CN107099692A - A kind of fibre-reinforced aerogel-metallic composite and preparation method thereof - Google Patents
A kind of fibre-reinforced aerogel-metallic composite and preparation method thereof Download PDFInfo
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- CN107099692A CN107099692A CN201610093349.3A CN201610093349A CN107099692A CN 107099692 A CN107099692 A CN 107099692A CN 201610093349 A CN201610093349 A CN 201610093349A CN 107099692 A CN107099692 A CN 107099692A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
- B22D23/04—Casting by dipping
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1005—Pretreatment of the non-metallic additives
- C22C1/1015—Pretreatment of the non-metallic additives by preparing or treating a non-metallic additive preform
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1073—Infiltration or casting under mechanical pressure, e.g. squeeze casting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
- C22C47/06—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/08—Making alloys containing metallic or non-metallic fibres or filaments by contacting the fibres or filaments with molten metal, e.g. by infiltrating the fibres or filaments placed in a mould
Abstract
The present invention relates to a kind of fibre-reinforced aerogel-metallic composite and preparation method.Fibre-reinforced aerogel-the metallic composite, using fibre-reinforced aeroge as strengthening material, using metal as matrix, is filled with metal, forms the composite that metal interweaves with aeroge nanoscale three-dimensional network in the three-D nano hole structure of aeroge.The present invention can lift heat-resisting quantity, wearability, crushing resistance, impact resistance, fold resistance, anti-corrosive properties of metal-base composites etc..Present invention process process is simple and easy to apply, is conducive to industrialized production, can promote the upgrading of conventional metals based composites industry, and product has significant application value in fields such as defence and military, space flight and aviation, bullet train, wheel Ship, automobiles.
Description
Technical field
The present invention relates to the preparation method of metal-base composites, fibre-reinforced aerogel-Metal Substrate is more particularly to utilized
Composite.
Background technology
Requirement of the development of Modern High-Tech to material property is increasingly improved, and homogenous material has been difficult to meet to the comprehensive of performance
Close and require, the Composite of material is one of inexorable trend of Materials.
Ceramics have excellent resistance to elevated temperatures, and such as high temperature compression strength is big, modulus of elasticity is high, creep resistance, anti-oxidant, resistance to
Burn into is wear-resistant etc., but its fatal defects is that fragility is big, shows that resistance to mechanical impact and thermal impact are all very low, therefore in high temperature
It is very limited in field as structural material.
By ceramic particle, chopped fiber, whisker reinforcement metal-base composites (MMC) combine the plasticity and toughness of metal, into
Type, conduction, thermal conductivity, and strengthen the performances such as high intensity, high-modulus, heat-resisting, the wear-resisting, high temperature resistant of multiphase ceramics material, system
Standby metal-base composites has high specific strength, specific modulus；Heat conduction, electric conductivity；Thermal coefficient of expansion is small, dimensional stability
It is good；Good high-temperature behavior；Wearability is good；The advantages of good fatigue behaviour and fracture property, in such as fretting wear class material
The field such as material, aerospace structure part, high-temperature-resistant structure part, automobile component, anti-bullet protective materials has broad application prospects.
Network structure Ceramic Reinforced MMCs are to use casting method casting metals in prefabricated porous ceramics
A class composite, it is continuous that its essential characteristic is that matrix forms respective three dimensions with reinforcement in whole material
Network structure and be intertwined mutually, relative to fibre reinforced materials, it has isotropic in overall structure
Feature, and relative to particle or whisker reinforcement material, the characteristics of it has mutually continuous again, this structure type has such material
There is the performance of uniqueness, with preferable development and application prospect.
Aeroge, is a kind of novel inorganic nano-porous materials, can be divided into aerosil, aluminum oxide gas by composition
The metal oxide aerogels such as gel, zirconia aerogels, titania aerogel and organic aerogel, carbon aerogels etc..Gas
Gel is mutually assembled with nanometer scale ultramicro powder is constituted nanoporous network structure, and average cell size is 20 ~ 50nm, density
Low it can reach 0.003g/cm3, spiracular slit rate is up to 80~99.8%, and specific surface area is up to 1000m2/ g, heat resisting temperature up to 1300 ~
1800 DEG C, room temperature thermal conductivity factor low can reach 0.013w/ (mk), be the best material of most light so far solid and heat-insulating property
Material, has wide practical use in fields such as calorifics, acoustics, mechanics, optics, electricity, chemistry.With the nanometer three-dimensional apertures of aeroge
Hole replaces the micron or even millimetre-sized macropore and metal composite of porous ceramics, will obtain a kind of brand-new metal-based compound material
Material.
