CN103757617B - A kind of Ni-Cu-La-B quaternary alloy plating solution and the method for the plating of glass fibre chemistry - Google Patents

Abstract

The invention discloses a Ni-Cu-La-B quaternary alloy plating solution. The composition of the Ni-Cu-La-B quaternary alloy plating solution is as follows: nickel chloride 20-40g/L, copper sulfate 10-20g /L, lanthanum sulfate 0.5~10g/L, sodium borohydride 0.5~3g/L, potassium sodium tartrate 40~50g/L, ethylenediamine 15~30g/L, sodium hydroxide 35~60g/L. The present invention uses sodium borohydride as a reducing agent, adds lanthanum sulfate which is easily soluble in water, and performs electroless Ni-Cu-La-B quaternary alloy plating on glass fibers under strong alkalinity and low temperature conditions; the coating is Ni-Cu-La ‑B alloy coating, low boron content (only 0.5~5wt%), high nickel content in the coating, good adhesion, conductivity and wear resistance of the coating. The coated Ni-Cu-La-B glass fiber prepared by the method of the present invention is compact through microscope observation, and the surface chemical composition is tested with an X-ray energy spectrometer, containing Ni15-50wt%, Cu2-15wt%, La0.5-5wt %, B0.5~5wt%. The conductive glass fiber can be used in special fields such as electromagnetic wave shielding, wave absorption, stealth and antistatic.

Description

A kind of Ni-Cu-La-B quaternary alloy plating solution and the method for glass fiber electroless plating

technical field

The invention relates to the technical field of chemical plating, in particular to a Ni-Cu-La-B quaternary alloy plating solution and a method for chemical plating of glass fibers.

Background technique

With the rapid development of modern science and technology, a kind of electromagnetic radiation pollution called "invisible killer" has attracted increasing attention from all walks of life. Electromagnetic interference, electromagnetic information leakage and electromagnetic environmental pollution caused by electromagnetic radiation have a great impact on economic construction, national defense security and social life. The impact is becoming more and more serious, and electromagnetic radiation pollution has become a major public hazard in today's society. Using electromagnetic shielding coatings to shield stray electromagnetic waves that interfere with the normal operation of electronic and electrical products is an effective method to prevent and control electromagnetic radiation pollution. For electromagnetic wave shielding coatings, the cost, conductivity and specific gravity of conductive fillers have become the key factors restricting its cost performance and application. Although traditional metals such as gold, silver, aluminum, nickel, and copper have good electrical conductivity, their market promotion and use are greatly limited due to their high cost and large specific gravity.

Electroless plating is a green, environmentally friendly, low-cost, and widely used surface metallization modification method. The plating layer prepared by electroless plating technology is uniform, firm and easy to control. Electroless plating has become a common preparation for new electromagnetic shielding composite fillers. One of the techniques. At present, a variety of new electromagnetic shielding composite conductive fillers have been successfully prepared by electroless plating technology using plastics, fabrics, fibers, glass beads, wood, metal or mineral whiskers as substrates.

Glass fiber is an inorganic non-metallic material with excellent performance. It has good insulation, heat resistance and corrosion resistance, and high mechanical strength. It is often used as reinforcing material, electrical insulation material, heat insulation material and circuit substrate material in composite materials. etc., widely used in construction, transportation, electronics, electrical, chemical industry, metallurgy, environmental protection, national defense and many other areas of the national economy. Glass fiber is brittle, has poor wear resistance and electrical conductivity, which reduces the cost performance of glass fiber to a certain extent and limits its application range. Conductive glass fibers can be prepared by electroless metal plating on glass fibers. The principle of electroless metal plating on the surface of glass fiber is: using glass fiber as the matrix, using a reducing agent to chemically reduce metal ions (such as nickel, copper metal ions) in the solution to the surface of the catalytically active glass fiber, without external current passing In some cases, it forms a conductive coating to obtain a metal-coated (eg, nickel-copper) glass fiber.

At present, the published patents on electroless plating of multi-component alloys on the surface of glass fibers mainly include: electroless plating of glass fibers Ni-Fe-La-P quaternary alloy plating solution and its preparation method (patent number: 200710017925.7), electroless plating on glass fibers Five-element alloy plating solution and its preparation method (patent number: 200710017926.1), glass fiber electroless Ni-Co-La-P quaternary alloy plating solution and its preparation method (patent number: 200710017929.5).

