CN103831436B - The preparation method of nucleocapsid structure Cu/BaTiO3 composite granule - Google Patents
The preparation method of nucleocapsid structure Cu/BaTiO3 composite granule Download PDFInfo
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- CN103831436B CN103831436B CN201410106066.9A CN201410106066A CN103831436B CN 103831436 B CN103831436 B CN 103831436B CN 201410106066 A CN201410106066 A CN 201410106066A CN 103831436 B CN103831436 B CN 103831436B
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Abstract
The invention discloses a kind of nucleocapsid structure Cu/BaTiO
3the preparation method of composite granule, described powder is for internal layer nuclear material, BaTiO with Cu powder
3for the spheric granules of outer shell material, employing hydro-thermal method is prepared, controlling hydrothermal temperature is 180 DEG C ~ 200 DEG C, and the reaction time is 21 ~ 24 hours, and the mol ratio of each material addition is barium acetate: butyl titanate: KOH:Cu=1.2:1.0:20.0:2.9 ~ 4.0.The feature of the method is at Hydrothermal Synthesis BaTiO
3process in the ultra-fine Cu powder of access control amount, achieve BaTiO
3in formation and the growth on ultra-fine Cu powder surface, obtain with Cu powder for internal layer nuclear material, BaTiO
3for the Cu/BaTiO of outer shell material
3nucleocapsid structure composite granule.This synthetic method craft step is simple, and the combined coefficient of product is high, and production cost is low.
Description
Technical field
The present invention relates to a kind of composite granule and preparation method thereof, particularly a kind of its preparation method with the metal/ceramic composite granule of nucleocapsid structure.
Background technology
The composite of nucleocapsid structure is with its distinctive composition structure and scale effect, and distinctive sound, optical, electrical, hot and physicochemical property, to receive the extensive concern of each field scholar in recent years.Composite material of core-shell structure forms with the Shell Materials be coated on outside core material by being positioned at inner core material usually.Compared with the material system of single composition, nucleocapsid structure system is due to special material composition and geometry, and the regulation and control that can realize integral material physics and chemical property by the means such as chemical synthesis, therefore have application prospect very widely.
In the past in more than ten years research process, researcher is by various physical chemistry means preparation and synthesized multiple ultra-fine and micron level, and there is the composite material of core-shell structure of particular geometric configuration, physical property and surface characteristics, and be widely used in the numerous areas such as functional paint, chemical catalysis, element sepatation, medical diagnosis.By the setting to material composition and geometry, can realize regulating and controlling the orientation of each side character such as Core-shell structure material mechanical strength, optical property, magnetic performance, electric property.By setting and process the functionalization of Shell Materials, directionally can modify the surface charge of integral material, surface-catalyzed reactions is active, and significantly can strengthen dispersion and the stability of particle., can play a very good protection to the core material of inside particles, not by the impact of extraneous physicochemical environment meanwhile.As at gold particle Surface coating SiO
2functional layer, not only can protect inner gold particle but also can control overall optical property.At magnetic core outer cladding SiO
2functional layer, effectively can improve the stability of magnetic fluid.At hydroxyapatite surface coated Si O
2functional layer effectively can improve biocompatibility.In addition, at a-Fe
2o
3surface coating TiO
2functional layer, while playing a protective role, also improves the absorbability of powder at visible region.
Summary of the invention
The object of the present invention is to provide a kind of nucleocapsid structure Cu/BaTiO
3composite granule and be there is by hydrothermal method one-step synthesis the Cu/BaTiO of nucleocapsid structure
3the method of composite granule.The feature of the method is at Hydrothermal Synthesis BaTiO
3process in the ultra-fine Cu powder of access control amount, achieve BaTiO
3in formation and the growth on ultra-fine Cu powder surface, obtain with Cu powder for internal layer nuclear material, BaTiO
3for the Cu/BaTiO of outer shell material
3nucleocapsid structure composite granule.This synthetic method craft step is simple, and the combined coefficient of product is high, and production cost is low.
The object of the invention is to be achieved through the following technical solutions:
A kind of nucleocapsid structure Cu/BaTiO
3composite granule, with Cu powder for internal layer nuclear material, BaTiO
3for outer shell material.
A kind of Cu/BaTiO by hydrothermal method one-step synthesis with nucleocapsid structure
3the method of composite granule, its step is as follows:
(1) KOH taking certain mass is dissolved in distilled water, under stirring, a certain amount of butyl titanate is slowly added drop-wise in KOH solution, then adds the barium acetate of certain mass, be stirred to dissolving, add a certain amount of ultra-fine Cu powder again, obtain mixed solution.
(2) in the mixed solution of step (1), a certain amount of KOH is added again, Keep agitation 20 ~ 40min.
(3) sample step (2) obtained loads in high pressure water heating kettle, carries out hydro-thermal reaction.
(4) after reaction terminates, the sample in water heating kettle is taken out, by acetic acid adjust ph to neutral, then wash.
(5) by step (4) gained sample drying, namely Cu/BaTiO is obtained
3nucleocapsid structure composite granule.
In the present invention, described ultra-fine Cu powder is prepared by hydro-thermal method.
