CN106477896A - A kind of oxygen fluorine glass ceramic material of nickel ion doping and preparation method thereof - Google Patents

A kind of oxygen fluorine glass ceramic material of nickel ion doping and preparation method thereof Download PDF

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CN106477896A
CN106477896A CN201610857378.2A CN201610857378A CN106477896A CN 106477896 A CN106477896 A CN 106477896A CN 201610857378 A CN201610857378 A CN 201610857378A CN 106477896 A CN106477896 A CN 106477896A
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ceramic material
glass ceramic
oxygen fluorine
nickel ion
ion doping
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林常规
李乐刚
朱二伟
焦清
戴世勋
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Ningbo University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/16—Halogen containing crystalline phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

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  • Dispersion Chemistry (AREA)
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Abstract

The invention discloses a kind of oxygen fluorine glass ceramic material of nickel ion doping and preparation method thereof, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, a mole composition for the oxygen fluorine glass ceramic material is expressed as by chemical formula：(1‑y)[xKF·xZnF2·(1‑2x)SiO2]·yNiO, whereinx=0.2 ~ 0.3,y=0.0005~0.02；Its preparation method is workable, its by controlled nano-crystallization process, the KZnF of precipitating nickel ion doping in parent glass3Nanocrystalline, the oxygen fluorine glass ceramic material of the nickel ion doping for preparing, its light emitting region is 1300 2400nm, the centre of luminescence is 1700nm, halfwidth is 330nm, be a kind of have ultra-wideband near-infrared luminous new photonic material, its light emitting region completely covers near-infrared communication window, with preferable application prospect in 1800 2200nm wave bands.

Description

A kind of oxygen fluorine glass ceramic material of nickel ion doping and preparation method thereof
Technical field
The invention belongs to functional glass technical field of ceramic material, and in particular to a kind of oxygen fluorine glass pottery of nickel ion doping Ceramic material and preparation method thereof.
Background technology
1993, Wang and Ohwaki reported first Er3+And Yb3+The excellent luminance performance of oxygen fluorine glass ceramics is co-doped with, After fluoride crystallization being separated out in glass matrix, its luminous intensity enhances nearly 100 times, can be comparable with fluoride glass [Appl. Phys. Lett. 1993, 63, 3268−3270.].Since then, oxygen fluorine glass ceramic material both had because of which The crystal of fluoride of low phonon energy, the chemical stability for having oxide glass good again and mechanical strength, in luminous and photon Field causes extensive concern.In the more than two decades in past, researcher is in the research to oxygen fluorine glass ceramic material In, almost cover all of possess optically active rare earth ion, the crystal of fluoride for wherein separating out mainly has MF2(M = Ca, Sr, Ba, Pb)、RF3(R = La, Y, Cd)、ARF4(A = Li, Na, K;R=La, Y, Gd) and B2RF7 (B = Sr, Ba;R=La, Y, Gd) etc. several classes [J. Fluorine Chem. 2015, 172, 22−50.].Wherein, Rare earth ion replaces the position of the alkaline-earth metal in these crystal of fluoride and rare earth element, and the local for entering low phonon energy is brilliant In lattice ring border, so as to show all kinds of charming optics and photonic propulsion attribute, have in fields such as solid-state laser, light amplification and LED Good potential application.
From above-mentioned background, although oxygen fluorine glass ceramic material has a preferable achievement in research at luminous aspect, but extremely The crystal of fluoride of modern report is all adapted for rare earth ion doped, is not appropriate for doped transition metal ionses and lights.It is true that Compared to the f-f electron transition of rare earth ion, the d-d electron transition of transition metal ions is more sensitive to its local environment, more It is also easy to produce some novel optical properties.Design and prepare be suitable to doped transition metal ionses oxygen fluorine glass ceramics will be send out One of existing new effective means of performance more preferably photonic material, carries out the research work by great meaning.In consideration of it, this Bright oxygen fluorine glass ceramic material for proposing a kind of doping of nickel ion and preparation method thereof.
