CN100545309C - A kind of metal surface modification method - Google Patents
A kind of metal surface modification method Download PDFInfo
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- CN100545309C CN100545309C CNB2008100555404A CN200810055540A CN100545309C CN 100545309 C CN100545309 C CN 100545309C CN B2008100555404 A CNB2008100555404 A CN B2008100555404A CN 200810055540 A CN200810055540 A CN 200810055540A CN 100545309 C CN100545309 C CN 100545309C
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Abstract
A kind of metal surface modification method belongs to the metallic substance technical field, is used to solve metallic surface composite carbon nanometer tube layer technology production cost height, complex process, problem such as wayward.Technical scheme is: choose the carbon nanometer tube material with the preparation of iron-containing catalyst catalytic chemical vapor deposition technique, through steps such as former abrasive lapping, allotment carbon nanotube composite bed melt, magnetophoresis deposition aligned carbon nanotube suspended layer, the cold embeddings of pressure rolling, obtain having 0.05～1.0mm aligned carbon nanotube composite bed in the metallic surface.The inventive method can make the carbon nanotube of metallic surface composite bed directed in order, and can regulate the thickness of composite bed according to application purpose.Be somebody's turn to do the excellent specific property of having given carbon nanotube, make it anti-oxidant to the ordinary metallic material top layer, wear resistance, self lubricity, technical indicators such as intensity increase substantially.Compared with prior art, the inventive method raw materials for production are with low cost, technological process is simple and easy to control, and facility investment is few, are suitable for continuous batch production.
Description
Technical field
The present invention relates to a kind of preparation method of metallic substance, particularly, belong to the metallic substance technical field at the metal surface modification method of metallic surface composite carbon nanometer tube layer.
Background technology
It is the destruction of equipment and a large amount of wastes of material that the oxidation of metallic surface, corrosion not only bring us, but also the pollution that brings environment.The metallic surface has better tension, resistance to compression and flexural capacity and good wear-resisting property, anti-oxidant, self lubricity means that materials consumption still less, is more conducive to environmental protection.
The seamless nano level pipe that carbon nanotube is curled and forms by certain helix angle around central shaft by the single or multiple lift graphite flake, carbon nanotube has very strong tension, resistance to compression and flexural capacity.The tensile strength of carbon nanotube is about 100 times of steel, and its Young's modulus can be about 5 times of steel up to identical with adamantine Young's modulus, and its recoverable strain is about 5%, reaches as high as 12%, be about 60 times of steel, and density only is 1/6～1/7 of steel.Carbon nanotube has excellent physics, chemistry, mechanical property.As: no matter high-wearing feature, high thermal stability and erosion resistance are intensity or toughness, all are far superior to any filamentary material.As composite material reinforcement body, can make matrix material show good intensity, elasticity, fatigue resistance carbon nanotube.
Production costs such as arc discharge method, laser evaporation method and catalytic pyrolysis chemical Vapor deposition process are higher in the several different methods of preparation carbon nanotube, but along with development of technology, the production cost of carbon nanotube progressively reduces, production cost as the carbon nanotube with magnetic of iron-containing catalyst catalytic chemical vapor deposition technique batch preparations is relatively low, and this gives the development space that provides bigger of applying of carbon nanotube.
At present; the method that adopts carbon nanotube to participate in metal surface modification generally is divided into two classes; one class is the directed and nondirectional carbon nanotube layer of direct growth on metallic matrix; this method is that transition layer adopts chemical vapour deposition uniform carbon nano-tube bundle of preparation size on the stainless steel-based end with the aluminium film of handling; these class methods need higher temperature, the protective atmosphere of regulation, and technology, equipment are comparatively complicated.Another kind of is based on carbon nano tube suspension, adopts electric plating method to prepare the carbon nanotube composite deposite.Adopt electrochemical deposition method and electroless deposition to prepare the method for composite deposite and chemical codeposition in addition.The bonding force of the dispersion degree of mixedness of this class methods cladding wearability, hardness, thickness, density and carbon nanotube and the form in composite deposite and other elements is relevant, controlling factor is more, and fails to make that the carbon nanotube in the coating aligns in order.
Summary of the invention
It is raw material with low-cost carbon nanotube that the present invention is used to overcome the defective of prior art and provide a kind of, adopts the compound cold embedding of the attitude film metallic surface that dissolves of aligned carbon nanotube to make it obtain the metal surface modification method of carbon nano tube surface composite bed.
