CN101113011B - Method for preparing nanometer-grade spherical YAG powder - Google Patents

Abstract

The invention discloses a method to produce nanometer grade spherical yttrium aluminum garnet powder which pertains to the preparation field of inorganic powder. The invention adopts micro-emulsion system of water in oil structure, which means to solubilize oil phase transparent solution that contains oil phase material, surfactant and cosurfactant and water phase liquid that contains reactant solution and precipitant solution according to the volume ratio 2-10:1 or weight ratio 1-5:1 to react and generate the precipitate of single particle spherical aluminum and yttrium uniform heterocaryon; the precipitate is extracted to be cleaned, filtrated, dried and calcined to get pure phase spherical YAG powder with excellent dispersion and high sintering activity. The method has simple process, low energy consumption and low cost; besides, all organic waste liquid can be recycled. Therefore, the invention has no environmental pollution and is suitable for industrial production.

Description

A kind of method that is used to prepare nanometer-grade spherical YAG powder

Technical field

The invention belongs to the preparation field of inorganic powder, particularly a kind of method that is used to prepare nanometer-grade spherical YAG powder.

Background technology

Yttrium aluminum garnet (Y ₃Al ₅O ₁₂, yttrium aluminum garnet is by Y YAG) ₂O ₃And Al ₂O ₃A kind of complex oxide that forms, belong to isometric system, have garnet structure, have optical homogeneity, the free of birefringence effect, stable chemical performance, the high-temperature creep resistance excellence is widely used laser and luminous base mateiral, and the YAG micro mist can be used for preparing the required YAG crystalline ceramics of large size high power solid state laser operation material, thereby replace the YAG monocrystal material that is difficult to produce, also can be used for preparing the YAG high-temperature structural material.Studies have shown that the YAG nano powder that preparation spheroidal particle, narrow diameter distribution, nothing are reunited helps the sintering of crystalline ceramics, therefore how to prepare the YAG nano powder that spherical no agglomerating particles is evenly distributed and caused extensive concern.Present preparation method have solid reaction process, sol-gel method, the precipitator method, hydrothermal method etc. (see document 1: Xu Guogang, Zhang Xudong, Li Hong is etc. Shandong pottery, 2005,28 (4): 15-18. and document 2: Xu Fengxiu, Li Xia, Deng. Chinese pottery industry, 2004,11 (3): 38-41.).Solid reaction process synthesis temperature height, the particle of synthetic powder is big, and it is serious to reunite, and the resultant The Nomenclature Composition and Structure of Complexes often is nonquantitative and heterogeneity; The sol-gel method craft complexity, reaction process is wayward, and the bad dispersibility of the powder of final preparation is substantially all reunited; Hydrothermal method is to conditional request strictnesses such as equipment, and the production cost height is unsuitable for batch process; Precipitator method powder dispersity is poor, and the powder reuniting problem is difficult to solve, and grain diameter is difficult to control, and size distribution is wide.

Microemulsion method is eighties of last century a kind of method for preparing nanoparticle that the eighties, new development was got up, this method is to be microreactor with the micro emulsion drop in the microemulsion system, by size and other reaction conditions of artificial control microreactor, size distribution is even to obtain, the spheroidal particle of favorable dispersity.This method that also is out of use at present prepares the YAG nano powder.

For solving the above problem that exists in the YAG powder preparing, the present invention adopts micro emulsion drop in water-in-oil (W/O) the type microemulsion system as microreactor, react by the aluminium salt of solubilising in the microreactor and the mixing solutions and the precipitation agent of yttrium salt, under lower synthesis temperature, successfully prepare the nano-level sphere YAG powder of the good pure phase of powder dispersity.

Summary of the invention

The objective of the invention is to propose a kind of method for preparing nano-level sphere YAG powder, it is characterized in that: this method adopts the microemulsion system of water-in-oil (W/O) structure, be about to comprise the oil phase transparent emulsion of oil phase substance, tensio-active agent, cosurfactant and comprise reactant solution and the aqueous phase liquid of two kinds of precipitant solution by volume 2～10: 1 or in mass ratio 1～5: 1 ratio solubilising, reaction generates the spherical aluminium of single particle and the throw out of yttrium homogeneous mixture; Extract that throw out washs, suction filtration, drying, through calcining, obtain spherical YAG powder favorable dispersity, pure phase, that sintering activity is high.

