CN101892407B - Method for preparing aluminum-based in-situ composite materials at low temperature in presence of catalysts - Google Patents
Method for preparing aluminum-based in-situ composite materials at low temperature in presence of catalysts Download PDFInfo
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- CN101892407B CN101892407B CN 201010228666 CN201010228666A CN101892407B CN 101892407 B CN101892407 B CN 101892407B CN 201010228666 CN201010228666 CN 201010228666 CN 201010228666 A CN201010228666 A CN 201010228666A CN 101892407 B CN101892407 B CN 101892407B
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Abstract
The invention belongs to the technical field of material preparation and particularly provides a method for preparing aluminum-based composite materials at low temperature in the presence of catalysts. In the method, catalysts added to the salts used in the reaction for preparing the composite materials can enable the salts used in the reaction and aluminum melt to conduct the in-situ reaction under the condition that the reaction temperature is lower than the conventional synthesis temperature, increase the reaction rate, shorten the reaction time and ensure that the microstructure characteristics of the composite materials, including the type, dimensions and distribution of particles are unchanged. Therefore, the method of the invention is suitable for the preparation of aluminum-based composite materials on an industrial scale.
Description
Technical field
The present invention relates to the preparing technical field of metal-base composites, by allocate catalyzer in the reaction mixing salt, purpose is to realize the low-temperature catalyzed preparation of aluminum matrix composite.
Background technology
Aluminum matrix composite has been concentrated the advantage of aluminum substrate and wild phase, has the advantageous properties such as high specific tenacity, specific rigidity, high abrasion, is the important component part in the novel material research and development.From the particle introducing method, add and two kinds of interior lifes, endogenetic particle has the advantages such as interface cleanness, particle size be little, many in-situ endogenic methods of correspondingly having derived.This wherein, direct reaction method is that the reacting salt powder that will contain particle elements is added in aluminium/aluminium alloy melt under synthesis temperature, makes it abundant reaction, prepares endogenetic particle in melt, can directly pour into a mould complex-shaped foundry goods.Thereby have that technique is simple, cost is low, the cycle is short, and be easy to the advantages such as suitability for industrialized production, unanimously thought the new technology of industrial applications to be hopeful to realize by the insider.
From existing bibliographical information, in field of research of metal, study hotspot mainly concentrates on following several respects:
1, research and development NEW TYPE OF COMPOSITE system, such as Al-O, Al-Ti-C, Al-Ti/Zr-B, Al-Ti/Zr etc., main wild phase particle comprises intermetallic compound, oxide compound, nitride, carbide and boride etc. at present;
2, according to system characteristics optimal preparation technology, generally comprise: temperature of reaction, reaction times, reactant species and broiler diets etc.;
3, optimize reaction conditions by number of ways, comprise using adding physical field, such as ultrasonic field, electromagnetic field or sound magnetic coupling field.
But, from the industrial scale applications prospect, advance matrix material to prepare in industry, need to overcome and solve following key " bottleneck " difficult problem:
1, require aluminium liquid that comparatively high temps is arranged.Reacting salt will react with aluminium liquid, and generates thermodynamically stable strengthening phase, needs higher temperature of reaction.From present bibliographical information, generally all require the overheated 100-150 of aluminium liquid ℃, namely the initial melt temperature requirement is at 800-1000 ℃.Because aluminium meeting when high temperature is air-breathing and generation is mingled with, and with air-breathing the increasing the weight of of temperature rising, aluminium liquid quality severe exacerbation.Simultaneously under high overheated condition, the particle motivating force of growing up is large, and the part particle grows up to easily large size and is mingled with phase.If so can under lower temperature conditions, prepare aluminum matrix composite, then can advance matrix material industry application process;
2, require the long reaction times.Reaction in－situ be to finish between solid state reaction salt and aluminium liquid, long time realization solid phase and contact, mass transfer and the reaction between the liquid phase needed.Time range is generally at 25-50min, and preparation cycle is long, and aluminium liquid at high temperature the residence time long, strengthened air-breathing and scaling loss.If can prepare matrix material within a short period of time, then can advance matrix material industry application process.
