CN104876265A - Preparation method of mixed crystal type zirconium oxide nanoparticle - Google Patents

Abstract

The invention discloses a preparation method of a mixed crystal type zirconium oxide nanoparticle. A nitrogen-containing surfactant is added into a reaction solution when the mixed crystal type zirconium oxide nanoparticle is prepared. Compared with an oxygen-containing surfactant, the nitrogen-containing surfactant adopted in the preparation method is more easily coordinated with Zr<4+> in the reaction solution to form a complex compound; and a monoclinic crystal and a square crystal of zirconium oxide can coexist at lower temperature after being calcined, and the grain size is relatively small.

Description

A kind of preparation method mixing crystal formation Zirconium oxide nano grain

Technical field

The present invention relates to a kind of preparation method of Zirconium oxide nano grain, particularly relate to a kind of preparation method mixing crystal formation Zirconium oxide nano grain.

Background technology

Zirconium white, namely zirconium dioxide is white heavy amorphous powder or monoclinic crystal, and odorless is tasteless.Zirconium dioxide has three kinds of crystal formations, and low temperature is oblique system, density 5.65g/cm ³; Tetragonal system is formed, density 6.10g/cm more than 1100 DEG C ³; More than 2370 DEG C, form isometric system, density is 6.27g/cm ³.Because zirconium white has outstanding process based prediction model, so it is extensive in industrial application, such as pottery, sensor, battery, electric capacity, corrosion-resistant with thermal barrier coating, fuel cell, solid electrolyte, catalyzer etc.Further, zirconic nano shape is more conducive to improving its application performance.But pure zirconium white tetragonal phase is easily transformed into monocline crystalline phase, there is volume change, be unfavorable for zirconic promoting the use of, in order to avoid undergoing phase transition, extensively adopting and adding stablizer, such as, specifically adding yttrium oxide.

Nano zircite preparation method mainly contains chemical precipitation method, hydrolysis method, hydrothermal method, alcohol-aqueous solution heating method, sol-gel processing etc., and chemical precipitation method is because technique is simple, easy suitability for industrialized production and being used widely.At present, the tensio-active agent that chemical precipitation method is commonly used is the tensio-active agent containing oxygen class, such as PEG (polyoxyethylene glycol).When zirconic component is mixed phase, namely when tetragonal phase and monocline crystalline phases, be called partially stabilized zirconium white, be called for short PSZ, there is excellent mechanical property, especially fracture toughness property.Generally, in the zirconic process of preparation, more easily form tetragonal system, and along with the rising of calcining temperature, first unformed zirconium white presoma changes into Tetragonal, is converted into oblique crystal at higher temperature.But when using the chemical precipitation method containing oxygen class tensio-active agent to prepare zirconium white, temperature when producing oblique crystal is higher, makes oblique crystal and tetragonal to coexist at a higher temperature.

Summary of the invention

Technical problem to be solved by this invention is the preparation method mixing crystal formation Zirconium oxide nano grain providing a kind of oblique crystal can coexist at low temperatures with the zirconium white of tetragonal for the state of the art.

The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method mixing crystal formation Zirconium oxide nano grain, during preparation mixed type Zirconium oxide nano grain, in reaction solution, adds nitrogen-containing surfactants.The nitrogen-containing surfactants that the technical program is mentioned refers in tensio-active agent containing nitrogen element.

Wherein, described nitrogen-containing surfactants is polyvinylpyrrolidone (polyvinyl pyrrolidone, i.e. PVP), PVP multipolymer, polyetheramine (polyetheramine, i.e. jeffamine), a kind of in polymine, polyvinylamine, polyacrylamide or at least two kinds mixture.Wherein, PVP multipolymer refers to the material of vinyl pyrrolidone as wherein a kind of monomer and after being polymerized with other monomers.

Wherein, described nitrogen-containing surfactants is PVP or polyetheramine, such as PVP-8000, PVP-10000, PVP-20000, jeffamine D-230, jeffamine D-400, jeffamine D-2000.

Wherein, described nitrogen-containing surfactants accounts for 0.01 ~ 10% of reaction solution gross weight;

Preferably, described nitrogen-containing surfactants accounts for 1% of reaction solution gross weight.

The preparation method of above-mentioned mixing crystal formation Zirconium oxide nano grain, comprises the steps:

(1) with ZrOCl ₂8H ₂o and Y (NO ₃) ₃for raw material preparation feedback liquid, in described reaction solution, add nitrogen-containing surfactants, stir, obtained mixed solution;

(2) in described mixed solution, add ammoniacal liquor, regulate pH=8 ~ 10 of mixed solution, filtering and washing, obtained crude product;

(3) described crude product is through forced air drying, after high-temperature calcination, and obtained mixing crystal formation Zirconium oxide nano grain.

In step (1), ZrOCl ₂8H ₂o and Y (NO ₃) ₃mol ratio be 90 ~ 100:2 ~ 8, such as 90:2,95:6,97:7, in described reaction solution, ZrOCl ₂8H ₂the volumetric molar concentration of O is 0.1 ~ 0.5mol/L, such as 0.2mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L;

Preferably, ZrOCl ₂8H ₂o and Y (NO ₃) ₃mol ratio be 97:6;

Preferably, in described reaction solution, ZrOCl ₂8H ₂the volumetric molar concentration of O is 0.2mol/L.