Therefore, the present invention proposes a kind of fibre-reinforced aerogel-metallic composite and preparation method.
The content of the invention
The invention discloses a kind of fibre-reinforced aerogel-metallic composite, the composite is with fibre-reinforced
Aeroge is strengthening material, using metal as matrix, in the three-D nano hole structure of aeroge be filled with metal, formed metal with
The composite that aeroge three-dimensional network interweaves.
Described fibre-reinforced aerogel, including airsetting adhesive plaster, Aerogel paper, aerogel blanket, aerogel plate and aeroge
It is one or more of in shaped piece.
Described aeroge, density is 3 ~ 600kg/m3, average pore size is 2 ~ 100nm, and porosity is 50% ~ 99%.
Described aeroge include silica aerogel, alumina aerogels, zirconia aerogels, titania aerogel,
Magnesia aeroge, cupric oxide aeroge, iron oxide aeroge, cobalt oxide aeroge, nickel oxide aeroge, manganese oxide airsetting
Glue, zinc oxide aeroge, tin oxide aeroge, cadmium oxide aeroge, chromium oxide aeroge, niobium oxide aeroge, tantalum oxide gas
Gel, cerium oxide aeroge, vanadium oxide aeroge, molybdenum oxide aeroge, tungsten oxide aeroge, hafnium oxide aeroge, thorium oxide
Aeroge, beryllium oxide aeroge, yittrium oxide aeroge, scandium oxide aeroge, cerium oxide aeroge, strontium oxide strontia aeroge, oxidation
Indium aeroge, gallium oxide aeroge, bismuth oxide aeroge, lanthana aeroge, ytterbium oxide aeroge, europium oxide aeroge, oxygen
Change neodymium aeroge, terbium oxide aeroge, praseodymium oxide aeroge, samarium oxide aeroge carbonization silica aerogel, nitridation silica aerogel, carbon
It is one or more of in aeroge, graphene aerogel.
Described fiber, its component includes quartz fibre, high silica fiber, alumina fibre, alumina silicate fibre, mullite
Fiber, silicon carbide fibre, boron carbide fibre, silicon nitride fiber, boron nitride fiber, titanium nitride fiber, boron fibre, carbon fiber, carbon
It is one or more of in nanotube, tungsten filament, molybdenum filament, thorium silk.
Described fiber, its form includes whisker, chopped strand, continuous fiber, one-way fiber fabric, two-dimensional fiber braiding
It is a kind of or several in cloth, three-dimensional fiber woven cloth, fiber non-woven, fibrofelt, fiberboard, fiber honeycomb plate, fiber shaped piece
Kind.
Described metal include aluminium, copper, magnesium, titanium, zinc, tin, iron, silver, nickel, beryllium, cobalt, lead, chromium, tungsten, molybdenum, tantalum, niobium, cerium,
It is one or more of in zirconium, and the corresponding alloy of above-mentioned metal.
The invention also discloses a kind of preparation method of fibre-reinforced aerogel-metallic composite, preparation process includes
Following steps：
(1) fibre-reinforced aerogel is laid；
(2) molten metal is infiltrated up to fibre-reinforced aerogel；
(3) composite is formed after cooling and solidifying.
The preparation method of the composite, step（2）Described is infiltrated up to molten metal fibre-reinforced aerogel, leaching
Cementation process include it is a kind of in infiltration by squeeze casting method, gas pressure infiltration method, pressure-free impregnation method, vacuum pressure infiltration method and vacuum infiltration method or
It is several.
The preparation method of the composite, can take one kind or several in solvent infiltration, ultrasonic infiltration and electromagnetism infiltration
Plant to improve the infiltration of molten metal and fibre-reinforced aerogel.
The preparation method of the composite, can be in metal to improve the wellability of molten metal and fibre-reinforced aerogel
Size is added in liquid, or high-energy ultrasonic is incorporated into the blend melt of reinforcement and liquid metal.
Fibre-reinforced aerogel-metallic composite of the present invention, using fibre-reinforced aerogel material as Rankine
Material, using metal as matrix, is filled with metal, forms metal and aeroge nanoscale in the three-D nano hole structure of aeroge
The composite that three-dimensional network interweaves, it is intended to improve the heat-resisting quantity of original fiber-reinforced metal matrix composite, wearability, anti-
Pressure property, impact resistance, fold resistance, anti-corrosive properties etc..
