CN100443223C - Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel - Google Patents
Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel Download PDFInfo
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- CN100443223C CN100443223C CNB2007100566917A CN200710056691A CN100443223C CN 100443223 C CN100443223 C CN 100443223C CN B2007100566917 A CNB2007100566917 A CN B2007100566917A CN 200710056691 A CN200710056691 A CN 200710056691A CN 100443223 C CN100443223 C CN 100443223C
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Abstract
The process of preparing alumina-base composite material includes the following steps: dropping sodium hydroxide solution or ammonia water to solution with nickel nitrate hexahydrate and aluminum powder for reaction to produce Ni(OH)2/Al/Al(OH)3, dewatering and calcining the obtain ternary colloid to obtain NiO/Al/Al2O3, reducing the obtained NiO/Al/Al2O3 into Ni/Al/Al2O3, introducing mixed methane and nitrogen gas after stopping hydrogen introduction and reacting catalytically at certain temperature for several hours to obtain carbon nanotube/Ni/Al/Al2O3 composite powder with controllable carbon nanotube content, and final powder metallurgy and hot extruding to obtain carbon nanotube/Ni/Al/Al2O3 composite material. The present invention has the advantages of well controlled proportion of Ni, Al and Al2O3, excellent dispersion of Al and carbon nanotube in the composite material, high comprehensive performance of the composite material, etc.
Description
Technical field
The present invention relates to a kind of carbon nano-tube in situ/nickel/aluminum improving and toughening alumina based composites preparation method, belong to the technology of preparing of alumina matrix composite.
Background technology
Ceramic material has the intensity height, hardness is big, high temperature resistant, anti-oxidant, resistance to wear under the high temperature, advantages such as chemical resistance is good, these excellent performances are that general common metal material, macromolecular material etc. are not available, therefore more and more are subject to people's attention.But because the weakness of the fragility of ceramic material own makes to lack when structural material uses enough reliabilities.Thereby the fragility of improving ceramic material has become one of ceramic material field problem demanding prompt solution.
Fine aluminium, nickel metal are ductile, the conduction, heat conductivility is good and some other performance, as magnetic, wave absorbtion etc., yet its relative hardness intensity is lower, density is higher relatively.If can combine pottery and metal, given play to the cooperative effect between matrix and nano particle, we might obtain a kind of very desirable material.And CNT (CNTs) has been generally acknowledged it has been a kind of structural material of excellent performance in the world, its intensity, toughness height, and percentage elongation, elastic modelling quantity are big, high abrasion resistance.Because CNTs is a kind of novel self-composed monomolecular material, have minimum yardstick and excellent mechanical property, its sealing hollow tubular structure has good stable, and has excellent mechanical property, its Young's modulus of theoretical calculation is up to 5TPa, and with adamantine identical, intensity is about 100 times of steel, and density has only 1/6 of steel, may be present specific strength and the highest material of specific stiffness.CNT also has physical characteristics such as excellent heat conductivility and electric property.Therefore, CNT is considered to optimal nano whisker toughening material, is the ultimate form of fiber-like hardening constituent.
Yet CNT in composite dispersion and and matrix between infiltration combine closely and the retentivity problem of the intact structure of CNT is the difficult problem that such composite of development faces.The method that the carbon current nanotube is applied to main employing in the ceramic matric composite has the original position method of formation, heterocoagulation and mechanical ball milling method.It is that employing directly generates CNT and obtains the carbon nanotube-ceramic based composites in ceramic matrix that original position generates rule, and this method can make CNT better disperse in matrix, but the bond strength between CNT and the matrix is not high.Heterocoagulation is dispersed in matrix respectively in the different electrolyte with wild phase mutually, suitably regulate the medium of decentralized photo solution, it is the pH value of medium, these factors such as the ratio of the number of electrolyte concentration and two kinds of particles, make the two-phase particle have opposite electric charge, by electrostatic adsorption, two-phase combines well, and make electrolyte be electroneutral, thereby make the flocculation phenomenon take place.This method can only can be improved the dispersion of CNT in matrix to a certain extent, can not better solve the dispersion difficult problem of CNT.And mechanical ball milling method [3] is that ceramic powder and scattered CNT are mixed, and ball milling mixes in ball-milling medium (ethanol).The method technical process is simpler, but be difficult to solve CNT in alumina matrix composite dispersion and and matrix between the infiltration problem.