In step (1), the preparation process of described reaction solution is: by ZrOCl ₂8H ₂o and Y (NO ₃) ₃by proportioning mixing, with deionized water and/or dissolve with ethanol, be uniformly mixed, obtained described reaction solution.

In step (1), the addition of nitrogen-containing surfactants is 0.01 ~ 10% of reaction solution gross weight, such as 0.05%, 0.8%, 1.2%, 1.5%, 2%, 3%, 4.3%, 5%, 6%, 7%, 8%, 9%;

Preferably, the addition of nitrogen-containing surfactants is 1% of reaction solution gross weight.

After step (2), also comprise step (2a) before step (3), chloride test is carried out to described crude product.

In step (1), add nitrogen-containing surfactants in described reaction solution after, at 75 DEG C, stir 2h, obtained described mixed solution;

Preferably, in step (2), in described mixed solution, add ammoniacal liquor, regulate the pH=9 of mixed solution;

Preferably, in step (3), the temperature of described forced air drying is 110 DEG C, and the time is 2h;

Preferably, in step (3), the time of described high-temperature calcination is 2h, and temperature is 500 ~ 900 DEG C, such as 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C,

Compared with prior art, the invention has the advantages that: this preparation method adopts chemical precipitation method preparation mixing crystal formation Zirconium oxide nano grain, and what adopt nitrogen-containing surfactants replacement routine contains oxygen tensio-active agent simultaneously.The nitrogen-containing surfactants that this preparation method adopts with containing compared with oxygen tensio-active agent, the Zr more easily and in reaction solution ⁴⁺coordination, forms complex compound; After calcining, zirconic oblique crystal and tetragonal can coexist at lower temperatures, and grain fineness number is less.

Accompanying drawing explanation

Fig. 1 is the XRD figure spectrum of mixing crystal formation Zirconium oxide nano grain prepared by the embodiment of the present invention 1;

Fig. 2 is the XRD figure spectrum of mixing crystal formation Zirconium oxide nano grain prepared by the embodiment of the present invention 2;

Fig. 3 is the XRD figure spectrum of the mixing crystal formation Zirconium oxide nano grain of comparative example 1 of the present invention preparation.

Embodiment

Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.

Embodiment 1

The preparation method of the mixing crystal formation Zirconium oxide nano grain of the present embodiment, comprises the steps:

(1) quantitative ZrOCl is weighed ₂8H ₂o and Y (NO ₃) ₃, wherein, ZrOCl ₂8H ₂o and Y (NO ₃) ₃mol ratio be 97:6, then use deionized water dissolving, make ZrOCl ₂8H ₂the volumetric molar concentration of O is 0.2mol/L, after being uniformly mixed, and obtained reaction solution;

In reaction solution, add nitrogen-containing surfactants jeffamine D-2000, stir, obtained mixed solution, in mixed solution, the addition of nitrogen-containing surfactants is 1% of reaction solution gross weight;

(2) in mixed solution, add ammoniacal liquor, regulate the pH=9 of mixed solution, filtering and washing, obtained crude product;

(2a) carry out chloride test to obtained crude product, the detection method of chlorion adopts conventional common method, does not repeat them here;

(3) after not containing chlorion in crude product, crude product is forced air drying 2h at 100 DEG C, and after high-temperature calcination 2h, the high-temperature calcination time is respectively 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, obtained 5 parts of Zirconium oxide nano grains.

The 5 parts of Zirconium oxide nano grains prepared through above-mentioned steps carry out XRD sign respectively, and as shown in Figure 1, it is 110 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C that 6 XRD figure in Fig. 1 compose the calcining temperature be corresponding in turn to from bottom to up to the XRD figure spectrum of acquisition.

Embodiment 2

The preparation process difference from Example 1 of the present embodiment is: the nitrogen-containing surfactants that step (1) uses is PVP-100000.

Other operation steps reference examples 1 of the present embodiment; As shown in Figure 2, it is 110 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C that 6 XRD figure in Fig. 2 compose the calcining temperature be corresponding in turn to from bottom to up to the XRD figure spectrum of 5 parts of Zirconium oxide nano grains that the present embodiment is prepared under different calcining temperature.

Comparative example 1

The preparation process difference from Example 1 of the present embodiment is: what step (1) used is PEG-4000 containing oxygen tensio-active agent.

Other operation steps reference examples 1 of the present embodiment; As shown in Figure 3, it is 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C that 5 XRD figure in Fig. 3 compose the calcining temperature be corresponding in turn to from bottom to up to the XRD figure spectrum of 5 parts of Zirconium oxide nano grains that the present embodiment is prepared under different calcining temperature.

The different peak values of Fig. 1 to Fig. 3 are as shown in table 1:

From Fig. 1, Fig. 2, Fig. 3 and table 1, embodiment 1 and embodiment 2 just have obvious oblique crystal peak after 600 DEG C of calcinings, and comparative example 1 just has small and weak peak to occur at 700 DEG C; In addition, have above-mentioned chart to find out, after tensio-active agent adopts PVP or jeffamine process, the grain fineness number of the Zirconium oxide nano grain of acquisition is less.

