CN105256291A - Method for preparing aramid fiber nickel/copper plating double-plating-layer composite conductive fibers - Google Patents

Abstract

The invention relates to a method for preparing aramid fiber nickel/copper plating double-plating-layer composite conductive fibers and a palladium-free activation method. The methods include the following specific steps that (1) washing and oil removal are performed; (2) the fiber surfaces are pretreated by pretreatment reagents, the fibers are swollen, a layer of metal ions with catalytic activity after being reduced is adsorbed to the surfaces, and the surface area and the wettability of the fibers are increased; (3) reduction is conducted; (4) chemical nickel-plating is carried out; and (5) chemical copper plating is carried out. According to the prepared aramid fiber nickel/copper plating double-plating-layer composite conductive fibers, the binding force of the plating layers with the fiber substrates is high; the chemical properties of the plating layers are stable, the plating layers are not prone to be oxidized in air, and the excellent conductive property can be maintained for a long time; meanwhile, characteristics of heat resistance, inflaming retarding, small weight, flexibility, high strength and the like are achieved. The composite conductive fibers can be used for preparing anti-static electricity and electromagnetic shielding fabrics and shielding layers of special cables and conductor materials. Meanwhile, compared with a palladium activation method, the palladium-free activation method has the advantages of being economical, easy and convenient to operate and the like.

Description

The preparation method of the two coating composite conducting fiber of a kind of aramid fiber nickel plating/copper

Technical field

The invention provides the preparation method of the two coating composite conducting fiber of a kind of aramid fiber nickel plating/copper.The natural characteristicss such as this technique at aramid fiber surface metal lining electrically conductive layer, thus gives resistant fiber electrostatic and conducting function by chemical plating method, remains the high-strength light of fiber, heat-proof combustion-resistant simultaneously, soft are a kind of advanced composite materials.The specials such as Aeronautics and Astronautics, navigation, military project, medical treatment can be widely used in, as electromagnetic shielding material and the lightweight conductive material of individual protection.Meanwhile, the invention provides the palladium-free activation process of the two coating of a kind of chemical nickel plating/copper.

Background technology

Aromatic polyamide fibre is called for short aramid fiber, English is Aramidfiber, is developed at first by du pont company, is a kind of novel high-tech synthon, there is superstrength, high-modulus and high temperature resistant, acid-fast alkali-proof, the premium properties such as lightweight, its intensity is 5 ~ 6 times of steel wire, and modulus is 2 ~ 3 times of steel wire or glass fibre, and toughness is 2 times of steel wire, and weight is only about 1/5 of steel wire, at the temperature of 560 degree, do not decompose, non-fusible.It has good insulativity and ageing resistance, has very long life cycle.Aramid fiber and matrix material thereof have been widely used in aerospace and military use, as the housing of the aircrafts such as Boeing 757,767, flak jackets, bullet-proof vest, the helmet, space flight compression garments, high strength parachute, missile case material, extraordinary cable, rocket body, space shuttle energy storage tank and other high pressure vessels etc.The discovery of aramid fiber, is considered to material circle very important historical progress, is therefore called as " fiber of dream ".

But aramid fiber is the same with other macromolecular material, its good electrical insulating property and dielectric properties, limit the application of aramid fiber in some fields.At present, the method for giving aramid fiber electroconductibility mainly contains the methods such as magnetron sputtering, co-blended spinning, electroless plating.Patent CN101705615A teaches a kind of preparation method of nickel-plated and copper-plated aromatic polyamide conductive fibers, but adopt method of roughening to destroy the epidermal structure of fiber in its preparation process, damage the mechanical property of fiber, reduce the range of application of fiber, and have employed palladium activation method, cost is higher, is unfavorable for scale operation.

Current state inner conductive fiber is mainly with terylene, and nylon, cotton fibre etc. are substrate.Be that the electro-conductive fiber of substrate rarely has report with aramid fiber, and there is a lot of defect, the bonding force of coating and fibrous matrix is very poor.External Jin You du pont company grasps the core technology of producing this series products.

The two coating composite conducting fiber of aramid fiber nickel plating/copper that this patent adopts chemical plating method to prepare, as shown in Figure 1, the fiber after copper facing as shown in Figure 2 for the fiber after nickel plating.With domestic existing about conduct electricity aramid fiber report compared with, the no-palladium activating preparation method that this patent adopts, not only simple to operate in technique, economical, and preprocessing process does not adopt the method for roughening of damaged fiber mechanical property, thus ensure that fiber is in the application to the higher field of mechanical property requirements, the bonding force of the coating and the fibrous matrix that obtain by force, the stable in properties of coating.The two coating conjugated fibre conductivity of prepared aramid fiber nickel plating/copper is excellent, has broad application prospects in lightweight conductive material field and electromagnetic shielding field.

Summary of the invention

One of the object of the invention is to provide the preparation method of the two coating composite conducting fiber of a kind of aramid fiber nickel plating/copper.

Two of the object of the invention is to provide the palladium-free activation process of the two coating composite conducting fiber of a kind of aramid fiber nickel plating/copper.

