CN103146387A - Process for preparing porous rare-earth luminescent material by freeze-drying method - Google Patents
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Abstract
The invention relates to a process for preparing a porous rare-earth luminescent material by a freeze-drying method. The process comprises the following steps of: firstly, preparing solution from nanosized silica, sodium carboxymethylcellulose and sodium dodecyl sulfate and water, dipping the solution in liquid nitrogen so that the solution is frozen into solid state, conducting freeze-drying on the solid solution in vacuum and then calcining the same in a resistance furnace, thereby obtaining porous silicon oxide; preparing rare-earth mixed aqueous solution of yttrium nitrate and europium nitrate, steeping the prepared porous silicon oxide in the prepared rare-earth mixed aqueous solution for a while, and then performing freeze-drying in vacuum, thereby obtaining the finished product. The preparation method provided by the invention is low in cost, stable in preparation process, simple in operation and treatment and high in production efficiency; and the product is good in performance and high in porosity.
Description
Technical field
The present invention relates to a kind of ceramic preparation method, especially a kind ofly prepare porous material based on freeze-drying method, and with the preparation method of supported rare earth element.
Background technology
Rare earth has the title of industry " gold ", because it has the good physical propertys such as photoelectromagnetism, and type material that can be different, various in style with the other materials component property, its most significant function is exactly the quality and performance that increases substantially other products.Current in the world the competition of rare earth element is growed in intensity, rare earth element will occupy in the development of future technology immeasurable low level, and efficient wherein how effectively to bring into play rare earth element will be a great problem that faces now.Yttrium oxide and europium sesquioxide are a kind of as rare earth element, can send monochromatic ruddiness under burst of ultraviolel.But utilize to the full extent its luminescent properties to still have deficiency, how to make rare-earth luminescent material excite light efficiency high, consumption is few, the most perfectly improves the consistence of good article rate and production shipment, reduce production costs, economizing on resources avoids waste is to need now the problem of solution.
At present, rare-earth oxide is as catalyzer, loads to have obtained in porous material using more widely.Such as, adopt the oxyhalogenation method of the catalyzer of porous rare earth halide support, can will utilize its higher reference area to bring into play its catalytic performance in rare earth element load road porous material.But rare earth luminous porous material also is not applied.The preparation of current rare earth luminescent material focuses mostly in the preparation of powder fluorescent powder, but the powder granule particle diameter is many in the micron grating, and the preparation of the fluorescent RE powder of nanometer grating needs higher energy consumption and more complicated process.
Summary of the invention
The objective of the invention is for overcoming above-mentioned the deficiencies in the prior art, the technique that provides a kind of freeze-drying to prepare the porous rare earth luminescent material, the method stable preparation process, manipulation is simple, and production efficiency is high, good product performance.
For achieving the above object, the present invention adopts following technical proposals:
A kind of freeze-drying prepares the technique of porous rare earth luminescent material, comprises that step is as follows:
(1) be mixed with solution with nano silicon oxide, high polymer cemented dose (sodium cellulosate, polyvinyl alcohol etc.) and sodium laurylsulfonate and water, wherein high polymer cemented agent concentration is 0.3wt%, sodium laurylsulfonate concentration is 0.3wt%, silica concentration is 0.3wt%～0.9wt%, makes nano silicon oxide be dispersed in uniformly in solution with stirring under the solution room temperature;
(2) solution that step (1) is made is placed in beaker and is immersed in liquid nitrogen, makes solution freezing for solid-state, guarantee in refrigerating process that liquid nitrogen floods the solution face in beaker fully, and liquid nitrogen can not splash in beaker;
(3) sample of step (2) preparation is put into freezing temp and reach the vacuum freeze drier of-60 ℃, open vacuum mode, vacuum freeze drier operates 48 hours under the vacuum freezing pattern, takes out sample;
(4) sample is placed in crucible, and puts it in resistance furnace and calcine, be warming up to 1000 ℃ with 5 ℃/min, be incubated stopped heating after 4 hours, make it naturally cool to room temperature in stove, obtain the porous silica finished product;
(5) the rare earth mixed aqueous solution of preparation Yttrium trinitrate and europium nitrate, the mol ratio of Yttrium trinitrate and europium nitrate is 4:1, in the rare earth mixed aqueous solution, the total mol concentration of nitrate is 0.05～0.7molL-1, the porous alumina of step (4) preparation is immersed in the rare earth mixed aqueous solution of preparation, and extracting vacuum, vacuum tightness is-0.08Mpa, take out sample after pressurize 30min, use the dehydrated alcohol clean surface, be placed in baking oven, dry 1h under 100 ℃;
(6) sample that step (5) is obtained is put into resistance furnace and is calcined, and is warming up to 500～1000 ℃ with 5 ℃/min, and stopped heating after soaking time 1～4h makes it naturally cool to room temperature in stove, takes out sample, makes final porous rare earth luminescent material.
