CN105004681B - A kind of chemical stability evaluation method of fluor-apatite ceramic solidification body - Google Patents
A kind of chemical stability evaluation method of fluor-apatite ceramic solidification body Download PDFInfo
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Abstract
The invention discloses a kind of chemical stability evaluation method of fluor-apatite ceramic solidification body, it is characterized in that：Prepare simulation time actinium series nucleic fluor-apatite ceramic solidification body；Shell is used as stainless steel, liner is used as the hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) and leaches container；Using deionized water as leaching agent, it is 5~9 to adjust pH value；It is leached at 100~200 DEG C of temperature and 0.101~1.554MPa of pressure, test the conductivity of leachate, analyze the concentration of leachate intermediate ion, the normalization leaching rate of calculating simulation time actinium series nucleic, it analyzes firming body and leaches front and rear object phase change, chemical stability of the evaluation fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.Brief and practical of the present invention, strong operability, evaluation index is rationally intuitive, and evaluation result accurately and reliably, can provide effective experimental basis and technical support for long-time stability and safety of the evaluation high-level waste firming body in deep geological disposal environment.
Description
Technical field
The invention belongs to high-level radwastes（Abbreviation high-level waste）Processing and disposition, be related to a kind of fluor-apatite
The chemical stability evaluation method of ceramic solidification body.Suitable for deep geological disposal environment, secondary actinium series high-level waste firming body
Chemical stability evaluation under the effect of " thermal field, water flow field, the field of force, chemical fields " various factors coupling.
Background technology
With the continuous increase of human society energy demand, the increasingly exhausted and greenhouse gas emission of conventional fossil fuel
Control requirement steps up, the selection that the mankind will must face follow-up alternative energy source.Nuclear energy is as a kind of safe and clean, warp
The energy of Ji is expected to substitute traditional fossil energy on a large scale, is the essential energy of human social.So
And Devoting Major Efforts To Developing and utilization with nuclear energy, generated high level radwaste（Abbreviation high-level waste）It is also more and more,
The type of high-level waste is more, and chemical composition is complicated, particularly containing it is toxic it is big, radioactivity is strong, long half time secondary Excitation Bands
Plain [neptunium（Np）, americium（Am）, curium（Cm）] high-level waste, greatly long-term potential danger is constituted to ecological environment and human health
Evil, safe disposal causes the highest attention of the today's society public, it has also become restrict nuclear industry sustainable development it is crucial because
One of element.
At present, the Nuclear waste disposal technology that countries in the world generally use is as follows：Glass is carried out to high-level waste first to consolidate
Glass solidified body or ceramic solidification body, are then fitted into dedicated waste tanks by change or ceramic solidification, and finally dedicated waste tanks are put into positioned at ground
In lower 500-1000 meters of deep geological disposal library, realize that high-level waste is isolated with the long-term, safe of biosphere.High-level waste
Usually no less than 10,000 years deep geological disposal library projected life, the firming body containing high-level waste is in initial centuries Storage period
The β decays of generation can make deep geological disposal library temperature be increased to hundreds of degree, underground moisture or influence on groundwater and come from addition
To the irradiation damage of firming body, the long-time stability of high-level waste firming body and safety will be chosen by sternness for internal various decays
War.Under the conditions of deep geological disposal, high-level waste firming body can be by thermal field（Thermal field）, water flow field
（Hydrodynamic field）, the field of force（Mechanical field）, chemical fields（Chemical field）Etc. multifactor coupling
The influence of cooperation, the stability particularly chemical stability of high-level waste firming body will be by baptism.Therefore, it studies
High-level waste firming body is at " thermal field, water flow field, the field of force, chemical fields "（Referred to as " heat, water, power, chemistry "）Change under coupling
Stability is learned, to evaluating long-time stability and safety of the high-level waste firming body in deep geological disposal environment with very heavy
The meaning wanted.
Fluor-apatite is one of most stable of mineral on the earth, is to find that 2,000,000,000 can be stabilized in nature so far
A kind of mineral in year have high geological stability, irradiation stability, mechanical stability, thermal stability and chemical stability,
Time requirement of the actinium series high-level waste to curing medium material can be met well.Fluor-apatite has very strong solid solution Excitation Bands
The ability of element, the actinium series nucleic of the natural usual association high concentration of fluor-apatite（Thorium, uranium, plutonium）And its radioactive fission product.Root
According to the isomorph principle on mineralogy, secondary actinium series nucleic has quite similar ionic radius with the calcium ion in fluor-apatite
And chemical property, fluor-apatite can be firmly secured at secondary actinium series nucleic as a part for crystal on its lattice-site position,
The fluorine phosphorus ash ceramic solidification body of acquisition has excellent long-time stability and safety.Therefore, fluor-apatite be curing height put it is useless
One of ideal ceramic solidification base material of object, the secondary Excitation Bands with very long half-lift being particularly suitable in safe cured high-level waste
Plain [neptunium（Np）, americium（Am）, curium（Cm）].In the prior art, scientific research personnel both domestic and external is only to fluor-apatite ceramic solidification body
The solid solution capacity of synthesis technology, actinium series nucleic in fluor-apatite ceramic solidification body etc. has carried out certain research.However, for mould
Intend deep geological disposal environment（100-200 DEG C of temperature, pressure 0.101-1.554MPa, pH value 5-9）, fluor-apatite ceramic solidification body
Chemical stability under the effect of " heat, water, power, chemistry " various factors coupling, is not reported both at home and abroad；It makes pottery for fluor-apatite
Chemical stability of the porcelain firming body in deep geological disposal environment still lacks experimental basis and suitable evaluation method at present.
Invention content
The purpose of the present invention is intended to overcome deficiency of the prior art, provides a kind of chemistry of fluor-apatite ceramic solidification body
Method for estimating stability is especially to provide a kind of simulation depth geological disposal environment of high-level waste firming body, studies fluor-apatite
The chemical stability of ceramic solidification body fluor-apatite ceramic solidification body under the effect of " heat, water, power, chemistry " various factors coupling, is commented
The method of long-time stability and safety of the valency fluor-apatite ceramic solidification body in deep geological disposal environment.Due to consideration that examination
The safety tested, the present invention use nontoxic, "dead" lanthanide series [samarium（Sm）, europium（Eu）, gadolinium（Gd）] respectively simulation have
Malicious, hot, ionic radius and the most similar secondary actinium series nucleic [neptunium of chemical property（Np）, americium（Am）, curium（Cm）].
Present disclosure is：A kind of chemical stability evaluation method of fluor-apatite ceramic solidification body, it is characterized in that by
Following steps are completed：
A, it prepares（Simulation time actinium series nucleic）Fluor-apatite ceramic solidification body：
With Ca2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-3a/2MA a (PO4)6F2
It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤a≤3；
According to the mass percent of dispensing 35~65%, abrading-ball 15~55%, absolute ethyl alcohol or/and water 5~50%, it is mixed in
It is ground 2~5 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
Expect the polyvinyl alcohol colloidal sol of quality 3~10%, then mixing granulation carried out using sieve, take the minus mesh of 12~25 mesh with 170~
The oversize of 270 mesh is granulation material；Granulation material is fitted into steel die, in hydraulic press（Equipment can be that Tianjin section device is high
The 769YP-24B type hydraulic machines of New Tech S. R. L.'s production）It is upper to be pressed using the pressure of 8~35MPa, then cold etc.
Static pressure machine（Equipment can be that the LDJ100/320-300 types of Sichuan Aviation Industry Chuanxi Machine Co., Ltd.'s production are cold etc. quiet
Press）The upper pressure using 80~260MPa carries out cold isostatic compaction, obtains molding blank；It is right at a temperature of 400~600 DEG C
Molding blank is heat-treated 5~10 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace（Equipment can be
The ZT-45-20Y30T type vacuum sintering funaces of Shanghai Guan Sheng vacuum equipments Co., Ltd production）In, temperature 1000~
1200 DEG C, 15~35MPa of pressure, vacuum heating-press sintering is carried out under conditions of 1~10Pa of vacuum degree 2~12 hours, obtain（Mould
Intend time actinium series nucleic）Fluor-apatite ceramic solidification body；
B, container is leached in cleaning：
Enclosure material is used as stainless steel, the hydrothermal reaction kettle that liner material is polytetrafluoroethylene (PTFE)（Equipment can be Shanghai
The YH-200 type hydrothermal reaction kettles of more experimental instruments and equipment limited productions）As container is leached, by the liner of hydrothermal reaction kettle
It is impregnated 2~3 hours in the aqueous solution of nitric acid for being 0.1~3mol/L in molar concentration, rinses liner 2 times with deionized water, then
It is impregnated 2~3 hours in the sodium hydrate aqueous solution for being 5~30% in mass percent concentration, liner is rinsed 2 times with deionized water；
It is impregnated 2~3 hours in the ethanol water for being 90~99% in mass percent concentration again, liner is rinsed 2 times with deionized water,
It impregnates 3~6 hours in 90 DEG C of deionized waters, then is boiled 1~2 hour with deionized water, finally rinse liner with deionized water,
Until the difference of the pH value of flushing liquor is less than or equal to 0.5 pH unit twice in succession；Leaching container drying after cleaning is standby
With；
C, leaching agent is prepared：
The deionized water that conductivity is taken to be less than or equal to 150 μ S/m, the pH value for adjusting deionized water are 5~9（It may be used
Acetic acid adjust deionized water pH value for less than 7 and more than or equal to 5 or use ammonium hydroxide adjusting deionized water pH value for more than
7 and less than or equal to 9）, leaching agent is made；
D, leaching test and test：
It will（Simulation time actinium series nucleic）Fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, is consolidated according to fluor-apatite ceramics
Change surface area/leaching agent volume=10m of body-1Pour into leaching agent, control extraction temperature is 100~200 DEG C, pressure be 0.101~
1.554MPa leachate（Liquid i.e. in hydrothermal reaction kettle）PH value 5~9, extraction time 1 day, 3 days, 7 days, 10 days, 14
My god, 21 days, 28 days, 35 days, after 42 days, the conductivity of leachate is tested respectively using conductivity meter, then using inductive coupling
Plasma mass（Abbreviation ICP-MS）, inductively coupled plasma optical emission spectra（Abbreviation ICP-OES）And Atomic absorption
Spectrum（Abbreviation AAS）（Wait analysis means）Sm in leachate is tested respectively3+、Eu3+Or Gd3+Ion concentration；
E, it evaluates（Simulation time actinium series nucleic）The chemical stability of fluor-apatite ceramic solidification body：
With Sm in leachate3+、Eu3+Or Gd3+Ion concentration calculate the normalization leaching rate of samarium, europium or gadolinium element, normalizing
The calculation formula for changing leaching rate is as follows：LR=c·V/f·A·t, in formula：LRNormalization leaching rate for samarium, europium or gadolinium element
（Unit gm-2·d-1）,cFor Sm in leachate3+、Eu3+Or Gd3+Ion concentration（Unit g/m3）,VFor leachate volume（It is single
Position m3）,fMass percentage content for samarium, europium or gadolinium element in fluor-apatite ceramic solidification body（Unit wt.%）,AFor fluorine phosphorus
The surface area of lime stone ceramic solidification body（Unit m2）,tFor extraction time（Unit d）；Using X-ray diffraction（Abbreviation XRD）, the back of the body dissipate
Penetrate secondary electron image（Abbreviation BSE）, scanning electron microscope-X-ray energy spectrum（Abbreviation SEM-EDX）Analysis（Simulation time actinium series nucleic）Fluorine phosphorus
Object phase change before and after lime stone ceramic solidification body leaching test, with reference to the leachate conductivity variations before and after leaching test and leaching
The normalization leaching rate variation of samarium, europium or gadolinium element, overall merit in liquid（Simulation time actinium series nucleic）Fluor-apatite ceramic solidification
Chemical stability of the body under " heat, water, power, chemistry " coupling.