In the present invention, the temperature of described hydro-thermal reaction is 180 ~ 200 DEG C, 21 ~ 24 hours time.
In the present invention, the mol ratio of described each material addition is: barium acetate: butyl titanate: KOH: Cu=1.2: 1.0: 20.0: 2.9 ~ 4.0.
In the present invention, described Cu/BaTiO
3composite granule is spheric granules, granularity 15 ~ 25 μm.
In the present invention, described baking temperature is 100 DEG C, and the time is 18 ~ 24h.
Cu superfine powder has lower room temperature resistivity, be the more satisfactory conductive powder body of electric property, but its chemical stability is not high, burn into oxidation easily occurs and lost efficacy.Therefore the present invention is by forming the higher BaTiO of chemical stability on its surface
3ceramic layer, obtains the Cu/BaTiO with nucleocapsid structure
3composite granule, to strengthen its chemical stability.
Cu/BaTiO prepared by the present invention
3composite granule has following characteristics:
(1) resistivity of Cu powder prepared by the present invention is 6.0 × 10
-6~ 9.0 × 10
-6within the scope of Ω m, and through BaTiO
3cu/BaTiO after Surface coating
3the resistivity of composite granule is 7.0 × 10
7~ 1.0 × 10
8within the scope of Ω m, illustrate that copper powder is all coated on core, skin is BaTiO
3, by BaTiO
3composition design feature determine anti-oxidant, anticorrosion and the long-time stability on composite granule surface.Cu/BaTiO of the present invention
3the metal material that composite granule internal layer is good conductivity, cost is low, skin is anti-oxidant, etch-proof ceramic material, has had the electric conductivity of metal and the stability of pottery concurrently.
(2) Cu/BaTiO
3composite granule belongs to low, the eco-friendly new material of energy consumption, compared with the composite granule of some other types in studying at present, has price advantage.
(3) Cu/BaTiO
3composite powder has a extensive future, and can obtain composite conductive powder, can be applicable to the fields such as electronic apparatus, Aero-Space, military affairs, railway, communication, electric power to its further modification.Such as, technology (ZL 201110089175.0 is oozed by the expansion of rare earth gas chemistry heat; ZL 201110347307.5) surperficial BaTiO to this composite granule
3ceramic layer carries out modification, significantly can promote the electric conductivity of this ceramic layer, because penetration modification carries out for powder top layer, ultra-fine Cu phase its performance unaffected of composite granule inside is stablized, and can obtain the rare earth modified Cu/BaTiO with nucleocapsid structure that electric conductivity is excellent
3conductive powder body.
Accompanying drawing explanation
The SEM figure of Fig. 1 ultra-fine Cu powder prepared by the embodiment of the present invention 1.
Fig. 2 is Cu/BaTiO prepared by the embodiment of the present invention 2
3the XRD figure of composite granule.
Fig. 3 is Cu/BaTiO prepared by the embodiment of the present invention 2
3the SEM figure of composite granule.
Fig. 4 is nucleocapsid structure Cu/BaTiO prepared by the embodiment of the present invention 3
3the SEM figure of composite granule.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
The preparation of superfine cupper powder, concrete grammar is: take 3.12g CuSO in experiment
45H
2o and 2.80g KOH is dissolved in 40mL deionized water, adds 3.00g sorbierite and makes reducing agent, at room temperature after magnetic agitation 20 ~ 30min, is moved into by gained solution in the polytetrafluoroethylene (PTFE) reactor of 50mL, in 180 DEG C of reaction 18h after sealing.Filter after taking-up is cooled to room temperature, wash and use BaCl
2solution inspection, without white precipitate, in 80 DEG C of dryings, namely obtains superfine cupper powder.
As shown in Figure 1, the superfine cupper powder synthesized by the present embodiment is comparatively uniform acicular texture, and resistivity is 6.12 × 10
-6Ω m.
Embodiment 2:
Take 2.80g KOH and be dissolved in 33.2ml water, under stirring, 6.80g butyl titanate is slowly added drop-wise in KOH solution.Add 6.13g barium acetate, be stirred to dissolving, then add 3.75gCu powder.KOH 19.60g is added, Keep agitation 30min under strong agitation.Sample is loaded reactor, in 180 DEG C of reaction 24h.Sample in water heating kettle is taken out and puts into beaker, by acetic acid adjust ph to neutral.Then wash once with distillation, ethanol washes twice.Sample is put into drying box dry 18h under 100 DEG C of conditions, namely obtain Cu/BaTiO
3nucleocapsid structure composite granule, its resistivity is 7.1 × 10
7Ω m.
In the present embodiment, barium acetate: butyl titanate: KOH: Cu=1.2: 1.0: 20.0: 2.9.
The XRD test result of powder prepared by the present embodiment as shown in Figure 2.As can be seen from Figure 2, Emission in Cubic BaTiO is presented in XRD spectra
3the diffraction maximum of crystal diffraction peak and Cu, illustrates Cu/BaTiO
3composite granule synthesizes.
The SEM characterization result of the prepared powder of this enforcement as shown in Figure 3.As can be seen from Figure 3, synthesized composite granule is spherical, and particle diameter is greatly about 20 μm.