Aeroge is mutually assembled with nanometer scale ultramicro powder is constituted overall homogeneous nanoporous three-dimensional net structure, is put down
Equal bore hole size is 20 ~ 50nm, and specific surface area is up to 1000g/m2, because the coordination of nano-material surface seriously is not enough, performance
Go out extremely strong activity, aeroge is easy to occur bonding action with metallic molecule, improves intermolecular bonding force.While aeroge
Interior three-dimensional net structure passage forms the network-like parcel that is cross-linked with each other with metal material, optimizes the micro-arrangement knot of metal
Structure so that composite has more preferable resistance to compression, tensile strength and toughness.
Metal formation three-dimensional network composite is penetrated into aeroge skeleton hole, its metal phase is mutually to connect with aeroge
Continuous distribution, the Dispersed precipitate with particulates reinforcements is dramatically different.Wherein aeroge skeleton is three-dimensional communication network structure, its own
Load can be not only transmitted, load can also be born, this is that (disperse strengthens in composite not available for any disperse reinforcement
Reinforcement can only transmit load and can not carry).Therefore in this metallic composite of aeroge one, metal phase can be due to
The rigid carrying of aeroge skeleton is acted on and strengthened, and can significantly improve the intensity and modulus of elasticity of material；On the other hand,
Aeroge skeleton obtains toughness reinforcing because of the toughness that metal phase has, therefore both mutually rely on, mutual reinforcement.
Because the density of aeroge directly affects aperture and the porosity of aeroge, by selecting different densities airsetting glue material
Material, it is possible to obtain without porosity and the aerogel material in aperture, so as to regulate and control metal and aeroge composite quality ratio and body
Product ratio, and then obtain the composite of different requirements.
In addition, some intrinsic characteristics of aeroge will also be obviously improved metallic composite performance.Such as aeroge nanoparticle
Higher wearability is shown after the high intensity and small-size effect, with metal composite of son.Alumina aerogels, zirconium oxide gas
Gel etc. can bear 1800 degree of high temperature, so the heat resistance of aeroge-metallic composite can be obviously improved.Carbon airsetting
Glue and graphene aerogel have good electric conductivity, and can put forward a step improves the electric conductivity of metallic composite.
Preparation dense structure, composite of good performance can be realized using metal liquid Infiltration Technics, is a kind of ratio
More economical complex method.But it is nonwetting between reinforcement such as carbon fiber, carbonization silica aerogel and matrix alloy such as magnesium, aluminium
Property, and the physical property and chemical property and the incompatibility of mechanical properties that often exist therebetween are all easily caused
Difficulty prepared by composite.Therefore, improve the wetability and compatibility between the reinforcement and matrix of composite, improve multiple
The interfacial structure and interfacial property of condensation material are the important topics that metal liquid infiltration prepares metal-base composites.In the present invention
Solvent infiltration, ultrasonic infiltration and electromagnetism infiltration are introduced, the wellability of molten metal and fibre-reinforced aerogel can be effectively improved.
Beneficial effect：
Compared with prior art, fibre-reinforced aerogel-metallic composite that prepared by the present invention has following significant effect.
1) aeroge skeleton forms the three-dimensional pilotaxitic texture of three-dimensional network with metal in nanoscale in the present invention, gained
Adhesion is stronger between composite each component, and aeroge, fiber, three kinds of components of metal are established one's own system and integral altogether, are one
Plant and be respectively provided with overall homogeneity advanced composite material (ACM) in microcosmic and macroscopic aspect.
2) present invention gained composite strengthens metallic composite relative to traditional fibre, with more preferable high temperature resistant
Property, wearability, crushing resistance, impact resistance, fold resistance, anti-corrosive properties etc..
3) present invention process process is simple and easy to apply, is conducive to industrialized production, can promote conventional metals based composites
The upgrading of industry.
4) present invention opens brand-new field for aerogel material, by the application of aeroge from the function material such as heat-insulation and heat-preservation
Material field is converted into the structural material field of high-strength wearable.
5) present invention gained composite is in fields such as defence and military, space flight and aviation, bullet train, wheel Ship, automobiles
There is significant application value.
Brief description of the drawings
Fig. 1 fibre-reinforced aerogel structural representations.
In Fig. 1,1 is fiber, and 2 be aeroge, and 2 be aeroge interior three-dimensional UNICOM hole.