In present disclosure：The preparation method of polyvinyl alcohol colloidal sol described in step a is：By polyvinyl alcohol 8~16%,
The percent mass ratio of glycerine 5~10%, absolute ethyl alcohol 2~5% and deionized water 77~85% takes each raw material；By deionized water
It pours into container, is heated to 90~95 DEG C, then under stiring, add in polyvinyl alcohol, after treating polyvinyl alcohol dissolving, add in sweet
Oil is stirred 10~adds absolute ethyl alcohol after twenty minutes, finally stirs 2~5 hours, that is, make at a temperature of 90~95 DEG C
Obtain polyvinyl alcohol colloidal sol.
The polyvinyl alcohol is the polyvinyl alcohol that the degree of polymerization is 1750~2700；Polyvinyl alcohol molecule amount ranging from 77000
~118800, the concrete model of polyvinyl alcohol can be polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 2499 and poly- second
Enol 2699；The manufacturing enterprise of polyvinyl alcohol has：Sinopharm Chemical Reagent Co., Ltd., the brilliant pure biochemical technology share in Shanghai have
Limit company, Sigma-Aldrich（Shanghai）Trade Co., Ltd etc..
In present disclosure：Polytetrafluoroethylene (PTFE) described in step b is the polytetrafluoroethyl-ne that the degree of polymerization is 5000~10000
Alkene；Polytetrafluoroethylene (PTFE) molecular weight ranges are 500000~1000000, and the concrete model of polyvinyl alcohol can be polytetrafluoroethylene (PTFE)
5000th, polytetrafluoroethylene (PTFE) 7500, polytetrafluoroethylene (PTFE) 10000；The manufacturing enterprise of polytetrafluoroethylene (PTFE) has：Shandong Eastern Mountain high molecular material
Co., Ltd, 3M China Co., Ltd., Sinopharm Chemical Reagent Co., Ltd., Sigma-Aldrich（Shanghai）Trade is limited
Company etc..
In present disclosure：Acetic acid described in step c could alternatively be any one of oxalic acid, sulfuric acid, hydrochloric acid.
In present disclosure：With Ca described in step a2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For raw material,
According to chemical formula Ca10-3a/2MA a (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤a
≤3；It replaces with：With Ca2P2O7, CaF2, Na2CO3And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10- 2b MA b Na b (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤b≤3。
In present disclosure：With Ca described in step a2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For raw material,
According to chemical formula Ca10-3a/2MA a (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤a
≤3；It replaces with：With Ca2P2O7, CaF2, SiO2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-c MA c
(PO4)6-c (SiO4) c F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤c≤4。
In present disclosure：With Ca described in step a2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For raw material,
According to chemical formula Ca10-3a/2MA a (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤a
≤3；It replaces with：With Ca2P2O7, CaF2, Na2CO3, SiO2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula
Ca10-3d MA2d Na d (PO4)6-d (SiO4) d F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤d
≤2。
Compared with prior art, the present invention has following features and advantageous effect：
（1）Invention emulates the deep geological disposal lab environments of high-level waste firming body, use hydrothermal reaction kettle（Outer shell material
Matter is stainless steel, and liner material is polytetrafluoroethylene (PTFE)）As container is leached, select deionized water as leaching agent, using acetic acid,
The pH value of the acid-base accommodations leaching agent such as oxalic acid, sulfuric acid, hydrochloric acid, ammonium hydroxide controls leaching test temperature using baking oven；The leaching of the present invention
Go out test parameters to choose rationally, including 100~200 DEG C of temperature, 0.101~1.554MPa of pressure, pH value 5~9, more than parameter is all
It is to be chosen according to practical deep geological disposal lab environment parameter；Therefore, the present invention more can truly evaluate height and put
Chemical stability of the solidification of waste body in deep geological disposal lab environment；
（2）Using the present invention, in closed hydrothermal reaction kettle, the temperature of leachate can be with the pressure of leachate（Pressure
By force）And synchronize and increase or reduce, it overcomes and only considers in single factor test in the prior art（Temperature or pressure）The lower evaluation height of effect is put
The deficiency of solidification of waste body chemical stability；Fluor-apatite ceramic solidification body is studied under " heat, water, power, chemistry " coupling
Leaching performance, can systematically evaluate water of the fluor-apatite ceramic solidification body in different temperatures, different pressures and different pH value
Chemical stability in solution；
（3）Using the present invention, the acid-base pairs depth geological disposal such as deionized water, acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, ammonium hydroxide is used
" water flow field " and " chemical fields " in environment is simulated, and method is easy, and low-cost, technique effect is good；It is anti-using hydro-thermal
Kettle and baking oven is answered to simulate " thermal field " and " field of force " in deep geological disposal environment, equipment is simple, of low cost, operation letter
Easy row；Therefore, the present invention can realize well makees " heat, water, power, chemistry " various factors coupling in deep geological disposal environment
Simulation；
（4）The present invention provides a kind of effective quantitative evaluation fluor-apatite ceramic solidification body in deep geological disposal environment
The method of chemical stability under middle various factors coupling effect, equipment is simple, of low cost, strong operability, and evaluation procedure is simple
Clearly, evaluation index is rationally intuitive, and accurately and reliably, evaluation method is advantageously implemented the peace of high-level waste firming body to evaluation result
Full disposition can be that long-time stability and safety of the effective evaluation fluor-apatite ceramic solidification body in deep geological disposal environment carry
For experimental basis and technical support, established for protection human health, ecological environment and propulsion nuclear industry sustainable development solid
Basis；
（5）The method of the present invention is simple, easy to operate, highly practical.
Specific embodiment
The invention will be further described, but is not to be construed as to the scope of the present invention for example given below plan
Limitation, some nonessential improvement and tune that person skilled in art makes the present invention according to the content of the invention described above
It is whole, still fall within protection scope of the present invention.
Embodiment 1：
With Ca2P2O7、CaF2、Sm2O3For raw material, according to chemical formula Ca9.85Sm0.1(PO4)6F2Weigh the progress of each component raw material
Dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in planetary ball mill
Grinding 2 hours, the mixture drying of acquisition, you can the powder dried adds in the polyethylene of the powder quality 3% of drying
Alcosol, then mixing granulation, the minus mesh of 12 mesh and the oversize granulation material as obtained of 170 mesh are carried out using sieve；It will
Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, then on cold isostatic press
Cold isostatic compaction is carried out using the pressure of 80MPa, obtains molding blank；It is small to molding blank heat treatment 5 at a temperature of 400 DEG C
Shi Jinhang dumpings, then the green body after dumping is put into vacuum sintering funace, in 1000 DEG C of temperature, pressure 15MPa, vacuum degree
Vacuum heating-press sintering is carried out under conditions of 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；It adopts
By the use of enclosure material be stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach hold
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L is impregnated 2 hours, is rushed with deionized water by device
It washes liner 2 times, impregnates 2 hours in the sodium hydrate aqueous solution for being then 5% in mass percent concentration, rinsed with deionized water
Liner 2 times；It is impregnated 2 hours in the ethanol water for being 90% in mass percent concentration again, liner is rinsed 2 times with deionized water,
It impregnates 3 hours in 90 DEG C of deionized waters, then is boiled 1 hour with deionized water, finally rinse liner with deionized water, until even
The difference of the continuous pH value of flushing liquor twice is 0.1 pH unit；Leaching container after cleaning is dried for standby；It is 5 μ to take conductivity
The deionized water of S/m uses acetic acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation time actinium series nucleic fluorine phosphorus ash
Ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1It pours into
Leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value 5, in the leaching test time 1
My god, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, after 42 days, using conductivity meter test leachate conductivity, so
Hand is analyzed using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum etc. afterwards
Ca in section test leachate2+、Sm3+Ion concentration；With Ca in leachate2+、Sm3+Ion concentration calculate Ca2+、Sm3+Return
One changes leaching rate, and the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization for element is soaked
Extracting rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluor-apatite ceramics
The mass fraction of element in firming body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tDuring for leaching test
Between（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series nucleic fluorine phosphorus
Object phase change before and after lime stone ceramic solidification body leaching test, with reference to the leachate conductivity variations before and after leaching test and leaching
Ca in liquid2+、Sm3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body " heat,
Chemical stability under water, power, chemistry " coupling.
Embodiment 2：
With Ca2P2O7、CaF2、Sm2O3For raw material, according to chemical formula Ca7.75Sm1.5(PO4)6F2Weigh the progress of each component raw material
Dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent, is mixed in planetary ball mill
Grinding 3 hours, the mixture drying of acquisition, you can the powder dried adds in the polyethylene of the powder quality 6% of drying
Alcosol, then mixing granulation, the minus mesh of 18 mesh and the oversize granulation material as obtained of 220 mesh are carried out using sieve；It will
Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then on cold isostatic press
Cold isostatic compaction is carried out using the pressure of 170MPa, obtains molding blank；To molding blank heat treatment 7 at a temperature of 500 DEG C
Hour carries out dumping, then the green body after dumping is put into vacuum sintering funace, in 1100 DEG C of temperature, pressure 25MPa, vacuum
Vacuum heating-press sintering is carried out under conditions of degree 5Pa 7 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；
Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach hold
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 2mol/L is impregnated 3 hours, is rinsed with deionized water by device
Liner 2 times is impregnated 3 hours in the sodium hydrate aqueous solution for being then 17% in mass percent concentration, rinsed with deionized water in
Lining 2 times；It is impregnated 3 hours in the ethanol water for being 95% in mass percent concentration again, liner is rinsed 2 times with deionized water,
90 DEG C of deionized water is impregnated 4 hours, then is boiled 2 hours with deionized water, finally rinses liner with deionized water, until continuous
The difference of the pH value of flushing liquor is 0.3 pH unit twice；Leaching container after cleaning is dried for standby；It is 50 μ to take conductivity
The deionized water of S/m, the pH value of deionized water is 7, and leaching agent is made；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put
Enter in hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1Leaching agent is poured into, is controlled
150 DEG C of leaching test temperature, leaching test pressure 0.828MPa, leaching agent pH value is 7, in 1 day leaching test time, 3 days, 7
My god, 10 days, 14 days, 21 days, 28 days, 35 days, after 42 days, using conductivity meter test leachate conductivity, then using electricity
Feel the test leaching of the analysis means such as coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum
Go out Ca in liquid2+、Sm3+Ion concentration；With Ca in leachate2+、Sm3+Ion concentration calculate Ca2+、Sm3+Normalization leach
Rate, the calculation formula for normalizing leaching rate are as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·
m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor in fluor-apatite ceramic solidification body
The mass fraction of element（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor the leaching test time（d）；It adopts
With X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series nucleic fluor-apatite ceramics
Object phase change before and after firming body leaching test, with reference to Ca in the leachate conductivity variations before and after leaching test and leachate2+、
Sm3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body is in " heat, water, power, change
Chemical stability under " coupling.