Content of the invention
The technical problem to be solved is, for the deficiencies in the prior art, to provide a kind of oxygen of nickel ion doping Fluorine glass ceramic material and preparation method thereof, the light emitting region of the oxygen fluorine glass ceramic material of the nickel ion doping is 1300- 2400nm, the centre of luminescence are 1700nm, and halfwidth is 330nm, compared with common oxide glass-ceramics, luminescent spectrum scope More move to long wave, the halfwidth of 330nm also than conventional oxide glass ceramics～300nm is wide, is that one kind has ultra broadband Near-infrared luminous new photonic material, its light emitting region completely covers near-infrared communication window, in 1800-2200nm wave band Interior with good application prospect.
The present invention solves the technical scheme that adopted of above-mentioned technical problem：A kind of oxygen fluorine glass ceramics of nickel ion doping Material, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, mole composition of the oxygen fluorine glass ceramic material is by chemical formula It is expressed as：(1-y)[xKF·xZnF2·(1-2x)SiO2]·yNiO, whereinx=0.2 ~ 0.3,y=0.0005~0.02.
A kind of preparation method of the oxygen fluorine glass ceramic material of nickel ion doping, founds basic glass using melt quenching method Glass, then will found the parent glass that obtains carries out crystallization heat treatment, that is, obtain the oxygen fluorine glass ceramic material of nickel ion doping, Concrete technology step is：
1）According to chemical formula (1-y) [xKF·xZnF2·(1-2x)SiO2]·yMole composition of NiO, whereinx=0.2 ~ 0.3,y =0.0005 ~ 0.02, calculate and each raw material is weighed, then each raw material is mixed；
2）Take clean platinum crucible to be placed in the middle part of intermediate frequency furnace, the power of intermediate frequency furnace is adjusted, is made in stove in 30min Temperature rises to 1150 ~ 1300 DEG C；
3）The raw material for mixing is put in platinum crucible, lid is added, 0.5 ~ 1h of insulation makes raw material liquefy；In-furnace temperature is made again 1400 ~ 1500 DEG C are risen to, 1 ~ 2h is incubated, makes raw material reaction complete；Then, by platinum stirrer with the speed of 30 ~ 90r/min Stirring liquation, homogenizes liquation；It is slowly withdrawn platinum stirrer afterwards, liquation is stood 0.5 ~ 1h, then pours preheated mould into Quenching shaping in tool, is subsequently put into rapidly in annealing furnace and is incubated, and holding temperature is lower than glass transformation temperature 10 ~ 40 DEG C, and insulation 3 ~ Along with the furnace cooling after 5h, then cut into slices polishing obtain parent glass；
4）Parent glass to obtaining carries out crystallization heat treatment in crystallization furnace, and heat treatment temperature is higher than glass transformation temperature by 40 ~ 80 DEG C, heat treatment time is 5 ~ 80h, finally along with the furnace cooling again, the KZnF of precipitating nickel ion doping in parent glass3Nanometer Crystalline substance, obtains the oxygen fluorine glass ceramic material of nickel ion doping, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, the oxygen A mole composition for fluorine glass ceramic material is expressed as by chemical formula：(1-y)[xKF·xZnF2·(1-2x)SiO2]·yNiO, its Inx=0.2 ~ 0.3,y=0.0005~0.02.
Preferably, step 3）In, the preheating temperature of mould is 420 ~ 480 DEG C, and holding temperature in the lehr is 420 ~480℃.
Preferably, step 4）In, heat treatment temperature is 460 ~ 560 DEG C.
Preferably, described KZnF3Nanocrystalline is smaller in size than 50nm.
Preferably, step 1）In, the introducing form of each raw material is potassium fluoride, zinc fluoride, quartz sand and nickel oxide.Enter one Step ground, the potassium fluoride of introducing and the purity of zinc fluoride are 3N, and the quartz sand of introducing and the purity of nickel oxide are 4N, to ensure to be obtained The purity of oxygen fluorine glass ceramic material and the uniformity of component.