Embodiment 3:
Take 2.80g KOH and be dissolved in 33.2ml water, under stirring, 6.80g butyl titanate is slowly added drop-wise in KOH solution.Add 6.13g barium acetate, be stirred to dissolving, then add 5.00gCu powder.KOH 19.60g is added, Keep agitation 30min under strong agitation.Sample is loaded reactor, in 200 DEG C of reaction 21h.Sample in water heating kettle is taken out and puts into beaker, by acetic acid adjust ph to neutral.Then wash once with distillation, ethanol washes twice.Sample is put into drying box dry 18h under 100 DEG C of conditions, namely obtain Cu/BaTiO
3nucleocapsid structure composite granule, its resistivity is 8.9 × 10
7Ω m.
In the present embodiment, barium acetate: butyl titanate: KOH: Cu=1.2: 1.0: 20.0: 3.9.
Similar Fig. 2 of the XRD spectra of powder prepared by the present embodiment, its pattern is also spheric granules similar to Figure 3.
Fig. 4 illustrates the Cu/BaTiO that spherical shell breaks
3the SEM photo of powder, the particle diameter of synthesized powder is about 18 ~ 24 μm as can be seen from Figure 4, and inside is full of the ultra-fine Cu powder of needle-like, and external shell structure is the BaTiO that compact arranged thickness is about 1 μm
3powder.Respectively EDS analysis is carried out to the position of core and shell simultaneously, confirmed that the main component at outer shell layer position is BaTiO
3, its content is for reaching 89.91Wt%; And the main component at inner layer core position is Cu, its content is for reaching 92.44Wt%.Explanation the method can obtain with Cu powder for inner layer core material, with BaTiO
3for the Cu/BaTiO of outer shell layer material
3nucleocapsid structure composite granule.
Cu/BaTiO is obtained to the present embodiment
3composite powder carries out rare-earth penetration, can obtain composite conductive powder, can be used as the preparation that conductive filler is applied to conducting resinl, electrically-conducting paint, and the field such as electronic apparatus, Aero-Space, military affairs, railway, communication, electric power.Specific experiment process is as follows: take 20g LaCl
36H
2o is dissolved in 500ml methyl alcohol, expands and ooze 4h at 900 DEG C.Expand and ooze rear powder still for having the spheric granules of obvious nucleocapsid structure, resistivity reaches 2.8 Ω m.
Claims (7)
1. nucleocapsid structure Cu/BaTiO
3the preparation method of composite granule, powder is for internal layer nuclear material, BaTiO with Cu powder
3for the spheric granules of outer shell material, it is characterized in that described method adopts hydro-thermal method preparation to have the Cu/BaTiO of nucleocapsid structure
3spheric granules, with Cu powder for inner layer material, BaTiO
3for cladding material, hydrothermal temperature is 180 ~ 200 DEG C, and the reaction time is 21 ~ 24 hours.
2. nucleocapsid structure Cu/BaTiO according to claim 1
3the preparation method of composite granule, is characterized in that described method concrete steps are as follows:
(1) KOH taking certain mass is dissolved in distilled water, under stirring, a certain amount of butyl titanate is slowly added drop-wise in KOH solution, then adds the barium acetate of certain mass, be stirred to dissolving, add a certain amount of ultra-fine Cu powder again, obtain mixed solution;
(2) in the mixed solution of step (1), a certain amount of KOH is added again, Keep agitation 20 ~ 40min, in mixed solution, the mol ratio of each material addition is barium acetate: butyl titanate: KOH: Cu=1.2: 1.0: 20.0: 2.9 ~ 4.0;
(3) sample step (2) obtained loads in high pressure water heating kettle, carries out hydro-thermal reaction, and the temperature controlling hydro-thermal reaction is 180 ~ 200 DEG C, 21 ~ 24 hours time;
(4) after reaction terminates, taken out by the sample in water heating kettle, adjust ph, to neutral, is then washed;
(5) by step (4) gained sample drying, namely Cu/BaTiO is obtained
3nucleocapsid structure composite granule.
3. nucleocapsid structure Cu/BaTiO according to claim 2
3the preparation method of composite granule, is characterized in that, in described step (1), ultra-fine Cu powder is prepared by hydro-thermal method.
4. nucleocapsid structure Cu/BaTiO according to claim 2
3the preparation method of composite granule, it is characterized in that, in described step (5), baking temperature is 100 DEG C, the time is 18 ~ 24h.
5. nucleocapsid structure Cu/BaTiO according to claim 2
3the preparation method of composite granule, is characterized in that described barium acetate: butyl titanate: KOH: Cu=1.2: 1.0: 20.0: 2.9.
6. nucleocapsid structure Cu/BaTiO according to claim 2
3the preparation method of composite granule, is characterized in that described barium acetate: butyl titanate: KOH: Cu=1.2: 1.0: 20.0: 3.9.
7. nucleocapsid structure Cu/BaTiO according to claim 1 and 2
3the preparation method of composite granule, is characterized in that described Cu/BaTiO
3the granularity of composite granule is 15 ~ 25 μm.
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