Embodiment 3：
With Ca2P2O7、CaF2、Sm2O3For raw material, according to chemical formula Ca5.5Sm3(PO4)6F2Each component raw material is weighed to be matched
Material, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent, is mixed in planetary ball mill and grinds
Mill 5 hours, the mixture drying of acquisition, you can the powder dried adds in the polyvinyl alcohol of the powder quality 10% of drying
Colloidal sol, then mixing granulation, the minus mesh of 25 mesh and the oversize granulation material as obtained of 270 mesh are carried out using sieve；It will make
Pellet is fitted into steel die, is pressed using the pressure of 35MPa, is then adopted on cold isostatic press on a hydraulic press
Cold isostatic compaction is carried out with the pressure of 260MPa, obtains molding blank；It is small to molding blank heat treatment 10 at a temperature of 600 DEG C
Shi Jinhang dumpings, then the green body after dumping is put into vacuum sintering funace, in 1200 DEG C of temperature, pressure 35MPa, vacuum degree
Vacuum heating-press sintering is carried out under conditions of 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；
Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L is impregnated 3 hours, is rushed with deionized water by container
It washes liner 2 times, impregnates 3 hours in the sodium hydrate aqueous solution for being then 30% in mass percent concentration, rinsed with deionized water
Liner 2 times；It is impregnated 3 hours in the ethanol water for being 99% in mass percent concentration again, liner is rinsed 2 times with deionized water,
It impregnates 6 hours in 90 DEG C of deionized waters, then is boiled 2 hours with deionized water, finally rinse liner with deionized water, until even
The difference of the continuous pH value of flushing liquor twice is 0.5 pH unit；Leaching container after cleaning is dried for standby；The conductivity is taken to be
The deionized water of 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time actinium series nucleic fluorine
Phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1
Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9, in leaching test
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days time, using the conductance of conductivity meter test leachate
Rate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum etc.
Ca in analysis means test leachate2+、Sm3+Ion concentration；With Ca in leachate2+、Sm3+Ion concentration calculate Ca2+、Sm3 +Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor returning for element
One changes leaching rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluorine phosphorus ash
The mass fraction of element in feldspar firming body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tTo leach
Test period（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time Excitation Bands
Object phase change before and after plain fluor-apatite ceramic solidification body leaching test, with reference to the leachate conductivity variations before and after leaching test
With Ca in leachate2+、Sm3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body
Chemical stability under " heat, water, power, chemistry " coupling.
Embodiment 4：
With Ca2P2O7、CaF2、Sm2O3、Na2CO3For raw material, according to chemical formula Ca9.8Sm0.1Na0.1(PO4)6F2Weigh each group
Raw material is divided to carry out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in planet
It is ground 2 hours in formula ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality of drying
3% polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the minus mesh of 12 mesh and the oversize of 170 mesh are as obtained
Granulation material；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 80MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 400 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 5 hours, in 1000 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite pottery is made
Porcelain firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle
As container is leached, the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L is impregnated 2 hours, is used
Deionized water rinses liner 2 times, impregnates 2 hours, spends in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 2 hours in the ethanol water for being 90% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 3 hours in 90 DEG C of deionized waters, then boiled 1 hour with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 5 μ S/m uses oxalic acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation time actinium
It is that nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent of fluor-apatite ceramic solidification body
Volume=10m-1Pour into leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value 5,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and leached using conductivity meter
Then the conductivity of liquid is inhaled using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Receive Ca in the analysis means such as spectrum test leachate2+、Sm3+、Na+Ion concentration；With Ca in leachate2+、Sm3+、Na+From
Sub- concentration calculates Ca2+、Sm3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VTo leach
Liquid accumulates（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramic solidification body
Surface area（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X ray
Object phase change before and after energy spectrum analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, before leaching test
Ca in rear leachate conductivity variations and leachate2+、Sm3+、Na+The variation of normalization leaching rate, overall merit simulation time actinium
It is chemical stability of the nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 5：
With Ca2P2O7、CaF2、Sm2O3、Na2CO3For raw material, according to chemical formula Ca7Sm1.5Na1.5(PO4)6F2Weigh each component
Raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent is mixed in planetary
It is ground 3 hours in ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality 6% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the oversizes of the minus mesh of 18 mesh and 220 mesh be made from make
Pellet；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 170MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 500 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 7 hours, in 1100 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium series nucleic fluor-apatite pottery is made
Porcelain firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle
As container is leached, the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 2mol/L is impregnated 3 hours, is spent
Ionized water rinses liner 2 times, is impregnated 3 hours in the sodium hydrate aqueous solution for being then 17% in mass percent concentration, spend from
Sub- water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 95% in mass percent concentration again, is rinsed with deionized water
Liner 2 times impregnates 4 hours in 90 DEG C of deionized waters, then boils 2 hours with deionized water, finally rinsed with deionized water in
Lining, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；Leaching container after cleaning is dried for standby；It takes
Conductivity is the deionized water of 50 μ S/m, and the pH value of deionized water is 7, and leaching agent is made；It will simulation time actinium series nucleic fluorine phosphorus ash
Ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1It pours into
Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature, leaching agent pH value is 7, in leaching test
Between after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days, using conductivity meter test leachate conductivity,
Then using analyses such as inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrums
Ca in means test leachate2+、Sm3+、Na+Ion concentration；With Ca in leachate2+、Sm3+、Na+Ion concentration calculate Ca2 +、Sm3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor
The normalization leaching rate of element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,f
Mass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation
Object phase change before and after secondary actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leachate electricity before and after leaching test
Conductance changes and Ca in leachate2+、Sm3+、Na+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus ash
Chemical stability of the feldspar firming body under " heat, water, power, chemistry " coupling.
Embodiment 6：
With Ca2P2O7、CaF2、Sm2O3、Na2CO3For raw material, according to chemical formula Ca7Sm3Na3(PO4)6F2Weigh each component original
Material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent is mixed in planetary ball
It is ground 5 hours in grinding machine, the mixture drying of acquisition, you can the powder dried adds in the powder quality 10% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation, the minus mesh of 25 mesh and the oversize granulation as obtained of 270 mesh are carried out using sieve
Material；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa, then cold etc. quiet
Cold isostatic compaction is carried out using the pressure of 260MPa on press, obtains molding blank；To molding blank heat at a temperature of 600 DEG C
Processing carries out dumping, then the green body after dumping is put into vacuum sintering funace in 10 hours, in 1200 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 35MPa, vacuum degree 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 3 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L, uses
Deionized water rinses liner 2 times, impregnates 3 hours, spends in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 99% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and soaked using conductivity meter
Go out the conductivity of liquid, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Ca in the analysis means such as absorption spectrum test leachate2+、Sm3+、Na+Ion concentration；With Ca in leachate2+、Sm3+、Na+'s
Ion concentration calculates Ca2+、Sm3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leaching
Go out liquid product（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramic solidification
The surface area of body（m2）,tFor the leaching test time（d）；It is penetrated using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X
Object phase change before and after line energy spectrum analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to leaching test
Ca in front and rear leachate conductivity variations and leachate2+、Sm3+、Na+Normalization leaching rate variation, overall merit simulation time
Chemical stability of the actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 7：
With Ca2P2O7、CaF2、Sm2O3、SiO2For raw material, according to chemical formula Ca9.9Sm0.1(PO4)5.9(SiO4)0.1F2It weighs
Each component raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in
It is ground 2 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
The polyvinyl alcohol colloidal sol of quality 3%, then mixing granulation is carried out using sieve, the minus mesh of 12 mesh and the oversize of 170 mesh are as made
The granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, Ran Hou
Cold isostatic compaction is carried out using the pressure of 80MPa on cold isostatic press, obtains molding blank；To molding at a temperature of 400 DEG C
Green body is heat-treated 5 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in 1000 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of power 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 2 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L,
Liner is rinsed with deionized water 2 times, is impregnated 2 hours, is used in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
Deionized water rinses liner 2 times；It is impregnated 2 hours in the ethanol water for being 90% in mass percent concentration again, uses deionized water
It rinses liner 2 times, impregnates 3 hours in 90 DEG C of deionized waters, then boiled 1 hour with deionized water, finally rushed with deionized water
Liner is washed, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；Leaching container drying after cleaning is standby
With；The deionized water that conductivity is taken to be 5 μ S/m uses hydrochloric acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation
Secondary actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Go out agent volume=10m-1Pour into leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value
5, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested using conductivity meter
The conductivity of leachate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and original
Ca in the analysis means such as sub- absorption spectrum test leachate2+、Sm3+Ion concentration；With Ca in leachate2+、Sm3+Ion it is dense
Degree calculates Ca2+、Sm3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume
（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface for fluor-apatite ceramic solidification body
Product（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X-ray energy spectrum point
Object phase change before and after analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leaching before and after leaching test
Go out Ca in liquid conductivity variations and leachate2+、Sm3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus
Chemical stability of the lime stone ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 8：
With Ca2P2O7、CaF2、Sm2O3、SiO2For raw material, according to chemical formula Ca8.5Sm1.5(PO4)4.5(SiO4)1.5F2It weighs
Each component raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent, is mixed in
It is ground 3 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
The polyvinyl alcohol colloidal sol of quality 6%, then mixing granulation is carried out using sieve, the minus mesh of 18 mesh and the oversize of 220 mesh are as made
The granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then
Cold isostatic compaction is carried out using the pressure of 170MPa on cold isostatic press, obtains molding blank；At a temperature of 500 DEG C into
Parison body heat handles 7 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, 1100 DEG C of temperature,
Vacuum heating-press sintering is carried out under conditions of pressure 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium series nucleic fluorine phosphorus ash is made
Feldspar firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydro-thermal it is anti-
Kettle is answered to impregnate the liner of hydrothermal reaction kettle 3 hours in aqueous solution of nitric acid of the molar concentration for 2mol/L as container is leached,
Liner is rinsed with deionized water 2 times, is impregnated 3 hours, is used in the sodium hydrate aqueous solution for being then 17% in mass percent concentration
Deionized water rinses liner 2 times；It is impregnated 3 hours in the ethanol water for being 95% in mass percent concentration again, uses deionized water
It rinses liner 2 times, impregnates 4 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rushed with deionized water
Liner is washed, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；Leaching container drying after cleaning is standby
With；The deionized water that conductivity is 50 μ S/m is taken, the pH value of deionized water is 7, and leaching agent is made；It will simulation time actinium series nucleic fluorine
Phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1
Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature are poured into, leaching agent pH value is 7, is tried leaching
After testing 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days time, using the electricity of conductivity meter test leachate
Conductance, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum
Wait Ca in analysis means test leachate2+、Sm3+Ion concentration；With Ca in leachate2+、Sm3+Ion concentration calculate Ca2+、
Sm3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor element
Normalize leaching rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluorine phosphorus
The mass fraction of element in lime stone ceramic solidification body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor leaching
Go out test period（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series
Object phase change before and after nucleic fluor-apatite ceramic solidification body leaching test becomes with reference to the leachate conductivity before and after leaching test
Change and Ca in leachate2+、Sm3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification
Chemical stability of the body under " heat, water, power, chemistry " coupling.
