CN1772707A - Composite ceramic/metal core-shell microballoon and its prepn - Google Patents
Composite ceramic/metal core-shell microballoon and its prepn Download PDFInfo
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- CN1772707A CN1772707A CN 200510094459 CN200510094459A CN1772707A CN 1772707 A CN1772707 A CN 1772707A CN 200510094459 CN200510094459 CN 200510094459 CN 200510094459 A CN200510094459 A CN 200510094459A CN 1772707 A CN1772707 A CN 1772707A
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Abstract
The present invention discloses one kind of composite ceramic/metal core-shell microballoon and its preparation process. The composite ceramic/metal core-shell microballoon has ceramic powder as core and at least one layer of coating of nanometer ferromagnetic metal Fe, Co or Ni or their alloy, and may have one other insulating ceramic grain film in the surface of the metal layer or between two metal layers to form layered compound structure. It is prepared through non-homogeneous phase deposition-hot reduction process, and is used as wave absorbing material with high electromagnetic wave absorbing performance.
Description
Technical field:
The present invention relates to a kind of ceramic/metal composite materials and preparation technology thereof, refer in particular to a kind of ceramic base/ferromagnetic metal-core/shell composite structure micro-sphere material and preparation technology thereof.
Background technology:
Along with improving constantly of detection early warning system performance, the battlefield threatening environment that weaponry faces will be more abominable, and it is more and more important that stealthy technique seems in military struggle.Countries in the world, especially current military power has stronger advantage technically, successfully stealthy technique has been widely used in numerous aspects in space flight and modern armament field.Simultaneously, the develop rapidly of electronic information industry makes absorbing material break through military stealthy category, is deep into that communication is anti-interference, numerous areas such as ELECTRONIC INFORMATION SECURITY, environmental protection and physical protection.Therefore, the research that strengthens novel wave-absorbing material is all having crucial meaning and market outlook aspect the military and civilian of China.
The absorbing property of absorbing material depends on the hertzian wave loss receptivity of absorption agent, and therefore the research to absorption agent is the research emphasis of absorbing material always.Nanometer magnetic metal powder compatibility the two-fold advantage of magneticmetal and nano material, have complex permeability and complex dielectric permittivity, microwave magnetic permeability is higher, the condition that possesses a large amount of absorption electromagnetic wave energies, frequency electromagnetic waves had the excellent absorption performance, when temperature stability waits outstanding advantage, particularly particle size to be nano level well, have the nano effect that differs from conventional particle, therefore be subjected to domestic and international researchist's great attention.But research shows simultaneously, depends merely on a kind of magneticmetal absorption agent, and promptly one deck structure cartridge with a kind of magneticmetal preparation can not reach the desired multiband of modern absorbing material, wide band wave-absorbing effect.Many researchists adopt plate multilayered medium composite wave-absorbing structure, make wave-absorbing effect that certain raising arranged, but the plate multi-layer compound structure absorbing material that adopts has only when hertzian wave impinges perpendicularly on the cartridge usually, and it is best that its wave-sucking performance just can reach.Along with the variation of hertzian wave incident angle, wave-sucking performance will weaken, and multilayer dielectric structure relates to factors such as interfacial bonding strength, impedance matching again and is difficult to problems such as control, complex technical process.Simultaneously, anti-oxidant, acid and alkali-resistance ability that the nanometer magnetic metal powder exists, and powder is difficult to shortcomings such as homodisperse.
