The preparation method of a kind of terbium sesquioxide and yttrium oxide co-stabilized zirconium white nano fluorescent ceramic powder
Technical field
The invention belongs to technical field of material, particularly the preparation method of rare earth luminescent material.
Background technology
ZrO
2belong to novel stupalith, there is very excellent physics and chemistry performance.ZrO
2extremely low thermal conductivity and special crystalline structure and comparatively approach its thermal expansivity with metallic substance and make it to become a kind of important structural ceramics and electronic material.Due to ZrO
2high high-temp stability and high heat-proof quality, suitable especially ceramic coating and the high-temperature refractory done.In recent years, along with ZrO
2the discovery of transformation toughening technology, ZrO
2the fragility of pottery is improved greatly, and its Application Areas at engineering ceramics is also expanded greatly.
ZrO
2crystal has higher specific refractory power, good optical transparence and chemical stability, and good power, heat, electricity and optical property make it be widely used in photoelectron and other industrial circle.Especially its average phonon energy is only 470cm
-1, lower than other matrix, can improve the radiative transistion probability of mixing rare earth ion wherein, therefore, ZrO
2material is also a kind of extraordinary luminous host material, mixes terbium ion and not only can be used as active ions and give fluorescence property, and can stablize ZrO in yttria-stabilized zirconia
2the effect of crystalline phase.
Up to now, the preparation ZrO that had a large amount of literature research both at home and abroad
2the method of nano-powder, as sol-gel method, coprecipitation method, high temperature solid-state method, hydrothermal method, microemulsion method, spray pyrolysis etc.But prepare ZrO with solution combustion method
2: Tb
3+fluorescence ceramics powder but has no report.But solution combustion synthetic powder ubiquity particle aggregation sintering is serious, the problems such as specific surface area is little, make this method apply and be restricted aspect the synthetic high dispersive high-specific surface area high-performance nano fluorescence ceramics powder of preparation, therefore, become one of focus of researchist's concern.
Summary of the invention
The object of the invention provides a kind of preparation method simple, mild condition, and generated time is short, and pollution-free power consumption is few, and specific surface is large and can become mutually good powder without aftertreatment.
A preparation method for terbium sesquioxide and yttrium oxide co-stabilized zirconium white nano fluorescent ceramic powder, it comprises the following steps.
(1) according to (Tb
4o
7)
x(Y
2o
3)
y(ZrO
2)
1-4x-2y(0.010≤x+y≤0.150 wherein, 0.002≤x≤0.040) stoichiometric ratio of each metallic chemical element in, take respectively chlorine hydrate zirconium white, terbium raw material and yttrium raw material, terbium raw material and yttrium material dissolution are changed into the mixing solutions of corresponding nitrate, and chlorine hydrate zirconium white is dissolved in wherein completely, be made into the metallic mixing salt solution of target product.
(2) in the resulting mixing solutions of step (1), add soluble salt and organic-fuel, heating for dissolving obtains mixing solutions, continue heating mixing solutions and be concentrated into and approach thickness state, the heating furnace chamber of putting into design temperature and be 400 ~ 1000 ℃ ignites, and rear taking-up sample has burnt.
(3) product that step (3) obtains is through washing, filtration, dry, obtains final product.
In step (1), described terbium raw material is terbium sesquioxide, Terbium trinitrate, terbium hydroxide or terbium carbonate, and yttrium raw material is yttrium oxide, Yttrium trinitrate, yttrium hydroxide or yttrium carbonate.
In step (2), described soluble salt is NaCl, KCl, LiCl, CaCl
2in one or more, add soluble salt mole number be 0.5 ~ 7.0 times of metal ion total moles in products therefrom.
In step (3), described organic-fuel is one or both in glycine and urea, and added organic-fuel mole number is 0.5 ~ 5.0 times of metal ion total moles in products therefrom.
In step (4), described washing refers to that the specific conductivity that is washed till washings with deionized water is lower than 10 μ s/cm
2.
