CN105948751B - Neodymium adulterates strontium fluoride laser transparent ceramic and preparation method thereof - Google Patents

Neodymium adulterates strontium fluoride laser transparent ceramic and preparation method thereof Download PDF

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CN105948751B
CN105948751B CN201610250499.0A CN201610250499A CN105948751B CN 105948751 B CN105948751 B CN 105948751B CN 201610250499 A CN201610250499 A CN 201610250499A CN 105948751 B CN105948751 B CN 105948751B
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transparent ceramic
laser transparent
butanol
strontium fluoride
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宋京红
房亚华
梅炳初
朱春辉
张紫微
周志伟
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a kind of neodymiums to adulterate strontium fluoride laser transparent ceramic, it forms consistency close to 99.8% laser transparent ceramic for neodymium ion and strontium fluoride matrix by chemically reacting the displaced type solid solution formed, then through the operations such as hot pressed sintering and post-processing.First Nd is prepared with azeotropic distillation method3+:SrF2Nano-powder, carrying out azeotropic distillation as entrainer using n-butanol makes the moisture in gel be removed to greatest extent, and gained powder is not easy to reunite, even particle size distribution, and crystallite dimension is 15~30nm；Then using LiF as sintering aid, using vacuum hot pressing sintering technique, laser transparent ceramic is prepared, is 85.83% in the maximum transmission of visible light, near infrared band, there is stronger absorption peak at 576nm, 735nm, 796nm.Moulding process of the present invention is simple, is suitble to large-scale production, at low cost, and the laser transparent ceramic optical homogeneity prepared is good.

Description

Neodymium adulterates strontium fluoride laser transparent ceramic and preparation method thereof
Technical field
The invention belongs to first entering light function crystalline ceramics research fields, and in particular to a kind of neodymium doping strontium fluoride laser-light transparent Ceramics and preparation method thereof.
Background technology
Since nineteen sixty Maiman develops first ruby solid state laser (bibliography Maiman T H.Optical and microwave-optical experiments in ruby.Phys.Rev.Lett.,1960,4 (11):564-566), Solid State Laser technology is grown rapidly.In all solid laser materials, the comprehensive performance of YAG crystal is most It is excellent.However the shortcomings that being difficult to overcome there are some due to laser crystal, material supply section scholar is exploring always novel Solid State Laser Material.1964, Hatch (bibliography Hatch S E, Parsons W F, Weagley R J.Hot pressed polycrystalline CaF2:Dy2+laser.Appl.Phys.Lett.,1964,5(8):153-154) with DyF3And CaF3Powder Body is raw material, and the powder of particle size 150um is ground into after melting in a vacuum, then vacuum hot pressing sintering technique is used to prepare Dy3+:CaF2Crystalline ceramics.Sample is by annealing process, to eliminate thermal stress, then makes under the x-ray irradiation of 0.25Mev Dy3+It is reduced into Dy2+.Under Liquid Nitrogen Cooling Condition, using xenon flash lamp pumping Dy3+:CaF2Crystalline ceramics realizes laser output, laser Threshold values is 24.6J (similar to monocrystalline), this is first historically solid ceramic laser.
In the developing history of laser ceramics, oxide series laser ceramics are always the object of most study, most excellent Laser activity be also to be generated from the yttrium-aluminium-garnet (YAG) in oxide.First block of oxide laser ceramics is the U.S. Nd prepared by scholar Greskovic3+：Y2O3-Th2O3(10%) ceramics are (referring to document Greskovich C, Chernoch J P.Polycrystalline Ceramic Lasers[J].Journal of Applied Physics,1973,44(10)： 4599-4606.).In addition to oxide laser ceramics, most study also has fluoride laser ceramics, Russian Basiev researchs Group Yb3+Adulterate CaF2-SrF2Ceramics are (referring to document Basiev T T, Doroshenko M E, Fedorov P P, et al.Efficient Laser Based on CaF2-SrF2-YbF3Nanoceramics[J].Optics Letters,2008, 33(5):521-523.)。
The atom of rare earth element has abundant electron energy level, and there are 4f tracks in electron configuration, are a variety of energy level transitions Condition is created, is widely used in light, electricity, magnetic field.Neodymium ion (Nd3+) relative to other rare earth ions have it is as follows Advantage：1. laser, including crystal, glass, ceramics, liquid can be generated in nearly hundred kinds of different substrates.2. belong to four-level system, And has the metastable energy level there are one high-quantum efficiency.3. from visible near infrared region, there are many absorption bands, can ensure that Effective pumping.4. some absorption bands can effectively be coupled with the transmitting band of GaAs-GaAlAs lasers, therefore Nd3+It is well suited for For in the photonics or device based on GaAs.Sr and Ca is same family's element in the periodic table of elements, with SrF2 Nd is prepared for matrix3+：SrF2Laser ceramics is extremely important.
