CN105647532B - A kind of red long afterglow material and preparation method thereof - Google Patents
A kind of red long afterglow material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of red long afterglow material and preparation method, the chemical formula of red long afterglow material is M0.8Zn0.2TiO3:In RE, X, formula, M0.8Zn0.2TiO3For matrix, M is any one in Ca, Sr, Mg and Ba, and RE and X are doping component, and RE is Pr3+Or Eu3+, X is Al3+、Mg2+、Mn3+At least one of, doping component RE content is 0.1 ~ 0.3wt% of matrix, and doping component X content is 0.1 ~ 1wt% of matrix.Preparation method includes：Dispensing, crystallization and thermal cracking.The granularity of red lanthanide long after glow luminous material prepared by the present invention is small, particle diameter distribution is uniform, and purity is high, with low cost with longer persistence, solves inconsistent and high energy consumption the deficiency such as conventional solid sintering process product purity, granularity, pattern.
Description
Technical field
The present invention relates to the invention belongs to long after glow luminous material field, it is related to a kind of red long afterglow material
M0.8Zn0.2TiO3:RE, X and its Continuous Heat solvent preparation.
Background technology
Overlength green long afterglow material Sr is reported from Matsuzawa2Al2O4:Eu2+,Dy3+Excellent properties since, it is dilute
The superior function of native ion doping long-afterglow material is greatly promoted the development of long after glow luminous material.Rare earth ion is special
Electron structure, can absorb or launch the electromagnetic radiation from ultraviolet light, visible ray to infrared light district multi-wavelength, with excellent
Energy translation function.The long lad phosphor of three kinds of colors of RGB is allocated by a certain percentage, can obtain any one color
Long-afterglow material, it is Sr to be currently known the best green long afterglow material of performance2Al2O4:Eu2+,Dy3+, persistence exceedes
20h；The blue long afterflow material of best performance is CaAl2O4:Eu2+,Nd3+, persistence is more than 12h；Combination property is best
Red long afterglow material is Y2O2S:Eu3+,Mg2+,Ti4+, persistence is about 5h.
Rare earth ion occupies certain lattice position in lattice, causes distortion of lattice, is produced between valence band and conduction band
Defect level be trapped electron trap.After the electronics of activator is stimulated from ground state transition to excitation state, part electricity
Sub- transition is returned low-lying level generation and lighted, and another part electronics is stored in defect level by relaxation process.When in defect level
Electron absorption energy when, again by the excited level for returning to activator is excited, then electronics again transition return activator
Ground state and luminous produce twilight sunset.The length of twilight sunset is relevant with the electron amount stored in defect level and the energy of absorption,
Electron amount in defect level is more, then persistence is long；The energy of absorption is more, and electronics is easy for overcoming one's shortcomings energy level with exciting
Energy bite between energy level, so as to produce the phenomenon of continuous illumination.The length of persistence is depended in defect level
The speed of the quantity of electronics and their return activator excited levels；The electronics that the intensity of twilight sunset is then depended in defect level
The speed returned within the unit interval.
In addition to the physicochemical properties of afterglowing material in itself can influence luminescent properties, the preparation method of afterglowing material is also
One crucial influence factor.Preparation method is different, and uniformity, granule size and particle diameter distribution of afterglowing material doping etc. are all
Can be different, and uniformity, granule size and particle diameter distribution of afterglowing material doping etc. are to the luminescent properties of afterglowing material
Important.
It is high temperature solid-state method to prepare the most common method of rare earth long-afterglow luminescent material at present, and this method is by higher degree
Raw material is proportionally added into fluxing agent ground and mixed uniformly, and then sintering 8 ~ 12h or so in more than 1300 DEG C under reducing atmosphere obtains
Arrive.The simple production process, it is ripe, but the calcining heat of this method is high, the time is long, can not only cause production cost too high, and
And prolonged sintering easily produces dephasign, influences the luminescent properties of product；Using grinding batch mixing, grinding batch mixing has material
The problem of mixing uniformity is difficult to ensure that and damaged to the particle shape of powder, influences the luminescent properties of product；Sintering is finished
The particle size that obtains afterwards is big, particle diameter distribution is uneven, it is necessary to which sintered product is further ground, but grinding can cause it is remaining
The centre of luminescence of brightness material is destroyed, and influences its luminescent properties.Therefore, milder, rapidly and effectively long afterglow material are developed
The preparation method of material, has great importance.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of red long afterglow material M0.8Zn0.2TiO3:RE, X and its
Preparation method, this method is using hypergravity reaction hybrid technology dispensing, the crystallization of continuous solvent thermal reaction and high temperature inert atmosphere
Red long afterglow material M is prepared in pyrolysis0.8Zn0.2TiO3:RE, X, the granularity of the red lanthanide long after glow luminous material is small, grain
Footpath is evenly distributed, and purity is high, with longer persistence, and with low cost, solves conventional solid sintering process product pure
Degree, granularity, pattern etc. be inconsistent and deficiency of high energy consumption.
