CN104164784B - Preparation method of composite fiber with high thermal conductivity through coating graphene on chemical fiber surface - Google Patents

Abstract

The invention discloses a preparation method of a composite fiber with a high thermal conductivity through coating graphene on the chemical fiber surface. The preparation method comprises the following steps: (1) preparing a pretreatment liquid, carrying out a pretreatment on the fiber surface including deoiling, roughening, sensitizing, and activating; (2) preparing a silver electroplating solution, carrying out silver electroplating on the fiber surface; (3) soaking the silver-coated fibers on a sulfhydrylated graphene solution to assemble a layer of graphene on the fiber surface; (4) taking out the fibers, and drying so as to obtain the coated composite fibers. The prepared composite fiber has the advantages of high thermal conductivity, high mechanical strength, and excellent tensile performance due to the chemical fiber substrate; and the thermal conductivity of the glass fiber is enhanced by taking graphene as the coating material.

Description

Graphene is coated in the method that chemical fibre surface makes high heat conduction composite fiber

Technical field

The present invention relates to a kind of method Graphene being coated in the high heat conduction composite fiber of chemical fibre surface making, utilize Graphene as enhanced thermal conduction Material coating on chemical fibre surface.

Background technology

At present along with electronics technology constantly develops rapidly, high power battery also gets more and more as the parts of energy body, so the material with high heat conduction and radiating efficiency receives much concern, how to improve the heat conduction and heat radiation rate of heat sink material, reduce the space occupied by it, the rigidity, the hardness that increase material are the problems that Heat Conduction Material field is paid close attention to always.

Chinese patent CN102560712A discloses a kind of high heat conduction composite fiber and manufacture method thereof in 2012-07-11, and this high heat conduction composite fiber by fiber bodies, and is blended in the bar shaped height heat conduction diaphragm composition in fiber bodies.Described high heat conduction diaphragm is high conductive graphite diaphragm or Graphene diaphragm.The preparation method of this composite fibre is: the high heat conduction diaphragm making bar shaped; By the liquid fiber base material of fusing and the mixing of high heat conduction diaphragm; Wire drawing process is carried out to fiber base material, solidifies rear formation composite fibre.Another preparation method of this composite fibre is: the high heat conduction diaphragm making bar shaped; By the high heat conduction diaphragm of bar shaped and fiber base material, carry out pressing close to operation or being mutually wound around; Improve environment temperature, fiber base material is melted, high heat conduction diaphragm that is rear and bar shaped to be solidified mixes, and forms composite fibre.

Graphene is a kind of new material of the individual layer laminated structure be made up of carbon atom.It is a kind of two-dimensional material only having a carbon atom thickness.2004, Univ Manchester UK physicist An Deliehaimu and Constantine Nuo Woxiaoluofu, successfully isolated Graphene in an experiment, and confirms that it can individualism from graphite.Graphene is the minimum material of world resistivity.Because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, and is therefore expected to can be used to develop thinner, conduction speed electronic component of new generation or transistor faster.Because Graphene is in fact a kind of transparent, good conductor, be also applicable to for manufacturing transparent touch screen, tabula rasa or even solar cell.

Chemical fibre fibrous insulation performance is good, corrosion resistance is good, mechanical strength is high, as packing material, can strengthen the crushing resistance of base material, pull resistance, impact resistance.Utilize the packing material with high power battery outer packing plates, can greatly increase its mechanical performance.

Chemical silvering is one of people's chemical plating method of developing the earliest, comes from ancient silver mirror reaction, so far existing century-old history.Different from galvanoplastic, the coating that chemical silvering is formed not is the electronics that provided by outside as reductant self-catalyzed deposition, but is formed by the chemical reaction between reductant and metal ion solution.Although Electroless Silver Plating was employed more than 50 years.