Embodiment 9：
With Ca2P2O7、CaF2、Sm2O3、SiO2For raw material, according to chemical formula Ca7Sm3(PO4)3(SiO4)3F2Weigh each component
Raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent is mixed in planetary
It is ground 5 hours in ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality 10% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the oversizes of the minus mesh of 25 mesh and 270 mesh be made from make
Pellet；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 260MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 600 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 10 hours, in 1200 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 35MPa, vacuum degree 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 3 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L, uses
Deionized water rinses liner 2 times, impregnates 3 hours, spends in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 99% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and soaked using conductivity meter
Go out the conductivity of liquid, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Ca in the analysis means such as absorption spectrum test leachate2+、Sm3+Ion concentration；With Ca in leachate2+、Sm3+Ion concentration
Calculate Ca2+、Sm3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LR
Normalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume
（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface for fluor-apatite ceramic solidification body
Product（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X-ray energy spectrum point
Object phase change before and after analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leaching before and after leaching test
Go out Ca in liquid conductivity variations and leachate2+、Sm3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus
Chemical stability of the lime stone ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 10：
With Ca2P2O7、CaF2、Sm2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca9.7Sm0.2Na0.1(PO4)5.9
(SiO4)0.1F2It weighs each component raw material and carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 quality
Percentage is mixed in planetary ball mill and grinds 2 hours, the mixture drying of acquisition, you can the powder dried adds
Enter the polyvinyl alcohol colloidal sol of the powder quality 3% of drying, then mixing granulation, the minus mesh of 12 mesh and 170 purposes are carried out using sieve
Oversize is granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa
Type is made, cold isostatic compaction is then carried out using the pressure of 80MPa on cold isostatic press, obtains molding blank；At 400 DEG C
At a temperature of molding blank is heat-treated 5 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in temperature
Vacuum heating-press sintering is carried out under conditions of 1000 DEG C of degree, pressure 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series is made
Nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoroethyl-ne that stainless steel, liner material are that the degree of polymerization is 5000
The hydrothermal reaction kettle of alkene is as container is leached, by the liner of hydrothermal reaction kettle in the aqueous solution of nitric acid that molar concentration is 0.1mol/L
It is middle to impregnate 2 hours, liner is rinsed 2 times with deionized water, in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
It impregnates 2 hours, liner is rinsed 2 times with deionized water；It is small that 2 are impregnated in the ethanol water for being 90% in mass percent concentration again
When, liner 2 times is rinsed with deionized water, is impregnated 3 hours in 90 DEG C of deionized waters, then 1 hour is boiled with deionized water, finally
Liner is rinsed with deionized water, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；By the leaching after cleaning
Container is dried for standby；The deionized water that conductivity is taken to be 5 μ S/m uses the pH value that sulfuric acid adjusts deionized water that leaching is made for 5
Agent；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to fluor-apatite ceramic solidification body
Surface area/leaching agent volume=10m-1Leaching agent is poured into, controls 100 DEG C, leaching test pressure 0.101MPa of leaching test temperature,
Leaching agent pH value 5, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, using electricity
Electrical conductivity instrument tests the conductivity of leachate, is then sent out using inductivity coupled plasma mass spectrometry, inductively coupled plasma optics
Penetrate Ca in the analysis means such as spectrum and atomic absorption spectrum test leachate2+、Sm3+、Na+Ion concentration；With Ca in leachate2 +、Sm3+、Na+Ion concentration calculate Ca2+、Sm3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate
（g/m3）,VFor leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluorine phosphorus ash
The surface area of feldspar firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, sweep
Retouch the object phase change before and after Electronic Speculum-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, knot
Ca in leachate conductivity variations and leachate before and after conjunction leaching test2+、Sm3+、Na+The variation of normalization leaching rate, it is comprehensive
Chemical stability of the Simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 11：
With Ca2P2O7、CaF2、Sm2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca5.5Sm3Na1.5(PO4)4.5
(SiO4)1.5F2It weighs each component raw material and carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 quality
Percentage is mixed in planetary ball mill and grinds 3 hours, the mixture drying of acquisition, you can the powder dried adds
Enter the polyvinyl alcohol colloidal sol of the powder quality 6% of drying, then mixing granulation, the minus mesh of 18 mesh and 220 purposes are carried out using sieve
Oversize is granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa
Type is made, cold isostatic compaction is then carried out using the pressure of 170MPa on cold isostatic press, obtains molding blank；500
Molding blank is heat-treated 7 hours at a temperature of DEG C and carries out dumping, then the green body after dumping is put into vacuum sintering funace,
Vacuum heating-press sintering is carried out under conditions of 1100 DEG C of temperature, pressure 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium is made
It is nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoro that stainless steel, liner material are that the degree of polymerization is 7500
The hydrothermal reaction kettle of ethylene is as container is leached, by the liner of hydrothermal reaction kettle in the aqueous solution of nitric acid that molar concentration is 2mol/L
It is middle to impregnate 3 hours, liner is rinsed 2 times with deionized water, in the sodium hydrate aqueous solution for being then 17% in mass percent concentration
It impregnates 3 hours, liner is rinsed 2 times with deionized water；It is small that 3 are impregnated in the ethanol water for being 95% in mass percent concentration again
When, liner 2 times is rinsed with deionized water, is impregnated 4 hours in 90 DEG C of deionized waters, then 2 hours are boiled with deionized water, finally
Liner is rinsed with deionized water, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；By the leaching after cleaning
Container is dried for standby；The deionized water that conductivity is 50 μ S/m is taken, the pH value of deionized water is 7, and leaching agent is made；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature are poured into, leaching agent pH value is
7, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested using conductivity meter
The conductivity of leachate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and original
Ca in the analysis means such as sub- absorption spectrum test leachate2+、Sm3+、Na+Ion concentration；With Ca in leachate2+、Sm3+、Na+
Ion concentration calculate Ca2+、Sm3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,V
For leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramics
The surface area of firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electricity
Object phase change before and after mirror-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to leaching
Go out Ca in the front and rear leachate conductivity variations of experiment and leachate2+、Sm3+、Na+Normalization leaching rate variation, overall merit
Chemical stability of the simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 12：
With Ca2P2O7、CaF2、Sm2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca1Sm6Na3(PO4)3(SiO4)3F2Claim
Each component raw material is taken to carry out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent, mixing
It is ground 5 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
Expect the polyvinyl alcohol colloidal sol of quality 10%, then mixing granulation is carried out using sieve, the minus mesh of 25 mesh and the oversize of 270 mesh are
For granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa,
Then cold isostatic compaction is carried out using the pressure of 260MPa on cold isostatic press, obtains molding blank；At a temperature of 600 DEG C
Molding blank is heat-treated 10 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in temperature
1200 DEG C, pressure 35MPa, vacuum heating-press sintering is carried out under conditions of vacuum degree 10Pa 12 hours, you can simulation time actinium series is made
Nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoroethyl-ne that stainless steel, liner material are that the degree of polymerization is 10000
The hydrothermal reaction kettle of alkene is as leaching container, in the aqueous solution of nitric acid for being 3mol/L in molar concentration by the liner of hydrothermal reaction kettle
It impregnates 3 hours, rinses liner 2 times with deionized water, soaked in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Bubble 3 hours rinses liner 2 times with deionized water；It is impregnated 3 hours in the ethanol water for being 99% in mass percent concentration again,
Liner is rinsed with deionized water 2 times, is impregnated 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, is finally used
Deionized water rinses liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching after cleaning is held
Device is dried for standby；The deionized water that conductivity is taken to be 150 μ S/m uses the pH value that ammonium hydroxide adjusts deionized water that leaching is made for 9
Agent；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to fluor-apatite ceramic solidification body
Surface area/leaching agent volume=10m-1Leaching agent is poured into, controls 200 DEG C, leaching test pressure 1.554MPa of leaching test temperature,
Leaching agent pH value 9, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, using electricity
Electrical conductivity instrument tests the conductivity of leachate, is then sent out using inductivity coupled plasma mass spectrometry, inductively coupled plasma optics
Penetrate Ca in the analysis means such as spectrum and atomic absorption spectrum test leachate2+、Sm3+、Na+Ion concentration；With Ca in leachate2 +、Sm3+、Na+Ion concentration calculate Ca2+、Sm3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate
（g/m3）,VFor leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluorine phosphorus ash
The surface area of feldspar firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, sweep
Retouch the object phase change before and after Electronic Speculum-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, knot
Ca in leachate conductivity variations and leachate before and after conjunction leaching test2+、Sm3+、Na+The variation of normalization leaching rate, it is comprehensive
Chemical stability of the Simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 13：
With Ca2P2O7、CaF2、Eu2O3For raw material, according to chemical formula Ca9.85Eu0.1(PO4)6F2Weigh the progress of each component raw material
Dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in planetary ball mill
Grinding 2 hours, the mixture drying of acquisition, you can the powder dried adds in the polyethylene of the powder quality 3% of drying
Alcosol, then mixing granulation, the minus mesh of 12 mesh and the oversize granulation material as obtained of 170 mesh are carried out using sieve；It will
Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, then on cold isostatic press
Cold isostatic compaction is carried out using the pressure of 80MPa, obtains molding blank；It is small to molding blank heat treatment 5 at a temperature of 400 DEG C
Shi Jinhang dumpings, then the green body after dumping is put into vacuum sintering funace, in 1000 DEG C of temperature, pressure 15MPa, vacuum degree
Vacuum heating-press sintering is carried out under conditions of 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；It adopts
By the use of enclosure material be stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach hold
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L is impregnated 2 hours, is rushed with deionized water by device
It washes liner 2 times, impregnates 2 hours in the sodium hydrate aqueous solution for being then 5% in mass percent concentration, rinsed with deionized water
Liner 2 times；It is impregnated 2 hours in the ethanol water for being 90% in mass percent concentration again, liner is rinsed 2 times with deionized water,
It impregnates 3 hours in 90 DEG C of deionized waters, then is boiled 1 hour with deionized water, finally rinse liner with deionized water, until even
The difference of the continuous pH value of flushing liquor twice is 0.1 pH unit；Leaching container after cleaning is dried for standby；It is 5 μ to take conductivity
The deionized water of S/m uses acetic acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation time actinium series nucleic fluorine phosphorus ash
Ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1It pours into
Leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value 5, in the leaching test time 1
My god, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, after 42 days, using conductivity meter test leachate conductivity, so
Hand is analyzed using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum etc. afterwards
Ca in section test leachate2+、Eu3+Ion concentration；With Ca in leachate2+、Eu3+Ion concentration calculate Ca2+、Eu3+Return
One changes leaching rate, and the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization for element is soaked
Extracting rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluor-apatite ceramics
The mass fraction of element in firming body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tDuring for leaching test
Between（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series nucleic fluorine phosphorus
Object phase change before and after lime stone ceramic solidification body leaching test, with reference to the leachate conductivity variations before and after leaching test and leaching
Ca in liquid2+、Eu3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body " heat,
Chemical stability under water, power, chemistry " coupling.