Ceramic base nanometer magnetic metal-nuclear/shell complex microsphere, promptly wrap up one or more layers magnetic metal particle film and the ball material that forms at dielectric ceramic microsphere particle surface, because the symmetry of spheroid, no matter hertzian wave is from which direction incident, all be equivalent to the surface of vertical incidence at cartridge, thereby it can be absorbed to greatest extent, overcome the shortcoming of slab construction to a certain extent.European patent 0479438A2 is a carrier with 3 μ m left and right sides glass spheres, and adopting sputtering method to plate with Ni, Al, W etc. respectively is the film (about 10nm) of depletion layer, and the volume packing fraction is 50% o'clock, and wherein the massfraction of metal loss layer is 0.01%.When the coat-thickness that adopts this spherical multilayer particle film was 2mm, in 8GHz～18GHz range of frequency, specific absorption can reach 10dB, and when thickness was 2.5mm, in 8GHz～18GHz range of frequency, specific absorption was 20dB.Chinese patent 1644546A and 1657585A also disclose a kind of barium ferrite of sol-gel method preparation that adopts respectively and have coated glass micro mist and silica powder material, this matrix material is to the purer barium ferrite broadening of absorption of electromagnetic wave frequency, electromagnetic consumable angle tangent numerical value is bigger, to the hertzian wave generation absorption effectively of corresponding frequencies.In addition, electroless plating and vapour deposition process also are the effective means of preparation core/shell composite structure microballoon.These methods are better to realizing single-layer metal package structure effect, but are difficult for realizing the structure of multilayer continuous package structure, particularly metal level and ceramic insulating layer space, and technology is complicated.Heterogeneous precipitation method tentatively proves comparatively ideal parcel means, part Study personnel had made a few thing, but because they all adopt the irregular base material of pattern as the parcel core, fail simultaneously processing condition and reactor fluid movement state are rationally controlled and can not enwrapped granule pattern and parcel thickness be controlled, thereby also can't realize evenly complete multilayer parcel.
Goal of the invention
At the deficiency that has material and technology, one of purpose of the present invention is to provide a kind of ceramic base nanometer ferromagnetic metal-core/shell composite structure micro-sphere material; Another object of the present invention is to provide a kind of method for preparing ceramic base nanometer ferromagnetic metal-core/shell composite structure microballoon.
With the spherical ceramic powder is the parcel substrate; utilize non-homogeneous phase deposition-hot reducing method to prepare pottery/nanometer ferromagnetic metal-core/shell composite structure micro-sphere material; and, will play good insulation performance and provide protection to metal level by continuing parcel one deck ceramic insulating layer on every layer of metallic granular film surface.This composite structure microballoon (particularly multilayered structure complex microsphere) is applied in the absorbing material improving the absorption of electromagnetic wave rate and the broadening absorption band of unit mass magneticmetal, avoid the easy oxidation of nanometer magnetic metal, perishable, difficult dispersive shortcoming, and utilize the little characteristics of ceramic relative density to alleviate aspects such as the quality of absorbing material and thickness will to have important meaning.
Goal of the invention of the present invention is achieved through the following technical solutions:
A kind of ceramic base/metal core-/shell composite structure micro-sphere material is characterized in that: the spherical ceramic substrate surface has wrapped up one deck Fe, Co, Ni or its alloying pellet film at least; Or between metallic particles film surface or every double layer of metal membrana granulosa, continue parcel one deck ceramic particle film and make insulation layer, used spherical ceramic substrate is pure alumina or zirconium white or glass microballon, size distribution is at 0.5～40 μ m, insulation layer ceramic particle film is a kind of in γ type aluminum oxide or the zirconium white, and the mass ratio of ceramic matrix and coated metal shell is 1: 0.01～1: 1.
The preparation method of a kind of ceramic base/metal core-/shell composite structure micro-sphere material is characterized in that:
1, with the deionized water compound concentration be 0.2～0.6M nickel metal-salt, ferrous salt, cobalt metal-salt or etc. the mixed salt solution of mol ratio and bicarbonate of ammonia or the urea precipitant solution of 0.4～1.2M, the spherical ceramic powder that in the aqueous solution of pH7.5～9.0, adds 10～30g/L, the pH value of the aqueous solution is regulated with bicarbonate of ammonia or sodium hydroxide, and add the polymeric alcohol of 2～10mL/L therein, while stirring metal salt solution and the precipitant solution feed rate with 3～8mL/min is added drop-wise in the aqueous solution continuously lentamente, on suspended particle, forms integument.
2, after solution feeds in raw material and finishes, at room temperature continue to react more than half an hour, throw out is filtered, washs, in air,, promptly obtain wrapping up the microballoon presoma in 60～80 ℃ of drying 10～12h.
