CN104529454B - The preparation method of laser ceramics - Google Patents
The preparation method of laser ceramics Download PDFInfo
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Abstract
The preparation method that the invention discloses a kind of laser ceramics, comprises the following steps: be MF by molecular formula2Fluoride powder body and molecular formula be ReFnFluoride powder body mix by a certain percentage, as reaction raw materials；Or it is Re:MF by molecular formula2Fluoride single crystal pulverize after the powder crystal that obtains as reaction raw materials；Wherein, M is alkaline-earth metal ions, and Re is Mn2+And/or rare earth ion, n=2 or 3；Described reaction raw materials is ground, mix, obtain precursor powder after drying；Described precursor powder is put in mould, is placed in discharge plasma sintering stove, under vacuum environment or protective atmosphere, be warming up to 600 DEG C～1100 DEG C, be incubated 0min～60min, after cooling, obtain sintered body；After the polishing of described sintered body, polishing, obtain the alkali earth metal fluoride laser ceramics of ion doping.The method process is simple, it is easy to controls, contributes to realizing industrialized batch production；Meanwhile, reduce sintering temperature and energy consumption, shorten sintering time and manufacturing cycle.
Description
Technical field
The present invention relates to the preparation field of luminescent material, the preparation method particularly relating to a kind of laser ceramics.
Background technology
In alkali earth metal fluoride, with calcium fluoride (CaF2) for representative, owing to having a series of features such as transparency range width, absorptance is low, relative dispersion is big, refractive index is low, damage threshold is high, phonon energy is low, be widely studied as the laser gain material of a kind of excellence.
2009, P.Aubry et al. was prepared for Yb by coprecipitation method3+:CaF2Nanometer presoma, obtains Yb after presoma carries out vacuum-sintering and high temperature insostatic pressing (HIP)3+:CaF2Pottery (P.Aubry, et.al., SynthesisandopticalcharacterizationsofYb-dopedCaF2Ceramics.Opt.Mater., 31 (2009) 750-753).2013, GangLu et al. utilized Co deposited synthesis Nd3+:CaF2Powder body, and it is prepared for laser ceramics (GangLu, BingchuMei, et.al.FabricationandpropertiesofhighlytransparentNd-dope dCaF in conjunction with hot pressing vacuum-sintering2ceramic.MaterLett115(2014)162-164)。
There is following defect in said method: adopts coprecipitation to prepare the more difficult control of technical process of presoma; it is difficult to disposable prepare substantial amounts of powder body; and adopt vacuum-sintering or temperature height during hot pressed sintering, time length, energy consumption big, limit the large-scale production of the alkali earth metal fluoride laser ceramics that light emitting ionic adulterates.
Summary of the invention
The preparation method that the invention provides a kind of laser ceramics, this preparation method technique is simple, be easily controlled, sintering temperature is low, manufacturing cycle is short, it may be achieved industrialized mass production.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
The preparation method of a kind of laser ceramics, comprises the following steps:
S100: be MF by molecular formula2Fluoride powder body and molecular formula be ReFnFluoride powder body mix by a certain percentage, as reaction raw materials；Or it is Re:MF by molecular formula2Fluoride single crystal pulverize after the powder crystal that obtains as reaction raw materials；
Wherein, M is alkaline-earth metal ions, and Re is Mn2+Or rare earth ion, n=2 or 3；
S200: described reaction raw materials is ground, mix, obtain precursor powder after drying；
S300: put in mould by described precursor powder, is placed in discharge plasma sintering stove, under vacuum environment or protective atmosphere, is warming up to 600 DEG C～1100 DEG C, is incubated 0min～60min, obtains sintered body after being cooled to room temperature；
S400: after the polishing of described sintered body, polishing, obtain the alkali earth metal fluoride laser ceramics of ion doping.
Wherein in an embodiment, in step S100, described molecular formula is MF2Fluoride powder body and described molecular formula be ReFnThe mol ratio of fluoride powder body be (99.5～60): (0.5～40).