Invention content
The object of the present invention is to provide a kind of neodymiums to adulterate strontium fluoride laser transparent ceramic and preparation method thereof, prepared by this method Ceramics consistency is high, transmitance is high.
To achieve the above object, the technical solution adopted by the present invention is：A kind of neodymium doping strontium fluoride laser transparent ceramic, It is characterized in that it by Nd3+:SrF2Wet gel, n-butanol and sintering aid are prepared, and are carried out as entrainer using n-butanol Azeotropic distillation makes Nd3+:SrF2Water in wet gel is removed, and temperature continues the boiling point for being increased to n-butanol, by remaining azeotropic Agent n-butanol steams, dry, and grinding obtains Nd3+:SrF2Nano-powder；Then using LiF as sintering aid, Nd3+:SrF2Nanometer Powder uses vacuum heating-press sintering, obtains neodymium doping strontium fluoride laser transparent ceramic.
The Nd3+:SrF2Wet gel is by including Sr (NO3)2·4H2O、Nd(NO3)3·6H2O and KF2H2O prepare and At.
A kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic, it is characterised in that include the following steps：
1) Sr (NO are pressed3)2·4H2O、Nd(NO3)3·6H2O、KF·2H2The proportioning of O is 0.0398mol-0.1194mol: 0.0020mol-0.0063mol:0.0520mol-0.175mol chooses Sr (NO3)2·4H2O、Nd(NO3)3·6H2O and KF 2H2O；
By Sr (NO3)2·4H2O and Nd (NO3)3·6H2O is soluble in water be stirred with magnetic stirring apparatus be configured to sun from Sub- mixed liquor；By KF2H2Soluble in water are stirred with magnetic stirring apparatus of O is configured to anion solutions；
It 2) will be dissolved with F-Anion solutions instilled dropwise dissolved with Sr2+And Nd3+Cationic solution in, after the completion of titration, With magnetic stirrer, it is then allowed to stand products therefrom；
3) step 2) products therefrom is subjected to ultrasonic cleaning, is centrifugally separating to obtain Nd3+:SrF2Wet gel；
4) addition for pressing n-butanol is Nd3+:SrF2The 60%~70% of wet gel quality, by Nd obtained by step 3)3+: SrF2N-butanol is added in wet gel, and is sufficiently mixed under strength mechanical agitation, mixed suspension is transferred to three mouthfuls Oil bath heating is carried out in flask；
5) it when the temperature of step 4) system is increased to the boiling point of n-butanol, flows back at this temperature, so far entire azeotropic Process terminates, and obtains colloid；
6) colloid after distilling step 5) is placed in drying in baking oven, loose powder is obtained, using grinding, you can To Nd3+:SrF2Nano-powder；
7) using LiF as sintering aid, Nd in step 6) is weighed3+:SrF2Nano-powder is fitted into graphite jig, is put after compacting It is sintered in vacuum hotpressing stove；
8) the sintered sample of step 7) is taken out, is ground respectively with thick, fine sandpaper first, then in precise grinding polisher Upper twin polishing obtains neodymium doping strontium fluoride laser transparent ceramic.
In said program, Sr in cationic mixed liquor described in step 1)2+、Nd3+Molar concentration be 0.25~10mol/ L.F in anion solutions-Molar concentration be 0.5~20mol/L.Adulterate Nd3+For 1%mol~10%mol.
In said program, in step 2), rate of titration is 50~200ml/min, and the standing products therefrom time is 3~12h.
In said program, after centrifuge is detached three times in step 3), there is lamination in gained wet gel, and gained is white The wet gel of color is pure SrF on upper layer2, red wet gel is Nd in lower layer3+:SrF2, the wet gel of white is removed, is left red The wet gel of color.
In said program, when the temperature of system is increased to 117 DEG C of the boiling point of n-butanol in step 5), flow back at this temperature 30min can be observed continuously azeotropic temperature and remove the volume of moisture in azeotropic process, when suspension temperature rise is to altogether When the boiling point of boiling system, the moisture in gel is carried in the form of azeotropic mixture and is removed, when hydrone is complete in colloid After removing, the temperature of system continues the boiling point for being increased to n-butanol, and remaining entrainer n-butanol is steamed, and is done using conventional Dry mode removes remaining entrainer n-butanol.