3, will wrap up the microballoon presoma at N
2/ H
2N reduced 1～5 hour in 500～900 ℃ in the mixed gas
2: H
2Volume ratio be 2: 1～8: 1, H
2Flow velocity be 20～80mL/min, promptly obtain metal parcel ceramic powder nuclear/shell complex microsphere.
4, multilayer package structure microballoon is after process 1 is finished, continue to stir more than half an hour, and the aqueous solution of preparation second layer salt-exsiccated ammonium alum or zirconium oxychloride, its concentration is 0.2～0.4M, a kind of precipitant solution in bicarbonate of ammonia or the urea, its concentration are 0.2～1.6M.Repetitive process 1 continues to drip the salts solution and the precipitation agent of second layer encapsulate substances, forms second integument, and the 3rd layer, the 4th layer ... carry out in the same way, the even level of multilayer package structure microballoon integument is an insulation layer, and odd-level is a metal level.
5, after process 4 was finished, repetitive process 2,3 was finished experiment.
This patent adopts non-homogeneous phase deposition-hot reducing method at first to wrap up one or more layers metal salt precipitate presoma at the spherical ceramic powder surface; after heat treatment promptly obtain ceramic/metal core-shell composite structure microballoon; raw material sources are extensive, and processing unit is simple, are easy to large-scale production.Parcel shell composition can be wherein any one or a few such as Fe, Co, Ni or its alloy, parcel nuclear is for a kind of in ball-aluminium oxide, zirconium white or the glass microballon, can there be a kind of insulation layer of doing in γ type aluminum oxide or the zirconium white at least one layer of the parcel number of plies between metallic granular film integument surface or the metallic particles rete.By control parcel nuclear particle concentration, reactant feed rate, tensio-active agent add-on, pH value size, technological factors such as thermal treatment temp, time, atmosphere, it is even to obtain the integument particle distribution, and particle diameter is nano level composite structure microballoon.Newly-generated nano metal particles membrana granulosa or multilayer particle film, closely be coated on the spherical ceramic microsphere surface, make metallographic phase along spheroid radian uniform distribution, form zigzag arc sphere, be applied to fully to absorb electromagnetic wave energy in the absorbing material, increasing will have wave-absorbing effect better to attenuation of Electromagnetic than pure magneticmetal powder.The continuous package structure of multilayer particle symphysis can make different metal with the laminate structure uniform distribution, can utilize the difference suction ripple frequency band of different metal to widen the absorption band scope in absorbing material.And the ceramic particle rete of interlayer and surface parcel both can play the insulation layer effect, again can protective money symbolic animal of the birth year oxidized, corrosion etc.This composite structure microballoon will solve the shortcoming and defect of traditional magnetic metal radio-radar absorber as the absorption agent of absorbing material, can make full use of the absorbing property of unit mass magneticmetal again, satisfy the requirements at the higher level of novel wave-absorbing material " thin, light, wide, strong ".
