CN104071837B

CN104071837B - Nanometer Gd is prepared with stearic acid 2zr 2o 7the method of powder

Info

Publication number: CN104071837B
Application number: CN201410300588.2A
Authority: CN
Inventors: 马雷; 马伟民; 陶胜龙
Original assignee: Shenyang University of Chemical Technology
Current assignee: Shenyang University of Chemical Technology
Priority date: 2014-06-30
Filing date: 2014-06-30
Publication date: 2015-11-18
Anticipated expiration: 2034-06-30
Also published as: CN104071837A

Abstract

Nanometer Gd is prepared with stearic acid ₂zr ₂o ₇the method of powder, relates to a kind of method preparing nano-powder, two parts of stearic acid is heated to 80 DEG C of fusings, adds respectively by ZrOCl ₂﹒ 8H ₂o and Gd ₂o ₃the nitrate solution be configured to stirs, adding cetyl trimethylammonium bromide (CATB) is tensio-active agent, two parts of solution fully mix, vigorous stirring, until form dense thick yellow transparent solution, solution naturally cools to gel formed at room temperature, is placed in heating flame on hot-plate, obtain black puffy presoma, presoma calcining after grinding obtains nanometer Gd ₂zr ₂o ₇powder.The invention provides a kind of stearic acid method and prepare nanometer Gd ₂zr ₂o ₇the method of powder, the method technique is simple, and the raw material adopted is simple and easy to get, and preparation cycle is short, gained Gd ₂zr ₂o ₇diameter of particle is little, is evenly distributed, and basic in spherical, burn-ability is good, holds out broad prospects in actual applications.

Description

Nanometer Gd is prepared with stearic acid 2zr 2o 7the method of powder

Technical field

The present invention relates to a kind of method preparing nano-powder, particularly relate to one stearic acid and prepare nanometer Gd ₂zr ₂o ₇the method of powder.

Background technology

Gd ₂zr ₂o ₇material has higher fusing point, thermal expansivity, chemically stable, radioresistance and thermostability, and the physics-chem characteristic such as lower thermal conductivity, therefore can be widely used in thermal barrier coating, the fields such as solid electrolyte and high radioactive waste curing body.In thermal barrier coating field, Gd ₂zr ₂o ₇material has the thermal conductivity lower than now widely used 6wt% ~ 8wt% yttria-stabilized zirconia (YSZ), good effect of heat insulation, at high temperature there is good chemical stability and phase stability simultaneously, the use temperature of thermal barrier coating can be improved and extend its work-ing life; In antiradiation material field, Gd ₂zr ₂o ₇than the s-generation high-level waste cured body metatitanic acid alkali pottery of generally acknowledging at present to bear radiation injury performance more superior, be solidification ²³⁹the desirable ceramic base material of Pu (transformation period 24500a); In field of solid oxide fuel, Gd ₂zr ₂o ₇material has than conventional solid oxide electrolyte 8mol%Y ₂o ₃-ZrO ₂(8mol%YSZ) lower working temperature (working temperature can be reduced 300-500K), reduces the erosion rate of metal assembly, expands the range of choice of material, improves the work-ing life of Solid Oxide Fuel Cell.There are some researches show, along with the reduction of powder granule size, its thermal property and mechanical property have very large enhancing.Therefore, Gd is studied ₂zr ₂o ₇the preparation of nano-powder has its necessity.

The pattern of sintering ceramic powder drastically influence the performance of ceramic sintered bodies, and particle diameter is little and uniform subsphaeroidal particle can significantly improve sintering activity, reduces sintering temperature.At present, the method preparing nano-powder mainly contains mechanical ball milling reaction method, high temperature solid-state method, hydrothermal method, coprecipitation method, sol-gel and combustion method etc.Mechanical ball milling reaction method and sol-gel method synthesis technique very complicated, generated time longer (not generally being shorter than 48h).Although solid phase method is simple, for multi-component material system, easily cause component skewness, and there is the problems such as synthesis temperature is higher.Coprecipitation method is simple to operate, but easily occurs particle agglomeration.The preparation method of a kind of novel nano-powder that stearic acid method immediate development is got up, utilize stearic acid as solvent and dispersion agent, cetyl trimethylammonium bromide (CATB) is as tensio-active agent, raw material can be made to mix at molecular level and to be incorporated in lower temperature synthesis, gained diameter of particle little (particle diameter is about 10nm), easily sinters.The stearic acid method synthetic powder cycle is short, simple, has wide practical use in the preparation field of nano material.