In said program, in step 5), azeotropic distillation method handles forerunner using Organic Alcohol (n-butanol) as entrainer Powder makes moisture be removed by alcohol and the moisture on precursor powder surface form azeotropic mixture, so significantly between decrease particle The formation of chemical bond inhibits the aggregation between particle, to prevent the formation of hard aggregation in drying process.
It is Nd by the addition of sintering aid LiF in step 7) in said program3+:SrF2Nano-powder quality 0.5%~5%, weigh the Nd of 2g3+:SrF2Nano-powder and wet mixing two hours in alcohol sintering aid LiF, in 80 DEG C of bakings Dry, gained powder pours into the graphite jig that internal diameter is 16mm.
In said program, be sintered in step 7), in vacuum hotpressing stove for：It is warming up to 400 DEG C -800 DEG C for the first time, protects The warm time is 60 minutes, then is warming up to 620 DEG C -1000 DEG C, and soaking time is 30-40 minutes, is cooled down as furnace cooling.
In said program, vacuum hotpressing stove used is the KZG-113 type vacuum hotpressing stoves of Shanghai occasion honor production in step 7), Its key technical indexes is：2000 DEG C of rated temperature, maximum pressure 20T, vacuum degree is 6.67 × 10-3Under Pa, maximum heating speed Rate is 50 DEG C/min, and calandria is graphite material.
In said program, sample is first polished on coarse sandpaper in step 8), and the fineness of sand paper is higher and higher, ensures sample Surface scratch is more and more tiny, while polishing on sand paper, it should be noted that ensures that each position of sample is condition of equivalent thickness；Work as polishing To after certain thickness, it is polished using the aluminium oxide nano powder of different fineness on polishing machine, the fineness of aluminium oxide is same It is first big after small, polishes 30 minutes every time.
The present invention prepares Nd with azeotropic distillation method first3+：SrF2Nano-powder, the method is relative to the currently used precipitation method Prepared powder dispersity is good, and crystal habit is good, even particle size distribution, fluorescent emission intensity enhancing.Then LiF conducts are used Sintering aid prepares laser transparent ceramic with hot pressing and sintering technique, and gained sample optical homogeneity is good.
The present invention has the following advantages that compared with prior art：
1) present invention prepares nano-powder using azeotropic distillation method first, is dehydrated with micro Nano material, positive fourth It after alcohol replaces the water of wet gel, can not only reduce the capillary force in drying process, prevent in removing process hydrogen between particle The formation of key, while the butoxy that particle surface esterification is formed can also generate space steric effect, inhibit glue to a certain extent Intergranular it is close, all these effects can effectively eliminate the formation of gel particle chemical bond, prevent intergranular in drying process Hard aggregation.
2) it uses LiF as sintering aid, sintering activity and the transmitance of laser transparent ceramic can be significantly improved.It is easy system It is standby go out large scale laser transparent ceramic, and shape is easy to control.Ceramic material sintering process is simple, and manufacturing cycle is a couple of days, It is suitble to large-scale production, cost relatively low.Due to not limited by the effect of segregation, high-concentration dopant, optical homogeneity may be implemented It is good.
Description of the drawings
Fig. 1 is the XRD diagram that 1 gained neodymium of the embodiment of the present invention adulterates strontium fluoride laser transparent ceramic.It can be seen from the figure that It is Scherrer constants according to Scherrer formula L=k λ/β cos θ, K, value 0.89, β is integral halfwidth degree, in the mistake of calculating Cheng Zhong need to be converted into radian (rad), and θ is the angle of diffraction, and λ is X-ray wavelength, and value 0.154056nm, can obtain crystallite dimension is 53.40nm, lattice constant 4.903nm.
Fig. 2 is the schematic diagram that 1 gained neodymium of the embodiment of the present invention adulterates strontium fluoride laser transparent ceramic.It can from figure Go out, is clear that the rare earth ion neodymium that red is doping is presented in following word, a diameter of 16mm of sample through sample Color.
Fig. 3 is the transmitance that 1 gained neodymium of the embodiment of the present invention adulterates strontium fluoride laser transparent ceramic.It can from figure Go out, the transmitance of laser transparent ceramic is higher, visible light, near infrared band maximum transmission be more than 80%, 576nm, There are stronger absorption peak, optical homogeneity good at 735nm, 796nm.