Embodiment 14：
With Ca2P2O7、CaF2、Eu2O3For raw material, according to chemical formula Ca7.75Eu1.5(PO4)6F2Weigh the progress of each component raw material
Dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent, is mixed in planetary ball mill
Grinding 3 hours, the mixture drying of acquisition, you can the powder dried adds in the polyethylene of the powder quality 6% of drying
Alcosol, then mixing granulation, the minus mesh of 18 mesh and the oversize granulation material as obtained of 220 mesh are carried out using sieve；It will
Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then on cold isostatic press
Cold isostatic compaction is carried out using the pressure of 170MPa, obtains molding blank；To molding blank heat treatment 7 at a temperature of 500 DEG C
Hour carries out dumping, then the green body after dumping is put into vacuum sintering funace, in 1100 DEG C of temperature, pressure 25MPa, vacuum
Vacuum heating-press sintering is carried out under conditions of degree 5Pa 7 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；
Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach hold
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 2mol/L is impregnated 3 hours, is rinsed with deionized water by device
Liner 2 times is impregnated 3 hours in the sodium hydrate aqueous solution for being then 17% in mass percent concentration, rinsed with deionized water in
Lining 2 times；It is impregnated 3 hours in the ethanol water for being 95% in mass percent concentration again, liner is rinsed 2 times with deionized water,
90 DEG C of deionized water is impregnated 4 hours, then is boiled 2 hours with deionized water, finally rinses liner with deionized water, until continuous
The difference of the pH value of flushing liquor is 0.3 pH unit twice；Leaching container after cleaning is dried for standby；It is 50 μ to take conductivity
The deionized water of S/m, the pH value of deionized water is 7, and leaching agent is made；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put
Enter in hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1Leaching agent is poured into, is controlled
150 DEG C of leaching test temperature, leaching test pressure 0.828MPa, leaching agent pH value is 7, in 1 day leaching test time, 3 days, 7
My god, 10 days, 14 days, 21 days, 28 days, 35 days, after 42 days, using conductivity meter test leachate conductivity, then using electricity
Feel the test leaching of the analysis means such as coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum
Go out Ca in liquid2+、Eu3+Ion concentration；With Ca in leachate2+、Eu3+Ion concentration calculate Ca2+、Eu3+Normalization leach
Rate, the calculation formula for normalizing leaching rate are as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·
m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor in fluor-apatite ceramic solidification body
The mass fraction of element（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor the leaching test time（d）；It adopts
With X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series nucleic fluor-apatite ceramics
Object phase change before and after firming body leaching test, with reference to Ca in the leachate conductivity variations before and after leaching test and leachate2+、
Eu3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body is in " heat, water, power, change
Chemical stability under " coupling.
Embodiment 15：
With Ca2P2O7、CaF2、Eu2O3For raw material, according to chemical formula Ca5.5Eu3(PO4)6F2Each component raw material is weighed to be matched
Material, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent, is mixed in planetary ball mill and grinds
Mill 5 hours, the mixture drying of acquisition, you can the powder dried adds in the polyvinyl alcohol of the powder quality 10% of drying
Colloidal sol, then mixing granulation, the minus mesh of 25 mesh and the oversize granulation material as obtained of 270 mesh are carried out using sieve；It will make
Pellet is fitted into steel die, is pressed using the pressure of 35MPa, is then adopted on cold isostatic press on a hydraulic press
Cold isostatic compaction is carried out with the pressure of 260MPa, obtains molding blank；It is small to molding blank heat treatment 10 at a temperature of 600 DEG C
Shi Jinhang dumpings, then the green body after dumping is put into vacuum sintering funace, in 1200 DEG C of temperature, pressure 35MPa, vacuum degree
Vacuum heating-press sintering is carried out under conditions of 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；
Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L is impregnated 3 hours, is rushed with deionized water by container
It washes liner 2 times, impregnates 3 hours in the sodium hydrate aqueous solution for being then 30% in mass percent concentration, rinsed with deionized water
Liner 2 times；It is impregnated 3 hours in the ethanol water for being 99% in mass percent concentration again, liner is rinsed 2 times with deionized water,
It impregnates 6 hours in 90 DEG C of deionized waters, then is boiled 2 hours with deionized water, finally rinse liner with deionized water, until even
The difference of the continuous pH value of flushing liquor twice is 0.5 pH unit；Leaching container after cleaning is dried for standby；The conductivity is taken to be
The deionized water of 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time actinium series nucleic fluorine
Phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1
Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9, in leaching test
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days time, using the conductance of conductivity meter test leachate
Rate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum etc.
Ca in analysis means test leachate2+、Eu3+Ion concentration；With Ca in leachate2+、Eu3+Ion concentration calculate Ca2+、Eu3 +Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor returning for element
One changes leaching rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluorine phosphorus ash
The mass fraction of element in feldspar firming body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tTo leach
Test period（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time Excitation Bands
Object phase change before and after plain fluor-apatite ceramic solidification body leaching test, with reference to the leachate conductivity variations before and after leaching test
With Ca in leachate2+、Eu3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body
Chemical stability under " heat, water, power, chemistry " coupling.
Embodiment 16：
With Ca2P2O7、CaF2、Eu2O3、Na2CO3For raw material, according to chemical formula Ca9.8Eu0.1Na0.1(PO4)6F2Weigh each group
Raw material is divided to carry out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in planet
It is ground 2 hours in formula ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality of drying
3% polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the minus mesh of 12 mesh and the oversize of 170 mesh are as obtained
Granulation material；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 80MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 400 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 5 hours, in 1000 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite pottery is made
Porcelain firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle
As container is leached, the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L is impregnated 2 hours, is used
Deionized water rinses liner 2 times, impregnates 2 hours, spends in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 2 hours in the ethanol water for being 90% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 3 hours in 90 DEG C of deionized waters, then boiled 1 hour with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 5 μ S/m uses oxalic acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation time actinium
It is that nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent of fluor-apatite ceramic solidification body
Volume=10m-1Pour into leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value 5,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and leached using conductivity meter
Then the conductivity of liquid is inhaled using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Receive Ca in the analysis means such as spectrum test leachate2+、Eu3+、Na+Ion concentration；With Ca in leachate2+、Eu3+、Na+From
Sub- concentration calculates Ca2+、Eu3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VTo leach
Liquid accumulates（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramic solidification body
Surface area（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X ray
Object phase change before and after energy spectrum analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, before leaching test
Ca in rear leachate conductivity variations and leachate2+、Eu3+、Na+The variation of normalization leaching rate, overall merit simulation time actinium
It is chemical stability of the nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 17：
With Ca2P2O7、CaF2、Eu2O3、Na2CO3For raw material, according to chemical formula Ca7Eu1.5Na1.5(PO4)6F2Weigh each component
Raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent is mixed in planetary
It is ground 3 hours in ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality 6% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the oversizes of the minus mesh of 18 mesh and 220 mesh be made from make
Pellet；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 170MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 500 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 7 hours, in 1100 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium series nucleic fluor-apatite pottery is made
Porcelain firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle
As container is leached, the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 2mol/L is impregnated 3 hours, is spent
Ionized water rinses liner 2 times, is impregnated 3 hours in the sodium hydrate aqueous solution for being then 17% in mass percent concentration, spend from
Sub- water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 95% in mass percent concentration again, is rinsed with deionized water
Liner 2 times impregnates 4 hours in 90 DEG C of deionized waters, then boils 2 hours with deionized water, finally rinsed with deionized water in
Lining, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；Leaching container after cleaning is dried for standby；It takes
Conductivity is the deionized water of 50 μ S/m, and the pH value of deionized water is 7, and leaching agent is made；It will simulation time actinium series nucleic fluorine phosphorus ash
Ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1It pours into
Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature, leaching agent pH value is 7, in leaching test
Between after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days, using conductivity meter test leachate conductivity,
Then using analyses such as inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrums
Ca in means test leachate2+、Eu3+、Na+Ion concentration；With Ca in leachate2+、Eu3+、Na+Ion concentration calculate Ca2 +、Eu3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor
The normalization leaching rate of element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,f
Mass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation
Object phase change before and after secondary actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leachate electricity before and after leaching test
Conductance changes and Ca in leachate2+、Eu3+、Na+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus ash
Chemical stability of the feldspar firming body under " heat, water, power, chemistry " coupling.
Embodiment 18：
With Ca2P2O7、CaF2、Eu2O3、Na2CO3For raw material, according to chemical formula Ca7Eu3Na3(PO4)6F2Weigh each component original
Material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent is mixed in planetary ball
It is ground 5 hours in grinding machine, the mixture drying of acquisition, you can the powder dried adds in the powder quality 10% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation, the minus mesh of 25 mesh and the oversize granulation as obtained of 270 mesh are carried out using sieve
Material；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa, then cold etc. quiet
Cold isostatic compaction is carried out using the pressure of 260MPa on press, obtains molding blank；To molding blank heat at a temperature of 600 DEG C
Processing carries out dumping, then the green body after dumping is put into vacuum sintering funace in 10 hours, in 1200 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 35MPa, vacuum degree 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 3 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L, uses
Deionized water rinses liner 2 times, impregnates 3 hours, spends in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 99% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and soaked using conductivity meter
Go out the conductivity of liquid, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Ca in the analysis means such as absorption spectrum test leachate2+、Eu3+、Na+Ion concentration；With Ca in leachate2+、Eu3+、Na+'s
Ion concentration calculates Ca2+、Eu3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leaching
Go out liquid product（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramic solidification
The surface area of body（m2）,tFor the leaching test time（d）；It is penetrated using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X
Object phase change before and after line energy spectrum analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to leaching test
Ca in front and rear leachate conductivity variations and leachate2+、Eu3+、Na+Normalization leaching rate variation, overall merit simulation time
Chemical stability of the actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 19：
With Ca2P2O7、CaF2、Eu2O3、SiO2For raw material, according to chemical formula Ca9.9Eu0.1(PO4)5.9(SiO4)0.1F2It weighs
Each component raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in
It is ground 2 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
The polyvinyl alcohol colloidal sol of quality 3%, then mixing granulation is carried out using sieve, the minus mesh of 12 mesh and the oversize of 170 mesh are as made
The granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, Ran Hou
Cold isostatic compaction is carried out using the pressure of 80MPa on cold isostatic press, obtains molding blank；To molding at a temperature of 400 DEG C
Green body is heat-treated 5 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in 1000 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of power 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 2 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L,
Liner is rinsed with deionized water 2 times, is impregnated 2 hours, is used in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
Deionized water rinses liner 2 times；It is impregnated 2 hours in the ethanol water for being 90% in mass percent concentration again, uses deionized water
It rinses liner 2 times, impregnates 3 hours in 90 DEG C of deionized waters, then boiled 1 hour with deionized water, finally rushed with deionized water
Liner is washed, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；Leaching container drying after cleaning is standby
With；The deionized water that conductivity is taken to be 5 μ S/m uses hydrochloric acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation
Secondary actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Go out agent volume=10m-1Pour into leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value
5, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested using conductivity meter
The conductivity of leachate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and original
Ca in the analysis means such as sub- absorption spectrum test leachate2+、Eu3+Ion concentration；With Ca in leachate2+、Eu3+Ion it is dense
Degree calculates Ca2+、Eu3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume
（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface for fluor-apatite ceramic solidification body
Product（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X-ray energy spectrum point
Object phase change before and after analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leaching before and after leaching test
Go out Ca in liquid conductivity variations and leachate2+、Eu3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus
Chemical stability of the lime stone ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 20：
With Ca2P2O7、CaF2、Eu2O3、SiO2For raw material, according to chemical formula Ca8.5Eu1.5(PO4)4.5(SiO4)1.5F2It weighs
Each component raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent, is mixed in
It is ground 3 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
The polyvinyl alcohol colloidal sol of quality 6%, then mixing granulation is carried out using sieve, the minus mesh of 18 mesh and the oversize of 220 mesh are as made
The granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then
Cold isostatic compaction is carried out using the pressure of 170MPa on cold isostatic press, obtains molding blank；At a temperature of 500 DEG C into
Parison body heat handles 7 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, 1100 DEG C of temperature,
Vacuum heating-press sintering is carried out under conditions of pressure 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium series nucleic fluorine phosphorus ash is made
Feldspar firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydro-thermal it is anti-
Kettle is answered to impregnate the liner of hydrothermal reaction kettle 3 hours in aqueous solution of nitric acid of the molar concentration for 2mol/L as container is leached,
Liner is rinsed with deionized water 2 times, is impregnated 3 hours, is used in the sodium hydrate aqueous solution for being then 17% in mass percent concentration
Deionized water rinses liner 2 times；It is impregnated 3 hours in the ethanol water for being 95% in mass percent concentration again, uses deionized water
It rinses liner 2 times, impregnates 4 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rushed with deionized water
Liner is washed, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；Leaching container drying after cleaning is standby
With；The deionized water that conductivity is 50 μ S/m is taken, the pH value of deionized water is 7, and leaching agent is made；It will simulation time actinium series nucleic fluorine
Phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1
Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature are poured into, leaching agent pH value is 7, is tried leaching
After testing 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days time, using the electricity of conductivity meter test leachate
Conductance, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum
Wait Ca in analysis means test leachate2+、Eu3+Ion concentration；With Ca in leachate2+、Eu3+Ion concentration calculate Ca2+、
Eu3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor element
Normalize leaching rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluorine phosphorus
The mass fraction of element in lime stone ceramic solidification body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor leaching
Go out test period（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series
Object phase change before and after nucleic fluor-apatite ceramic solidification body leaching test becomes with reference to the leachate conductivity before and after leaching test
Change and Ca in leachate2+、Eu3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification
Chemical stability of the body under " heat, water, power, chemistry " coupling.
