CN106753378A - High-pure anhydrous compound rare-earth halide and preparation method thereof - Google Patents
High-pure anhydrous compound rare-earth halide and preparation method thereof Download PDFInfo
- Publication number
- CN106753378A CN106753378A CN201510823855.9A CN201510823855A CN106753378A CN 106753378 A CN106753378 A CN 106753378A CN 201510823855 A CN201510823855 A CN 201510823855A CN 106753378 A CN106753378 A CN 106753378A
- Authority
- CN
- China
- Prior art keywords
- halide
- earth halide
- compound rare
- rare
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7719—Halogenides
- C09K11/772—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a kind of method for preparing high-pure anhydrous compound rare-earth halide, the formula of the compound rare-earth halide is AxMyXzWherein A is one or more of alkali metal, M is one or more of rare earth element, X is one or more of halogens, and x, y, z is integer or non-integer, and meets 1≤x≤3,1≤y≤2, x+3y=z, the method prepares mixed solution, (2) concentration, (3) dehydration and (4) de- ammonium step including (1), and the step (1) is using ammonium halide NH4X is used as dehydrating agent.Additionally, present invention also offers the high-pure anhydrous compound rare-earth halide obtained by foregoing preparation method.The compound rare-earth halide prepared using this method is free of the crystallization water and oxide impurity, with purity and good uniformity very high, can meet the application demand of the materials such as scintillation crystal, scintillating ceramic.
Description
Technical field
The invention belongs to field of light emitting materials, and in particular to inorganic scintillation material, more particularly, to one kind
High-pure anhydrous compound rare-earth halide and preparation method thereof.
Background technology
Scintillation material is that a class can send ultraviolet or optical photon after the energy of high-energy ray or particle is absorbed
Material.It can be used for the spy of the high energy particles such as the high-energy rays such as alpha ray, gamma-rays, X-ray and neutron
Survey, at aspects such as nuclear medicine, high-energy physics, safety inspection, industrial non-destructive flaw detection, space physics and core mine locatings
Extensive application.They are generally applied in the form of monocrystal, can also be in some circumstances glass,
Ceramics or other forms.
Because of its High Light Output, the scintillation properties of high energy resolution, Ce3+The compound rare-earth halide of activation dodges
Bright material (such as K2LaI5:Ce3+) get more and more people's extensive concerning, in high-energy physics, safety inspection, oil
There is good application prospect in the fields such as well logging, medical imaging.These scintillation materials are generally with high-pure anhydrous alkali gold
Belong to halide and rare earth halide for raw material carries out crystal growth or preparation.However, due to rare earth halide easily
Deliquescence and oxidation, preparation are very difficult, and cost is very expensive, and existing market price is up to tens thousand of first per kilograms,
So as to seriously hinder the further development and application of scintillation material.Therefore, can directly be made if one kind can be found
For the simple efficient and with low cost method of the high-pure anhydrous compound rare-earth halide for going out pure phase, will be to multiple
Great impetus is played in the development and application for closing rare earth halide scintillation material.
The content of the invention
An object of the present invention is to provide a kind of simple and effective and with low cost high-pure anhydrous compound
The preparation method of rare earth halide.The second object of the present invention is to provide high-purity nothing that above-mentioned preparation method is obtained
Water compound rare-earth halide, this compound rare-earth halide effectively overcomes thing skew present in prior art
The defects such as analysis, higher, the activator skewness of impurity content, can fully meet scintillation crystal, ceramic or thin
The preparation demand of membrane material.The third object of the present invention is to provide one kind comprising above-mentioned high-pure anhydrous compound rare-earth
The scintillation crystal of halide, ceramic or thin-film material.
To achieve these goals, inventor has made intensive studies, and as a result finds, when using a kind of new
During synthetic method manufacture compound rare-earth halide, impurity (such as crystallization water and oxide) content can be dropped to
Bottom line, especially crystal water content are substantially dropped to close to zero；And gained compound rare-earth halide
Thing is mutually more pure, and activator distribution is more uniform.