The present invention the used technical scheme that solves the above problems is：
A kind of red long afterglow material, chemical formula is M0.8Zn0.2TiO3:In RE, X, formula, M0.8Zn0.2TiO3For matrix, M is
Any one in Ca, Sr, Mg and Ba, RE and X are doping component, and RE is Pr3+Or Eu3+, X is Al3+、Mg2+、Mn3+In extremely
Few one kind, doping component RE content is 0.1 ~ 0.3wt% of matrix, and doping component X content is 0.1 ~ 1 wt % of matrix.
A kind of preparation method of red long afterglow material, comprises the following steps：
（1）, dispensing：By the stoichiometric proportion of above-mentioned chemical formula measure M salting liquid, Zn salting liquid, RE salting liquid,
X salting liquid, the acid solution of butyl titanate, add them into and mixed liquor are formed in container, then add dispersant and overweight
It is well mixed under the conditions of power, solid phase is washed with water in separation of solid and liquid, and the solid phase after washing is well mixed with organic solvent, obtained
Feed liquid；
（2）, crystallization：By step（1）In gained feed liquid input closed container, feed liquid is warming up to 160 ~ 300 under agitation
DEG C and in 0.5 ~ 6h of the temperature, crystallization reaction is then carried out with the endless form of continuous feed, continuous discharge under agitation
Presoma slurry is obtained, the temperature for controlling crystallization reaction is 160 ~ 300 DEG C, the residence time is in 0.5 ~ 6h, control closed container
Pressure be 0.2 ~ 4MPa；
（3）, pyrolysis：By step（2）Gained presoma slurry is continuously inputted in pyrolysis installation, and heat is carried out at 800 ~ 1000 DEG C
Solution reaction obtains red long afterglow material, and gained red long afterglow material is continuously exported and room temperature is cooled to, and controls presoma
Residence time of the slurry in pyrolysis installation is 5 ~ 30min.
In the above method, step（2）The pH value for adjusting mixed liquor is needed before middle addition dispersant to 8 ~ 10.
In the above method, the concentration of M salting liquid is 0.2 ~ 1.5 mol/L, the concentration of Zn salting liquid for 0.2 ~
The concentration of 1.5mol/L, RE salting liquid is 0.2 ~ 1.5 mol/L, and the concentration of X salting liquid is 0.2 ~ 1.5mol/L；It is described
In the acid solution of butyl titanate, Ti4+Concentration be 0.5 ~ 1.5mol/L, acid and Ti4+Mol ratio be（2~3）:1；It is described scattered
The addition of agent is 2 ~ 5g in every liter of mixed liquor；The amount of the organic solvent should make the solid content of feed liquid be 3 ~ 10wt%.
In the above method, step（1）Described dispersant be polyvinyl alcohol, polyethylene glycol or HPMA,
Step（1）Described organic solvent is ethylene glycol, propane diols, glycerine or ethanol.
In the above method, the acid solution of the butyl titanate is butyl titanate and citric acid or the mixed liquor of glacial acetic acid.
In the above method, step（2）In mixing speed be 300 ~ 600rpm, step（2）According to 2 ~ 8 DEG C/min liter
The temperature of feed liquid is risen to 160 ~ 300 DEG C by warm speed.
In the above method, the salting liquid of the M can be：Ca(NO3)2The aqueous solution, Sr (NO3)2The aqueous solution, Mg (NO3)2Water
Solution or Ba (NO3)2The aqueous solution.
In the above method, the salting liquid of the RE can be Pr (NO3)3The aqueous solution or Eu (NO3)3The aqueous solution.
In the above method, the salting liquid of the X can be Al (NO3)3Solution, Mg (NO3)2The aqueous solution or Mn (NO3)3It is water-soluble
Liquid, Zn salting liquid is Zn (NO3)2The aqueous solution.
