CN107619280A - A kind of preparation method of stratiform calcirm-fluoride crystalline ceramics - Google Patents
A kind of preparation method of stratiform calcirm-fluoride crystalline ceramics Download PDFInfo
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- 229910002106 crystalline ceramic Inorganic materials 0.000 title claims abstract description 42
- 239000011222 crystalline ceramic Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000919 ceramic Substances 0.000 claims abstract description 83
- 239000011858 nanopowder Substances 0.000 claims abstract description 40
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 238000007731 hot pressing Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 45
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 239000011698 potassium fluoride Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 238000005422 blasting Methods 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009837 dry grinding Methods 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005498 polishing Methods 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 5
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 description 63
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 14
- 238000004080 punching Methods 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 244000137852 Petrea volubilis Species 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- SHBJBKDGPFDENU-UHFFFAOYSA-I calcium;yttrium(3+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[Ca+2].[Y+3] SHBJBKDGPFDENU-UHFFFAOYSA-I 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 ions calcium fluoride Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a kind of preparation method of stratiform calcirm-fluoride crystalline ceramics, step is：1）Using commercially chemical reagent as Material synthesis CaF2With Ca1‑xRExF2+xNano-powder, wherein RE are the element that is adulterated；2）By step 1）The nano-powder of synthesis carries out dry-pressing formed mode and obtains the ceramic body with layer structure；3）By step 2）Obtain laminated structure ceramics base substrate to be put into the suitable graphite jig of diameter, kept apart mould and ceramic body with graphite paper, and graphite jig is put into pressure sintering in vacuum hotpressing stove；4）Ceramics are taken out after terminating, twin polishing processing is carried out, that is, obtains the calcirm-fluoride transparent ceramic material with layer structure.Compared with the existing homogeneous component single structure calcirm-fluoride transparent ceramic material prepared, the invention provides one kind to utilize dry-pressing formed combination vacuum hot pressing sintering technique, and the method for preparing stratiform calcirm-fluoride crystalline ceramics, technique is simple, and cost is cheap.
Description
Technical field
The present invention relates to crystalline ceramics preparation field, specially a kind of CaF for being less than 100 nm with particle size2With
Ca1-xRExF2+xPowder is raw material, using dry-pressing formed combination vacuum hot pressing sintering technique, prepares the fluorination with layer structure
The method of calcium crystalline ceramics.
Background technology
All solid state laser has the advantages that small volume, efficiency high, stability is good and long lifespan, is laser application field weight
One of developing direction is wanted, has important application in fields such as material processing, defence engineering and scientific researches.Gain media is complete
One of solid-state laser core component, in the course of the work, gain media can produce heat so that medium own temperature raises simultaneously
Cause a series of fuel factors, including thermal lensing effect, thermally induced birefringence, temperature gradient effect and thermal stress etc., to laser
Operating brings adverse effect, the serious beam quality for reducing laser output.
The fuel factor of gain media greatly derives from the medium uneven absorption to pump energy in itself, during work
Incident end face nearby has higher temperature and thermograde.In recent years, researcher demonstrates carries out layer to gain medium
Shape structure design, active ions doping concentration is changed in gradient, the capacity of heat transmission of medium can be improved, promote radiating, so as to drop
Low gain medium caused fuel factor at work.Prepare this gain media with layer structure must by means of it is certain into
Type technology is realized.From nineteen ninety-five, Ikesue etc. with Nd:Since YAG crystalline ceramics is the output of media implementation laser, crystalline ceramics
With its short preparation period, doping concentration is high, easily realizes the advantages that prepared by large scale and composite construction and obtains fast development.And phase
Than the layer structure of various configurations can be obtained by different moulding process in the dielectric materials such as monocrystalline, transparent ceramic material.It is dry
Molded also known as compression molding, it is a kind of by after powder packed to mould inside, by unidirectional or Bidirectional-pressure, by powder pressure
Into required dense green shape.It is dry-pressing formed that there is simple to operate, efficiency high, the density of resulting product are higher and cost is low etc.
Advantage, it is molded suitable for the layer structure crystalline ceramics of small size and simple shape, in layered oxide crystalline ceramics
To application（Referring to document J. Li, Y. Wu, Y. Pan, et al. Laminar-structured YAG/Nd:YAG/YAG
transparent ceramics for solid-state lasers. Int. J. Appl. Ceram. Technol., 5
(2008) 360-364.）.
