CN1834304A - Method of preparing thin sheet net-like metallic short fiberous material - Google Patents
Method of preparing thin sheet net-like metallic short fiberous material Download PDFInfo
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- CN1834304A CN1834304A CN 200610024281 CN200610024281A CN1834304A CN 1834304 A CN1834304 A CN 1834304A CN 200610024281 CN200610024281 CN 200610024281 CN 200610024281 A CN200610024281 A CN 200610024281A CN 1834304 A CN1834304 A CN 1834304A
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Abstract
This invention relates to a method for manufacturing a thin-layer network of metallized short carbon fibers, which comprises the steps of: (1) adding an appropriate amount of short carbon fibers into the plating solution of a conventional metal or alloy and uniformly dispersing; (2) performing foam floatation method so that the short carbon fibers are floated on the surface of the plating solution and interconnected to form a network precursor of short carbon fibers; and (3) contacting one side of the precursor with a cathode for electroplating, and controlling the current density and plating time so that a metal layer is uniformly deposited on the precursor to obtain a thin-layer network of metallized short carbon fibers. The method has such advantages of simple process and low cost, and can effectively control the thickness of the plating layer, the thickness of the thin-layer network of metallized short carbon fibers and the metal composition. The thin-layer network of metallized short carbon fibers can be used as electromagnetic shielding materials, antistatic materials, and wave-absorbing materials, metal-based and resin-based composite materials.
Description
Technical field
The present invention relates to a kind of preparation method of short fiberous material, be specifically related to a kind of preparation method of thin sheet net-like metallic short fiberous material, can be used for the preparation of electromagnetic shielding material, antistatic material, absorbing material, structured material etc.Belong to the surface treatment technology of material field.
Background technology
Carbon fiber has a series of advantages such as high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, conduction, heat conduction and low-expansion coefficient, is a kind of important composite material reinforcement body.The application of carbon fiber aspect functional materials in recent years is also increasingly extensive, especially the two dimensional surface of carbon fiber or lamellar material receive much attention, as carbon fiber felt, carbon fiber paper, and laminar plastics of carbon fiber reinforced etc., be applied to electromagnetic shielding, antistatic, inhale fields such as ripple, battery electrode, planar exothermic material, such material also can be applied in the metal-base composites simultaneously.Carbon fiber after the metallization is better than naked carbon fiber at aspect of performances such as conduction, heat conduction, and still can keep the good mechanical performance, but is difficult to obtain with a kind of simple preparation technology the carbon fibre material of required two-dimensional metallicization at present.
The metallization process that the two dimensional surface carbon fibre material is carried out generally is methods such as plating, electroless plating, but they respectively have shortcoming: traditional electroplating technology, be difficult to obtain the uniform carbon fiber of coating, and the normal phenomenons such as " evil minds " that occurs, thickness of coating is wayward; Chemical plating technology cost height, technology is restive, and the metal plating conductivity that electroless plating obtains is not as galvanized height.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of thin sheet net-like metallic short fiberous material is proposed, simple for process, with low cost, by the concentration of adjusting short carbon fiber and mesh size, thickness of coating and the metal plating composition of the effective control material of electroplating technological parameter energy.
For realizing this purpose, the present invention adds an amount of short carbon fiber and makes it to be uniformly dispersed in the plating bath of conventional monometallic or alloy, add an amount of whipping agent and trapping agent again, bubbling air makes short carbon fiber be suspended in the plating bath surface, and the short carbon fiber overlap joint is linked to each other, and form the netted prefabricated component in one deck short carbon fiber plane, electroplate with an end of negative electrode contact prefabricated component then, control current density and electroplating time obtain the uniform thin sheet net-like metallic short fiberous material of coating.
Concrete steps of the present invention are as follows:
1, by the monometallic of required metal plating preparation routine or the plating bath of alloy, in plating bath, adds short carbon fiber, whipping agent and trapping agent, and the short carbon fiber in the plating bath is uniformly dispersed.Wherein, the short carbon fiber length range is 0.2mm～5cm, and the content of short carbon fiber is 0.05～2g/L in the plating bath, and foaming agents content is 0.1～5g/L; The content of trapping agent is 0.1～5g/L.