Wherein in an embodiment, Re is Dy3+、Yb3+、Nd3+、Er3+、Ce3+、Eu3+、Gd3+、Ho3+、Tm3+、Sm3+And Mn2+In one.
Wherein in an embodiment, in step S200, adopt ball mill that described reaction raw materials is ground；
In mechanical milling process, the atmosphere adopted is argon gas atmosphere, nitrogen atmosphere or vacuum environment, and the auxiliary agent adopted is ethanol or deionized water.
Wherein in an embodiment, rotational speed of ball-mill >=250r/min, Ball-milling Time >=1h.
Wherein in an embodiment, in step S200, drying condition is: vacuum environment, dry 1h～24h at 60 DEG C～120 DEG C.
Wherein in an embodiment, before step S300, further comprising the steps of:
It is ground sieving by the precursor powder obtained in step S200, obtains the precursor powder of granularity≤100 order.
Wherein in an embodiment, in step S300, temperature controlled processes is: be warming up to 600 DEG C～1100 DEG C with the heating rate of 10 DEG C/min～200 DEG C/min, after insulation 0min～60min, cools to room temperature with the furnace or is down to room temperature with the rate of temperature fall of≤200 DEG C/min.
Wherein in an embodiment, in step S300, described protective atmosphere is nitrogen atmosphere or argon gas atmosphere.
Wherein in an embodiment, in step S300, the pressure in discharge plasma sintering stove described in sintering process is 10MPa～80MPa.
Beneficial effects of the present invention is as follows:
In the preparation method of the laser ceramics of the present invention, adopt the alkali earth metal fluoride powder crystal of alkali earth metal fluoride powder body or doping light emitting ionic as reaction raw materials, it is not necessary to can obtaining precursor powder through co-precipitation, process is simple, it is easily controlled, contributes to realizing industrialized batch production；Meanwhile, adopt plasma discharging mode to be sintered, reduce sintering temperature and energy consumption, shorten sintering time and manufacturing cycle.
Accompanying drawing explanation
Fig. 1 is the process chart of preparation method one embodiment of laser ceramics of the present invention；
Fig. 2 is the XRD diffracting spectrum of sample in embodiment 1.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The preparation method that the invention provides a kind of laser ceramics, it is adaptable to the preparation of the alkali earth metal fluoride laser ceramics of ion doping, is particularly suited for the CaF of ion doping2The preparation of laser ceramics.Referring to Fig. 1, the preparation method of the laser ceramics of the present invention comprises the following steps:
S100: obtain reaction raw materials, including following two mode:
Mode one, is MF by molecular formula2Fluoride powder body and molecular formula be ReFnFluoride powder body mix by a certain percentage, as reaction raw materials；Mode two, is Re:MF by molecular formula2Fluoride single crystal pulverize after the powder crystal that obtains as reaction raw materials；Wherein, M is alkaline-earth metal ions, and Re is Mn2+Or rare earth ion, n=2 or 3.
In mode one, molecular formula is MF2Fluoride powder body be main reaction raw materials, including CaF2、BaF2、SrF2Deng alkali earth metal fluoride powder body, this alkali earth metal fluoride powder body is commercially available powder body, is generally polycrystalline structure.It is preferred that the purity of this commercially available powder body is more than 99.99%.
Molecular formula is ReFnThe Main Function of fluoride powder body be provide Re ion for laser ceramics, wherein, Re ion is light emitting ionic, can be luminous under certain shooting condition, and in the present invention, Re ion is manganese ion or rare earth ion.Preferably, rare earth ion is selected from Dy2+、Yb3+、Nd3+、Er3+、Ce3+、Eu3+、Gd3+、Ho3+、Tm3+And Sm3+In one.In the present invention, the molecular formula ReF usednFluoride powder body be commercially available powder body, purity is preferably more than 99.99%.
