CN102206793B - Preparation method of carbon nanotube-alumina composite reinforced magnesium-based composite material - Google Patents
Preparation method of carbon nanotube-alumina composite reinforced magnesium-based composite material Download PDFInfo
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- CN102206793B CN102206793B CN201110134858A CN201110134858A CN102206793B CN 102206793 B CN102206793 B CN 102206793B CN 201110134858 A CN201110134858 A CN 201110134858A CN 201110134858 A CN201110134858 A CN 201110134858A CN 102206793 B CN102206793 B CN 102206793B
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Abstract
The invention discloses a preparation method of a carbon nanotube-alumina composite reinforced magnesium-based composite material, which relates to the manufacture of magnesium-based alloy by using a casting method. The preparation method comprises the steps of: step 1, calcining and reducing raw materials of ferric nitrate nonahydrate and alumina in the ratio of (0.07-1.00):1 to obtain an iron/alumina composite catalyst, and finally, performing catalytic pyrolysis reaction by using the mixed gas of nitrogen gas and ethylene in the volume ratio of (6-12):1 for uniformly dispersing carbon nanotubes on the surface of the alumina, so as to prepare a carbon nanotube-alumina composite reinforced phase; and step 2, adding the carbon nanotube-alumina composite reinforced phase to a molten magnesium base material, and stirring and casting to prepare the carbon nanotube-alumina composite reinforced magnesium-based composite material, wherein the added carbon nanotube-alumina composite reinforced phase accounts for 1-15% of the molten magnesium base material by mass percentage. According to the invention, the defect of a magnesium-based alloy texture in the magnesium-based composite material produced in the prior art is overcome, the excellent enhancing effect of the carbon nanotubes in a magnesium matrix can be brought into full play, and the comprehensive performance of the magnesium-based composite material is ensured to be enhanced.
Description
Technical field
Technical scheme of the present invention relates to casting makes Magnuminium, specifically the compound enhancing method of preparing magnesium-based composite material of carbon nanotube-aluminum oxide.
Background technology
As the lightest structural metallic materials; Magnesiumalloy has specific tenacity and specific rigidity height, conduction and many characteristics such as thermal conductivity is strong, castability is good, machining property is good, easy recovery; Be described as the green structured material of 21st century, have wide application prospect at high-technology fields such as aerospace, automobile, electronics, communication and machineries.But, increasingly high, the traditional magnesiumalloy that requires of magnesiumalloy is exposed weak point gradually at aspects such as physicals and mechanical properties along with the development of modernization industry.Shortcoming such as for example, magnesiumalloy exists that Young's modulus is little, thermal expansivity is high, poor dimensional stability, hot strength and creep resistance are low and wear no resistance.These shortcomings become the bottleneck of restriction magnesiumalloy widespread use, therefore, how to improve the magnesiumalloy over-all properties and become one of focus of metallic substance research field in recent years.
Magnesium base composite material is to be matrix with magnesium or its alloy, with particulate state, whisker shape or fibrous other materials heterogeneous body mixture that is wild phase.Because excellent comprehensive performances such as magnesium base composite material has that thermal expansivity is low, Young's modulus is high and wear resistance is good; Overcome the weak point of traditional magnesiumalloy at aspects such as mechanical property and physicalies; Therefore; Magnesium base composite material has obtained widespread use in many industry and civil area, and new magnesium base composite material constantly is developed.CN201010292488.1 has reported that a kind of semi-solid state vacuum hotpressing prepares the method for granule reinforced magnesium alloy composite materials, and it can satisfy preparation of granule reinforced magnesium alloy composite materials and the needs that are shaped; CN200710192236.X has reported a kind of mixed carbon fibre enhanced composite material of magnesium alloy, it is characterized in that this matrix material is is the matrix material of matrix with the magnesiumalloy by high-strength carbon fiber and HM carbon fibre mixing enhanced; CN200910216219.4 has reported a kind of magnesium borate crystal whisker reinforced magnesium-base composite material, and modification has also been optimized the preparation technology at the contact surface-interface between magnesium alloy substrate and wild phase.Though the preparation of above-mentioned magnesium base composite material can improve the hardness and the intensity of magnesium alloy substrate to a certain extent, these magnesium base composite material high temperature degrees of expansion are big, intensity is low and creep is serious etc., and problem still remains further to be improved; In addition, compare with magnesium alloy substrate, the density of above-mentioned conventional particles, whisker or fiber reinforcement phase material is big, intensity and Young's modulus is low and electrical and thermal conductivity performance is poor, and it is added in the magnesium alloy substrate, and the original lightweight effect of magnesiumalloy is affected.
