CN101851005B

CN101851005B - Preparation method of high-dispersion zirconium oxide nano powder

Info

Publication number: CN101851005B
Application number: CN2010101825751A
Authority: CN
Inventors: 魏春城; 牛金叶; 孟凡涛; 田贵山; 周立娟
Original assignee: Shandong University of Technology
Current assignee: Shandong University of Technology
Priority date: 2010-05-17
Filing date: 2010-05-17
Publication date: 2011-08-31
Anticipated expiration: 2030-05-17
Also published as: CN101851005A

Abstract

The invention provides a preparation method of high-dispersion zirconium oxide nano powder, which belongs to the technical field of nano material preparation. The preparation method is characterized by comprising the following steps of: (1) titrating a precipitating agent into a zirconium salt solution while stirring to produce gel, and then, suction filtering and washing the gel with ion water for several times until the washing solution becomes neutral; (2) adding camphene into the gel, and ball milling to form a slurry at the temperature of 50-70 DEG C; (3) concreting and shaping the slurry at room temperature, placing the concreted slurry in an air environment at room temperature for 7-10 days, placing the slurry in a sintering furnace after the camphene completely volatilizes, and calcining at 700-900 DEG C to obtain the high-dispersion zirconium oxide nano powder. The zirconium oxide nano powder obtained by the invention has good dispersion, no hard agglomeration, granules smaller than 50 nm, simple process, safe operation, low cost and easy industrialization.

Description

The preparation method of high-dispersion zirconium oxide nano powder

Technical field

The invention provides a kind of preparation method of high-dispersion zirconium oxide nano powder, belong to the nano material preparation technical field.

Background technology

The preparation method of nm-class powder of zirconium oxide has multiple, comprises vapor phase process and liquid phase method two big classes, and wherein liquid chemical method has stronger competitive edge, because the commercial run relevant with this method control is comparatively ripe with the amplifying technique of equipment, cost is lower.Liquid phase method comprises sol-gel method, alkoxide hydrolysis, hydrothermal method, emulsion method and coprecipitation method etc., wherein sol-gel method is valued especially a kind of method in the liquid phase wet chemistry method, it has, and temperature of reaction is low, technology simply reaches advantages such as easy to control, is a kind of effective ways of energy suitability for industrialized production.But can produce more serious agglomeration in the sol-gel method preparation process, the existence of hard aggregation can reduce the activity and the processability of powder, and causes the higher sintering temperature of needs when firing ceramics, and material structure is inhomogeneous, be easy to generate defective, reduce the performance of goods.Therefore, prevent or reduce the generation that sol-gel method prepares hard aggregation phenomenon in the nm-class powder of zirconium oxide process, meet the requirements to obtain particle diameter, the particle of narrow distribution range, good dispersity, be to be engaged in one of problem that the scientific and technical personnel of this area research are concerned about most at present.Studies show that, the formation of coacervate and the whole process of preparation of nm-class powder of zirconium oxide, all closely related from reaction nucleation, nucleus growth to the steps such as washing, drying and calcining of hydration presoma.As seen, realize just must controlling to its whole process of preparation to the control of nano-powder reunion.In order to reduce the reunion of nanoparticle, at titration process: people attempt to add some tensio-active agents or other organism in reaction system, it can be controlled on the one hand be reacted into nuclear process; Organic molecule is adsorbed on the presoma micelle that has generated on the other hand, can strengthen the space steric effect between the particle, improve the dispersion of particles performance, but effect is bad.At washing process: will precipitate presoma with dehydrated alcohol or other organic solvent washing, and replace its surface adsorption water, and reduce the hard aggregation that micelle forms owing to the hydroxyl bridging action with oxyethyl group or other organo-functional group; Simultaneously because organic solvent has lower surface tension, also will reduce the capillary force that produces in the dehydration, the bonding strength between the particle is reduced, reduce the generation of coacervate, but effect is bad, only uses special technology just can obtain the nano-powder of good dispersity in drying process.In drying process: use supercritical drying, vacuum lyophilization and azeotropic distillation process can better eliminate reunion, but supercritical drying and vacuum lyophilization be to the equipment requirements height, equipment has high input, and is subjected to the influence of equipment box size, and production efficiency is low; Component distillation is the cost height with an organic solvent, influenced by the distillation plant volumetrical, and efficient is low.

