CN102277168A - Gadolinium thulium vanadate/borate blue light-emitting material and preparation method thereof - Google Patents
Gadolinium thulium vanadate/borate blue light-emitting material and preparation method thereof Download PDFInfo
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- CN102277168A CN102277168A CN2011101687953A CN201110168795A CN102277168A CN 102277168 A CN102277168 A CN 102277168A CN 2011101687953 A CN2011101687953 A CN 2011101687953A CN 201110168795 A CN201110168795 A CN 201110168795A CN 102277168 A CN102277168 A CN 102277168A
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Abstract
The invention provides a gadolinium thulium vanadate/borate blue light-emitting material. The material is characterized in that the chemical formula is Gd1-y(VO4)x(BO3)1-x:Tmy; and in the formula, x is not less than 0.1 and not more than 0.9 and y is not less than 0.01 and not more than 0.05. In a preparation method of the material, ammonium metavanadate, gadolinium nitrate, thulium nitrate, boric acid and citric acid are selected as raw materials, and the preparation method comprises the following steps: (1) putting ammonium metavanadate and boric acid into a container, adding deionized water to form a solution defined as solution A, putting gadolinium nitrate, thulium nitrate and citric acid into the container, adding deionized water to form a solution defined as solution B, adding the solution A to the solution B, stirring the solution uniformly, thus forming sol, adjusting the pH value of the sol to be not less than 4 and not more than 10, continuing stirring at 60-80 DEG C until gel is formed and then drying the gel, thus obtaining a precursor; (2) grinding and dispersing the precursor, then roasting the product at normal pressure and 700-900 DEG C for 1-4 hours, then taking out the product and air-cooling the product; and (3) grinding and dispersing the roasted product, then washing the product and drying the washed powder.
Description
Technical field
The invention belongs to field of light emitting materials, particularly a kind of rare earth blue emitting material and preparation method thereof.
Background technology
The rare-earth vanadate luminescent material has high thermostability and chemical stability, especially under the vacuum ultraviolet (VUV) irradiation, have stable luminous efficiency and energy transfer efficiency advantages of higher, be mainly used in the fluorescent material and the high voltage mercury lamp fluorescent powder material in PDP, FED field.What research was maximum at present is to adopt Eu activated red illuminating material, as YVO commonly used
4: Eu, then add P, the modification red illuminating material of elements such as Gd preparation on its basis.The preparation method of luminescent material is based on solid sintering technology, and the granularity of products therefrom is all in the micron number magnitude.Blue emitting material is less, and the blue-light-emitting powder on the market mainly is Eu
2+Activated aluminate luminescent powder is as BaMgAl
10O
17: Eu
2+(BAM), this is to use more blue powder at present in compact fluorescent lamp, and the heating process time of this powder is long, and uviolizing and ion bombardment all easily cause aging, cause luminescent properties to reduce.In addition, this finished product blue powder need be produced in reducing atmosphere, sometimes can be insufficient because of reducing, and cause luminous intensity to reduce.In addition, the raw material of activator Eu adopts high-purity Eu
2O
3, the product cost height.Hu Bin etc. disclose a kind of employing Prepared by Sol Gel Method GdVO
4: the method for the blue emitting material of Tm and luminescent properties (see Rare Metals Materials and engineering, 37 (1), 176-179), but the luminescent powder particulate dimensional homogeneity of this method preparation is relatively poor, and pattern is irregular, and this will influence luminous intensity.
Summary of the invention
The object of the present invention is to provide vanadium boric acid gadolinium thulium blue emitting material and preparation method thereof,, improve luminous intensity to improve the homogeneity of luminescent powder particle size.
Vanadium boric acid gadolinium thulium blue emitting material of the present invention, its chemical constitution is: Gd
1-y(VO
4)
x(BO
3)
1-x: Tm
y, in the formula, 0.1≤x≤0.9,0.01≤y≤0.05.