Compared with prior art, it is an advantage of the current invention that：The oxygen fluorine glass ceramics of nickel ion doping disclosed by the invention Contain KZnF in material3Nanocrystalline, KZnF3Crystal has [ZnF as one kind6] octahedral unit cubic perovskite type crystal, KZnF3Lattice belong to P3m (No. 221) space group, Zn in its composition2+Ion is located at the centre of inversion, is in [ZnF6] fluorine Among the octahedral unit of coordination, Zn2+Ni with doping2+Metal ion has close ionic radius, Zn2+Ion can be Ni2+ Ion provides almost PerfectSymmetrical centre, is extremely suitable to Ni2+Ion doping lights, therefore, this cubic perovskite type structure KZnF3Crystal is highly suitable as the host material of the oxygen fluorine glass ceramic material of nickel ion doping.Nickel disclosed by the invention The oxygen fluorine glass ceramic material preparation method of ion doping is workable, its by controlled nano-crystallization process, on basis The KZnF of precipitating nickel ion doping in glass3Nanocrystalline, the oxygen fluorine glass ceramic material of the nickel ion doping for preparing, its Optical range is 1300-2400nm, and the centre of luminescence is 1700nm, and halfwidth is 330nm, with common oxide glass-ceramics phase More move to long wave than, luminescent spectrum scope, the halfwidth of 330nm also than conventional oxide glass ceramics～300nm is wide, be A kind of have ultra-wideband near-infrared luminous new photonic material, its light emitting region completely covers near-infrared communication window, With preferable application prospect in 1800-2200nm wave band.
Description of the drawings
Fig. 1 is oxygen fluorine glass ceramic material and the common nickel doping oxide glass pottery of the nickel ion doping of embodiment 1 The Near-infrared luminescence contrast of ceramic material；
The nanocrystalline TEM picture in the oxygen fluorine glass ceramic material for the nickel ion doping of embodiment 1 of Fig. 2.
Specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
Embodiment 1：TakexIt is 0.005 to be worth for 0.25, y, mole composition of the oxygen fluorine glass ceramic material of the nickel ion doping It is expressed as by chemical formula：0.995[0.25KF·0.25ZnF2·0.5SiO2] 0.005NiO, its preparation method is：Using molten Melt quenching method and parent glass is founded, then will found the parent glass that obtains carries out crystallization heat treatment, that is, obtain nickel ion doping Oxygen fluorine glass ceramic material, concrete technology step is：
1）According to 0.995 [0.25KF 0.25ZnF of chemical formula2·0.5SiO2] 0.005NiO mole composition, with purity be The KF of 3N and ZnF2And purity is the SiO of 4N2It is raw material with NiO, calculates KF, ZnF2、SiO2And the weight of NiO, with precision Electronic balance is weighed to each raw material, is then mixed each raw material；
2）Take clean platinum crucible to be placed in the middle part of intermediate frequency furnace, the power of intermediate frequency furnace is adjusted, is made in stove in 30min Temperature rises to 1200 DEG C；
3）The raw material for mixing is put in platinum crucible with ceramics spoon, lid is added, insulation 0.5h makes raw material liquefy；Stove is made again Interior temperature rises to 1440 DEG C, is incubated 1h, makes raw material reaction complete；Then, stirred with the speed of 50r/min by platinum stirrer Liquation, homogenizes liquation；It is slowly withdrawn platinum stirrer afterwards, liquation is stood 0.5h, then the stone for pouring preheated to 450 DEG C into Quenching shaping in black mould, is subsequently put into rapidly in annealing furnace and is incubated, with cold with stove after 450 DEG C of holding temperature insulation 5h But, then cut into slices polishing obtain parent glass；
4）Parent glass to obtaining carries out crystallization heat treatment in crystallization furnace, and heat treatment temperature is 520 DEG C, and heat treatment time is 20h, last along with the furnace cooling again, the KZnF of precipitating nickel ion doping in parent glass3Nanocrystalline, obtain the nickel of embodiment 1 from The oxygen fluorine glass ceramic material of son doping, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, the oxygen fluorine glass ceramics material A mole composition for material is expressed as by chemical formula：0.995[0.25KF·0.25ZnF2·0.5SiO2]·0.005NiO.