Since carbon nanotube comes to light, rely on excellent properties such as its specific tenacity and specific rigidity height, the axial expansion coefficient is low, density is little, unique thermal conductivity and electroconductibility, carbon nanotube becomes the desirable wild phase of metal-base composites.In recent years, also carry out about the research of carbon nanotube-magnesium base composite material.Prior art mainly adopts casting or powder metallurgic method to carry out carbon nanotube-magnesium base composite material preparation, in the preparation process, carries out the dispersion of carbon nanotube in magnesium matrix through methods such as mechanical stirring, high-energy ball millings.As everyone knows, the distribution of wild phase in matrices of composite material is most important to its reinforced effects.Wild phase homodisperse in matrix is the prerequisite that matrix material obtains premium properties, and it gathers partially or reunion causes the metal-base composites mis-behave.Specific surface area of carbon nanotube is big, and stronger Van der Waals force can cause its difficulties in dispersion, serious agglomeration in matrices of composite material between the carbon nanotube, and this is the subject matter that carbon nano-tube reinforced metal-matrix composite material faces.
CN101435059 discloses the method for manufacture of magnesium base-carbon nano tube compound material, at first magnesium base melt and carbon nanotube mixing is obtained mixed slurry, then above-mentioned mixed slurry is injected mould and obtains precast body; At last above-mentioned precast body is carried out extrusion molding and handle, make magnesiumalloy-carbon nano tube compound material.Visible by the summary of the invention of this patented claim and embodiment, its dispersion to carbon nanotube is to prepare the mechanical stirring in the process and in type prefab is carried out crimp realize through mixed slurry.But, because the density of carbon nanotube is low, the about 1.2～1.3g/cm of SWCN density
3, the also only about 1.7g/cm of multi-walled carbon nano-tubes density
3, much smaller than the density of magnesium base melt, the two big density difference like this causes this method to prepare in the process at mixed slurry, even mechanical stirring is arranged, also can't avoid carbon nanotube to float on bath surface; Equally, carbon nanotube also will gather in prefabricated section top partially in the prefabricated section casting process, cause prefabricated section carbon nanotube skewness up and down, and this be the also insurmountable problem of follow-up extrusion molding processing.There is performance difference between each position of magnesium base composite material that these defectives cause finally obtaining.In addition; Specific surface area of carbon nanotube is big high with specific surface energy, join it in magnesium base melt after, stronger Van der Waals force makes their reunite and is difficult to dispersion between carbon nanotube; Mechanical stirring only possibly separated the carbon nano tube cluster of reuniting to a certain extent; And can not realize the homodisperse of single-root carbon nano-tube, therefore, the coacervate of carbon nanotube will remain in the prefabricated section; Though the viscous deformation of magnesium matrix can change the form and the distribution of coacervate to a certain extent in the follow-up extrusion molding treating processes in deformation range, can't solve the homodisperse problem of carbon nanotube in magnesium matrix at all.In the aforesaid method; The problem of partially gathering and reuniting of carbon nanotube in magnesium matrix; Not only influenced the performance of the good reinforced effects of carbon nanotube, and the carbon nanotube coacervate becomes the tissue defects in the magnesium matrix, magnesium base composite material structure and performance are had detrimentally affect.
CN101376932 has disclosed method of preparing magnesium-based composite material and preparation facilities, and this inventive method can't realize the homodisperse of single-root carbon nano-tube in semi solid slurry and magnesium base composite material at all.At first; Length-to-diameter ratio big with the high carbon nanotube of specific surface energy form coacervate before the mixtinite preparation with regard to existence; Promptly in the commercially available common carbon nanotube starting material that this patent adopted; Carbon nanotube just exists with the group bunch or the form of coacervate; Can't alleviate or avoid its agglomeration, controlling carbon nanotube add-on that the quantity of carbon nanotube coacervate in the mixtinite and content are reduced because of the carbon nanotube add-on is few, can not influence the dispersion effect of single-root carbon nano-tube.Next, big quantity research shows that the carbon nanotube agglomeration of nanoscale is very serious, in the carbon nanotube coacervate, between carbon nanotube, exists strong Van der Waals force that they are difficult to the dispersion, length-to-diameter ratio is big, and (length-to-diameter ratio can reach 10
3More than) the carbon nanotube phenomenon of twining each other each other also make its agglomeration be difficult to eliminate.Therefore, only the dispersion of single-root carbon nano-tube in semi solid slurry can't be realized, and the dispersion of carbon nanotube coacervate can only be realized to a certain extent with the stirring action of whipping device in the closed unit.Once more; Though can promoting semi solid slurry, induction stirring moves with the mode that integral body stirs; The phenomenon that can avoid carbon nanotube to float to the semi solid slurry surface takes place; But can not destroy Van der Waals force carbon nanotube coacervate form strong and that twine each other, can not realize the homodisperse of single-root carbon nano-tube in semi solid slurry; Simultaneously, the existence form of coacervate makes carbon nanotube and magnesium matrix consistency poor, can't realize that effective interface soaks into and the interface combination.The commercially available common carbon nanotube add-on that this patent adopts is low, and the ratio between its quality and the magnesium granules quality is 1: 50-1: 200, can estimate the quality percentage composition of carbon nanotube in magnesium base composite material between 0.5～2%.As everyone knows, factors such as the strengthening effect of metal-base composites and wild phase type, structure, content are closely related.This patent wild phase add-on narrow range receives and avoids carbon nanotube to be difficult to the dispersive restriction, can't realize the wild phase add-on of high level.This patented process adopts commercially available common carbon nanotube, receives the selling market restriction, can't adjust length of carbon nanotube, structure, type flexibly as required.In addition, this patent has adopted the single carbon nanotube wild phase, and its dislocations strengthening effect in magnesium matrix does not have other large size wild phase (like SiC, Al
2O
3Deng) the dislocations strengthening effect is obvious.In sum, this patent is limited to the reinforced effects of magnesium base composite material, and is poor to its performance ability of regulation and control, makes matrix material be of limited application.