The present invention passes through first to carry out cleaning oil removal treatment to aramid fiber, the finish that removing fiber adsorbs in the course of processing and surface smut; After oil removing, pre-treatment is carried out to fiber surface, make fiber swelling, increased fiber surface-area and wettability, and after the reduction of surface adsorption one deck, there is the metal ion of catalytic activity, improve the binding strength of fibrous matrix and subsequent plating layer; Flooded by the solution that reductive agent put into by pretreated fiber, make the metal ion being adsorbed on fiber surface be reduced into metallic particles, this metal particle layer as the anchor point between fiber and subsequent plating layer, can also have the function of catalysis simultaneously; Then at the chemical nickel plating on surface of fiber, electroless copper, finally obtains a kind of nickel-plated and copper-plated aramid fiber electro-conductive fiber.

The preparation method of the two coating composite conducting fiber of a kind of aramid fiber nickel plating/copper of the present invention, is characterized in that having following process and step:

A. washing and oil removing: aramid fiber is put into acetone, takes out after ultrasonic cleaning 40 ~ 80min, use deionized water rinsed clean;

B. pre-treatment: the methyl-sulphoxide aqueous solution fiber after oil removing being put into 5 ~ 50g/L Silver Nitrate, wherein the volumetric concentration of methyl-sulphoxide is 10 ~ 30%, at 30 ~ 100 DEG C, takes out, use deionized water rinsed clean after dipping 1 ~ 4h;

C. reduce: pretreated fiber is put into 5 ~ 25g/L borane reducing agent sodium hydride aqueous solution or the POTASSIUM BOROHYDRIDE aqueous solution floods, at 20 ~ 50 DEG C, take out after dipping 20 ~ 60min;

D. chemical nickel plating:

Nickel-plating liquid with following material and water formulated, in reaction solution, the content of each material is:

Single nickel salt 15 ~ 40g/L

Inferior sodium phosphate (reductive agent) 10 ~ 20g/L

Dimethylamino borine (reductive agent) 3 ~ 10g/L

Trisodium Citrate (complexing agent) 20 ~ 30g/L

Ammoniacal liquor (PH conditioning agent) 5 ~ 15ml/L

Aramid fiber after reduction is immersed in nickel-plating liquid, at 40 ~ 80 DEG C, take out after reaction 0.5 ~ 1h, use deionized water rinsed clean, obtain the aramid fiber that surface uniform plating has nickel;

E. electroless copper:

Copper plating bath with following material and water formulated, in reaction solution, the content of each material is:

Cupric sulfate pentahydrate 10 ~ 15g/L

Seignette salt (complexing agent) 10 ~ 20g/L

Na ₂eDTA(disodium ethylene diamine tetraacetate, complexing agent) 15 ~ 20g/L

NaOH(PH conditioning agent) 10 ~ 15g/L

HCHO12～17g/L

Duplex pyridine (stablizer) 0.015 ~ 0.020g/L

Yellow prussiate of potash (stablizer) 0.007 ~ 0.010g/L

Immersed by nickel plating fiber in copper plating bath, at 40 ~ 60 DEG C, take out, use deionized water rinsed clean, be placed in the dry 30min of loft drier after reaction 0.5 ~ 1h, obtaining internal layer is nickel, outer two coating conduction aramid fibers for copper.

Accompanying drawing explanation

Fig. 1 is the embodiment of the present invention 1 gained nickel plating aramid fiber scanning electronic microscope (SEM) figure.

Fig. 2 is the embodiment of the present invention 1 gained nickel-plated and copper-plated conduction aramid fiber scanning electronic microscope (SEM) figure.

Embodiment

after now specific embodiments of the invention being described in.

embodiment 1

preparation process in the present embodiment and step as described below:

(1) oil removing, puts into acetone soln by aramid fiber, takes out after ultrasonic cleaning 60min, uses deionized water rinsed clean.

(2) pre-treatment, immersed in the methyl-sulphoxide aqueous solution containing 5g/L Silver Nitrate by fiber, wherein the volume content of methyl-sulphoxide is take out after soaking 1h at 30%, 100 DEG C.

(3) reduce, pretreated fiber is put into 15g/L sodium borohydride solution and carries out reduction treatment, temperature is 20 DEG C, takes out after 60min.

(4) chemical nickel plating, the fiber after reduction is put into nickel plating solution, and chemical nickel-plating liquid consists of: single nickel salt 40g/L, inferior sodium phosphate 10g/L, dimethylamino borine 10g/L, Trisodium Citrate 30g/L, ammoniacal liquor 15ml/L, bath temperature is 40 DEG C, plating time 0.5h.

(5) electroless copper, nickel plating aramid fiber is put into copper plating bath, and chemical bronze plating liquid consists of: cupric sulfate pentahydrate 10g/L, Seignette salt 15g/L, disodium ethylene diamine tetraacetate 15g/L, NaOH15g/L, HCHO12g/L, duplex pyridine 0.020g/L, yellow prussiate of potash 0.007g/L.Bath temperature is 40 DEG C, plating time 30min.

embodiment 2

preparation process in the present embodiment and step as described below:

(1) oil removing, puts into acetone soln by aramid fiber, takes out after ultrasonic cleaning 40min, uses deionized water rinsed clean.

