CN1557723A

CN1557723A - Method for preparing zirconia powder with low specific surface area and high sintering activity

Info

Publication number: CN1557723A
Application number: CNA2004100161438A
Authority: CN
Inventors: 施剑林; 蒋丹宇; 张玉峰; 黄德信
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2004-02-05
Filing date: 2004-02-05
Publication date: 2004-12-29
Anticipated expiration: 2024-02-05
Also published as: CN1278940C

Abstract

The preparation process of zirconia powder with small crystal size, less aggregation, small specific surface area and high sintering activity adopts zirconium oxichloride and yttrium nitrate as main material and ammonia water as precipitant, and includes reaction to produce hydroxide precipitate, water washing, drying, calcining, ball milling and spraying to pelletize. The process is simple, has easily controlled technological parameters and is suitable for large scale production. The obtained zirconia powder is suitable for various flexible forming process and has good sintering performance and 1450 deg.c sintered density higher than 99.0 TD% or 6.02 g/cu cm after being isostatic pressed.

Description

The making method of the high sintering active zirconia of low specific surface area powder

Technical field

The present invention relates to a kind of scattered, reunite less, the preparation method of specific surface area is low, sintering activity is high nano zirconium oxide powder, belong to field of fine chemical.

Background technology

Add 3mol%Y ₂O ₃The tetragonal zirconia polycrystal body (TZP) of Zirconium powder preparation, when being subjected to stress, the four directions transformation of monocline phase in opposite directions can take place, play toughness reinforcing effect.Therefore tetragonal zirconia polycrystal body pottery has excellent mechanical property.In the optical communication field,, therefore be used to prepare fiber active linker lock pin and sleeve in a large number because zirconium white has and quartzy good matching.The zirconium white full-ceramic bearing therefore to the environmental requirement harshness, to the food and the filed of daily-use chemical industry of being strictly on guard against pollution, just progressively substitutes stainless steel, plastic or other material owing to have good wear-resisting acidproof corrosion resistance characteristic, uses increasingly extensive.In automobile industry, the intensity height, the hardness height, the toughness height, the tiny zirconium white mould of microstructure is widely used in the panel beating punch die, has improved die life greatly, has improved quality product, has reduced cost etc.The pad printer sealing China ink cup that adopts zirconia ceramics edge of a knife ring to make has solved old-fashioned pad printer printing ink and has opened wide the evaporable problem, has avoided pollution, has protected environment.

Zirconia ceramics is increasingly extensive in the application in optical communication, automobile, food, chemical industry and environmental protection field as structure unit, has promoted the demand of market to the high-performance zirconia raw material greatly.The high-performance zirconia powder must possess two conditions, the one, good sintering character be arranged, sintered density need reach more than 99%, simultaneously moulding for convenience, powder must with various binding agent good mixings, make the material that mixes be fit to various flexible forming process.Yet these two requirements are conflicting often, if promptly sintering character is good, require powder granule thin, cause powder and organism mixed performance poor, the insufficient formability of material; Otherwise, increase particle size, cause sintering character to descend.Therefore, the high sintering active zirconia of low specific surface area powder is exactly the key of advanced oxidation zircon-structure pottery.

Chinese patent 99124041.3 relate to a kind of can low sintering Zirconium powder.This powder sintering is better active, can low-temperature sintering, but the specific surface area of powder reaches 110m ²Therefore/g is difficult to carry out flexible formation.Chinese patent 02115615.8 relates to a kind of Zirconium powder of controlled specific surface area, but the sintering temperature of this powder is greater than 1530 ℃, and the powder sintering activity is relatively poor, and this powder adopts hydrothermal method, and use alcohol as washing composition, increased the powder cost greatly.

Summary of the invention

The purpose of this invention is to provide a kind of can be mass-produced scattered, reunite less, the preparation method of low specific surface area, the active Zirconium powder of high sintering.This method technology is simple, constant product quality, cost are low.

The making method of the high sintering active zirconia of low specific surface area powder is as follows:

(1), makes the solution that concentration is 1-3M with the zirconium oxychloride deionized water dissolving.

(2), make the solution that concentration is 1-3M with the Yttrium trinitrate deionized water dissolving

(3) with (1) described solution and (2) described solution, be that the ratio of 1-5mol% is mixed with mother liquor in yttrium, the concentration of control mother liquor solution is at 0.3-2M.

(4) select ammoniacal liquor as precipitation agent, add 1-5 times of deionized water and be made into precipitant solution

(5) ammonia soln is splashed in the mother liquor solution, the flow of two kinds of solution of control, the maintenance pH value is 8-11, constantly stirs simultaneously, generates precipitation of hydroxide.

(6) wash throw out 1-5 time with deionized water.

(7) throw out after the washing is at 80-110 ℃ of dry 5-12h.

(8) the dried presoma of washing is at 600-1200 ℃ temperature lower calcination 2-8h.

(9) with sintering aid magnesium oxide, calcium oxide, the Zirconium powder of in aluminum oxide or the silicon oxide one or more after in 0.01-3% ratio and calcination processing mixes, the blended powder is put into the zirconia ball wet-milling of ball milling bucket, the ratio of pellet water is 1: 0.5-2: 0.5-2, the ball milling time is 2-72 hour.

