CN108264078A - Hydrogeneous rare earth fluoride, preparation method and application - Google Patents
Hydrogeneous rare earth fluoride, preparation method and application Download PDFInfo
- Publication number
- CN108264078A CN108264078A CN201611264006.5A CN201611264006A CN108264078A CN 108264078 A CN108264078 A CN 108264078A CN 201611264006 A CN201611264006 A CN 201611264006A CN 108264078 A CN108264078 A CN 108264078A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- fluoride
- hydrogeneous
- content
- hydrogen
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/265—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/02—Hydrides of transition elements; Addition complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention provides a kind of hydrogeneous rare earth fluoride, preparation method and applications.Wherein, O content≤50ppm in the hydrogeneous rare earth fluoride, C, N, S element respectively content≤10ppm, H2O content≤20ppm, H content are 5~100ppm, are more suitably applied to the high-end rare earth material field such as infrared Coating Materials, luminescent material and crystalline material.Contain micro hydride high-purity rare earth fluoride materials to obtain, the present invention uses rare earth hydride and hydrogen fluoride to carry out reaction for raw material and prepares rare earth fluoride, it can obtain the hydrogeneous rare earth fluoride of extremely low oxygen content and extremely low water content, and it is easy to produce in enormous quantities, there is preferable industrial applications prospect.
Description
Technical field
The present invention relates to optical material fields, in particular to a kind of hydrogeneous rare earth fluoride, preparation method and answer
With.
Background technology
Rare earth fluoride because having wide transparent area, compared with low-refraction the features such as gradually develop into infrared, especially long wave
Preferred low-index material in being developed with very long wave infrared optical thin film device, with YF3、LaF3、CeF3And YbF3Deng for representative
REF3Ideal suitable low-refraction infrared coating materials, and be current ray machine have excellent performance but have centainly put
The ThF of penetrating property and toxicity3The potential alternative materials of membrane material, are widely applied in infrared regime.
The preparation of rare earth fluoride by the qualitative classification of method, can be divided into wet method fluorination and two major class of dry type fluoride process.Make
It is etching acid precipitation (or fluoride salt precipitation)-vacuum dehydration method with the fluorination of extensive wet method.Dry type fluoride process is divided into ammonium acid fluoride
Fluoride process and hydrogen fluoride fluoride process.Wet process technique is easy to operate, but the rare earth fluoride being settled out is jelly, has and is not easy
Filtering and washing, the shortcomings of settling time is long, the non-rare earth impurity content that introduces is high and oxygen and water content residual volume are high.Dry type
Fluoride process has the characteristics that step is short, rare-earth yield is high, and a small amount of waste water generated can do the productions such as fluorinated, acid or sodium chloride
Product are sold, and can realize floride-free discharge, but the rare earth fluoride that this method is prepared is low there are purity, wherein iron, aluminium, silicon etc.
Metal impurities, oxygen impurities and water content are higher, can not still directly apply to infrared Coating Materials, luminescent material and crystalline material etc.
High-end rare earth material field.
Although the prior art, which also has been reported that, can prepare the rare earth fluoride that purity is higher than 99.99%, purity is
No is the mass content eliminated after all impurity, usually not explicitly stated, and more from the angle of rare earth fluoride
To emphasize its purity.But in fact, the rare earth fluoride of purity >=99.99%, the difference on coating performance more embodies
In terms of the height of impurity content contained by it.Thus, the content of the impurity in rare earth fluoride how is more effectively reduced, is sought
It asks and is more suitably applied to the high-end rare earth material field high-performance rare-earth fluorine such as infrared Coating Materials, luminescent material and crystalline material
Compound material is the technical issues of optical material preparation field institute is urgently to be resolved hurrily.
Invention content
It is existing to solve it is a primary object of the present invention to provide a kind of hydrogeneous rare earth fluoride, preparation method and application
There is the problem of being difficult to obtain hydrogeneous rare earth fluoride in technology.
To achieve these goals, according to an aspect of the invention, there is provided a kind of hydrogeneous rare earth fluoride, this is hydrogeneous
5~100ppm of content of H element in rare earth fluoride, hydrogeneous rare earth fluoride further include inevitable impurity element C, N, O,
S, wherein, O content≤50ppm, the respective content≤10ppm of C, N and S element, part H element and O elements are with H2The form of O is deposited
, and H2O content≤20ppm.
Further, H element existing in the form of rare earth hydride is further included in hydrogeneous rare earth fluoride.
Further, in the form of rare earth hydride existing for H element content be 10~50ppm.
Further, the impurity element in hydrogeneous rare earth fluoride further include Fe, Ca, Si, Al, Cu, Cr, V, Mn, Co,
Any one or more in Zr, Mg, Zn, Ni and rare-earth impurity element, wherein, Ca, Si and Al element respectively content≤
Respectively content≤5ppm, the total content of rare-earth impurity element exist 10ppm, Fe, Cu, Cr, V, Mn, Co, Zr, Mg, Zn and Ni element
Below 10ppm.