The test that lights is carried out to the oxygen fluorine glass ceramic material that the nickel ion of embodiment 1 adulterates using XRF, and Contrasted with the Near-infrared luminescence of common nickel doping oxide glass ceramic material, under the exciting of 800nm laser The nickel ion emission spectrum for obtaining is as shown in Figure 1.Test result shows, the nickel ion of the oxygen fluorine glass ceramic material of embodiment 1 Light emitting region is 1300 ~ 2400nm, and the centre of luminescence is 1700nm, and halfwidth is 330nm, and light emitting region compares common oxide Glass ceramics（As LiGa5O8、β-Ga2O3Deng）More move to long wave, near-infrared communication window is completely covers, is presented Preferable application prospect in 1800 ~ 2200nm wave band.
In the oxygen fluorine glass ceramic material of the nickel ion doping of embodiment 1, Fig. 2 is shown in by nanocrystalline TEM picture, shows KZnF3 Nanocrystalline is smaller in size than 50nm.
Embodiment 2：TakexIt is 0.001 to be worth for 0.225, y, mole group of the oxygen fluorine glass ceramic material of the nickel ion doping Become and be expressed as by chemical formula：0.999[0.225KF·0.225ZnF2·0.55SiO2] 0.001NiO, its preparation method is：Adopt Parent glass is founded with melt quenching method, then will found the parent glass that obtains carries out crystallization heat treatment, that is, obtain nickel ion The oxygen fluorine glass ceramic material of doping, concrete technology step is：
1）According to 0.999 [0.225KF 0.225ZnF of chemical formula2·0.55SiO2] 0.001NiO mole composition, with pure Spend the KF and ZnF for 3N2And purity is the SiO of 4N2It is raw material with NiO, calculates KF, ZnF2、SiO2And the weight of NiO, use Precision electronic balance is weighed to each raw material, is then mixed each raw material；
2）Take clean platinum crucible to be placed in the middle part of intermediate frequency furnace, the power of intermediate frequency furnace is adjusted, is made in stove in 30min Temperature rises to 1250 DEG C；
3）The raw material for mixing is put in platinum crucible with ceramics spoon, lid is added, insulation 40min makes raw material liquefy；Make again In-furnace temperature rises to 1480 DEG C, is incubated 2h, makes raw material reaction complete；Then, stirred with the speed of 60r/min by platinum stirrer Liquation is mixed, homogenizes liquation；It is slowly withdrawn platinum stirrer afterwards, liquation is stood 1h, then the stone for pouring preheated to 480 DEG C into Quenching shaping in black mould, is subsequently put into rapidly in annealing furnace and is incubated, with cold with stove after 480 DEG C of holding temperature insulation 3h But, then cut into slices polishing obtain parent glass；
4）Parent glass to obtaining carries out crystallization heat treatment in crystallization furnace, and heat treatment temperature is 560 DEG C, and heat treatment time is 40h, last along with the furnace cooling again, the KZnF of precipitating nickel ion doping in parent glass3Nanocrystalline, obtain the nickel of embodiment 2 from The oxygen fluorine glass ceramic material of son doping, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, the oxygen fluorine glass ceramics material A mole composition for material is expressed as by chemical formula：0.999[0.225KF·0.225ZnF2·0.55SiO2]·0.001NiO.
The test that lights is carried out to the oxygen fluorine glass ceramic material that the nickel ion of embodiment 2 adulterates using XRF.Survey Test result shows that the nickel ion of the oxygen fluorine glass ceramic material of embodiment 2 lights same scope for 1300 ~ 2400nm, in lighting The heart is 1700nm, and halfwidth is 330nm, and light emitting region compares common oxide glass-ceramics（As LiGa5O8、β-Ga2O3Deng） More move to long wave, near-infrared communication window is completely covers, is presented before the preferable application in 1800 ~ 2200nm wave band Scape.