In crystalline ceramics, CaF2It is the host material of excellent combination property, there is wide transmission peak wavelength scope, low sound
Sub- energy and low refraction coefficient, are highly suitable as rear-earth-doped host material, and it is good can to give full play to rare earth element
Luminescent properties.2009, there is document report to prepare Yb by raw material of nano-powder:CaF2Crystalline ceramics（Referring to document P.
Aubry, A. Bensalah, P. Gredin, et al. Synthesis and optical characterizations
of Yb-doped CaF2ceramics. Opt. Mater., 31 (2009) 750-753.）.Since then, researcher's system
It is standby gone out the calcirm-fluoride crystalline ceramics of different element dopings.However, calcirm-fluoride crystalline ceramics is that component is equally distributed at present
Single structure, it yet there are no the document report of the calcirm-fluoride crystalline ceramics with layer structure.
The content of the invention
It is cheap the invention provides a kind of technique is simple, by using dry-pressing formed combination vacuum heating-press sintering system
The preparation method of the standby calcirm-fluoride crystalline ceramics with layer structure.
The object of the present invention is achieved like this：
A kind of preparation method of stratiform calcirm-fluoride crystalline ceramics, its specific steps include：
1）The synthesis of nano-powder：Using commercially nitrate and potassium fluoride reagent as raw material, synthesis in aqueous contains CaF2With
Ca1-xRExF2+xThe suspension of particle, suspension dry grinding after centrifugation-washing, obtain CaF2With Ca1-xRExF2+xNano powder
Body；
2）The preparation of ceramic layered base substrate：By step 1）The nano-powder of synthesis claims according to the gradient layer component and thickness of setting
Amount, then successively through dry-pressing formed, the ceramic body with layer structure is obtained in a manner of layering laminates；
3）The sintering of layered, transparent ceramics：By step 2）The ceramic body of obtained layer structure is loaded into graphite jig, is put
Enter and pressure sintering is carried out in vacuum hotpressing stove；
4）Ceramics sample processing：Step 3）After sintering process terminates, ceramics are taken out and are processed by shot blasting, that is, are obtained with layer
The calcirm-fluoride crystalline ceramics of shape structure.
Described step 1）It is middle to synthesize obtained CaF2With Ca1-xRExF2+xPowder granule size is less than 100 nm, is adulterated
RE be cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and yttrium in one kind.
Described step 2）The middle ceramic body number of plies is 3~11 layers, and thickness in monolayer is in the mm of 0.2 mm~1.
Described step 2）In the uniaxial pressure that applies to each gradient layer respectively in the MPa of 5 MPa~20, dwell time
The min of respectively 10 min~30.
Described step 3）The process conditions of sintering are：Heating rate is 5 DEG C/min~15 DEG C/min, sintering temperature
For 700 DEG C~900 DEG C, pressure is the MPa of 20 Mpa~60, and soaking time is the h of 1 h~5.
Positive beneficial effect：1. the present invention is with artificial synthesized CaF2With Ca1-xRExF2+xNano-powder is raw material, using dry
Molded combination vacuum hot pressing sintering technique, the calcirm-fluoride crystalline ceramics with layer structure is prepared, by the transparent pottery of calcirm-fluoride
Porcelain is developed from single structure to layer structure；2. the present invention uses dry-pressing formed combination vacuum hot pressing sintering technique, stratiform is prepared
Calcirm-fluoride crystalline ceramics, technique is simple, and cost is cheap；3. the stratiform calcirm-fluoride crystalline ceramics consistency that the present invention prepares is high,
It is transparent good.
Brief description of the drawings：
Fig. 1 is the Ca of different levels of doping1-xYxF2+xNano-powder pattern picture, wherein a are that 3%, b of doping is doping 7%；
Fig. 2 is using the dry-pressing formed general flow chart for obtaining ceramic layered base substrate；
Fig. 3 is prepared stratiform calcirm-fluoride crystalline ceramics sample pictures；
Fig. 4 is the microstructure of different layers in ceramics sample, and wherein a is that 3%, b of doping is doping 7%.
Specific embodiment：
In order to be better understood from the present invention, below in conjunction with the accompanying drawings, preferred embodiment is described in detail, but should not be limited with this
Protection scope of the present invention.Conversely, there is provided these examples be in order to explain and illustrate the present invention general principle and practical application,
So that others skilled in the art can understand the present invention and make specific expected modification.Unless otherwise noted, originally
The various raw materials and other consumptive materials used in invention can be commercially available by market.
