in a 60°C oven to dry.

(4) The copper plating treatment is performed by immersing in the copper plating solution.

The components in the copper plating solution, in terms of mass concentration, include: 9.6 g/L copper sulfate, 1.08 g/L nickel sulfate, 20 g/L citric acid, 30 g/L boric acid, and 40 g/L sodium hypophosphite.

Among them, copper sulfate and nickel sulfate are first dissolved in distilled water, then citric acid and boric acid are added to dissolve, and finally the reducing agent sodium hypophosphite is dissolved again. The copper plating solution is stirred with a timed two-way magnetic constant temperature stirrer, so that the solution can be fully dissolved , the bath ratio is 1:150, and the pH value is adjusted to 9 with 20% NaOH solution.

The activated fabric is soaked in a copper plating solution at a temperature of 30-50 DEG C for 1-3 hours, washed with distilled water, and dried at 50-70 DEG C to obtain a copper-plated fabric.

The ZC36 high insulation resistance measuring instrument was used to test the specific resistance of the original fabric, copper-plated fabric and oil-water separation fabric of different types of fabrics, and analyze their electrical conductivity. The results are shown in Table 5.

table 5

According to Table 4, the cotton, polyester, polypropylene, and polyester-cotton fabrics used as copper-plated fabric substrates do not have electrical conductivity. After the fabric is treated with copper plating, the fabric has good electrical conductivity, and the best electrical conductivity is copper-plated. Cotton fabrics; after copper-plated fabrics are corroded by zinc nitrate and modified with dodecanoic acid, the resistance becomes larger and the conductivity becomes worse.

The anti-ultraviolet performance is to measure the protection factor (UPF) of the copper-plated fabric of the original fabric by using the YG (B) 912E textile anti-ultraviolet performance tester. The standard used is GB/T18830-2009. The transmittance test range is 0-100; the wavelength range of the test: 250-450nm; the wavelength accuracy is: ±2%. The results are shown in Table 6.

Table 6

It can be seen from Table 5 that the transmittance of the fabric after copper plating is reduced, and the protection coefficient UPF value is increased, which shows that the UV resistance of the fabric is improved after copper plating. 1.93%, the UVB transmittance of copper-coated cotton fabric is only 2.42%, and the UPF value of copper-coated cotton fabric is the largest at 41.7, which achieves a better protection level, mainly because the cotton fabric has a small gap and can resist well. penetration of ultraviolet light.

Based on the copper-plated fabric prepared in Example 2, an oil-water separation experiment was carried out on the copper-plated fabric, and the following examples were carried out.

Example 5

(1) immersing the copper-plated fabric in a corrosion solution, the corrosion solution is a zinc nitrate solution;

Keep the solution concentration and time unchanged, prepare 0.01mol/L zinc nitrate solution, and place the copper-plated fabrics in immersion for 3 hours at room temperature of 20°C, 40°C, 60°C and 80°C respectively.

(2) After cleaning, it can be immersed in dodecanoic acid ethanol solution.

A dodecanoic acid ethanol solution with a concentration of 0.15 mol/L was prepared, and the fabric was soaked in the solution at room temperature for 10 min without washing, and then dried in an oven at 60°C to prepare an oil-water separation fabric.

The contact angle of the oil-water separation fabric prepared by corrosion with zinc nitrate solution and modification with ethanol solution of dodecanoic acid was tested. The JC2000D3 contact angle measuring instrument of Shanghai Zhongchen Company was used for testing. Hold and adjust the tightness, the volume of the dripping water droplets is 3ul, and the image is frozen after the water droplets are in contact with the fabric for 10s and read. Then, the contact angle was measured by the goniometric method, and 3 to 5 different parts of each sample were selected for testing, and the average value was taken.

