CN104003437B - Low-temperature solid phase reaction prepares the method for strontium titanate nanometer powder - Google Patents

Low-temperature solid phase reaction prepares the method for strontium titanate nanometer powder Download PDF

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CN104003437B
CN104003437B CN201410201919.7A CN201410201919A CN104003437B CN 104003437 B CN104003437 B CN 104003437B CN 201410201919 A CN201410201919 A CN 201410201919A CN 104003437 B CN104003437 B CN 104003437B
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srtio
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CN104003437A (en
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张俊豪
袁爱华
张龙梅
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Jiangsu University of Science and Technology
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Abstract

Low-temperature solid phase reaction prepares the method for strontium titanate nanometer powder, step is: by Strontium carbonate powder, titanium dioxide and sodium-chlor according to mol ratio 1:1:0-16, employing ethanol is dispersion agent, ball milling becomes pasty state, then, 80 DEG C of dryings 6 hours, ground sieve series obtains the powder that particle size is no more than 150 microns, again powder is loaded porcelain boat, and put into tube furnace, under water vapour existence condition, be heated to 500 ~ 900 DEG C, react 2 hours, products in water and washing with alcohol, centrifugation and drying, namely obtain strontium titanate nanoparticles.The present invention adopts solid state reaction technology, at NaCl (l)-H 2under O (g) subsidiary conditions, SrCO 3and TiO 2solid state reaction is all converted into the SrTiO of nano-scale 3powder, compared with existing reaction technology: the features such as process is simple and easy to control, temperature of reaction is low, raw material is cheap, product grain is little, green non-pollution.