A kind of preparation method of stratiform calcirm-fluoride crystalline ceramics, its specific steps include：
1）The synthesis of nano-powder：Using commercially nitrate and potassium fluoride reagent as raw material, synthesis in aqueous contains CaF2With
Ca1-xRExF2+xThe suspension of particle, suspension dry grinding after centrifugation-washing, obtain CaF2With Ca1-xRExF2+xNano powder
Body；
2）The preparation of ceramic layered base substrate：By step 1）The nano-powder of synthesis claims according to the gradient layer component and thickness of setting
Amount, then successively through dry-pressing formed, the ceramic body with layer structure is obtained in a manner of layering laminates；
3）The sintering of layered, transparent ceramics：By step 2）The ceramic body of obtained layer structure is loaded into graphite jig, is put
Enter and pressure sintering is carried out in vacuum hotpressing stove；
4）Ceramics sample processing：Step 3）After sintering process terminates, ceramics are taken out and are processed by shot blasting, that is, are obtained with layer
The calcirm-fluoride crystalline ceramics of shape structure.
Described step 1）It is middle to synthesize obtained CaF2With Ca1-xRExF2+xPowder granule size is less than 100 nm, is adulterated
RE be cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and yttrium in one kind.
Described step 2）The middle ceramic body number of plies is 3~11 layers, and thickness in monolayer is in the mm of 0.2 mm~1.
Described step 2）In the uniaxial pressure that applies to each gradient layer respectively in the MPa of 5 MPa~20, dwell time
The min of respectively 10 min~30.
Described step 3）The process conditions of sintering are：Heating rate is 5 DEG C/min~15 DEG C/min, sintering temperature
For 700 DEG C~900 DEG C, pressure is the MPa of 20 MPa~60, and soaking time is the h of 1 h~5.
Embodiment 1
1）Ca1-xYxF2+xThe synthesis of nano-powder：With commercially Ca (NO3)2、Y(NO3)3It is raw material with KF, synthesizes Ca1-xYxF2+xReceive
Ground rice body, grinding is dried after centrifugation-washing, obtains Ca1-xYxF2+xPowder, wherein x=0.03 and 0.07；
2）Stratiform calcium fluoride ceramic body preparation：Weigh 0.8g Ca0.97Y0.03F2.03Nano-powder, load a diameter of 16 mm's
In steel mold, apply 20 MPa pressure, the min of pressurize 10 to punching block.Then 0.6g is loaded into same mould
Ca0.93Y0.07F2.07Nano-powder, apply 20 MPa pressure, the min of pressurize 10 to punching block.0.8g is weighed again
Ca0.97Y0.03F2.03Nano-powder, it is fitted into steel mold, applies 20 MPa pressure to punching block, pressurize 10min, obtaining the number of plies is
3 layers of doped yttrium calcium fluoride ceramic base substrate；
3）The sintering of layered, transparent ceramics：By step 2）Obtain stratiform calcium fluoride ceramic base substrate to be fitted into graphite jig, use graphite
Paper keeps apart mould and ceramic body, and then the graphite jig filled is put into vacuum hotpressing stove, with 10 DEG C/min's
Speed is warming up to 900 DEG C, then applies the MPa of pressure 30, is incubated 3 h；
4）The processing of layered, transparent ceramics：After terminating, ceramic layered sample is taken out, successively from different model sand paper pair
Ceramics sample carries out two-sided polishing, then carries out twin polishing to ceramics sample with diamond polishing liquid on automatic polishing machine,
Obtain the doped yttrium calcirm-fluoride crystalline ceramics that the number of plies is 3 layers.
It is respectively Ca as shown in Figure 10.97Y0.03F2.03With Ca0.93Y0.07F2.07Nano-powder pattern；Fig. 2 makes pottery to prepare stratiform
The general flow chart of porcelain billet body；Fig. 3 is the stratiform calcirm-fluoride crystalline ceramics sample being prepared, and can clearly tell Ceramic Like
Word under product；Fig. 4 is the microstructure of crystalline ceramics sample different component layer.