As shown in Figure 6, it is the effect of soaking temperature on the contact angle of the oil-water separation fabric. As shown in Figure 6, with the increase of temperature, the contact angle first increases and then decreases, and the highest contact angle is 151°. Figure 7 shows the contact angle of 154° image. When the temperature is low, the reaction is not complete, and when the temperature is high, the reaction will be destroyed and the result will be affected. The optimum temperature is 40 °C.

Example 6

(1) immersing the copper-plated fabric in a corrosion solution, the corrosion solution is a zinc nitrate solution;

Keep the temperature and time constant, prepare different concentrations of zinc nitrate solutions: 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L and 0.05mol/L, put the fabric in a water bath at 40°C Soak for 3h.

(2) After cleaning, it can be immersed in dodecanoic acid ethanol solution.

A dodecanoic acid ethanol solution with a concentration of 0.15 mol/L was prepared, and the fabric was soaked in the solution at room temperature for 10 min without washing, and then dried in an oven at 60°C to prepare an oil-water separation fabric.

The contact angle of the oil-water separation fabric prepared by corrosion with zinc nitrate solution and modification with ethanol solution of dodecanoic acid was tested. The JC2000D3 contact angle measuring instrument of Shanghai Zhongchen Company was used for testing. Hold and adjust the tightness, the volume of the dripping water droplets is 3ul, and the image is frozen after the water droplets are in contact with the fabric for 10s and read. Then, the contact angle was measured by the goniometric method, and 3 to 5 different parts of each sample were selected for testing, and the average value was taken.

As shown in Figure 8, it is the effect of zinc nitrate concentration on the contact angle of oil-water separation fabrics. It can be seen from Figure 8 that the contact angle increases first and then decreases with the increase of zinc nitrate solution concentration, and the highest contact angle is 149° . Figure 9 is an image of a maximum contact angle of 152° when measured, which has reached superhydrophobicity. The main reason is that the copper-plated fabric already has roughness. After modification with dodecanoic acid ethanol, the roughness increases again, and then there is modification with low surface energy substances, so that the contact angle changes little and fluctuates little. The hydrophobic effect was the best when the concentration of zinc nitrate solution was 0.04mol/L.

Example 7

(1) immersing the copper-plated fabric in a corrosion solution, the corrosion solution is a zinc nitrate solution;

Keeping the temperature and concentration unchanged, the fabrics were soaked in 0.04mol/L zinc nitrate solution at 40℃ for 2h, 3h and 4h respectively.

(2) After cleaning, it can be immersed in dodecanoic acid ethanol solution.

A dodecanoic acid ethanol solution with a concentration of 0.15 mol/L was prepared, and the fabric was soaked in the solution at room temperature for 10 min without washing, and then dried in an oven at 60°C to prepare an oil-water separation fabric.

The contact angle of the oil-water separation fabric prepared by corrosion with zinc nitrate solution and modification with ethanol solution of dodecanoic acid was tested. The JC2000D3 contact angle measuring instrument of Shanghai Zhongchen Company was used for testing. Hold and adjust the tightness, the volume of the dripping water droplets is 3ul, and the image is frozen after the water droplets are in contact with the fabric for 10s and read. Then, the contact angle was measured by the goniometric method, and 3 to 5 different parts of each sample were selected for testing, and the average value was taken.

As shown in Figure 10, it is the effect of soaking time on the contact angle of oil-water separation fabrics. As shown in Figure 10, the contact angle first increases and then decreases with the increase of corrosion time, and the highest contact angle is 151°. The maximum contact angle reached 158° when measured. The reaction time is short and the reaction is not complete. When the reaction time is too long, the effect is poor. According to the figure, the most suitable time is 3h.

Example 8

(1) immersing the copper-plated fabric in a corrosion solution, the corrosion solution is a zinc nitrate solution;

Keeping the temperature and concentration unchanged, the fabric was put into 0.04mol/L zinc nitrate solution and soaked in a 40°C water bath for 3h.

(2) After cleaning, it can be immersed in dodecanoic acid ethanol solution.