Get respectively a certain amount of sample, carry out other performance test.
The power of described baking oven is 4KW.
Described resistance furnace power is 120KW.
Described vacuum impregnation case is 150W.
Described vacuum freeze drier is 1200KW.
Dipping in above-mentioned steps (5) preferably floods 1-5 time.
The porous material of material of the present invention is that vacuum lyophilization prepares porous material, and it is a kind of based on make the technology of porous material take ice as masterplate, and under the vacuum and low temperature condition, the ice masterplate directly distils, thereby keeps the freezing pattern of nano particle.Remove organic binder bond in many matrixes by calcining, thereby form high porosity, have the porous material of certain special appearance.Porous material is applied in a lot of fields, such as at particulate filter, gas or chemical sensor, bio-reactor and the catalyzer of environmental purification and resource reutilization or absorption agent with propping material etc.Due to the restriction of the rare earth luminous fluorescent material grating of preparation, the efficient of rare earth luminous fluorescent material can't discharge fully.But the porous material loading rare earth nanometer particle by high porosity, both can effectively guarantee being evenly distributed on the porous material hole wall of rare earth element, can effectively bring into play its luminescent properties again, thereby it be few to reach rare earth element dosage, avoid waste, the purpose that reduces costs.
Beneficial effect of the present invention is: the porous silica of freeze-drying preparation has higher void content, can the more rare earth element particle of load, the nanometer rare earth oxide particle load is still keeping the higher void content of porous silica on the one hand on the porous silica hole wall; On the other hand, rare-earth oxide nano particles is in luminous power to greatest extent under ultraviolet excitation.The equipment that the present invention uses is simple and security good, and cost is lower, stable preparation process, and manipulation is simple, and production efficiency is higher.Good product performance can fully play the luminescent properties of rare earth oxide based on the porous rare earth luminescent material of lyophilize preparation, keep relatively single monochromatic ruddiness at λ=273nm burst of ultraviolel.Than the fluorescent material of micron grating, can greatly improve its luminescent properties, to bring into play to greatest extent its launching efficiency, thereby obtaining under the condition of identical luminous intensity, the porous rare earth luminescent material can effectively reduce the consumption of rare earth.On the other hand, the fluorescent material of preparation nanometer grating needs higher preparation condition and the energy consumption of Geng Gao, prepares the porous rare earth luminescent material based on simple preparation process and processing condition based on Freeze Drying Technique, more easily preparation.
Description of drawings
Fig. 1 is the x-ray diffraction pattern (a: through the dipping solution after the oven dry calcining of the sample that makes of the present invention; B: the porous matrix dipping of silicon oxide 0.45%wt 1 time; C: the porous matrix dipping of silicon oxide 0.3%wt 2 times);
Fig. 2 a is the scanning electron microscope shape appearance figure of the sample that makes of the present invention 1;
Fig. 2 b is the scanning electron microscope shape appearance figure of the sample that makes of the embodiment of the present invention 4;
Fig. 3 is the photo of sample under λ=273nm burst of ultraviolel that the present invention makes;
Fig. 4 is the excitation curve of sample under λ=273nm burst of ultraviolel that the present invention makes; (ab: the porous matrix of silicon oxide 0.3%wt floods respectively 1,2 time; Cd: the porous matrix of silicon oxide 0.45%wt floods respectively 1,2 time)
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
Embodiment 1:
Adopting the porous silica of vacuum freeze-drying method preparation is the load matrix, take rare earth nitrate solution as dipping solution, prepares the porous rare earth luminescent composite through calcination process.Weigh in the balance and get 0.036g polyvinyl alcohol and 0.036g sodium laurylsulfonate, all be dissolved in the 12ml deionized water, then take the 0.54g nano silicon, add in the above-mentioned solution that configures, stirred 3 hours on the 100r/min magnetic stirring apparatus under room temperature, obtain required silicon oxide slurry; Slip is put into freezing 5min in liquid nitrogen until fully freezing for solid-state, put into the vacuum lyophilization agent of having opened 48 hours; To be placed in resistance furnace through cryodesiccated sample and be warming up to 1000 ℃ of calcinings with 5 ℃/min, be incubated 4 hours, make its automatic cool to room temperature in stove, prepare porous silica.Take 1.016g yttrium oxide and 0.1759g europium sesquioxide with electronic balance, measuring 5ml deionized water and 5ml concentration is the concentrated nitric acid of 65wt%, and mixes; The rare earth oxide that takes is dissolved in the nitric acid of configuration, 80 ℃ of heat tracings dissolved after 1 hour, were configured to rare earth nitrate solution.Porous silica is immersed in rare earth nitrate solution, is evacuated down to-0.08Mpa, keep pressure to take out after 15 minutes, be put in 100 ℃ of dryings of loft drier 1 hour; Then, will be placed in through the sample after impregnation drying resistance furnace and be warming up to 1000 ℃ of calcinings with 5 ℃/min, be incubated 4 hours, make its automatic cool to room temperature in stove, prepare the porous rare earth luminescent composite.