Therefore, according to the first aspect of the invention, there is provided one kind prepares high-pure anhydrous compound rare-earth halide
Method, the formula of the compound rare-earth halide is AxMyXz, wherein A is one or more of alkali metal,
M is one or more of rare earth element, and X is one or more of halogens, x, y, z be integer or
Non-integer, and meet 1≤x≤3,1≤y≤2, x+3y=z, the method prepares mixed solution, (2) including (1)
Concentration, (3) dehydration and (4) de- ammonium step, it is characterised in that the step (1) is using ammonium halide NH4X makees
It is dehydrating agent.In the present invention, " alkali metal " represents Li, Na, K, Rb, Cs." rare earth element " table
Show La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y.
" halogens " represents Cl, Br, I.
The step (1) is：Prepare the mixed solution of alkali halide, rare earth halide, ammonium halide.Enter
One step, the step (1) is：By the carbonate or hydroxide of the alkali metal of purity >=99.9%, rare earth gold
The oxide or carbonate or hydroxide of category, ammonium halide, according to mol ratio A：M：NH4X=x/y：1：
T is codissolved in halogen acids after weighing, and obtains the mixed solution of alkali halide, rare earth halide and ammonium halide；
Wherein, 0<T≤8, preferably 1≤t≤6.In a detailed embodiment, 2≤t≤4.
The step (2) is：The mixed solution of step (1) is concentrated by evaporation, solid mixture is obtained.Further
, the step (2) is：Mixed solution is concentrated at a temperature of 80~150 DEG C, until aqueous water steams completely
Hair, obtains solid mixture.
The step (3) is：The solid mixture of step (2) is carried out into vacuum dehydration, product after being dehydrated.
Further, the step (3) is：Solid mixture is placed in quartz container, vacuum plant is connected and is added
Thermal is dehydrated to it, temperature be to slowly warm up to 200~250 DEG C by room temperature after constant temperature certain hour, taken off
Product after water.Constant temperature time is advantageously 2~48h, more preferably preferably 8~48h, 12~48h.
Heating rate is advantageously 2~30 DEG C/h, more preferably preferably 5~25 DEG C/h, 10~20 DEG C/h.
Quartz container vacuum≤3000Pa, preferably≤2800Pa are advantageously maintained in dehydration, it is further excellent
Elect≤2500Pa as.
The step (4) is：De- ammonium treatment is carried out to product after the dehydration of step (3), formula is obtained for AxMyXz
High-pure anhydrous compound rare-earth halide.Further, the step (4) is：In an inert atmosphere to dehydration
Product is heat-treated (for example, calcination) afterwards, and heating-up temperature is 400~600 DEG C.Inert atmosphere include but
It is not limited to high-purity dry Ar gas or N2Gas.In a specific embodiment, it is continually fed into heating process
It is high-purity to dry Ar gas.Heat time is advantageously 2~24h, more preferably preferably 3~12h, 3~10h.