Description

Low-temperature solid phase reaction prepares the method for strontium titanate nanometer powder
Technical field
The invention belongs to SrTiO 3nano ceramic powder preparing technical field, is specifically related to a kind of solid state reaction low-temperature growth strontium titanate (SrTiO 3) method of nano ceramic powder.
Background technology
ABO 3perovskite structure composite oxide is a class excellent performance, widely used new function material, has stable crystalline structure, unique electromagnetic performance and well redox, hydrogenolysis, isomerization, photochemical catalysis isoreactivity.Strontium titanate (SrTiO 3) as a kind of typical perovskite typed ternary oxide, not only because have the advantages such as specific inductivity is high, dielectric loss is low, Heat stability is good, be widely used in electronics, machinery and ceramic industry, but also because of its energy gap be 3.2eV, also by as a kind of excellent photocatalyst, the photocatalyst for degrading of organic pollutant and the photocatalytic cleavage of water is applied to prepare clean energy hydrogen.In recent years, about SrTiO 3preparation and performance study cause the great interest of people.
Preparation SrTiO 3the common method of nanometer powder has solid reaction process, sol-gel method, the precipitator method, the hot method of hydrothermal/solvent etc.But all there are some problems such as the high and poor performance of contaminate environment, preparation cost in these methods.Such as, although easily preparation particle size is little and temperature of reaction is lower for sol-gel method, costly, some raw material is organism to the cost of material used, insalubrity, and the time required for whole sol-gel process is longer.The advantage of coprecipitation method is the advantages such as cost is low, technique simple, favorable repeatability, preparation condition are easily controlled, synthesis cycle is short, but in throw out, the content of impurity and proportioning are difficult to accurate control, and the particle of product is larger.In numerous wet chemistry methods, hydrothermal method is compared other method and is had more advantage, and its temperature of reaction is low, save energy, and the powder dispersibility of synthesis is good, but the performance of its synthetic product is often not good.Solid reaction process is because turnout is large, operation is few and good product performance, and the solid reaction process be widely studied needs higher temperature, such as, adopts Solid phase synthesis SrTiO 3the temperature of reaction of powder is general all more than 950 DEG C, and this not only wastes energy and product is easily reunited.
Therefore, researcher strives to find a kind of low-temperature solid-phase method and synthesizes various ceramic powder material.Such as, BaTiO 3the traditional preparation methods of powder more than 1000 DEG C, carries out solid state reaction, with BaCO 3and TiO 2for raw material.If by BaCO 3and TiO 2particle grinds to form submicron particles in advance, within 6 hours, just can obtain BaTiO 900 DEG C of solid state reactions 3powder [J.Am.Ceram.S DEG C., 84 (2001) 2777-2782.]; If adopt the BaCO of 650,140 and 50 nanometers 3with 70 nano-TiOs 2nanocrystalline is raw material, within 8 hours, just can prepare the BaTiO of monocrystalline 800 DEG C of solid state reactions 3nanometer powder [J.Am.Ceram.S DEG C., 88 (2005) 2374-2379.]; If adopt the BaCO of 15 and 30 nanometers 3nanocrystalline is raw material, within 2 hours, just can prepare the BaTiO of monocrystalline 700 DEG C of solid state reactions 3nanometer powder [J.Am.Ceram.SOC., 91 (2008) 2862-2869.]; Research shows, mechanochemical effect is also the effective ways reducing solid state reaction, adopts the BaCO that business is bought by nebula formula ball mill 3and TiO 2after carrying out ball milling, within 2 hours, BaTiO can be obtained 800 DEG C of solid state reactions 3powder [J.Alloy.Compd., 337 (2002) 226-230.].In addition, adopting some to hold labile salt and replace carbonate, is also the method reducing solid state reaction.With K 2cO 3, Nb 2o 5with KF according to a certain percentage as raw material, adopt solid state reaction, more than 750 DEG C, just can prepare K 2nbO 3f; And adopt K 2c 2o 4replace K 2cO 3as raw material, within 2 hours, just K can be obtained 500 DEG C of solid state reactions 2nbO 3f powder, then temperature of reaction reduces about 250 DEG C [J.FluorineChem., 84 (2011) 2777-2782.].But occurring in nature carbonate content enriches, and low price, be that raw material is more conducive to suitability for industrialized production with carbonate.For this reason, employing carbonate is raw material, and the temperature of reaction reducing solid state reaction has more practical significance.
At present, at 675 DEG C, adopt business-like SrCO 3and TiO 2for raw material, a single-step solid phase reaction prepares SrTiO 3there is not been reported for nanometer powder.
Summary of the invention
Technical problem: prepare SrTiO for prior art 3the temperature of reaction that nanometer powder exists is high, reaction raw materials cost is high, easily cause the problems such as environmental pollution, the present invention proposes a kind of NaCl (l)-H 2o (g) fluid auxiliary solid phase reaction prepares SrTiO 3the method of nanometer powder, namely low-temperature solid phase reaction prepares the method for strontium titanate nanometer powder, has the features such as temperature of reaction is low, raw material is cheap, product grain is little, green non-pollution.