Summary of the invention
Technical problem to be solved by this invention is: provide carbon nanotube-aluminum oxide compound enhancing method of preparing magnesium-based composite material; Prepare in the process at the compound wild phase of carbon nanotube-aluminum oxide; Make iron catalyst be dispersed in alumina surface through calcining and reducing process; Make even carbon nanotube be dispersed in alumina surface through catalytic cracking reaction again, do not have interface pollution between the two, combine closely; After joining the compound wild phase of this carbon nanotube-aluminum oxide in the magnesium base melt; Alumina particle can be in magnesium base melt under mechanical agitation uniform distribution, combining closely between alumina substrate and carbon nanotube played the effect of similar " pinning " to carbon nanotube, realized the homodisperse of single-root carbon nano-tube in magnesium base melt indirectly; Avoided the come-up of single-root carbon nano-tube in magnesium base melt to gather partially and reunion each other; Overcome the defective of Magnuminium tissue in the magnesium base composite material that prior art produces, made the reinforced effects of carbon nanotube excellence in magnesium matrix, to be not fully exerted, guaranteed the raising of magnesium base composite material over-all properties.
The present invention solves this technical problem the technical scheme that is adopted: the compound enhancing method of preparing magnesium-based composite material of carbon nanotube-aluminum oxide, and its step is following:
The first step, the preparation of the compound wild phase of carbon nanotube-aluminum oxide
In mass ratio is nine nitric hydrate iron: aluminum oxide=0.07～1.00: 1 ratio; The nine nitric hydrate iron that take by weighing institute's expense join in the deionized water with 200～400 order alumina particles; Being mixed with volumetric molar concentration is the iron nitrate aqueous solution of 0.01～0.10mol/L and the system that wherein has alumina particle; With this system place put into again in the container Constant Temp. Oven in 60～90 ℃ of dehydrations to thick, should put into a quartz boat by thick thing, again this quartz boat is placed the tube furnace flat-temperature zone; And in this tube furnace, feed nitrogen with the flow velocity of 60～120ml/min; Then this tube furnace is warming up to 400～500 ℃ and calcine 0.5～2h, obtains calcinate red stone/aluminum oxide, close nitrogen afterwards; Flow velocity with 60～120ml/min feeds hydrogen and keeps 0.5～2h in this tube furnace; Calcinate red stone/aluminum oxide is reduced to iron/aluminum oxide composite catalyst, afterwards this tube furnace is warming up to 800～1000 ℃, close hydrogen; Be nitrogen with volume ratio again: ethene=6～12: 1 gas mixture continues to feed in this tube furnace with the flow velocity of 140～780ml/min; Under 800～1000 ℃, carry out catalytic cracking reaction 0.5～1.5h, make the even carbon nanotube that grows be dispersed in alumina surface through this catalytic cracking reaction, this tube furnace is chilled to room temperature under the nitrogen atmosphere of 60～120ml/min flow velocity afterwards; From quartz boat, take out the compound wild phase of carbon nanotube-aluminum oxide that makes, the quality percentage composition of carbon nanotube is 3.2～19.7% in this compound wild phase.
Second step, the preparation of the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide
The plumbago crucible that mg-based material is housed is put into the crucible type resistance furnace; Under argon shield, being heated to 690～730 ℃ makes magnesium substrates be fused into melt; In above-mentioned magnesium substrates melt, add account for this melt quality per-cent 1～15% by the compound wild phase of the prepared carbon nanotube-aluminum oxide of the first step; And the employing electric mixer is with speed stirring 1～3min of 500～1000 rev/mins; Then be poured into it in casting mold and be cooled to room temperature and make the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide, the quality percentage composition of carbon nanotube is 0.032～2.955% in this matrix material, and the quality percentage composition of aluminum oxide is 0.968～12.045%.
The compound enhancing method of preparing magnesium-based composite material of above-mentioned carbon nanotube-aluminum oxide, said mg-based material is pure magnesium or magnesiumalloy.
The compound enhancing method of preparing magnesium-based composite material of above-mentioned carbon nanotube-aluminum oxide; Said magnesiumalloy is cast magnesium alloys commonly used; Wherein the mass percent of contained element is: zinc 0.2～9.0%, aluminium 7.5～10.2%, zirconium 0.4～1.0%, rare earth 0.75～4.0%, manganese 0.1～0.5%, silver 0.6～1.2%, silicon 0～0.3%, copper 0.1～0.2%, iron 0～0.05% and nickel 0.01%; All the other are magnesium, can be commercially available.
The compound enhancing method of preparing magnesium-based composite material of above-mentioned carbon nanotube-aluminum oxide, said red stone/aluminum oxide is meant the complex body that is carried on the red stone on the aluminum oxide; Said iron/aluminum oxide is meant the complex body that is carried on the iron on the aluminum oxide.