Further, the D of hydrogeneous rare earth fluoride50It is 6~30 μm；It is preferred that hydrogeneous rare earth fluoride is YF3、ScF3、
LaF3、CeF3、PrF3、NdF3、SmF3、GdF3、TbF3、DyF3、HoF3、ErF3、TmF3、YbF3Or LuF3。
According to another aspect of the present invention, a kind of preparation method of hydrogeneous rare earth fluoride, the preparation method packet are provided
It includes：Fluorination treatment is carried out to rare earth hydride using hydrogen fluoride gas, obtains hydrogeneous rare earth fluoride.
Further, before fluorination treatment, preparation method further includes the step of preparing hydrogeneous rare earth hydride, preferably prepares
The step of hydrogeneous rare earth hydride, includes：Hydrogenation treatment is carried out to rare earth metal using hydrogen, obtains rare earth hydride.
Further, the size≤20mm in rare earth metal block maximum gauge direction；Preferably, the purity of rare earth metal >=
99.99%.
Further, purity >=99.999% of hydrogen；Preferred fluorinated hydrogen is anhydrous hydrogen fluoride gas.
Further, hydrotreated temperature is 350~550 DEG C；It is preferred that the hydrotreated time is 1~5h.
Further, the temperature of fluorination treatment is 500~700 DEG C；The time of preferred fluorinated processing is 8~20h.
According to the third aspect of the application, a kind of infrared detector optical filming material product is provided, including rare earth
Fluoride, the rare earth fluoride are any of the above-described kind of hydrogeneous rare earth fluoride.
It applies the technical scheme of the present invention, compared to common dry fluorination process hydrofluorination method, the present invention is hydrogenated using rare earth
Object and hydrogen fluoride carry out reaction for raw material and prepare rare earth fluoride, obtain containing micro hydride high-purity rare earth fluoride materials,
And the rare earth fluoride of extremely low oxygen content and extremely low water content can be obtained, it is also easier to produce in enormous quantities, have preferable
Industrial applications prospect.
Description of the drawings
The accompanying drawings which form a part of this application are used to provide further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation do not constitute improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Attached drawing 1 shows the macro morphology photo of hydrogenation cerium particle；
Attached drawing 2 shows the SEM figures of hydrogenation cerium particle；
Attached drawing 3 shows the grain size analysis report of hydrogeneous cerium fluoride product；And
Attached drawing 4 shows the XRD spectrum of hydrogeneous cerium fluoride product.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
It should be noted that the application moderate purity refers to mass content, for example, the purity of rare earth fluoride >=
99.995%, refer to mass content >=99.995% of the rare earth fluoride in addition to gaseous impurity, that is, contain Si, non-rare earth gold
Total mass percentage >=99.995% of rare earth fluoride including category and rare earth metal.The purity connotation of other substances
It is identical, it is understood as mass percentage.
For impurity content in terms of ppm, 1ppm refers to hundred a ten thousandths of quality in the application, refers to miscellaneous in hydrogeneous rare earth fluoride
The mass content of matter is less than or equal to a few millionths of gross mass.Such as O content≤50ppm, refer to O members in hydrogeneous rare earth fluoride
The mass content of element is less than or equal to 50/1000000ths.
As background technology part is previously mentioned, there are purity is low, metal impurities for hydrogeneous rare earth fluoride of the prior art
It is higher with oxygen impurities content and cause application the defects of being restricted, in order to improve the prior art this defect, in the application one
In the typical embodiment of kind, a kind of preparation method of hydrogeneous rare earth fluoride is provided, which includes：Using fluorination
Hydrogen carries out fluorination treatment to rare earth hydride, obtains hydrogeneous rare earth fluoride.
The above-mentioned preparation method of the application, by using rare earth hydride as raw material, being prepared using dry type fluoride process hydrogeneous dilute
Native fluoride not only has the characteristics that simple for process, rare earth fluoride high income, but also oxide is miscellaneous in hydrogeneous rare earth hydride
Matter is less, even if there is small amounts object, rare earth fluoride is similarly generated with hydrogen fluoride reaction, in addition, selection rare earth hydride
For raw material, avoid conventional dry fluoride process that rare earth oxide (or carbonization rare earth is for raw material) is used to generate water (or H2O and CO2), subtract
H in few product2O content and C content.Thus the hydrogeneous rare earth fluoride prepared by the above method is compared with containing prepared by the prior art
The gaseous impurities content such as hydrogen rare earth fluoride, O, C is low, and H2O content is low.In addition, the application uses hydrogen fluoride dry type fluoride process
Hydrogeneous rare earth fluoride is prepared, because it is with the characteristics of simple for process, flow is short, the introducing of impurity easy to control in reaction process,
Secondary pollution is avoided, the metals content impurity in hydrogeneous rare earth fluoride is caused to maintain reduced levels.
In order to further reduce O, N, H in hydrogeneous rare earth hydride2The content of the gaseous impurities such as O, and then reduce in product
The content of gaseous impurity.In a kind of preferred embodiment of the application, above-mentioned preparation method, which further includes, prepares rare earth hydride
Step, the step of preferably preparing rare earth hydride, include：Hydrogenation treatment is carried out to rare earth metal using hydrogen, obtains rare earth hydrogenation
Object.