Embodiment 2:
Adopting the porous silica of vacuum freeze-drying method preparation is the load matrix, take rare earth nitrate solution as dipping solution, prepares the porous rare earth luminescent composite through calcination process.Weigh in the balance and get 0.036g polyvinyl alcohol and 0.036g sodium laurylsulfonate, all be dissolved in the 12ml deionized water, then take the 0.36g nano silicon, add in the above-mentioned solution that configures, stirred 3 hours on the 100r/min magnetic stirring apparatus under room temperature, obtain required silicon oxide slurry; Slip is put into freezing 5min in liquid nitrogen until fully freezing for solid-state, put into the vacuum lyophilization agent of having opened 48 hours; To be placed in resistance furnace through cryodesiccated sample and be warming up to 1000 ℃ of calcinings with 5 ℃/min, be incubated 4 hours, make its automatic cool to room temperature in stove, prepare porous silica.Take 1.016g yttrium oxide and 0.1759g europium sesquioxide with electronic balance, measuring 5ml deionized water and 5ml concentration is the concentrated nitric acid of 65wt%, and mixes; The rare earth oxide that takes is dissolved in the nitric acid of configuration, 80 ℃ of heat tracings dissolved after 1 hour, were configured to rare earth nitrate solution.Porous silica is immersed in rare earth nitrate solution, is evacuated down to-0.08Mpa, keep pressure to take out after 15 minutes, be put in 100 ℃ of dryings of loft drier 1 hour; Then, will be placed in through the sample after impregnation drying resistance furnace and be warming up to 1000 ℃ of calcinings with 5 ℃/min, be incubated 4 hours, make its automatic cool to room temperature in stove, prepare the porous rare earth luminescent composite.
Embodiment 3:
Adopting the porous silica of vacuum freeze-drying method preparation is the load matrix, take rare earth nitrate solution as dipping solution, prepares the porous rare earth luminescent composite through calcination process.Weigh in the balance and get 0.036g polyvinyl alcohol and 0.036g sodium laurylsulfonate, all be dissolved in the 12ml deionized water, then take the 0.54g nano silicon, add in the above-mentioned solution that configures, stirred 3 hours on the 100r/min magnetic stirring apparatus under room temperature, obtain required silicon oxide slurry; Slip is put into freezing 5min in liquid nitrogen until fully freezing for solid-state, put into the vacuum lyophilization agent of having opened 48 hours; To be placed in resistance furnace through cryodesiccated sample and be warming up to 1000 ℃ of calcinings with 5 ℃/min, be incubated 4 hours, make its automatic cool to room temperature in stove, prepare porous silica.Take 1.016g yttrium oxide and 0.1759g europium sesquioxide with electronic balance, measuring 5ml deionized water and 5ml concentration is the concentrated nitric acid of 65wt%, and mixes; The rare earth oxide that takes is dissolved in the nitric acid of configuration, 80 ℃ of heat tracings dissolved after 1 hour, were configured to nitrate solution.Porous silica is immersed in rare earth nitrate solution, is evacuated down to-0.08Mpa, keep pressure to take out after 15 minutes, be put in 100 ℃ of dryings of loft drier 1 hour; Repeated impregnations drying process 2 times; Then, will be placed in through the sample after impregnation drying resistance furnace and be warming up to 1000 ℃ of calcinings with 5 ℃/min, be incubated 4 hours, make its automatic cool to room temperature in stove, prepare the porous rare earth luminescent composite.