Technical scheme: low-temperature solid phase reaction prepares the method for strontium titanate nanometer powder, step is: by Strontium carbonate powder, titanium dioxide and sodium-chlor according to mol ratio 1:1:0-16, employing ethanol is dispersion agent, ball milling becomes pasty state, then, 80 DEG C of dryings 6 hours, ground sieve series obtains the powder that particle size is no more than 150 microns, again powder is loaded porcelain boat, and put into tube furnace, under water vapour existence condition, be heated to 500 ~ 900 DEG C, react 2 hours, products in water and washing with alcohol, centrifugation and drying, namely obtain strontium titanate nanoparticles.
The amount of substance of described Strontium carbonate powder, titanium dioxide and sodium-chlor is than being preferably 1:1:1 ~ 12.
The amount of substance of described Strontium carbonate powder, titanium dioxide and sodium-chlor is than being preferably 1:1:4 ~ 8.
The amount of substance of described Strontium carbonate powder, titanium dioxide and sodium-chlor is than being preferably 1:1:8.
Describedly under water vapour existence condition, be heated to 700 DEG C.
The addition of described water vapour in tube furnace is 0.5-4.0mL/min.
Beneficial effect: water vapour can accelerate the thermolysis of carbonate, mainly because the water vapor being adsorbed on carbonate surface can weaken M-CO 3key [J.Ceram.SOC.Jpn., 121 (2013) 103-105.].NaCl is ionic crystal, and it can provide fluid conditions for crystal growth, and the viscosity of NaCl nonaqueous ionic liquid is low, can improve the diffustivity of reactant.At NaCl (l)-H 2o (g) fluid carries out SrCO under existing 3and TiO 2solid state reaction, not only can SrCO in accelerate equation (1) 3decomposition, SrO and TiO in equation (2) can be improved again 2phase mutual diffusion, thus reduce temperature of reaction, shorten the reaction times.
Reaction principle is as follows:
SrCO 3→SrO+CO 2(1)
SrO+TiO 2→SrTiO 3(2)
1. the present invention adopts solid state reaction technology, at NaCl (l)-H 2under O (g) subsidiary conditions, SrCO 3and TiO 2solid state reaction is all converted into the SrTiO of nano-scale 3powder, compared with existing reaction technology: the features such as process is simple and easy to control, temperature of reaction is low, raw material is cheap, product grain is little, green non-pollution.
2. the SrTiO of the inventive method acquisition 3nanometer powder, nanoparticle size is about 200nm, and good dispersity.
Accompanying drawing explanation
Fig. 1 is that the amount of substance of embodiment 1 Strontium carbonate powder, titanium dioxide and sodium-chlor is than the SrTiO be mixed with for 1:1:8 3the X-ray powder diffraction spectrogram of nanometer powder.
Fig. 2 is that the amount of substance of embodiment 1 Strontium carbonate powder and titanium dioxide is than the low power Flied emission scintigram for raw material after the mixing of 1:1 ball milling.
Fig. 3 is that the amount of substance of embodiment 1 Strontium carbonate powder and titanium dioxide is than the high power Flied emission scintigram for raw material after the mixing of 1:1 ball milling.
Fig. 4 is that the amount of substance of embodiment 1 Strontium carbonate powder, titanium dioxide and sodium-chlor is than the SrTiO prepared for 1:1:8 3the low power Flied emission scintigram of nanometer powder.
Fig. 5 is that the amount of substance of embodiment 1 Strontium carbonate powder, titanium dioxide and sodium-chlor is than the SrTiO prepared for 1:1:8 3the high power Flied emission scintigram of nanometer powder.
Fig. 6 is that the amount of substance of embodiment 2 Strontium carbonate powder, titanium dioxide and sodium-chlor is than the SrTiO prepared for 1:1:0 3the Flied emission scintigram of nanometer powder.
Fig. 7 is that the amount of substance of embodiment 3 Strontium carbonate powder, titanium dioxide and sodium-chlor is than the SrTiO prepared for 1:1:1 3the Flied emission scintigram of nanometer powder.
Fig. 8 is that the amount of substance of embodiment 4 Strontium carbonate powder, titanium dioxide and sodium-chlor is than the SrTiO prepared for 1:1:4 3the Flied emission scintigram of nanometer powder.
Fig. 9 is that the amount of substance of embodiment 5 Strontium carbonate powder, titanium dioxide and sodium-chlor is than the SrTiO prepared for 1:1:12 3the Flied emission scintigram of nanometer powder.
Figure 10 is that the amount of substance of embodiment 6 Strontium carbonate powder, titanium dioxide and sodium-chlor is than the SrTiO prepared for 1:1:16 3the Flied emission scintigram of nanometer powder.
Embodiment:
Technical scheme of the present invention is illustrated below with reference to embodiment.
Embodiment 1:
By Strontium carbonate powder (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group), titanium dioxide (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group) and sodium-chlor (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group) mix than 1:1:8 by amount of substance, employing ethanol is dispersion agent, take rotating speed as 280rpm ball milling 6 hours, obtain mashed prod, then, 80 DEG C of dryings 6 hours in an oven, ground sieve series obtains the powder that particle size is 150 microns, again powder is loaded porcelain boat, put into tube furnace, 700 DEG C are heated under water vapour existence condition, the addition of water vapour in tube furnace is 1.0mL/min, react 2 hours, products in water and washing with alcohol, centrifugation and drying, namely SrTiO is obtained 3nano particle.