3, literature search shows, the patent of invention relevant with this technology has: national inventing patent 200810134310.4, proposition reduces the metal-base composites synthesis temperature by polynary flux combined method, that one or more low melting points are allocated in the mixing salt as fusing assistant, reacting salt is melted under the temperature of reaction in position to be in a liquid state, the efficient of liquid-liquid phase reaction is higher than the solid-liquid phase reaction, the temperature that liquid-liquid phase reacts also is lower than the temperature that generic reaction salt reacts with the solid-liquid phase state, can be so that the reduction of reaction in－situ temperature.Its weak point has: the villiaumite of adding is fluxed into branch and is further deepened villiaumite to the harm of human body and environment, and the villiaumite that adds meeting and reacting salt generation partial reaction, causes the partial reaction salt neutralization, affects the particle recovery rate; The two, for some high-melting-point reacting salt, such as some carbonate, the fusing assistant of adding can not make it become liquid from solid state transformation under the temperature of reaction condition, reduces the DeGrain of temperature of reaction.The present invention and its difference are: allocate graphite-like or spinels catalyzer in mixing salt into, do not pollute the environment, simultaneously to reacting salt kind and fusing point height without limits, the mechanism and the foundation that reduce synthesis temperature behind the adding catalyzer are catalytic theories, that is: effectively reduce reactant molecule activation energy, improve reaction efficiency, shorten generated time.
In sum, the present invention is applied to the metallic substance preparation field with catalysis technique commonly used in the chemical field, be used for realizing the low-temperature catalyzed preparation of metal-base composites, make that the original position building-up process has in short-term, efficient feature, satisfy " energy-conservation, efficient " requirement of modern industry, the industry that helps to promote the high-performance metal based composites prepares process.
Summary of the invention
Content of the present invention provides the broad variety catalyzer, certain kind, a certain amount of catalyzer are incorporated in the reacting salt, guarantee the two even mixing, can play the effect that reduces temperature of reaction, improves speed of reaction, Reaction time shorten, be a kind of low consumption, efficiently prepare the novel method of high-performance metal based composites
The objective of the invention is to be achieved through the following technical solutions:
The first step: the preparation of raw material.
Ready reaction salt, control its preheating temperature at 200-250 ℃, granularity at 200 orders, and calculate with addition of ratio according to reaction equation, in the reacting salt for preparing, add catalyzer, described catalyzer is: carbon nanotube, synthetic graphite, aluminum-spinel or natural graphite, the ratio that the catalyzer add-on accounts for the reacting salt total amount is: 1-5wt.%; Fully obtain the mixing salt powder after the ground and mixed, for subsequent use; The aluminum or aluminum alloy ingot melts in molten aluminium stove, low 40-80 ℃ of the more conventional synthesis temperature of temperature.
Second step: synthetic composite material.
With bell jar the mixing salt powder of preheating is added in the high-temperature fusant, fully stir, guarantee that powder has fully with melt to contact.After certain reaction times, finish reaction in－situ, a small amount of scum silica frost of desurfacing this moment.Pour into a mould after the refining, cool off with mould.
The add-on of above-mentioned catalyzer is adjusted because catalyst effect is different with reaction system.Allocate into when the original synthesis temperature of excellent catalytic effect or reaction system (synthesis temperature when not adding catalyzer) is low and measure lower limit, such as 1-2wt.%; Capping when the poor or original synthesis temperature of reaction system of catalytic effect is high; Such as 4-5wt.%; Excellent catalytic effect, but original synthesis temperature is high, also or, catalytic effect is poor, but original synthesis temperature is got intermediate value when low, such as 3wt.%.Being followed successively by by the good and bad ordering of result of use of above-mentioned catalyzer: carbon nanotube, synthetic graphite, aluminum-spinel, natural graphite.
Compared with prior art, the present invention has the following advantages and effect:
1, can prepare at a lower temperature particle enhanced aluminum-based composite material, the synthetic temperature that needs of melting is low, and aluminium is overheated little, is suitable for the industry preparation;
2, catalyzer can increase speed of reaction, and Reaction time shorten helps to enhance productivity, and is suitable for the industry preparation;
3, catalyst levels is few, and cost is low, is suitable for the industry preparation;
4, behind the use catalyzer, can prepare matrix material in low-temperature short-time, the tissue signature of material can not be affected, and has high cost performance, and important value has been applied in the industry of metal-base composites.