Summary of the invention

One stearic acid is the object of the present invention is to provide to prepare nanometer Gd ₂zr ₂o ₇the method of powder, the method adopts stearic acid to be solvent and dispersion agent, adds a small amount of cetyl trimethylammonium bromide (CATB) for synthesis of surfactant nanometer Gd ₂zr ₂o ₇powder.The method technique is simple, and powder preparation cycle is short, and preparation temperature is lower, gained Gd ₂zr ₂o ₇diameter of particle is little, and burn-ability is good.

The object of the invention is to be achieved through the following technical solutions:

Nanometer Gd is prepared with stearic acid ₂zr ₂o ₇the method of powder, described method comprises following preparation process: two parts of stearic acid are heated to 80 DEG C of fusings, add respectively by ZrOCl ₂﹒ 8H ₂o and Gd ₂o ₃the nitrate solution be mixed with stirs, by two parts of solution mixing, adding cetyl trimethylammonium bromide (CATB) is tensio-active agent, vigorous stirring, until form dense thick yellow transparent solution, solution naturally cools to gel formed at room temperature, be placed in heating flame on hot-plate, obtain black puffy presoma, presoma is through grinding, and after sieving, calcining obtains nanometer Gd ₂zr ₂o ₇powder.

Described prepares nanometer Gd with stearic acid ₂zr ₂o ₇the method of powder, described stearic acid is as solvent and dispersion agent.

Described prepares nanometer Gd with stearic acid ₂zr ₂o ₇the method of powder, described stearic add-on controls in the total ion of rare earth and stearic acid mol ratio at 1:2-1:8.

Described prepares nanometer Gd with stearic acid ₂zr ₂o ₇the method of powder, the add-on of described tensio-active agent cetyl trimethylammonium bromide (CATB) is 1% ~ 5%(wt%).

Described prepares nanometer Gd with stearic acid ₂zr ₂o ₇the method of powder, described temperature of reaction controls at 110-150 DEG C, and the reaction times is 2h.

Described prepares nanometer Gd with stearic acid ₂zr ₂o ₇the method of powder, the temperature range of described presoma calcining controls at 500-900 DEG C, and calcination time is 4h.

Advantage of the present invention and effect are:

1. raw material of the present invention is simple, and preparation cycle is short, easy and simple to handle, holds out broad prospects in actual applications.

2. the present invention is by controlling stearic acid add-on, the add-on of reconciliation statement surface-active agent cetyl trimethylammonium bromide, and calcines the crystal formation, pattern and the size that control product at different temperatures.Presoma obtains the Gd that particle diameter is about 10nm under lower calcining temperature (700 DEG C, insulation 4h) ₂zr ₂o ₇nano-powder, pattern is spherical substantially, better dispersed.

Accompanying drawing explanation

Fig. 1 is that stearic acid method prepares Gd ₂zr ₂o ₇the process flow sheet of nano-powder;

Fig. 2 is the TG-DTA curve of presoma of the present invention;

Fig. 3 is in the present invention, the XRD diffracting spectrum of different calcining temperature (insulation 4h) prepared sample;

Fig. 4 is in the present invention, and the powder TEM obtained after 700 DEG C of calcining 4h schemes.

Embodiment

The present invention is described in detail with reference to the accompanying drawings.

Material selection in the present invention:

Raw material Gd ₂o ₃and ZrOCl ₂﹒ 8H ₂o purity is 99.99%, cetyl trimethylammonium bromide, and ammoniacal liquor and nitric acid etc. are analytical reagent, and distilled water is intermediate water.Above reagent is not all through purification process.

Concrete preparation process of the present invention:

First by ZrOCl ₂﹒ 8H ₂o is dissolved in excessive ammonia, is fully obtained by reacting white gum throw out, by sedimentation and filtration, and repeatedly washs with deionized water, removes Cl ^-, precipitation is dissolved in excessive dust technology, stirs and obtain ZrO (NO ₃) ₂solution.Again by Gd ₂o ₃be dissolved in dilute nitric acid solution by accurate stoicheiometry, form Gd (NO ₃) ₃solution.Get two parts of stearic acid n (SA): [n (Gd ³⁺)+n (Zr ⁴⁺)]=4:1, be heated to 80 DEG C of fusings, add respectively by ZrO (NO ₃) ₂with Gd (NO ₃) ₃solution fully mixes 30min, the cetyl trimethylammonium bromide (CATB) that two parts of solution mixing add 2wt% is made tensio-active agent, in 120 DEG C of vigorous stirring 2h, form dense thick yellow transparent solution, solution naturally cools to gel formed at room temperature, is placed in heating on hot-plate until burning, obtain black puffy presoma, presoma, through grinding, after crossing 200 order square hole plugs, obtains nanometer Gd in 700 DEG C of calcining 4h ₂zr ₂o ₇powder.