Description of drawings:
Fig. 1 is Al
2O
3/ Co core/shell composite structure microballoon stereoscan photograph;
Fig. 2 is Al
2O
3/ Ni/Al
2O
3Core/shell composite structure microballoon stereoscan photograph;
Fig. 3 is Al
2O
3/ Ni/Al
2O
3Core/shell composite structure microballoon profile scanning electromicroscopic photograph;
Fig. 4 is Al
2O
3/ Ni/Al
2O
3Core/shell composite structure microballoon core energy spectrogram;
Fig. 5 is Al
2O
3/ Ni/Al
2O
3Core/shell composite structure microballoon middle layer energy spectrogram;
Fig. 6 is Al
2O
3/ Ni/Al
2O
3Core/shell composite structure microballoon outermost layer energy spectrogram;
Fig. 7 is Al
2O
3/ FeNi core/shell composite structure microballoon stereoscan photograph;
Fig. 8 Al
2O
3/ FeCo/ZrO
2Core/shell composite structure microballoon stereoscan photograph;
Fig. 9 is Al
2O
3/ FeCoNi core/shell composite structure microballoon stereoscan photograph;
Figure 10 is Al
2O
3/ FeCoNi core/shell composite structure microsphere surface structure stereoscan photograph;
Figure 11 is glass microballon/FeNi/Al
2O
3/ Ni/Al
2O
3/ Fe/Al
2O
3Multilayer core/shell composite structure microballoon stereoscan photograph;
Embodiment one: 1: 0.01 ball-aluminium oxide of nuclear/shell mass ratio substrate/cobalt metal complex microsphere
At first prepare the cobalt sulfate solution A of 45mL 0.2M and the urea soln B of 0.2M respectively with deionized water.To pH value is to add the α-Al of 10g/L size distribution at 1～10 μ m among 7.5 the 5L aqueous solution C
2O
3The molecular weight of powder 50g and 3mL/L is 400 polyoxyethylene glycol 15mL, and the feed rate with 3mL/min under mechanical stirring is added drop-wise to A and B in the mother solution C continuously slowly, and following reaction takes place in suspension:
In order to reduce the loss of cobalt salt as far as possible, control solution pH value is 7.5, behind reinforced the finishing, at room temperature continues reaction half an hour, filter, washing is more than three times, in air 80 ℃ dry 10 hours down, promptly obtain cobaltous hydroxide parcel α-Al
2O
3Composite micro-powder.With composite granule at N
2/ H
2Promptly obtained α-Al in 1 hour in 500 ℃ of reduction in the mixed gas
2O
3/ Co core/shell composite structure microballoon, N
2/ H
2Volume ratio is 8: 1, H
2Flow velocity be 50mL/min, the pattern of prepared complex microsphere is as shown in Figure 1.
Embodiment two: nuclear/shell mass ratio is ball-aluminium oxide substrate/nickel complex microsphere of 1: 0.1
At first prepare the nickel sulfate solution A of 170mL 0.5M and the ammonium bicarbonate soln B of 1.0M respectively with deionized water.Same is the aluminum ammonium sulfate solution 500mL of 0.3M with the deionized water compound concentration, is designated as the ammonium bicarbonate soln 500mL of C and 1.2M, is designated as D.To pH value is to add the α-Al of 20g/L size distribution at 10～40 μ m among 8 the 5L aqueous solution E
2O
3Powder 100g and 5mL/L molecular weight are 300 polyoxyethylene glycol 25mL, and the feed rate with 5mL/min under mechanical stirring is added drop-wise to A and B among the mother liquor E continuously slowly, and following reaction takes place in suspension:
In order to reduce the loss of nickel salt as far as possible, control solution pH value is 8, behind reinforced the finishing, at room temperature continue to react half an hour, throw out is static, removing top section clear liquid to mother liquor volume is 5L, and continuation feed rate with 5mL/min under mechanical stirring is added drop-wise to C and D in the mother liquor continuously slowly, and reacts
After reaction finishes, continue to stir half an hour, filter, washing is more than three times, in air 60 ℃ dry 12 hours down, promptly obtain Aluminum Carbonate Basic ammonium/basic nickel carbonate parcel α-Al
2O
3Composite micro-powder.With composite granule at N
2/ H
2Hour promptly obtain α-Al in 500 ℃ of reductase 12s in the mixed gas
2O
3/ Ni/ γ-Al
2O
3Composite micro-powder, N
2/ H
2Be volume ratio 4: 1, H
2Flow velocity be 20mL/min, prepared complex microsphere pattern as shown in Figure 2, section and different sites composition such as Fig. 3, Fig. 4, Fig. 5, shown in Figure 6.
Embodiment three: at the bottom of 1: 0.5 the zirconia base of nuclear/shell mass ratio/and the iron-nickel alloy complex microsphere
At first be the ammonium bicarbonate soln B 2.6L of nickelous chloride, 1: 1 mixed solution A 2.6L of iron protochloride mol ratio and the 1.0M of 0.5M with deionized water preparing metal ionic concn.In the 10L of pH8.5 aqueous solution C, add the 15g/L size distribution at the spherical zirconia powder 150g of 1～20 μ m and the polyvinyl alcohol 50mL of 5mL/L, feed rate with 8mL/min under mechanical stirring is added drop-wise in the mother solution C solution A and B continuously lentamente, generating polynomial in suspension (1) and formula (2) wherein, the conversion of iron protocarbonate very fast generating polynomial again (3) in air that formula (2) generates forms hydrous iron oxide.