The compound enhancing method of preparing magnesium-based composite material of above-mentioned carbon nanotube-aluminum oxide, wherein related starting material, equipment and technology all are that the technician in present technique field knows.
The invention has the beneficial effects as follows:
I. the compound enhancing method of preparing magnesium-based composite material of carbon nanotube-aluminum oxide of the present invention has outstanding substantive distinguishing features and is:
(1) solved the homodisperse problem of carbon nanotube in magnesium base composite material.Prepare in the process at the compound wild phase of carbon nanotube-aluminum oxide; Make iron catalyst be dispersed in alumina surface through technologies such as calcining and reduction; Make even carbon nanotube be dispersed in alumina surface through catalytic cracking reaction again, do not have interface pollution between the two, combine closely.After joining the compound wild phase of this carbon nanotube-aluminum oxide in the magnesium base melt; The density alumina particle close with magnesium base melt can be in magnesium base melt under mechanical agitation uniform distribution; Combining closely between alumina substrate and carbon nanotube played the effect of similar " pinning " to carbon nanotube; Realize the homodisperse of carbon nanotube in magnesium base melt indirectly, avoided the come-up of carbon nanotube in magnesium base melt to gather partially and reunion each other, avoided the tissue defects generation; Make the excellent reinforced effects of carbon nanotube can in magnesium matrix, obtain performance, guaranteed the raising of magnesium base composite material over-all properties.
(2) in the magnesium base composite material that adopts the inventive method to make, the quality percentage composition of compound wild phase is 1～15%, and wherein, the quality percentage composition of carbon nanotube is 0.032～2.955%, and the quality percentage composition of aluminum oxide is 0.968～12.045%.This shows; Not only the variable range of wild phase add-on is wide in range; And can through control, realize the structure and the wherein adjusting of content of carbon nanotubes, size, structure and type of compound wild phase according to the performance requriements of magnesium base composite material to compound wild phase preparation technology.Thereby the performance that realizes magnesium base composite material is controlled diversified with performance, satisfies the request for utilization of this matrix material at aspects such as different field, different performance demands.
(3) the inventive method has made the compound wild phase of the carbon nanotube-aluminum oxide with unique texture, and this structure is core with the alumina particle, and carbon nanotube is thorn-like above that and distributes.Alumina particle has been realized the homodisperse of carbon nanotube in magnesium base melt except that prepare the process indirect at magnesium base composite material, itself also is one of wild phase commonly used in the preparation magnesium base composite material process; And; The carbon nanotube loaded compound wild phase structure that has formed uniqueness in the alumina particle surface; Make it have the advantage of the two concurrently; Except that the various reinforced effects that can realize carbon nanotube in the magnesium matrix, alumina particle also can play strengthening effect through various strengthening mechanisms in magnesium matrix, makes that the strengthening effect of this magnesium base composite material is better.
The obvious improvement of the compound enhancing method of preparing magnesium-based composite material of carbon nanotube-aluminum oxide II. of the present invention is:
(1) over-all properties that adopts the composite material of magnesium alloy that the inventive method makes improves than the over-all properties of the composite material of magnesium alloy that adopts prior art to make.
Existing magnesium base composite material technology of preparing generally adopts particle (like TiC, SiC, Al
2O
3, SiO
2Deng), fiber is (like B, C, SiC, Al
2O
3Deng), whisker is (like SiC, Si
3N
4, K
2Ti
6O
13, Mg
2B
2O
5, Al
18B
4O
13, Al
2O
3, ZnO etc.) as wild phase, can improve the Young's modulus of magnesium matrix to a certain extent, reduce thermal expansivity; Improve intensity and wear resistance, but receive the restriction of above-mentioned traditional wild phase self performance, its improved performance effect to magnesium base composite material is limited; Be mainly reflected in: (a) the wild phase density of prior art employing is big; Its adding has influenced the original lightweight effect of magnesium matrix, and for example, the density of TiC is 4.93g/cm
3, SiC density be 3.2g/cm
3, K
2Ti
6O
13Density be 3.3g/cm
3, and pure magnesium density is 1.74g/cm
3, the routine casting magnesiumalloy density at 1.77～1.87g/cm
3Between, traditional wild phase adds must cause the increase of magnesium base composite material density; (b) the wild phase physics and the mechanical property of prior art employing are limited; The improvement of its Young's modulus to magnesium matrix, intensity etc. is limited in one's ability; For example; Generally between 300～450GPa, the tensile strength of wild phases such as whisker is between 3～14GPa for the Young's modulus of conventional particles, whisker, fiber reinforcement phase; (c) prior art generally is that adding through wild phase changes this single mode of the wear mechanism of magnesium base composite material in process of friction and wear and realizes to the raising of magnesium base composite material wear resistance.As the outstanding person in the carbon nanomaterial, since coming to light, carbon nanotube is with aspect characteristics such as its unique structure, physics, electricity and machineries and get most of the attention.For example, the density of carbon nanotube is low, the only about 1.7g/cm of the multi-walled carbon nano-tubes density that is adopted in the inventive method