Chemical silvering is actual is redox reaction.Oxidation solution is generally made up of silver nitrate and ammoniacal liquor, because the aqueous solution of silver nitrate is unstable, easily decomposes, and generates the Ag2O precipitation of brown.Therefore in liquor argenti nitratis ophthalmicus, a small amount of ammoniacal liquor is dripped during dosing, separate out Ag2O precipitation, continue to drip ammoniacal liquor form silver ammonia complex and Ag2O is dissolved, Ag (NH3) 2OH forms Ag (NH3) 2OH complexing body more further with product NH4NO3.Reaction equation is as follows:

$2\mathrm{Ag}{\mathrm{NO}}_3+2{\mathrm{NH}}_4\mathrm{OH}\⇔{\mathrm{Ag}}_{2}O+2{\mathrm{NH}}_4{\mathrm{NO}}_3+H_{2}O$

${\mathrm{Ag}}_2+4{\mathrm{NH}}_4\mathrm{OH}\⇔2\left[\mathrm{Ag}{\left({\mathrm{NH}}_3\right)}_2\right]\mathrm{OH}+3H_{2}O$

$\left[\mathrm{Ag}{\left({\mathrm{NH}}_3\right)}_2\right]\mathrm{OH}+{\mathrm{NH}}_4{\mathrm{NO}}_3\⇔\left[\mathrm{Ag}{\left({\mathrm{NH}}_3\right)}_2\right]{\mathrm{NO}}_3+{\mathrm{NH}}_3\↑+H_{2}O$

In reduction reaction, conventional reductant mainly glucose, sucrose, formaldehyde, tartrate etc.The present invention adopts glucose as reductant, and its reaction is as follows:

$C_6{H}_{12}{O}_6+2\mathrm{Ag}{\left({\mathrm{No}}_3\right)}_2\mathrm{OH}\stackrel{\mathrm{\Δ}}{\→}{\mathrm{RCOONH}}_4+2\mathrm{Ag}\↓+H_{2}O+3{\mathrm{NH}}_3\↑$

Summary of the invention

For the above-mentioned deficiency of prior art, according to embodiments of the invention, desirable to provide a kind of composite fibre being coated in fiberglass surfacing by Graphene, it has comparatively high-heat conductive efficency, has certain mechanical strength, can be used as packing material; And propose Graphene to be coated in the method that chemical fibre surface makes high heat conduction composite fiber, utilize Graphene as enhanced thermal conduction Material coating on chemical fibre surface.

According to embodiment, a kind of method Graphene being coated in chemical fibre surface making composite fibre that technical solution of the present invention provides, comprises the steps:

(1) oil removing: with volumetric concentration be the ethanolic solution of 180-240ml/L as solvent, remove the oil stain on chemical fibre surface, the processing time is 10-20min, after oil removing, cleans and dry chemical fibre with deionized water;

(2) alligatoring: according to different chemical fibres, is immersed in the sodium hydroxide solution of 70-90g/L by the chemical fibre after oil removing, and at 70-85 DEG C of temperature, process 10-25min, cleans with deionized water;

(3) sensitization: utilize dissolving with hydrochloric acid stannous chloride, until completely dissolved, then adds the sensitizing solution that deionized water is mixed with 10-30g/L, and adds a small amount of tin grain in sensitizing solution; Chemical fibre after alligatoring is immersed in sensitizing solution, take out after at room temperature processing 10-20min, with buck cleaning, then clean with deionized water.In order to prevent divalent tin ion to be oxidized, in sensitizing solution, add a small amount of tin grain; Be beneficial to two valency tin ions with buck cleaning be hydrolyzed.