Whipping agent of the present invention can select polyoxyethylene glycol, pine tar, Terpineol 350, cresols oil, isobutyl-methyl benzyl must alcohol, C4 poly alkyl alcohol oxyethane (23,42) ether, three polypropylene glycols etc.
The present invention adopts hydrophobic surfactant as trapping agent, as hydro carbons non-polar compound, alkyl xanthogenate, oleic acid, dialkyl dithiophosphate, lipid acid and soda soap thereof, alkyl sulfonate, phosphoric acid fat, hydroximic acid and salt thereof, quaternary ammonium salt, alkyl benzyl pyridine etc.
2, bubbling air in plating bath produces a large amount of bubbles and makes short carbon fiber carry down evenly come-up at foamy, is suspended on the liquid level and the unanimity that is evenly distributed, and obtains plane reticulated structure prefabricated component.
3, negative electrode is contacted the prefabricated component of gained, connect power supply and electroplate.Current density is controlled at 0.5A/dm
2～5.0A/dm
2, electroplating time is 10～60 minutes, finally obtains thin sheet net-like metallic short fiberous material.
Electroplate after 1～2 minute, can observe with the naked eye the growing state of coating, metal plating on prefabricated component from negative electrode slowly anode extend, until obtaining thin sheet net-like metallic short fiberous material.Thickness of coating can wait by adjusting current density and electroplating time and control, and is controlled in 1 μ m～20 mu m ranges.The thickness of thin sheet net-like metallic short fiberous material is can be controlled in 30 μ m～1mm scope by the content decision that the synergetic short carbon fiber number of plies is a carbon fiber.
The present invention can obtain the coating of different compositions by selecting different electroplating bath solutions and technology, is applicable to the plating of present various metal ingredients, and coating can be monometallics such as nickel, copper, iron, also can be various binary, ternary alloy etc.
The present invention is applied to the method for pneumatic flotation in the electroplating technology first, makes the short carbon fiber come-up to overlap mutually, and forms the netted prefabricated component in plane, obtains metallized short carbon fiber web of sheet material thereby electroplate.The present invention electroplate the coating obtain very evenly, reason is: the mutual overlap joint between the short carbon fiber, feasible short carbon fiber conductive capability near negative electrode is better than the short carbon fiber after leaning on, so electrodepositing speed height of its metal, but prolongation along with electroplating time, away from metal on the short carbon fiber of negative electrode also plating, strengthened conductive capability greatly, they have very strong electric field shielding effect to the short carbon fiber near negative electrode, therefore with regard to the netted prefabricated component in whole plane, the deposition of metal all about equally.The equipment that the present invention adopts is simple, simple for process, and is similar to the common electrical depositing process.The short carbon fiber web of sheet material of the prepared metal lining of the present invention is expected to be applied at electromagnetic shielding material, antistatic material, absorbing material, exothermic material, structured material (as metal-base composites) etc.
Embodiment
Below by several specific embodiments technical scheme of the present invention is further described.Following examples do not constitute the qualification to technical solution of the present invention.
Embodiment 1:
Coating composition is that nickel, thickness of coating are the netlike carbon fiber material of 50 microns of 2 microns, sheet thickness
With reference to common nickel-plating liquid prescription, as the sulfamate plating bath: nickel sulfamic acid 400g/L, nickelous chloride 5g/L, boric acid 40g/L prepares and is placed in the plating tank, and about heating in water bath to 50 ℃.Getting length is the short carbon fiber 0.05g/L of 5cm, pours in the plating tank and stirs.Add the 0.1g/L polyoxyethylene glycol and make whipping agent, add 5g/L oleic acid as trapping agent.As anode, copper sheet is made negative electrode with the pure nickel plate.The plating bath pH regulator is about 4.0.Employing pressurized air stirs, and short carbon fiber floats to the netted prefabricated component in liquid level formation plane behind the bubbling air.Negative electrode is put into a end near prefabricated component, and anode is placed on the other end and away from prefabricated component (anode parcel electrolysis cloth).Current density is 0.5A/dm
2, the time was controlled at about 60 minutes, and this moment, coating was covered with whole prefabricated component, stopped to electroplate, and obtained required nickel plating thin sheet net-like carbon fibre material at last, and thickness of coating is about 2 μ m, and sheet thickness is about 50 μ m.