It is preferred that as a kind of embodiment, molecular formula is MF2Fluoride powder body and molecular formula be ReFnThe mol ratio of fluoride powder body be (99.5～60): (0.5～40).The present invention can realize the high concentration Uniform Doped of light emitting ionic, can prepare that luminous intensity is higher, the better laser ceramics of luminescent properties.
In mode two, reaction raw materials is the alkali earth metal fluoride powder crystal of light emitting ionic doping, belongs to mono-crystalline structures.The alkali earth metal fluoride of this mono-crystalline structures is prepared from typically via czochralski method, Bridgman-Stockbarger method, temperature gradient method, it is possible to for commercially available monocrystalline.
S200, prepares precursor powder: ground by reaction raw materials, mix, obtain precursor powder after drying.
As a kind of embodiment, adopt ball mill that reaction raw materials is ground.It is preferred that in order to prevent reaction raw materials oxidation by air, in mechanical milling process, the atmosphere adopted is argon gas atmosphere, nitrogen atmosphere or vacuum environment；More preferably, reaction raw materials adds auxiliary agent to accelerate grinding rate, and make raw material be sufficiently mixed.Wherein, auxiliary agent can be selected for deionized water or ethanol.Meanwhile, in order to ensure grinding rate and Grinding Quality, rotational speed of ball-mill is be more than or equal to 250 revs/min, and Ball-milling Time was be more than or equal to 1 hour.Further, the ball grinder that ball milling uses is preferably agate jar, zirconium oxide and politef ball grinder.
It is preferred that under vacuum environment during ball milling, vacuum≤10-1Pa。
Additionally, may be used without other modes, reaction raw materials is ground, such as hand lapping.
In step S200, after reaction raw materials is ground, it is necessary to it is dried process.It is preferred that drying condition is: vacuum environment, dry 1h～24h at 60 DEG C～120 DEG C.
In the present invention, only reaction raw materials need to be ground, mix, dry can obtain precursor powder, avoid and conventional art utilizes coprecipitation method prepare technical process problem rambunctious during precursor powder, simplify technical process, simultaneously, a large amount of powder body can be prepared by the method for the present invention is disposable, contribute to realizing industrialized batch production.
S300: put into by precursor powder in mould, is placed in discharge plasma sintering stove, under vacuum environment or protective atmosphere, is warming up to 600 DEG C～1100 DEG C, is incubated 0min～60min, obtains sintered body after being cooled to room temperature.
In this step, the mould used at high temperature can keep original shape and structure, and not with other material generation chemical reactions.It is preferred that this mould is graphite material mould, more preferably, the surface-coated of this graphite jig has boron nitride coating.The present invention can select suitable mould to be sintered according to the shape of required laser ceramics and size, thus reducing the following process difficulty of laser ceramics, saving cost, improving production efficiency.
Protective atmosphere is the atmosphere being not easily decomposed under high temperature and not easily being formed with the gas of other material generation chemical reactions, it is preferred to argon gas atmosphere or nitrogen atmosphere.When adopting protective atmosphere, in sintering process, the pressure in discharge plasma sintering stove (i.e. sintering pressure) is preferably 10MPa～80MPa, to ensure the Effective Doping of light emitting ionic, improves the consistency of sintered body.It is preferred that under vacuum environment during sintering, the air pressure≤5Pa in body of heater.
It is preferred that in step S300, temperature controlled processes is: be warming up to 600 DEG C～1100 DEG C with the heating rate of 10 DEG C/min～200 DEG C/min, after insulation 0min～60min, cools to room temperature with the furnace or be down to room temperature with the rate of temperature fall of≤200 DEG C/min.Under this heating rate and rate of temperature fall, by increasing capacitance it is possible to increase the consistency of sintered body, improve the luminescent properties of laser ceramics.