(4) activate: compound concentration is the liquor argenti nitratis ophthalmicus of 0.5-3g/L, drip ammoniacal liquor and occur reddish brown precipitation, continue to drip until precipitation disappears, add deionized water and be mixed with activating solution to 100-300ml; Chemical fibre after sensitized treatment is immersed in activating solution, takes out after processing 5-20min under room temperature, wash with deionized water and dry;

(5) chemical silvering: be slowly add ammoniacal liquor in the liquor argenti nitratis ophthalmicus of 5-10g/L and stir in concentration, until precipitation disappears, adds the NaOH that concentration is 2-4g/L, there is precipitation, slowly add ammoniacal liquor again and stir, until precipitation just disappears, being mixed with oxidation solution; By glucose deionized water dissolving, be mixed with the reducing solution that concentration is 10-20g/L; Chemical fibre through pre-treatment is placed in reducing solution, oxidation solution is dripped in reducing solution, ultrasonic process 10-20min, after question response is complete, chemical fibre is taken out, cleans with deionized water and dry;

(6) apply: the ethanolic solution silver-plated chemical fibre being put into the sulfhydrylation Graphene of 1-5%, fully react in a kettle., the combination between sulfydryl and silver ion obtains the chemical fibre of Graphene coating after sulfhydrylation Graphene is coated in silver-plated chemical fibre surface.

According to an embodiment, the aforementioned chemical fibre surface that is coated in by Graphene of the present invention makes in the method for composite fibre, and chemical fibre is terylene, polypropylene fibre or polyamide fibre.

According to an embodiment, the aforementioned chemical fibre surface that is coated in by Graphene of the present invention makes in the method for composite fibre, in step (4)-(5), and the concentration <2% of ammoniacal liquor.

The composite fibre obtained according to the inventive method mainly consist of sulfhydrylation Graphene, silver and chemical fibre, first carry out surface treatment to fiber, carry out chemical silvering, sulfhydrylation Graphene and silver plated fiber are in the combination of fiber surface afterwards.This composite fibre has high-heat conductive efficency and high mechanical properties simultaneously, and chemical fibre has superior stretch-proof performance as base, and selects Graphene as the thermal conductivity of coating material reinforcing glass fiber.

The present invention, by forming a layer graphene coating at fiber surface, improves the heat conduction and heat radiation efficiency of fiber effectively.

The composite fibre that the present invention obtains is with terylene, polyamide fibre, polypropylene fiber for base material, and composite not only has toughness and the intensity of fiber, and has possessed good heat conductivility on this basis.

The composite fibre that the present invention obtains as the filler of injected plastics material, can increase the mechanical performance of sheet material, bulk.Experiment proves, the composite fibre that the present invention obtains has better heat conduction and heat radiation performance compared to common fiber, and can keep original mechanical performance.

The composite fibre that the present invention obtains has that preparation is simple, heat transfer efficiency is high, and mechanical strength is high, high temperature resistant, the advantage of corrosion resistance, can be widely used in the filler of Heat Conduction Material on market, with the heat conductivility of reinforcing material and mechanical strength.

Accompanying drawing explanation

Fig. 1 is that the graphene coated rear surface SEM of polyster fibre schemes.

Detailed description of the invention

Below in conjunction with the drawings and specific embodiments, set forth the present invention further.These embodiments are interpreted as only being not used in for illustration of the present invention limiting the scope of the invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalence changes and modification fall into the scope of the claims in the present invention equally.

Embodiment 1

Graphene is coated in the method that PET fiber surface makes highly heat-conductive material

1, pre-treatment process

(1) oil removing: with volumetric concentration be the ethanolic solution of 200ml/L as solvent, remove the oil stain on terylene surface, the processing time is 15min, after oil removing, cleans and dry terylene with deionized water;

(2) alligatoring: the terylene after oil removing is immersed in the sodium hydroxide solution of 80g/L, at 80 DEG C of temperature, process 15min, cleans with deionized water;

(3) sensitization: utilize dissolving with hydrochloric acid stannous chloride, until completely dissolved, then adds the sensitizing solution that deionized water is mixed with 15g/L, and adds a small amount of tin grain in sensitizing solution; Terylene after alligatoring is immersed in sensitizing solution, take out after at room temperature processing 15min, with buck cleaning, then clean with deionized water.In order to prevent divalent tin ion to be oxidized, in sensitizing solution, add a small amount of tin grain; Be beneficial to two valency tin ions with buck cleaning be hydrolyzed.