According to the second aspect of the invention, there is provided a kind of high-pure anhydrous compound rare-earth halide, its feature exists
In it is obtained by foregoing preparation method.Singly for chemical composition, the compound rare-earth halide
Formula be AxMyXz, wherein A is one or more of alkali metal, and M is one or more of rare earth element,
X is one or more of halogens, and x, y, z is integer or non-integer, and meets 1≤x≤3,1
≤ y≤2, x+3y=z.Preferably, x, y, z is integer.In a specific embodiment, x, y,
The value of z can be the one kind in following combination：X=1, y=1, z=4；X=1, y=2, z=7；X=2, y=1,
Z=5；X=3, y=1, z=6；X=3, y=2, z=9.More specifically, being obtained by foregoing preparation method
The high-pure anhydrous compound rare-earth halide for obtaining can be any one in following halide：LiGdCl4,
LiCeCl4, LiGd0.8Ce0.2Cl4, NaGdCl4, NaCeCl4, NaGd0.8Ce0.2Cl4, RbGd2Br7,
RbCe2Br7, RbGd1.8Ce0.2Br7, K2LaCl5, K2CeCl5, K2La0.9Ce0.1Cl5, K2LaBr5, K2CeBr5,
K2La0.9Ce0.1Br5, K2LaI5, K2CeI5, K2La0.9Ce0.1I5, Cs3GdCl6, Cs3CeCl6,
Cs3Gd0.95Ce0.05Cl6, Cs3GdBr6, Cs3CeBr6, Cs3Gd0.95Ce0.05Br6, Cs3GdI6, Cs3CeI6,
Cs3Gd0.95Ce0.05I6, Cs3LaCl6, Cs3CeCl6, Cs3La0.95Ce0.05Cl6, Cs3LaBr6, Cs3CeBr6,
Cs3La0.95Ce0.05Br6, Cs3LaI6, Cs3CeI6, Cs3La0.95Ce0.05I6, Cs3Gd2I9, Cs3Ce2I9,
Cs3Gd1.9Ce0.1I9, Cs3Lu2I9, Cs3Lu1.9Ce0.1I9.Additionally, for purity, the height that the present invention is obtained
Purity >=99.9% of pure anhydrous compound rare-earth halide, water content≤20ppm, oxygen content≤100ppm；
Preferably, water content≤17ppm, oxygen content≤80ppm；It is highly preferred that water content≤15ppm, oxygen contains
Amount≤50ppm；Most preferably, water content≤12ppm, oxygen content≤40ppm；Can meet scintillation crystal,
The preparation demand of ceramics or thin-film material.Certainly, by foregoing preparation method obtain it is high-pure anhydrous multiple
The rare earth compound product that rare earth halide purity a kind of absolutely not is limited is closed, but high-energy physics, safety can be met
The direct applied rare earth material in the fields such as inspection, oil well logging, medical imaging.Not only purity is higher for this material,
And thing is mutually more pure, activator distribution is more uniform, is substantially distinguished from other known material of the prior art
Material.
According to the third aspect of the invention we, there is provided a kind of comprising above-mentioned high-pure anhydrous compound rare-earth halide
Scintillation crystal, ceramics or thin-film material.This material has the scintillation properties of High Light Output, high energy resolution.
Below will be with K2LaI5Preparation as a example by, technical scheme is illustrated.For this area
It is obvious to the skilled person that can be changed to disclosed implementation method.Therefore, this description should
When being considered nonrestrictive.
In the prior art, K2LaI5Generally with high-pure anhydrous KI, LaI3Be raw material, will the two in molar ratio 2:1
High―temperature nuclei is obtained after mixing.Due to above two raw material particularly LaI3Easily deliquescence, its high-pure anhydrous original
The preparation of material is very difficult, and cost is also prohibitively expensive.Therefore, two kinds of raw materials are prepared respectively to be mixed again, no
Only technically have difficulties, it is costly, it is also relatively complicated in operation, and easily cause because mixing is uneven
Thing phase segregation.If being capable of K that is inexpensive, quickly and efficiently preparing single-phase2LaI5, will be to K2LaI5
The growth of scintillation crystal provides great convenience.
For this problem, inventor has attempted a kind of new synthetic method, i.e., with metal hydroxides, carbon
Hydrochlorate or oxide are initial feed, and KI, LaI are first produced according to stoichiometric proportion3Mixed solution, then lead to
Concentration, dehydration are crossed, the anhydrous K of single-phase is directly obtained2LaI5.Test result indicate that, the method is simple to operate,
It is with low cost, it is obtained in that the K of single-phase2LaI5Product.But shortcoming is, due to dehydration middle rare earth
The hydrolysis tendency of halide is excessively strong, and the anhydrous compound rare-earth halide product prepared using the method is still easy to
The higher problem of existing oxide impurity content, its purity is difficult to ensure that the requirement for meeting scintillator crystal materials preparation.