The preparation method of vanadium boric acid gadolinium thulium blue emitting material of the present invention, as activator, boron is as the matrix sensitizing agent with thulium, and processing step is as follows:
(1) preparation of precursor
With metavanadic acid ammonia, Gadolinium trinitrate, thulium nitrate, boric acid, citric acid is raw material, according to the chemical constitution Gd of vanadium boric acid gadolinium thulium blue emitting material of the present invention
1-y(VO
4)
x(BO
3)
1-x: Tm
y(0.1≤x≤0.9,0.01≤y≤0.05) metering metavanadic acid ammonia, Gadolinium trinitrate, thulium nitrate and boric acid, mol ratio by gadolinium+thulium and citric acid is 1: 3～7 metering citric acids (described " mol ratio of gadolinium+thulium and citric acid " is meant the total mole number of gadolinium and thulium and the ratio of the mole number of citric acid), and operation steps is:
1. will put into container and add deionized water by the metavanadic acid ammonia and the boric acid of said ratio metering, the add-on of deionized water is exceeded can dissolve metavanadic acid ammonia and boric acid, under normal pressure, room temperature～60 ℃, stir, till metavanadic acid ammonia and boric acid dissolved fully, formed solution was defined as A solution;
2. will put into container and add deionized water by Gadolinium trinitrate, thulium nitrate, the citric acid of said ratio metering, the add-on of deionized water is exceeded can dissolve Gadolinium trinitrate, thulium nitrate and citric acid, under normal pressure, room temperature～60 ℃, stir, till Gadolinium trinitrate, thulium nitrate and citric acid dissolved fully, formed solution was defined as B solution;
3. A solution is joined in the B solution, under normal pressure, 30 ℃～60 ℃, stir and promptly form colloidal sol, regulate pH value to 4≤pH≤10 of described colloidal sol with rare nitric acid, and under 60 ℃～80 ℃, continue to stir until forming gel, continue after with gel normal pressure, 100 ℃～120 ℃ following dryings at least 24 hours, promptly obtain presoma;
(2) roasting of precursor
The presoma of step (1) preparation ground put into process furnace after disperseing, normal pressure, 700 ℃～900 ℃ following roastings 1 hour～4 hours, roasting time back was at the expiration taken out be cooled to room temperature in air;
(3) processing of product of roasting
The product of roasting that step (2) is obtained grinds dispersion, and uses rare nitric acid, washed with de-ionized water successively, and the powder after will cleaning then carries out drying, promptly obtains vanadium boric acid gadolinium thulium blue emitting material of the present invention.
In the aforesaid method, regulating the pH value of described colloidal sol and the mass concentration of the used rare nitric acid of cleaning product of roasting is 5%～10%.
The present invention has following beneficial effect:
(1) the vanadium boric acid gadolinium thulium blue emitting material of the method for the invention preparation is compared with the vanadic acid Ga Thulium blue emitting material that adopts prior art for preparing, and the size of powder granule is littler more even, form more regular (seeing Fig. 1, Fig. 2);
(2) the vanadium boric acid gadolinium thulium blue emitting material of the method for the invention preparation, the strongest wavelength of transmitted light shows pure blueness at 476nm, compares with the vanadic acid Ga Thulium blue emitting material that adopts prior art for preparing, luminous intensity increases substantially (see figure 3);
(3) preparation method is simpler, and synthesis temperature is low, and roasting need not reducing atmosphere.
(4) raw material of activator Tm is a thulium nitrate, with respect to the high-purity Eu of the raw material of activator Eu
2O
3, help reducing cost.
Description of drawings
Fig. 1 is the shape appearance figure of vanadium boric acid gadolinium thulium blue emitting material of the present invention (embodiment 1);
Fig. 2 is the shape appearance figure that adopts the vanadic acid Ga Thulium blue emitting material (Comparative Examples) of prior art for preparing;
Fig. 3 is the luminescent spectrum comparison diagram of the prepared blue emitting material of embodiment 1 and Comparative Examples.
Embodiment
Below by embodiment the glucose modified method for preparing vanadic acid Ga Thulium blue emitting material of usefulness of the present invention is described further.