3, being lower than the density of magnesium matrix, it adds the lightweight effect that can not influence magnesium; The physics of carbon nanotube and mechanical property are much better than traditional wild phase, the about 5000GPa of its Young's modulus, the about 40000GPa of intensity, and its reinforced effects to magnesium base composite material is remarkable; Carbon nanotube has the intrinsic property of graphite; Has good self-lubricating effect; Its wild phase as magnesium base composite material not only can improve the wear resistance of magnesium base composite material from the wear mechanism angle, and makes magnesium base composite material have certain self-lubricating ability, and wear resistance is able to obvious raising; In addition, the capacity of heat transmission of carbon nanotube, conductive capability etc. also all are superior to traditional wild phase, limit by self hollow geometric properties, and the thermal expansivity of carbon nanotube is low, and therefore, the thermal conductivity of matrix material and excellent electric conductivity, thermal expansivity are little.But the subject matter that carbon nanotube is used in matrix material is less density, great length-to-diameter ratio and strong to each other Van der Waals force makes carbon nanotube in matrix material, be difficult to disperse; Although prior art has adopted some dispersion measures, all there is tangible limitation.Prepare the structure that the high-energy ball milling that adopts in carbon nanotube-magnesium base composite material has destroyed carbon nanotube like powder metallurgic method; The mechanical stirring that casting adopts can't realize the homodisperse of single-root carbon nano-tube; In-situ synthesis is confined to laboratory stage, can't realize the batch process of carbon nanotube-magnesium base composite material.Compare with prior art; The inventive method is through the synthetic and application of the compound wild phase structure of carbon nanotube-aluminum oxide; Not only realized the uniform distribution of carbon nanotube in magnesium base composite material, and brought into play carbon nanotube and the two performance advantage separately of aluminum oxide, magnesium base composite material is being kept on the light-weight basis; Characteristics such as have that intensity height, wear resistance are strong, the heat-conductivity conducting performance is good and thermal expansivity is low have realized the raising of magnesium base composite material over-all properties.
(2) the inventive method is in implementation process; Through control to compound wild phase preparation technology parameters such as iron nitrate add-on, aluminum oxide grain size, gas flow, catalytic pyrolysis temperature and times; Can realize the control of carbon nanotube quality percentage composition, type, size and structure in the compound wild phase of carbon nanotube-aluminum oxide; In conjunction with the adjusting that magnesium base composite material is prepared compound wild phase add-on in the process; Can realize physicalies such as magnesium base composite material density, thermal expansivity and thermal conductivity; Mechanical property such as tensile strength and unit elongation and wear resistance controlled can be realized the flexible adjustment of physicals, mechanical property and wear resistance, satisfies in the request for utilization of different field such as aerospace, automobile, electronics, communication and machinery to this material.For example; When magnesium base composite material is applied to aerospace, automotive field, as wheel hub, deceleration casing, watchfully rib machine etc. low density, HS are arranged, the coefficient of expansion is little and during the structural part of the high requirement of thermal conductivity, the inventive method can adopt higher iron nitrate add-on, less aluminum oxide grain size, greater catalytic cracking temperature and long catalytic pyrolysis time; Realize carbon nanotube quality percentage composition higher in the compound wild phase; Make carbon nanotube have ideal tubular graphene layer structure, its caliber and length are big, and degree of hollowness is high; The carbon nanotube of this type has excellent mechanical property in the compound wild phase; And thermal expansivity is low, thermal conductivity is high, adopts higher compound wild phase add-on simultaneously, after heat treatment can make magnesium base composite material density less than 1.7g/cm
3, tensile strength reaches 290～310MPa, polar expansion less than 22 * 10
-6/ K, thermal conductivity reach 140W/mK, can satisfy the performance requriements of such structural part fully.Magnesium-based composite material parts to the general requirement that is used for mechanical industry; It is not high to performance requriementss such as density, intensity, the coefficient of expansion, thermal conductivities; The inventive method can adopt low iron nitrate add-on, big aluminum oxide grain size, low catalytic pyrolysis temperature and short catalytic pyrolysis time, and carbon nanotube quality percentage composition is lower in compound wild phase, and carbon nanotube has herring-bone form graphite linings structure, its degree of hollowness is low and length is little; The synthetic cost of such carbon nanotube is low; Performance is general, in conjunction with lower compound wild phase add-on, after heat treatment can make magnesium base composite material density less than 1.8g/cm
3, tensile strength reaches 120～140Mpa, polar expansion 23 * 10
-6About/K, about thermal conductivity 120W/mK, satisfiability can require the working conditions of low part.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is the high resolution scanning electron microscope photo of the compound wild phase of instance 3 prepared carbon nanotube-aluminum oxide of the present invention.
Fig. 2 is the high resolution transmission electron microscopy photo of instance 3 prepared carbon nanotubes of the present invention.
Fig. 3 is the compound enhancing magnesium base composite material of instance 3 a prepared carbon nanotube-aluminum oxide of the present invention coupon photo.