Inventor can be successfully solved it has furthermore been found that be used as dehydrating agent by adding a certain amount of ammonium halide
This problem.Ammonium halide is strong acid weak base salt, with certain acidity, therefore can play suppression in dehydration
The effect of brewed brine compound hydrolysis, so that the oxide impurity content in reducing product.Test result indicate that, even if
Add minimal amount of ammonium halide, product purity also can be improved significantly.When its consumption reaches rare earth halide
When 8 times (mole), its improvement to product purity tends to saturation, therefore the consumption of ammonium halide should be with
8 times (moles) no more than rare earth halide are advisable.This method is generalized to other similar AxMyXz
The preparation of type alkali metal-rare earth metal binary complex halide, also all has very similar beneficial effect.
In view of AxMyXzType scintillation crystal is with Ce3+It is active ions, the present invention can also be directly synthesized and include
The high-pure anhydrous compound rare-earth halide of single-phase of certain activator component.For example, the present invention can be by preparing
During mixed solution with a certain amount of cerium salt (cerium oxide, cerous carbonate or cerium hydroxide) replace lanthanum salt (lanthana,
Lanthanum carbonate or lanthanum hydroxide), directly obtain similar to K2La0.9Ce0.1I5Such single-phase halide, and can
As needed, the cerium concentration in halide is adjusted by adjusting raw material proportioning.Compared to conventional method, this hair
Activator Ce in the product that bright method is obtained3+Ion distribution is more uniformly distributed, and this is for improving the homogeneous of scintillation material
Property is of great advantage.
Compared with prior art, preparation method of the invention is simple to operate, and cost is more cheap, it is easy to large quantities of
Amount production.Product of the invention has following advantages：(1) purity is higher, oxide impurity and crystal water content
Significantly reduce；(2) thing is mutually more pure, substantially single-phase halide；(3) activator is distributed more
Uniformly, it is well suited for the demand of the materials such as scintillation crystal, ceramics；(4) compared to like product, more cost is excellent
Gesture.
Specific embodiment
The described purpose/of invention or scheme will be given in the form of preferred embodiment.To these implementation methods
Illustrate to be used to help the understanding of the present invention, and unrestricted other feasible implementation methods, these other feasible
Implementation method can be learnt by practice of the invention.Illustrated with reference to specific embodiment.
Comparative example 1：Accurately weigh 138.2g K2CO3And 162.9g La (99.99%)2O3(99.99%),
It is codissolved in obtaining mixing settled solution in HI acid, 90 DEG C are concentrated into material without aqueous water.After cooling, obtain
Blocks of solid.It is contained in quartzy dehydrating tube after blocks of solid is crushed, is put into dehydration in tube furnace.Dehydration temperaturre
220 DEG C being to slowly warm up to by room temperature and being incubated 4h, 5 DEG C/h of heating rate, period is vacuumized using water ring pump,
Vacuum about 2400Pa.Material is K after dehydration2LaI5.Its water content is detected for 20ppm, oxygen content is 226
ppm。
Embodiment 1：Accurately weigh 138.2g K2CO3(99.99%), 162.9g La2O3(99.99%),
144.9g NH4I (99.9%) is codissolved in obtaining mixing settled solution in hydroiodic acid, and 110 DEG C are concentrated into material not
Containing aqueous water.After cooling, blocks of solid is obtained.It is contained in quartzy dehydrating tube after blocks of solid is crushed, is put into
It is dehydrated in tube furnace.Dehydration temperaturre is to slowly warm up to 200 DEG C and is incubated 12h by room temperature, 10 DEG C of heating rate
/ h, period is vacuumized using water ring pump, vacuum about 2300Pa.Material is under the conditions of high-purity Ar gas after dehydration
450 DEG C of calcination 6h, resultant product is K2LaI5.Its water content is detected for 12ppm, oxygen content is 42ppm.