Prepare dodecanoic acid ethanol solutions with concentrations of 0.05mol/L, 0.1mol/L, 0.15mol/L and 0.2mol/L respectively, soak the fabric in the solution for 10min at room temperature, do not wash with water, and put it in an oven at 60°C After drying, an oil-water separation fabric is prepared.

The contact angle of the oil-water separation fabric prepared by corrosion with zinc nitrate solution and modification with ethanol solution of dodecanoic acid was tested. The JC2000D3 contact angle measuring instrument of Shanghai Zhongchen Company was used for testing. Hold and adjust the tightness, the volume of the dripping water droplets is 3ul, and the image is frozen after the water droplets are in contact with the fabric for 10s and read. Then, the contact angle was measured by the goniometric method, and 3 to 5 different parts of each sample were selected for testing, and the average value was taken.

As shown in Figure 12, it is the effect of dodecanoic acid concentration on the contact angle of the oil-water separation fabric. As shown in Figure 12, with the increase of dodecanoic acid ethanol concentration, the contact angle first increases and then decreases. The contact angle is the largest when the concentration of dodecanoic acid ethanol is 0.015mol/L. Figure 13 shows that the maximum contact angle is 152° during the measurement, mainly because dodecanoic acid ethanol is also an organic acid, not only a low surface energy modified substance. When the concentration is low, it only reacts with part of the copper hydroxide on the surface of the copper-plated fabric; when it reaches a certain concentration, it reacts with all the copper hydroxide on the surface of the fabric; when the concentration of dodecanoic acid ethanol continues to increase. At this point the reaction has reached saturation and no further reaction can take place.

Example 9

Polyester fabrics were selected for electroless copper plating experiments.

(1) Treat fabric with sodium alginate;

Prepare a sodium alginate solution with a concentration of 0.5g/L, put the degreasing treated fabrics into the sodium alginate solution and soak for 3-5min, the liquor ratio is 1:100, and then use a small rolling mill to press out the excess solution , more dipping and more rolling, repeat this step 3 to 5 times. After the fabric is taken out, it is placed in an oven and dried at 60°C.

(2) immersing in nickel salt solution to carry out nickel absorption treatment;

Prepare a nickel sulfate solution with a concentration of 60g/L, soak the fabric treated with sodium alginate in the nickel sulfate solution, the bath ratio is 1:50, soak it at room temperature for 1 hour, and stir and turn from time to time to make the fabric fully contact the solution. Absorb, then take out the fabric, do not wash, put it directly into the oven to dry at 60°C.

(3) immersing in sodium borohydride solution after cleaning to carry out activation treatment;

Prepare a sodium borohydride solution with a concentration of 10g/L, soak the dried fabric after the nickel absorption treatment in the sodium borohydride solution for 40min at room temperature, the bath ratio is 1:150, and adjust the pH value with 20% NaOH solution. 10.5, stirring from time to time to make it fully react to reduce the nickel; after washing the fabric, put it in a 60°C oven to dry.

(4) The copper plating treatment is performed by immersing in the copper plating solution.

The components in the copper plating solution, in terms of mass concentration, include: 9.6 g/L copper sulfate, 1.08 g/L nickel sulfate, 20 g/L citric acid, 30 g/L boric acid, and 40 g/L sodium hypophosphite.

Among them, copper sulfate and nickel sulfate are first dissolved in distilled water, then citric acid and boric acid are added to dissolve, and finally the reducing agent sodium hypophosphite is dissolved again. The copper plating solution is stirred with a timed two-way magnetic constant temperature stirrer, so that the solution can be fully dissolved , the liquor ratio is 1:150, and the pH value is adjusted to 9 with 20% NaOH solution.

The activated fabric is soaked in a copper plating solution at a temperature of 30-50 DEG C for 1-3 hours, washed with distilled water, and dried at 50-70 DEG C to obtain a copper-plated fabric.