Embodiment
Embodiment 1
The first step, the preparation of the compound wild phase of carbon nanotube-aluminum oxide
In mass ratio is nine nitric hydrate iron: the ratio of aluminum oxide=0.07: 1; The nine nitric hydrate iron that take by weighing institute's expense join in the deionized water with 200 order alumina particles, be mixed with volumetric molar concentration and be the iron nitrate aqueous solution of 0.01mol/L and wherein have the system of alumina particle, with this system place put into again in the container Constant Temp. Oven in 60 ℃ of dehydrations to thick; Should put into quartz boat by thick thing; Again this quartz boat is placed the tube furnace flat-temperature zone, and in this tube furnace, feed nitrogen, then this tube furnace is warming up to 400 ℃ and calcine 0.5h with the flow velocity of 60ml/min; Obtain calcinate red stone/aluminum oxide; Close nitrogen afterwards, in this tube furnace, feed hydrogen and keep 0.5h, calcinate red stone/aluminum oxide is reduced to iron/aluminum oxide composite catalyst with the flow velocity of 60ml/min; Afterwards this tube furnace is warming up to 800 ℃; Closing hydrogen, is nitrogen with volume ratio again: the gas mixture of ethene=6: 1 continues to feed in this tube furnace with the flow velocity of 140ml/min, under 800 ℃, carries out catalytic cracking reaction 0.5h; Make the even carbon nanotube that grows be dispersed in alumina surface through this catalytic cracking reaction; This tube furnace is chilled to room temperature under the nitrogen atmosphere of 60ml/min flow velocity afterwards, from quartz boat, takes out the compound wild phase of carbon nanotube-aluminum oxide that makes, and the quality percentage composition of carbon nanotube is 3.2% in this compound wild phase.
Second step, the preparation of the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide
The plumbago crucible that pure magnesium substrates is housed is put into the crucible type resistance furnace; Under argon shield, being heated to 690 ℃ makes magnesium substrates be fused into melt; In above-mentioned magnesium substrates melt, add account for this melt quality per-cent 1% by the compound wild phase of the prepared carbon nanotube-aluminum oxide of the first step; And the employing electric mixer is with 500 rev/mins speed stirring 1min; Then be poured into it in casting mold and be cooled to room temperature and make the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide, the quality percentage composition of carbon nanotube is 0.032% in this matrix material, and the quality percentage composition of aluminum oxide is 0.968%.
Embodiment 2
Except that with the magnesiumalloy base material instead of pure magnesium substrates, other steps and technology make the compound enhancing magnesium base composite material of same carbon nanotube-aluminum oxide thus all with embodiment 1.
Embodiment 3
The first step, the preparation of the compound wild phase of carbon nanotube-aluminum oxide
In mass ratio is nine nitric hydrate iron: the ratio of aluminum oxide=0.50: 1; The nine nitric hydrate iron that take by weighing institute's expense join in the deionized water with 300 order alumina particles, be mixed with volumetric molar concentration and be the iron nitrate aqueous solution of 0.05mol/L and wherein have the system of alumina particle, with this system place put into again in the container Constant Temp. Oven in 75 ℃ of dehydrations to thick; Should put into quartz boat by thick thing; Again this quartz boat is placed the tube furnace flat-temperature zone, and in this tube furnace, feed nitrogen, then this tube furnace is warming up to 450 ℃ and calcine 1h with the flow velocity of 90ml/min; Obtain calcinate red stone/aluminum oxide; Close nitrogen afterwards, in this tube furnace, feed hydrogen and keep 1h, calcinate red stone/aluminum oxide is reduced to iron/aluminum oxide composite catalyst with the flow velocity of 90ml/min; Afterwards this tube furnace is warming up to 900 ℃; Closing hydrogen, is nitrogen with volume ratio again: the gas mixture of ethene=9: 1 continues to feed in this tube furnace with the flow velocity of 600ml/min, under 900 ℃, carries out catalytic cracking reaction 1h; Make the even carbon nanotube that grows be dispersed in alumina surface through this catalytic cracking reaction; This tube furnace is chilled to room temperature under the nitrogen atmosphere of 80ml/min flow velocity afterwards, from quartz boat, takes out the compound wild phase of carbon nanotube-aluminum oxide that makes, and the quality percentage composition of carbon nanotube is 8.6% in this compound wild phase.
The high resolution scanning electron microscope photo of the compound wild phase of the prepared carbon nanotube-aluminum oxide of present embodiment is as shown in Figure 1.Visible from this figure, through catalytic cracking reaction, formed the compound wild phase structure of unique alumina load carbon nanotube.In this compound wild phase, the carbon nanotube body is straight, no bending and wrapping phenomena; Combining closely between alumina substrate and carbon nanotube played the effect of similar " pinning " to carbon nanotube, make even carbon nanotube be dispersed in alumina surface, do not have interface pollution between the two, combines closely.