Above preferred embodiment is by using rare earth metal as starting material, due to rare earth metal simple substance compact structure,
Hydrogenation treatment is carried out in fluorination stove under the conditions of the hydrogen atmosphere in advance to prepare after the rare earth hydride of loose porous state (referring to Fig. 1
Hydrogenation cerium structure under the macro morphology of shown hydrogenation cerium and Electronic Speculum shown in Fig. 2), hydrogen atmosphere valve is turned off, is continued
It directly opens hydrogen fluoride and enters valve, be passed through hydrogen fluoride gas and carry out fluorination reaction, above-mentioned preferred embodiments can significantly reduce dilute
O, N, H in native hydride2The content of the gaseous impurities such as O, and then reduce the gaseous impurity content that rare earth hydride raw material introduces；On
Process is stated compared to more long rare earth hydride is placed in the environment, is avoided in the operating process such as rare earth hydride shove charge and environment
The possibility of gas contact, i.e., freshly prepared rare earth hydride oxygen impurities content is lower before fluorination treatment；In addition, this Shen
Please preferential hydrogenation treatment rare earth metal scheme, hydrogenation process with flaorination process is combined, hydride cooling is eliminated and comes out of the stove step
Suddenly and fluorination process heating step is simplified, fluorination efficiency can be effectively improved, while produce reduction energy consumption and cost.
When preparing rare earth hydride, the block of rare earth metal is smaller, and the time required to hydrogenation treatment and effect is more apparent, hydrogenation
It is also lower that the gaseous impurities contents such as O, N are introduced in object.In a kind of preferred embodiment of the application, above-mentioned rare earth metal block is most
Size≤the 20mm in major diameter direction；Preferably, purity >=99.99% of rare earth metal.Using purity higher rare earth in itself
Metal carries out hydrogenation, and the impurity content of obtained rare earth hydride is relatively low.
Similarly, the hydrogen purity for participating in reaction is higher, and the purity of product is also higher.In an advantageous embodiment, on
State purity >=99.999% of hydrogen；Preferred fluorinated hydrogen is anhydrous hydrogen fluoride gas.Consider from the aqueous measuring angle of control product,
H in preparation condition2The lower O Gas contents the better, thus, contribute to reduce the H in product using anhydrous hydrogen fluoride gas2O content.
In above-mentioned hydrotreatment step, hydrotreated temperature and time can according to the difference of specific rare earth type and into
Row rationally adjustment.In a kind of preferred embodiment, above-mentioned hydrotreated temperature is 350~550 DEG C, preferably hydrotreated
Time is 1~5h.
Hydrogenation treatment is carried out within the said temperature range, and there is rare earth metal to absorb, and hydrogen gas rate is fast, and volume expansion is formed
Hydride particle shortens hydrogen treat time advantageous effect.It and can be by rare earth gold in 1~5h by hydrotreated time control
Category is fully converted into rare earth hydride particle, avoids time deficiency that hydrogenation is caused not exclusively to be unfavorable for follow-up fluorination treatment, simultaneously
Reduce the advantageous effect of the time relatively long possibility that rare earth hydride is caused to be introduced with the impurity in environment.
In above-mentioned fluorination treatment step, the temperature and time of fluorination treatment can also be carried out according to different rare earth types
Rationally adjustment.In a kind of preferred embodiment, the temperature of above-mentioned fluorination treatment is 500~700 DEG C；Preferred fluorinated processing when
Between be 8~20h.
Fluorination treatment is carried out within the said temperature range, and there is best fluorination effect, hydrogen fluoride utilization rate height and impurity
The preferable advantageous effect of content control effect.And the time control of fluorination treatment is had in 8~20h fluorination effect it is best,
Hydrogen fluoride utilization rate is higher and the preferable advantageous effect of impurity content control effect.
In another typical embodiment of the application, a kind of hydrogeneous rare earth fluoride is provided, the hydrogeneous rare earth fluorine
5~100ppm of content of H element, hydrogeneous rare earth fluoride further include inevitable impurity element C, N, O and S in compound,
In, O content≤50ppm, the respective content≤10ppm of C, N and S element, part H element and O elements are with H2The form of O exists, and
H2O content≤20ppm.
The above-mentioned hydrogeneous rare earth fluoride of the application, H content is 5~100ppm, mainly with rare earth hydride and H2The shape of O
State exist, in the form of rare earth hydride there are the content of protium be 10~50ppm.The atomic weight and atomic radius of H element are small,
And with very strong reproducibility, therefore will not only harmful effect be generated to the characteristic of material, on the contrary can also in coating process
Strong reducing property atmosphere in coating process is provided, and then reduces the advantageous effect of oxygen content in Coating Materials.
The above-mentioned hydrogeneous rare earth fluoride purity of the application is high, and impurity content is low, is suitably applied infrared Coating Materials, hair
The high-end rare earth material application field such as luminescent material and crystalline material.
The above-mentioned hydrogeneous rare earth fluoride of the application, Ca, Si and Al element as impurity respective content≤10ppm, Fe,
Respective content≤the 5ppm of Cu, Cr, V, Mn, Co, Zr, Mg, Zn and Ni element, the gross mass content of rare-earth impurity element is in 10ppm
Below.
The content of various impurity is all relatively low in above-mentioned hydrogeneous rare earth fluoride, thus purity higher, is more suitably applied to red
The high-end rare earth material field such as outer Coating Materials, luminescent material and crystalline material.
The above-mentioned hydrogeneous rare earth fluoride purity higher of the application and its D50In 6~30 μ ms, have that particle is big, ratio
The characteristics of surface area is small, the advantage of the ability decline of the adsorbed gas of powder.