(4) activate: compound concentration is the liquor argenti nitratis ophthalmicus of 0.5-3g/L, drip ammoniacal liquor and occur reddish brown precipitation, continue to drip until precipitation disappears, add deionized water and be mixed with activating solution to 200ml; Terylene after sensitized treatment is immersed in activating solution, takes out after processing 10min under room temperature, wash with deionized water and dry.

2, Electroless Silver Plating

(1) oxidation solution preparation: first the 8g silver nitrate weighed up is dissolved in 1L deionized water, slowly add ammoniacal liquor (concentration <2%) and stir, until precipitation disappears, then 2.5g NaOH is added, there is precipitation, slowly add ammoniacal liquor again and stir, until precipitation just disappears.

(2) reducing solution preparation: by the 15g/L glucose deionized water dissolving prepared.

(3) be placed in reducing solution by the terylene through pre-treatment, dripped by oxidation solution in reducing solution, ultrasonic process 15min, after question response is complete, taken out by terylene, oven dry clean with deionized water obtains chemical silvering terylene.

3, Graphene coating processes:

(1) configuration concentration is the sulfhydrylation Graphene-ethanolic solution of 1%;

(2) 3g chemical silvering terylene is put into polytetrafluoroethylene (PTFE) reactor, add sulfhydrylation Graphene-ethanolic solution that 80ml configures, put into 60 DEG C, baking oven reflection 2h;

(3) take out terylene, dry and obtain the graphene coated terylene in surface.Surface after polyster fibre is graphene coated as shown in Figure 1.

Measure mechanical performance and the heat conductivility of terylene and the obtained surperficial graphene coated terylene of embodiment 1 according to usual method, result is as following table 1-2:

Table 1. mechanical performance contrasts

Sample	Fracture strength (cN/dtex)	Extension at break (%)
			Terylene	4.6	27.36
The terylene of Graphene coating	3.9	20.39

Table 2. heat conductivility contrasts

Sample	Thermal conductivity factor (W/m DEG C)	Specific heat capacity J/g.k
			Terylene	0.35	2.01
Graphene coating terylene	0.42	2.22

Embodiment 2

Graphene is coated in the method that polypropylene fiber surface makes highly heat-conductive material

1, pre-treatment process

(1) oil removing: with volumetric concentration be the ethanolic solution of 220ml/L as solvent, remove the oil stain on polypropylene fibre surface, the processing time is 15min, after oil removing, cleans and dry polypropylene fibre with deionized water;

(2) alligatoring: the polypropylene fibre after oil removing is immersed in the sodium hydroxide solution of 90g/L, at 85 DEG C of temperature, process 20min, cleans with deionized water;

(3) sensitization: utilize dissolving with hydrochloric acid stannous chloride, until completely dissolved, then adds the sensitizing solution that deionized water is mixed with 20g/L, and adds a small amount of tin grain in sensitizing solution; Polypropylene fibre after alligatoring is immersed in sensitizing solution, take out after at room temperature processing 15min, with buck cleaning, then clean with deionized water.In order to prevent divalent tin ion to be oxidized, in sensitizing solution, add a small amount of tin grain; Be beneficial to two valency tin ions with buck cleaning be hydrolyzed.

(4) activate: compound concentration is the liquor argenti nitratis ophthalmicus of 0.5-3g/L, drip ammoniacal liquor and occur reddish brown precipitation, continue to drip until precipitation disappears, add deionized water and be mixed with activating solution to 250ml; Polypropylene fibre after sensitized treatment is immersed in activating solution, takes out after processing 15min under room temperature, wash with deionized water and dry;

2, Electroless Silver Plating

(1) oxidation solution preparation: first the 5g silver nitrate weighed up is dissolved in 1L deionized water, slowly add ammoniacal liquor (concentration <2%) and stir, until precipitation disappears, then 2.5g NaOH is added, there is precipitation, slowly add ammoniacal liquor again and stir, until precipitation just disappears.