As a kind of embodiment, before step S300, further comprising the steps of: to be ground sieving by the precursor powder obtained in step S200, obtain the precursor powder of granularity≤100 order.Which may filter that bigger granule, it is ensured that the homogeneity of precursor powder granularity, improves purity and the consistency of sintered body.Herein be ground to simple dry grinding, it is not necessary to add auxiliary agent.
Compared with conventional high temperature sintering mode, the present invention adopts discharge plasma sintering mode, greatly reduces sintering temperature, decreases sintering time, thus reducing energy expenditure, shortens manufacturing cycle；Further, utilize the sintered body crystalline quality that discharge plasma sintering obtains good, uniform small grains, be conducive to the raising of product quality.
S400: after sintered body polishing, polishing, obtain the alkali earth metal fluoride laser ceramics of ion doping.
In this step, generally first sintered body is carried out double-side rough grinding, tentatively obtain the sample of surfacing, be then aided with polishing agent and carry out a degree of twin polishing, finally give the alkali earth metal fluoride laser ceramics of required ion doping.
The preparation method of the laser ceramics of the present invention, it is not necessary to can obtaining precursor powder by coprecipitation method, technique is simple, it is easy to control, it may be achieved industrialized batch production；Meanwhile, adopt discharge plasma sintering mode, greatly reduce sintering temperature and sintering time, reduce energy consumption, shorten manufacturing cycle, improve the quality of laser ceramics.
In order to be more fully understood that the present invention, below by specific embodiment, the preparation method of the laser ceramics of the present invention is further described.It should be noted that following example are prepared the reaction raw materials CaF of laser ceramics2、BaF2、ReFnIt is selected from commercially available powder body, and purity is all higher than being equal to 99.99%.
Embodiment 1
(1) CaF is weighed respectively according to the molar ratio of 98:22And YbF3As reaction raw materials；
(2) by agate jar repeatedly evacuation and put into the glove box of argon gas atmosphere after argon air purge, agate jar adds the reaction raw materials that step (1) weighs, and add appropriate dehydrated alcohol as grinding aid；Then being sealed by agate jar and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 2min～5min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 50MPa, temperature controlled processes is: first with the ramp of 100 DEG C/min to 900 DEG C, insulation 15min, then it is cooled to room temperature with the speed of 10 DEG C/min, obtains sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the CaF of 2%2Laser ceramics.
Referring to Fig. 2, the XRD diffracting spectrum of the laser ceramics for obtaining in the present embodiment, it can be seen that the laser ceramics that the present embodiment obtains is CaF2Phase, and without dephasign generate, describe and utilize laser ceramics prepared by the method for the present invention to have good crystal property.
Embodiment 2
(1) with Nd3+Doping content is the CaF of 0.5% (molar content)2As reaction raw materials after monocrystalline pulverizing, and weigh certain amount；
(2) by agate jar repeatedly evacuation and put into the glove box of argon gas atmosphere after argon air purge, agate jar adds the reaction raw materials that step (1) weighs, and add appropriate dehydrated alcohol as grinding aid；Then being sealed by agate jar and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 2min～5min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 50MPa, temperature controlled processes is: first with the ramp of 100 DEG C/min to 900 DEG C, insulation 15min, then it is cooled to room temperature with the speed of 30 DEG C/min, obtains sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Nd3+Doping content is the CaF of 0.5%2Laser ceramics.
Embodiment 3
(1) CaF is weighed respectively according to the molar ratio of 95:52And ErF3As reaction raw materials；
(2) by agate jar repeatedly evacuation and put into the glove box of argon gas atmosphere after argon air purge, agate jar adds the reaction raw materials that step (1) weighs, and add appropriate dehydrated alcohol as grinding aid；Then being sealed by agate jar and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 250r/min, and Ball-milling Time is 20h, is placed in vacuum drying oven by the powder after ball milling at 90 DEG C and dries 10h, obtains precursor powder；
(3) put in the graphite jig of discharge plasma sintering stove after the precursor powder obtained in step (2) being ground 3min～6min, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 80MPa, temperature controlled processes is: first with the ramp of 50 DEG C/min to 1100 DEG C, insulation 0min, then it is cooled to room temperature with the speed of 50 DEG C/min, obtains sintered body；
(4) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Er3+Doping content is the CaF of 5%2Laser ceramics.