Certain M salting liquid, RE salting liquid, X salting liquid, Zn salting liquid can also be other aqueous solution, not
It is confined to above-mentioned nitrate aqueous solution.Closed container can be the closed reaction vessels such as reactor.It can also be set in closed container
It is equipped with for forcing the equipment of liquid circulation such as to force reaction pump.
To sum up, the beneficial effects of the invention are as follows：
1st, the invention provides a kind of new method for preparing red long afterglow material, this method reacts mixing using hypergravity
Red long afterglow material is prepared in technology dispensing, the crystallization of continuous solvent thermal reaction and the pyrolysis of high temperature inert atmosphere
M0.8Zn0.2TiO3:RE, X, the granularity of the red lanthanide long after glow luminous material is small, particle diameter distribution is uniform, and purity is high, with compared with
Long persistence, and with low cost, solve conventional solid sintering process product purity, granularity, pattern etc. it is inconsistent and
The deficiency of high energy consumption.
2nd, hybrid technology is reacted present invention employs hypergravity, because under Elevated Gravity, different size is intermolecular
Molecule spread and interphase mass transfer process all than under normal gravitational field much faster, therefore, it is possible to be greatly promoted microcosmic mixing and mass transfer
Process, produces great degree of supersaturation, the grain of the presoma after hypergravity mixing in feed liquid in extremely short liquid residence time
Degree is small and is evenly distributed, so as to be conducive to the uniformity of afterglowing material Granularity Distribution finally prepared, overcomes existing side
The problem of batch mixing that method uses grinding batch mixing to exist is uneven.
3rd, present invention employs continuous solvent thermal reaction crystallization technique, due to the temperature during crystallization reaction, pressure with
And the speed of input and output material is all sufficiently stable, this advantageously ensures that the uniform and stable property of slurry degree of supersaturation in reactor, so as to protect
Demonstrate,prove the uniformity of purity, crystal formation and the granularity of afterglowing material product.
4th, the high temperature continuous pyrolysis technique due to material of the present invention, the technique can quickly be adulterated at 800 ~ 1000 DEG C
Heat treatment, and the secondary agglomeration of afterglowing material product can be avoided, product prepared by the technique needs not move through the grinding in later stage
Process, it is thus possible to avoid grinding from damaging the centre of luminescence of product, so as to ensure that the luminous mass of product.
5th, the technological process of the method for the invention is simple, process conditions are gentle, and process control parameters temperature is easy to control
System, suitable for large-scale industrial production.
Brief description of the drawings
Fig. 1 is the exciting light spectrogram of red long afterglow material；
Fig. 2 is the launching light spectrogram of red long afterglow material.
Embodiment
With reference to embodiment and accompanying drawing, make detailed description further, but embodiments of the present invention to the present invention
Not limited to this.
Embodiment 1
（1）, measure by the stoichiometric proportion of above-mentioned chemical formula Ca salting liquid, Zn salting liquid or Eu3+Salting liquid,
Al3+Salting liquid, the acid solution of butyl titanate, add them into and mixed liquor formed in container, then add dispersant and super
It is well mixed under gravity condition, solid phase is washed with water in separation of solid and liquid, and the solid phase after washing is well mixed with organic solvent, obtained
To feed liquid；
（2）, by step（1）In gained feed liquid input reactor, feed liquid is warming up to 160 ~ 300 DEG C and at this under agitation
0.5 ~ 6h of temperature, then carries out crystallization reaction with the endless form of continuous feed, continuous discharge under agitation and obtains forerunner
Body slurry, the temperature for controlling crystallization reaction is 160 ~ 300 DEG C, and the residence time is 0.5 ~ 6h, and it is 0.2 to control the pressure in reactor
~4MPa；
（3）, by step（2）Gained presoma slurry is continuously inputted in pyrolysis installation, carries out being pyrolyzed instead at 800 ~ 1000 DEG C
Red long afterglow material should be obtained, gained red long afterglow material is continuously exported and room temperature is cooled to, presoma slurry is controlled
Residence time in pyrolysis installation is 5 ~ 30min.