Embodiment
A kind of specific implementation of the preparation method of the fibre-reinforced aerogel-metallic composite provided below the present invention
Mode is described in further detail.These embodiments are merely to illustrate the present invention, and not limitation of the present invention.
Embodiment 1.
According to patent CN2014102703529 method, quartz fiber felt enhancing silica aerogel plate, silica are prepared
The size of aerogel plate is 300mm*300mm*10mm, and the wherein density of silica aerogel is 110kg/m3, and average pore size is
37nm, porosity is 91%.Metal uses aluminium, metallic aluminium is heated into 780 DEG C of obtained aluminium liquids, and add 1%wt crome metal conducts
Help vadose solution agent.Combination process uses infiltration by squeeze casting technology, and glass fiber reinforcement silicon dioxide aerogel plate is laid on into envelope in advance
In the die cavity closed, locking die injects aluminium liquid, is slowly pressurized to 85MPa, extrusion speed is 1cm/s, pressurize 20min, is impregnated with increasing
Cooled and solidified after strong material, then stripping forming obtains composite.
Embodiment 2.
According to patent CN2015102953891 method, carbon fiber unidirectional cloth enhancing silica-titania aeroge is prepared
Cloth, the size of silica-titania airsetting adhesive plaster is 300mm*300mm*2mm, and the density of wherein silica aerogel is
80kg/m3, average pore size is 45nm, and porosity is 93%.Metal uses the aluminium alloy of following component：Si is that 10%, Ca is 0.5%,
Mg is 6%, and being heated to 850 DEG C turns into after aluminum alloy melt, and the nano-sized iron oxide for adding 3% does penetration-assisting agent.Combination process is used without pressure
Impregnation technology, one-way fiber fabric enhancing silica-titania airsetting adhesive plaster is laid in the die cavity of closing in advance, is passed through argon gas
Protective gas is done, aluminum alloy melt is injected, ultrasonic wave is introduced, infiltration is finished after 20 minutes, and composite is obtained after cooling.
Embodiment 3.
According to patent CN2015102953891 method, tungsten filament enhancing zirconia aerogels mat, tungsten filament enhancing oxygen are prepared
It is 200mm*200mm*1mm to change zirconium aeroge mat size, and wherein the density of zirconia aerogels is 108kg/m3, average pore size
For 32nm, porosity is 90%.Metal uses following component nickel alloy, and Ni is that 32%, Cr is 21%, is made in 1480 DEG C of smelting furnace
Obtain nickel alloy solution.Combination process uses vacuum infiltration technique, and tungsten filament enhancing zirconia aerogels mat is laid on closing in advance
In die cavity, die cavity is vacuumized, vacuum is 20 supports, keep injecting to infiltrate after nickel alloy solution, 18min after 3min finishing, cool down
Composite is obtained afterwards.
Embodiment 4.
According to patent CB2012104041035 method, silicon carbide fiber reinforced silicon carbide aerogel plate, carborundum are prepared
Silicon carbide fiber reinforced aerogel plate size is 200mm*200mm*5mm, wherein the density of carbonization silica aerogel is 210kg/m3,
Average pore size is 55nm, and porosity is 87%.Metal uses following component titanium alloy, and titanium is that 91%, Cr is that 4%, Al is 5%,
Titanium alloy liquid is made in 1710 DEG C of smelting furnace.Combination process uses vacuum pressure infiltration technology, silicon carbide fiber reinforced silicon carbide
Aerogel plate is laid in the die cavity of closing in advance, and die cavity is vacuumized, and vacuum is 20 supports, and nickel alloy is injected after keeping 3min
Liquid, backward nickel alloy solution plus-pressure 7Mpa, 20min after infiltrate and finish, after cooling composite.
1 fibre-reinforced aerogel of table-metallic composite test data
| Sequence number | Compression strength/Mpa | Hardness/HV |
| Embodiment 1 | 508 | 201 |
| Embodiment 1 is contrasted | 462 | 182 |
| Embodiment 2 | 580 | 215 |
| Embodiment 2 is contrasted | 520 | 195 |
| Embodiment 3 | 1230 | 840 |
| Embodiment 3 is contrasted | 1100 | 772 |
| Embodiment 4 | 2104 | 406 |
| Embodiment 4 is contrasted | 1975 | 361 |
Note：Comparative run is using composite obtained by similar fiber type and metal and same combination process.