The above-mentioned hydrogeneous rare earth fluoride of the application includes but are not limited to YF3、ScF3、LaF3、CeF3、PrF3、NdF3、
SmF3、GdF3、TbF3、DyF3、HoF3、ErF3、TmF3、YbF3Or LuF3.From meeting infrared Coating Materials, luminescent material and crystal
The demand angle consideration of Material Field, the above-mentioned hydrogeneous preferred YF of rare earth fluoride3、LaF3、CeF3、NdF3、DyF3、HoF3、ErF3、
YbF3And LuF3。
In a kind of typical embodiment of the application, a kind of infrared detector optical filming material system is additionally provided
Product, including rare earth fluoride, wherein, hydrogeneous rare earth fluoride is any of the above-described kind of hydrogeneous rare earth fluoride.Using the application's
Infrared detector prepared by hydrogeneous rare earth fluoride is more excellent with optical filming material product properties.
In a kind of most preferred embodiment of the application, hydrogeneous rare earth fluoride is prepared using following steps：
Step 1：The rare earth metal that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby is most
The size Control in major diameter direction, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and vacuumize vacuum system and be evacuated to vacuum degree to reach 10-3Pa heats up hereinafter, proceed by heating
Rate control is in 2~10 DEG C/min；
Step 3：After temperature is increased to 350~550 DEG C of 0.5~2h of heat preservation, after metal temperature is uniform, vacuum system is closed
Valve；
Step 4：Hydrogen valve is opened, high-purity hydrogen is passed through, controls the air pressure of vacuum cavity in 0.05~0.25MPa ranges
It is interior, 350~550 DEG C of furnace temperature is controlled, keeps the temperature 1~5h, obtains rare earth hydride particle；
Step 5：Close hydrogen valve, open fluorination hydrogen valve, hydrogen fluoride flow velocity be 0.1~4kg/h, 500~700 DEG C of temperature
8~20h of lower heat preservation closes fluorination hydrogen valve, stops heating.
Step 6：Treat that furnace temperature is cooled to 50 DEG C hereinafter, opening fire door, takes out hydrogeneous rare earth fluoride, and will with double rod mills
The hydrogeneous rare earth fluoride of gained high purity anhydrous crushes, and the hydrogeneous rare earth fluoride product under different grain size range is obtained after sieving.
Further illustrate the advantageous effect of the application below in conjunction with specific embodiments.
Embodiment 1
Step 1：The rare earth metal yttrium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and vacuumize vacuum system and be evacuated to vacuum degree to reach 10-3Pa heats up hereinafter, proceed by heating
Rate control is in 2 DEG C/min；
Step 3：After temperature is increased to 450 DEG C of heat preservation 0.5h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the hydrogen that purity is 99.999% is passed through, controls the air pressure of vacuum cavity in 0.05MPa
In the range of, 450 DEG C of furnace temperature is controlled, keeps the temperature 5h, obtains hydrogenation yttrium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 550 DEG C of temperature
20h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out yttrium fluoride, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 8.14 μm of hydrogeneous yttrium fluoride product.
Embodiment 2
Step 1：The rare earth lanthanum that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 400 DEG C of heat preservation 0.5h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the hydrogen that purity is 99.999% is passed through, controls the air pressure of vacuum cavity in 0.05MPa
In the range of, 400 DEG C of furnace temperature is controlled, keeps the temperature 1h, obtains hydrogenation lanthanum particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 700 DEG C of temperature
8h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out lanthanum fluoride, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 8.95 μm of hydrogeneous lanthanum fluoride product.
Embodiment 3
Step 1：The rare earth metal cerium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 450 DEG C of heat preservation 1h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 500 DEG C of furnace temperature is controlled, keeps the temperature 2h, obtains hydrogenation cerium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 600 DEG C of temperature
15h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out cerium fluoride, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 10.14 μm of hydrogeneous cerium fluoride product.Wherein, the granularity Detection of hydrogeneous cerium fluoride product
Fig. 3 is shown in report, and XRD spectrum is shown in Fig. 4.
Embodiment 4
Step 1：The rare earth metal gadolinium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 450 DEG C of heat preservation 1h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 500 DEG C of furnace temperature is controlled, keeps the temperature 2h, obtains hydrogenation gadolinium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 600 DEG C of temperature
15h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out gadolinium fluoride, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 17.12 μm of hydrogeneous gadolinium fluoride product.
Embodiment 5
Step 1：The rare earth metal holmium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 450 DEG C of heat preservation 1h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 500 DEG C of furnace temperature is controlled, keeps the temperature 2h, obtains hydrogenation holmium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 600 DEG C of temperature
15h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out holmium fluoride, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 26.52 μm of hydrogeneous holmium fluoride product.
Embodiment 6
Step 1：The rare earth element erbium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 450 DEG C of heat preservation 1h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 500 DEG C of furnace temperature is controlled, keeps the temperature 2h, obtains hydrogenation erbium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 600 DEG C of temperature
15h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out ErF_3 films, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 18.80 μm of hydrogeneous ErF_3 films product.