Embodiment 1
In the present embodiment, the chemical constitution of prepared vanadium boric acid gadolinium thulium blue emitting material is Gd
0.98(VO
4)
0.6(BO
3)
0.4: Tm
0.02, processing step is as follows:
(1) preparation of precursor
With NH
4VO
3(metavanadic acid ammonia), Gd (NO
3)
3.6H
2O (Gadolinium trinitrate), Tm (NO
3)
3.5H
2O (thulium nitrate), H
3BO
3(boric acid), citric acid are raw material, according to the chemical constitution metering NH of prepared vanadium boric acid gadolinium thulium blue emitting material
4VO
3, Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and H
3BO
3, be 1: 6 metering citric acid by the mol ratio of gadolinium+thulium and citric acid, operation steps is:
1. will be by the NH of said ratio metering
4VO
3And H
3BO
3Put into container and add deionized water, the add-on of deionized water is can dissolve NH
4VO
3And H
3BO
3Exceed, under normal pressure, 50 ℃, stir, until NH
4VO
3And H
3BO
3Till the dissolving, formed solution is defined as A solution fully;
2. will be by the Gd (NO of said ratio metering
3)
3.6H
2O, Tm (NO
3)
3.5H
2O, citric acid are put into container and are added deionized water, and the add-on of deionized water is can dissolve Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and citric acid exceed, and stir under normal pressure, 50 ℃, until Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2Till O and citric acid dissolved fully, formed solution was defined as B solution;
3. A solution is joined in the B solution, under normal pressure, 50 ℃, stir and promptly form colloidal sol, regulate the pH value to 6 of described colloidal sol with rare nitric acid of mass concentration 5%, and under 70 ℃, continue to stir until forming gel, continue after with gel normal pressure, 120 ℃ dry 24 hours down, promptly obtain presoma;
(2) roasting of precursor
The presoma of step (1) preparation ground put into process furnace after disperseing, normal pressure, 900 ℃ of following roastings 3 hours, roasting time back was at the expiration taken out be cooled to room temperature in air;
(3) processing of product of roasting
The product of roasting that step (2) is obtained grinds dispersion, and respectively cleans three times with rare nitric acid, the deionized water of mass concentration 5% successively, and the powder usefulness baking oven after will cleaning then is 100 ℃ of oven dry, and promptly obtaining chemical constitution is Gd
0.98(VO
4)
0.6(BO
3)
0.4: Tm
0.02Vanadium boric acid gadolinium thulium blue emitting material.
The vanadium boric acid gadolinium thulium blue emitting material that obtains is scanned with scanning electron microscope, and analytical results is seen Fig. 1, and the vanadium boric acid gadolinium thulium blue emitting material that obtains is carried out the emmission spectrum test with fluorescence spectrophotometer, and test result is seen Fig. 3.
Comparative Examples
It is Gd that this Comparative Examples prepares chemical constitution
0.98(VO
4): Tm
0.02Vanadic acid Ga Thulium blue emitting material, processing step is as follows:
(1) preparation of precursor
With NH
4VO
3(metavanadic acid ammonia), Gd (NO
3)
3.6H
2O (Gadolinium trinitrate), Tm (NO
3)
3.5H
2O (thulium nitrate), citric acid are raw material, press the mol ratio V of vanadium, gadolinium, thulium: Gd: Tm=1: 0.98: 0.02 metering NH
4VO
3, Gd (NO
3)
3.6H
2O and Tm (NO
3)
3.5HXO, be 1: 6 metering citric acid by the mol ratio of Gd+Tm and citric acid, operation steps is:
1. will be by the NH of said ratio metering
4VO
3Put into container and add deionized water, the add-on of deionized water is can dissolve NH
4VO
3Exceed, stir under normal pressure, 50 ℃, till metavanadic acid ammonia dissolved fully, formed solution was defined as A solution;
2. will be by the Gd (NO of said ratio metering
3)
3.6H
2O, Tm (NO
3)
3.5H
2O, citric acid are put into container and are added deionized water, and the add-on of deionized water is can dissolve Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and citric acid exceed, and stir under normal pressure, 50 ℃, make Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and citric acid dissolve fully, and formed solution is defined as B solution,
3. under agitation described A solution is joined in the described B solution in normal pressure, 50 ℃, regulate the pH value to 6 of described colloidal sol with rare nitric acid of mass concentration 5%, and continue down to stir until forming gel at 70 ℃, continue after with gel normal pressure, 120 ℃ dry 24 hours down, promptly obtain presoma;
(2) roasting of precursor
The presoma of step (1) preparation ground put into process furnace after disperseing, normal pressure, 900 ℃ of following roastings 3 hours, roasting time back was at the expiration taken out be cooled to room temperature in air;
(3) processing of product of roasting
The product of roasting that step (2) is obtained grinds dispersion, and respectively cleans three times with rare nitric acid, the deionized water of mass concentration 5% successively, and the powder usefulness baking oven after will cleaning then promptly obtains vanadic acid Ga Thulium blue emitting material 100 ℃ of oven dry.
The vanadic acid Ga Thulium blue emitting material that obtains is scanned with scanning electron microscope, and analytical results is seen Fig. 2, and the vanadic acid Ga Thulium blue emitting material that obtains is carried out the emmission spectrum test with fluorescence spectrophotometer, and test result is seen Fig. 3.