Description of drawings
Fig. 1 K
2TiF
6-KBF
4Constituent element prepares the scanning electron microscope (SEM) photograph of matrix material, and Particle Phase is TiB among the figure
2
K behind Fig. 2 doped carbon nanometer pipe
2TiF
6-KBF
4Constituent element prepares the scanning electron microscope (SEM) photograph of matrix material, and Particle Phase is TiB among the figure
2
Fig. 3 K
2ZrF
6-KBF
4Constituent element prepares the scanning electron microscope (SEM) photograph of matrix material, and Particle Phase is ZrB among the figure
2
Fig. 4 K behind the synthetic graphite that mixes
2ZrF
6-KBF
4Constituent element prepares the scanning electron microscope (SEM) photograph of matrix material, and Particle Phase is ZrB among the figure
2
K behind Fig. 5 doped spinel
2ZrF
6-KBF
4Constituent element prepares the scanning electron microscope (SEM) photograph of matrix material, and Particle Phase is ZrB among the figure
2
Fig. 6 Zr (CO
3)
2Constituent element prepares the scanning electron microscope (SEM) photograph of matrix material, and Particle Phase is Al among the figure
2O
3
Fig. 7 Zr (CO behind the natural graphite that mixes
3)
2Constituent element prepares the scanning electron microscope (SEM) photograph of matrix material, and Particle Phase is Al among the figure
2O
3
Embodiment
The invention will be further elaborated below in conjunction with embodiment.Embodiment only is used for explanation the present invention, rather than limits by any way the present invention.
Embodiment one: TiB
2The low-temperature catalyzed preparation of the carbon nanotube of particle enhanced aluminum-based composite material
With potassium fluotitanate K
2TiF
6With potassium fluoborate KBF
4As reacting salt, prepare TiB by the mixing salt reaction method
2Particle enhanced aluminum-based composite material.Add in the high-temperature fusant with the mixing salt powder of bell jar with preheating in batches, fully stir, guarantee that powder has fully with melt to contact.When not adding catalyzer, the synthesis temperature of optimization is 870-900 ℃, and the suitable reaction times is 25-30min, and the microstructure of composite of preparation as shown in Figure 1.
In mixing salt, mix the carbon nanotube of salt quality 1.2wt.%.Then reaction in－situ can be finished between 820-830 ℃, and the reaction times can shorten to 10-15min, and the microstructure of composite of preparation does not have notable difference with Fig. 1 tissue as shown in Figure 2.
The result shows: behind a certain amount of catalyzer that mixes in the mixing salt, can reduce temperature of reaction 40-80 ℃, the reaction times shortens 10-20min, and does not affect the microstructure of composite feature.
Embodiment two ZrB
2The low-temperature catalyzed preparation of the synthetic graphite of particle enhanced aluminum-based composite material
With potassium fluozirconate K
2ZrF
6With potassium fluoborate KBF
4As reacting salt, prepare ZrB by the mixing salt reaction method
2Particle enhanced aluminum-based composite material.Add in the high-temperature fusant with the mixing salt powder of bell jar with preheating in batches, fully stir, guarantee that powder has fully with melt to contact.When not adding catalyzer, the synthesis temperature of optimization is 880-900 ℃, and the suitable reaction times is 20-25min, and the microstructure of composite of preparation as shown in Figure 3.
In mixing salt, mix the graphous graphite powder of salt quality 2wt.%.Then reaction in－situ can be finished between 830-840 ℃, and the reaction times can shorten to 10min, and the microstructure of composite of preparation does not have notable difference with Fig. 3 tissue as shown in Figure 4.
The result shows: behind a certain amount of catalyzer that mixes in the mixing salt, can reduce temperature of reaction 40-70 ℃, the reaction times shortens 10-15min, and does not affect the microstructure of composite feature.
Embodiment three ZrB
2The low-temperature catalyzed preparation of the sodium aluminum fluoride of particle enhanced aluminum-based composite material
With potassium fluozirconate K
2ZrF
6With potassium fluoborate KBF
4As reacting salt, prepare ZrB by the mixing salt reaction method
2Particle enhanced aluminum-based composite material.Add in the high-temperature fusant with the mixing salt powder of bell jar with preheating in batches, fully stir, guarantee that powder has fully with melt to contact.When not adding catalyzer, the synthesis temperature of optimization is 880-900 ℃, and the suitable reaction times is 20-25min, and the microstructure of composite of preparation as shown in Figure 3.
In mixing salt, mix the aluminum-spinel of salt quality 3wt.%.Then reaction in－situ can be finished in the time of 830 ℃, and the reaction times can shorten to 10min, and the microstructure of composite of preparation does not have notable difference with Fig. 3 tissue as shown in Figure 5.
The result shows: behind a certain amount of catalyzer that mixes in the mixing salt, can reduce temperature of reaction 50-70 ℃, the reaction times shortens 10-15min, and does not affect the microstructure of composite feature.
Embodiment four Al
2O
3The low-temperature catalyzed preparation of the natural graphite of particle enhanced aluminum-based composite material
As reacting salt, prepare Al by direct reaction method with zirconium carbonate
2O
3Particle enhanced aluminum-based composite material.When not adding catalyzer, the synthesis temperature of optimization is 850-870 ℃, and the suitable reaction times is 25-30min, and the microstructure of composite of preparation as shown in Figure 6.