The alleged problem of the present invention solves with following technical proposals:
A kind of metal surface modification method, it is at metallic surface composite carbon nanometer tube layer, and its special feature is: described method comprises the steps:
A. former abrasive lapping: raw material is ground to 350～450 orders for the carbon nanotube with the preparation of iron-containing catalyst catalytic chemical vapor deposition technique;
B. allocate carbon nanotube composite bed melt: extracting epoxy resin and xylene solvent are according to weight ratio 1: the ratio modulation composite bed matrix thing of (1～3), again with above-mentioned ground carbon nanotube and the composite bed matrix thing that modulates according to weight ratio (0.05～0.15): 1 mixed forms melt, melt viscosity 70～150Pa.s is with 30～60w/c m
2High-energy ultrasound disperses melt 30～60min;
C. magnetophoresis deposits the aligned carbon nanotube suspended layer: above-mentioned melt is spread on the sheet metal surface, make the metallic surface obtain the suspended layer that contains carbon nanotube of thickness 0.5～2mm, again above-mentioned sheet metal is introduced magnetic field and carried out the magnetophoresis deposition, magneticstrength 300～500mT, field direction parallels with the carbon nanotube suspended layer, formation contains the aligned carbon nanotube suspended layer, magnetophoresis depositing time 30～120min;
D. the cold embedding of pressure rolling: above-mentioned aligned carbon nanotube suspended layer is imposed the pressure rolling power of 40～80T, the aligned carbon nanotube suspended layer is embedded the metallic surface, obtain having the metal surface modifying material of 0.05～1.0mm aligned carbon nanotube composite bed.
Above-mentioned metal surface modification method processing method, described magnetophoresis deposition aligned carbon nanotube suspended layer step is carried out under the condition of 25～80 ℃ of temperature.
Above-mentioned metal surface modification method processing method, the cold embedding step of described pressure rolling is carried out under 25～50 ℃ condition.
The inventive method is the metal composite layer main raw material with the low-cost carbon nanotube of iron-containing catalyst catalytic chemical vapor deposition technique batch preparations, adopt that aligned carbon nanotube is compound to dissolve-and the processing method of the cold embedding of magnetophoresis deposition-pressure rolling makes metallic surface acquisition carbon nanotube composite bed.This method can make the carbon nanotube of metallic surface composite bed directed in order, and can regulate the thickness of composite bed according to application purpose.The present invention has given the excellent specific property of carbon nanotube for the ordinary metallic material top layer, makes it anti-oxidant, wear resistance, and self lubricity, technical indicators such as intensity increase substantially, and can be widely used in black, and the surface modification of non-ferrous metal has good development prospect.Compared with prior art, the inventive method raw materials for production are with low cost, technological process is simple and easy to control, and facility investment is few, are suitable for continuous batch production.
Embodiment
That the inventive method is chosen is with low cost, with the carbon nanotube of iron-containing catalyst catalytic chemical vapor deposition technique batch preparations basic raw material as metal surface modification, have the characteristics of magnetic according to such carbon nanometer tube material, adopt the processing method of compound dissolving-cold embedding of magnetophoresis deposition-pressure rolling to make the metallic surface obtain the carbon nanotube composite bed.The main process of this method is as follows: will arrive certain order number with the carbon nanotube ball milling of iron-containing catalyst catalytic chemical vapor deposition technique batch preparations, add in the Resins, epoxy composite bed matrix thing of dissolution with solvents, provide ultrasonication that carbon nanotube is well-dispersed in the matrix melt, melt is spread on the sheet metal surface, formation contains the suspended layer of carbon nanotube, adopt the magnetophoresis sedimentation to make the metallic surface obtain containing the aligned carbon nanotube suspended layer, adopt the carbon nanotube embedding metallic surface of the method for pressure rolling again this suspended layer.Above-mentioned magnetophoresis deposition is meant that magnetic particle in the resisting medium is in the motion that adds under the action of a magnetic field, the electrophoresis motion analogy mutually that it can produce under the extra electric field effect with charged particle in the resisting medium, the directed mobile deposition technique of this induced by magnetic field is the magnetophoresis sedimentation.The magnetophoresis sedimentation can be regulated the direction of carbon nanotube by magnetic field force, and carbon nanotube is aligned in order; And the regulating and controlling composite bed thickness by melt coating thickness and magneticstrength.Below provide several specific embodiments of the inventive method:
Embodiment 1: the carbon nanometer tube material of getting with the preparation of iron-containing catalyst catalytic chemical vapor deposition technique is ground to 350 orders; Extracting epoxy resin and xylene solvent are according to 1: 3 ratio of weight ratio modulation composite bed matrix thing, again above-mentioned ground carbon nanotube and the composite bed matrix thing that modulates are formed melt according to 0.05: 1 mixed of weight ratio, melt viscosity 70Pa.s uses 60w/cm
2High-energy ultrasound disperses melt 30min, and carbon nanotube is well-dispersed in the melt; Above-mentioned melt is spread on the sheet metal surface, make the metallic surface obtain the suspended layer that contains carbon nanotube of thickness 0.5mm, again above-mentioned sheet metal is introduced magnetic field and carried out the magnetophoresis deposition, magneticstrength 300mT, field direction parallels with the carbon nanotube suspended layer, magnetophoresis depositing time 30min, 25 ℃ of temperature condition make the sheet metal surface obtain containing the aligned carbon nanotube suspended layer; Above-mentioned aligned carbon nanotube suspended layer is imposed the pressure rolling power of 40T under 25 ℃ of conditions, the aligned carbon nanotube suspended layer is embedded the metallic surface, obtain having the metal surface modifying material of 0.05mm aligned carbon nanotube composite bed.