From embodiment 1 and Comparative Examples as can be seen, vanadium boric acid gadolinium thulium blue emitting material of the present invention is compared with the vanadic acid Ga Thulium blue emitting material that adopts prior art for preparing, and the size of powder granule is littler, more even, and form is more regular; Vanadium boric acid gadolinium thulium blue emitting material of the present invention, the strongest wavelength of transmitted light is compared with the vanadic acid Ga Thulium blue emitting material that adopts prior art for preparing at 476nm, and luminous intensity increases substantially.
Embodiment 2
In the present embodiment, the chemical constitution of prepared vanadium boric acid gadolinium thulium blue emitting material is Gd
0.99(VO
4)
0.6(BO
3)
0.4: Tm
0.01, processing step is as follows:
(1) preparation of precursor
With NH
4VO
3(metavanadic acid ammonia), Gd (NO
3)
3.6H
2O (Gadolinium trinitrate), Tm (NO
3)
3.5H
2O (thulium nitrate), H
3BO
3(boric acid), citric acid are raw material, according to the chemical constitution metering NH of prepared vanadium boric acid gadolinium thulium blue emitting material
4VO
3, Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and H
3BO
3, be 1: 3 metering citric acid by the mol ratio of gadolinium+thulium and citric acid, operation steps is:
1. will be by the NH of said ratio metering
4VO
3And H
3BO
3Put into container and add deionized water, the add-on of deionized water is exceeded can dissolve metavanadic acid ammonia and boric acid, stirs under normal pressure, room temperature (22 ℃), and till metavanadic acid ammonia and boric acid dissolved fully, formed solution was defined as A solution;
2. will be by the Gd (NO of said ratio metering
3)
3.6H
2O, Tm (NO
3)
3.5H
2O, citric acid are put into container and are added deionized water, and the add-on of deionized water is can dissolve Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and citric acid exceed, and stir under normal pressure, room temperature (22 ℃), until Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2Till O and citric acid dissolved fully, formed solution was defined as B solution;
3. A solution is joined in the B solution, under normal pressure, 30 ℃, stir and promptly form colloidal sol, regulate the pH value to 4 of described colloidal sol with rare nitric acid of mass concentration 8%, and under 60 ℃, continue to stir until forming gel, continue after with gel normal pressure, 100 ℃ dry 30 hours down, promptly obtain presoma;
(2) roasting of precursor
The presoma of step (1) preparation ground put into process furnace after disperseing, normal pressure, 700 ℃ of following roastings 4 hours, roasting time back was at the expiration taken out be cooled to room temperature in air;
(3) processing of product of roasting
The product of roasting that step (2) is obtained grinds dispersion, and respectively cleans three times with rare nitric acid, the deionized water of mass concentration 8% successively, and the powder usefulness baking oven after will cleaning then is 100 ℃ of oven dry, and promptly obtaining chemical constitution is Gd
0.99(VO
4)
0.6(BO
3)
0.4: Tm
0.01Vanadium boric acid gadolinium thulium blue emitting material.
Embodiment 3
In the present embodiment, the chemical constitution of prepared vanadium boric acid gadolinium thulium blue emitting material is Gd
0.97(VO
4)
0.1(BO
3)
0.9: Tm
0.03, processing step is as follows:
(1) preparation of precursor
With NH
4VO
3(metavanadic acid ammonia), Gd (NO
3)
3.6H
2O (Gadolinium trinitrate), Tm (NO
3)
3.5H
2O (thulium nitrate), H
3BO
3(boric acid), citric acid are raw material, according to the chemical constitution metering NH of prepared vanadium boric acid gadolinium thulium blue emitting material
4VO
3, Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and H
3BO
3, be 1: 4 metering citric acid by the mol ratio of gadolinium+thulium and citric acid, operation steps is:
1. will be by the NH of said ratio metering
4VO
3And H
3BO
3Put into container and add deionized water, the add-on of deionized water is can dissolve NH
4VO
3And H
3BO
3Exceed, under normal pressure, 60 ℃, stir, until NH
4VO
3And H
3BO
3Till the dissolving, formed solution is defined as A solution fully;
2. will be by the Gd (NO of said ratio metering
3)
3.6H
2O, Tm (NO
3)
3.5H
2O, citric acid are put into container and are added deionized water, and the add-on of deionized water is can dissolve Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and citric acid exceed, and stir under normal pressure, 60 ℃, until Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2Till O and citric acid dissolved fully, formed solution was defined as B solution;
3. A solution is joined in the B solution, under normal pressure, 60 ℃, stir and promptly form colloidal sol, regulate the pH value to 7 of described colloidal sol with rare nitric acid of mass concentration 10%, and under 80 ℃, continue to stir until forming gel, continue after with gel normal pressure, 100 ℃ dry 30 hours down, promptly obtain presoma;
(2) roasting of precursor
The presoma of step (1) preparation ground put into process furnace after disperseing, normal pressure, 900 ℃ of following roastings 1 hour, roasting time back was at the expiration taken out be cooled to room temperature in air;
(3) processing of product of roasting
The product of roasting that step (2) is obtained grinds dispersion, and respectively cleans three times with rare nitric acid, the deionized water of mass concentration 10% successively, and the powder usefulness baking oven after will cleaning then is 100 ℃ of oven dry, and promptly obtaining chemical constitution is Gd
0.97(VO
4)
0.1(BO
3)
0.9: Tm
0.03Vanadium boric acid gadolinium thulium blue emitting material.