Described preparation nano-level sphere YAG powder carries out as follows:

(1) raw material that contains Al and Y is dissolved in deionized water or the acid, and in molar ratio, Al: Y=5: 3 mix, and are prepared into reactant solution A;

(2) with in ammoniacal liquor, oxalic acid, the ammonium hydrogencarbonate one or both with deionized water dilution or dissolving, thorough mixing is even, makes the precipitant solution B that concentration is 0.5～6 mol;

(3) in proportion: when tensio-active agent is TritonX-100 with oil phase substance, tensio-active agent, cosurfactant, the volume of oil phase substance is considered as 100, then according to volume ratio, oil phase substance: Triton X-100: the proportional range of cosurfactant is: 100: 47～82: 13～76.When tensio-active agent is CTAB, the quality of oil phase substance is considered as 100, then according to mass ratio, oil phase substance: Triton X-100: the proportional range of cosurfactant is: 100: 20～36: 17～29; Thorough mixing obtains transparent oil-phase solution C;

(4) with oil phase and water by volume 2～10: 1 or in mass ratio 1～5: 1 ratio is solubilizing reaction thing solution A and precipitant solution B respectively, obtains stable water-in-oil (W/O) type microemulsion D, E respectively;

(5) with microemulsion D, E thorough mixing, the precipitation that reaction generates is the spherical aluminium of single particle and the sedimentary homogeneous mixture of yttrium;

(6) above-mentioned throw out is extracted after, wash, suction filtration, drying, through 400～1600 ℃ of calcinings, calcine and obtained spherical YAG powder favorable dispersity, pure phase, that sintering activity is high in 1～6 hour.

Described oil phase substance is one or both in benzene, normal hexane, hexanaphthene, the octane.

Described tensio-active agent is a kind of among Soxylat A 25-7 Triton X-100, the hexadecyl three first class ammonia bromide CTAB.

Described cosurfactant is one or both in n-hexyl alcohol, n-propyl alcohol or the propyl carbinol.

Described water is divided into two kinds of reactant solution and precipitant solution.

The invention has the beneficial effects as follows that the present invention adopts micro emulsion drop in water-in-oil (W/O) the type microemulsion system as microreactor, react by the aluminium salt of solubilising in the microreactor and the mixing solutions and the precipitation agent of yttrium salt, under lower synthesis temperature, successfully prepare the nano-level sphere YAG powder of the finely disseminated pure phase of powder.This method technology is simple, energy consumption is low, and cost is low, non-environmental-pollution, be suitable for the preparation method of suitability for industrialized production, organic liquid waste in the production process of the present invention all can reclaim, and after organic liquid waste is reclaimed, can fractionation handle, reuse, avoid causing environmental pollution, save cost, cut down the consumption of energy.

Embodiment

The present invention proposes a kind of method for preparing nano-level sphere YAG powder.This method adopts the microemulsion system of water-in-oil (W/O) structure, be about to comprise the oil phase transparent emulsion of oil phase substance, tensio-active agent, cosurfactant and comprise reactant solution and the aqueous phase liquid of two kinds of precipitant solution by volume 2～10: 1 or in mass ratio 1～5: 1 ratio solubilising, obtain microemulsion system, with the micro emulsion drop in the microemulsion system as the nanometer microreactor, in microreactor, react, generate the spherical aluminium of single particle and the throw out of yttrium homogeneous mixture; Extract that throw out washs, suction filtration, drying, through 400～1600 ℃ of calcinings, calcine and obtained spherical YAG powder favorable dispersity, pure phase, that sintering activity is high in 1～6 hour.

This method is carried out successively as follows:

(1) raw material that contains Al and Y is dissolved in deionized water or the acid, and in molar ratio, Al: Y=5: 3 mix, and are prepared into reactant solution A;

(2) in ammoniacal liquor, oxalic acid, the ammonium hydrogencarbonate one or both are diluted with deionized water, thorough mixing is even, makes the precipitant solution B that concentration is 0.5～6.0 mol;

(3) in proportion: when tensio-active agent is TritonX-100 with oil phase substance, tensio-active agent, cosurfactant, the volume of oil phase substance is considered as 100, then according to volume ratio, oil phase substance: Triton X-100: the proportional range of cosurfactant is: 100: 47～82: 13～76.When tensio-active agent is CTAB, the quality of oil phase substance is considered as 100, then according to mass ratio, oil phase substance: Triton X-100: the proportional range of cosurfactant is: 100: 20～36: 17～29, thorough mixing obtains transparent oil-phase solution C;