Embodiment 21：
With Ca2P2O7、CaF2、Eu2O3、SiO2For raw material, according to chemical formula Ca7Eu3(PO4)3(SiO4)3F2Weigh each component
Raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent is mixed in planetary
It is ground 5 hours in ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality 10% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the oversizes of the minus mesh of 25 mesh and 270 mesh be made from make
Pellet；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 260MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 600 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 10 hours, in 1200 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 35MPa, vacuum degree 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 3 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L, uses
Deionized water rinses liner 2 times, impregnates 3 hours, spends in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 99% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and soaked using conductivity meter
Go out the conductivity of liquid, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Ca in the analysis means such as absorption spectrum test leachate2+、Eu3+Ion concentration；With Ca in leachate2+、Eu3+Ion concentration
Calculate Ca2+、Eu3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LR
Normalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume
（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface for fluor-apatite ceramic solidification body
Product（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X-ray energy spectrum point
Object phase change before and after analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leaching before and after leaching test
Go out Ca in liquid conductivity variations and leachate2+、Eu3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus
Chemical stability of the lime stone ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 22：
With Ca2P2O7、CaF2、Eu2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca9.7Eu0.2Na0.1(PO4)5.9
(SiO4)0.1F2It weighs each component raw material and carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 quality
Percentage is mixed in planetary ball mill and grinds 2 hours, the mixture drying of acquisition, you can the powder dried adds
Enter the polyvinyl alcohol colloidal sol of the powder quality 3% of drying, then mixing granulation, the minus mesh of 12 mesh and 170 purposes are carried out using sieve
Oversize is granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa
Type is made, cold isostatic compaction is then carried out using the pressure of 80MPa on cold isostatic press, obtains molding blank；At 400 DEG C
At a temperature of molding blank is heat-treated 5 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in temperature
Vacuum heating-press sintering is carried out under conditions of 1000 DEG C of degree, pressure 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series is made
Nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoroethyl-ne that stainless steel, liner material are that the degree of polymerization is 5000
The hydrothermal reaction kettle of alkene is as container is leached, by the liner of hydrothermal reaction kettle in the aqueous solution of nitric acid that molar concentration is 0.1mol/L
It is middle to impregnate 2 hours, liner is rinsed 2 times with deionized water, in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
It impregnates 2 hours, liner is rinsed 2 times with deionized water；It is small that 2 are impregnated in the ethanol water for being 90% in mass percent concentration again
When, liner 2 times is rinsed with deionized water, is impregnated 3 hours in 90 DEG C of deionized waters, then 1 hour is boiled with deionized water, finally
Liner is rinsed with deionized water, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；By the leaching after cleaning
Container is dried for standby；The deionized water that conductivity is taken to be 5 μ S/m uses the pH value that sulfuric acid adjusts deionized water that leaching is made for 5
Agent；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to fluor-apatite ceramic solidification body
Surface area/leaching agent volume=10m-1Leaching agent is poured into, controls 100 DEG C, leaching test pressure 0.101MPa of leaching test temperature,
Leaching agent pH value 5, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, using electricity
Electrical conductivity instrument tests the conductivity of leachate, is then sent out using inductivity coupled plasma mass spectrometry, inductively coupled plasma optics
Penetrate Ca in the analysis means such as spectrum and atomic absorption spectrum test leachate2+、Eu3+、Na+Ion concentration；With Ca in leachate2 +、Eu3+、Na+Ion concentration calculate Ca2+、Eu3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate
（g/m3）,VFor leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluorine phosphorus ash
The surface area of feldspar firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, sweep
Retouch the object phase change before and after Electronic Speculum-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, knot
Ca in leachate conductivity variations and leachate before and after conjunction leaching test2+、Eu3+、Na+The variation of normalization leaching rate, it is comprehensive
Chemical stability of the Simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 23：
With Ca2P2O7、CaF2、Eu2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca5.5Eu3Na1.5(PO4)4.5
(SiO4)1.5F2It weighs each component raw material and carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 quality
Percentage is mixed in planetary ball mill and grinds 3 hours, the mixture drying of acquisition, you can the powder dried adds
Enter the polyvinyl alcohol colloidal sol of the powder quality 6% of drying, then mixing granulation, the minus mesh of 18 mesh and 220 purposes are carried out using sieve
Oversize is granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa
Type is made, cold isostatic compaction is then carried out using the pressure of 170MPa on cold isostatic press, obtains molding blank；500
Molding blank is heat-treated 7 hours at a temperature of DEG C and carries out dumping, then the green body after dumping is put into vacuum sintering funace,
Vacuum heating-press sintering is carried out under conditions of 1100 DEG C of temperature, pressure 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium is made
It is nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoro that stainless steel, liner material are that the degree of polymerization is 7500
The hydrothermal reaction kettle of ethylene is as container is leached, by the liner of hydrothermal reaction kettle in the aqueous solution of nitric acid that molar concentration is 2mol/L
It is middle to impregnate 3 hours, liner is rinsed 2 times with deionized water, in the sodium hydrate aqueous solution for being then 17% in mass percent concentration
It impregnates 3 hours, liner is rinsed 2 times with deionized water；It is small that 3 are impregnated in the ethanol water for being 95% in mass percent concentration again
When, liner 2 times is rinsed with deionized water, is impregnated 4 hours in 90 DEG C of deionized waters, then 2 hours are boiled with deionized water, finally
Liner is rinsed with deionized water, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；By the leaching after cleaning
Container is dried for standby；The deionized water that conductivity is 50 μ S/m is taken, the pH value of deionized water is 7, and leaching agent is made；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature are poured into, leaching agent pH value is
7, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested using conductivity meter
The conductivity of leachate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and original
Ca in the analysis means such as sub- absorption spectrum test leachate2+、Eu3+、Na+Ion concentration；With Ca in leachate2+、Eu3+、Na+
Ion concentration calculate Ca2+、Eu3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,V
For leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramics
The surface area of firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electricity
Object phase change before and after mirror-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to leaching
Go out Ca in the front and rear leachate conductivity variations of experiment and leachate2+、Eu3+、Na+Normalization leaching rate variation, overall merit
Chemical stability of the simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 24：
With Ca2P2O7、CaF2、Eu2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca1Eu6Na3(PO4)3(SiO4)3F2Claim
Each component raw material is taken to carry out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent, mixing
It is ground 5 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
Expect the polyvinyl alcohol colloidal sol of quality 10%, then mixing granulation is carried out using sieve, the minus mesh of 25 mesh and the oversize of 270 mesh are
For granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa,
Then cold isostatic compaction is carried out using the pressure of 260MPa on cold isostatic press, obtains molding blank；At a temperature of 600 DEG C
Molding blank is heat-treated 10 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in temperature
1200 DEG C, pressure 35MPa, vacuum heating-press sintering is carried out under conditions of vacuum degree 10Pa 12 hours, you can simulation time actinium series is made
Nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoroethyl-ne that stainless steel, liner material are that the degree of polymerization is 10000
The hydrothermal reaction kettle of alkene is as leaching container, in the aqueous solution of nitric acid for being 3mol/L in molar concentration by the liner of hydrothermal reaction kettle
It impregnates 3 hours, rinses liner 2 times with deionized water, soaked in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Bubble 3 hours rinses liner 2 times with deionized water；It is impregnated 3 hours in the ethanol water for being 99% in mass percent concentration again,
Liner is rinsed with deionized water 2 times, is impregnated 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, is finally used
Deionized water rinses liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching after cleaning is held
Device is dried for standby；The deionized water that conductivity is taken to be 150 μ S/m uses the pH value that ammonium hydroxide adjusts deionized water that leaching is made for 9
Agent；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to fluor-apatite ceramic solidification body
Surface area/leaching agent volume=10m-1Leaching agent is poured into, controls 200 DEG C, leaching test pressure 1.554MPa of leaching test temperature,
Leaching agent pH value 9, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, using electricity
Electrical conductivity instrument tests the conductivity of leachate, is then sent out using inductivity coupled plasma mass spectrometry, inductively coupled plasma optics
Penetrate Ca in the analysis means such as spectrum and atomic absorption spectrum test leachate2+、Eu3+、Na+Ion concentration；With Ca in leachate2 +、Eu3+、Na+Ion concentration calculate Ca2+、Eu3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate
（g/m3）,VFor leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluorine phosphorus ash
The surface area of feldspar firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, sweep
Retouch the object phase change before and after Electronic Speculum-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, knot
Ca in leachate conductivity variations and leachate before and after conjunction leaching test2+、Eu3+、Na+The variation of normalization leaching rate, it is comprehensive
Chemical stability of the Simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 25：
With Ca2P2O7、CaF2、Gd2O3For raw material, according to chemical formula Ca9.85Gd0.1(PO4)6F2Weigh the progress of each component raw material
Dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in planetary ball mill
Grinding 2 hours, the mixture drying of acquisition, you can the powder dried adds in the polyethylene of the powder quality 3% of drying
Alcosol, then mixing granulation, the minus mesh of 12 mesh and the oversize granulation material as obtained of 170 mesh are carried out using sieve；It will
Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, then on cold isostatic press
Cold isostatic compaction is carried out using the pressure of 80MPa, obtains molding blank；It is small to molding blank heat treatment 5 at a temperature of 400 DEG C
Shi Jinhang dumpings, then the green body after dumping is put into vacuum sintering funace, in 1000 DEG C of temperature, pressure 15MPa, vacuum degree
Vacuum heating-press sintering is carried out under conditions of 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；It adopts
By the use of enclosure material be stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach hold
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L is impregnated 2 hours, is rushed with deionized water by device
It washes liner 2 times, impregnates 2 hours in the sodium hydrate aqueous solution for being then 5% in mass percent concentration, rinsed with deionized water
Liner 2 times；It is impregnated 2 hours in the ethanol water for being 90% in mass percent concentration again, liner is rinsed 2 times with deionized water,
It impregnates 3 hours in 90 DEG C of deionized waters, then is boiled 1 hour with deionized water, finally rinse liner with deionized water, until even
The difference of the continuous pH value of flushing liquor twice is 0.1 pH unit；Leaching container after cleaning is dried for standby；It is 5 μ to take conductivity
The deionized water of S/m uses acetic acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation time actinium series nucleic fluorine phosphorus ash
Ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1It pours into
Leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value 5, in the leaching test time 1
My god, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, after 42 days, using conductivity meter test leachate conductivity, so
Hand is analyzed using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum etc. afterwards
Ca in section test leachate2+、Gd3+Ion concentration；With Ca in leachate2+、Gd3+Ion concentration calculate Ca2+、Gd3+Return
One changes leaching rate, and the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization for element is soaked
Extracting rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluor-apatite ceramics
The mass fraction of element in firming body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tDuring for leaching test
Between（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series nucleic fluorine phosphorus
Object phase change before and after lime stone ceramic solidification body leaching test, with reference to the leachate conductivity variations before and after leaching test and leaching
Ca in liquid2+、Gd3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body " heat,
Chemical stability under water, power, chemistry " coupling.