The preparation technology of metal current and ceramic matric composite then mainly contains mechanical mixture dispersion method, sol-gel process and microemulsion and reversed micelle method.The mechanical mixture dispersion method be nanometer powder is incorporated in the matrix powder mix, ball milling, shaping, sintering obtain nano heterogeneous ceramic.Preparation technology is simple for this method, and weak point is that ball milling itself can not destroy the reunion between nano particle fully, can not accomplish the even dispersion of two phase compositions.Sol-gel process be with the organic alkoxide of metal or inorganic salt solution through hydrolysis, make solute aggregate into colloidal sol gel solidification again, in low temperature drying, levigate after calcining obtains nano particle.This technology has unique advantage aspect the preparation of ceramic matric composite especially metal-ceramic: compare with the conventional powder mixing method, decentralization is higher between metal and the ceramic phase, more helps strengthening toughness and is ductile.Microemulsion and reversed micelle method are to utilize two kinds of mutual exclusive solvents (organic solvent and the aqueous solution), by option table surface-active agent and control relative amount, its water drop size can be controlled at nanoscale, different micro emulsion drops collide the generation mass exchange mutually, and chemical reaction takes place in water.Each water microcell is equivalent to the size that " microreactor " limited the product particle, obtains nano particle.Adopt suitable surfactant to can be adsorbed on nanoparticle surface, the particle that generates is played stable and protective effect, prevent the particle further growth, and can play the surface chemical modification effect particle.Can also control the shape of water microcell by the option table surface-active agent, thereby obtain difform nano particle.
Summary of the invention
The present invention aims to provide a kind of carbon nano-tube in situ/nickel/aluminum improving and toughening alumina based composites preparation method.This method can make the controlled and disperse of aluminium and CNT content in composite evenly distribute, and the carbon pipe soaks into well the bond strength height with matrix simultaneously.
The present invention is realized that by following technical proposals a kind of carbon nano-tube in situ/nickel/aluminum improving and toughening alumina based composites preparation method is characterized in that comprising following process:
1, Ni/Al/Al
2O
3Preparation of catalysts: with six water nickel nitrate (commercially available prod, purity＞96%) and aluminium powder (commercially available prod, 400 orders) be 0.127 with mass ratio: 1-1.24: 1 joins in the 1L deionized water, be 36% ammoniacal liquor then with 0.01-1mol/L NaOH or mass concentration, under the condition of magnetic stirrer, be added drop-wise in the above-mentioned solution and be 7-12 until the pH of solution value, reaction generates the Ni element and Al element mass ratio is 0.025: 1-0.25: 1, and Al and Al (OH)
3Mass ratio is 0.01: 1-0.654: 1 Ni (OH)
2/ Al/Al (OH)
3The ternary colloid, again with dehydration 2-4 hour under 150-300 ℃ and 150-350mL/min blanket of nitrogen of ternary colloid, then 350-500 ℃ of calcining 2-4 hour down, the stove programming rate is 8 ℃/min, thereby obtains NiO/Al/Al
2O
3The complex catalyst precursor powder.