(2) pre-treatment, immerses in the methyl-sulphoxide aqueous solution of 30g/L Silver Nitrate by fiber, wherein the volumetric concentration of methyl-sulphoxide is take out after soaking 2h at 20%, 60 DEG C.

(3) reduce, pretreated fiber is put into 5g/L solution of potassium borohydride and carries out reduction treatment, temperature is 50 DEG C, takes out after 30min.

(4) chemical nickel plating, the fiber after reduction is put into nickel plating solution, and chemical nickel-plating liquid consists of: single nickel salt 15g/L, inferior sodium phosphate 20g/L, dimethylamino borine 3g/L, Trisodium Citrate 20g/L, ammoniacal liquor 5ml/L, bath temperature is 60 DEG C, plating time 1h.

(5) electroless copper, nickel plating aramid fiber is put into copper plating bath, and chemical bronze plating liquid consists of: cupric sulfate pentahydrate 15g/L, Seignette salt 10g/L, disodium ethylene diamine tetraacetate 20g/L, NaOH10g/L, HCHO15g/L, duplex pyridine 0.015g/L, yellow prussiate of potash 0.010g/L.Bath temperature is 50 DEG C, plating time 60min.

embodiment 3

preparation process in the present embodiment and step as described below:

(1) oil removing, puts into acetone soln by aramid fiber, takes out after ultrasonic cleaning 80min, uses deionized water rinsed clean.

(2) pre-treatment, immerses in the methyl-sulphoxide aqueous solution of 50g/L Silver Nitrate by fiber, wherein the volumetric concentration of methyl-sulphoxide is take out after soaking 4h at 10%, 30 DEG C.

(3) reduce, pretreated fiber is put into 25g/L sodium borohydride solution and carries out reduction treatment, temperature is 35 DEG C, takes out after 20min.

(4) chemical nickel plating, the fiber after reduction is put into nickel plating solution, and chemical nickel-plating liquid consists of: single nickel salt 25g/L, inferior sodium phosphate 15g/L, dimethylamino borine 6g/L, Trisodium Citrate 25g/L, ammoniacal liquor 10ml/L, bath temperature is 80 DEG C, plating time 1h.

(5) electroless copper, nickel plating aramid fiber is put into copper plating bath, and chemical bronze plating liquid consists of: cupric sulfate pentahydrate 12g/L, Seignette salt 20g/L, disodium ethylene diamine tetraacetate 17g/L, NaOH12g/L, HCHO17g/L, duplex pyridine 0.017g/L, yellow prussiate of potash 0.009g/L.Bath temperature is 60 DEG C, plating time 40min.

Claims (1)

1. a preparation method for the two coating composite conducting fiber of aramid fiber nickel plating/copper, is characterized in that having following process and step:

A. washing and oil removing: aramid fiber is put into acetone, takes out after ultrasonic cleaning 40 ~ 80min, use deionized water rinsed clean;

B. pre-treatment: the fiber after oil removing is put into the methyl-sulphoxide aqueous solution containing 5 ~ 50g/L Silver Nitrate, wherein the volumetric concentration of methyl-sulphoxide is 10 ~ 30%, at 30 ~ 100 DEG C, takes out after dipping 1 ~ 4h, uses deionized water rinsed clean;

C. reduce: pretreated fiber is put into 5 ~ 25g/L borane reducing agent sodium hydride aqueous solution or the POTASSIUM BOROHYDRIDE aqueous solution floods, at 20 ~ 50 DEG C, take out after dipping 20 ~ 60min;

D. chemical nickel plating:

Nickel-plating liquid with following material and water formulated, in reaction solution, the content of each material is:

Single nickel salt 15 ~ 40g/L

Inferior sodium phosphate (reductive agent) 10 ~ 20g/L

Dimethylamino borine (reductive agent) 3 ~ 10g/L

Trisodium Citrate (complexing agent) 20 ~ 30g/L

Ammoniacal liquor (PH conditioning agent) 5 ~ 15ml/L

Aramid fiber after reduction is immersed in nickel-plating liquid, at 40 ~ 80 DEG C, take out after reaction 0.5 ~ 1h, use deionized water rinsed clean, obtain the aramid fiber that surface uniform plating has nickel;

E. electroless copper:

Copper plating bath with following material and water formulated, in reaction solution, the content of each material is:

Cupric sulfate pentahydrate 10 ~ 15g/L

Seignette salt (complexing agent) 10 ~ 20g/L

Na ₂eDTA(disodium ethylene diamine tetraacetate, complexing agent) 15 ~ 20g/L

NaOH(PH conditioning agent) 10 ~ 15g/L

HCHO12～17g/L

Duplex pyridine (stablizer) 0.015 ~ 0.020g/L

Yellow prussiate of potash (stablizer) 0.007 ~ 0.010g/L

Immersed by nickel plating fiber in copper plating bath, at 40 ~ 60 DEG C, take out, use deionized water rinsed clean, be placed in the dry 30min of loft drier after reaction 0.5 ~ 1h, obtaining internal layer is nickel, outer two coating conduction aramid fibers for copper.