Embodiment 26：
With Ca2P2O7、CaF2、Gd2O3For raw material, according to chemical formula Ca7.75Gd1.5(PO4)6F2Weigh the progress of each component raw material
Dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent, is mixed in planetary ball mill
Grinding 3 hours, the mixture drying of acquisition, you can the powder dried adds in the polyethylene of the powder quality 6% of drying
Alcosol, then mixing granulation, the minus mesh of 18 mesh and the oversize granulation material as obtained of 220 mesh are carried out using sieve；It will
Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then on cold isostatic press
Cold isostatic compaction is carried out using the pressure of 170MPa, obtains molding blank；To molding blank heat treatment 7 at a temperature of 500 DEG C
Hour carries out dumping, then the green body after dumping is put into vacuum sintering funace, in 1100 DEG C of temperature, pressure 25MPa, vacuum
Vacuum heating-press sintering is carried out under conditions of degree 5Pa 7 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；
Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach hold
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 2mol/L is impregnated 3 hours, is rinsed with deionized water by device
Liner 2 times is impregnated 3 hours in the sodium hydrate aqueous solution for being then 17% in mass percent concentration, rinsed with deionized water in
Lining 2 times；It is impregnated 3 hours in the ethanol water for being 95% in mass percent concentration again, liner is rinsed 2 times with deionized water,
90 DEG C of deionized water is impregnated 4 hours, then is boiled 2 hours with deionized water, finally rinses liner with deionized water, until continuous
The difference of the pH value of flushing liquor is 0.3 pH unit twice；Leaching container after cleaning is dried for standby；It is 50 μ to take conductivity
The deionized water of S/m, the pH value of deionized water is 7, and leaching agent is made；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put
Enter in hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1Leaching agent is poured into, is controlled
150 DEG C of leaching test temperature, leaching test pressure 0.828MPa, leaching agent pH value is 7, in 1 day leaching test time, 3 days, 7
My god, 10 days, 14 days, 21 days, 28 days, 35 days, after 42 days, using conductivity meter test leachate conductivity, then using electricity
Feel the test leaching of the analysis means such as coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum
Go out Ca in liquid2+、Gd3+Ion concentration；With Ca in leachate2+、Gd3+Ion concentration calculate Ca2+、Gd3+Normalization leach
Rate, the calculation formula for normalizing leaching rate are as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·
m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor in fluor-apatite ceramic solidification body
The mass fraction of element（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor the leaching test time（d）；It adopts
With X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series nucleic fluor-apatite ceramics
Object phase change before and after firming body leaching test, with reference to Ca in the leachate conductivity variations before and after leaching test and leachate2+、
Gd3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body is in " heat, water, power, change
Chemical stability under " coupling.
Embodiment 27：
With Ca2P2O7、CaF2、Gd2O3For raw material, according to chemical formula Ca5.5Gd3(PO4)6F2Each component raw material is weighed to be matched
Material, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent, is mixed in planetary ball mill and grinds
Mill 5 hours, the mixture drying of acquisition, you can the powder dried adds in the polyvinyl alcohol of the powder quality 10% of drying
Colloidal sol, then mixing granulation, the minus mesh of 25 mesh and the oversize granulation material as obtained of 270 mesh are carried out using sieve；It will make
Pellet is fitted into steel die, is pressed using the pressure of 35MPa, is then adopted on cold isostatic press on a hydraulic press
Cold isostatic compaction is carried out with the pressure of 260MPa, obtains molding blank；It is small to molding blank heat treatment 10 at a temperature of 600 DEG C
Shi Jinhang dumpings, then the green body after dumping is put into vacuum sintering funace, in 1200 DEG C of temperature, pressure 35MPa, vacuum degree
Vacuum heating-press sintering is carried out under conditions of 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite ceramic solidification body is made；
Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle as leach
The liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L is impregnated 3 hours, is rushed with deionized water by container
It washes liner 2 times, impregnates 3 hours in the sodium hydrate aqueous solution for being then 30% in mass percent concentration, rinsed with deionized water
Liner 2 times；It is impregnated 3 hours in the ethanol water for being 99% in mass percent concentration again, liner is rinsed 2 times with deionized water,
It impregnates 6 hours in 90 DEG C of deionized waters, then is boiled 2 hours with deionized water, finally rinse liner with deionized water, until even
The difference of the continuous pH value of flushing liquor twice is 0.5 pH unit；Leaching container after cleaning is dried for standby；The conductivity is taken to be
The deionized water of 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time actinium series nucleic fluorine
Phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1
Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9, in leaching test
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days time, using the conductance of conductivity meter test leachate
Rate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum etc.
Ca in analysis means test leachate2+、Gd3+Ion concentration；With Ca in leachate2+、Gd3+Ion concentration calculate Ca2+、Gd3 +Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor returning for element
One changes leaching rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluorine phosphorus ash
The mass fraction of element in feldspar firming body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tTo leach
Test period（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time Excitation Bands
Object phase change before and after plain fluor-apatite ceramic solidification body leaching test, with reference to the leachate conductivity variations before and after leaching test
With Ca in leachate2+、Gd3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification body
Chemical stability under " heat, water, power, chemistry " coupling.
Embodiment 28：
With Ca2P2O7、CaF2、Gd2O3、Na2CO3For raw material, according to chemical formula Ca9.8Gd0.1Na0.1(PO4)6F2Weigh each group
Raw material is divided to carry out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in planet
It is ground 2 hours in formula ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality of drying
3% polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the minus mesh of 12 mesh and the oversize of 170 mesh are as obtained
Granulation material；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 80MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 400 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 5 hours, in 1000 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite pottery is made
Porcelain firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle
As container is leached, the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L is impregnated 2 hours, is used
Deionized water rinses liner 2 times, impregnates 2 hours, spends in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 2 hours in the ethanol water for being 90% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 3 hours in 90 DEG C of deionized waters, then boiled 1 hour with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 5 μ S/m uses oxalic acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation time actinium
It is that nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent of fluor-apatite ceramic solidification body
Volume=10m-1Pour into leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value 5,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and leached using conductivity meter
Then the conductivity of liquid is inhaled using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Receive Ca in the analysis means such as spectrum test leachate2+、Gd3+、Na+Ion concentration；With Ca in leachate2+、Gd3+、Na+From
Sub- concentration calculates Ca2+、Gd3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VTo leach
Liquid accumulates（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramic solidification body
Surface area（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X ray
Object phase change before and after energy spectrum analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, before leaching test
Ca in rear leachate conductivity variations and leachate2+、Gd3+、Na+The variation of normalization leaching rate, overall merit simulation time actinium
It is chemical stability of the nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 29：
With Ca2P2O7、CaF2、Gd2O3、Na2CO3For raw material, according to chemical formula Ca7Gd1.5Na1.5(PO4)6F2Weigh each component
Raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent is mixed in planetary
It is ground 3 hours in ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality 6% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the oversizes of the minus mesh of 18 mesh and 220 mesh be made from make
Pellet；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 170MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 500 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 7 hours, in 1100 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium series nucleic fluor-apatite pottery is made
Porcelain firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydrothermal reaction kettle
As container is leached, the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 2mol/L is impregnated 3 hours, is spent
Ionized water rinses liner 2 times, is impregnated 3 hours in the sodium hydrate aqueous solution for being then 17% in mass percent concentration, spend from
Sub- water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 95% in mass percent concentration again, is rinsed with deionized water
Liner 2 times impregnates 4 hours in 90 DEG C of deionized waters, then boils 2 hours with deionized water, finally rinsed with deionized water in
Lining, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；Leaching container after cleaning is dried for standby；It takes
Conductivity is the deionized water of 50 μ S/m, and the pH value of deionized water is 7, and leaching agent is made；It will simulation time actinium series nucleic fluorine phosphorus ash
Ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1It pours into
Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature, leaching agent pH value is 7, in leaching test
Between after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days, using conductivity meter test leachate conductivity,
Then using analyses such as inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrums
Ca in means test leachate2+、Gd3+、Na+Ion concentration；With Ca in leachate2+、Gd3+、Na+Ion concentration calculate Ca2 +、Gd3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor
The normalization leaching rate of element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,f
Mass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation
Object phase change before and after secondary actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leachate electricity before and after leaching test
Conductance changes and Ca in leachate2+、Gd3+、Na+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus ash
Chemical stability of the feldspar firming body under " heat, water, power, chemistry " coupling.