(5) Immerse the copper-plated fabric in a corrosion solution, which is a zinc nitrate solution, prepare a 0.01 mol/L zinc nitrate solution, and place the copper-plated fabric at room temperature of 40°C for 3 hours.

(6) After cleaning, immerse in dodecanoic acid ethanol solution, prepare a dodecanoic acid ethanol solution with a concentration of 0.15mol/L, soak the fabric in the solution for 10 minutes at room temperature, do not wash with water, put it in an oven to dry at 60 ° C, and prepare Superhydrophobic oil-water separation fabric.

As shown in Figure 14, it is the actual picture of the fabric after each step in the above experimental process, and it can be seen that the appearance of the fabric changes in the whole process. (a) is the appearance of the original fabric is white. The sodium alginate solution is a transparent colloid, so the fabric (b) treated with sodium alginate is white. (c) is the appearance of the light green fabric after nickel absorption treatment. Then, the fabric after absorbing nickel is put into sodium borohydride solution, and the nickel ions are reduced and attached to the surface of the fabric, namely (d) the fabric with black appearance. Then, the fabric is copper-plated to obtain (e) a brick-red copper-plated fabric. Finally, the copper-coated fabrics were etched with zinc nitrate and modified with dodecanoic acid to prepare superhydrophobic oil-water separation fabrics. The hydrophobic effect is shown in (f).

The oil-water separation experiment was carried out on the mixture of methylene chloride and water with the prepared superhydrophobic fabric. The oil-water separation test adopts gravity separation, because the density of oil and water is different, and the lighter components are in the gravity condition. In the upper layer, the heavier component liquid settles below, and the two layers of oil and water are not fused to achieve the purpose of separating oil or water. Superhydrophilic/superoleophobic fabrics are used for oil-water separation with lighter density than water, and superhydrophobic/superoleophilic fabrics are used for oil-water separation with heavier density than water. The superhydrophobic oil-water separation fabric was tested for oil-water separation with a mixture of dichloromethane and water, and the experiment was repeated. The separation efficiency is expressed by the ratio of the volume of oil before and after separation, and the separation efficiency is calculated by formula (2) every 10 times of separation. The separation efficiency is high, indicating that the oil-water separation is good.

δ=W ₂ /W ₁ ×100% (2)

In the formula: δ: separation efficiency, %; W ₁ : volume of oil before separation, mL; W ₂ : volume of oil after separation, mL.

As shown in Figure 15, an oil-water separation experiment was carried out for the mixture of dichloromethane/water for the fabric. For the convenience of observation during the experiment, the distilled water was dyed orange with a methyl orange water-soluble dye, and the heavy oil dichloromethane was colorless. Take the volume ratio of oil and water as 1:1. As shown in Figure 15, the dichloromethane permeated the fabric and dripped into the measuring cylinder below, and the blue-dyed distilled water was isolated by the fabric and could not penetrate, indicating that the oil-water separation was good, and the separation efficiency reached 99%.

The relationship between the separation efficiency of dichloromethane/water by the oil-water separation fabric and the number of cycles, the experimental results are shown in Figure 16. It can be seen from Figure 16 that with the increase of the number of tests, the separation efficiency remains stable and can be maintained at 96%. This shows that the oil-water separation of the fabric is relatively stable and can be used repeatedly.

The superhydrophobic fabric was treated in NaOH solution for 10min. After drying, water droplets and oil droplets were placed on the surface of the fabric. It was found that both of them quickly infiltrated the surface of the fabric, showing the effect of superhydrophilic and superoleophilic. The superhydrophobic fabric irreversibly becomes a superoleophobic fabric.

It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be Modifications or equivalent substitutions without departing from the spirit and scope of the technical solutions of the present invention should be included in the scope of the claims of the present invention.