Embodiment 2：Accurately weigh 138.2g K2CO3(99.99%), 146.6g La2O3(99.99%),
23.0g Ce2(CO3)3(99.99%), 53.5g NH4Cl (99.9%) is codissolved in obtaining mixing clarification in hydrochloric acid
Solution, 100 DEG C are concentrated into material without aqueous water.After cooling, blocks of solid is obtained.Blocks of solid is crushed
After be contained in quartzy dehydrating tube, be put into tube furnace and be dehydrated.Dehydration temperaturre is to slowly warm up to 230 DEG C simultaneously by room temperature
Insulation 12h, 12 DEG C/h of heating rate, period is vacuumized using water ring pump, vacuum about 2200Pa.Dehydration
Material 450 DEG C of calcination 3h under the conditions of high-purity Ar gas afterwards, resultant product is K2La0.9Ce0.1Cl5.Detect its water
Content is 16ppm, and oxygen content is 47ppm.
Embodiment 3：Accurately weigh 115.5g Rb2CO3(99.99%), 362.5g Gd2O3(99.99%),
391.8g NH4Br (99.9%) is codissolved in obtaining mixing settled solution in hydrobromic acid, and 150 DEG C are concentrated into material
Without aqueous water.After cooling, blocks of solid is obtained.It is contained in quartzy dehydrating tube after blocks of solid is crushed, is put
Enter dehydration in tube furnace.Dehydration temperaturre is to slowly warm up to 210 DEG C and is incubated 48h by room temperature, 25 DEG C of heating rate
/ h, period is vacuumized using water ring pump, vacuum about 2800Pa.Material is under the conditions of high-purity Ar gas after dehydration
500 DEG C of calcination 10h, resultant product is RbGd2Br7.Its water content is detected for 15ppm, oxygen content is 27
ppm。
Embodiment 4：Accurately weigh 325.8g Cs2CO3(99.99%), 114.8g Gd2O3(99.99%),
7.67g Ce2(CO3)3、93.1g NH4Br (99.9%) is codissolved in obtaining mixing settled solution, 80 DEG C in hydrobromic acid
Material is concentrated into without aqueous water.After cooling, blocks of solid is obtained.Quartz is contained in after blocks of solid is crushed de-
In water pipe, dehydration in tube furnace is put into.Dehydration temperaturre is to slowly warm up to 250 DEG C and is incubated 24h by room temperature, rises
15 DEG C/h of warm speed, period is vacuumized using water ring pump, vacuum about 3000Pa.Material is high-purity after dehydration
N2550 DEG C of calcination 4h under the conditions of gas, resultant product is Cs3Gd0.95Ce0.05Br6.Detect that its water content is 12
Ppm, oxygen content is 44ppm.
Embodiment 5：Accurately weigh 73.9g Li2CO3(99.99%), 362.5g Gd2O3(99.99%),
427.9g NH4Cl (99.9%) is codissolved in obtaining mixing settled solution in hydrochloric acid, and 120 DEG C are concentrated into material and are free of
Aqueous water.After cooling, blocks of solid is obtained.It is contained in quartzy dehydrating tube after blocks of solid is crushed, is put into pipe
It is dehydrated in formula stove.Dehydration temperaturre is to slowly warm up to 240 DEG C and is incubated 12h by room temperature, 18 DEG C/h of heating rate,
Period is vacuumized using water ring pump, vacuum about 2400Pa.Material is in high-purity N after dehydration2400 DEG C under the conditions of gas
Calcination 20h, resultant product is LiGdCl4.Its water content is detected for 13ppm, oxygen content is 36ppm.
Embodiment 6：Accurately weigh 325.8g Cs2CO3(99.99%), 153.4g Ce2(CO3)3(99.99%)
g、98.0g NH4Br (99.9%) is codissolved in obtaining mixing settled solution in hydrobromic acid, and 90 DEG C are concentrated into thing
Material is free of aqueous water.After cooling, blocks of solid is obtained.It is contained in quartzy dehydrating tube after blocks of solid is crushed,
It is put into dehydration in tube furnace.Dehydration temperaturre is to slowly warm up to 220 DEG C and is incubated 8h by room temperature, 5 DEG C of heating rate
/ h, period is vacuumized using water ring pump, vacuum about 2500Pa.Material is under the conditions of high-purity Ar gas after dehydration
600 DEG C of calcination 2h, resultant product is Cs3CeBr6.Its water content is detected for 14ppm, oxygen content is 37ppm.