Embodiment 4
In the present embodiment, the chemical constitution of prepared vanadium boric acid gadolinium thulium blue emitting material is Gd
0.95(VO
4)
0.3(BO
3)
0.7: Tm
0.05, processing step is as follows:
(1) preparation of precursor
With NH
4VO
3(metavanadic acid ammonia), Gd (NO
3)
3.6H
2O (Gadolinium trinitrate), Tm (NO
3)
3.5H
2O (thulium nitrate), H
3BO
3(boric acid), citric acid are raw material, according to the chemical constitution metering NH of prepared vanadium boric acid gadolinium thulium blue emitting material
4VO
3, Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and H
3BO
3, be 1: 7 metering citric acid by the mol ratio of gadolinium+thulium and citric acid, operation steps is:
1. will be by the NH of said ratio metering
4VO
3And H
3BO
3Put into container and add deionized water, the add-on of deionized water is can dissolve NH
4VO
3And H
3BO
3Exceed, under normal pressure, 40 ℃, stir, until NH
4VO
3And H
3BO
3Till the dissolving, formed solution is defined as A solution fully;
2. will be by the Gd (NO of said ratio metering
3)
3.6H
2O, Tm (NO
3)
3.5H
2O, citric acid are put into container and are added deionized water, and the add-on of deionized water is can dissolve Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and citric acid exceed, and stir under normal pressure, 40 ℃, until Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2Till O and citric acid dissolved fully, formed solution was defined as B solution;
3. A solution is joined in the B solution, under normal pressure, 40 ℃, stir and promptly form colloidal sol, regulate the pH value to 7 of described colloidal sol with rare nitric acid of mass concentration 10%, and under 65 ℃, continue to stir until forming gel, continue after with gel normal pressure, 110 ℃ dry 26 hours down, promptly obtain presoma;
(2) roasting of precursor
The presoma of step (1) preparation ground put into process furnace after disperseing, normal pressure, 800 ℃ of following roastings 2 hours, roasting time back was at the expiration taken out be cooled to room temperature in air;
(3) processing of product of roasting
The product of roasting that step (2) is obtained grinds dispersion, and respectively cleans three times with rare nitric acid, the deionized water of mass concentration 10% successively, and the powder usefulness baking oven after will cleaning then is 100 ℃ of oven dry, and promptly obtaining chemical constitution is Gd
0.95(VO
4)
0.3(BO
3)
0.7: Tm
0.05Vanadium boric acid gadolinium thulium blue emitting material.