Fig. 4 is the absorption spectrum that 1 gained neodymium of the embodiment of the present invention adulterates strontium fluoride laser transparent ceramic.It can from figure Go out, the absorption peak that center is located at 352nm, 521nm, 576nm, 735nm, 796nm and 865nm, these absorption peaks occurs in spectrum The characteristic absorption peak for belonging to trivalent Nd ions corresponds respectively to Nd ions from ground state4I9/2To excitation state4D1/2+4D3/2+4G5/2+2I11/2、4G7/2+4G9/2+2K13/2、4G5/2+2G7/2、4F7/2+4S3/2、4F5/2+2H9/2With4F3/2Transition.
Fig. 5 is the photoluminescence intensity that 1 gained neodymium of the embodiment of the present invention adulterates strontium fluoride laser transparent ceramic.It can from figure To find out, the fluorescence spectrum excited under the wavelength of 796nm, there are three transmitting band 850-950nm, 1000-1150nm in spectrum, 1300-1400nm is corresponded to respectively4F3/2→4I9/2,4F3/2→4I11/2,4F3/2→4I13/2Transition.
As can be seen from Figure 3：The optical homogeneity of ceramics prepared by the present invention is good.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not It is limited only to the following examples.
Embodiment is with the Sr (NO of purity >=99.0%3)2·4H2O, purity >=99.9%Nd (NO3)3·6H2O purity >= 99.0%KF2H2O, n-butanol are raw material, use LiF as sintering aid, are sintered using vacuum hotpressing stove.
Embodiment 1
A kind of neodymium strontium doping calcirm-fluoride laser ceramics, preparation method include the following steps：
1) 0.0796molSr (NO are weighed3)2·4H2O、0.0042molNd(NO3)3·6H2O, which is dissolved in 80ml water, uses magnetic force Blender, which is stirred, is configured to cationic mixed liquor；Weigh 0.175molKF2H2O, which is dissolved in 100ml water, uses magnetic agitation Device, which is stirred, is configured to anion solutions；
It 2) will be dissolved with F-Anion solutions instilled dropwise dissolved with Sr with 90ml/min speed2+And Nd3+Cationic solution In, after the completion of titration, with magnetic stirrer 30 minutes, it is made fully to react, products therefrom divides after standing 7 hours Layer phenomenon, sinking to bottom, (red wet gel is Nd in lower layer3+:SrF2, it is required product, following embodiment phase Together)；
3) by step 2) products therefrom carry out ultrasonic cleaning, with TG16-WS table model high speed centrifuges in 11000r/min Under the conditions of centrifuge (15min, 4 times) obtain Nd3+:SrF2Wet gel；
4) addition for pressing n-butanol is Nd3+:SrF2The 60% of wet gel quality, by Nd obtained by step 3)3+:SrF2It is wet solidifying N-butanol is added in glue, and is sufficiently mixed under strength mechanical agitation, mixed suspension is transferred to 250ml three-necked flasks Middle carry out oil bath heating；
5) when the temperature of step 4) system rises to 92 DEG C, water-n-butanol azeotropic, the moisture in colloidal sol is by n-butanol with altogether The form of boiling object is taken out of and is removed.When the temperature of system continues to rise to 117 DEG C of the boiling point of n-butanol, the moisture of colloid is complete Removing, the 30min that flows back at this temperature is to steam extra n-butanol, and so far entire azeotropic process terminates；
6) colloid after distilling step 5) is placed in air dry oven in 120 DEG C of dry 12h, obtains loose powder, Nd is can be obtained using grinding3+:SrF2Nano-powder；
7) addition for pressing sintering aid LiF is Nd3+:SrF2The 0.5%~5% of nano-powder quality weighs about 2g Nd3+:SrF2Nano-powder and wet mixing two hours in alcohol sintering aid LiF, in 80 DEG C of drying, gained powder pours into internal diameter For in the graphite jig of 16mm；It is sintered with vacuum hotpressing stove as sintering aid using LiF, is warming up to 400 DEG C for the first time, Soaking time is 60 minutes, then is warming up to 620 DEG C, and soaking time is 40 minutes, is cooled down as furnace cooling.
8) the sintered sample of step 8) is taken out, is ground respectively with thick, fine sandpaper first, then in precise grinding polisher Upper twin polishing finally can be obtained neodymium doping strontium fluoride laser transparent ceramic.