Embodiment 3：TakexIt is 0.01 to be worth for 0.275, y, mole composition of the oxygen fluorine glass ceramic material of the nickel ion doping It is expressed as by chemical formula：0.99[0.275KF·0.275ZnF2·0.45SiO2] 0.01NiO, its preparation method is：Using molten Melt quenching method and parent glass is founded, then will found the parent glass that obtains carries out crystallization heat treatment, that is, obtain nickel ion doping Oxygen fluorine glass ceramic material, concrete technology step is：
1）According to 0.999 [0.225KF 0.225ZnF of chemical formula2·0.55SiO2] 0.001NiO mole composition, with KF, ZnF2、SiO2It is raw material with NiO, calculates KF, ZnF2、SiO2And the weight of NiO, each raw material is carried out with precision electronic balance Weigh, then each raw material is mixed；
2）Take clean platinum crucible to be placed in the middle part of intermediate frequency furnace, the power of intermediate frequency furnace is adjusted, is made in stove in 30min Temperature rises to 1200 DEG C；
3）The raw material for mixing is put in platinum crucible with ceramics spoon, lid is added, insulation 40min makes raw material liquefy；Make again In-furnace temperature rises to 1430 DEG C, is incubated 2h, makes raw material reaction complete；Then, stirred with the speed of 80r/min by platinum stirrer Liquation is mixed, homogenizes liquation；It is slowly withdrawn platinum stirrer afterwards, liquation is stood 1h, then the stone for pouring preheated to 440 DEG C into Quenching shaping in black mould, is subsequently put into rapidly in annealing furnace and is incubated, with cold with stove after 440 DEG C of holding temperature insulation 3h But, then cut into slices polishing obtain parent glass；
4）Parent glass to obtaining carries out crystallization heat treatment in crystallization furnace, and heat treatment temperature is 500 DEG C, and heat treatment time is 10h, last along with the furnace cooling again, the KZnF of precipitating nickel ion doping in parent glass3Nanocrystalline, obtain the nickel of embodiment 3 from The oxygen fluorine glass ceramic material of son doping, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, the oxygen fluorine glass ceramics material A mole composition for material is expressed as by chemical formula：0.99[0.275KF·0.275ZnF2·0.45SiO2]·0.01NiO.
The test that lights is carried out to the oxygen fluorine glass ceramic material that the nickel ion of embodiment 3 adulterates using XRF.Survey Test result shows that the nickel ion of the oxygen fluorine glass ceramic material of embodiment 3 lights same scope for 1300 ~ 2400nm, in lighting The heart is 1700nm, and halfwidth is 330nm, and light emitting region compares common oxide glass-ceramics（As LiGa5O8、β-Ga2O3Deng） More move to long wave, near-infrared communication window is completely covers, is presented before the preferable application in 1800 ~ 2200nm wave band Scape.
Embodiment 4：TakexIt is 0.012 to be worth for 0.21, y, mole composition of the oxygen fluorine glass ceramic material of the nickel ion doping It is expressed as by chemical formula：0.988[0.21KF·0.21ZnF2·0.58SiO2] 0.012NiO, its preparation method is：Using molten Melt quenching method and parent glass is founded, then will found the parent glass that obtains carries out crystallization heat treatment, that is, obtain nickel ion doping Oxygen fluorine glass ceramic material, concrete technology step is：
1）According to 0.988 [0.21KF 0.21ZnF of chemical formula2·0.58SiO2] 0.012NiO mole composition, with purity KF and ZnF for 3N2And purity is the SiO of 4N2It is raw material with NiO, calculates KF, ZnF2、SiO2And the weight of NiO, with essence Close electronic balance is weighed to each raw material, is then mixed each raw material；
2）Take clean platinum crucible to be placed in the middle part of intermediate frequency furnace, the power of intermediate frequency furnace is adjusted, is made in stove in 30min Temperature rises to 1280 DEG C；
3）The raw material for mixing is put in platinum crucible with ceramics spoon, lid is added, insulation 45min makes raw material liquefy；Make again In-furnace temperature rises to 1450 DEG C, is incubated 1.5h, makes raw material reaction complete；Then, by platinum stirrer with the speed of 40r/min Stirring liquation, homogenizes liquation；It is slowly withdrawn platinum stirrer afterwards, liquation is stood 40min, then is poured into preheated to 430 DEG C graphite jig in quenching shaping, be subsequently put into rapidly in annealing furnace and be incubated, with after 430 DEG C of holding temperature insulation 4h with Stove is cooled down, then polishing of cutting into slices obtains parent glass；
4）Parent glass to obtaining carries out crystallization heat treatment in crystallization furnace, and heat treatment temperature is 530 DEG C, and heat treatment time is 35h, last along with the furnace cooling again, the KZnF of precipitating nickel ion doping in parent glass3Nanocrystalline, obtain the nickel of embodiment 4 from The oxygen fluorine glass ceramic material of son doping, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, the oxygen fluorine glass ceramics material A mole composition for material is expressed as by chemical formula：0.988[0.21KF·0.21ZnF2·0.58SiO2]·0.012NiO.