Embodiment 5
In the present embodiment, the chemical constitution of prepared vanadium boric acid gadolinium thulium blue emitting material is Gd
0.96(VO
4)
0.9(BO
3)
0.1: Tm
0.04, processing step is as follows:
(1) preparation of precursor
With NH
4VO
3(metavanadic acid ammonia), Gd (NO
3)
3.6H
2O (Gadolinium trinitrate), Tm (NO
3)
3.5H
2O (thulium nitrate), H
3BO
3(boric acid), citric acid are raw material, according to the chemical constitution metering NH of prepared vanadium boric acid gadolinium thulium blue emitting material
4VO
3, Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and H
3BO
3, be 1: 5 metering citric acid by the mol ratio of gadolinium+thulium and citric acid, operation steps is:
1. will be by the NH of said ratio metering
4VO
3And H
3BO
3Put into container and add deionized water, the add-on of deionized water is can dissolve NH
4VO
3And H
3BO
3Exceed, under normal pressure, 30 ℃, stir, until NH
4VO
3And H
3BO
3Till the dissolving, formed solution is defined as A solution fully;
2. will be by the Gd (NO of said ratio metering
3)
3.6H
2O, Tm (NO
3)
3.5H
2O, citric acid are put into container and are added deionized water, and the add-on of deionized water is can dissolve Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2O and citric acid exceed, and stir under normal pressure, 30 ℃, until Gd (NO
3)
3.6H
2O, Tm (NO
3)
3.5H
2Till O and citric acid dissolved fully, formed solution was defined as B solution;
3. A solution is joined in the B solution, under normal pressure, 30 ℃, stir and promptly form colloidal sol, regulate the pH value to 7 of described colloidal sol with rare nitric acid of mass concentration 10%, and under 70 ℃, continue to stir until forming gel, continue after with gel normal pressure, 100 ℃ dry 30 hours down, promptly obtain presoma;
(2) roasting of precursor
The presoma of step (1) preparation ground put into process furnace after disperseing, normal pressure, 800 ℃ of following roastings 3 hours, roasting time back was at the expiration taken out be cooled to room temperature in air;
(3) processing of product of roasting
The product of roasting that step (2) is obtained grinds dispersion, and respectively cleans three times with rare nitric acid, the deionized water of mass concentration 10% successively, and the powder usefulness baking oven after will cleaning then is 100 ℃ of oven dry, and promptly obtaining chemical constitution is Gd
0.96(VO
4)
0.9(BO
3)
0.1: Tm
0.04Vanadium boric acid gadolinium thulium blue emitting material.
Claims (3)
1. vanadium boric acid gadolinium thulium blue emitting material is characterized in that chemical constitution is: Gd
1-y(VO
4)
x(BO
3)
1-x: Tm
y, in the formula, 0.1≤x≤0.9,0.01≤y≤0.05.
2. the preparation method of the described vanadium boric acid of claim 1 a gadolinium thulium blue emitting material is characterized in that processing step is as follows:
(1) preparation of precursor
With metavanadic acid ammonia, Gadolinium trinitrate, thulium nitrate, boric acid, citric acid is raw material, chemical constitution metering metavanadic acid ammonia, Gadolinium trinitrate, thulium nitrate and boric acid according to the described vanadium boric acid of claim 1 gadolinium thulium blue emitting material, mol ratio by gadolinium+thulium and citric acid is 1: 3～7 metering citric acids, and operation steps is:
1. will put into container and add deionized water by the metavanadic acid ammonia and the boric acid of said ratio metering, the add-on of deionized water is exceeded can dissolve metavanadic acid ammonia and boric acid, under normal pressure, room temperature～60 ℃, stir, till metavanadic acid ammonia and boric acid dissolved fully, formed solution was defined as A solution;
2. will put into container and add deionized water by Gadolinium trinitrate, thulium nitrate, the citric acid of said ratio metering, the add-on of deionized water is exceeded can dissolve Gadolinium trinitrate, thulium nitrate and citric acid, under normal pressure, room temperature～60 ℃, stir, till Gadolinium trinitrate, thulium nitrate and citric acid dissolved fully, formed solution was defined as B solution;
3. A solution is joined in the B solution, under normal pressure, 30 ℃～60 ℃, stir and promptly form colloidal sol, regulate pH value to 4≤pH≤10 of described colloidal sol with rare nitric acid, and under 60 ℃～80 ℃, continue to stir until forming gel, continue after with gel normal pressure, 100 ℃～120 ℃ following dryings at least 24 hours, promptly obtain presoma;
(2) roasting of precursor
The presoma of step (1) preparation ground put into process furnace after disperseing, normal pressure, 700 ℃～900 ℃ following roastings 1 hour～4 hours, roasting time back was at the expiration taken out be cooled to room temperature in air;
(3) processing of product of roasting
The product of roasting that step (2) is obtained grinds dispersion, and uses rare nitric acid, washed with de-ionized water successively, and the powder after will cleaning then carries out drying, promptly obtains the described vanadium boric acid of claim 1 gadolinium thulium blue emitting material.
3. according to the preparation method of the described vanadium boric acid of claim 2 gadolinium thulium blue emitting material, it is characterized in that the mass concentration of regulating the pH value of described colloidal sol and cleaning the used rare nitric acid of product of roasting is 5%～10%.
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| 史春婷等: "新型(Y,Gd)(BO3)(VO4):Eu荧光粉的合成及发光性能研究", 《稀有金属材料与工程》 * |
| 徐晨等: "Yb掺杂蓝色荧光材料GdVO4：Tm的发光性能", 《稀有金属材料与工程》 * |
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