In order to reduce the loss of metal-salt as far as possible, control pH value of solution value is about 8.5.After solution feeds in raw material and finishes, at room temperature continue to react half an hour, throw out is filtered, washs, 80 ℃ of dry 12h promptly obtain wrapping up the microballoon presoma in a vacuum.To wrap up the microballoon presoma at N
2/ H
2Promptly obtain ZrO in 720 ℃ of reductase 12 h in the mixed gas
2/ FeNi composite structure microballoon, N
2/ H
2Volume ratio 2: 1, H
2Flow velocity be 80mL/min, prepared complex microsphere pattern is as shown in Figure 7
Embodiment four: 1: 1 alumina substrate/ferrocobalt complex microsphere of nuclear/shell mass ratio
Be the ferrous sulfate of 0.6M and the ammonium bicarbonate soln B2.16L of 1: 1 mixed solution A 2.16L of Xiao Suangu mol ratio and 1.2M at first with deionized water preparing metal ionic concn.Same is the zirconium oxychloride liquid 500mL of 0.2M with the deionized water compound concentration, is designated as the urea soln 500mL of C and 0.2M, is designated as D.In the aqueous solution E of PH9, add the spherical α-Al of 15g/L size distribution at 10～40 μ m
2O
3The molecular weight of powder 75g and 2mL/L is 600 polyoxyethylene glycol 10mL, the aqueous solution is regulated with sodium hydroxide, volume 5L, feed rate with 5mL/min under mechanical stirring is added drop-wise to solution A and B among the mother liquor E continuously lentamente, generating polynomial in suspension (1) and formula (3) reaction, wherein, the conversion of iron protocarbonate very fast generating polynomial again (2) in air of formula (1) generation forms hydrous iron oxide.
In order to reduce the loss of metal-salt as far as possible, control pH value of solution value is about 9.After solution feeds in raw material and finishes, at room temperature continue to react half an hour, throw out is static, and removing top section clear liquid to mother liquor volume is 5L, and continuation feed rate with 5mL/min under mechanical stirring is added drop-wise to C and D in the mother liquor continuously slowly, and reacts:
Throw out is filtered, washs, in air,, promptly obtain wrapping up the microballoon presoma in 60 ℃ of dry 12h.To wrap up the microballoon presoma at N
2/ H
2(volume ratio 4: 1, H
2Flow velocity be 80mL/min) promptly obtain α-Al in 600 ℃ of reduction 4h in the mixed gas
2O
3/ FeCo/ZrO
2The composite structure microballoon.Prepared composite structure microballoon pattern as shown in Figure 8.
Embodiment five: 1: 0.3 alumina substrate/iron cobalt nickel alloy complex microsphere of nuclear/shell mass ratio
At first be the ammonium bicarbonate soln B778mL of nickelous nitrate, ferrous sulfate and 1: 1: 1 mixed solution A 778mL of Xiao Suangu mol ratio and the 1.0M of 0.5M with deionized water preparing metal ionic concn.In the aqueous solution C of pH7.5～8, add the spherical α-Al of 15g/L size distribution at 10～40 μ m
2O
3Powder 75g and 5mL/L molecular weight are 400 polyoxyethylene glycol 25mL, the aqueous solution is regulated pH value with bicarbonate of ammonia, volume 5L, feed rate with 5mL/min under induction stirring is added drop-wise in the mother solution C solution A and B continuously lentamente, generating polynomial in suspension (1), formula (2) and formula (4) reaction, wherein, the conversion of iron protocarbonate very fast generating polynomial again (3) in air of formula (2) generation forms hydrous iron oxide.