Embodiment 7
Step 1：The rare earth metal ytterbium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 400 DEG C of heat preservation 2h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 400 DEG C of furnace temperature is controlled, keeps the temperature 3h, obtains hydrogenation ytterbium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 650 DEG C of temperature
18h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out fluorination ytterbium, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 15.49 μm of the product of ytterbium containing hydrofluorination.
Embodiment 8
Step 1：The rare earth metal lutetium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 400 DEG C of heat preservation 2h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 400 DEG C of furnace temperature is controlled, keeps the temperature 3h, obtains hydrogenation lutetium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 650 DEG C of temperature
18h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out fluorination lutetium, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 19.15 μm of the product of lutetium containing hydrofluorination.
Embodiment 9
Step 1：The rare earth metal neodymium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 440 DEG C of heat preservation 2h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 440 DEG C of furnace temperature is controlled, keeps the temperature 3h, obtains hydrogenation yttrium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 650 DEG C of temperature
15h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out neodymium fluoride, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 13.12 μm of hydrogeneous neodymium fluoride product.
Embodiment 10
Step 1：The rare earth metal dysprosium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 420 DEG C of heat preservation 2h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 420 DEG C of furnace temperature is controlled, keeps the temperature 3h, obtains hydrogenation dysprosium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 650 DEG C of temperature
18h closes fluorination hydrogen valve, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out dysprosium fluoride, and with pair rod mills by products therefrom
It crushes, granularity D is obtained after sieving50For 18.54 μm of hydrogeneous dysprosium fluoride product.
Embodiment 11
Step 1：The rare earth metal dysprosium that purity is 4N (mass content 99.99%) is broken into metal derby, metal derby
Size controlling, hereinafter, in the platinum crucible boat being then charged into fluorination stove, closes fire door in 20mm；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 10 DEG C/
min；
Step 3：After temperature is increased to 580 DEG C of heat preservation 2h, after metal temperature is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is opened, the wherein purity of hydrogen is 99.999%, is passed through hydrogen, controls the air pressure of vacuum cavity
In the range of 0.05MPa, 580 DEG C of furnace temperature is controlled, keeps the temperature 0.5h, obtains hydrogenation yttrium particle；
Step 5：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 720 DEG C of temperature
For 24 hours, fluorination hydrogen valve is closed, stops heating.
Step 6：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out dysprosium fluoride, and with pair rod mills by products therefrom
It crushes, the hydrogeneous dysprosium fluoride product that granularity D50 is 17.12 μm is obtained after sieving.
Embodiment 12
Step 1：By the hydrogenation yttrium particle of commercially available best quality, i.e., purity is that (mass content is 4N in addition to gaseous impurity
99.99%) hydrogenation yttrium particle is then charged into the platinum crucible boat in fluorination stove, closes fire door；
Step 2：After being evacuated to below 0.01Pa, burner hearth 2 times or more is cleaned with high-purity argon gas, cleaning burner hearth finishes
Afterwards, continue out vacuum system and be evacuated to vacuum degree to reach 10-3Pa hereinafter, proceed by heating, heating rate control 2 DEG C/
min；
Step 3：After temperature is increased to 450 DEG C of heat preservation 0.5h, after the temperature of yttrium to be hydrogenated is uniform, vacuum valve is closed；
Step 4：Hydrogen valve is closed, opens fluorination hydrogen valve, hydrogen fluoride flow velocity is 0.1kg/h, is kept the temperature at 550 DEG C of temperature
20h closes fluorination hydrogen valve, stops heating.
Step 5：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out yttrium fluoride, and with pair rod mills by products therefrom
It crushes, the hydrogeneous yttrium fluoride product that granularity D50 is 9.64 μm is obtained after sieving.
Comparative example 1
Step 1：It is raw material by the yttrium oxide powder that commercially available most purity is 5N (mass content 99.999%), is then charged into
It is fluorinated in the platinum crucible boat in stove, closes fire door；
Step 2：After temperature is increased to 550 DEG C of heat preservation 0.5h, fluorination hydrogen valve is opened, hydrogen fluoride flow velocity is 0.1kg/h, warm
20h is kept the temperature at 550 DEG C of degree, fluorination hydrogen valve is closed, stops heating.
Step 3：It treats that furnace temperature is cooled to 50 DEG C hereinafter, open fire door, takes out yttrium fluoride, and with pair rod mills by products therefrom
It crushes, the yttrium fluoride product that granularity D50 is 3.64 μm is obtained after sieving.