Embodiment 2
In the present embodiment, the chemical formula of red long afterglow material is Ca0.8Zn0.2TiO3:Pr3+,Al3+,Mg2+, in formula, Pr3+
Content be matrix Ca0.8Zn0.2TiO30.1wt%, Al3+And Mg2+Content is respectively matrix Ca0.8Zn0.2TiO30.15wt%
And 0.1wt%, its preparation method is as follows：
（1）Calcium nitrate is dissolved in the calcium nitrate aqueous solution that 0.2mol/L is configured in deionized water；Zinc nitrate is dissolved
0.5mol/L zinc nitrate aqueous solution is configured in deionized water；Praseodymium nitrate is dissolved in deionized water and is configured to
The 1.0mol/L praseodymium nitrate aqueous solution；Aluminum nitrate is dissolved in the aluminum nitrate aqueous solution that 1.0mol/L is configured in deionized water；
Magnesium nitrate is dissolved in the magnesium nitrate aqueous solution that 1.0mol/L is configured in deionized water；Sodium hydroxide is dissolved in deionized water
In be configured to 200g/L sodium hydrate aqueous solution.Butyl titanate is added the sour molten of butyl titanate is formed in citric acid solution
Liquid, wherein, citric acid and Ti4+Mol ratio be 2:1, Ti4+Concentration be 0.5 mol/L.
（2）It is water-soluble by stoichiometric proportion metering calcium nitrate aqueous solution, the zinc nitrate of above-mentioned red long afterglow material chemical formula
Liquid, the praseodymium nitrate aqueous solution, aluminum nitrate aqueous solution, magnesium nitrate aqueous solution, the acid solution of butyl titanate, add them into hypergravity anti-
Answer in device, then the pH value for adjusting the mixed liquor with sodium hydrate aqueous solution adds polyethylene of dispersing agent alcohol and open super to 8
Each material is well mixed and obtains dispersed suspension by gravity reactor, filters and solid phase is washed with deionized to remove
Aqueous by-product, the solid phase after washing is added in ethylene glycol and feed liquid is uniformly mixing to obtain；The amount of the polyvinyl alcohol is
4g is added in every liter of mixed liquor, the amount of the ethylene glycol should make the solid content in feed liquid be 6wt%.
（3）By step（2）Gained feed liquid is inputted in reactor with metering diaphragm feed pump, with 300r/min mixing speed
It is stirred, while opening the forced circulation pump in reactor, feed liquid is warming up to 200 DEG C and at this with 6 DEG C/min speed
Temperature 5h, then opens metering diaphragm feed pump and high pressure measurement discharging pump continuous-stable input and output material, is stirred foregoing simultaneously
Progress crystallization reaction obtains presoma slurry under the conditions of mixing and stirring forced circulation, and the temperature for controlling crystallization reaction is 200 DEG C, during stop
Between be 4h, use counterbalance valve to control to answer the pressure in kettle for 0.35MPa.
（4）By step（3）During the presoma slurry discharged from high pressure measurement discharging pump continuously inputs high temperature pyrolysis stove,
1000 DEG C carry out pyrolytic reaction and obtain red long afterglow material, and gained red long afterglow material is continuously exported and room is cooled to
Temperature, it is 15min to control residence time of the presoma slurry in high temperature pyrolysis stove.
The excitation and emission spectra of red long afterglow material manufactured in the present embodiment as depicted in figs. 1 and 2, by Fig. 1 and Fig. 2
Understand, the excitation and emission spectra of red long afterglow material manufactured in the present embodiment is broadband spectral, corresponding excitation peak λmax
For 330nm；Emission peak λmaxFor 612nm, persistence is 60min.
Embodiment 3
In the present embodiment, the chemical formula of red long afterglow material is Ca0.8Zn0.2TiO3:Pr3+,Al3+,Mg2+, in formula, Pr3+
Content be matrix Ca0.8Zn0.2TiO30.3wt%, Al3+And Mg2+Content is respectively matrix Ca0.8Zn0.2TiO31wt% and
0.15wt%, its preparation method is as follows：
（1）Calcium nitrate is dissolved in the calcium nitrate aqueous solution that 0.5mol/L is configured in deionized water；Zinc nitrate is dissolved
1.5mol/L zinc nitrate aqueous solution is configured in deionized water；Praseodymium nitrate is dissolved in deionized water and is configured to
The 1.5mol/L praseodymium nitrate aqueous solution；Aluminum nitrate is dissolved in the aluminum nitrate aqueous solution that 1.5mol/L is configured in deionized water；
Magnesium nitrate is dissolved in the magnesium nitrate aqueous solution that 1.0mol/L is configured in deionized water；Potassium hydroxide is dissolved in deionized water
In be configured to 100g/L sodium hydrate aqueous solution.Butyl titanate is added the sour molten of butyl titanate is formed in glacial acetic acid solution
Liquid, wherein, glacial acetic acid and Ti4+Mol ratio be 3:1, Ti4+Concentration be 1.5 mol/L.