In mixing salt, mix the natural graphite of salt quality 5wt.% as catalyzer.Then reaction in－situ can be finished between 820-830 ℃, and the reaction times can shorten to 10-15min, and the microstructure of composite of preparation does not have notable difference with Fig. 6 tissue as shown in Figure 7.
Claims (4)
1. the method for a preparing aluminum-based in-situ composite materials at low temperature in presence of catalysts, it is characterized in that: in reacting salt, allocate catalyzer into, be lower than the reaction in－situ of finishing under the conventional synthesis temperature condition between reacting salt and molten aluminium, reach the experiment purpose of preparation particle enhanced aluminum-based composite material, described catalyzer is carbon nanotube, synthetic graphite, aluminum-spinel or natural graphite, and the ratio that the add-on of described catalyzer accounts for the reacting salt total amount is: 1-5wt%; Be specially:
(1) preparation of raw material
Ready reaction salt, control its preheating temperature at 200-250 ℃, granularity at 200 orders, and calculate with addition of ratio according to reaction equation, in the reacting salt for preparing, add catalyzer, selectable catalyzer has: carbon nanotube, synthetic graphite, aluminum-spinel or natural graphite, the ratio that the catalyzer add-on accounts for the reacting salt total amount is: 1-5wt.%, fully obtain the mixing salt powder after the ground and mixed, and for subsequent use; The aluminum or aluminum alloy ingot melts in molten aluminium stove, low 40-80 ℃ of the more conventional synthesis temperature of temperature;
(2) synthetic composite material
With bell jar the mixing salt powder of preheating is added in the high-temperature fusant, fully stirs, guarantee that powder has fully with melt to contact, finish reaction in－situ after, a small amount of scum silica frost of desurfacing, pour into a mould after the refining, cool off with mould.
2. the method for a kind of preparing aluminum-based in-situ composite materials at low temperature in presence of catalysts as claimed in claim 1 is characterized in that: described catalyzer is followed successively by by the good and bad ordering of result of use: carbon nanotube, synthetic graphite, aluminum-spinel, natural graphite.
3. the method for a kind of preparing aluminum-based in-situ composite materials at low temperature in presence of catalysts as claimed in claim 1 is characterized in that: compare with the synthetic synthesis temperature of routine, add catalyzer after synthesis temperature reduce 40-80 ℃.
4. the method for a kind of preparing aluminum-based in-situ composite materials at low temperature in presence of catalysts as claimed in claim 1, it is characterized in that: the add-on of above-mentioned catalyzer is adjusted because catalyst effect is different with reaction system, allocates into when the original synthesis temperature of excellent catalytic effect or reaction system is low and measures lower limit; Capping when the poor or original synthesis temperature of reaction system of catalytic effect is high; Excellent catalytic effect but original synthesis temperature is high is got intermediate value when perhaps poor the but original synthesis temperature of catalytic effect is low.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6511754B1 (en) * | 1998-12-23 | 2003-01-28 | Rhodia Chimie | Silicone composition for coating textile material substrates |
| CN1730688A (en) * | 2005-08-29 | 2006-02-08 | 天津大学 | Vapour deposition in situ reaction method for preparing carbon nanotube reinforced aluminium matrix composite material |
| CN101032756A (en) * | 2007-02-01 | 2007-09-12 | 天津大学 | Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel |
| CN101407870A (en) * | 2008-11-11 | 2009-04-15 | 江苏大学 | Multicomponent flux composition method capable of lowering metal-matrix composite synthesis temperature |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6511754B1 (en) * | 1998-12-23 | 2003-01-28 | Rhodia Chimie | Silicone composition for coating textile material substrates |
| CN1730688A (en) * | 2005-08-29 | 2006-02-08 | 天津大学 | Vapour deposition in situ reaction method for preparing carbon nanotube reinforced aluminium matrix composite material |
| CN101032756A (en) * | 2007-02-01 | 2007-09-12 | 天津大学 | Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel |
| CN101407870A (en) * | 2008-11-11 | 2009-04-15 | 江苏大学 | Multicomponent flux composition method capable of lowering metal-matrix composite synthesis temperature |
Non-Patent Citations (2)
| Title |
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| 廖恒成等.铝原位合成复合材料的反应模式与机理.《铸造》.1999,(第01期),43-47. |
| 铝原位合成复合材料的反应模式与机理;廖恒成等;《铸造》;19991231(第01期);43-47 * |
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