Embodiment 4
(1) CaF is weighed respectively according to the molar ratio of 96:42And MnF2As reaction raw materials；
(2) by zirconia ball grinding jar repeatedly evacuation and put into the glove box of argon gas atmosphere after argon air purge, zirconia ball grinding jar adds the reaction raw materials that step (1) weighs, and add appropriate deionized water as grinding aid；Then zirconia ball grinding jar being sealed and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 600r/min, and Ball-milling Time is 1h, is placed in vacuum drying oven by the powder after ball milling at 120 DEG C and dries 1h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 4min～6min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 60MPa, temperature controlled processes is: first with the ramp of 150 DEG C/min to 700 DEG C, insulation 10min, then it is cooled to room temperature with the speed of 130 DEG C/min, obtains sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Mn2+Doping content is the CaF of 4%2Laser ceramics.
Embodiment 5
(1) CaF is weighed respectively according to the molar ratio of 9:12And YbF3As reaction raw materials；
(2) by zirconia ball grinding jar repeatedly evacuation and put into the glove box of argon gas atmosphere after argon air purge, zirconia ball grinding jar adds the reaction raw materials that step (1) weighs, and add appropriate deionized water as grinding aid；Then zirconia ball grinding jar being sealed and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by powder body after ball milling at 60 DEG C and dries 24h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 2min～5min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 50MPa, temperature controlled processes is: first with the ramp of 100 DEG C/min to 900 DEG C, insulation 30min, then it is cooled to room temperature with the speed of 200 DEG C/min, obtains sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the CaF of 10%2Laser ceramics.
Embodiment 6
(1) CaF is weighed respectively according to the molar ratio of 6:42And YbF3As reaction raw materials；
(2) by zirconia ball grinding jar repeatedly evacuation and put into the glove box of argon gas atmosphere after argon air purge, zirconia ball grinding jar adds the reaction raw materials that step (1) weighs, and add appropriate dehydrated alcohol as grinding aid；Then zirconia ball grinding jar being sealed and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 2min～5min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 70MPa, temperature controlled processes is: first with the ramp of 60 DEG C/min to 1000 DEG C, insulation 20min, then it is cooled to room temperature with the speed of 180 DEG C/min, obtains sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the CaF of 40%2Laser ceramics.
Embodiment 7
(1) CaF is weighed respectively according to the molar ratio of 8:22And YbF3As reaction raw materials；
(2) reaction raw materials weighed is put in agate jar, add appropriate deionized water as grinding aid, by (vacuum≤10 after ball grinder evacuation-1Pa), being placed on ball mill and carry out ball milling, rotational speed of ball-mill is 300r/min, and Ball-milling Time is 24h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder obtained in step (2) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under nitrogen atmosphere, sintering pressure is 65MPa, temperature controlled processes is: first with the ramp of 120 DEG C/min to 900 DEG C, insulation 35min, then cool to room temperature with the furnace, obtain sintered body；
(4) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the CaF of 20%2Laser ceramics.
Embodiment 8
(1) CaF is weighed respectively according to the molar ratio of 3:12And YbF3As reaction raw materials；
(2) by politef ball grinder repeatedly evacuation and put into the glove box of nitrogen atmosphere after nitrogen air purge, politef ball grinder adds the reaction raw materials that step (1) weighs, and adds appropriate deionized water as grinding aid；Then being sealed by politef ball grinder and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 800r/min, and Ball-milling Time is 2h, is placed in vacuum drying oven by the powder after ball milling at 110 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in mortar and grinds 2min～5min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the mould of spark plasma sintering stove, spark plasma sintering is carried out under nitrogen atmosphere, sintering pressure is 50MPa, temperature controlled processes is: first with the ramp of 50 DEG C/min to 950 DEG C, insulation 20min, then it is cooled to room temperature with the speed of 50 DEG C/min, obtains sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the CaF of 25%2Laser ceramics.