(2) reducing solution preparation: by the 15g/L glucose deionized water dissolving prepared.

(3) be placed in reducing solution by the polypropylene fibre through pre-treatment, dripped by oxidation solution in reducing solution, ultrasonic process 15min, after question response is complete, taken out by fiber, oven dry clean with deionized water obtains chemical silvering polypropylene fibre.

3, Graphene coating processes:

(1) configuration concentration is the sulfhydrylation Graphene-ethanolic solution of 2%;

(2) silver-plated for 3g polypropylene fibre is put into polytetrafluoroethylene (PTFE) reactor, add sulfhydrylation Graphene-ethanolic solution that 80ml configures, put into 60 DEG C, baking oven reflection 2h;

(3) take out polypropylene fibre, dry and obtain the graphene coated polypropylene fibre in surface.

Measure mechanical performance and the heat conductivility of polypropylene fibre and the obtained surperficial graphene coated polypropylene fibre of embodiment 1 according to usual method, result is as following table 3-4:

Table 3. mechanical performance contrasts

Sample	Fracture strength (cN/dtex)	Extension at break (%)
			Polypropylene fibre	3.6	32.12
Graphene coating polypropylene fibre	2.9	24.38

Table 4. heat conductivility contrasts

Sample	Thermal conductivity factor (W/m DEG C)	Specific heat capacity J/g.k
			Polypropylene fibre	0.22	1.92
Graphene coating polypropylene fibre	0.31	2.11

Embodiment 3

Graphene is coated in the method that nylon fibre surface makes highly heat-conductive material

1, pre-treatment process

(1) oil removing: with volumetric concentration be the ethanolic solution of 200ml/L as solvent, remove the oil stain on polyamide fibre surface, the processing time is 15min, after oil removing, cleans and dry polyamide fibre with deionized water;

(2) alligatoring: the polyamide fibre after oil removing is immersed in the sodium hydroxide solution of 80g/L, at 80 DEG C of temperature, process 15min, cleans with deionized water;

(3) sensitization: utilize dissolving with hydrochloric acid stannous chloride, until completely dissolved, then adds the sensitizing solution that deionized water is mixed with 20g/L, and adds a small amount of tin grain in sensitizing solution; Polyamide fibre after alligatoring is immersed in sensitizing solution, take out after at room temperature processing 15min, with buck cleaning, then clean with deionized water.In order to prevent divalent tin ion to be oxidized, in sensitizing solution, add a small amount of tin grain; Be beneficial to two valency tin ions with buck cleaning be hydrolyzed.

(4) activate: compound concentration is the liquor argenti nitratis ophthalmicus of 0.5-3g/L, drip ammoniacal liquor and occur reddish brown precipitation, continue to drip until precipitation disappears, add deionized water and be mixed with activating solution to 250ml; Polyamide fibre after sensitized treatment is immersed in activating solution, takes out after processing 15min under room temperature, wash with deionized water and dry;

2, Electroless Silver Plating

(1) oxidation solution preparation: first the 10g silver nitrate weighed up is dissolved in 1L deionized water, slowly add ammoniacal liquor (concentration <2%) and stir, until precipitation disappears, then 2.5g NaOH is added, there is precipitation, slowly add ammoniacal liquor again and stir, until precipitation just disappears.

(2) reducing solution preparation: by the 15g/L glucose deionized water dissolving prepared.

(3) be placed in reducing solution by the polyamide fibre through pre-treatment, dripped by oxidation solution in reducing solution, ultrasonic process 15min, after question response is complete, taken out by polyamide fibre, oven dry clean with deionized water obtains chemical silvering polyamide fibre.