The test that lights is carried out to the oxygen fluorine glass ceramic material that the nickel ion of embodiment 4 adulterates using XRF.Survey Test result shows that the nickel ion of the oxygen fluorine glass ceramic material of embodiment 4 lights same scope for 1300 ~ 2400nm, in lighting The heart is 1700nm, and halfwidth is 330nm, and light emitting region compares common oxide glass-ceramics（As LiGa5O8、β-Ga2O3Deng） More move to long wave, near-infrared communication window is completely covers, is presented before the preferable application in 1800 ~ 2200nm wave band Scape.
Embodiment 5：TakexIt is 0.008 to be worth for 0.24, y, mole composition of the oxygen fluorine glass ceramic material of the nickel ion doping It is expressed as by chemical formula：0.992[0.24KF·0.24ZnF2·0.52SiO2] 0.008NiO, its preparation method is：Using molten Melt quenching method and parent glass is founded, then will found the parent glass that obtains carries out crystallization heat treatment, that is, obtain nickel ion doping Oxygen fluorine glass ceramic material, concrete technology step is：
1）According to 0.992 [0.24KF 0.24ZnF of chemical formula2·0.52SiO2] 0.008NiO mole composition, with purity KF and ZnF for 3N2And purity is the SiO of 4N2It is raw material with NiO, calculates KF, ZnF2、SiO2And the weight of NiO, with essence Close electronic balance is weighed to each raw material, is then mixed each raw material；
2）Take clean platinum crucible to be placed in the middle part of intermediate frequency furnace, the power of intermediate frequency furnace is adjusted, is made in stove in 30min Temperature rises to 1300 DEG C；
3）The raw material for mixing is put in platinum crucible with ceramics spoon, lid is added, insulation 0.5h makes raw material liquefy；Stove is made again Interior temperature rises to 1460 DEG C, is incubated 1.5h, makes raw material reaction complete；Then, stirred with the speed of 70r/min by platinum stirrer Liquation is mixed, homogenizes liquation；It is slowly withdrawn platinum stirrer afterwards, liquation is stood 0.5h, then pours preheated to 460 DEG C into Quenching shaping in graphite jig, is subsequently put into rapidly in annealing furnace and is incubated, with cold with stove after 460 DEG C of holding temperature insulation 5h But, then cut into slices polishing obtain parent glass；
4）Parent glass to obtaining carries out crystallization heat treatment in crystallization furnace, and heat treatment temperature is 490 DEG C, and heat treatment time is 70h, last along with the furnace cooling again, the KZnF of precipitating nickel ion doping in parent glass3Nanocrystalline, obtain the nickel of embodiment 5 from The oxygen fluorine glass ceramic material of son doping, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, the oxygen fluorine glass ceramics material A mole composition for material is expressed as by chemical formula：0.992[0.24KF·0.24ZnF2·0.52SiO2]·0.008NiO.
The test that lights is carried out to the oxygen fluorine glass ceramic material that the nickel ion of embodiment 5 adulterates using XRF.Survey Test result shows that the nickel ion of the oxygen fluorine glass ceramic material of embodiment 5 lights same scope for 1300 ~ 2400nm, in lighting The heart is 1700nm, and halfwidth is 330nm, and light emitting region compares common oxide glass-ceramics（As LiGa5O8、β-Ga2O3Deng） More move to long wave, near-infrared communication window is completely covers, is presented before the preferable application in 1800 ~ 2200nm wave band Scape.