Embodiment 7：Accurately weigh 244.4g Cs2CO3(99.99%), 181.3g Gd2O3(99.99%),
195.9g NH4Br (99.9%) is codissolved in obtaining mixing settled solution in hydrobromic acid, and 110 DEG C are concentrated into material not
Containing aqueous water.After cooling, blocks of solid is obtained.It is contained in quartzy dehydrating tube after blocks of solid is crushed, is put into
It is dehydrated in tube furnace.Dehydration temperaturre is to slowly warm up to 240 DEG C and is incubated 24h by room temperature, 15 DEG C/h of heating rate,
Period is vacuumized using water ring pump, vacuum about 2300Pa.Material is 500 DEG C under the conditions of high-purity Ar gas after dehydration
Calcination 6h, resultant product is Cs3Gd2Br9.Its water content is detected for 17ppm, oxygen content is 49ppm.
Compared with prior art, preparation method of the invention is simple to operate, and cost is more cheap, it is easy to large quantities of
Amount production.Product purity of the invention is higher, and oxide impurity and crystal water content are significantly reduced；Thing phase is more
For pure, substantially single-phase halide；Activator distribution is more uniform, is well suited for scintillation crystal, pottery
The demand of the materials such as porcelain；Compared to like product, more cost advantage.
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for ability
For the technical staff in domain, the present invention can have various modifications and variations.It is all the spirit and principles in the present invention it
Interior, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (18)
1. a kind of method for preparing high-pure anhydrous compound rare-earth halide, the formula of the compound rare-earth halide is
AxMyXz, wherein A is one or more of alkali metal, and M is one or more of rare earth element, and X is halogen
One or more of prime element, x, y, z is integer or non-integer, and meets 1≤x≤3,1≤y≤2,
X+3y=z, the method prepares mixed solution, (2) concentration, (3) dehydration and (4) de- ammonium step including (1),
Characterized in that, the step (1) is using ammonium halide NH4X is used as dehydrating agent.
2. preparation method according to claim 1, wherein, the step (1) is：Prepare alkali halide,
The mixed solution of rare earth halide, ammonium halide.
3. preparation method according to claim 2, wherein, the step (1) is：By the alkali of purity >=99.9%
The carbonate or hydroxide of metal, the oxide of rare earth metal or carbonate or hydroxide, ammonium halide, press
According to mol ratio A：M：NH4X=x/y：1：T is codissolved in halogen acids after weighing, obtain alkali halide,
The mixed solution of rare earth halide and ammonium halide；Wherein, 0<t≤8.
4. preparation method according to claim 1, wherein, the step (2) is：The mixing of step (1) is molten
Liquid is concentrated by evaporation, and obtains solid mixture.
5. preparation method according to claim 4, wherein, the step (2) is：By mixed solution 80~
Concentrated at a temperature of 150 DEG C, until aqueous water evaporating completely, obtain solid mixture.
6. preparation method according to claim 1, wherein, the step (3) is：The solid of step (2) is mixed
Compound carries out vacuum dehydration, product after being dehydrated.
7. preparation method according to claim 6, wherein, the step (3) is：Solid mixture is placed in
In quartz container, connection vacuum plant and heater are dehydrated to it, and temperature is to slowly warm up to 200 by room temperature~
Constant temperature certain hour after 250 DEG C, product after being dehydrated.
8. preparation method according to claim 1, wherein, the step (4) is：After the dehydration of step (3)
Product carries out de- ammonium treatment, obtains formula for AxMyXzHigh-pure anhydrous compound rare-earth halide.
9. preparation method according to claim 8, wherein, the step (4) is：In an inert atmosphere to de-
Product is heat-treated after water, and heating-up temperature is 400~600 DEG C.