On thick, thin different degrees of sand paper successively by neodymium doping strontium fluoride laser transparent ceramic sample obtained by the present embodiment Polishing, the fineness of sand paper is higher and higher, ensures that the surface scratch of sample is more and more tiny, after being polished to certain thickness, is throwing It is polished using the aluminium oxide nano powder of different fineness on ray machine, you can obtain Nd3+:SrF2Laser transparent ceramic measures Its consistency>99.8%, transmitance>85% (i.e. consistency is high, transmitance is high), in optic communication, medical treatment, laser acquisition and survey Away from and up-conversion luminescence field have potential application.
Embodiment 2
A kind of neodymium strontium doping calcirm-fluoride laser ceramics, preparation method include the following steps：
1) 0.0637molSr (NO are weighed3)2·4H2O、0.0033molNd(NO3)3·6H2O, which is dissolved in 80ml water, uses magnetic force Blender, which is stirred, is configured to cationic mixed liquor；Weigh 0.0764molKF2H2O, which is dissolved in 100ml water, uses magnetic agitation Device, which is stirred, is configured to anion solutions；
It 2) will be dissolved with F-Anion solutions instilled dropwise dissolved with Sr with 80ml/min speed2+And Nd3+Cationic solution In, after the completion of titration, with magnetic stirrer 30 minutes, it is made fully to react, products therefrom divides after standing 6 hours Layer phenomenon, sinks to bottom；
3) by step 2) products therefrom carry out ultrasonic cleaning, with TG16-WS table model high speed centrifuges in 11000r/min Under the conditions of centrifuge (15min, 4 times) obtain Nd3+:SrF2Wet gel；
4) addition for pressing n-butanol is Nd3+:SrF2The 63% of wet gel quality, by Nd obtained by step 3)3+:SrF2It is wet solidifying N-butanol is added in glue, and is sufficiently mixed under strength mechanical agitation, mixed suspension is transferred to 250ml three-necked flasks Middle carry out oil bath heating；
5) when the temperature of step 4) system rises to 92 DEG C, water-n-butanol azeotropic, the moisture in colloidal sol is by n-butanol with altogether The form of boiling object is taken out of and is removed.When the temperature of system continues to rise to 117 DEG C of the boiling point of n-butanol, the moisture of colloid is complete Removing, the 30min that flows back at this temperature is to steam extra n-butanol, and so far entire azeotropic process terminates；
6) colloid after distilling step 5) is placed in air dry oven in 120 DEG C of dry 12h, obtains loose powder, Nd is can be obtained using grinding3+:SrF2Nano-powder；
7) addition for pressing sintering aid LiF is Nd3+:SrF2The 0.5%~5% of nano-powder quality weighs about 2g Nd3+:SrF2Nano-powder and wet mixing two hours in alcohol sintering aid LiF, in 80 DEG C of drying, gained powder pours into internal diameter For in the graphite jig of 16mm；It uses LiF to be sintered in vacuum hotpressing stove for sintering aid, is warming up to 500 DEG C for the first time, Soaking time is 60 minutes, then is warming up to 700 DEG C, and soaking time is 40 minutes, is cooled down as furnace cooling.
8) the sintered sample of step 6) is taken out, is ground respectively with thick, fine sandpaper first, then in precise grinding polisher Upper twin polishing finally can be obtained neodymium doping strontium fluoride laser transparent ceramic.
On thick, thin different degrees of sand paper successively by neodymium doping strontium fluoride laser transparent ceramic sample obtained by the present embodiment Polishing, the fineness of sand paper is higher and higher, ensures that the surface scratch of sample is more and more tiny, after being polished to certain thickness, is throwing It is polished using the aluminium oxide nano powder of different fineness on ray machine, you can obtain Nd3+:SrF2Laser transparent ceramic measures Its consistency>99.8%, light transmittance>85% (i.e. consistency is high, transmitance is high), in optic communication, medical treatment, laser acquisition and survey Away from and up-conversion luminescence field have potential application.