(4) with oil phase and water 2～10: 1 ratio solubilizing reaction thing solution A and precipitant solution B respectively by volume, obtain stable water-in-oil (W/O) type microemulsion D, E respectively; Microemulsion D, E are mixed; In mixing process, cause the collision between the micro emulsion drop, the mutual exchange of material in the water nuclear has taken place, cause chemical reaction takes place in the nuclear; Because of reactant is limited in being scattered in equably in the oil phase in the dispersive nano level water nuclear fully, the water of the inner solubilising of drop is good chemical reaction environment, and droplet profile is the sphere of rule, and size can artificially be controlled; Collision process depends on the diffusion in external phase (being oil phase) of water nuclear, and exchange process depends on when water and examines the adelphotaxy of tensio-active agent afterbody when adjacent to each other and the rigidity at interface.Mutual collision between drop can form instantaneous dimer G, and instantaneous dimer provides the pond passage for two drops, and the material of the interior solubilising of water exchanges at this moment and reacts.Dimeric forming process has changed the shape of tensio-active agent film, so dimer is in upper state, can separate very soon.In constantly polymerization, sepn process, chemical reaction takes place and generates the product molecule, and a plurality of product molecular aggregatess are nucleation together.The nuclear that generates accelerates reaction as catalyzer, and product grows up nuclear attached on the nuclear, finally becomes the product particle.Because shape and size that water is examined are fixed, it is inner that nucleus increases the water nuclear that is confined to microemulsion, forms the size of particle and size and the shape decision that shape is examined by water.The precipitation that reaction generates almost is the spherical aluminium of single particle and the sedimentary homogeneous mixture of yttrium;

(5) above-mentioned throw out is extracted after, wash, suction filtration, drying, through 400～1600 ℃ of calcinings, calcination time is to obtain spherical YAG powder favorable dispersity, pure phase, that sintering activity is high in 1～6 hour.

Above-mentioned oil-phase solution is made according to certain mixed by oil phase substance, tensio-active agent, cosurfactant, and wherein, oil phase substance is one or both in benzene, normal hexane, hexanaphthene, the octane; Tensio-active agent is a kind of among Triton X-100 (Soxylat A 25-7), the CTAB (hexadecyl three first class ammonia bromides); Cosurfactant is one or both in n-hexyl alcohol, n-propyl alcohol or the propyl carbinol;

Above-mentioned water is divided into two kinds of reactant solution and precipitant solution, and wherein, reactant solution (yttrium salt and aluminum salt solution) is made by the carbonate that contains Al and Y, acetate, oxymuriate, nitrate, vitriol, oxyhydroxide, oxide compound; Precipitant solution can be made by in ammoniacal liquor, ammonium hydrogencarbonate, the oxalic acid one or both.

The present invention can come the characteristic of gained powder is controlled by regulating oil-phase solution and each components contents of water and concentration.The diameter of particle of gained powder: 10～150nm, adjustable grain; The granule-morphology of almost spherical; Size-grade distribution is a unimodal distribution; Favorable dispersity, powder crystalline phase are 100%YAG.

Further specify with embodiment below.

Embodiment 1, at room temperature is with Yttrium trinitrate (Y (NO ₃) ₃6H ₂O) and aluminum nitrate (Al (NO ₃) ₃9H ₂O) ratio according to 3: 5 mol ratio is mixed with the precursor solution that the positively charged ion total concn is 1.0mol/L, because system is the aqueous solution of homogeneous, aluminium and yttrium can be realized uniform mixing on molecular level; Ammoniacal liquor is mixed with the precipitant solution of 4.0mol/L.

With (normal hexane+hexanaphthene) is 100 (normal hexane+hexanaphthenes) by volume: Triton X-100: n-hexyl alcohol=(90+10): 44: 60 ratio preparation oil-phase solution, according to 10: 2 oil-water ratios, the mixed aqueous solution and the precipitant solution that in oil-phase solution, add isopyknic aluminium salt and yttrium salt respectively, jiggle, obtain water white microemulsion C, D.Get 50ml C, D microemulsion respectively, mix the back and under magnetic agitation, react 5min-24h.Adopt one or both methods in heating (70～80 ℃) backflow, vacuum filtration, the centrifugation to extract the throw out gel then.Gel is with dehydrated alcohol or acetone repetitive scrubbing; In 40 ℃ of-150 ℃ of air dry ovens or vacuum oven 3-48h, perhaps dry 24-48h in freeze drier through 400 ℃-1600 ℃ calcining 1-6h, obtains nano level YAG powder then.

The microemulsion behind the extraction throw out gel and the organic solvent of washing precipitation are reclaimed, and fractionation is handled, and separates and purifies, repeated use.

Embodiment 2, yttrium oxide is dissolved in an amount of nitric acid makes Yttrium trinitrate, then and aluminum chloride (AlCl ₃6H ₂O) ratio according to 3: 5 mol ratios is mixed with the precursor solution that concentration is respectively 0.5mol/L, and oxalic acid is mixed with the solution of 2.0mol/L, adds the character of other auxiliary agent with regulator solution again in this solution, is made into precipitant solution.

At room temperature, be 100 (normal hexane+hexanaphthene): TritonX-100 by volume with (normal hexane+hexanaphthene): n-hexyl alcohol=(86+14): 35: 33 ratio preparation oil-phase solution.According to 6: 1 oil-water ratio, in this solution, add the mixed aqueous solution and the precipitant solution of isopyknic aluminium salt and yttrium salt respectively, remaining preparation process is with described in the embodiment 1.