The present invention introduces inertia soluble salt in redox reaction mixed solution, the inhibition of the salt that utilization is separated out in nanoparticle surface original position, solved the difficult problem that in the synthetic zirconium base oxide process of solution combustion, particles sintering is reunited seriously, specific surface area is little, one-step synthesis out obtains the terbium sesquioxide of high dispersive Tetragonal and yttrium oxide co-stabilized zirconium white nano phosphor powder, high 269 m of its specific surface area
2g
-1, grain diameter is in 3 ~ 7 nm left and right, and luminescent properties is good, much larger than the specific surface data of existing solution combustion synthesis method report.For fluorescence yttrium oxide zircon ceramic powder, specific surface area is large and crystal grain is little of reducing the sintering temperature of yttrium oxide zircon ceramic, improves the density of ceramic body, and improving its mechanical property has vital effect.The present invention be take chlorine hydrate zirconium white as zirconium source, compares with the nitrate of zirconium, and raw material is more easy to get, and price is cheaper, is conducive to preparation of industrialization.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of comparative example 1 gained sample, as seen from Figure 1, and (the Tb that comparative example 1 obtains
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder granule reunion sintering is serious, crystal grain large (50 ~ 80 nm).
Fig. 2 is the X ray diffracting spectrum of comparative example 1 gained sample, is shown (the Tb that comparative example 1 obtains by Fig. 2 analysis
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is Tetragonal, and its JCPDS card number is 49-1642.
Fig. 3 is the X ray diffracting spectrum of embodiment 1 gained sample, is shown (the Tb that embodiment 1 obtains by Fig. 3 analysis
4o
7)
0.0025(Y
2o
3)
0.0150(ZrO
2)
0.9600powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean particle size is 6.6 nm.
Fig. 4 is the fluorescence spectrum figure of embodiment 1 gained sample, and left side is the (Tb that embodiment 1 obtains
4o
7)
0.0025(Y
2o
3)
0.0150(ZrO
2)
0.9600powder is the emmission spectrum under 545 nm monitorings at wavelength, and right side is for being the excitation spectrum under 278nm excites at wavelength, and as shown in Figure 4, this powder can effectively be excited in 200 ~ 350nm ultraviolet range, and the strongest emission peak is 545 nm.
Fig. 5 is the X ray diffracting spectrum of embodiment 2 gained samples, is shown (the Tb that embodiment 2 obtains by Fig. 5 analysis
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean grain size is 3.7 nm.
Fig. 6 is the fluorescence spectrum figure of embodiment 2 gained samples, and left side is the (Tb that embodiment 1 obtains
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is the emmission spectrum under 545 nm monitorings at wavelength, and right side is for being the excitation spectrum under 278nm excites at wavelength, and as shown in Figure 6, this powder can effectively be excited in 200 ~ 350nm ultraviolet range, and the strongest emission peak is 545 nm.
Fig. 7 is the X ray diffracting spectrum of embodiment 3 gained samples, is shown (the Tb that embodiment 3 obtains by Fig. 7 analysis
4o
7)
0.03(Y
2o
3)
0.015(ZrO
2)
0.85powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean grain size is 3.4 nm.
Fig. 8 is the fluorescence spectrum figure of embodiment 3 gained samples, and left side is the (Tb that embodiment 1 obtains
4o
7)
0.03(Y
2o
3)
0.015(ZrO
2)
0.85powder is the emmission spectrum under 545 nm monitorings at wavelength, and right side is for being the excitation spectrum under 278nm excites at wavelength, and as shown in Figure 8, this powder can effectively be excited in 200 ~ 350nm ultraviolet range, and the strongest emission peak is 545 nm.
Fig. 9 is the X ray diffracting spectrum of embodiment 4 gained samples, is shown (the Tb that embodiment 4 obtains by Fig. 9 analysis
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean grain size is 3.0 nm.
Figure 10 is the transmission electron microscope photo of embodiment 4 gained samples, as shown in figure 10, and (the Tb that embodiment 4 obtains
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder granule is uniformly dispersed, and particle is tiny, and particle diameter is at 3 ~ 4 nm.
Figure 11 is the electron diffraction of embodiment 4 gained samples, as shown in figure 11, and (the Tb that embodiment 4 obtains
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is polycrystalline.
Figure 12 is the X ray diffracting spectrum of embodiment 5 gained samples, is shown (the Tb that embodiment 5 obtains by Figure 12 analysis
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean grain size is 3.0 nm.
Figure 13 is the X ray diffracting spectrum of embodiment 6 gained samples, is shown (the Tb that embodiment 6 obtains by Figure 13 analysis
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean particle size is 4.5 nm.
Figure 14 is the X ray diffracting spectrum of embodiment 7 gained samples, is shown (the Tb that embodiment 7 obtains by Figure 14 analysis
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean grain size is 3.1nm.