Comparative example 2
Step 1：In M3PVC tank diameters by 800L rare earth chloride liquids concentration (1mol/L) compared with N235 is according to volume
It is 1:1 single-stage for carrying out not less than 2h purifies, and stops stirring clarification split-phase, obtains the purification that the non-rare earth such as Fe is less than 0.03mg/L
Liquid；
Step 2：Upper scavenging solution is gone into 3M3It precipitates in conversion tank, modulates pH value to 5~7 generals with ammonium hydroxide and ammonium bicarbonate respectively
It is converted to yttrium carbonate crystalline solid；By the yttrium carbonate crystalline solid by lautertuns filtrated stock, be washed with deionized more than washing
The conductivity of liquid is less than 20 μ S/cm, centrifugal dehydration obtains high-purity yttrium carbonate solid again；
Step 3：In the stirred autoclave of liner Teflon resins, by high-purity yttrium carbonate solid obtained above with passing through
The deionized water of heating is according to weight ratio 1:2 size mixing, and temperature control is for use at 55 DEG C；
Step 4：Simultaneously with 35 DEG C of deionized waters, ammonium hydroxide, hydrogenations in the stirred autoclave of another liner Teflon resins
Acid is configured to compound fluorinating HF/NH4F=1.0, F/RE=4.0 (molar ratio), concentration (HF+NH4F)=4N, temperature control exist
25~35 DEG C for use；
Step 5：The compound fluorinating that step 4 obtains is added in step 3 and is converted, addition nucleating agent grass before converting
Acid is slowly added to compound fluorinating in the case where being stirred continuously, and reaction temperature maintains 55 DEG C, hatches final pH value control and exists
1.5, still aging 2h；
Step 6：The high-purity rare-earth yttrium fluoride slurry that step 5 obtains is put into liner Teflon resin lautertuns and was carried out
Filter is 6, then centrifugal dehydration obtains high-purity rare-earth yttrium fluoride solid with being heated to 50 DEG C of deionized waters to wash to pH value；
Step 7：The rare earth yttrium fluoride solid that step 6 obtains uniformly is prevented from being lined in the pallet of Teflon resins, then
Continuous drying 15h in drying box, temperature are 170 DEG C, obtain anhydrous high-purity rare earth yttrium fluoride；
Step 8：The anhydrous high-purity rare earth yttrium fluoride product that step 7 obtains is ground with double rod mills, sieving obtains
Granularity D50 is 4.8 μm of yttrium fluoride product.
Detection：
Using dry laser particle size analyzer, oxygen nitrogen hydrogen analyzer, carbon and sulfur analytical instrument, water content analysis instrument and ICP-MS mass spectrums point
Analyzer device or method are to the size, oxygen nitrogen hydrogen content, carbon of the rare earth fluoride prepared by the various embodiments described above and comparative example
Sulfur content and the content of each impurity are detected, and testing result is shown in Table 1, and (in addition to purity unit is weight percentage, remaining is attached most importance to
Measure ppm).
Table 1：
It indicates：* it represents with H2H element existing for O forms.
1 (Continued) of table：
| Fe | Cu | Cr | V | Mn | Co | Zr | Mg | Zn | Ni | |
| Embodiment 1 | 1.3 | 1.3 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 1.3 | ＜ 0.1 | 2.2 |
| Embodiment 2 | 2.1 | 0.8 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 0.7 | ＜ 0.1 | 1.7 |
| Embodiment 3 | 0.6 | 1.2 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 0.5 | ＜ 0.1 | 1.7 |
| Embodiment 4 | 0.5 | 0.3 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 0.9 | ＜ 0.1 | 1.5 |
| Embodiment 5 | 0.8 | 0.2 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 1.2 | ＜ 0.1 | 1.1 |
| Embodiment 6 | 1.9 | 0.6 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 1.0 | ＜ 0.1 | 1.5 |
| Embodiment 7 | 0.4 | 0.7 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 0.5 | ＜ 0.1 | 0.9 |
| Embodiment 8 | 0.3 | 0.9 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 1.4 | ＜ 0.1 | 0.7 |
| Embodiment 9 | 0.1 | 1.0 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 1.3 | ＜ 0.1 | 13 |
| Embodiment 10 | 0.5 | 0.6 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 1.1 | ＜ 0.1 | 1.8 |
| Embodiment 11 | 1.0 | 0.4 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 1.0 | ＜ 0.1 | 1.5 |
| Embodiment 12 | 0.5 | 0.7 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | ＜ 0.1 | 0.7 | ＜ 0.1 | 1.1 |
| Comparative example 1 | 12 | 17 | 9.0 | 4.2 | ＜ 0.1 | 0.5 | 0.5 | 6.3 | 51 | 6.7 |
| Comparative example 2 | 1.2 | 5.3 | 3.0 | 2.6 | 3.9 | 2.1 | 6.2 | 14 | 4.1 | 7.0 |
It is seen from the above data that the above embodiments of the present invention realize following technique effect：Compared to common
Dry fluorination process hydrofluorination method, method of the invention can be obtained containing a small amount of rare earth hydride and containing extremely low oxygen content and pole
The hydrogeneous rare earth fluoride of low water content, is also easier to produce in enormous quantities, has preferable industrial applications prospect.
Moreover, compared with using rare earth oxide from comparative example 1 as raw material, the application is hydrogenated using commercially available rare earth
Object or freshly prepared rare earth hydride prepare hydrogeneous rare earth fluoride, since the structure of rare earth hydride is more conducive to hydrogen fluoride
Gas penetrates into, thus reacts more abundant, and corresponding impurity content is also lower.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is made any repaiies
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of hydrogeneous rare earth fluoride, which is characterized in that in the hydrogeneous rare earth fluoride content of H element for 5~
100ppm, the hydrogeneous rare earth fluoride further include inevitable impurity element C, N, O and S, wherein, O content≤50ppm,
C, the respective content≤10ppm of N and S elements, part H element and O elements are with H2The form of O exists, and H2O content≤20ppm.
2. hydrogeneous rare earth fluoride according to claim 1, which is characterized in that further included in the hydrogeneous rare earth fluoride with
H element existing for rare earth hydride form.