(10) ball milling is good powder carries out mist projection granulating.

Outstanding feature of the present invention is:

1, the specific surface area of obtained Zirconium powder is less than 12m ²/ g is suitable for various flexible formation methods, and sintering character is good simultaneously, and behind the static pressure such as powder, 1450 ℃ of sintered densities are higher than 99.0TD% (6.02g/cm ³).

2, preparation technology is simple, processing parameter is easy to control, be easy to the large-scale low-cost industrial production.

Embodiment

Further specify outstanding feature of the present invention by following example, but the present invention absolutely not only is confined to described embodiment.

Embodiment 1

With the zirconium oxychloride deionized water dissolving, make the solution that concentration is 1M, with the Yttrium trinitrate deionized water dissolving, make the solution that concentration is 1M.With these two kinds of solution, be that the ratio of 3mol% is mixed with mother liquor in yttrium, the concentration of control mother liquor is at 0.5M.Select ammoniacal liquor as precipitation agent, add 2 times of deionized waters and be made into precipitant solution.Ammonia soln is splashed in the mother liquor, the flow of two kinds of solution of control, keeping the pH value is 10, constantly stirs simultaneously, generates precipitation of hydroxide.Deionization washing throw out 4 times.Throw out after the washing is at 80 ℃ of dry 6h.Wash dried presoma at 850 ℃ temperature lower calcination 9h.With sintering aid magnesium oxide, calcium oxide, the aluminum oxide Zirconium powder after in 0.3wt% ratio and calcination processing mixes, and the blended powder is put into the zirconia ball wet-milling of ball milling bucket, and the ratio of pellet water is 1: 1: 1,, the ball milling time is 6 hours.The powder that ball milling is good carries out mist projection granulating.Specific surface area with the high sintering active zirconia of the low specific surface area powder of this method preparation is 10-12m ²/ g.Behind the static pressure such as powder, 1450 ℃ of sintered densities are higher than 99.0TD% (6.02g/cm ³).This powder is fit to various flexible formation methods.

Embodiment 2

With the zirconium oxychloride deionized water dissolving, make the solution that concentration is 1M, with the Yttrium trinitrate deionized water dissolving, make the solution that concentration is 1M.With these two kinds of solution, be that the ratio of 3mol% is mixed with mother liquor in yttrium, the concentration of mother liquor is at 0.75M.Select ammoniacal liquor as precipitation agent, add 2 times of deionized waters and be made into precipitant solution.Ammonia soln is splashed in the mother liquor, the flow of two kinds of solution of control, keeping the pH value is 9, constantly stirs simultaneously, generates precipitation of hydroxide.Deionization washing throw out 4 times.Throw out after the washing is at 110 ℃ of dry 6h.Wash dried presoma at 950 ℃ temperature lower calcination 9h.With sintering aid magnesium oxide, calcium oxide, aluminum oxide, the silicon oxide Zirconium powder after in 0.3wt% ratio and calcination processing mixes, and the blended powder is put into the zirconia ball wet-milling of ball milling bucket, and the ratio of pellet water is 1: 1: 1, and the ball milling time is 6 hours.The powder that ball milling is good carries out mist projection granulating.Specific surface area with the high sintering active zirconia of the low specific surface area powder of this method preparation is 7-9m ²/ g.Behind the static pressure such as powder, 1450 ℃ of sintered densities are higher than 99.0TD% (6.02g/cm ³).This powder is fit to the moulding of various flexible formation method.

Claims

1, the making method of the high sintering active zirconia of low specific surface area powder is characterized in that comprising the steps:

(1), makes the solution that concentration is 1-3M with the zirconium oxychloride deionized water dissolving;

(2), make the solution that concentration is 1-3M with the Yttrium trinitrate deionized water dissolving;

(3) with (1) described solution and (2) described solution, be that the ratio of 1-5mol% is mixed with mother liquor in yttrium, the concentration of control mother liquor solution is at 0.3-2M;

(4) select ammoniacal liquor as precipitation agent, add 1-5 times of deionized water and be made into precipitant solution;

(5) ammonia soln is splashed in the mother liquor solution, constantly stir simultaneously, generate precipitation of hydroxide;

(6) precipitated product of gained is through washing, dry, calcining;

(7) with sintering aid magnesium oxide, the Zirconium powder mixing wet-milling after in 0.01-3wt% ratio and calcination processing of calcium oxide, one or more in aluminum oxide or the silicon oxide;

(8) ball milling is good powder carries out mist projection granulating.

2,, by the making method of the high sintering active zirconia of the described low specific surface area of claim 1 powder, it is characterized in that keeping pH value when ammonia soln splashes into mother liquor solution in the step 5 is 8-11.

3, by the making method of claim 1 or the high sintering active zirconia of 2 described low specific surface areas powder, the calcination condition that it is characterized in that step 6 is the temperature lower calcination 2-8h at 600-1200 ℃.

4, press the making method of claim 1 or the high sintering active zirconia of 2 described low specific surface areas powder, the wet-milling condition that it is characterized in that step 7 is to carry out wet-milling with zirconia ball, the ratio of pellet water is 1: 0.5-2: 0.5-2, the ball milling time is 2-72 hour.