Embodiment 6：TakexIt is 0.015 to be worth for 0.3, y, mole composition of the oxygen fluorine glass ceramic material of the nickel ion doping It is expressed as by chemical formula：0.985[0.3KF·0.3ZnF2·0.4SiO2] 0.015NiO, its preparation method is：Using melting Quenching method founds parent glass, and then will found the parent glass that obtains carries out crystallization heat treatment, that is, obtain nickel ion doping Oxygen fluorine glass ceramic material, concrete technology step is：
1）According to 0.985 [0.3KF 0.3ZnF of chemical formula2·0.4SiO2] 0.015NiO mole composition, with KF, ZnF2、 SiO2It is raw material with NiO, calculates KF, ZnF2、SiO2And the weight of NiO, each raw material is weighed with precision electronic balance, Then each raw material is mixed；
2）Take clean platinum crucible to be placed in the middle part of intermediate frequency furnace, the power of intermediate frequency furnace is adjusted, is made in stove in 30min Temperature rises to 1270 DEG C；
3）The raw material for mixing is put in platinum crucible with ceramics spoon, lid is added, insulation 1h makes raw material liquefy；Made in stove again Temperature rises to 1470 DEG C, is incubated 2h, makes raw material reaction complete；Then, molten with the speed stirring of 65r/min by platinum stirrer Liquid, homogenizes liquation；It is slowly withdrawn platinum stirrer afterwards, liquation is stood 0.5h, then the graphite for pouring preheated to 470 DEG C into Quenching shaping in mould, is subsequently put into rapidly in annealing furnace and is incubated, with along with the furnace cooling after 470 DEG C of holding temperature insulation 4h, Polishing of cutting into slices again obtains parent glass；
4）Parent glass to obtaining carries out crystallization heat treatment in crystallization furnace, and heat treatment temperature is 480 DEG C, and heat treatment time is 80h, last along with the furnace cooling again, the KZnF of precipitating nickel ion doping in parent glass3Nanocrystalline, obtain the nickel of embodiment 6 from The oxygen fluorine glass ceramic material of son doping, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, the oxygen fluorine glass ceramics material A mole composition for material is expressed as by chemical formula：0.985[0.3KF·0.3ZnF2·0.4SiO2]·0.015NiO.
The test that lights is carried out to the oxygen fluorine glass ceramic material that the nickel ion of embodiment 6 adulterates using XRF.Survey Test result shows that the nickel ion of the oxygen fluorine glass ceramic material of embodiment 6 lights same scope for 1300 ~ 2400nm, in lighting The heart is 1700nm, and halfwidth is 330nm, and light emitting region compares common oxide glass-ceramics（As LiGa5O8、β-Ga2O3Deng） More move to long wave, near-infrared communication window is completely covers, is presented before the preferable application in 1800 ~ 2200nm wave band Scape.
From above example, the sending out of the oxygen fluorine glass ceramic material of the nickel ion doping obtained using the inventive method Optical range is 1300 ~ 2400nm, the centre of luminescence（1700nm）Compare common oxide glass-ceramics（As LiGa5O8、β-Ga2O3 Deng）More move to long wave, halfwidth be 330nm also than oxide glass-ceramics ~ 300nm is wider, is that one kind has ultra broadband Near-infrared luminous new photonic material, its light emitting region completely covers near-infrared communication window, in 1800-2200nm wave band Interior with preferable application prospect.

Claims (7)

1. the oxygen fluorine glass ceramic material that a kind of nickel ion adulterates, it is characterised in that：Contain in the oxygen fluorine glass ceramic material KZnF3Nanocrystalline, a mole composition for the oxygen fluorine glass ceramic material is expressed as by chemical formula：(1-y)[xKF·xZnF2·(1- 2x)SiO2]·yNiO, whereinx=0.2 ~ 0.3,y=0.0005~0.02.