Embodiment 3
A kind of neodymium doping strontium fluoride laser transparent ceramic, preparation method include the following steps：
1) 0.0398molSr (NO are weighed3)2·4H2O、0.0020molNd(NO3)3·6H2O, which is dissolved in 80ml water, uses magnetic force Blender, which is stirred, is configured to cationic mixed liquor；Weigh 0.0520molKF2H2O, which is dissolved in 100ml water, uses magnetic agitation Device, which is stirred, is configured to anion solutions；
It 2) will be dissolved with F-Anion solutions instilled dropwise dissolved with Sr with 70ml/min speed2+、Nd3+Cationic solution In, after the completion of titration, with magnetic stirrer 30 minutes, it is made fully to react, products therefrom divides after standing 5 hours Layer phenomenon, sinks to bottom；
3) by step 2) products therefrom carry out ultrasonic cleaning, with TG16-WS table model high speed centrifuges in 11000r/min Under the conditions of centrifuge (15min, 4 times) obtain Nd3+:SrF2Wet gel；
4) addition for pressing n-butanol is Nd3+:SrF2The 65% of wet gel quality, by Nd obtained by step 3)3+:SrF2It is wet solidifying N-butanol is added in glue, and is sufficiently mixed under strength mechanical agitation, mixed suspension is transferred to 250ml three-necked flasks Middle carry out oil bath heating；
5) when the temperature of step 4) system rises to 92 DEG C, water-n-butanol azeotropic, the moisture in colloidal sol is by n-butanol with altogether The form of boiling object is taken out of and is removed.When the temperature of system continues to rise to 117 DEG C of the boiling point of n-butanol, the moisture of colloid is complete Removing, the 30min that flows back at this temperature is to steam extra n-butanol, and so far entire azeotropic process terminates；
6) colloid after distilling step 5) is placed in air dry oven in 120 DEG C of dry 12h, obtains loose powder, Nd is can be obtained using grinding3+:SrF2Nano-powder；
7) addition for pressing sintering aid LiF is Nd3+:SrF2The 0.5%~5% of nano-powder quality weighs about 2g Nd3+:SrF2Nano-powder and wet mixing two hours in alcohol sintering aid LiF, in 80 DEG C of drying, gained powder pours into internal diameter For in the graphite jig of 16mm；It uses LiF to be sintered in vacuum hotpressing stove for sintering aid, is warming up to 600 DEG C for the first time, Soaking time is 60 minutes, then is warming up to 800 DEG C, and soaking time is 30 minutes, is cooled down as furnace cooling.
8) the sintered sample of step 7) is taken out, is ground respectively with thick, fine sandpaper first, then in precise grinding polisher Upper twin polishing finally can be obtained neodymium doping strontium fluoride laser transparent ceramic.
On thick, thin different degrees of sand paper successively by neodymium doping strontium fluoride laser transparent ceramic sample obtained by the present embodiment Polishing, the fineness of sand paper is higher and higher, ensures that the surface scratch of sample is more and more tiny, after being polished to certain thickness, is throwing It is polished using the aluminium oxide nano powder of different fineness on ray machine, you can obtain Nd3+:SrF2Laser transparent ceramic measures Its consistency>99.7%, light transmittance>80% (i.e. consistency is high, transmitance is high), in optic communication, medical treatment, laser acquisition and survey Away from and up-conversion luminescence field have potential application.
Embodiment 4
A kind of neodymium doping strontium fluoride laser transparent ceramic, preparation method include the following steps：
1) 0.1035molSr (NO are weighed3)2·4H2O、0.0054molNd(NO3)3·6H2O, which is dissolved in 80ml water, uses magnetic force Blender, which is stirred, is configured to cationic mixed liquor；Weigh 0.1242molKF2H2O, which is dissolved in 100ml water, uses magnetic agitation Device, which is stirred, is configured to anion solutions；
It 2) will be dissolved with F-Anion solutions instilled dropwise dissolved with Sr with 100ml/min speed2+、Nd3+Cationic solution In, after the completion of titration, with magnetic stirrer 30 minutes, it is made fully to react, products therefrom divides after standing 4 hours Layer phenomenon, sinks to bottom；
3) by step 2) products therefrom carry out ultrasonic cleaning, with TG16-WS table model high speed centrifuges in 11000r/min Under the conditions of centrifuge (15min, 4 times) obtain Nd3+:SrF2Wet gel；
4) addition for pressing n-butanol is Nd3+:SrF2The 67% of wet gel quality, by Nd obtained by step 3)3+:SrF2It is wet solidifying N-butanol is added in glue, and is sufficiently mixed under strength mechanical agitation, mixed suspension is transferred to 250ml three-necked flasks Middle carry out oil bath heating；
5) when the temperature of step 4) system rises to 92 DEG C, water-n-butanol azeotropic, the moisture in colloidal sol is by n-butanol with altogether The form of boiling object is taken out of and is removed.When the temperature of system continues to rise to 117 DEG C of the boiling point of n-butanol, the moisture of colloid is complete Removing, the 30min that flows back at this temperature is to steam extra n-butanol, and so far entire azeotropic process terminates；
6) colloid after distilling step 5) is placed in air dry oven in 120 DEG C of dry 12h, obtains loose powder, Nd is can be obtained using grinding3+:SrF2Nano-powder；
7) addition for pressing sintering aid LiF is Nd3+:SrF2The 0.5%~5% of nano-powder quality weighs about 2g Nd3+:SrF2Nano-powder and wet mixing two hours in alcohol sintering aid LiF, in 80 DEG C of drying, gained powder pours into internal diameter For in the graphite jig of 16mm；It uses LiF to be sintered in vacuum hotpressing stove for sintering aid, is warming up to 700 DEG C for the first time, Soaking time is 60 minutes, then is warming up to 900 DEG C, and soaking time is 40 minutes, is cooled down as furnace cooling.