In order to reduce the loss of metal-salt as far as possible, control pH value of solution value is about 8.After solution feeds in raw material and finishes, at room temperature continue to react half an hour, throw out is filtered, repeatedly washs, in air,, promptly obtain wrapping up the microballoon presoma in 80 ℃ of dry 10h.To wrap up the microballoon presoma at N
2/ H
2Promptly obtain α-Al in 720 ℃ of reductase 12 h in the mixed gas
2O
3/ FeCoNi composite structure microballoon, N
2/ H
2Volume ratio is 4: 1, H
2Flow velocity be 80mL/min, complex microsphere pattern and surface tissue such as accompanying drawing 9 and shown in Figure 10.
Embodiment six: nuclear/single-layer metal shell mass ratio is glass microballon/FeNi/ γ-Al of 1: 0.05
2O
3/ Ni/ γ-Al
2O
3/ Fe/ γ-Al
2O
3The multi-layer compound structure microballoon
(1) with deionized water respectively compound concentration be single nickel salt, ferrous sulfate and 1: 1 single nickel salt of mol ratio and each 500mL of ferrous sulfate mixing solutions of 0.3M, be labeled as A, B, C, and the ammonium bicarbonate soln 1500mL of 0.6M, be designated as D.Same is the aluminum ammonium sulfate solution 1500mL of 0.4M with the deionized water compound concentration, is designated as the ammonium bicarbonate soln 1500mL of E and 1.6M, is designated as F.
(2) in the aqueous solution G of pH8, add the 30g/L size distribution at the poly-propyl alcohol 80mL of the molecular weight 300 of the spherical glass microballon powder 240g of 0.5～10 μ m and 10mL/L as mother liquor, regulate the pH value with bicarbonate of ammonia and remain on about 8, the mother liquor volume is 8L in the reactor.
(3) feed rate with 5mL/min is added drop-wise to solution C and D among the mother liquor G continuously lentamente under mechanical stirring, while generating polynomial (1) and formula (2) reaction form basic nickel carbonate and iron protocarbonate mixture precipitation in suspension, wherein, the conversion of iron protocarbonate very fast generating polynomial again (3) in air of formula (2) generation forms the hydrous iron oxide precipitation.
(4) after reinforced the finishing, at room temperature continue reaction half an hour,, take out the top section clear liquid, obtain mother liquor 2, be designated as H to 8L with suspension static half an hour.
(5) feed rate with 5mL/min is added drop-wise to each 500mL solution E and F among the mother liquor H simultaneously continuously lentamente under mechanical stirring, and generating polynomial in suspension (4) generates Aluminum Carbonate Basic ammonium precipitation.
(6) after process (5) is finished, repeat (4) and obtain mother liquor 3, be designated as I.
(7) feed rate with 5mL/min is added drop-wise to solution A and D among the mother liquor I by volume pump simultaneously continuously lentamente under mechanical stirring, and react (1) generates the basic nickel carbonate precipitation.
(8) repetitive process (5) and (4) obtain mother liquor 4, are designated as J.
(9) feed rate with 5mL/min is added drop-wise to solution B and D among the mother liquor J by volume pump simultaneously continuously lentamente under mechanical stirring, and generating polynomial in suspension (2) (3) generates the hydrous iron oxide precipitation.
(10) repetitive process (5) continues to stir half an hour after reaction finishes, and the throw out filtration washing more than three times, in 80 ℃ of dry 12h, is promptly obtained multilayer package structure microballoon presoma in air.
(11) will wrap up the microballoon presoma at N
2/ H
2Promptly obtained glass microballon/FeNi/ γ-Al in 5 hours in 900 ℃ of reduction in the mixed gas
2O
3/ Ni/ γ-Al
2O
3/ Fe/ γ-Al
2O
3The multi-layer compound structure microballoon, N
2/ H
2Volume ratio is 2: 1, H
2Flow velocity be 60mL/min, composite structure microballoon pattern is as shown in Figure 11.