Embodiment 4:
Adopting the porous silica of vacuum freeze-drying method preparation is the load matrix, take rare earth nitrate solution as dipping solution, prepares the porous rare earth luminescent composite through calcination process.Weigh in the balance and get 0.036g polyvinyl alcohol and 0.036g sodium laurylsulfonate, all be dissolved in the 12ml deionized water, then take the 0.72g nano silicon, add in the above-mentioned solution that configures, stirred 3 hours on the 100r/min magnetic stirring apparatus under room temperature, obtain required silicon oxide slurry; Slip is put into freezing 5min in liquid nitrogen until fully freezing for solid-state, put into the vacuum lyophilization agent of having opened 48 hours; To be placed in resistance furnace through cryodesiccated sample and be warming up to 1000 ℃ of calcinings with 5 ℃/min, be incubated 4 hours, make its automatic cool to room temperature in stove, prepare porous silica.Take 1.016g yttrium oxide and 0.1759g europium sesquioxide with electronic balance, measuring 5ml deionized water and 5ml concentration is the concentrated nitric acid of 65wt%, and mixes; The rare earth oxide that takes is dissolved in the nitric acid of configuration, 80 ℃ of heat tracings dissolved after 1 hour, were configured to rare earth nitrate solution.Porous silica is immersed in rare earth nitrate solution, is evacuated down to-0.08Mpa, keep pressure to take out after 15 minutes, be put in 100 ℃ of dryings of loft drier 1 hour; Repeated impregnations drying course 4 times; Then, will be placed in through the sample after impregnation drying resistance furnace and be warming up to 1000 ℃ of calcinings with 5 ℃/min, be incubated 4 hours, make its automatic cool to room temperature in stove, prepare the porous rare earth luminescent composite.
Fig. 1: a be concentration be the mixing solutions of the Yttrium trinitrate of 0.5wt% and europium nitrate through 5h, 100 ℃ fully after oven dry through the rare earth oxide X after 1000 ℃ of high-temperature calcination 1h-x ray diffration pattern x.Diffraction peak in figure is all Y
1.8Eu
0.2O
3, and diffraction peak is obvious, and the well-crystallized of rare earth oxide is described.B is that the porous oxidation silicon substrate is through flooding rare earth nitrate solution 1 time, and the porous rare earth luminescent material of calcination process preparation, wherein the matrix of silicon oxide is that the diffraction peak in figure is divided into SiO by the porous silica of the nano silicon oxide solution process freeze-drying method preparation of 0.45%wt
2And Y
1.8Eu
0.2O
3, two kinds of compound crystal degree are good.C is that the porous oxidation silicon substrate is through flooding rare earth nitrate solution 2 times, and the porous rare earth luminescent material of calcination process preparation, wherein the matrix of silicon oxide is that the diffraction peak in figure is divided into SiO by the porous silica of the nano silicon oxide solution process freeze-drying method preparation of 0.3%wt
2And Y
1.8Eu
0.2O
3, two kinds of compound crystal degree are good.The diffraction peak comparative analysis of abc finds that porous material can the supported rare earth oxide compound, and keeps good crystalline structure.
Fig. 2 (a) is that the porous oxidation silicon substrate is through flooding rare earth nitrate solution 1 time, and the SEM photo of the porous rare earth luminescent material of calcination process preparation, wherein the matrix of silicon oxide is the porous silica by the nano silicon oxide solution process freeze-drying method preparation of 0.45%wt.The silicon oxide for preparing porous due to freeze-drying presents straight hole road structure, but because the dipping number of times is few, the charge capacity of nanometer rare earth oxide particle is less, can't directly see in figure.Fig. 2 (b) is that the porous oxidation silicon substrate is through flooding rare earth nitrate solution 5 times, and the SEM photo of the porous rare earth luminescent material of calcination process preparation, wherein the matrix of silicon oxide is the porous silica by the nano silicon oxide solution process freeze-drying method preparation of 0.3%wt, the nano particle that can see rare earth oxide in figure loads on hole wall, impact on the pore structure size is less, thereby can fully inspire ruddiness under burst of ultraviolel.