China's patent application 200710017925.7 relates to a glass fiber electroless plating Ni-Fe-La-P quaternary alloy plating solution and its preparation method, the plating solution is composed of nickel chloride, ferrous sulfate, lanthanum oxide, sodium citrate, malic acid , succinic acid, sodium hypophosphite, ammonium sulfate, distilled water, thiourea, urea and concentrated hydrochloric acid. Since an appropriate amount of La ₂ O ₃ is added to the chemical plating solution, the phosphorus content in the prepared alloy coating is between 1.8% and 17%.

China's patent application 200710017926.1 relates to a glass fiber electroless Ni-Co-Fe-La-P five-element alloy plating solution and its preparation method. The plating solution consists of nickel chloride, cobalt sulfate, sodium hypophosphite, and ferrous sulfate. , lanthanum oxide, sodium citrate, malic acid, succinic acid, ammonium sulfate, distilled water, thiourea, urea and concentrated hydrochloric acid, due to the addition of an appropriate amount of La ₂ O ₃ in the chemical plating solution, the phosphorus in the prepared alloy coating The content is between 3% and 17%.

China's patent application 200710017929.5 relates to a glass fiber electroless Ni-Co-La-P quaternary alloy plating solution and its preparation method. The plating solution consists of nickel chloride, cobalt sulfate, lanthanum oxide, sodium citrate, malic acid, Composed of succinic acid, sodium hypophosphite, ammonium sulfate, distilled water, thiourea, urea and concentrated hydrochloric acid, due to adding an appropriate amount of La ₂ O ₃ to the chemical plating solution, the phosphorus content in the prepared alloy coating is between 6% and 23 %.

After searching, no patent application or literature report on the Ni-Cu-La-B quaternary alloy plating solution and its preparation method for glass fiber electroless plating was found.

Plated Ni-Cu-La-B glass fiber can be used as a functional filler for conductive coatings in the fields of electromagnetic wave shielding, wave absorption, stealth, antistatic and heat generation. Electroless plating of Ni-Cu-La-B on the surface of glass fiber is expected to provide a new technical method for increasing the added value of glass fiber and improving the comprehensive development and utilization of non-metallic materials.

The traditional glass fiber electroless plating technology uses sodium hypophosphite (also known as sodium hypophosphite) as the reducing agent. Sodium hypophosphite has certain toxicity, and the sodium hypophosphite solution will explode when heated and evaporated under normal pressure; Phosphorus precipitation and co-deposition of phosphorus and nickel form a nickel-phosphorus alloy coating with high phosphorus content and phosphorus in a dispersed state, which increases the brittleness of the coating and reduces the bonding force and conductivity of the coating, thereby affecting the quality of the coating. The La ₂ O ₃ added in the electroless plating solution is insoluble in water, which reduces the effect of rare earths in the electroless plating.

Contents of the invention

The object of the present invention is to provide a kind of Ni-Cu-La-B quaternary alloy plating solution and the method for glass fiber electroless plating. Mainly after the glass fiber is pretreated by degreasing, coarsening, sensitization, activation, etc., the nickel, copper, and lanthanum metal ions in the solution are chemically reduced to the surface of the catalytically active glass fiber by using a reducing agent. In some cases, make it form a metal coating, so as to prepare conductive glass fibers with Ni-Cu-La-B on the surface, and improve the conductivity of the glass fibers.

The technical scheme that the present invention takes is:

The composition of Ni-Cu-La-B quaternary alloy plating solution of the present invention is as follows:

The solvent is distilled water.

Preferred:

The solvent is distilled water.

Utilize quaternary alloy plating solution of the present invention to carry out the concrete steps of the method for glass fiber surface electroless plating as follows:

(1) Firstly weigh nickel chloride, copper sulfate, lanthanum sulfate, sodium borohydride, potassium sodium tartrate, ethylenediamine, and sodium hydroxide according to the ratio;

(2) Put the nickel chloride, copper sulfate, lanthanum sulfate, potassium sodium tartrate, sodium hydroxide and ethylenediamine weighed in step (1) into a container, add distilled water, stir and mix with a magnetic stirrer at room temperature Uniform;

(3) Slowly add sodium hypoborohydride to the solution prepared in step (2), stir until dissolved, add ammonia water to adjust the pH value to 12-13.5, and make an electroless plating solution;

(4) Put the glass fiber into the electroless plating solution prepared in step (3) for electroless Ni-Cu-La-B plating, the plating temperature is 60-90°C, and the plating time is 1-8h;

(5) Dry the Ni-Cu-La-B-coated glass fiber prepared above at a drying temperature of 80-100°C to obtain the Ni-Cu-La-B-coated glass fiber.