Embodiment 2
1）Ca1-xYxF2+xThe synthesis of nano-powder：With commercially Ca (NO3)2、Y(NO3)3It is raw material with KF, synthesizes Ca1-xYxF2+xReceive
Ground rice body, grinding is dried after centrifugation-washing, obtains Ca1-xYxF2+xPowder, wherein x=0 and 0.03；
2）Stratiform calcium fluoride ceramic body preparation：Weigh 0.8g CaF2Nano-powder, it is fitted into a diameter of 16 mm steel mold,
Apply 20 MPa pressure, the min of pressurize 10 to punching block.Then 0.6g Ca are loaded into same mould0.97Y0.03F2.03Nano powder
Body, apply 20 MPa pressure, the min of pressurize 10 to punching block.0.8g CaF are weighed again2Nano-powder, it is fitted into steel mold,
Apply 20 MPa pressure to punching block, pressurize 10min, obtain the calcium fluoride ceramic base substrate that the number of plies is 3 layers；
3）The sintering of layered, transparent ceramics：By step 2）Obtain stratiform calcium fluoride ceramic base substrate to be fitted into graphite jig, use graphite
Paper keeps apart mould and ceramic body, and then the graphite jig filled is put into vacuum hotpressing stove, with 15 DEG C/min's
Speed is warming up to 900 DEG C, then applies the MPa of pressure 60, is incubated 5 h；
4）The processing of layered, transparent ceramics：After terminating, ceramic layered sample is taken out, successively from different model sand paper pair
Ceramics sample carries out two-sided polishing, then carries out twin polishing to ceramics sample with diamond polishing liquid on automatic polishing machine,
Obtain the calcirm-fluoride crystalline ceramics that the number of plies is 3 layers.
Embodiment 3
1）Ca1-xYbxF2+xThe synthesis of nano-powder：With commercially Ca (NO3)2、Yb(NO3)3It is raw material with KF, synthesizes Ca1-xYbxF2+x
Nano-powder, grinding is dried after centrifugation-washing, obtains Ca1-xYbxF2+xPowder, wherein x=0.03 and 0.07；
2）Stratiform calcium fluoride ceramic body preparation：Weigh 0.8g Ca0.97Yb0.03F2.03Nano-powder, load a diameter of 16 mm's
In steel mold, apply 5 MPa pressure to punching block, the min of pressurize 30, then load 0.6g into same mould
Ca0.93Yb0.07F2.07Nano-powder, apply 5 MPa pressure to punching block, the min of pressurize 30, weigh 0.8g again
Ca0.97Yb0.03F2.03Nano-powder, it is fitted into steel mold, applies 5 MPa pressure to punching block, the min of pressurize 30, obtain the number of plies
Calcium fluoride ceramic base substrate is adulterated for 3 layers of ytterbiums；
3）The sintering of layered, transparent ceramics：By step 2）Obtain stratiform calcium fluoride ceramic base substrate to be fitted into graphite jig, use graphite
Paper keeps apart mould and ceramic body, and then the graphite jig filled is put into vacuum hotpressing stove, with 15 DEG C/min's
Speed is warming up to 800 DEG C, then applies the MPa of pressure 60, is incubated 1 h；
4）The processing of layered, transparent ceramics：After terminating, ceramic layered sample is taken out, successively from different model sand paper pair
Ceramics sample carries out two-sided polishing, then carries out twin polishing to ceramics sample with diamond polishing liquid on automatic polishing machine,
Obtain the ytterbium that the number of plies is 3 layers and adulterate calcirm-fluoride crystalline ceramics.
Embodiment 4
1）Ca1-xErxF2+xThe synthesis of nano-powder：With commercially Ca (NO3)2、Er(NO3)3It is raw material with KF, synthesizes Ca1-xErxF2+x
Nano-powder, grinding is dried after centrifugation-washing, obtains Ca1-xErxF2+xPowder, wherein x=0.03 and 0.07；；
2）Stratiform calcium fluoride ceramic body preparation：Weigh 0.8g Ca0.97Er0.03F2.03Nano-powder, load a diameter of 16 mm's
In steel mold, apply 10 MPa pressure, the min of pressurize 20 to punching block.Then 0.6g is loaded into same mould
Ca0.93Er0.07F2.07Nano-powder, apply 10 MPa pressure, the min of pressurize 20 to punching block.0.8g is weighed again
Ca0.97Er0.03F2.03Nano-powder, it is fitted into steel mold, applies 10 MPa pressure to punching block, the min of pressurize 20, obtain the number of plies
For 3 layers of Er ions calcium fluoride ceramic base substrate；
3）The sintering of layered, transparent ceramics：By step 2）Obtain stratiform calcium fluoride ceramic base substrate to be fitted into graphite jig, use graphite
Paper keeps apart mould and ceramic body, and then the graphite jig filled is put into vacuum hotpressing stove, with 10 DEG C/min's
Speed is warming up to 800 DEG C, then applies the MPa of pressure 30, is incubated 2 h；
4）The processing of layered, transparent ceramics：After terminating, ceramic layered sample is taken out, successively from different model sand paper pair
Ceramics sample carries out two-sided polishing, then carries out twin polishing to ceramics sample with diamond polishing liquid on automatic polishing machine,
Obtain the Er ions calcirm-fluoride crystalline ceramics that the number of plies is 3 layers.
