CN101298337A - Preparation of Y2O3: Eu3+ nanosphere powder - Google Patents

Abstract

The invention relates to a method for producing Y2O3:Eu3plus nanometer ball powder, which belongs to the technical field of the inorganic nanophase material. The production method of the invention comprises the following steps of: (1) weighting the raw materials (counted by chemical mass): 1.0-3.0 mmol of yttrium nitrate, 0.05-0.15 mmol of europium nitrate, 20-60mmol of urea and 0.1-0.3mmol of cetyl trimethylammonium bromide, and then dissolving the materials in 40-100ml of de-ionized water; (2) placing the mixed solution into a round flask and leading reflux reaction to carry out without heating under the magnetic stirring for 30-60 min; cooling the solution to normal temperature and then carrying out separation, washing and drying for the obtained precipitate; (3) calcining for 2-4 hours under 600-1000 DEG C and finally obtaining the Y2O3:Eu3plus nanometer ball powder with the average particle diameter of 100 nm. The instrument test indicates that the sample obtained by the method of the invention has good dispersibility, uniform article size and has excellent luminous property.

Description

Y 2O 3: Eu 3+The preparation method of nanosphere powder

Technical field

The present invention relates to a kind of Y ₂O ₃: Eu ³⁺The preparation method of nanosphere powder belongs to the inorganic nano material preparation process technology field.

Background technology

The rare earth resources of China is very abundant, accounts for the world's more than 80% of proven reserve, and industrial reserves is the first in the world.Rare earth material is having a wide range of applications aspect high energy magnetic device, luminescent device, catalyzer and other functional materialss owing to its unique electricity, optics and chemical property.Among this, be the treasure-house of luminescent material on rare always.Yttrium oxide has good stability and useful energy transmitting characteristic, and the thermal conductivity height, is easy to realize the doping of rare earth ion, and these advantages make it become a kind of good luminescent material matrix (solid luminescence, Jilin physics Suo ﹠amp; China Science ﹠ Technology University, 1976, p57-p60).In yttrium oxide, mix into a small amount of europium, can be used as red fluorescence powder and up-conversion luminescence and laserable material.Y ₂O ₃: Eu ³⁺Material luminescent properties excellence, the luminous efficiency height, be widely used in photoluminescence, the luminous field of cathodoluminescence and X ray, as high definition television (HDTV), cathode ray tube (CRT), plasma shows (PDP) and field-emitter display (FED) [Junying Zhanget al.Journal of Material Processing Technology, 2002,121:265-268].Has intact spherical morphology, the Y of size little and narrowly distributing and good dispersion ₂O ₃: Eu ³⁺Particle, because having less loading capacity, it just can reach higher loading density and lower scattering of light rate, it is applied in cathodoluminescence and the kinds of displays, under low voltage, just can have high brightness and sharpness (Gareth Wakefield et al.Adv.Mater.2001,13,1557-1560).Therefore, Y ₂O ₃: Eu ³⁺The nanometer ball luminescent material has many advantages, and important potential application foreground will be arranged.At present, to having the Y of spherical morphology ₂O ₃: Eu ³⁺Material synthetic, and its size and dispersiveness regulated and control just to become a research of inorganic material preparation process technical field focus.

U.S. Pat 005525259 has been introduced a kind of under the fusing assistant effect, and yttrium oxide and europium sesquioxide mixture are incubated 5 hours for 1288 ℃ at high temperature, and through grinding and screening technology, obtaining mean sizes is micron-sized Y ₂O ₃: Eu ³⁺The luminescent lamp powder.Though this preparation method is not very complicated, and is higher to equipment requirements, power consumption is big, be difficult for applying, and the product size is bigger, can increase the probability of radiationless transition, has reduced its luminescent properties.U.S. Pat 5116560, US5100598, US5116559 adopt the ammonium salt or the ammoniacal liquor of different acid to do precipitation agent respectively in these three patents, the two-step precipitation legal system of carrying out subsequent disposal with oxalic acid is equipped with Y again ₂O ₃: Eu ³⁺Powder.These method shortcomings mainly are the technology more complicated.Proposed a kind of employing ammoniacal liquor and bicarbonate mixture among the Chinese patent CN1239674 as compound precipitants, also calcined subsequently with coprecipitation method and prepared Y ₂O ₃: Eu ³⁺Nano-powder, the product single particle is of a size of 60～80nm.Though this preparation method's condition is relatively gentleer, preparation procedure is loaded down with trivial details, and gained nano particle pattern is irregular, and it is serious to reunite, and has reduced luminous intensity.And at present relevant Y ₂O ₃: Eu ^{3 +}The preparation of nanosphere powder does not have report as yet in patent.