8) the sintered sample of step 7) is taken out, is ground respectively with thick, fine sandpaper first, then in precise grinding polisher Upper twin polishing can be obtained neodymium doping strontium fluoride laser transparent ceramic after most example.
Neodymium doping strontium fluoride laser transparent ceramic sample obtained by this implementation is beaten successively on thick, thin different degrees of sand paper Mill, the fineness of sand paper is higher and higher, ensures that the surface scratch of sample is more and more tiny, after being polished to certain thickness, is polishing It is polished using the aluminium oxide nano powder of different fineness on machine, you can obtain Nd3+:SrF2Laser transparent ceramic measures it Consistency>99.7%, light transmittance>75% (i.e. consistency is high, transmitance is high), optic communication, medical treatment, lidar light detection and ranging, And up-conversion luminescence field has potential application.
Embodiment 5
A kind of neodymium strontium doping calcirm-fluoride laser ceramics, preparation method include the following steps：
1) 0.1194molSr (NO are weighed3)2·4H2O、0.0063molNd(NO3)3·6H2O, which is dissolved in 80ml water, uses magnetic force Blender, which is stirred, is configured to cationic mixed liquor；Weigh 0.1431molKF2H2O, which is dissolved in 100ml water, uses magnetic agitation Device, which is stirred, is configured to anion solutions；
It 2) will be dissolved with F-Anion solutions instilled dropwise dissolved with Sr with 110ml/min speed2+、Nd3+Cationic solution In, after the completion of titration, with magnetic stirrer 30 minutes, it is made fully to react, products therefrom divides after standing 3 hours Layer phenomenon, sinks to bottom；
3) by step 2) products therefrom carry out ultrasonic cleaning, with TG16-WS table model high speed centrifuges in 11000r/min Under the conditions of centrifuge (15min, 4 times) obtain Nd3+:SrF2Wet gel；
4) addition for pressing n-butanol is Nd3+:SrF2The 70% of wet gel quality, by Nd obtained by step 3)3+:SrF2It is wet solidifying N-butanol is added in glue, and is sufficiently mixed under strength mechanical agitation, mixed suspension is transferred to 250ml three-necked flasks Middle carry out oil bath heating；
5) when the temperature of step 4) system rises to 92 DEG C, water-n-butanol azeotropic, the moisture in colloidal sol is by n-butanol with altogether The form of boiling object is taken out of and is removed.When the temperature of system continues to rise to 117 DEG C of the boiling point of n-butanol, the moisture of colloid is complete Removing, the 30min that flows back at this temperature is to steam extra n-butanol, and so far entire azeotropic process terminates；
6) colloid after distilling step 5) is placed in air dry oven in 120 DEG C of dry 12h, obtains loose powder, Nd is can be obtained using grinding3+:SrF2Nano-powder；
7) addition for pressing sintering aid LiF is Nd3+:SrF2The 0.5%~5% of nano-powder quality weighs about 2g Nd3+:SrF2Nano-powder and wet mixing two hours in alcohol sintering aid LiF, in 80 DEG C of drying, gained powder pours into internal diameter For in the graphite jig of 16mm；It is sintered in vacuum hotpressing stove as sintering aid using LiF, is warming up to 800 for the first time DEG C, soaking time is 60 minutes, then is warming up to 1000 DEG C, and soaking time is 40 minutes, is cooled down as furnace cooling.
8) the sintered sample of step 7) is taken out, is ground respectively with thick, fine sandpaper first, then in precise grinding polisher Upper twin polishing finally can be obtained neodymium doping strontium fluoride laser transparent ceramic.
On thick, thin different degrees of sand paper successively by neodymium doping strontium fluoride laser transparent ceramic sample obtained by the present embodiment Polishing, the fineness of sand paper is higher and higher, ensures that the surface scratch of sample is more and more tiny, after being polished to certain thickness, is throwing It is polished using the aluminium oxide nano powder of different fineness on ray machine, you can obtain Nd3+:SrF2Laser transparent ceramic measures Its consistency>99.65%, light transmittance>75% (i.e. consistency is high, transmitance is high), in optic communication, medical treatment, laser acquisition and survey Away from and up-conversion luminescence field have potential application.