Its reaction mechanism: rare earth ion (Gd ³⁺) and Zr ⁴⁺form macromolecule network shape structure with the stearic acid of fusing, stearic acid, as solvent and dispersion agent, gets rid of moisture by vigorous stirring, form gluey thick liquid, and heating makes stearic acid burn, self-propagating forms black puffy presoma, then obtains nanometer zirconic acid gadolinium powder through thermal treatment.

In conjunction with specific examples, the present invention is further described

Embodiment:

According to the preparation process of Fig. 1, precise 3.222g, ZrOCl ₂﹒ 8H ₂o is dissolved in 100ml distilled water, drips 40ml ammoniacal liquor, fully stirs and obtains white gum throw out, by sedimentation and filtration, and spends distilled water and repeatedly washs, remove Cl ^-, precipitation is dissolved in 100ml, in the dust technology of 0.05mol/L, stirs and obtain ZrO (NO ₃) ₂solution.Again by 1.733g, Gd ₂o ₃be dissolved in 100ml, in 0.05mol/L dilute nitric acid solution, form Gd (NO ₃) ₃solution.Take two parts of 11.38g stearic acid and at 80 DEG C, be heated to fusing, now n (Gd ³⁺): n (Zr ⁴⁺): n (SA)=1:1:4, adds respectively by ZrO (NO ₃) ₂with Gd (NO ₃) ₃solution mixing 30min, by two parts of solution mixing, add 0.33g cetyl trimethylammonium bromide (CATB), in 120 DEG C of vigorous stirring 2h, form dense thick yellow transparent solution, solution naturally cools to gel formed at room temperature, gel is placed in heating on hot-plate until burning, obtain black puffy presoma, presoma is through grinding, after crossing 200 order square hole plugs, obtain nanometer Gd in 700 DEG C of calcining 4h ₂zr ₂o ₇powder.Adopt Japanese Shimadzu (Shimadzu) DTG-60H type TG-DTA analyser to carry out thermal analyses to presoma, determine the heat treating regime of presoma, as Fig. 2; Rigaku (Rigaku) D/MAX-RB type X-ray diffractometer and JEOLJEM-2100F type field emission transmission electron microscope is adopted to analyze sample, result shows, powder structure be typical pyrochlore constitution as Fig. 3, pattern is spherical substantially, particle diameter is approximately 10nm, as shown in Figure 4.

Claims

1. prepare nanometer Gd with stearic acid ₂zr ₂o ₇the method of powder, is characterized in that, described method comprises following preparation process: precise 3.222g, ZrOCl ₂﹒ 8H ₂o is dissolved in 100ml distilled water, drips 40ml ammoniacal liquor, fully stirs and obtains white gum throw out, by sedimentation and filtration, and repeatedly wash with distilled water, remove Cl ^-, precipitation is dissolved in 100ml, in the dust technology of 0.05mol/L, stirs and obtain ZrO (NO ₃) ₂solution; Again by 1.733g, Gd ₂o ₃be dissolved in 100ml, in 0.05mol/L dilute nitric acid solution, form Gd (NO ₃) ₃solution; Take two parts of 11.38g stearic acid and at 80 DEG C, be heated to fusing, now n (Gd ³⁺): n (Zr ⁴⁺): n (stearic acid)=1:1:4, adds respectively by ZrO (NO ₃) ₂with Gd (NO ₃) ₃solution mixing 30min, by two parts of solution mixing, add 0.33g cetyl trimethylammonium bromide, in 120 DEG C of vigorous stirring 2h, form dense thick yellow transparent solution, solution naturally cools to gel formed at room temperature, gel is placed in heating on hot-plate until burning, obtain black puffy presoma, presoma is through grinding, after crossing 200 order square hole sieves, obtain nanometer Gd in 700 DEG C of calcining 4h ₂zr ₂o ₇powder; Nanometer Gd ₂zr ₂o ₇morphology microstructure is spherical, and particle diameter is 10nm.