Claims (10)

1. A preparation method of a chemical copper plating based super-hydrophobic oil-water separation fabric is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,

carrying out copper plating treatment on the fabric to obtain a copper plated fabric;

and immersing the copper-plated fabric into a corrosive solution, cleaning, and then immersing into a dodecanoic acid ethanol solution.

2. The method for preparing the chemical copper plating-based super-hydrophobic oil-water separation fabric according to claim 1, wherein the method comprises the following steps: soaking the immersed corrosive solution in 0.01-0.05 mol/L corrosive solution at the temperature of 20-80 ℃ for 2-4 h, washing with distilled water and drying at the temperature of 60 ℃;

the corrosion solution is one of zinc nitrate, antimony chloride and tin chloride.

3. The method for preparing the chemical copper plating-based super-hydrophobic oil-water separation fabric according to claim 1, wherein the method comprises the following steps: immersing the substrate in a dodecanoic acid ethanol solution, immersing the substrate in the dodecanoic acid ethanol solution with the concentration of 0.05-0.2 mol/L for 10min at normal temperature, and drying at 60 ℃.

4. The method for preparing an electroless copper plating-based superhydrophobic oil-water separation fabric according to any of claims 1 to 3, wherein: the copper plating treatment comprises the steps of,

treating the fabric with sodium alginate;

firstly immersing the substrate into a nickel salt solution for nickel absorption treatment, and then immersing the substrate into a sodium borohydride solution for activation treatment after cleaning;

immersing the copper-plated steel sheet into a copper-plating solution to carry out copper plating treatment.

5. The method for preparing the chemical copper plating-based super-hydrophobic oil-water separation fabric according to claim 4, wherein the method comprises the following steps: the method comprises the steps of treating with sodium alginate, soaking the fabric in a sodium alginate solution with the concentration of 0.25-0.75 g/L for 3-5 min, taking out, rolling, repeating for 3-5 times, and drying at 50-70 ℃.

6. The method for preparing the chemical copper plating-based super-hydrophobic oil-water separation fabric according to claim 4, wherein the method comprises the following steps: the nickel absorption treatment comprises the steps of soaking the fabric treated by the sodium alginate in a nickel salt solution with the concentration of 60g/L for 1 hour at normal temperature, washing with distilled water and drying at 60 ℃;

and in the activation treatment, the fabric after the nickel absorption treatment is soaked in a sodium borohydride solution with the concentration of 10g/L for 40min at normal temperature, the pH value is adjusted to 10.5 by using a 20% NaOH solution, and the fabric is washed by distilled water and dried at the temperature of 60 ℃.

7. The method for preparing the ultra-hydrophobic oil-water separation fabric based on electroless copper plating according to claim 5 or 6, wherein the method comprises the following steps: and immersing the fabric into a copper plating solution, soaking the activated fabric in the copper plating solution at the temperature of 30-50 ℃ for 1-3 h, washing with distilled water, and drying at the temperature of 50-70 ℃.

8. The method for preparing the chemical copper plating-based super-hydrophobic oil-water separation fabric according to claim 7, wherein the method comprises the following steps: the copper plating solution comprises the following components in percentage by mass:

。

9. the method for preparing the chemical copper plating-based superhydrophobic oil-water separation fabric according to claim 8, wherein: the accelerator is nickel sulfate or zinc bromide, the complexing agent is citric acid, the buffering agent is boric acid, and the reducing agent is one of sodium hypophosphite, dimethylamine borane, glyoxylic acid, ethylene diamine cobalt, potassium ferrocyanide and calcium ferrocyanide dipotassium.

10. The method for preparing the ultra-hydrophobic oil-water separation fabric based on electroless copper plating according to claim 8 or 9, wherein the method comprises the following steps: the preparation method of the copper plating solution comprises the steps of adding copper sulfate and an accelerant into distilled water for dissolving, adding a complexing agent and a buffering agent for dissolving, and then adding a reducing agent for dissolving; with Na₂CO₃Adjusting the pH value of the solution or NaOH solution to 8.5-9.5.

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