Fig. 3 be concentration be the mixing solutions of the Yttrium trinitrate of 0.5wt% and europium nitrate through 5h, 100 ℃ fully after oven dry through the rare earth oxide after 1000 ℃ of high-temperature calcination 1h at λ=273nm burst of ultraviolel spectrum.Fig. 4 is that the porous oxidation silicon substrate is through the dipping rare earth nitrate solution, and the porous rare earth luminescent material of calcination process preparation is at λ=273nm burst of ultraviolel spectrum, wherein in collection of illustrative plates ab be the matrix of silicon oxide be by the nano silicon oxide solution of 0.3%wt through the porous silica dipping rare earth nitrate solution of freeze-drying method preparation 1 time, 2 times, cd is that the matrix of silicon oxide is through the porous silica dipping rare earth nitrate solution of freeze-drying method preparation 1 time, 2 times by the nano silicon oxide solution of 0.45%wt.As can be seen from the figure, porous silica after dipping spectrum and rare earth oxide similar under λ=273nm burst of ultraviolel found in contrast, all can show good monochromatic ruddiness, along with increasing of dipping number of times, porous adsorboluminescence silicon oxide also can show good monochromatic ruddiness.
Although above-mentionedly by reference to the accompanying drawings the specific embodiment of the present invention is described; but be not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various modifications that creative work can make or distortion still in protection scope of the present invention.
Claims (3)
1. a freeze-drying prepares the technique of porous rare earth luminescent material, it is characterized in that, comprises that step is as follows:
(1) be mixed with solution with nano silicon oxide, high polymer cemented dose and sodium laurylsulfonate and water, wherein high polymer cemented agent concentration is 0.3wt%, sodium laurylsulfonate concentration is 0.3wt%, silica concentration is 0.3wt%～0.9wt%, makes nano silicon oxide be dispersed in uniformly in solution with stirring under the solution room temperature;
(2) solution that step (1) is made is placed in beaker and is immersed in liquid nitrogen, makes solution freezing for solid-state, guarantee in refrigerating process that liquid nitrogen floods the solution face in beaker fully, and liquid nitrogen can not splash in beaker;
(3) sample of step (2) preparation is put into freezing temp and reach the vacuum freeze drier of-60 ℃, open vacuum mode, vacuum freeze drier operates 48 hours under the vacuum freezing pattern, takes out sample;
(4) sample is placed in crucible, and puts it in resistance furnace and calcine, be warming up to 1000 ℃ with 5 ℃/min, be incubated stopped heating after 4 hours, make it naturally cool to room temperature in stove, obtain the porous silica finished product;
(5) the rare earth mixed aqueous solution of preparation Yttrium trinitrate and europium nitrate, the mol ratio of Yttrium trinitrate and europium nitrate is 4:1, in the rare earth mixed aqueous solution, the total mol concentration of nitrate is 0.05～0.7molL-1, the porous alumina of step (4) preparation is immersed in the rare earth mixed aqueous solution of preparation, and extracting vacuum, vacuum tightness is-0.08Mpa, take out sample after pressurize 30min, use the dehydrated alcohol clean surface, be placed in baking oven, dry 1h under 100 ℃;
(6) sample that step (5) is obtained is put into resistance furnace and is calcined, and is warming up to 500～1000 ℃ with 5 ℃/min, and stopped heating after soaking time 1～4h makes it naturally cool to room temperature in stove, takes out sample, makes final porous rare earth luminescent material.
2. a kind of freeze-drying according to claim 1 prepares the technique of porous rare earth luminescent material, it is characterized in that, in step (1), high polymer cemented dose is sodium cellulosate or polyvinyl alcohol.
3. a kind of freeze-drying according to claim 1 prepares the technique of porous rare earth luminescent material, it is characterized in that the dipping choosing dipping in step (5) 1-5 time.
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| CN113044864A (en) * | 2021-03-05 | 2021-06-29 | 北京工业大学 | Method for preparing alkaline earth metal aluminate for cathode by freeze drying method |
| CN113044864B (en) * | 2021-03-05 | 2022-06-24 | 北京工业大学 | Method for preparing alkaline earth metal aluminate for cathode by freeze drying method |
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