In step (4), the plating temperature is preferably 70-80°C.

In step (4), the plating time is preferably 3-6 hours.

In step (5), the drying temperature is preferably 80-90°C.

The glass fibers in step (4) are pretreated before use, and the pretreatment steps are as follows:

(1) Soak the glass fibers in 0.5-10% sodium carbonate aqueous solution for 8-24 hours, then wash with distilled water, filter and dry;

(2) Immerse the glass fiber treated in step (1) in a silane coupling agent solution with a concentration of 0.5-5%, soak for 2-20 minutes, filter, and dry;

(3) Immerse the glass fiber treated in step (2) in a nitric acid solution with a concentration of 40-65% for roughening treatment for 10-60 minutes, and maintain the temperature of the nitric acid solution at 40-80°C;

(4) Immersing the glass fibers treated in step (3) in a mixed solution with a concentration of 5-20g/LSnCl ₂ ·2H ₂ O and 10-30g/L HCl for sensitization treatment;

(5) Activate the glass fibers treated in step (4) in a mixed solution of 0.1-2g/LPdCl ₂ and 1-20mL/L HCl.

The coated Ni-Cu-La-B glass fiber prepared by the method of the present invention is dense through microscope observation, and the surface chemical composition is tested by X-ray energy spectrometer, containing Ni15-50wt%, Cu2-15wt%, La0.5-5wt %, B0.5~5wt%. The conductive glass fiber can be used in special fields such as electromagnetic wave shielding, wave absorption, stealth and antistatic.

In the present invention, sodium borohydride is used as a reducing agent, lanthanum sulfate which is easily soluble in water is added, and glass fiber is electroless plated with Ni-Cu-La-B quaternary alloy under strong alkalinity and low temperature conditions; the coating is Ni-Cu-La -B alloy coating, low boron content (only 0.5% to 5%), high nickel content in the coating, good adhesion, conductivity and wear resistance of the coating.

The positive effect of the present invention is as follows:

The present invention has following characteristics:

1. The electroless Ni-Cu-La-B glass fiber coating prepared by the present invention contains high nickel content, and the coating has good adhesion, electrical conductivity and wear resistance.

2. Compared with the commonly used spherical and flake-shaped fillers with electromagnetic functions, electroless Ni-Cu-La-B glass fiber is a micron-sized conductive fiber material, which has a good effect on improving the electromagnetic wave shielding function of the coating.

3. The preparation of electroless Ni-Cu-La-B glass fiber is carried out at low temperature, which saves energy and is easy to use.

4. The preparation method of electroless Ni-Cu-La-B glass fiber plating is simple, convenient, easy to operate and control, completely using conventional equipment, less investment, less risk, and easy to popularize.

detailed description

The following examples are further detailed descriptions of the present invention.

Example 1

Use glass fiber as the base material, soak in 1% sodium carbonate aqueous solution for 24 hours, wash with distilled water, filter, dry, immerse in 1.5% silane coupling agent solution, soak for 10 minutes, filter, dry , immersed in a 50% nitric acid solution at 60°C for 30 minutes, washed with water, and immersed in a mixed solution of 10g/LSnCl ₂ ·2H ₂ O and 20g/LHCl for sensitization treatment, with an immersion concentration of 0.3g/L LPdCl ₂ and 1.5mL/LHCl mixed solution for activation treatment. Then immerse in the plating solution at 60°C for 180 minutes. The formulation of the plating solution is 35g/L of nickel chloride, 15g/L of copper sulfate, 1g/L of lanthanum sulfate, 1g/L of sodium borohydride, 45g/L of sodium potassium tartrate, and Diamine 18g/L, sodium hydroxide 45g/L, pH value 12.5. The electroless Ni-Cu-La-B glass fiber was obtained on the surface, and after drying at 100°C, it was observed with a microscope that the coating was compact.