Fig. 2 is the high resolution transmission electron microscopy photo of the prepared carbon nanotube of present embodiment.Visible from this figure, institute's synthetic carbon nanotube has ideal structure, is the hollow tubule that is formed by coaxial cylindrical graphite linings cover structure, the about 8nm of caliber, and degree of hollowness is higher; The carbon nanotube body is straight, and the no obvious decolorizing carbon in the outside exists in the tube wall, and crystallization degree is good, and the type carbon nanotube density is low, has better mechanical property, and conduction, heat conduction and self-lubricating ability are strong, are comparatively ideal matrix material wild phases.
Second step, the preparation of the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide
The plumbago crucible that the magnesiumalloy base material is housed is put into the crucible type resistance furnace; Under argon shield, being heated to 710 ℃ makes magnesium substrates be fused into melt; In above-mentioned magnesium substrates melt, add account for this melt quality per-cent 8% by the compound wild phase of the prepared carbon nanotube-aluminum oxide of the first step; And the employing electric mixer is with 800 rev/mins speed stirring 2min; Then be poured into it in casting mold and be cooled to room temperature and make the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide, the quality percentage composition of carbon nanotube is 0.688% in this matrix material, and the quality percentage composition of aluminum oxide is 7.312%.
Fig. 3 is the compound enhancing magnesium base composite material of the prepared carbon nanotube-aluminum oxide of a present embodiment coupon photo.This coupon adopts the bottom filling metal type dies to make; Object shown in Fig. 3 two portions cylinder up and down is that diameter is that Φ 15mm and length are the compound enhancing magnesium base composite material of the carbon nanotube-aluminum oxide coupon of 128～132mm, after mechanical workout, can be used for this Material Physics, mechanical property detection; Rectangular parallelepiped of middle parts of objects shown in Fig. 3 and right part rectangular parallelepiped partly are gained part after the magnesium base composite material melt cooled and solidified in sprue and the cross gate of metal type dies gating system, can be used for this material composition, fabric analysis.
Embodiment 4
Except that substituting the magnesiumalloy base material with pure magnesium substrates, other steps and technology make the compound enhancing magnesium base composite material of same carbon nanotube-aluminum oxide thus all with embodiment 3.
Embodiment 5
The first step, the preparation of the compound wild phase of carbon nanotube-aluminum oxide
In mass ratio is nine nitric hydrate iron: the ratio of aluminum oxide=1: 1; The nine nitric hydrate iron that take by weighing institute's expense join in the deionized water with 400 order alumina particles, be mixed with volumetric molar concentration and be the iron nitrate aqueous solution of 0.10mol/L and wherein have the system of alumina particle, with this system place put into again in the container Constant Temp. Oven in 90 ℃ of dehydrations to thick; Should put into quartz boat by thick thing; Again this quartz boat is placed the tube furnace flat-temperature zone, and in this tube furnace, feed nitrogen, then this tube furnace is warming up to 500 ℃ and calcine 2h with the flow velocity of 120ml/min; Obtain calcinate red stone/aluminum oxide; Close nitrogen afterwards, in this tube furnace, feed hydrogen and keep 2h, calcinate red stone/aluminum oxide is reduced to iron/aluminum oxide composite catalyst with the flow velocity of 120ml/min; Afterwards this tube furnace is warming up to 1000 ℃; Closing hydrogen, is nitrogen with volume ratio again: the gas mixture of ethene=12: 1 continues to feed in this tube furnace with the flow velocity of 780ml/min, under 1000 ℃, carries out catalytic cracking reaction 1.5h; Make the even carbon nanotube that grows be dispersed in alumina surface through this catalytic cracking reaction; This tube furnace is chilled to room temperature under the nitrogen atmosphere of 120ml/min flow velocity afterwards, from quartz boat, takes out the compound wild phase of carbon nanotube-aluminum oxide that makes, and the quality percentage composition of carbon nanotube is 19.7% in this compound wild phase.
Second step, the preparation of the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide
The plumbago crucible that the magnesiumalloy base material is housed is put into the crucible type resistance furnace; Under argon shield, being heated to 730 ℃ makes magnesium substrates be fused into melt; In above-mentioned magnesium substrates melt, add account for this melt quality per-cent 15% by the compound wild phase of the prepared carbon nanotube-aluminum oxide of the first step; And the employing electric mixer is with 1000 rev/mins speed stirring 3min; Then be poured into it in casting mold and be cooled to room temperature and make the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide, the quality percentage composition of carbon nanotube is 2.955% in this matrix material, and the quality percentage composition of aluminum oxide is 12.045%.
Embodiment 6
Except that substituting the magnesiumalloy base material with pure magnesium substrates, other steps and technology make the compound enhancing magnesium base composite material of same carbon nanotube-aluminum oxide thus all with embodiment 5.
Among above-mentioned all embodiment; Said magnesiumalloy is cast magnesium alloys commonly used; Wherein the mass percent of contained element is: zinc 0.2～9.0%, aluminium 7.5～10.2%, zirconium 0.4～1.0%, rare earth 0.75～4.0%, manganese 0.1～0.5%, silver 0.6～1.2%, silicon 0～0.3%, copper 0.1～0.2%, iron 0～0.05% and nickel 0.01%; All the other are magnesium, can be commercially available.
Among above-mentioned all embodiment, said red stone/aluminum oxide is meant the complex body that is carried on the red stone on the aluminum oxide; Said iron/aluminum oxide is meant the complex body that is carried on the iron on the aluminum oxide.