Embodiment 2: the carbon nanometer tube material of getting with the preparation of iron-containing catalyst catalytic chemical vapor deposition technique is ground to 400 orders; Extracting epoxy resin and xylene solvent are according to 1: 2 ratio of weight ratio modulation composite bed matrix thing, again above-mentioned ground carbon nanotube and the composite bed matrix thing that modulates are formed melt according to 0.1: 1 mixed of weight ratio, melt viscosity 100Pa.s uses 30w/cm
2High-energy ultrasound disperses melt 60min, and carbon nanotube is well-dispersed in the melt; Above-mentioned melt is spread on the sheet metal surface, make the metallic surface obtain the suspended layer that contains carbon nanotube of thickness 1mm, again above-mentioned sheet metal is introduced magnetic field and carried out the magnetophoresis deposition, magneticstrength 400mT, field direction parallels with the carbon nanotube suspended layer, magnetophoresis depositing time 60min, 50 ℃ of temperature condition make the sheet metal surface obtain containing the aligned carbon nanotube suspended layer; Above-mentioned aligned carbon nanotube suspended layer is imposed the pressure rolling power of 60T under 40 ℃ of conditions, the aligned carbon nanotube suspended layer is embedded the metallic surface, obtain having the metal surface modifying material of 0.2mm aligned carbon nanotube composite bed.
Embodiment 3: the carbon nanometer tube material of getting with the preparation of iron-containing catalyst catalytic chemical vapor deposition technique is ground to 450 orders; Extracting epoxy resin and xylene solvent are according to 1: 1 ratio of weight ratio modulation composite bed matrix thing, again above-mentioned ground carbon nanotube and the composite bed matrix thing that modulates are formed melt according to 0.15: 1 mixed of weight ratio, melt viscosity 150Pa.s uses 50w/cm
2High-energy ultrasound disperses melt 40min, and carbon nanotube is well-dispersed in the melt; Above-mentioned melt is spread on the sheet metal surface, what make that the metallic surface obtains thickness 2mm contains the carbon nanotube suspended layer, again above-mentioned sheet metal is introduced magnetic field and carried out the magnetophoresis deposition, magneticstrength 500mT, field direction parallels with the carbon nanotube suspended layer, magnetophoresis depositing time 120min, 80 ℃ of temperature condition make the sheet metal surface obtain containing the aligned carbon nanotube suspended layer; Above-mentioned aligned carbon nanotube suspended layer is imposed the pressure rolling power of 80T under 50 ℃ of conditions, the aligned carbon nanotube suspended layer is embedded the metallic surface, obtain having the metal surface modifying material of 1mm aligned carbon nanotube composite bed.
Claims (3)
1. metal surface modification method, it is characterized in that at metallic surface composite carbon nanometer tube layer: described method comprises the steps:
A. former abrasive lapping: raw material is ground to 350～450 orders for the carbon nanotube with the preparation of iron-containing catalyst catalytic chemical vapor deposition technique;
B. allocate carbon nanotube composite bed melt: extracting epoxy resin and xylene solvent are according to weight ratio 1: the ratio modulation composite bed matrix thing of (1～3), again with above-mentioned ground carbon nanotube and the composite bed matrix thing that modulates according to weight ratio (0.05～0.15): 1 mixed forms melt, melt viscosity 70～150Pa.s is with 30～60w/cm
2High-energy ultrasound disperses melt 30～60min;
C. magnetophoresis deposits the aligned carbon nanotube suspended layer: above-mentioned melt is spread on the sheet metal surface, make the metallic surface obtain the suspended layer that contains carbon nanotube of thickness 0.5～2mm, again above-mentioned sheet metal is introduced magnetic field and carried out the magnetophoresis deposition, described magneticstrength 300～500mT, field direction parallels with the carbon nanotube suspended layer, formation contains the aligned carbon nanotube suspended layer, magnetophoresis depositing time 30～120min;
D. the cold embedding of pressure rolling: above-mentioned aligned carbon nanotube suspended layer is imposed the pressure rolling power of 40～80T, the aligned carbon nanotube suspended layer is embedded the metallic surface, obtain having the metal surface modifying material of 0.05～1.0mm aligned carbon nanotube composite bed.
2. metal surface modification method processing method according to claim 1 is characterized in that: described magnetophoresis deposition aligned carbon nanotube suspended layer step is carried out under the condition of 25～80 ℃ of temperature.
3. metal surface modification method processing method according to claim 2 is characterized in that: the cold embedding step of described pressure rolling is carried out under 25～50 ℃ condition.
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| CN103206533B (en) * | 2013-01-25 | 2016-03-30 | 祥天控股（集团）有限公司 | The cylinder of swing type variable multi-cylinder aerodynamic engine and piston |
| CN107217224A (en) * | 2017-06-14 | 2017-09-29 | 合肥博创机械制造有限公司 | A kind of method of modifying of metal material surface |
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| CN100999319A (en) * | 2006-12-31 | 2007-07-18 | 哈尔滨工业大学 | Preparation method of magnetic controlled ultra paramagnetism nanometer carbon pipe |
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