Claims (8)

1. a kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic, it is characterised in that include the following steps：
1) Sr (NO are pressed3)2·4H2O、Nd(NO3)3·6H2O、KF·2H2The proportioning of O is 0.0398mol-0.1194mol: 0.0020mol-0.0063mol:0.0520mol-0.175mol chooses Sr (NO3)2·4H2O、Nd(NO3)3·6H2O and KF 2H2O；
By Sr (NO3)2·4H2O and Nd (NO3)3·6H2Soluble in water are stirred with magnetic stirring apparatus of O is configured to cationic mix Close liquid；By KF2H2Soluble in water are stirred with magnetic stirring apparatus of O is configured to anion solutions；
It 2) will be dissolved with F-Anion solutions instilled dropwise dissolved with Sr2+And Nd3+Cationic solution in, after the completion of titration, use magnetic Power blender stirs, and is then allowed to stand products therefrom；
3) step 2) products therefrom is subjected to ultrasonic cleaning, is centrifugally separating to obtain Nd3+:SrF2Wet gel；
4) addition for pressing n-butanol is Nd3+:SrF2The 60%~70% of wet gel quality, by Nd obtained by step 3)3+:SrF2It is wet N-butanol is added in gel, and is mixed under strength mechanical agitation, mixed suspension is transferred in three-necked flask and is carried out Oil bath heating；
5) it when the temperature of step 4) system is increased to the boiling point of n-butanol, flows back at this temperature, so far entire azeotropic process Terminate, obtains colloid；
6) colloid after distilling step 5) is placed in drying in baking oven, obtains loose powder, using grinding, obtains Nd3+: SrF2Nano-powder；
7) using LiF as sintering aid, Nd in step 6) is weighed3+:SrF2Nano-powder is fitted into graphite jig, is placed on after compacting true It is sintered in empty hot pressing furnace；
8) the sintered sample of step 7) is taken out, it is then double on precise grinding polisher first respectively with thick, fine sandpaper mill Mirror polish obtains neodymium doping strontium fluoride laser transparent ceramic.
2. a kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic according to claim 1, which is characterized in that step It is rapid 1) described in Sr in cationic mixed liquor2+、Nd3+Molar concentration be 0.25~10mol/L.
3. a kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic according to claim 1, which is characterized in that step It is rapid 1) described in F in anion solutions-Molar concentration be 0.5~20mol/L.
4. a kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic according to claim 1, which is characterized in that step It is rapid 1) described in step 2), rate of titration is 50~200ml/min, and the standings products therefrom time is 3~12h.
5. a kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic according to claim 1, which is characterized in that step It is rapid 1) described in after centrifuge is detached three times in step 3), there is lamination in gained wet gel, gained white it is wet solidifying Glue is pure SrF on upper layer2, red wet gel is Nd in lower layer3+:SrF2, the wet gel of white is removed, the wet solidifying of red is left Glue.
6. a kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic according to claim 1, which is characterized in that step It is rapid 1) described in when the temperature of system is increased to 117 DEG C of the boiling point of n-butanol in step 5), flow back 30min at this temperature, In azeotropic process, azeotropic temperature can be observed continuously and remove the volume of moisture, when suspension temperature rise arrives azeotropic system When boiling point, the moisture in gel is carried in the form of azeotropic mixture and is removed, after hydrone is substantially completely removed in colloid, body The temperature of system continues the boiling point for being increased to n-butanol, and remaining entrainer n-butanol is steamed, will using conventional drying mode Remaining entrainer n-butanol removes.
7. a kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic according to claim 1, which is characterized in that step It is rapid 7) in, by sintering aid LiF addition be Nd3+:SrF2The 0.5%~5% of nano-powder quality weighs the Nd of 2g3+: SrF2Nano-powder and wet mixing two hours in alcohol sintering aid LiF, in 80 DEG C of drying, it is 16mm that gained powder, which pours into internal diameter, Graphite jig in.
8. a kind of preparation method of neodymium doping strontium fluoride laser transparent ceramic according to claim 1, which is characterized in that step It is rapid 7) in, be sintered in vacuum hotpressing stove for：It is warming up to 400 DEG C -800 DEG C for the first time, soaking time is 60 minutes, then is heated up To 620 DEG C -1000 DEG C, soaking time is 30-40 minutes, is cooled down as furnace cooling.
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