3. hydrogeneous rare earth fluoride according to claim 2, which is characterized in that the H existing in the form of rare earth hydride
The content of element is 10~50ppm.
4. according to any one of claims 1 to 3 hydrogeneous rare earth fluoride, which is characterized in that the impurity element also wraps
Any one or more in Fe, Ca, Si, Al, Cu, Cr, V, Mn, Co, Zr, Mg, Zn, Ni and rare-earth impurity element is included,
In, the respective content≤10ppm of Ca, Si and Al element, Fe, Cu, Cr, V, Mn, Co, Zr, Mg, Zn and Ni element respectively content≤
5ppm, the total content of rare-earth impurity element is in below 10ppm.
5. hydrogeneous rare earth fluoride according to claim 1, which is characterized in that the D of the hydrogeneous rare earth fluoride50It is 6
~30 μm；It is preferred that the hydrogeneous rare earth fluoride is YF3、ScF3、LaF3、CeF3、PrF3、NdF3、SmF3、GdF3、TbF3、DyF3、
HoF3、ErF3、TmF3、YbF3Or LuF3。
6. a kind of preparation method of hydrogeneous rare earth fluoride, which is characterized in that the preparation method includes：
Fluorination treatment is carried out to rare earth hydride using hydrogen fluoride gas, obtains the hydrogeneous rare earth fluoride.
7. preparation method according to claim 6, which is characterized in that before the fluorination treatment, the preparation method is also
The step of including preparing rare earth hydride, preferably described the step of preparing rare earth hydride, include：
Hydrogenation treatment is carried out to rare earth metal using hydrogen, obtains the rare earth hydride.
8. preparation method according to claim 7, which is characterized in that the rare earth metal be block, preferably described block
Greatest diametrical dimension≤20mm；
Preferably, purity >=99.99% of the rare earth metal；
Preferably, purity >=99.999% of the hydrogen；
Preferably, the hydrogen fluoride gas is anhydrous hydrogen fluoride gas.
9. preparation method according to claim 7, which is characterized in that
The hydrotreated temperature is 350~550 DEG C；It is preferred that the hydrotreated time is 1~5h；
It is highly preferred that the temperature of the fluorination treatment is 500~700 DEG C；The time of the further preferred fluorination treatment for 8~
20h。
A kind of 10. infrared detector optical filming material product, including rare earth fluoride, which is characterized in that the rare earth fluorine
Compound is the hydrogeneous rare earth fluoride described in any one of claim 1 to 5.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611264006.5A CN108264078B (en) | 2016-12-30 | 2016-12-30 | Hydrogen-containing rare earth fluoride, preparation method and application thereof |
| MYPI2017705002A MY196081A (en) | 2016-12-30 | 2017-12-22 | A Hydrogen-Containing Rare Earth Fluoride Compound, the Preparation Method and its Application |
| JP2017247906A JP6521404B2 (en) | 2016-12-30 | 2017-12-25 | Hydrogen-containing rare earth fluoride, method for producing the same and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611264006.5A CN108264078B (en) | 2016-12-30 | 2016-12-30 | Hydrogen-containing rare earth fluoride, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108264078A true CN108264078A (en) | 2018-07-10 |
| CN108264078B CN108264078B (en) | 2020-03-27 |
Family
ID=62753790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611264006.5A Active CN108264078B (en) | 2016-12-30 | 2016-12-30 | Hydrogen-containing rare earth fluoride, preparation method and application thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6521404B2 (en) |
| CN (1) | CN108264078B (en) |
| MY (1) | MY196081A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112744854A (en) * | 2020-12-25 | 2021-05-04 | 中国科学院江西稀土研究院 | Rare earth fluoride and preparation method and application thereof |
| CN115259206A (en) * | 2022-07-22 | 2022-11-01 | 承德莹科精细化工股份有限公司 | Preparation method of high-purity thulium carbonate and high-purity thulium trifluoride |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3577074B1 (en) * | 2017-02-03 | 2023-09-20 | The South African Nuclear Energy Corporation Soc Limited | Preparation process for rare earth metal fluorides |
| CN114804028B (en) * | 2022-05-09 | 2024-04-30 | 西安稀有金属材料研究院有限公司 | Crack-free yttrium hydride neutron moderating material for space reactor and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2404602A1 (en) * | 1977-10-03 | 1979-04-27 | Anvar | Calcium, barium or strontium hydrogen-fluoro cpds. - prepd. as very pure solid solutions for use e.g. as reducing agent or in batteries as ionic conductors |
| CN101805008A (en) * | 2010-04-26 | 2010-08-18 | 赣州虔东稀土集团股份有限公司 | Anhydrous high-purity rare earth fluoride and preparation method thereof |
| CN103641149A (en) * | 2013-12-14 | 2014-03-19 | 福建师范大学 | Method of synthesizing monodisperse hexagonal rare earth fluoride nanosheet by adopting rheological phase reaction method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02289422A (en) * | 1989-04-28 | 1990-11-29 | Idemitsu Petrochem Co Ltd | Production of fine particles of rare earth metal fluoride and production of ceramic sintered body using the same particles |