Japanese RigakuD/max-γ A type X-ray powder diffraction (XRD) instrument is adopted to carry out material phase analysis to powder, Cu graphite monochromator, pipe pressure and electric current are respectively 40kV and 20mA, sweep velocity 10.0 ° of min -1.Fig. 1 is the X-ray diffraction spectra of product prepared by embodiment 1.As seen from Figure 1, in x-ray diffraction spectra, 2 θ have 7 stronger diffraction peaks at 10-80 °, be respectively (100), (110), (111), (200), (211), (220), (311), the SrTiO of perovskite structure can be demarcated as 3, there are not other impurity peaks in (JCPDS card JCPDS35-0734), illustrates that the product purity adopting the inventive method to prepare is higher.
Field emission scanning electron microscope (FESEM, JEOLJSM-6300F) is used to observe the pattern, particle size etc. of raw material and product; Fig. 2 is SrCO 3and TiO 2the low power Flied emission scanned photograph of mixing raw material after the mixing of raw material ball milling, structure shows to adopt the inventive method to obtain SrCO 3and TiO 2it is more even that raw material mixes; Fig. 3 is the Flied emission scanned photograph of amplifying, and result shows, SrCO in mixing raw material 3the size of particle is about 1 micron, TiO 2the size of particle is about 200 nanometers.Fig. 4 adopts the inventive method to obtain SrTiO 3the low power scanned photograph of nanometer powder, result shows, product S rTiO 3the particle size uniformity of nanometer powder, pattern productive rate almost 100%, particle dispersion is good, does not reunite.Fig. 5 is the Flied emission scanned photograph of amplifying, and result shows, SrTiO 3the particle size of nanometer powder is about 200 nanometers.
More than analyze confirmation, NaCl (l)-H 2o (g) fluid auxiliary solid phase reaction method can prepare consistent appearance, size uniform and pattern productive rate is the SrTiO of 100% at lower temperature (675 DEG C) 3nanometer powder.
Embodiment 2:
Difference from Example 1 is, is 1:1:0 mixing, then carries out solid state reaction by the amount of substance ratio of Strontium carbonate powder, titanium dioxide and sodium-chlor, need 900 DEG C of reactions 2 hours, SrCO 3and TiO 2srTiO could be changed into completely 3nanometer powder, SrTiO 3the Average Particle Diameters of nano particle is about 200nm, but reunion especially severe, nano particle is assembled into the particle that size is about 50 microns, as shown in Figure 6.
Embodiment 3:
Difference from Example 1 is, is 1:1:1 mixing, then carries out solid state reaction by the amount of substance ratio of Strontium carbonate powder, titanium dioxide and sodium-chlor, need 750 DEG C of reactions 2 hours, SrCO 3and TiO 2srTiO could be changed into completely 3nanometer powder, SrTiO 3the Average Particle Diameters of nano particle is about 200 nanometers, but it is relatively more serious to reunite, and nano particle is assembled into the particle that size is about 20 microns, as shown in Figure 7.
Embodiment 4:
Difference from Example 1 is, is 1:1:4 mixing, then carries out solid state reaction by the amount of substance ratio of Strontium carbonate powder, titanium dioxide and sodium-chlor, need 700 DEG C of reactions 2 hours, SrCO 3and TiO 2srTiO could be changed into completely 3nanometer powder, SrTiO 3the Average Particle Diameters of nano particle is about 200nm, and better dispersed, nano particle is bonded together mutually, as shown in Figure 8.
Embodiment 5:
Difference from Example 1 is, is 1:1:12 mixing, then carries out solid state reaction by the amount of substance ratio of Strontium carbonate powder, titanium dioxide and sodium-chlor, need 675 DEG C of reactions 4 hours, SrCO 3and TiO 2srTiO could be changed into completely 3nanometer powder, SrTiO 3the Average Particle Diameters of nano particle is about 200nm, good dispersity, as shown in Figure 9.
Embodiment 6:
Difference from Example 1 is, is 1:1:16 mixing, then carries out solid state reaction by the amount of substance ratio of Strontium carbonate powder, titanium dioxide and sodium-chlor, need 675 DEG C of reactions 5 hours, SrCO 3and TiO 2srTiO could be changed into completely 3nanometer powder, SrTiO 3the Average Particle Diameters of nano particle is about 200nm, good dispersity, as shown in Figure 10.

Claims (1)

1. low-temperature solid phase reaction prepares the method for strontium titanate nanometer powder, it is characterized in that step is: by Strontium carbonate powder, titanium dioxide and sodium-chlor mix than 1:1:8 by amount of substance, employing ethanol is dispersion agent, take rotating speed as 280rpm ball milling 6 hours, obtain mashed prod, then, 80 DEG C of dryings 6 hours in an oven, ground sieve series obtains the powder that particle size is 150 microns, again powder is loaded porcelain boat, put into tube furnace, 700 DEG C are heated under water vapour existence condition, the addition of water vapour in tube furnace is 1.0mL/min, react 2 hours, products in water and washing with alcohol, centrifugation and drying, namely SrTiO is obtained 3nano particle.
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