Embodiment 5
1）Ca1-xYxF2+xThe synthesis of nano-powder：With commercially Ca (NO3)2、Y(NO3)3It is raw material with KF, synthesizes Ca1-xYxF2+xReceive
Ground rice body, grinding is dried after centrifugation-washing, obtains Ca1-xYxF2+xPowder, wherein x=0.03,0.05 and 0.07；
2）Stratiform calcium fluoride ceramic body preparation：Load 0.8g into a diameter of 16 mm steel mold successively
Ca0.97Y0.03F2.03、0.6g Ca0.95Y0.05F2.05、0.6g Ca0.93Y0.07F2.07、0.6g Ca0.95Y0.05F2.05And 0.8g
Ca0.97Y0.03F2.03Nano-powder, it is every addition one layer of nano-powder after, respectively to punching block apply 5 MPa pressure, pressurize
30min, finally obtain the doped yttrium calcium fluoride ceramic base substrate that the number of plies is 5 layers；
3）The sintering of layered, transparent ceramics：By step 2）Obtain stratiform calcium fluoride ceramic base substrate to be fitted into graphite jig, use graphite
Paper keeps apart mould and ceramic body, and then the graphite jig filled is put into vacuum hotpressing stove, with 5 DEG C/min's
Speed is warming up to 800 DEG C, then applies the MPa of pressure 30, is incubated 3 h；
4）The processing of layered, transparent ceramics：After terminating, ceramic layered sample is taken out, successively from different model sand paper pair
Ceramics sample carries out two-sided polishing, then carries out twin polishing to ceramics sample with diamond polishing liquid on automatic polishing machine,
Obtain the doped yttrium calcirm-fluoride crystalline ceramics that the number of plies is 5 layers.
Embodiment 6
1）Ca1-xYxF2+xThe synthesis of nano-powder：With commercially Ca (NO3)2、Y(NO3)3It is raw material with KF, synthesizes Ca1-xYxF2+xReceive
Ground rice body, grinding is dried after centrifugation-washing, obtains Ca1-xYxF2+xPowder, wherein x=0.03,0.04,0.05,0.07,0.1
With 0.12；
2）Stratiform calcium fluoride ceramic body preparation：Load 0.4g into a diameter of 16 mm steel mold successively
Ca0.97Y0.03F2.03、0.3g Ca0.96Y0.04F2.04、0.3g Ca0.95Y0.05F2.05、0.3g Ca0.93Y0.07F2.07、0.3g
Ca0.9Y0.1F2.1、0.3g Ca0.88Y0.12F2.12、0.3g Ca0.9Y0.1F2.1、0.3g Ca0.93Y0.07F2.07、0.3g
Ca0.95Y0.05F2.05、0.3g Ca0.96Y0.04F2.04、0.4g Ca0.97Y0.03F2.03Nano-powder, it is every addition one layer of nano powder
After body, apply 10 MPa pressure to punching block respectively, pressurize 30min, finally obtain the doped yttrium calcirm-fluoride that the number of plies is 11 layers and make pottery
Porcelain billet body；
3）The sintering of layered, transparent ceramics：By step 2）Obtain stratiform calcium fluoride ceramic base substrate to be fitted into graphite jig, use graphite
Paper keeps apart mould and ceramic body, and then the graphite jig filled is put into vacuum hotpressing stove, with 15 DEG C/min's
Speed is warming up to 700 DEG C, then applies the MPa of pressure 20, is incubated 5 h；
4）The processing of layered, transparent ceramics：After terminating, ceramic layered sample is taken out, successively from different model sand paper pair
Ceramics sample carries out two-sided polishing, then carries out twin polishing to ceramics sample with diamond polishing liquid on automatic polishing machine,
Obtain the doped yttrium calcirm-fluoride crystalline ceramics that the number of plies is 11 layers.