Among above-mentioned all embodiment, wherein related starting material, equipment and technology all are that the technician in present technique field knows.
Claims (3)
1. the compound enhancing method of preparing magnesium-based composite material of carbon nanotube-aluminum oxide is characterized in that step is following:
The first step, the preparation of the compound wild phase of carbon nanotube-aluminum oxide
In mass ratio is nine nitric hydrate iron: aluminum oxide=0.07～1.00: 1 ratio; The nine nitric hydrate iron that take by weighing institute's expense join in the deionized water with 200～400 order alumina particles; Being mixed with volumetric molar concentration is the iron nitrate aqueous solution of 0.01～0.10mol/L and the system that wherein has alumina particle; With this system place put into again in the container Constant Temp. Oven in 60～90 ℃ of dehydrations to thick, should put into a quartz boat by thick thing, again this quartz boat is placed the tube furnace flat-temperature zone; And in this tube furnace, feed nitrogen with the flow velocity of 60～120mL/min; Then this tube furnace is warming up to 400～500 ℃ and calcine 0.5～2h, obtains calcinate red stone/aluminum oxide, close nitrogen afterwards; Flow velocity with 60～120mL/min feeds hydrogen and keeps 0.5～2h in this tube furnace; Calcinate red stone/aluminum oxide is reduced to iron/aluminum oxide composite catalyst, afterwards this tube furnace is warming up to 800～1000 ℃, close hydrogen; Be nitrogen with volume ratio again: ethene=6～12: 1 gas mixture continues to feed in this tube furnace with the flow velocity of 140～780mL/min; Under 800～1000 ℃, carry out catalytic cracking reaction 0.5～1.5h, make the even carbon nanotube that grows be dispersed in alumina surface through this catalytic cracking reaction, this tube furnace is chilled to room temperature under the nitrogen atmosphere of 60～120mL/min flow velocity afterwards; From quartz boat, take out the compound wild phase of carbon nanotube-aluminum oxide that makes, the quality percentage composition of carbon nanotube is 3.2～19.7% in this compound wild phase;
Second step, the preparation of the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide
The plumbago crucible that mg-based material is housed is put into the crucible type resistance furnace; Under argon shield, being heated to 690～730 ℃ makes magnesium substrates be fused into melt; In above-mentioned magnesium substrates melt, add account for this melt quality per-cent 1～15% by the compound wild phase of the prepared carbon nanotube-aluminum oxide of the first step; And the employing electric mixer is with speed stirring 1～3min of 500～1000 rev/mins; Then be poured into it in casting mold and be cooled to room temperature and make the compound enhancing magnesium base composite material of carbon nanotube-aluminum oxide, the quality percentage composition of carbon nanotube is 0.032～2.955% in this matrix material, and the quality percentage composition of aluminum oxide is 0.968～12.045%.
2. according to the compound enhancing method of preparing magnesium-based composite material of the said carbon nanotube-aluminum oxide of claim 1, it is characterized in that: said mg-based material is pure magnesium or magnesiumalloy.
3. according to the compound enhancing method of preparing magnesium-based composite material of the said carbon nanotube-aluminum oxide of claim 2; It is characterized in that: said magnesiumalloy is cast magnesium alloys commonly used; Wherein the mass percent of contained element is: zinc 0.2～9.0%, aluminium 7.5～10.2%, zirconium 0.4～1.0%, rare earth 0.75～4.0%, manganese 0.1～0.5%, silver 0.6～1.2%, silicon 0～0.3%, copper 0.1～0.2%, iron 0～0.05% and nickel 0.01%, all the other are magnesium.
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| CN105543598B (en) * | 2016-03-01 | 2017-05-03 | 河北工业大学 | Preparation method of reinforced magnesium matrix composite |
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| CN106498225B (en) * | 2016-12-21 | 2017-12-15 | 河北工业大学 | CNT aluminum oxide mixing strengthens the preparation method of magnesium alloy composite |
| CN107267826A (en) * | 2017-05-16 | 2017-10-20 | 苏州莱特复合材料有限公司 | A kind of modified graphene enhancing magnesium-base metal material and preparation method thereof |
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| CN110578064A (en) * | 2019-09-03 | 2019-12-17 | 天津大学 | Preparation method of in-situ generated aluminum oxide and carbon nanotube reinforced aluminum matrix composite |
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| CN112916799B (en) * | 2021-01-15 | 2023-05-26 | 安徽应流航源动力科技有限公司 | Preparation process of master alloy test bar |
| CN116287894A (en) * | 2023-02-13 | 2023-06-23 | 凤阳爱尔思轻合金精密成型有限公司 | Aluminum magnesium alloy material for structural part and preparation process |
| CN117023697B (en) * | 2023-10-08 | 2023-12-08 | 中国地质调查局长沙自然资源综合调查中心 | Sewage treatment process for ore collection area |
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| CN101435059A (en) * | 2007-11-16 | 2009-05-20 | 清华大学 | Method for preparing magnesium base-carbon nanotube composite material |
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