Summary of the invention

The purpose of this invention is to provide a kind ofly can overcome that above-mentioned defective, technology are simple, the preparation method of operational safety, high-dispersion zirconium oxide nano powder that cost is low, its technical scheme is:

A kind of preparation method of high-dispersion zirconium oxide nano powder, it is characterized in that adopting following steps: it is characterized in that adopting following steps: (1) is under agitation condition, precipitation agent is titrated in the zirconium salt solution, generate gel, then with the gel filtering and washing for several times, till washing lotion shows neutrality with deionized water; (2) add amphene in gel, ball milling mixes the formation slip under 50～70 ℃ of environment; (3) with slip at the room temperature coagulation forming, the slip that solidifies is placed on stopped in the air at room temperature environment 7～10 days again, treat to be put in the sintering oven after amphene volatilizees fully, 700～900 ℃ of calcinings, zirconium oxide nano powder promptly secures satisfactory grades.

The preparation method of described high-dispersion zirconium oxide nano powder, precipitation agent is a kind of in the ammoniacal liquor, 1～2mol/L volatile salt of 0.1～0.5mol/L sodium borohydride, dilution in the step (1).

Zirconium salt solution is zirconyl chloride solution or the zirconium nitrate solution of 0.1～0.5mol/L among the preparation method of described high-dispersion zirconium oxide nano powder, step (1).

The mass ratio of gel and amphene is 1: 0.5～2 among the preparation method of described high-dispersion zirconium oxide nano powder, step (2).

Principle of work of the present invention is: because the fusing point of amphene is lower, and fusing about 45 ℃, and be solid under the normal temperature state, the mold temperature of base substrate is low.Simultaneously, amphene is as easy evaporable material, and the formation hole that just can volatilize naturally in air improves powder dispersity.

The present invention compared with prior art has following advantage:

1, utilize amphene to be higher than 45 ℃ for liquid, it is solid-state that room temperature becomes, and be easy to the evaporable characteristic, disperses the zirconium white gel, prepares the nm-class powder of zirconium oxide of high dispersive, and technology is simple, is easy to suitability for industrialized production;

2, the nm-class powder of zirconium oxide good dispersity of the present invention's preparation, hard aggregation-free, particle have bigger specific surface area less than 50nm;

3, do not use special drying processes such as supercritical drying, vacuum lyophilization and component distillation, just can obtain the nano-powder of good dispersity, not limited by the drying plant volumetrical, production efficiency height, equipment less investment.

Description of drawings

Fig. 1 is the XRD spectrum of the embodiment of the invention after 700 ℃ of calcinings;

Fig. 2 is the SEM photo of the embodiment of the invention after 700 ℃ of calcinings.

Embodiment

Embodiment 1

(1) ZrOCl of 3.2g ₂8H ₂The water that O is dissolved in 100ml is configured to the 0.1mol/L zirconyl chloride solution, under agitation condition, the 0.2mol/L sodium borohydride solution is titrated in the zirconyl chloride solution, generate gel, then with the deionized water filtering and washing for several times, till washing lotion shows neutrality, obtain the 12g gel with gel; (2) add the 12g amphene in gel, ball milling mixes the formation slip under 50 ℃ of environment; (3) at the room temperature coagulation forming, the slip that will solidify is placed in the air at room temperature environment and stopped 7 days, treat to be put in the sintering oven after amphene volatilizees fully, and 700 ℃ of calcinings, zirconium oxide nano powder promptly secures satisfactory grades.

By the XRD test, visible powder crystal type is the monocline phase; By the SEM test, visible nm-class powder of zirconium oxide particle diameter is about 40nm, and hard aggregation-free has than polymolecularity.

Embodiment 2

(1) Zr (NO of 4.3g ₃) ₄5H ₂The water that O is dissolved in 100ml is configured to the 0.1mol/L zirconium nitrate solution, under agitation condition, the 0.5mol/L sodium borohydride solution is titrated in the zirconium nitrate solution, generate gel, then with the deionized water filtering and washing for several times, till washing lotion shows neutrality, obtain the 20g gel with gel; (2) add the 20g amphene in gel, ball milling mixes the formation slip under 50 ℃ of environment; (3) at the room temperature coagulation forming, the slip that will solidify is placed in the air at room temperature environment and stopped 7 days, treat to be put in the sintering oven after amphene volatilizees fully, and 700 ℃ of calcinings, zirconium oxide nano powder promptly secures satisfactory grades.