（2）It is water-soluble by stoichiometric proportion metering calcium nitrate aqueous solution, the zinc nitrate of above-mentioned red long afterglow material chemical formula
Liquid, the praseodymium nitrate aqueous solution, aluminum nitrate aqueous solution, magnesium nitrate aqueous solution, the acid solution of butyl titanate, add them into hypergravity anti-
Answer in device, then the pH value for adjusting the mixed liquor with sodium hydrate aqueous solution adds dispersant polyethylene glycol 400 to 10
（PEG400）And open supergravity reactor and obtain dispersed suspension by each material is well mixed, filter and use deionization
Solid phase after washing is added in glycerine to remove aqueous by-product and is uniformly mixing to obtain feed liquid by water washing solid phase；Institute
PEG400 amount is stated to add 2g in every liter of mixed liquor, the amount of the glycerine should make the solid content in feed liquid be 5wt%.
（3）By step（2）Gained feed liquid is inputted in reactor with metering diaphragm feed pump, with 600r/min mixing speed
It is stirred, feed liquid is warming up to 300 DEG C and in temperature 2h with 8 DEG C/min speed, barrier film meter is then opened simultaneously
Feed pump and high pressure measurement discharging pump continuous-stable input and output material are measured, crystallization reaction is carried out under foregoing stirring condition and obtains presoma
Slurry, control crystallization reaction temperature be 300 DEG C, the residence time is 3h, use counterbalance valve control to answer the pressure in kettle for
0.5MPa。
（4）By step（3）During the presoma slurry discharged from high pressure measurement discharging pump continuously inputs high temperature pyrolysis stove,
1000 DEG C carry out pyrolytic reaction and obtain red long afterglow material, and gained red long afterglow material is continuously exported and room is cooled to
Temperature, it is 30min to control residence time of the presoma slurry in high temperature pyrolysis stove.
The excitation and emission spectra of red long afterglow material manufactured in the present embodiment is broadband spectral, correspondence excitation peak
λmaxFor 328nm；Emission peak λmaxFor 610nm, persistence is 12min.
Embodiment 4
In the present embodiment, the chemical formula of red long afterglow material is Sr0.8Zn0.2TiO3: Eu3+,Mn3+, in formula, Eu3+'s
Content is matrix Sr0.8Zn0.2TiO30.2wt%, Mn3+Content be matrix Sr0.8Zn0.2TiO30.1wt%, its preparation method
It is as follows：
（1）Strontium nitrate is dissolved in the strontium nitrate aqueous solution that 1.0mol/L is configured in deionized water；Zinc nitrate is dissolved
0.2mol/L zinc nitrate aqueous solution is configured in deionized water；Europium nitrate is dissolved in deionized water and is configured to
The 0.5mol/L europium nitrate aqueous solution；Manganese nitrate is dissolved in the manganese nitrate aqueous solution that 0.5mol/L is configured in deionized water；
Sodium hydroxide is dissolved in the sodium hydrate aqueous solution that 200g/L is configured in deionized water.Butyl titanate is added into glacial acetic acid molten
The acid solution of butyl titanate is formed in liquid, wherein, glacial acetic acid and Ti4+Mol ratio be 3:1, Ti4+Concentration be 1.5 mol/L.
（2）It is water-soluble by the stoichiometric proportion metering strontium nitrate aqueous solution, the zinc nitrate of above-mentioned red long afterglow material chemical formula
Liquid, the europium nitrate aqueous solution, the acid solution of manganese nitrate butyl titanate, are added them into supergravity reactor, use sodium hydroxide water
Solution adjusts the pH value of the mixed liquor to 9, and then adding dispersant HPMA and open supergravity reactor will
Each material is well mixed to obtain dispersed suspension, filters and solid phase is washed with deionized to remove water-soluble by-product
Thing, the solid phase after washing is added in ethanol and feed liquid is uniformly mixing to obtain；The amount of the HPMA is every liter and mixed
Close and 5g is added in liquid, the amount of the ethanol should make the solid content in feed liquid be 3wt%.