Example 2

Use glass fiber as the base material, soak in 1.5% sodium carbonate aqueous solution for 12 hours, wash with distilled water, filter, dry, immerse in 1.5% silane coupling agent solution, soak for 10 minutes, filter and dry , immersed in a 50% nitric acid solution at 60°C for 30 minutes, washed with water, and immersed in a mixed solution of 10g/LSnCl ₂ ·2H ₂ O and 20g/LHCl for sensitization treatment, with an immersion concentration of 0.3g/L LPdCl ₂ and 1.5mL/LHCl mixed solution for activation treatment. Then immerse in the 70°C plating solution for 120 minutes, the plating solution formula is nickel chloride 30g/L, copper sulfate 20g/L, lanthanum sulfate 1.5g/L, sodium borohydride 0.8g/L, potassium sodium tartrate 40g/L , Ethylenediamine 25g/L, sodium hydroxide 50g/L, pH value 13. The electroless Ni-Cu-La-B glass fiber was obtained on the surface, and after drying at 100°C, it was observed with a microscope that the coating was compact.

Example 3

Use glass fiber as the base material, soak in 1% sodium carbonate aqueous solution for 24 hours, wash with distilled water, filter, dry, immerse in 1.5% silane coupling agent solution, soak for 10 minutes, filter, dry , immersed in a 50% nitric acid solution at 60°C for 30 minutes, washed with water, and immersed in a mixed solution of 10g/LSnCl ₂ ·2H ₂ O and 20g/LHCl for sensitization treatment, with an immersion concentration of 0.3g/L LPdCl ₂ and 1.5mL/LHCl mixed solution for activation treatment. Then immerse in the 60 ℃ plating bath and apply plating for 150 minutes. Diamine 30g/L, sodium hydroxide 50g/L, pH 13.5. The electroless Ni-Cu-La-B glass fiber was obtained on the surface, and after drying at 100°C, it was observed with a microscope that the coating was compact.

Although the embodiments of the present invention have been shown and described, those skilled in the art can understand that various changes, modifications and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. and modifications, the scope of the invention is defined by the appended claims and their equivalents.

Claims (4)

1. a Ni-Cu-La-B quaternary alloy plating solution is characterized in that: the composition of described Ni-Cu-La-B quaternary alloy plating solution is as follows: The solvent is distilled water. 2. Ni-Cu-La-B quaternary alloy plating solution as claimed in claim 1, is characterized in that: the composition of described Ni-Cu-La-B quaternary alloy plating solution is as follows: The solvent is distilled water. 3. a method utilizing Ni-Cu-La-B quaternary alloy plating solution described in claim 1 or 2 to carry out glass fiber surface electroless plating, is characterized in that: the concrete steps of this method are as follows: (1) first take nickel chloride, copper sulfate, lanthanum sulfate, sodium borohydride, potassium sodium tartrate, ethylenediamine, sodium hydroxide respectively by proportioning; (2) Put the nickel chloride, copper sulfate and lanthanum sulfate, potassium sodium tartrate, sodium hydroxide and ethylenediamine weighed in step (1) into a container, add distilled water, and stir and mix with a magnetic stirrer at room temperature Uniform; (3) Slowly add sodium borohydride to the solution prepared in step (2), stir until dissolved, add ammonia water to adjust the pH value to 12-13.5, and make an electroless plating solution; (4) Put the glass fiber into the chemical plating solution prepared in step (3) to carry out chemical plating of Ni-Cu-La-B, the plating temperature is 60-90°C, and the plating time is 1-8h; (5) Dry the Ni-Cu-La-B-coated glass fiber prepared above at a drying temperature of 80-100° C. to obtain the Ni-Cu-La-B-coated glass fiber. 4. The method according to claim 3, characterized in that: the glass fibers in the step (4) are pretreated before use, and the pretreatment steps are as follows: (1) Put the glass fibers into 0.5-10% sodium carbonate aqueous solution and soak for 8-24 hours, then wash with distilled water, filter, and dry; (2) immerse the glass fiber treated in step (1) in 0.5-5% silane coupling agent solution, soak for 2-20 minutes, filter and dry; (3) immerse the glass fibers treated in step (2) in 40-65% nitric acid solution for roughening treatment for 10-60 minutes, and maintain the temperature of the nitric acid solution at 40-80°C; (4) immersing the glass fiber treated in step (3) in a mixed solution with a concentration of 5-20g/LSnCl ₂ ·2H ₂ O and 10-30g/L HCl for sensitization treatment; (5) Activate the glass fibers treated in step (4) in a mixed solution of 0.1-2g/LPdCl ₂ and 1-20mL/L HCl.