Figure 15 is the X ray diffracting spectrum of embodiment 8 gained samples, is shown (the Tb that embodiment 8 obtains by Figure 15 analysis
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean grain size is 3.0 nm.
Figure 16 is the X ray diffracting spectrum of embodiment 9 gained samples, is shown (the Tb that embodiment 9 obtains by Figure 16 analysis
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930powder is Tetragonal, and its JCPDS card number is 49-1642, by Scherrer formula, calculates, and mean grain size is 6.7 nm.
Embodiment
The present invention will be described further by following examples.
Comparative example 1.
Take 2.9993g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.0748g Tb
4o
7the nitric acid heating for dissolving Y that adds excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 1.7596g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thick, putting into design temperature is that 600 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 36 m
2g
-1(Tb
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930faint yellow powder.
Embodiment 1.
Take 3.0960g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.0187g Tb
4o
7, add heating for dissolving Y in the nitric acid of excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product,, then add 1.7532g NaCl and 1.7099g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thick, putting into design temperature is that 600 ℃ of constant temperature cavitys ignite, and rear taking-up sample has burnt, again through washing, filter, dry, obtaining specific surface area is 123 m
2g
-1(Tb
4o
7)
0.0025(Y
2o
3)
0.015(ZrO
2)
0.96faint yellow powder.
Embodiment 2.
Take 2.993g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.0748g Tb
4o
7, add in the nitric acid of excessive 1:1 and be heated to dissolve Y
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 1.7532g NaCl and 1.7596g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thick, putting into design temperature is that 600 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 171m
2g
-1(Tb
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930faint yellow powder.
Embodiment 3.
Take 2.7410g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.2244g Tb
4o
7, add heating for dissolving Y in the nitric acid of excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 1.7532g NaCl and 1.8934g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thick, putting into design temperature is that 600 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 120m
2g
-1(Tb
4o
7)
0.030(Y
2o
3)
0.015(ZrO
2)
0.850faint yellow powder.
Embodiment 4.
Take 2.9993g ZrOCl
28H
2o, 0.0339g Y
2o
3with 0.0748g Tb
4o
7, add heating for dissolving Y in the nitric acid of excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 0.8766g NaCl and 1.7596g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thick, putting into design temperature is that 600 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 264 m
2g
-1(Tb
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930faint yellow powder.
Embodiment 5.
Take 2.9993g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.0748g Tb
4o
7add heating for dissolving Y in the nitric acid of excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 1.1688g NaCl and 1.7596g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thick, putting into design temperature is that 600 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 167 m
2g
-1(Tb
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930faint yellow powder.
Embodiment 6.
Take 2.9993g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.0748g Tb
4o
7, add heating for dissolving Y in the nitric acid of excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 1.7532g NaCl and 2.1121g urea in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thickness state, putting into design temperature is that 600 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 182 m
2g
-1(Tb
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930faint yellow powder.
Embodiment 7.
Take 2.9993g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.0748g Tb
4o
7, add heating for dissolving Y in the nitric acid of excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 0.8766g NaCl and 1.7596g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thickness state, putting into design temperature is that 400 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 173 m
2g
-1(Tb
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930faint yellow powder.
Embodiment 8.
Take 2.9993g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.0748g Tb
4o
7, add heating for dissolving Y in the nitric acid of excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 0.8766g NaCl and 1.7596g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thickness state, putting into design temperature is that 500 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 269 m
2g
-11(Tb
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930faint yellow powder.
Embodiment 9.
Take 2.9993g ZrOCl
28H
2o, 0.0339gY
2o
3with 0.0748g Tb
4o
7, add the nitric acid heating for dissolving Y of excessive 1:1
2o
3and Tb
4o
7, to the settled solution that forms Yttrium trinitrate and Terbium trinitrate, by the ZrOCl taking
28H
2o dissolves in wherein completely, obtain the metallic mixing salt solution of target product, then add 0.8766g NaCl and 1.7596g glycine in this solution, after heating is dissolved completely, continue the concentrated mixing solutions of heating to thickness state, putting into design temperature is that 700 ℃ of constant temperature cavitys ignite, and after having burnt, takes out sample, again through washing, filter, dry, obtaining specific surface area is 109 m
2g
-1(Tb
4o
7)
0.010(Y
2o
3)
0.015(ZrO
2)
0.930faint yellow powder.