（3）By step（2）Gained feed liquid is inputted in reactor with metering diaphragm feed pump, with 400r/min mixing speed
It is stirred, while opening the forced circulation pump in reactor, feed liquid is warming up to 160 DEG C and at this with 2 DEG C/min speed
Temperature 6h, then opens metering diaphragm feed pump and high pressure measurement discharging pump continuous-stable input and output material, is stirred foregoing simultaneously
Mix, crystallization reaction is carried out under the conditions of forced circulation obtain presoma slurry, control the temperature of crystallization reaction for 160 DEG C, during stop
Between be 6h, use counterbalance valve to control to answer the pressure in kettle for 2MPa.
（4）By step（3）During the presoma slurry discharged from high pressure measurement discharging pump continuously inputs high temperature pyrolysis stove,
800 DEG C carry out pyrolytic reaction and obtain red long afterglow material, and gained red long afterglow material is continuously exported and room temperature is cooled to,
It is 30min to control residence time of the presoma slurry in high temperature pyrolysis stove.
The excitation and emission spectra of red long afterglow material manufactured in the present embodiment is broadband spectral, correspondence excitation peak
λmaxFor 330nm；Emission peak λmax610nm, persistence 120min.
Embodiment 5
In the present embodiment, the chemical formula of red long afterglow material is Ba0.8Zn0.2TiO3:Pr3+,Al3+,Mg2+, in formula, Pr3+
Content be matrix Ba0.8Zn0.2TiO30.3wt%, Al3+And Mg2+Content is respectively matrix Ba0.8Zn0.2TiO30.5wt% and
0.5wt%, its preparation method is as follows：
（1）Barium nitrate is dissolved in the barium nitrate aqueous solution that 1.5mol/L is configured in deionized water；Zinc nitrate is dissolved
1.0mol/L zinc nitrate aqueous solution is configured in deionized water；Praseodymium nitrate is dissolved in deionized water and is configured to
The 0.2mol/L praseodymium nitrate aqueous solution；Aluminum nitrate is dissolved in the aluminum nitrate aqueous solution that 0.2mol/L is configured in deionized water；
Magnesium nitrate is dissolved in the magnesium nitrate aqueous solution that 0.5mol/L is configured in deionized water；Sodium hydroxide is dissolved in deionized water
In be configured to 200g/L sodium hydrate aqueous solution.Butyl titanate is added the sour molten of butyl titanate is formed in citric acid solution
Liquid, wherein, citric acid and Ti4+Mol ratio be 2:1, Ti4+Concentration be 0.5 mol/L.
（2）It is water-soluble by stoichiometric proportion metering barium nitrate aqueous solution, the zinc nitrate of above-mentioned red long afterglow material chemical formula
Liquid, the praseodymium nitrate aqueous solution, aluminum nitrate aqueous solution, magnesium nitrate aqueous solution, the acid solution of butyl titanate, add them into hypergravity anti-
Answer in device, then the pH value for adjusting the mixed liquor with sodium hydrate aqueous solution adds dispersant polyethylene glycol 200 to 9
（PEG200）And open supergravity reactor and obtain dispersed suspension by each material is well mixed, filter and use deionization
Solid phase after washing is added in propane diols to remove aqueous by-product and is uniformly mixing to obtain feed liquid by water washing solid phase；Institute
State polyethylene glycol 200（PEG200）Amount be every liter of mixed liquor in add 4g, the amount of the propane diols should contain consolidating in feed liquid
Measure as 10wt%.
（3）By step（2）Gained feed liquid is inputted in reactor with metering diaphragm feed pump, with 500r/min mixing speed
It is stirred, feed liquid is warming up to 260 DEG C and in temperature 0.5h with 5 DEG C/min speed, barrier film is then opened simultaneously
Metering feeding pump and high pressure measurement discharging pump continuous-stable input and output material, progress crystallization reaction obtains forerunner under foregoing stirring condition
Body slurry, control crystallization reaction temperature be 260 DEG C, the residence time is 0.5h, use counterbalance valve control to answer the pressure in kettle for
4MPa。
（4）By step（3）During the presoma slurry discharged from high pressure measurement discharging pump continuously inputs high temperature pyrolysis stove,
1000 DEG C carry out pyrolytic reaction and obtain red long afterglow material, and gained red long afterglow material is continuously exported and room is cooled to
Temperature, it is 5min to control residence time of the presoma slurry in high temperature pyrolysis stove.