Embodiment 9
(1) CaF is weighed respectively according to the molar ratio of 99.5:0.52And YbF3As reaction raw materials；
(2) by politef ball grinder repeatedly evacuation and put into the glove box of nitrogen atmosphere after nitrogen air purge, politef ball grinder adds the reaction raw materials that step (1) weighs, and adds appropriate dehydrated alcohol as grinding aid；Then being sealed by politef ball grinder and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder obtained in step (2) is put in the mould of spark plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 50MPa, temperature controlled processes is: first with the ramp of 10 DEG C/min to 900 DEG C, insulation 15min, then cool to room temperature with the furnace, obtain sintered body；
(4) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the CaF of 0.5%2Laser ceramics.
Embodiment 10
(1) CaF is weighed respectively according to the molar ratio of 98:22And YbF3As reaction raw materials；
(2) by politef ball grinder repeatedly evacuation and put into the glove box of nitrogen atmosphere after nitrogen air purge, politef ball grinder adds the reaction raw materials that step (1) weighs, and adds appropriate dehydrated alcohol as grinding aid；Then being sealed by politef ball grinder and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 4min～8min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 80MPa, temperature controlled processes is: first with the ramp of 110 DEG C/min to 700 DEG C, insulation 60min, then cool to room temperature with the furnace, obtain sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the CaF of 2%2Laser ceramics.
Embodiment 11
(1) CaF is weighed respectively according to the molar ratio of 90:102And YbF3As reaction raw materials；
(2) by politef ball grinder repeatedly evacuation and put into the glove box of nitrogen atmosphere after nitrogen air purge, politef ball grinder adds the reaction raw materials that step (1) weighs, and adds appropriate deionized water as grinding aid；Then being sealed by politef ball grinder and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 6min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 10MPa, temperature controlled processes is: first with the ramp of 200 DEG C/min to 1100 DEG C, insulation 60min, then cool to room temperature with the furnace, obtain sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the CaF of 10%2Laser ceramics.
Embodiment 12
(1) with Yb3+Doping content is the BaF of 1% (molar content)2As reaction raw materials after monocrystalline pulverizing, and weigh certain amount；
(2) by agate jar repeatedly evacuation and put into the glove box of argon gas atmosphere after argon air purge, agate jar adds the reaction raw materials that step (1) weighs；Then being sealed by agate jar and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 2min～5min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 50MPa, temperature controlled processes is: first with the ramp of 100 DEG C/min to 650 DEG C, insulation 15min, then it is cooled to room temperature with the speed of 20 DEG C/min, obtains sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the BaF of 1%2Laser ceramics.
Embodiment 13
(1) with Nd3+Doping content is the BaF of 1.5% (molar content)2As reaction raw materials after monocrystalline pulverizing, and weigh certain amount；
(2) by agate jar repeatedly evacuation and put into the glove box of argon gas atmosphere after argon air purge, agate jar adds the reaction raw materials that step (1) weighs；Then being sealed by agate jar and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 2min～5min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 60MPa, temperature controlled processes is: first with the ramp of 50 DEG C/min to 600 DEG C, insulation 15min, then it is cooled to room temperature with the speed of 10 DEG C/min, obtains sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Nd3+Doping content is the BaF of 1.5%2Laser ceramics.