10. a kind of high-pure anhydrous compound rare-earth halide, it is characterised in that it passes through any one of claim 1-9 institute
The preparation method stated is obtained.
11. high-pure anhydrous compound rare-earth halide according to claim 10, it is characterised in that x=1, y=1,
Z=4.
12. high-pure anhydrous compound rare-earth halide according to claim 10, it is characterised in that x=1, y=2,
Z=7.
13. high-pure anhydrous compound rare-earth halide according to claim 10, it is characterised in that x=2, y=1,
Z=5.
14. high-pure anhydrous compound rare-earth halide according to claim 10, it is characterised in that x=3, y=1,
Z=6.
15. high-pure anhydrous compound rare-earth halide according to claim 10, it is characterised in that x=3, y=2,
Z=9.
16. high-pure anhydrous compound rare-earth halide according to claim 10, it is characterised in that it can be
Any one in following halide：LiGdCl4, LiCeCl4, LiGd0.8Ce0.2Cl4, NaGdCl4, NaCeCl4,
NaGd0.8Ce0.2Cl4, RbGd2Br7, RbCe2Br7, RbGd1.8Ce0.2Br7, K2LaCl5, K2CeCl5,
K2La0.9Ce0.1Cl5, K2LaBr5, K2CeBr5, K2La0.9Ce0.1Br5, K2LaI5, K2CeI5, K2La0.9Ce0.1I5,
Cs3GdCl6, Cs3CeCl6, Cs3Gd0.95Ce0.05Cl6, Cs3GdBr6, Cs3CeBr6, Cs3Gd0.95Ce0.05Br6,
Cs3GdI6, Cs3CeI6, Cs3Gd0.95Ce0.05I6, Cs3LaCl6, Cs3CeCl6, Cs3La0.95Ce0.05Cl6,
Cs3LaBr6, Cs3CeBr6, Cs3La0.95Ce0.05Br6, Cs3LaI6, Cs3CeI6, Cs3La0.95Ce0.05I6,
Cs3Gd2I9, Cs3Ce2I9, Cs3Gd1.9Ce0.1I9, Cs3Lu2I9, Cs3Lu1.9Ce0.1I9。
17. high-pure anhydrous compound rare-earth halide according to claim 10, it is characterised in that purity >=
99.9%, water content≤20ppm, oxygen content≤100ppm.
A kind of 18. scintillation crystals, ceramics or thin-film material, comprising the high-purity nothing described in claim any one of 10-17
Water compound rare-earth halide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510823855.9A CN106753378A (en) | 2015-11-24 | 2015-11-24 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510823855.9A CN106753378A (en) | 2015-11-24 | 2015-11-24 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106753378A true CN106753378A (en) | 2017-05-31 |
Family
ID=58964557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510823855.9A Pending CN106753378A (en) | 2015-11-24 | 2015-11-24 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106753378A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107215887A (en) * | 2017-06-09 | 2017-09-29 | 厦门中烁光电科技有限公司 | The preparation method of anhydrous bromination cerium |
| CN111893568A (en) * | 2020-07-24 | 2020-11-06 | 燕山大学 | High-purity NaAlB14Method for producing crystal |
| CN114772627A (en) * | 2022-03-30 | 2022-07-22 | 蜂巢能源科技(无锡)有限公司 | Dehydration purification method and application of solid electrolyte |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1717466A (en) * | 2002-11-27 | 2006-01-04 | 圣戈班晶体及检测公司 | Method for preparing rare-earth halide blocks |
| CN1847359A (en) * | 2005-03-30 | 2006-10-18 | 通用电气公司 | Scintillator compositions based on lanthanide halides and alkali metals, and related methods and articles |
| CN102295931A (en) * | 2010-05-10 | 2011-12-28 | 美国西门子医疗解决公司 | Halide scintillator for radiation detection |
-
2015
- 2015-11-24 CN CN201510823855.9A patent/CN106753378A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1717466A (en) * | 2002-11-27 | 2006-01-04 | 圣戈班晶体及检测公司 | Method for preparing rare-earth halide blocks |
| CN1847359A (en) * | 2005-03-30 | 2006-10-18 | 通用电气公司 | Scintillator compositions based on lanthanide halides and alkali metals, and related methods and articles |