2, (Chemical Vapor Deposition, CVD) legal system is equipped with CNT/Ni/Al/Al with chemical vapour deposition (CVD)
2O
3Composite powder: get step 1 gained NiO/Al/Al
2O
3The complex catalyst precursor powder is layered in the quartz boat, and quartz boat is placed flat-temperature zone, crystal reaction tube middle part, at first feeds the nitrogen deaeration in reaction tube, rise to 500-650 ℃ with the programming rate of 8 ℃/min after, feed H with 25-250mL/min
2Gas 1.5-4 hour, with presoma NiO/Al/Al
2O
3Be reduced to catalyst n i/Al/Al
2O
3, stop to feed hydrogen, then feed 420-780mL/min methane and nitrogen mixture (V
N2: V
CH4=6: 1-12: 1), reacted 0.1-4 hour down, stop to feed mist, under the 5-75mL/min blanket of nitrogen, make furnace temperature reduce to room temperature 20-25 ℃, obtain CNT/Ni/Al/Al that content of carbon nanotubes is 0.1-50% at 500-650 ℃
2O
3Composite powder.
3, adopt two kinds of methods of powder metallurgy and hot extrusion to prepare CNT/Ni/Al/Al respectively
2O
3Composite:
(1) powder metallurgic method: at first under room temperature 20-25 ℃, step 2 gained composite powder is pressed into block with 350-1200MPa, dwell time is 30 seconds-2 minutes, then with block in vacuum (0.001-10KPa) sintering furnace 1000-1350 ℃ following sintering 0.5-6 hour, again block is carried out multiple pressure, multiple pressure pressure is 1250-2000MPa, dwell time is 0.25-2 minute, promptly obtains CNT/aluminium/nickel original position and strengthens the toughened aluminum oxide based composites.
(2) hot extrusion method: the mould of at first step 2 gained composite powder being packed into, under 500-1000 ℃, composite powder is pressed into block then with 100-1000MPa, dwell time is 2-12 hour, promptly obtains CNT/aluminium/nickel original position and strengthens the toughened aluminum oxide based composites.
The invention has the advantages that, the gained composite powder can be controlled the ratio of nickel, aluminium and aluminium oxide well, and can solve aluminium and the scattering problem of CNT in composite well, CNT is not reunited in composite powder, disperse to open to have nanometer size effect very much, and CNT and substrate combinating strength height, form network structure, therefore CNT and aluminium can strengthen the toughened aluminum oxide based composites effectively, make the hardness of composite, intensity, toughness, combination properties such as electrical property are greatly enhanced.
Description of drawings
Fig. 1: the CNT/Ni/Al/Al that adopts the embodiment of the invention 1 method to make
2O
3The transmission electron microscope photo of composite powder.
The specific embodiment
Example 1:
2.49 gram six water nickel nitrates and 19.6 gram aluminium powders are joined in the deionized water, dripping the 0.1mol/L sodium hydroxide solution then under 500 rev/mins of stirring condition of magnetic stirring apparatus is 7 until the pH of solution value in the above-mentioned solution, reaction generates the Ni element and Al element mass ratio is 0.025: 1, Al and Al (OH)
3Mass ratio is 0.01: 1 Ni (OH)
2/ Al/Al (OH)
3The ternary colloid, again with the dehydration 2 hours under 240 ℃ and 350mL/min blanket of nitrogen of the ternary colloid that makes, 350 ℃ of calcinings 2 hours down, the stove programming rate is 8 ℃/min, thereby obtains NiO/Al/Al
2O
3Complex catalyst precursor; Get gained NiO/Al/Al
2O
3Be layered in the quartz boat, and quartz boat placed flat-temperature zone, crystal reaction tube middle part, at first in reaction tube, feed the nitrogen deaeration, rise to 600 ℃ with the programming rate of 8 ℃/min after, feed H with 10mL/min
2Gas 2 hours is with NiO/Al/Al
2O
3Be reduced to Ni/Al/Al
2O
3, stop to feed hydrogen, then feed methane and nitrogen mixture (V with 600mL/min
N2: V
CH4=9: 1),, stop to feed mist, then under the blanket of nitrogen of 75mL/min, make furnace temperature reduce to 20 ℃ of room temperatures, obtain the CNT mass content and be CNT/Ni/Al/Al of 2% 600 ℃ of down reactions 0.5 hour
2O
3Composite powder; Under 20 ℃ of room temperatures, the gained composite powder is pressed into block then with 600MPa, dwell time is 1 minute, be 1150 ℃ of following sintering 2 hours in the sintering furnace of 10KPa with block in vacuum again, again block is carried out multiple pressure, multiple pressure pressure is 1250MPa, dwell time is 1 minute, promptly obtains CNT/aluminium/nickel original position and strengthens the toughened aluminum oxide based composites.