Embodiment 3, yttrium oxide is dissolved in an amount of nitric acid makes Yttrium trinitrate, aluminium hydroxide is dissolved in appropriate hydrochloric acid makes aluminum chloride, then according to yttrium: the ratio of aluminium=3: 5 mol ratio is mixed with the precursor solution that concentration is respectively 0.5mol/L, bicarbonate of ammonia is mixed with the solution of 2.0mol/L, in this solution, add the character of other auxiliary agent again, be made into precipitant solution with regulator solution.

At room temperature, with hexanaphthene, Triton X-100, n-hexyl alcohol, by 11: 6: 3 volume ratio preparation oil-phase solution.According to 10: 1 oil-water ratio, in this solution, add the mixed aqueous solution and the precipitant solution of isopyknic aluminium salt and yttrium salt respectively, following preparation process is with described in the embodiment 1.

Embodiment 4, present embodiment difference from Example 1 are: oil-phase solution is 100 with benzene, press benzene: Triton X-100: the volume ratio of n-propyl alcohol=100: 54: 27 is formulated, according to 3: 1 water oil ratio, in this solution, add the mixed aqueous solution and the precipitant solution of isopyknic aluminium salt and yttrium salt respectively.

Embodiment 5, present embodiment difference from Example 1 are: oil-phase solution is 100 with octane, and microemulsion system is according to octane: CTAB pressed powder: propyl carbinol: the aqueous solution=100: 28: 23: 77 mass ratio is formulated.

Claims (2)

1. A method for preparing nanoscale YAG powder, characterized in that: at room temperature, yttrium nitrate Y (NO ₃ ) ₃ 6H ₂ O and aluminum nitrate Al (NO ₃ ) ₃ 9H ₂ O according to 3: The ratio of the molar ratio of 5 is prepared into a precursor solution with a total concentration of cations of 1.0mol/L. Since the system is a uniform aqueous solution, aluminum and yttrium can be uniformly mixed at the molecular level; ammonia water is prepared into a precipitate of 4.0mol/L agent solution; With (n-hexane+cyclohexane) as 100, the oil phase solution is prepared in the ratio of volume ratio (n-hexane+cyclohexane): Triton X-100: n-hexanol=(90+10):44:60, according to 10 : 2 oil-water ratio, add equal volume of mixed aqueous solution of yttrium salt and aluminum salt and precipitant solution respectively to the oil phase solution, shake gently, obtain colorless and transparent microemulsion C, D; take 50mL C, D microemulsion respectively Emulsion, after mixing, react under magnetic stirring for 5min-24h, and then use one or two methods of heating to 70-80°C to reflux, vacuum filtration, and centrifugal separation to extract the precipitated gel; use absolute ethanol or acetone for the gel Repeated washing; drying in a 40°C-150°C blast drying oven or a vacuum oven for 3-48h, or drying in a freeze dryer for 24-48h, and then calcining at 400°C-1600°C for 1-6h to obtain nanoscale YAG Powder; The microemulsion after extracting the precipitate gel and the organic solvent washed and precipitated are recovered, fractionated, separated and purified, and reused. 2. A method for preparing nanoscale YAG powder, characterized in that: at room temperature, yttrium nitrate Y(NO ₃ ) ₃ 6H ₂ O and aluminum nitrate Al(NO ₃ ) ₃ 9H ₂ O according to 3: The ratio of the molar ratio of 5 is prepared into a precursor solution with a total concentration of cations of 1.0mol/L. Since the system is a uniform aqueous solution, aluminum and yttrium can be uniformly mixed at the molecular level; ammonia water is prepared into a precipitate of 4.0mol/L agent solution; With benzene as 100, the oil phase solution is prepared according to the volume ratio of benzene: TritonX-100: n-propanol = 100:54:27, and an equal volume of yttrium salt is added to the solution according to the oil-water ratio of 3:1 Mixed aqueous solution with aluminum salt and precipitant solution; shake lightly to obtain colorless and transparent microemulsions C and D; take 50ml of C and D microemulsions respectively, mix and react for 5min-24h under magnetic stirring, and then heat for 70 ~80°C reflux, vacuum filtration, centrifugation and one or two methods to extract the precipitated gel; the gel is washed repeatedly with absolute ethanol or acetone; in a blast drying oven or a vacuum oven at 40°C-150°C Internal drying for 3-48 hours, or drying in a freeze dryer for 24-48 hours, and then calcining at 400°C-1600°C for 1-6 hours to obtain nanoscale YAG powder; The microemulsion after extracting the precipitate gel and the organic solvent washed and precipitated are recovered, fractionated, separated and purified, and reused.