In the relevant report of document, there is the scholar to adopt solvent-thermal method to prepare the Y that forms by the nanoparticle random aggregation ₂O ₃: Eu ³⁺The micron ball, the products therefrom size is not a homogeneous very.This preparation method's condition harshness, High Temperature High Pressure, experimental result circulation ratio are not fine (Jun Yang et al.Crystal Growth ﹠amp; Design 2007, and Vol 7, No.4,730-735).There is the scholar to adopt the spraying high temperature pyrolytic cracking (HTP) to make Y ₂O ₃: Eu ³⁺Sub-micron ball can be regulated and control the sub-micron ball size by the control pyrolysis temperature.But this preparation method needs expensive production unit, has limited its application greatly.Simultaneously, particle size is bigger, luminous efficiency be not very high (Weining Wang et al.Chem.Mater.2007,19,1723-1730).There is the scholar to utilize urea to be precipitation agent, under solution boiling condition, carries out homogeneous deposition,, make the micron ball of size at 300-400nm then to the precipitation calcination processing.Though this method is simple, the micron pelletizing is poly-serious in the product, reduced luminous intensity (J.Silver, et al.J.Phys.Chem.B2001,105,9107-9112).In addition, preparation Y ₂O ₃: Eu ³⁺Spheroidal particle material method also has sol-gel method, but the various complexity of the common operation of this method; The powder luminescent properties that combustion method obtains is relatively poor, and needs aftertreatment.Current common preparation Y ₂O ₃: Eu ³⁺The total shortcoming of spheroidal particle material method is that sphere sizes is bigger, and it is more serious to reunite.

Summary of the invention

One of purpose of the present invention provides a kind of novel, the size homogeneous, difficult reunion, constitutionally stable Y ₂O ₃: Eu ³⁺Nanosphere powder.

Two of the object of the invention provides the Y that a kind of technology is simple, cost is low, the reaction times is short ₂O ₃: Eu ³⁺The preparation method of nanosphere powder.

A kind of Y of the present invention ₂O ₃: Eu ³⁺The preparation method of nanosphere powder is characterized in that having following process and step:

A. take by weighing following each raw material respectively: Yttrium trinitrate 1.0～3.0mmol in chemical quality; Europium nitrate 0.05～0.15mmol; Urea 20～60mmol; Cetyl trimethylammonium bromide 0.1～0.3mmol; Above-mentioned each material dissolution in the deionized water of 40～100ml, is obtained mixing solutions; Wherein the mol ratio of Yttrium trinitrate and europium nitrate is 20: 1; Its add-on of urea as precipitation agent is a benchmark with the Yttrium trinitrate consumption, and its usage ratio is 20: 1; Its add-on of cetyl trimethylammonium bromide as tensio-active agent is a benchmark with the Yttrium trinitrate consumption, and its usage ratio is 0.1: 1;

B. above-mentioned mixing solutions is transferred in the round-bottomed flask, under with the magnetic stir bar agitation condition, heating reflux reaction 30～60min; Heating temperature is 90～110 ℃; Be cooled to room temperature subsequently, the gained white depositions carried out centrifugation, then with deionized water wash repeatedly to remove unnecessary tensio-active agent, use absolute ethanol washing again; Place then under 60 ℃ of temperature of baking oven and dry, obtain white powder;

C. above-mentioned dry back gained powder is utilized the retort furnace of temperature programmed control, the temperature rise rate with 5 ℃/min under air conditions rose to 600～1000 ℃, this temperature lower calcination 2～4 hours; Finally obtain the Y that median size is 100nm ₂O ₃: Eu ³⁺Nanosphere powder.

The inventive method can make single-size, be difficult for reunion, constitutionally stable Y ₂O ₃: Eu ³⁺Nanosphere powder; Nanosphere powder can be regulated and control in 10～150nm scope.In addition, the nanosphere powder particle diameter is little, and narrow distribution range, its favorable dispersity.The prepared Y of the inventive method ₂O ₃: Eu ³⁺Nanosphere powder also has excellent luminescent properties.It is simple that the inventive method has technology, easy to operate, characteristics such as easy control of structure.

Description of drawings

Fig. 1 among the present invention through X-ray diffraction (XRD) collection of illustrative plates of 600 ℃ of calcinings sample after 4 hours.

Fig. 2 among the present invention through transmission electron microscope (TEM) photo of 600 ℃ of calcinings sample after 4 hours.

Fig. 3 is at wavelength being the emmission spectrum under the 254nm ultraviolet excitation.(a) Y of making for the inventive method wherein ₂O ₃: Eu ³⁺Nanosphere powder; (b) Y that makes for certain bibliographical information method ₂O ₃: Eu ³⁺Nano-bar material.