Example 2:
Concrete grammar and step are with example 1, and different condition is: the time of vapour deposition CNT is 1 hour, obtains the CNT mass content at last and be CNT/Ni/Al/Al of 5%
2O
3Composite powder.
Example 3:
Concrete grammar and step are with example 1, and different condition is: 1.25 gram six water nickel nitrates and 19.8 aluminium powders are joined in the deionized water, obtain Ni: Al: Al
2O
3=1: 9: 90, obtain the CNT mass content at last and be CNT/Ni/Al/Al of 1.%
2O
3Composite powder.
Example 4:
Concrete grammar and step are with example 1, and different condition is: 1.25 gram six water nickel nitrates and 19.8 aluminium powders are joined in the deionized water, obtain Ni: Al: Al
2O
3=1: 9: 90, the carbon nano-tube in situ time was 1 hour, obtained the CNT mass content at last and be CNT/Ni/Al/Al of 2.5%
2O
3Composite powder.
Example 5:
Concrete grammar and step are with example 1, and different condition is: 5 gram six water nickel nitrates and 19.0 aluminium powders are joined in the deionized water, obtain Ni: Al: Al
2O
3=1: 1: 18, obtain the CNT mass content at last and be CNT/Ni/Al/Al of 3.5%
2O
3Composite powder.
Claims (1)
1, the preparation method of a kind of carbon nano-tube in situ/nickel/aluminum improving and toughening alumina based composites is characterized in that comprising following process:
1) Ni/Al/Al
2O
3Preparation of catalysts: is 0.127 with purity＞96% 6 water nickel nitrate and aluminium powder with mass ratio: 1-1.24: 1 joins in the 1L deionized water, be 36% ammoniacal liquor then with 0.01-1mol/L NaOH or mass concentration, under the condition of magnetic stirrer, be added drop-wise in the above-mentioned solution and be 7-12 until the pH of solution value, reaction generates the Ni element and Al element mass ratio is 0.025: 1-0.25: 1, and Al and Al (OH)
3Mass ratio is 0.01: 1-0.654: 1 ternary colloid Ni (OH)
2/ Al/Al (OH)
3, again with dehydration 2-4 hour under 150-300 ℃ and 150-350mL/min blanket of nitrogen of prepared ternary colloid, then 350-500 ℃ of calcining 2-4 hour down, the stove programming rate is 8 ℃/min, thereby obtains NiO/Al/Al
2O
3The complex catalyst precursor powder;
2) prepare CNT/Ni/Al/Al with chemical vapour deposition technique
2O
3Composite powder: get step 1) gained NiO/Al/Al
2O
3The complex catalyst precursor powder is layered in the quartz boat, and quartz boat is placed flat-temperature zone, crystal reaction tube middle part, at first feeds the nitrogen deaeration in reaction tube, rise to 500-650 ℃ with the programming rate of 8 ℃/min after, feed H with 25-250mL/min
2Gas 1.5-4 hour, with presoma NiO/Al/Al
2O
3Be reduced to catalyst n i/Al/Al
2O
3, stop to feed hydrogen, then feed 420-780mL/min V
N2: V
CH4=6: 1-12: 1 methane and nitrogen mixture, reacted 0.1-4 hour down at 500-650 ℃, stop to feed mist, under the 5-75mL/min blanket of nitrogen, make furnace temperature reduce to room temperature 20-25 ℃, obtain CNT/Ni/Al/Al that the CNT mass content is 0.1-50%
2O
3Composite powder;
3) adopt two kinds of methods of powder metallurgy and hot extrusion to prepare CNT/Ni/Al/Al respectively
2O
3Composite:
With step 2) the gained composite powder is pressed into block with 350-1200MPa under room temperature 20-25 ℃, the dwell time is 30 seconds-2 minutes, then with block in 10