Embodiment 2:
Coating composition is that nickel, thickness of coating are the netlike carbon fiber material of 500 microns of 10 microns, sheet thickness
Electroplate liquid formulation is: nickel sulfamic acid 400g/L, and nickelous chloride 5g/L, boric acid 40g/L prepares and is placed in the plating tank, and about heating in water bath to 50 ℃.Get length and be the short carbon fiber 0.5g/L about 1cm, pour in the plating tank and stir, add the 1.0g/L pine tar and make whipping agent and the amino semi-annular jade pendant acid of 2.5g/L octadecyl sodium as trapping agent.As anode, copper sheet is made negative electrode with the pure nickel plate.The plating bath pH regulator is about 4.0.Employing pressurized air stirs, and short carbon fiber floats to the netted prefabricated component in liquid level formation plane behind the bubbling air.Negative electrode is put into a end near prefabricated component, and anode is placed on the other end and away from prefabricated component.Current density is 1.0A/dm
2, the time was about about 40 minutes, and this moment, coating was covered with whole prefabricated component, stopped to electroplate, and obtained required nickel plating thin sheet net-like carbon fibre material at last, and thickness of coating is about 10 μ m, and sheet thickness is about 500 μ m.
Embodiment 3:
Coating composition is that copper, thickness of coating are the netlike carbon fiber material of 50 microns of 2 microns, sheet thickness
By common electro-coppering formulated plating bath, wherein copper sulfate 200g/L, sulfuric acid 70g/L.Plating is in room temperature (25 ℃) operation down.Get length and be the short carbon fiber 1.0g/L about 5.0mm, pour in the plating tank and stir, add 1.0g/L three polypropylene glycols and make whipping agent and 1.5g/L methylbenzene phosphoric acid fat as trapping agent.As anode, copper sheet is made negative electrode with phosphorus copper plate.Employing pressurized air stirs, and short carbon fiber floats to the netted prefabricated component in liquid level formation plane behind the bubbling air.Negative electrode is put into a end near prefabricated component, and anode is placed on the other end and away from prefabricated component.Current density is 2.5A/dm
2, the time is 30 minutes, and this moment, coating was covered with whole prefabricated component, stopped to electroplate, and obtained required nickel plating thin sheet net-like carbon fibre material at last, and thickness of coating is about 2 μ m, and sheet thickness is about 50 μ m.
Embodiment 4:
Coating composition is that nickel-cobalt-base alloy, thickness of coating are the netlike carbon fiber material of 50 microns of 2 microns, sheet thickness
The prescription of this plating bath is: nickel sulfamic acid 600g/L, and thionamic acid cobalt 1.25g/L, nickelous chloride 10g/L, boric acid 35g/L prepares and is placed in the plating tank, and temperature is controlled at about 60 ℃.Short carbon fiber in the plating bath (length is approximately 1mm) content is 1.5g/L, whipping agent Terpineol 350 3.5g/L, trapping agent phenyl mercaptan 1.0g/L.Pour into short carbon fiber in the groove before using and be uniformly dispersed.Anode is the pure nickel plate, the negative electrode stainless steel plate, and current density is controlled at 3.5A/dm
2, the time is 20 minutes, electroplates the thin sheet net-like carbon fibre material that obtains plated nickel-cobalt-base alloy after finishing, and its thickness of coating is 2 microns, and sheet thickness is 50 microns.
Embodiment 5:
Coating composition is that copper-tin alloy, thickness of coating are the netlike carbon fiber material of 50 microns of 2 microns, sheet thickness:
Electroplate liquid formulation is: potassium pyrophosphate 250g/L, cupric pyrophosphate 15g/L, the inferior tin 2.0g/L of potassium pyrophosphate, Sodium phosphate dibasic 40g/L, Trisodium Citrate 7.5g/L, nitrilotriacetic acid(NTA) 35g/L, and pH is about 8.5, and temperature is 30 ℃.The soluble anode of anode for casting in proportion with copper and tin, negative electrode is a stainless steel plate.Short carbon fiber in the plating bath (length is about 0.2mm) content is 2.0g/L, whipping agent cresols oil 5.0g/L, trapping agent octyl group hydroximic acid 0.1g/L.Pour into short carbon fiber in the plating tank before using and be uniformly dispersed.Current density is controlled at 5.0A/dm
2, the time is 10 minutes, electroplates the thin sheet net-like carbon fibre material that obtains plated copper-tin alloy after finishing, and its thickness of coating is 2 microns, and sheet thickness is 50 microns.
Claims (3)
1, a kind of preparation method of thin sheet net-like metallic short fiberous material is characterized in that comprising the steps:
1) by the plating bath of required metal plating preparation monometallic or alloy, in plating bath, adds short carbon fiber, whipping agent and trapping agent, and the short carbon fiber in the plating bath is uniformly dispersed; Wherein, the short carbon fiber length range is 0.2mm～5cm, and the content of short carbon fiber is 0.05～2g/L in the plating bath, and foaming agents content is 0.1～5g/L; The content of trapping agent is 0.1～5g/L;
2) bubbling air in the plating bath produces bubble and makes short carbon fiber carry down evenly come-up at foamy, is suspended on the liquid level and the unanimity that is evenly distributed, and obtains plane reticulated structure prefabricated component;
3) negative electrode is contacted the prefabricated component of gained, connect power supply and electroplate, current density is 0.5A/dm
2～5.0A/dm
2, electroplating time is 10～60 minutes, obtains thin sheet net-like metallic short fiberous material.
2, according to the thin sheet net-like metallic short fiberous material preparation method of claim 1, it is characterized in that described whipping agent be polyoxyethylene glycol, pine tar, Terpineol 350, cresols oil, isobutyl-methyl benzyl must alcohol, C4 poly alkyl alcohol oxyethane (23,42) ether or three polypropylene glycols; Described trapping agent is a hydrophobic surfactant, is hydro carbons non-polar compound, alkyl xanthogenate, oleic acid, dialkyl dithiophosphate, lipid acid and soda soap thereof, alkyl sulfonate, phosphoric acid fat, hydroximic acid and salt thereof, quaternary ammonium salt or alkyl benzyl pyridine.
3, utilize the thin sheet net-like metallic short fiberous material of the method preparation of claim 1, it is characterized in that material thickness is 30 μ m～1mm, thickness of coating is 1 μ m～20 μ m.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102409386A (en) * | 2011-11-02 | 2012-04-11 | 上海交通大学 | Method for preparing novel ball-rod-shaped short carbon fiber compound reinforcing body |
| CN104674327A (en) * | 2015-03-03 | 2015-06-03 | 北京汽车股份有限公司 | Composite coating preparation method and composite coating |
| CN105460916A (en) * | 2015-11-20 | 2016-04-06 | 安徽工业大学 | Preparation method of hollow carbon nanospheres-assembled mesoporous carbon fiber material |
-
2006
- 2006-03-02 CN CNB200610024281XA patent/CN100485095C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102409386A (en) * | 2011-11-02 | 2012-04-11 | 上海交通大学 | Method for preparing novel ball-rod-shaped short carbon fiber compound reinforcing body |
| CN104674327A (en) * | 2015-03-03 | 2015-06-03 | 北京汽车股份有限公司 | Composite coating preparation method and composite coating |
| CN104674327B (en) * | 2015-03-03 | 2017-07-28 | 北京汽车股份有限公司 | The preparation method and composite deposite of composite deposite |
| CN105460916A (en) * | 2015-11-20 | 2016-04-06 | 安徽工业大学 | Preparation method of hollow carbon nanospheres-assembled mesoporous carbon fiber material |
| CN105460916B (en) * | 2015-11-20 | 2017-07-14 | 安徽工业大学 | A kind of preparation method of the assembly mesoporous carbon fibre material of hollow Nano carbon ball |
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| CN100485095C (en) | 2009-05-06 |
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Granted publication date: 20090506 Termination date: 20120302 |