It should finally be noted the foregoing is only the preferred embodiments of the present invention, it is served only for technical scheme
It is described in more detail.For those skilled in the art according to present inventive concept make it is some it is nonessential improvement and
Adjustment, belongs to protection scope of the present invention.
The present invention is with artificial synthesized CaF2With Ca1-xRExF2+xNano-powder is raw material, using dry-pressing formed combination vacuum
Hot pressing and sintering technique, prepare the calcirm-fluoride crystalline ceramics with layer structure, by calcirm-fluoride crystalline ceramics from single structure to
Layer structure develops；The present invention uses dry-pressing formed combination vacuum hot pressing sintering technique, prepares stratiform calcirm-fluoride crystalline ceramics, work
Skill is simple, and cost is cheap；The stratiform calcirm-fluoride crystalline ceramics consistency that the present invention prepares is high, and the transparency is good.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above, for this area skill
For art personnel, it is clear that the invention is not restricted to the details of above-mentioned one exemplary embodiment, and without departing substantially from the present invention spirit or
In the case of essential characteristic, the present invention can be realized in other specific forms.Which point therefore, no matter from the point of view of, all should incite somebody to action
Embodiment regards exemplary as, and be it is nonrestrictive, the scope of the present invention by appended claims rather than on state
Bright restriction, it is intended that all changes fallen in the implication and scope of the equivalency of claim are included in the present invention
It is interior.Any reference in claim should not be considered as to the involved claim of limitation.
Claims (5)
1. a kind of preparation method of stratiform calcirm-fluoride crystalline ceramics, its specific steps include：
1）The synthesis of nano-powder：Using commercially nitrate and potassium fluoride reagent as raw material, synthesis in aqueous contains CaF2With
Ca1-xRExF2+xThe suspension of particle, suspension dry grinding after centrifugation-washing, obtain CaF2With Ca1-xRExF2+xNano powder
Body；
2）The preparation of ceramic layered base substrate：By step 1）The nano-powder of synthesis claims according to the gradient layer component and thickness of setting
Amount, then successively through dry-pressing formed, the ceramic body with layer structure is obtained in a manner of layering laminates；
3）The sintering of layered, transparent ceramics：By step 2）The ceramic body of obtained layer structure is loaded into graphite jig, is put
Enter and pressure sintering is carried out in vacuum hotpressing stove；
4）Ceramics sample processing：Step 3）After sintering process terminates, ceramics are taken out and are processed by shot blasting, that is, are obtained with layer
The calcirm-fluoride crystalline ceramics of shape structure.
A kind of 2. preparation method of stratiform calcirm-fluoride crystalline ceramics according to claim 1, it is characterised in that：Described step
Rapid 1）It is middle to synthesize obtained CaF2With Ca1-xRExF2+xPowder granule size is less than 100 nm, the RE adulterated be cerium, praseodymium, neodymium,
One kind in samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and yttrium.
A kind of 3. preparation method of stratiform calcirm-fluoride crystalline ceramics according to claim 1, it is characterised in that：Described step
Rapid 2）The middle ceramic body number of plies is 3~11 layers, and thickness in monolayer is in the mm of 0.2 mm~1.
A kind of 4. preparation method of stratiform calcirm-fluoride crystalline ceramics according to claim 1, it is characterised in that：Described step
Rapid 2）In the uniaxial pressure that applies to each gradient layer respectively in the MPa of 5 MPa~20, the dwell time be respectively 10 min~
30 min。
A kind of 5. preparation method of stratiform calcirm-fluoride crystalline ceramics according to claim 1, it is characterised in that：Described step
Rapid 3）The process conditions of sintering are：Heating rate is 5 DEG C/min~15 DEG C/min, and sintering temperature is 700 DEG C~900
DEG C, pressure is the MPa of 20 MPa~60, and soaking time is the h of 1 h~5.
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| CN111362699A (en) * | 2020-05-07 | 2020-07-03 | 信阳师范学院 | Preparation method of composite-structure strontium fluoride optical material |
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| CN116462510A (en) * | 2023-04-10 | 2023-07-21 | 东华大学 | Calcium fluoride-based fluorescent ceramic material and preparation method thereof |
| CN116514552A (en) * | 2023-04-28 | 2023-08-01 | 中建材光子科技有限公司 | Yttrium doped magnesium barium fluoride transparent ceramic and its preparation method and use |
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