Embodiment 3

The preparation process difference from Example 1 of the present embodiment is: in step (1), and the addition of nitrogen-containing surfactants is 0.01% of reaction solution gross weight; Other operation steps reference examples 1.

Embodiment 4

The preparation process difference from Example 3 of the present embodiment is: the nitrogen-containing surfactants that step (1) uses is PVP-100000; Other operation steps reference examples 3.

Comparative example 2

The preparation process difference from Example 3 of the present embodiment is: what step (1) used is PEG-4000 containing oxygen tensio-active agent; Other operation steps reference examples 3.

Embodiment 5

The preparation process difference from Example 1 of the present embodiment is: in step (1), and the addition of nitrogen-containing surfactants is 10% of reaction solution gross weight; Other operation steps reference examples 1.

Embodiment 6

The preparation process difference from Example 5 of the present embodiment is: the nitrogen-containing surfactants that step (1) uses is PVP-100000; Other operation steps reference examples 5.

Comparative example 3

The preparation process difference from Example 5 of the present embodiment is: what step (1) used is PEG-4000 containing oxygen tensio-active agent; Other operation steps reference examples 5.

The Zirconium oxide nano grain of the preparation of comparative example 2, comparative example 3, embodiment 3 ~ embodiment 6 carries out XRD sign equally, corresponding XRD figure spectrum does not provide, but have followed the rule of embodiment 1, embodiment 2 and comparative example 1 equally: after the tensio-active agent of the quality such as employing, relative to containing oxygen tensio-active agent, after nitrogen-containing surfactants process, the oblique crystal of the Zirconium oxide nano grain obtained can obtain at lesser temps, and the grain fineness number of Zirconium oxide nano grain is less.

Above content is only preferred embodiment of the present invention, and for those of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, this description should not be construed as limitation of the present invention.

Claims (10)

1. mix a preparation method for crystal formation Zirconium oxide nano grain, it is characterized in that: during preparation mixed type Zirconium oxide nano grain, in reaction solution, add nitrogen-containing surfactants.

2. preparation method according to claim 1, is characterized in that: described nitrogen-containing surfactants is the mixture of a kind of in polyvinylpyrrolidone, PVP multipolymer, polyetheramine, polymine, polyvinylamine, polyvinyl lactam or at least two kinds.

3. preparation method according to claim 1, is characterized in that: described nitrogen-containing surfactants is PVP or polyetheramine.

4. preparation method according to claim 1, is characterized in that: described nitrogen-containing surfactants accounts for 0.01 ~ 10% of reaction solution gross weight;

Preferably, described nitrogen-containing surfactants accounts for 1% of reaction solution gross weight.

5. preparation method according to claim 1, is characterized in that, comprises the steps:

(1) with ZrOCl ₂8H ₂o and Y (NO ₃) ₃for raw material preparation feedback liquid, in described reaction solution, add nitrogen-containing surfactants, stir, obtained mixed solution;

(2) in described mixed solution, add ammoniacal liquor, regulate pH=8 ~ 10 of mixed solution, filtering and washing, obtained crude product;

(3) described crude product is through forced air drying, after high-temperature calcination, and obtained mixing crystal formation Zirconium oxide nano grain.

6. preparation method according to claim 5, is characterized in that: in step (1), ZrOCl ₂8H ₂o and Y (NO ₃) ₃mol ratio be 90 ~ 100:2 ~ 8, in described reaction solution, ZrOCl ₂8H ₂the volumetric molar concentration of O is 0.1 ~ 0.5mol/L;

Preferably, ZrOCl ₂8H ₂o and Y (NO ₃) ₃mol ratio be 97:6;

Preferably, in described reaction solution, ZrOCl ₂8H ₂the volumetric molar concentration of O is 0.2mol/L.

7. preparation method according to claim 6, is characterized in that, in step (1), the preparation process of described reaction solution is: by ZrOCl ₂8H ₂o and Y (NO ₃) ₃by proportioning mixing, with deionized water and/or dissolve with ethanol, be uniformly mixed, obtained described reaction solution.

8. preparation method according to claim 5, is characterized in that: in step (1), and the addition of nitrogen-containing surfactants is 0.01 ~ 10% of reaction solution gross weight;

Preferably, the addition of nitrogen-containing surfactants is 1% of reaction solution gross weight.

9. preparation method according to claim 5, is characterized in that, after step (2), also comprises step (2a), carry out chloride test to described crude product before step (3).

10. preparation method according to claim 5, is characterized in that: in step (1), after adding nitrogen-containing surfactants, at 75 DEG C, stirs 2h in described reaction solution, obtained described mixed solution;

Preferably, in step (2), in described mixed solution, add ammoniacal liquor, regulate the pH=9 of mixed solution;

Preferably, in step (3), the temperature of described forced air drying is 110 DEG C, and the time is 2h;

Preferably, in step (3), the time of described high-temperature calcination is 2h, and temperature is 500 ~ 900 DEG C.