3, Graphene coating processes:

(1) configuration concentration is the sulfhydrylation Graphene-ethanolic solution of 1.5%;

(2) silver-plated for 3g polyamide fibre is put into polytetrafluoroethylene (PTFE) reactor, add sulfhydrylation Graphene-ethanolic solution that 80ml configures, put into 60 DEG C, baking oven reflection 2h;

(3) take out fiber, dry and obtain the graphene coated polyamide fibre in surface.

Measure mechanical performance and the heat conductivility of polyamide fibre and the obtained surperficial graphene coated polyamide fibre of embodiment 1 according to usual method, result is as following table 5-6:

Table 5. mechanical performance contrasts

Sample	Fracture strength (cN/dtex)	Extension at break (%)
			Polyamide fibre	4.35	32.21
Graphene coating polyamide fibre	3.92	27.63

Table 6. heat conductivility contrasts

Sample	Thermal conductivity factor (W/m DEG C)	Specific heat capacity J/g.k
			Polyamide fibre	0.25	1.67
Graphene coating polyamide fibre	0.32	1.93

Claims (4)

1. Graphene is coated in the method that chemical fibre surface makes composite fibre, it is characterized in that, comprise the steps:

(1) oil removing: with volumetric concentration be the ethanolic solution of 180-240ml/L as solvent, remove the oil stain on chemical fibre surface, the processing time is 10-20min, after oil removing, cleans and dry chemical fibre with deionized water;

(2) alligatoring: according to different chemical fibres, is immersed in the sodium hydroxide solution of 70-90g/L by the chemical fibre after oil removing, and at 70-85 DEG C of temperature, process 10-25min, cleans with deionized water;

(3) sensitization: utilize dissolving with hydrochloric acid stannous chloride, until completely dissolved, then adds the sensitizing solution that deionized water is mixed with 10-30g/L, and in sensitizing solution, adds a small amount of tin grain; Chemical fibre after alligatoring is immersed in sensitizing solution, take out after at room temperature processing 10-20min, with buck cleaning, then clean with deionized water;

(4) activate: compound concentration is the liquor argenti nitratis ophthalmicus of 0.5-3g/L, drip ammoniacal liquor and occur reddish brown precipitation, continue to drip until precipitation disappears, add deionized water and be mixed with activating solution to 100-300ml; Chemical fibre after sensitized treatment is immersed in activating solution, takes out after processing 5-20min under room temperature, wash with deionized water and dry;

(5) chemical silvering: be slowly add ammoniacal liquor in the liquor argenti nitratis ophthalmicus of 5-10g/L and stir in concentration, until precipitation disappears, adds the NaOH that concentration is 2-4g/L, there is precipitation, slowly add ammoniacal liquor again and stir, until precipitation just disappears, being mixed with oxidation solution; By glucose deionized water dissolving, be mixed with the reducing solution that concentration is 10-20g/L; Chemical fibre through pre-treatment is placed in reducing solution, oxidation solution is dripped in reducing solution, ultrasonic process 10-20min, after question response is complete, chemical fibre is taken out, cleans with deionized water and dry;

(6) apply: the ethanolic solution silver-plated chemical fibre being put into the sulfhydrylation Graphene of 1-5%, fully react in a kettle., the combination between sulfydryl and silver ion obtains the chemical fibre of Graphene coating after sulfhydrylation Graphene is coated in silver-plated chemical fibre surface.

2. method Graphene being coated in chemical fibre surface making composite fibre according to claim 1, it is characterized in that, chemical fibre is terylene, polypropylene fibre or polyamide fibre.

3. method Graphene being coated in chemical fibre surface making composite fibre according to claim 1, is characterized in that, in step (4)-(5), and the concentration <2% of ammoniacal liquor.

4. the composite fibre that the method in claim 1-3 described in any one is obtained.