Embodiment 3

(1) ZrOCl of 9.6g ₂8H ₂The water that O is dissolved in 100ml is configured to the 0.3mol/L zirconyl chloride solution, under agitation condition, the 1mol/L sal volatile is titrated in the zirconyl chloride solution, generate gel, then with the deionized water filtering and washing for several times, till washing lotion shows neutrality, obtain the 45g gel with gel; (2) add the 90g amphene in gel, ball milling mixes the formation slip under 60 ℃ of environment; (3) at the room temperature coagulation forming, the slip that will solidify is placed in the air at room temperature environment and stopped 7 days, treat to be put in the sintering oven after amphene volatilizees fully, and 800 ℃ of calcinings, zirconium oxide nano powder promptly secures satisfactory grades.

Embodiment 4

(1) Zr (NO of 12.9g ₃) ₄5H ₂The water that O is dissolved in 100ml is configured to the 0.3mol/L zirconium nitrate solution, under agitation condition, the 2mol/L sal volatile is titrated in the zirconium nitrate solution, generate gel, then with the deionized water filtering and washing for several times, till washing lotion shows neutrality, obtain the 54g gel with gel; (2) add the 108g amphene in gel, ball milling mixes the formation slip under 60 ℃ of environment; (3) at the room temperature coagulation forming, the slip that will solidify is placed in the air at room temperature environment and stopped 7 days, treat to be put in the sintering oven after amphene volatilizees fully, and 800 ℃ of calcinings, zirconium oxide nano powder promptly secures satisfactory grades.

Embodiment 5

(1) ZrOCl of 16g ₂8H ₂The water that O is dissolved in 100ml is configured to the 0.5mol/L zirconyl chloride solution, under agitation condition, the ammoniacal liquor liquid that dilutes is titrated in the zirconyl chloride solution, generate gel, then with the deionized water filtering and washing for several times, till washing lotion shows neutrality, obtain the 60g gel with gel; (2) add the 30g amphene in gel, ball milling mixes the formation slip under 70 ℃ of environment; (3) at the room temperature coagulation forming, the slip that will solidify is placed in the air at room temperature environment and stopped 7 days, treat to be put in the sintering oven after amphene volatilizees fully, and 900 ℃ of calcinings, zirconium oxide nano powder promptly secures satisfactory grades.

Embodiment 6

(1) Zr (NO of 21.5g ₃) ₄5H ₂The water that O is dissolved in 100ml is configured to the 0.5mol/L zirconium nitrate solution, under agitation condition, the ammonia water titration of dilution in zirconium nitrate solution, is generated gel, then with gel with the deionized water filtering and washing for several times, till washing lotion shows neutrality, obtains the 90g gel; (2) add the 45g amphene in gel, ball milling mixes the formation slip under 70 ℃ of environment; (3) at the room temperature coagulation forming, the slip that will solidify is placed in the air at room temperature environment and stopped 7 days, treat to be put in the sintering oven after amphene volatilizees fully, and 900 ℃ of calcinings, zirconium oxide nano powder promptly secures satisfactory grades.

Claims

1. A preparation method for highly dispersed zirconia nanopowder, characterized in that the following steps are adopted: (1) under stirring conditions, the precipitation agent is titrated in the zirconium salt solution to generate a gel, and then the The gel is suction-filtered and washed several times until the lotion is neutral; (2) Add camphene to the gel, and mix it by ball milling at 50-70°C to form a slurry; (3) Solidify the slurry at room temperature , and then put the solidified slurry in the air environment at room temperature for 7 to 10 days, put the camphene into a sintering furnace after the camphene is completely volatilized, and calcinate at 700 to 900 ° C to obtain highly dispersed zirconia nanopowder; wherein the steps ( 1) The precipitant is one of 0.1-0.5mol/L sodium borohydride, diluted ammonia water, and 1-2mol/L ammonium carbonate, and the zirconium salt solution is 0.1-0.5mol/L zirconium oxychloride solution or nitric acid Zirconium solution, the mass ratio of gel and camphene in step (2) is 1: 0.5～2.