The excitation and emission spectra of red long afterglow material manufactured in the present embodiment is broadband spectral, correspondence excitation peak
λmaxFor 328nm；Emission peak λmaxFor 612nm, persistence is 60min.
As described above, the present invention can be realized preferably.
Claims (9)
1. a kind of red long afterglow material, it is characterised in that chemical formula is M0.8Zn0.2TiO3:In RE, X, formula, M0.8Zn0.2TiO3
For matrix, M is any one in Sr, Mg and Ba, and RE and X are doping component, and RE is Pr3+When, X is Mg2+And Al3+, or
RE is Eu3+When, X is Mn3+, doping component RE content is 0.1~0.3wt% of matrix, and doping component X content is matrix
0.1~1 wt %.
2. the preparation method of red long afterglow material as claimed in claim 1, it is characterised in that comprise the following steps：
（1）, dispensing：Measured by the stoichiometric proportion of above-mentioned chemical formula, by M salting liquid, Zn salting liquid, RE salting liquid, X
Salting liquid, butyl titanate acid solution formation mixed liquor, then add dispersant and under the conditions of hypergravity be well mixed, Gu
Liquid is separated, and solid phase is washed with water, the solid phase after washing is well mixed with organic solvent, feed liquid is obtained, dispersant is polyethylene
Alcohol, polyethylene glycol or HPMA, step（1）Described organic solvent be ethylene glycol, propane diols, glycerine or
Ethanol；
（2）, crystallization：By step（1）Gained feed liquid is added in closed container, and feed liquid is warming up into 160~300 DEG C simultaneously under agitation
In 0.5~6h of the temperature, crystallization reaction is then carried out with the endless form of continuous feed, continuous discharge under agitation and obtained
Presoma slurry, the temperature for controlling crystallization reaction is 160~300 DEG C, and the residence time is in 0.5~6h, control closed container
Pressure is 0.2~4MPa；
（3）, pyrolysis：By step（2）Gained presoma slurry is continuously inputted in pyrolysis installation, is pyrolyzed at 800~1000 DEG C
Reaction obtains red long afterglow material, and gained red long afterglow material is continuously exported and room temperature is cooled to, and controls presoma material
It is 5~30min to starch the residence time in pyrolysis installation.
3. preparation method according to claim 2, it is characterised in that step（2）Need regulation mixed before middle addition dispersant
The pH value of liquid is closed to 8~10.
4. preparation method according to claim 2, it is characterised in that the concentration of the salting liquid of the M is 0.2~1.5
The concentration of mol/L, Zn salting liquid is 0.2~1.5mol/L, and the concentration of RE salting liquid is 0.2~1.5 mol/L, X salt
The concentration of solution is 0.2~1.5mol/L；In the acid solution of the butyl titanate, Ti4+Concentration be 0.5~1.5mol/L, acid
With Ti4+Mol ratio be（2~3）:1；The addition of the dispersant is 2~5g in every liter of mixed liquor；The organic solvent
Amount should make the solid content of feed liquid be 3~10wt%.
5. preparation method according to claim 2, it is characterised in that the acid solution of the butyl titanate be butyl titanate with
The mixed liquor of citric acid or glacial acetic acid.
6. preparation method according to claim 2, it is characterised in that step（2）In mixing speed for 300~
600rpm。
7. the preparation method according to claim any one of 2-6, it is characterised in that step（2）According to 2~8 DEG C/min
Heating rate the temperature of feed liquid is risen to 160~300 DEG C.
8. the preparation method according to claim any one of 2-6, it is characterised in that the salting liquid of the M is：Ca(NO3)2
The aqueous solution, Sr (NO3)2The aqueous solution, Mg (NO3)2The aqueous solution or Ba (NO3)2The aqueous solution；The salting liquid of the RE is Pr (NO3)3Water
Solution or Eu (NO3)3The aqueous solution.
9. the preparation method according to claim any one of 2-6, it is characterised in that the salting liquid of the X is Al (NO3)3It is molten
Liquid, Mg (NO3)2The aqueous solution or Mn (NO3)3The aqueous solution, Zn salting liquid is Zn (NO3)2The aqueous solution.
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