Fig. 1, Fig. 2, Fig. 7, Fig. 8, Fig. 9, Figure 11 are respectively Al
2O
3/ Co, Al
2O
3/ Ni/Al
2O
3, Al
2O
3/ FeNi, Al
2O
3/ FeCo/ZrO
2, Al
2O
3/ FeCoNi and glass microballon/FeNi/Al
2O
3/ Ni/Al
2O
3/ Fe/Al
2O
3The stereoscan photograph of multi-layer compound structure microballoon, by photo as can be seen: composite particles has kept the spherical morphology of base material substantially, and integument is than even compact, cracking occurs, comes off and defective such as irregular reunion.Fig. 3 is Al
2O
3/ Ni/Al
2O
3The sectional view of composite structure microballoon, Fig. 4,5,6 is respectively the energy spectrogram of Fig. 3 different sites, as seen: composite particles is divided into the spherical substrate of aluminum oxide, intermediate metal nickel dam and external oxidation aluminum insulation layer, presents tangible core/shell structure.Figure 10 is Al
2O
3/ FeCoNi composite structure microsphere surface structure scanning spot mirror photo, as seen, the metallic granular film particle of surperficial integument is evenly distributed between 50～80nm, belongs to a kind of nano-metal particle film.
Claims (5)
1, a kind of ceramic base/metal-core/shell composite structure micro-sphere material is characterized in that: the spherical ceramic substrate surface has wrapped up one deck Fe, Co, Ni or its alloying pellet film at least; Or between metallic particles film surface or every double layer of metal membrana granulosa, continue parcel one deck ceramic particle film and make insulation layer, used spherical ceramic substrate is pure alumina or zirconium white or glass microballon, size distribution is at 0.5～40 μ m, insulation layer ceramic particle film is a kind of in γ type aluminum oxide or the zirconium white, and the mass ratio of ceramic matrix and coated metal shell is 1: 0.01～1: 1.
2, the preparation method of a kind of ceramic base/metal-core/shell composite structure micro-sphere material is characterized in that:
(1) with the deionized water compound concentration be 0.2～0.6M nickel metal-salt, ferrous salt, cobalt metal-salt or etc. the mixed salt solution of mol ratio and bicarbonate of ammonia or the urea precipitant solution of 0.4～1.2M, the spherical ceramic powder that in the aqueous solution of pH7.5～9.0, adds 10～30g/L, and add the polymeric alcohol of 2～10mL/L therein, while stirring metal salt solution and the precipitant solution feed rate with 3～8mL/min is added drop-wise in the aqueous solution, on suspended particle, forms integument;
(2) after solution feeds in raw material and finishes, at room temperature continue to react more than half an hour, throw out is filtered, washs, in air,, promptly obtain wrapping up the microballoon presoma in 60～80 ℃ of drying 10～12h;
(3) will wrap up the microballoon presoma at N
2/ H
2N reduced 1～5 hour in 500～900 ℃ in the mixed gas
2: H
2Volume ratio be 2: 1～8: 1, H
2Flow velocity be 20～80mL/min, promptly obtain metal parcel ceramic powder complex microsphere.
3, the preparation method of a kind of ceramic base/metal according to claim 2-core/shell composite structure micro-sphere material, it is characterized in that: multilayer package structure microballoon is after the process described in the claim 21 is finished, continue to stir more than half an hour, and the aqueous solution of preparation second layer salt-exsiccated ammonium alum or zirconium oxychloride, its concentration is 0.2～0.4M, a kind of precipitant solution in bicarbonate of ammonia or the urea, its concentration is 0.2～1.6M, repetitive process 1 continues to drip the salts solution and the precipitation agent of second layer encapsulate substances, forms second integument; The 3rd layer, the 4th layer ... carry out in the same way, repeat the described process 2,3 of claim 2 again, finish experiment.
4, the preparation method of a kind of ceramic base/metal according to claim 3-core/shell composite structure micro-sphere material is characterized in that: the even level of multilayer package structure microballoon integument is an insulation layer, and odd-level is a metal level.
5, the preparation method of a kind of ceramic base/metal according to claim 2-core/shell composite structure micro-sphere material is characterized in that: the pH value of the aqueous solution is regulated with bicarbonate of ammonia or sodium hydroxide.
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