Embodiment 14
(1) BaF is weighed respectively according to the molar ratio of 98:22And YbF3As reaction raw materials；
(2) by agate jar repeatedly evacuation and put into the glove box of nitrogen atmosphere after nitrogen air purge, agate jar adds the reaction raw materials that step (1) weighs, and add appropriate deionized water as grinding aid；Then being sealed by agate jar and be placed on ball mill and carry out ball milling, rotational speed of ball-mill is 500r/min, and Ball-milling Time is 12h, is placed in vacuum drying oven by the powder after ball milling at 80 DEG C and dries 12h, obtains precursor powder；
(3) precursor powder is placed in agate mortar and grinds 4min～8min, process of then sieving, obtain the granularity precursor powder less than or equal to 100 orders；
(4) precursor powder obtained in step (3) is put in the graphite jig of discharge plasma sintering stove, spark plasma sintering is carried out under argon gas atmosphere, sintering pressure is 80MPa, temperature controlled processes is: first with the ramp of 110 DEG C/min to 700 DEG C, insulation 60min, then cool to room temperature with the furnace, obtain sintered body；
(5) sintered body obtained is carried out double-side rough grinding and twin polishing, obtain Yb3+Doping content is the BaF of 2%2Laser ceramics.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for the person of ordinary skill of the art, without departing from the inventive concept of the premise, it is also possible to making some deformation and improvement, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the preparation method of a laser ceramics, it is characterised in that comprise the following steps:
S100: be MF by molecular formula2Fluoride powder body and molecular formula be ReFnFluoride powder body mix by a certain percentage, as reaction raw materials；Or it is Re:MF by molecular formula2Fluoride single crystal pulverize after the powder crystal that obtains as reaction raw materials；
Wherein, M is alkaline-earth metal ions, and Re is Mn2+Or rare earth ion, n=2 or 3；
S200: described reaction raw materials is ground, mix, obtain precursor powder after drying；
S300: put in mould by described precursor powder, is placed in discharge plasma sintering stove, under vacuum environment or protective atmosphere, is warming up to 600 DEG C～1100 DEG C, is incubated 0min～60min, obtains sintered body after being cooled to room temperature；
S400: after the polishing of described sintered body, polishing, obtain the alkali earth metal fluoride laser ceramics of ion doping.
2. the preparation method of laser ceramics according to claim 1, it is characterised in that in step S100, described molecular formula is MF2Fluoride powder body and described molecular formula be ReFnThe mol ratio of fluoride powder body be (99.5～60): (0.5～40).
3. the preparation method of laser ceramics according to claim 1, it is characterised in that Re is Dy3+、Yb3+、Nd3+、Er3+、Ce3+、Eu3+、Gd3+、Ho3+、Tm3+、Sm3+And Mn2+In one.
4. the preparation method of laser ceramics according to claim 1, it is characterised in that in step S200, adopts ball mill that described reaction raw materials is ground；
In mechanical milling process, the atmosphere adopted is argon gas atmosphere, nitrogen atmosphere or vacuum environment, and the auxiliary agent adopted is ethanol or deionized water.
5. the preparation method of laser ceramics according to claim 4, it is characterised in that rotational speed of ball-mill >=250r/min, Ball-milling Time >=1h.
6. the preparation method of laser ceramics according to claim 1, it is characterised in that in step S200, drying condition is: vacuum environment, dry 1h～24h at 60 DEG C～120 DEG C.
7. the preparation method of laser ceramics according to claim 1, it is characterised in that before step S300, further comprising the steps of:
It is ground sieving by the precursor powder obtained in step S200, obtains the precursor powder of granularity≤100 order.
8. the preparation method of laser ceramics according to claim 1, it is characterized in that, in step S300, temperature controlled processes is: be warming up to 600 DEG C～1100 DEG C with the heating rate of 10 DEG C/min～200 DEG C/min, after insulation 0min～60min, cool to room temperature with the furnace or be down to room temperature with the rate of temperature fall of≤200 DEG C/min.
9. the preparation method of laser ceramics according to claim 1, it is characterised in that in step S300, described protective atmosphere is nitrogen atmosphere or argon gas atmosphere.
10. the preparation method of laser ceramics according to claim 1, it is characterised in that in step S300, the pressure in discharge plasma sintering stove described in sintering process is 10MPa～80MPa.
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