-11-10
-7In the Torr vacuum sintering furnace 1000-1350 ℃ following sintering 0.5-6 hour, again block is carried out multiple pressure, multiple pressure pressure is 1250-2000MPa, the dwell time is 30 seconds-2 minutes, promptly obtains CNT/aluminium/nickel original position and strengthens the toughened aluminum oxide based composites;
Or with step 2) the gained composite powder mould of packing into, under 500-1000 ℃, composite powder is pressed into block then with 100-1000MPa, the dwell time is 2-12 hour, promptly obtains CNT/aluminium/nickel original position and strengthens the toughened aluminum oxide based composites.
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|---|---|---|---|
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|---|---|---|---|
| CNB2007100566917A CN100443223C (en) | 2007-02-01 | 2007-02-01 | Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel |
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Families Citing this family (12)
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| CN101486564B (en) * | 2009-02-16 | 2011-08-10 | 山东大学 | Preparation of boron nitride nano tube enhanced alumina ceramic |
| CN101864547B (en) * | 2010-06-09 | 2011-09-14 | 天津大学 | Preparation method of homodisperse carbon nano tube enhanced aluminium base composite material |
| CN102296279A (en) * | 2010-06-22 | 2011-12-28 | 中国人民解放军军事医学科学院卫生装备研究所 | Preparation method for carbon nanotube-aluminum oxide composite structure enhanced polyurethane based composite material |
| CN101892407B (en) * | 2010-07-15 | 2013-03-13 | 江苏大学 | Method for preparing aluminum-based in-situ composite materials at low temperature in presence of catalysts |
| CN103332937B (en) * | 2013-06-05 | 2015-05-27 | 武汉理工大学 | Method for preparing Al2O3 composite powder with uniformly dispersed carbon nanotubes by in-situ synthesis process |
| CN105195738A (en) * | 2015-10-28 | 2015-12-30 | 九江学院 | Wrapped Al2O3/Al compound powder and preparing method thereof |
| CN108856706B (en) * | 2017-05-10 | 2020-03-24 | 中国石油化工股份有限公司 | Carbon-coated nickel-aluminum composite material and preparation method and application thereof |
| CN108796259A (en) * | 2018-07-04 | 2018-11-13 | 湘潭大学 | A kind of preparation method of carbon nanotube enhancing Zn based composites |
| CN109338142A (en) * | 2018-10-12 | 2019-02-15 | 天津大学 | A kind of preparation method of the foamed aluminium of carbon nanotube synergistic oxidation alumina particles enhancing |
| CN110744045A (en) * | 2019-09-06 | 2020-02-04 | 西安交通大学 | Method for in-situ synthesis of carbon nano tube on surface of aluminum alloy spherical powder |
| CN110899717A (en) * | 2019-12-04 | 2020-03-24 | 上海理工大学 | Al (aluminum)2O3-CNTs/Cu composite material and preparation method thereof |
| CN115058129B (en) * | 2022-05-24 | 2023-09-12 | 武汉济能纳米流体技术有限公司 | Preparation method and application of functional micro powder for engine coolant |
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Assignee: Beijing Ausp Precision Electronic Co., Ltd. Assignor: Tianjin University Contract record no.: 2010110000170 Denomination of invention: Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel Granted publication date: 20081217 License type: Exclusive License Open date: 20070912 Record date: 20101008 |
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