2. the preparation method of the oxygen fluorine glass ceramic material of a kind of nickel ion doping, it is characterised in that：Molten using melt quenching method Parent glass processed, then will found the parent glass that obtains carries out crystallization heat treatment, that is, obtain the oxygen fluorine glass of nickel ion doping Ceramic material, concrete technology step is：
1）According to chemical formula (1-y) [xKF·xZnF2·(1-2x)SiO2]·yMole composition of NiO, whereinx=0.2 ~ 0.3,y= 0.0005 ~ 0.02, calculate and each raw material is weighed, then each raw material is mixed；
2）Take clean platinum crucible to be placed in the middle part of intermediate frequency furnace, the power of intermediate frequency furnace is adjusted, is made in stove in 30min Temperature rises to 1150 ~ 1300 DEG C；
3）The raw material for mixing is put in platinum crucible, lid is added, 0.5 ~ 1h of insulation makes raw material liquefy；In-furnace temperature is made again 1400 ~ 1500 DEG C are risen to, 1 ~ 2h is incubated, makes raw material reaction complete；Then, by platinum stirrer with the speed of 30 ~ 90r/min Stirring liquation, homogenizes liquation；It is slowly withdrawn platinum stirrer afterwards, liquation is stood 0.5 ~ 1h, then pours preheated mould into Quenching shaping in tool, is subsequently put into rapidly in annealing furnace and is incubated, and holding temperature is lower than glass transformation temperature 10 ~ 40 DEG C, and insulation 3 ~ Along with the furnace cooling after 5h, then cut into slices polishing obtain parent glass；
4）Parent glass to obtaining carries out crystallization heat treatment in crystallization furnace, and heat treatment temperature is higher than glass transformation temperature by 40 ~ 80 DEG C, heat treatment time is 5 ~ 80h, finally along with the furnace cooling again, the KZnF of precipitating nickel ion doping in parent glass3Nanometer Crystalline substance, obtains the oxygen fluorine glass ceramic material of nickel ion doping, contains KZnF in the oxygen fluorine glass ceramic material3Nanocrystalline, the oxygen A mole composition for fluorine glass ceramic material is expressed as by chemical formula：(1-y)[xKF·xZnF2·(1-2x)SiO2]·yNiO, its Inx=0.2 ~ 0.3,y=0.0005~0.02.
3. the preparation method of the oxygen fluorine glass ceramic material of a kind of nickel ion doping according to claim 2, its feature exist In：Step 3）In, the preheating temperature of mould is 420 ~ 480 DEG C, and holding temperature in the lehr is 420 ~ 480 DEG C.
4. the preparation method of the oxygen fluorine glass ceramic material of a kind of nickel ion doping according to claim 2, its feature exist In：Step 4）In, heat treatment temperature is 460 ~ 560 DEG C.
5. the preparation method of the oxygen fluorine glass ceramic material of a kind of nickel ion doping according to claim 2, its feature exist In：Described KZnF3Nanocrystalline is smaller in size than 50nm.
6. the preparation method of the oxygen fluorine glass ceramic material of a kind of nickel ion doping according to claim 2, its feature exist In：Step 1）In, the introducing form of each raw material is potassium fluoride, zinc fluoride, quartz sand and nickel oxide.
7. the preparation method of the oxygen fluorine glass ceramic material of a kind of nickel ion doping according to claim 6, its feature exist In：The purity of the potassium fluoride of introducing and zinc fluoride is 3N, and the quartz sand of introducing and the purity of nickel oxide are 4N.
CN201610857378.2A 2016-09-28 2016-09-28 A kind of oxygen fluorine glass ceramic material of nickel ion doping and preparation method thereof Pending CN106477896A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424001A (en) * 2018-04-04 2018-08-21 武汉理工大学 A kind of CsPbX3Nanocrystalline doping boron-containing glass and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHANGGUI LIN等: "Broadband near-IR emission from cubic perovskite KZnF3:Ni2+ nanocrystals embedded glass-ceramics", 《OPTICS LETTERS》 *
M.G. BRIK等: "Ab initio,crystal field and experimental spectroscopic studies of pure and Ni2+-doped KZnF3 crystals", 《MATERIALS CHEMISTRY AND PHYSICS》 *
方汉中主编: "《世界建筑材料-发展水平和趋势[M]第一版》", 30 April 1989 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108424001A (en) * 2018-04-04 2018-08-21 武汉理工大学 A kind of CsPbX3Nanocrystalline doping boron-containing glass and preparation method thereof

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