Embodiment

After now specific embodiments of the invention being described in.

Embodiment 1:

(1) takes by weighing following each raw material respectively: Yttrium trinitrate 1.0mmol in chemical quality; Europium nitrate 0.05mmol; Urea 20mmol; Cetyl trimethylammonium bromide 0.1mmol; Above-mentioned each material dissolution in the deionized water of 40ml, is obtained mixing solutions; In this solution, the concentration of Yttrium trinitrate is 25mmol/L, and the concentration of europium nitrate is 1.25mmol/L, and the concentration of urea is 500mmol/L; Add tensio-active agent 0.1mmol in addition;

(2) above-mentioned mixing solutions is transferred in the round-bottomed flask, under with the magnetic stir bar agitation condition, heating reflux reaction 50min; Heating temperature is 105 ℃; Be cooled to room temperature subsequently, the gained white depositions carried out centrifugation, then with deionized water wash 3 times to remove unnecessary tensio-active agent, use absolute ethanol washing again 1 time; Place then under 60 ℃ of temperature of baking oven and dry, obtain white powder;

(3) above-mentioned dry back gained powder is utilized the retort furnace of temperature programmed control, the temperature rise rate with 5 ℃/min under air conditions rose to 600 ℃, this temperature lower calcination 4 hours; Finally obtain the Y that median size is 100nm ₂O ₃: Eu ³⁺Nanosphere powder.

Detection test to the gained sample

1, the X-ray diffraction (XRD) through 600 ℃ of calcinings sample after 4 hours detects

Referring to Fig. 1, Fig. 1 is the XRD figure spectrum of specimen, and as can be seen from Figure 1, its diffraction peak does not have other impurity to occur mutually all corresponding to body-centered cubic yttrium oxide crystal formation, shows Eu ₂O ₃Solid solution is in Y fully ₂O ₃In the lattice.

2, measure through the transmission electron microscope (TEM) of 600 ℃ of calcinings sample after 4 hours.

Referring to Fig. 2, Fig. 2 is the TEM photo of test sample, as can be seen from Figure 2, spherical diameter average out to 100nm, size distribution is even, favorable dispersity.

3, emission spectrometry

Referring to Fig. 3, Fig. 3 is at wavelength being the emmission spectrum under the 254nm ultraviolet excitation.(a) Y of making for the inventive method wherein ₂O ₃: Eu ³⁺The nanosphere powder material; (b) Y that makes for certain bibliographical information method ₂O ₃: Eu ³⁺Nano-bar material.From Fig. 3 as seen, its emission main peak be positioned at the 611nm place, this owing to electronics at Eu ³⁺Scarce moving on two energy levels: ⁵D ₀→ ⁷F ₂From contrast, can see the Y of the present invention's preparation ₂O ₃: Eu ³⁺The nanometer ball material has than more excellent luminescent properties.

Certain document of above-mentioned (b) is meant documents and materials: [XingcaiWu et al.Journal of Crystal Groweh, 2005,277,643-649].

Claims (1)

1. Y ₂O ₃: Eu ³⁺The preparation method of nanosphere powder is characterized in that having following process and step:

A. take by weighing following each raw material respectively: Yttrium trinitrate 1.0～3.0mmol in chemical quality; Europium nitrate 0.05～0.15mmol; Urea 20～60mmol; Cetyl trimethylammonium bromide 0.1～0.3mmol; Above-mentioned each material dissolution in the deionized water of 40～100ml, is obtained mixing solutions; Wherein the mol ratio of Yttrium trinitrate and europium nitrate is 20: 1; Its add-on of urea as precipitation agent is a benchmark with the Yttrium trinitrate consumption, and its usage ratio is 20: 1; Its add-on of cetyl trimethylammonium bromide as tensio-active agent is a benchmark with the Yttrium trinitrate consumption, and its usage ratio is 0.1: 1;

B. above-mentioned mixing solutions is transferred in the round-bottomed flask, under with the magnetic stir bar agitation condition, heating reflux reaction 30～60min; Heating temperature is 90～110 ℃; Be cooled to room temperature subsequently, the gained white depositions carried out centrifugation, then with deionized water wash repeatedly to remove unnecessary tensio-active agent, use absolute ethanol washing again; Place then under 60 ℃ of temperature of baking oven and dry, obtain white powder;

C. above-mentioned dry back gained powder is utilized the retort furnace of temperature programmed control, the temperature rise rate with 5 ℃/min under air conditions rose to 600～1000 ℃, this temperature lower calcination 2～4 hours; Finally obtain the Y that median size is 100nm ₂O ₃: Eu ³⁺Nanosphere powder.

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