| CN102295931A (en) * | 2010-05-10 | 2011-12-28 | 美国西门子医疗解决公司 | Halide scintillator for radiation detection |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107215887A (en) * | 2017-06-09 | 2017-09-29 | 厦门中烁光电科技有限公司 | The preparation method of anhydrous bromination cerium |
| CN111893568A (en) * | 2020-07-24 | 2020-11-06 | 燕山大学 | High-purity NaAlB14Method for producing crystal |
| CN114772627A (en) * | 2022-03-30 | 2022-07-22 | 蜂巢能源科技(无锡)有限公司 | Dehydration purification method and application of solid electrolyte |
| CN114772627B (en) * | 2022-03-30 | 2024-02-13 | 蜂巢能源科技(无锡)有限公司 | Dehydration purification method and application of solid electrolyte |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106745163A (en) | High-pure anhydrous compound rare-earth halide and preparation method thereof | |
| Dubey et al. | Effect of europium concentration on photoluminescence and thermoluminescence behavior of Y 2 O 3: Eu 3+ phosphor | |
| CN111778017A (en) | Manganese-doped Cs with high light yield3Cu2I5Halide scintillator | |
| CN101665695B (en) | Preparation method of Pr3+ doped (Yx La (1-x)) 2O3 luminescent material | |
| CN106753378A (en) | High-pure anhydrous compound rare-earth halide and preparation method thereof | |
| Ayer et al. | BaWO 2 F 4: a mixed anion X-ray scintillator with excellent photoluminescence quantum efficiency | |
| Petrosyan et al. | A study of radiation effects on LuAG: Ce (Pr) co-activated with Ca | |
| Wang et al. | Eu3+ doped heavy germanate scintillating glasses | |
| CN1322173C (en) | Preparation method of cerium-doped lutetium disilicate high-temperature scintillation single crystal | |
| Sun et al. | Investigation on the luminescent properties of Eu3+-activated dense oxyfluoride borogermanate scintillating glasses | |
| Vedda et al. | Trap-center recombination processes by rare earth activators in YAlO 3 single crystal host | |
| CN111040764A (en) | Fluoride high-brightness X-ray scintillator and preparation method thereof | |
| Saraee et al. | Changes of Tb emission by non-radiative energy transfer from Dy in Gd 2 O 2 S: Tb phosphor | |
| CN110204336B (en) | Preparation method of gadolinium oxysulfide powder and flash crystal ceramic | |
| CN103951258B (en) | Rare earth ion doped SrI2Devitrified glass and preparation method thereof | |
| Su et al. | Synthesis and luminescence properties of Yb3+, Tm3+ and Ho3+ co-doped SrGd2 (WO4) 2 (MoO4) 2 nano-crystal | |
| Ren et al. | The effect of Pr3+ concentration on the microstructure, luminescence and scintillation properties of Pr: LuAG single crystals | |
| Silva et al. | Effect of terbium and silver co-doping on the enhancement of photoluminescence in CaSO4 phosphors | |
| CN115367767A (en) | Lithium sodium yttrium borate, cerium doped compound and crystal thereof, and preparation method and application thereof | |
| He et al. | Growth and optical properties of YBa3B9O18: Ce crystals | |
| CN105778901B (en) | Eu2+Activate high-pure anhydrous halide of alkaline-earth metal and preparation method thereof | |
| CN103951221A (en) | Rare-earth-ion-doped CaI2 microcrystalline glass and preparation method thereof | |
| CN103951222A (en) | Rare-earth-ion-doped SrBr2 microcrystalline glass and preparation method thereof | |
| CN109321246B (en) | La2Zr2O7Up-conversion luminescent material and preparation method thereof | |
| CN113563078A (en) | Trivalent bismuth ion enhanced manganese doped SrZn2S2O-oxysulfide scintillator and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |