CN101104893A - Metal/carbonyl composite foaming material and preparation method thereof - Google Patents
Metal/carbonyl composite foaming material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of foamed metal materials, specifically metal/carbon-based composite foamed material and the preparation method thereof. The preparation method comprises processing a foamed carbon blank from foamed plastic as matrix, and forming a metal coating on the foamed carbon by direct electroplating method after the foamed carbon is molded to obtain a metal/carbon-based composite foamed material. The composite foamed material is constituted by foamed carbon and metal coating thereon. The ratio of carbon to metal, by weight percentage, is (20-90):(80-10). In this invention, the metal coating is formed uniformly and continuously on the surface of the foamed carbon matrix by electroplating method, so as to obtain a novel metal/carbon-based composite foamed material; and the toughness and heat conduction capacity of material are improved greatly without changing the appearance of foamed carbon. The inventive metal/carbon-based composite foamed material can not only used as an electronic element in radiator but also a heat exchanger for industrial and domestic uses, additionally can be used as electrode, electronic shield, catalyst and catalyst carrier in automobile, chemical and aerospace industries.
Description
Technical field:
The present invention relates to the foam metal material field, be specially a kind of metal/carbon base composite foam material and preparation method thereof.
Background technology:
Foamed metal has the three-dimensional networks structure, the percentage of open area height, specific surface area is big, density is little, be the ideal material of making new type heat exchanger, chemical catalyst, electrode, screening of nucleus equipment, have broad application prospects in fields such as electronics, chemical industry, aerospace.
The Foam Plastic Surface metal deposition is the maximum foamed metal preparation method of current application, this method is matrix with the porous plastics, through alligatoring, activation, sensitization, electroless plating, plating thicken, come unstuck, a plurality of steps such as reduction, sintering, machine-shaping make foamed metals, the product that obtains has characteristics such as no blind hole, metal layer thickness are even.
Yet the Foam Plastic Surface metal deposition has the following disadvantages:
1, owing to porous plastics matrix softness, yielding, accurate poor in processability, so the forming process operation can only just can be carried out after plating thickens.A large amount of foamed metals are used as the scrap stock excision in the course of processing, cause bigger waste, increase electroplating cost simultaneously and directly cause the foamed metal product cost to rise;
2, the foamed metal modulus is low, can not be with the processing means moulding of milling, mill, car, brill etc. are commonly used, and can only be with expensive processing modes such as line cutting, tooling cost height;
3, be subjected to the restriction of processing means, make relatively difficulty of special-shaped workpiece, can not satisfy the requirement of some use occasion special construction with the foamed metal that this technology obtains.
Above-mentioned deficiency makes applying of foamed metal be subjected to certain limitation.
Summary of the invention:
The object of the present invention is to provide a kind of metal/carbon base composite foam material and preparation method thereof, with plating mode at the even successive metal level of foamy carbon skeleton surface preparation, keep under the constant prerequisite of foamy carbon profile the significantly toughness and the capacity of heat transmission of strongthener, thereby obtaining a kind of new type of metal/carbonyl composite foaming material.
For achieving the above object, the technical solution used in the present invention is:
A kind of metal/carbon base composite foam material, by foamy carbon be plated on its surperficial metal level and constitute, by weight percentage, carbon: metal=(20～90): (80～10).
The preparation method of described metal/carbon base composite foam material, adopting porous plastics is that matrix is made the foamy carbon blank, after foamy carbon machine-shaping, the Direct Electroplating metal level can obtain metal/carbon base composite foam material on foamy carbon, specifically comprises the steps:
1) foamy carbon blank preparation
The urethane foam of a, cutting suitable shape is standby;
B, with weight ratio resol: carbon dust: alcohol=2: (1～5): the ratio preparation slip of (1～6) and ball milling 1～3 hour;
C, porous plastics was soaked 10～100 seconds in b gained slip, guarantee that slip fully contacts with porous plastics, take out then, dry after blowing away unnecessary slip with pressurized air;
D, repetition c process are until reaching needed weight;
E, pyrolysis, the speed with 2～5 ℃/min under protective atmospheres such as nitrogen or argon gas is warming up to 600～1500 ℃, and is incubated 10～100 minutes, removes urethane foam, obtains the foamy carbon blank.
2) foamy carbon machine-shaping
With car, mill, mode such as machining such as plane, mill and line cutting is processed into needed shape and size with the foamy carbon blank;
3) electroplate
With the foamy carbon is matrix, at its directly electroplating on surface metal level, at the even successive metal level of foamy carbon skeleton surface preparation.
The preparation method of described metal/carbon base composite foam material, electroplated metal layer is one deck or two-layer even multilayer; The preparation method of described metal/carbon base composite foam material, plated metal is single metals such as copper, nickel, chromium or zinc and can be used for galvanized alloy.
Among the present invention, copper plating process be copper sulfate 200-220 grams per liter, sulfuric acid 30-40 milliliter/liter, chlorion 80-150ppm, 210 open cylinder agent 5-10 milliliter/liter, 210 key light agent A 0.5-0.8 milliliters/liter, 210 key light agent B 0.5-0.8 milliliters/liter, temperature 20-30 ℃, current density 1-6 ampere/square decimeter.
Among the present invention, electronickelling technology is that single nickel salt 240～300 grams per liters, nickelous chloride 55～75 grams per liters, boric acid 50～60 grams per liters, 10～12 milliliters/liter of PAA brightening agents, MRI are supplied 0.5～0.8 milliliter/liter of agent, pH3.8-4.2, current density 0.5-10 ampere/square decimeter.
Among the present invention, electrodeposited chromium technology is chromic acid 190～210 grams per liters, sulfuric acid 1.7～1.9 grams per liters, temperature 55-62 ℃, current density 30-70 ampere/square decimeter.
Among the present invention, galvanizing technique is zinc chloride 70～80 grams per liters, Repone K 210～230 grams per liters, boric acid 30～35 grams per liters, pH5.0-5.3, temperature 20-45 ℃, current density 1-6 ampere/square decimeter.
Preparation technology compares with the Foam Plastic Surface metal deposition, and the present invention has following beneficial effect:
1, to have good workability, acid-alkali-corrosive-resisting, degree of deformation little for foamy carbon of the present invention, thereby can directly be processed into needed shape of product before plated metal.After plating, need not processing, the waste of having avoided foamed metal processing to cause;
2, the present invention can adopt the machine-shaping of foamy carbon mill, special processing mode such as processing means commonly used such as mill, car, brill and line cutting, applied widely, tooling cost is low;
3, foamy carbon of the present invention can be processed into various special-shaped workpiece with comparalive ease, can be applicable to multiple a particular job occasion;
4, foamy carbon electroconductibility of the present invention is good, can directly electroplate, and need not steps such as alligatoring, activation, sensitization, electroless plating, and process complexity is lower than conventional foam metal fabrication methods;
5, the present invention be need not to remove by the foamy carbon matrix that electroplated metal layer wraps up, and the high-modulus of foamy carbon and the high tenacity of metal provide very high compressive property for metal/carbon base composite foam material.In addition, the heat-conductivity conducting ability that carbon material is good makes foamy carbon can substitute part metals, thereby reduces the deposition of plated metal, reduces electroplating cost;
6, the metal/carbon base composite foam material of the present invention's preparation not only can be used as the scatterer of electronic component, and can be used as electrode, screening of nucleus, catalysis and catalyst support material, is applied to industries such as automobile, chemical industry, aerospace.
Description of drawings
Fig. 1 is a metal/carbon base composite foam material synoptic diagram in the embodiment of the invention 1;
Fig. 2 is a metal/carbon base composite foam material synoptic diagram in the embodiment of the invention 2;
Fig. 3 is a metal/carbon base composite foam material synoptic diagram in the embodiment of the invention 6;
Fig. 4～Fig. 6 is the metal/carbon base composite foam material of the multiple shape of employing method preparation of the present invention.
Embodiment
Embodiment 1
The preparation process of present embodiment metal/carbon base composite foam material is specific as follows:
1, the preparation of foamy carbon:
The urethane foam (mean pore size 2mm) of a, cutting suitable shape is standby;
B, with weight ratio resol: carbon dust: the ratio preparation slip of alcohol=2: 1: 2 and ball milling 0.5 hour;
C, porous plastics is immersed the slip 10 seconds of b gained, guarantee that slip fully contacts with porous plastics, take out then, dry after blowing away unnecessary slip with pressurized air;
D, repetition c process are until reaching needed weight;
E, the speed with 2 ℃/min under nitrogen protection atmosphere are warming up to 800 ℃, and are incubated 0.5 hour, remove urethane foam, obtain the foamy carbon blank.In the present embodiment, the structure of foamy carbon is the three-dimensional networks structure, and porosity is 85%, mean pore size 2mm, and density is 0.25 grams per milliliter;
2, processing foamy carbon blank becomes needed shape, and processing mode can be with alternate manners such as mechanical workout or line cuttings;
3, with distilled water foamy carbon is cleaned, remove the chip that processing produces, then dry for standby;
4, in electroplating solution the foamy carbon that processes is carried out electroplating processes, electroplating time is set according to the actual requirements.Clean back Direct Electroplating the first layer metal, can continue to electroplate second layer metal in the first layer metallic surface, coating can be single metals such as copper, nickel, chromium, zinc, also can be other alloy layer.
Get the sample that foamy carbon cuts into Φ 30mm * 5mm, in copper electrolyte, electroplate.The electroplate liquid proportioning is: copper sulfate 200-220 grams per liter, sulfuric acid 30-40 milliliter/liter, chlorion 80-150ppm, 210 open cylinder agent 5-10 milliliter/liter, 210 key light agent A 0.5-0.8 milliliters/liter, 210 key light agent B 0.5-0.8 milliliters/liter.Electroplate 25 ℃ of working temperatures, 3 amperes/square decimeter of cathode current densities, electroplating time 30 minutes, the content of copper is 0.25～0.27 gram/cm in gained copper/carbon back foamed composite
3, the copper/carbonyl composite foaming material of acquisition as shown in Figure 1.
Embodiment 2
Difference from Example 1 is:
Present embodiment foamy carbon blank preparation process is as follows:
The urethane foam (mean pore size 2mm) of a, cutting suitable shape is standby;
B, with weight ratio resol: carbon dust: the ratio preparation slip of alcohol=2: 2: 6 and ball milling 2 hours;
C, porous plastics was soaked 50 seconds in b gained slip, guarantee that slip fully contacts with porous plastics, take out then, dry after blowing away unnecessary slip with pressurized air;
D, repetition c process are until reaching needed weight;
E, pyrolysis, the speed with 3 ℃/min under protective atmospheres such as nitrogen or argon gas is warming up to 1000 ℃, and is incubated 60 minutes, removes urethane foam, obtains the foamy carbon blank.In the present embodiment, the structure of foamy carbon is the three-dimensional networks structure, and porosity is 85%, mean pore size 2mm, and density is 0.25 grams per milliliter.
Get the sample that foamy carbon cuts into Φ 30mm * 5mm, in nickel plating bath, electroplate.The electroplate liquid proportioning is: single nickel salt 270 grams per liters, nickelous chloride 65 grams per liters, boric acid 50 grams per liters, 12 milliliters/liter of PAA brightening agents, MRI supply 0.712 milliliter/liter of agent.PH is controlled at 4.1, and current density is 5 amperes/square decimeter, electroplating time 30 minutes, and the content of nickel is 0.30～0.33 gram/cm in gained nickel/carbon back foamed composite
3, the nickel/carbonyl composite foaming material of acquisition as shown in Figure 2.
Embodiment 3
Get the sample after the electro-coppering among the embodiment 1, in the zinc plating bath, electroplate.The electro-galvanizing proportioning is: zinc chloride 75 grams per liters, Repone K 220 grams per liters, boric acid 30 grams per liters.Processing condition: pH5.2,30 ℃ of temperature, 4 amperes/square decimeter of current densities, electroplating time 10 minutes, the content of zinc is 0.1～0.12 grams per milliliter in gained zinc/carbon back foamed composite.
Embodiment 4
Get the sample after the electro-coppering among the embodiment 1, in nickel plating bath, electroplate.The electroplate liquid proportioning is: single nickel salt 270 grams per liters, nickelous chloride 65 grams per liters, boric acid 50 grams per liters, 12 milliliters/liter of PAA brightening agents, MRI supply 0.712 milliliter/liter of agent.PH is controlled at 4.1, and current density is 5 amperes/square decimeter, electroplating time 10 minutes, and the content of metal is 0.35～0.40 grams per milliliter in the gained metal/carbon base foamed composite.
Embodiment 5
Get the sample after the electro-coppering among the embodiment 1, in the chromium plating bath, electroplate.The electroplate liquid proportioning is: chromic acid 200 grams per liters, sulfuric acid 1.8 grams per liters.58 ℃ of electroplating temperatures, 50 amperes/square decimeter of current densities, electroplating time 5 minutes, the content of metal is 0.37～0.41 grams per milliliter in the gained metal/carbon base foamed composite.
The metal/carbon base composite foam material outward appearance that embodiment 3～5 obtains is similar to Fig. 2, no longer explanation herein.
Embodiment 6
Difference from Example 1 is:
Present embodiment foamy carbon blank preparation process is as follows:
The urethane foam (mean pore size 2mm) of a, cutting suitable shape is standby;
B, with weight ratio resol: carbon dust: the ratio preparation slip of alcohol=2: 5: 1 and ball milling 3 hours;
C, porous plastics was soaked 100 seconds in b gained slip, guarantee that slip fully contacts with porous plastics, take out then, dry after blowing away unnecessary slip with pressurized air;
D, repetition c process are until reaching needed weight;
E, pyrolysis, the speed with 5 ℃/min under protective atmospheres such as nitrogen or argon gas is warming up to 1500 ℃, and is incubated 100 minutes, removes urethane foam, obtains the foamy carbon blank.In the present embodiment, the structure of foamy carbon is the three-dimensional networks structure, and porosity is 85%, mean pore size 2mm, and density is 0.25 grams per milliliter.
Get foamy carbon and be processed into the square of 60mm * 60mm * 13mm, and mechanical workout goes out the groove of dark 10mm, wide 1.5mm, separation 5mm in the above.Electroplate in copper electrolyte then, plating bath proportioning and plating condition be with embodiment 1, electroplating time 60min, and the content of copper is 0.25～0.27 grams per milliliter in gained copper/carbon back foamed composite, the copper/carbonyl composite foaming material of acquisition is as shown in Figure 3.
As Fig. 4～shown in Figure 6, adopt the metal/carbon base composite foam material of the multiple shape of method preparation of the present invention.
Claims (4)
1. metal/carbon base composite foam material is characterized in that: by foamy carbon be plated on its surperficial metal level and constitute, by weight percentage, carbon: metal=(20～90): (80～10).
2. according to the preparation method of the described metal/carbon base of claim 1 composite foam material, it is characterized in that adopting porous plastics is that matrix is made the foamy carbon blank, after foamy carbon machine-shaping, the Direct Electroplating metal level can obtain metal/carbon base composite foam material on foamy carbon, specifically comprises the steps:
1) foamy carbon blank preparation
The urethane foam of a, cutting suitable shape is standby;
B, with weight ratio resol: carbon dust: alcohol=2: (1～5): the ratio preparation slip of (1～6) and ball milling 1～3 hour;
C, porous plastics was soaked 10～100 seconds in b gained slip, guarantee that slip fully contacts with porous plastics, take out then, dry after blowing away unnecessary slip with pressurized air;
D, repetition c process are until reaching needed weight;
E, pyrolysis, the speed with 2～5 ℃/min under protective atmospheres such as nitrogen or argon gas is warming up to 600～1500 ℃, and is incubated 10～100 minutes, removes urethane foam, obtains the foamy carbon blank.
2) foamy carbon machine-shaping
With car, mill, mode such as machining such as plane, mill and line cutting is processed into needed shape and size with the foamy carbon blank;
3) electroplate
With the foamy carbon is matrix, at its directly electroplating on surface metal level, at the even successive metal level of foamy carbon skeleton surface preparation.
3. according to the preparation method of the described metal/carbon base of claim 2 composite foam material, it is characterized in that: electroplated metal layer is one deck or two-layer even multilayer.
4. according to the preparation method of the described metal/carbon base of claim 2 composite foam material, it is characterized in that: plated metal is single metals such as copper, nickel, chromium or zinc and can be used for galvanized alloy.
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