| JP3134896B2 (en) * | 1992-03-12 | 2001-02-13 | 日本電信電話株式会社 | Production method of high purity rare earth fluoride |
| CN104291270B (en) * | 2014-07-02 | 2016-05-11 | 北京理工大学 | A kind of high temperature direct method is prepared the method for light rare earth hydride |
| CN105713596B (en) * | 2014-12-05 | 2018-10-19 | 有研稀土新材料股份有限公司 | Mix REF3Change colour Coating Materials and its preparation method and application |
-
2016
- 2016-12-30 CN CN201611264006.5A patent/CN108264078B/en active Active
-
2017
- 2017-12-22 MY MYPI2017705002A patent/MY196081A/en unknown
- 2017-12-25 JP JP2017247906A patent/JP6521404B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2404602A1 (en) * | 1977-10-03 | 1979-04-27 | Anvar | Calcium, barium or strontium hydrogen-fluoro cpds. - prepd. as very pure solid solutions for use e.g. as reducing agent or in batteries as ionic conductors |
| CN101805008A (en) * | 2010-04-26 | 2010-08-18 | 赣州虔东稀土集团股份有限公司 | Anhydrous high-purity rare earth fluoride and preparation method thereof |
| CN103641149A (en) * | 2013-12-14 | 2014-03-19 | 福建师范大学 | Method of synthesizing monodisperse hexagonal rare earth fluoride nanosheet by adopting rheological phase reaction method |
Non-Patent Citations (1)
| Title |
|---|
| NATHALIE KUNKEL ET AL.: ""Variation of the EuII Emission Wavelength by Substitution of Fluoride by Hydride in Fluorite-Type Compounds EuHxF2-x （0.20≤x≤0.67）"", 《INORG. CHEM.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112744854A (en) * | 2020-12-25 | 2021-05-04 | 中国科学院江西稀土研究院 | Rare earth fluoride and preparation method and application thereof |
| CN115259206A (en) * | 2022-07-22 | 2022-11-01 | 承德莹科精细化工股份有限公司 | Preparation method of high-purity thulium carbonate and high-purity thulium trifluoride |
| CN115259206B (en) * | 2022-07-22 | 2024-02-20 | 承德莹科精细化工股份有限公司 | Preparation method of high-purity thulium carbonate and high-purity thulium trifluoride |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018108923A (en) | 2018-07-12 |
| MY196081A (en) | 2023-03-14 |
| CN108264078B (en) | 2020-03-27 |
| JP6521404B2 (en) | 2019-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108264078A (en) | Hydrogeneous rare earth fluoride, preparation method and application | |
| AU2011201793B2 (en) | Reduction method | |
| JP5206152B2 (en) | Gallium oxide and method for producing the same | |
| Saladino et al. | Synthesis of Nd: YAG nanopowder using the citrate method with microwave irradiation | |
| Li et al. | Fabrication and properties of transparent Nd‐doped BaF2 ceramics | |
| CN112299861A (en) | AlON transparent ceramic pseudo-sintering agent and application thereof, and preparation method of transparent ceramic | |
| JP5640749B2 (en) | Gallium oxide and method for producing the same | |
| EP3048082B1 (en) | Ultrafine particles of titanium dioxide and method for producing same | |
| CN114275753A (en) | Preparation method of high-purity copper metaphosphate | |
| US10221076B2 (en) | Method for producing a plate-like alumina power | |
| JP2011144080A (en) | Method for producing gallium oxide | |
| CN109012653B (en) | Lithium bismuthate-bismuth oxide photocatalytic material and preparation method thereof | |
| US6042805A (en) | Method for synthesizing an essentially V2 O5 -free vanadium oxide | |
| US11827569B2 (en) | Yttrium aluminum garnet powder and processes for synthesizing same | |
| JP2835327B2 (en) | High activation and stabilization of hydrogen storage metal | |
| CN107416896A (en) | A kind of method of controllable preparation titanyl compound powder | |
| CN110963529B (en) | Pure-phase niobium lower-valence oxide nano powder and preparation method and application thereof | |
| JP4183539B2 (en) | Niobium oxide and method for producing the same | |
| Georgy et al. | Structure and optical properties of V3+ and Eu3+ ions co-doped nanocrystalline MgAl2O4 nanopowders for photoluminescent applications | |
| JPH0512301B2 (en) | ||
| Li et al. | Infrared transmission of Na+-doped γ-La2S3 ceramics densified by hot pressing | |
| JP7187356B2 (en) | Method for producing spherical boron carbide powder | |
| JPH0681011A (en) | Production of alloy powder | |
| CN117843030A (en) | Cesium tungsten bronze nano powder and preparation method and application thereof | |
| CN117285076A (en) | Application of atmospheric pressure microplasma discharge in preparing nano uranium dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100088 No.2, xinjiekouwai street, Xuanwu District, Beijing Patentee after: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee after: Youyan Technology Group Co.,Ltd. Address before: 100088 No.2, xinjiekouwai street, Xuanwu District, Beijing Patentee before: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee before: GENERAL Research Institute FOR NONFERROUS METALS Address after: 100088 No.2, xinjiekouwai street, Xuanwu District, Beijing Patentee after: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee after: China Youyan Technology Group Co.,Ltd. Address before: 100088 No.2, xinjiekouwai street, Xuanwu District, Beijing Patentee before: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee before: Youyan Technology Group Co.,Ltd. |