Above-described embodiment is only used for illustrating the inventive concept of the present invention, rather than the restriction to rights protection of the present invention,
Any simple modification, equivalent variations and modification that every technology and method according to the present invention is substantially made to above example,
Still fall within the present invention technology and method scheme in the range of.
Claims (10)
1. a kind of fibre-reinforced aerogel-metallic composite, it is characterized in that, the composite is with fibre-reinforced aeroge
For strengthening material, using metal as matrix, metal is filled with the three-D nano hole structure of aeroge, metal and aeroge is formed
The composite that three-dimensional network interweaves.
2. composite according to claim 1, it is characterized in that, described fibre-reinforced aerogel, including airsetting adhesive plaster, gas
It is one or more of in gel paper, aerogel blanket, aerogel plate and aeroge shaped piece.
3. composite according to claim 1, it is characterized in that, described aeroge, density is 3 ~ 600kg/m3, average hole
Footpath is 2 ~ 100nm, and porosity is 50% ~ 99%.
4. composite according to claim 1, it is characterized in that, described aeroge includes silica aerogel, aluminum oxide
Aeroge, zirconia aerogels, titania aerogel, magnesia aeroge, cupric oxide aeroge, iron oxide aeroge, oxidation
Cobalt aeroge, nickel oxide aeroge, manganese oxide aeroge, zinc oxide aeroge, tin oxide aeroge, cadmium oxide aeroge, oxygen
Change chromium aeroge, niobium oxide aeroge, tantalum oxide aeroge, cerium oxide aeroge, vanadium oxide aeroge, molybdenum oxide aeroge,
Tungsten oxide aeroge, hafnium oxide aeroge, thorium oxide aeroge, beryllium oxide aeroge, yittrium oxide aeroge, scandium oxide airsetting
Glue, cerium oxide aeroge, strontium oxide strontia aeroge, indium oxide aeroge, gallium oxide aeroge, bismuth oxide aeroge, lanthana gas
Gel, ytterbium oxide aeroge, europium oxide aeroge, neodymia aeroge, terbium oxide aeroge, praseodymium oxide aeroge, samarium oxide
It is one or more of in aeroge carbonization silica aerogel, nitridation silica aerogel, carbon aerogels, graphene aerogel.
5. composite according to claim 1, it is characterized in that, described fiber, its component includes quartz fibre, high silica
Fiber, alumina fibre, alumina silicate fibre, mullite fiber, silicon carbide fibre, boron carbide fibre, silicon nitride fiber, boron nitride
It is one or more of in fiber, titanium nitride fiber, boron fibre, carbon fiber, CNT, tungsten filament, molybdenum filament, thorium silk.
6. composite according to claim 1, it is characterized in that, described fiber, its form include whisker, chopped strand,
Continuous fiber, one-way fiber fabric, two-dimensional fiber woven cloth, three-dimensional fiber woven cloth, fiber non-woven, fibrofelt, fiberboard,
It is one or more of in fiber honeycomb plate, fiber shaped piece.
7. composite according to claim 1, it is characterized in that, described metal include aluminium, copper, magnesium, titanium, zinc, tin, iron,
It is one or more of in silver, nickel, beryllium, cobalt, lead, chromium, tungsten, molybdenum, tantalum, niobium, cerium, zirconium, and the corresponding alloy of above-mentioned metal.
8. a kind of preparation method according to any fibre-reinforced aerogel-metallic composite of claim 1 to 7, its feature
It is that preparation process comprises the following steps：
（1）Lay fibre-reinforced aerogel；
（2）Molten metal is infiltrated up to fibre-reinforced aerogel；
（3）Composite is formed after cooling and solidifying.
9. the preparation method of composite according to claim 8, it is characterized in that, step（2）Described soaks molten metal
Fibre-reinforced aerogel is seeped into, Infiltration Technics include infiltration by squeeze casting method, gas pressure infiltration method, pressure-free impregnation method, vacuum pressure infiltration
It is one or more of in method and vacuum infiltration method.
10. the preparation method of composite according to claim 8, it is characterized in that, can take solvent infiltration, ultrasonic infiltration and
One or more in electromagnetism infiltration improve the infiltration of molten metal and fibre-reinforced aerogel.
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| CN111041426A (en) * | 2019-12-31 | 2020-04-21 | 新疆烯金石墨烯科技有限公司 | Graphene-aluminum composite material and preparation method thereof |
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| CN114716229A (en) * | 2022-04-14 | 2022-07-08 | 中国科学技术大学先进技术研究院 | Silicon carbide aerogel and preparation method thereof |
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