Embodiment 30：
With Ca2P2O7、CaF2、Gd2O3、Na2CO3For raw material, according to chemical formula Ca7Gd3Na3(PO4)6F2Weigh each component original
Material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent is mixed in planetary ball
It is ground 5 hours in grinding machine, the mixture drying of acquisition, you can the powder dried adds in the powder quality 10% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation, the minus mesh of 25 mesh and the oversize granulation as obtained of 270 mesh are carried out using sieve
Material；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa, then cold etc. quiet
Cold isostatic compaction is carried out using the pressure of 260MPa on press, obtains molding blank；To molding blank heat at a temperature of 600 DEG C
Processing carries out dumping, then the green body after dumping is put into vacuum sintering funace in 10 hours, in 1200 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 35MPa, vacuum degree 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 3 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L, uses
Deionized water rinses liner 2 times, impregnates 3 hours, spends in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 99% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and soaked using conductivity meter
Go out the conductivity of liquid, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Ca in the analysis means such as absorption spectrum test leachate2+、Gd3+、Na+Ion concentration；With Ca in leachate2+、Gd3+、Na+'s
Ion concentration calculates Ca2+、Gd3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leaching
Go out liquid product（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramic solidification
The surface area of body（m2）,tFor the leaching test time（d）；It is penetrated using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X
Object phase change before and after line energy spectrum analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to leaching test
Ca in front and rear leachate conductivity variations and leachate2+、Gd3+、Na+Normalization leaching rate variation, overall merit simulation time
Chemical stability of the actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 31：
With Ca2P2O7、CaF2、Gd2O3、SiO2For raw material, according to chemical formula Ca9.9Gd0.1(PO4)5.9(SiO4)0.1F2It weighs
Each component raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 mass percent, is mixed in
It is ground 2 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
The polyvinyl alcohol colloidal sol of quality 3%, then mixing granulation is carried out using sieve, the minus mesh of 12 mesh and the oversize of 170 mesh are as made
The granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa, Ran Hou
Cold isostatic compaction is carried out using the pressure of 80MPa on cold isostatic press, obtains molding blank；To molding at a temperature of 400 DEG C
Green body is heat-treated 5 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in 1000 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of power 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 5000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 2 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 0.1mol/L,
Liner is rinsed with deionized water 2 times, is impregnated 2 hours, is used in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
Deionized water rinses liner 2 times；It is impregnated 2 hours in the ethanol water for being 90% in mass percent concentration again, uses deionized water
It rinses liner 2 times, impregnates 3 hours in 90 DEG C of deionized waters, then boiled 1 hour with deionized water, finally rushed with deionized water
Liner is washed, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；Leaching container drying after cleaning is standby
With；The deionized water that conductivity is taken to be 5 μ S/m uses hydrochloric acid to adjust the pH value of deionized water as 5, obtained leaching agent；It will simulation
Secondary actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Go out agent volume=10m-1Pour into leaching agent, 100 DEG C, leaching test pressure 0.101MPa of control leaching test temperature, leaching agent pH value
5, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested using conductivity meter
The conductivity of leachate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and original
Ca in the analysis means such as sub- absorption spectrum test leachate2+、Gd3+Ion concentration；With Ca in leachate2+、Gd3+Ion it is dense
Degree calculates Ca2+、Gd3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume
（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface for fluor-apatite ceramic solidification body
Product（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X-ray energy spectrum point
Object phase change before and after analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leaching before and after leaching test
Go out Ca in liquid conductivity variations and leachate2+、Gd3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus
Chemical stability of the lime stone ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 32：
With Ca2P2O7、CaF2、Gd2O3、SiO2For raw material, according to chemical formula Ca8.5Gd1.5(PO4)4.5(SiO4)1.5F2It weighs
Each component raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 mass percent, is mixed in
It is ground 3 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
The polyvinyl alcohol colloidal sol of quality 6%, then mixing granulation is carried out using sieve, the minus mesh of 18 mesh and the oversize of 220 mesh are as made
The granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa, then
Cold isostatic compaction is carried out using the pressure of 170MPa on cold isostatic press, obtains molding blank；At a temperature of 500 DEG C into
Parison body heat handles 7 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, 1100 DEG C of temperature,
Vacuum heating-press sintering is carried out under conditions of pressure 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium series nucleic fluorine phosphorus ash is made
Feldspar firming body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 7500 polytetrafluoroethylene (PTFE) hydro-thermal it is anti-
Kettle is answered to impregnate the liner of hydrothermal reaction kettle 3 hours in aqueous solution of nitric acid of the molar concentration for 2mol/L as container is leached,
Liner is rinsed with deionized water 2 times, is impregnated 3 hours, is used in the sodium hydrate aqueous solution for being then 17% in mass percent concentration
Deionized water rinses liner 2 times；It is impregnated 3 hours in the ethanol water for being 95% in mass percent concentration again, uses deionized water
It rinses liner 2 times, impregnates 4 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rushed with deionized water
Liner is washed, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；Leaching container drying after cleaning is standby
With；The deionized water that conductivity is 50 μ S/m is taken, the pH value of deionized water is 7, and leaching agent is made；It will simulation time actinium series nucleic fluorine
Phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent volume=10m of fluor-apatite ceramic solidification body-1
Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature are poured into, leaching agent pH value is 7, is tried leaching
After testing 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days time, using the electricity of conductivity meter test leachate
Conductance, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atomic absorption spectrum
Wait Ca in analysis means test leachate2+、Gd3+Ion concentration；With Ca in leachate2+、Gd3+Ion concentration calculate Ca2+、
Gd3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRFor element
Normalize leaching rate（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume（m3）,fFor fluorine phosphorus
The mass fraction of element in lime stone ceramic solidification body（wt.%）,ASurface area for fluor-apatite ceramic solidification body（m2）,tFor leaching
Go out test period（d）；Using X-ray diffraction, back scattering secondary electron image, scanned topographic map simulation time actinium series
Object phase change before and after nucleic fluor-apatite ceramic solidification body leaching test becomes with reference to the leachate conductivity before and after leaching test
Change and Ca in leachate2+、Gd3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluor-apatite ceramic solidification
Chemical stability of the body under " heat, water, power, chemistry " coupling.
Embodiment 33：
With Ca2P2O7、CaF2、Gd2O3、SiO2For raw material, according to chemical formula Ca7Gd3(PO4)3(SiO4)3F2Weigh each component
Raw material carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent is mixed in planetary
It is ground 5 hours in ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder quality 10% of drying
Polyvinyl alcohol colloidal sol, then mixing granulation is carried out using sieve, the oversizes of the minus mesh of 25 mesh and 270 mesh be made from make
Pellet；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa, then cold etc.
Cold isostatic compaction is carried out using the pressure of 260MPa on static pressure machine, obtains molding blank；To molding blank at a temperature of 600 DEG C
Heat treatment carries out dumping, then the green body after dumping is put into vacuum sintering funace in 10 hours, in 1200 DEG C of temperature, pressure
Vacuum heating-press sintering is carried out under conditions of 35MPa, vacuum degree 10Pa 12 hours, you can simulation time actinium series nucleic fluor-apatite is made
Ceramic solidification body；Use enclosure material for stainless steel, liner material be the degree of polymerization be 10000 polytetrafluoroethylene (PTFE) hydro-thermal reaction
Kettle impregnates 3 hours as container is leached, by the liner of hydrothermal reaction kettle in aqueous solution of nitric acid of the molar concentration for 3mol/L, uses
Deionized water rinses liner 2 times, impregnates 3 hours, spends in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Ionized water rinses liner 2 times；It impregnates 3 hours in the ethanol water for being 99% in mass percent concentration again, is rushed with deionized water
It washes liner 2 times, impregnates 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, finally rinsed with deionized water
Liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching container after cleaning is dried for standby；
The deionized water that conductivity is taken to be 150 μ S/m uses ammonium hydroxide to adjust the pH value of deionized water as 9, obtained leaching agent；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Pour into leaching agent, 200 DEG C, leaching test pressure 1.554MPa of control leaching test temperature, leaching agent pH value 9,
After 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested and soaked using conductivity meter
Go out the conductivity of liquid, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and atom
Ca in the analysis means such as absorption spectrum test leachate2+、Gd3+Ion concentration；With Ca in leachate2+、Gd3+Ion concentration
Calculate Ca2+、Gd3+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LR
Normalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,VFor leachate volume
（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,ASurface for fluor-apatite ceramic solidification body
Product（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electron microscope-X-ray energy spectrum point
Object phase change before and after analysis simulation time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to the leaching before and after leaching test
Go out Ca in liquid conductivity variations and leachate2+、Gd3+The variation of normalization leaching rate, overall merit simulation time actinium series nucleic fluorine phosphorus
Chemical stability of the lime stone ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 34：
With Ca2P2O7、CaF2、Gd2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca9.7Gd0.2Na0.1(PO4)5.9
(SiO4)0.1F2It weighs each component raw material and carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 35：15：50 quality
Percentage is mixed in planetary ball mill and grinds 2 hours, the mixture drying of acquisition, you can the powder dried adds
Enter the polyvinyl alcohol colloidal sol of the powder quality 3% of drying, then mixing granulation, the minus mesh of 12 mesh and 170 purposes are carried out using sieve
Oversize is granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 8MPa
Type is made, cold isostatic compaction is then carried out using the pressure of 80MPa on cold isostatic press, obtains molding blank；At 400 DEG C
At a temperature of molding blank is heat-treated 5 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in temperature
Vacuum heating-press sintering is carried out under conditions of 1000 DEG C of degree, pressure 15MPa, vacuum degree 1Pa 2 hours, you can simulation time actinium series is made
Nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoroethyl-ne that stainless steel, liner material are that the degree of polymerization is 5000
The hydrothermal reaction kettle of alkene is as container is leached, by the liner of hydrothermal reaction kettle in the aqueous solution of nitric acid that molar concentration is 0.1mol/L
It is middle to impregnate 2 hours, liner is rinsed 2 times with deionized water, in the sodium hydrate aqueous solution for being then 5% in mass percent concentration
It impregnates 2 hours, liner is rinsed 2 times with deionized water；It is small that 2 are impregnated in the ethanol water for being 90% in mass percent concentration again
When, liner 2 times is rinsed with deionized water, is impregnated 3 hours in 90 DEG C of deionized waters, then 1 hour is boiled with deionized water, finally
Liner is rinsed with deionized water, until the difference of the pH value of flushing liquor is 0.1 pH unit twice in succession；By the leaching after cleaning
Container is dried for standby；The deionized water that conductivity is taken to be 5 μ S/m uses the pH value that sulfuric acid adjusts deionized water that leaching is made for 5
Agent；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to fluor-apatite ceramic solidification body
Surface area/leaching agent volume=10m-1Leaching agent is poured into, controls 100 DEG C, leaching test pressure 0.101MPa of leaching test temperature,
Leaching agent pH value 5, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, using electricity
Electrical conductivity instrument tests the conductivity of leachate, is then sent out using inductivity coupled plasma mass spectrometry, inductively coupled plasma optics
Penetrate Ca in the analysis means such as spectrum and atomic absorption spectrum test leachate2+、Gd3+、Na+Ion concentration；With Ca in leachate2 +、Gd3+、Na+Ion concentration calculate Ca2+、Gd3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate
（g/m3）,VFor leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluorine phosphorus ash
The surface area of feldspar firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, sweep
Retouch the object phase change before and after Electronic Speculum-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, knot
Ca in leachate conductivity variations and leachate before and after conjunction leaching test2+、Gd3+、Na+The variation of normalization leaching rate, it is comprehensive
Chemical stability of the Simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 35：
With Ca2P2O7、CaF2、Gd2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca5.5Gd3Na1.5(PO4)4.5
(SiO4)1.5F2It weighs each component raw material and carries out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 55：25：20 quality
Percentage is mixed in planetary ball mill and grinds 3 hours, the mixture drying of acquisition, you can the powder dried adds
Enter the polyvinyl alcohol colloidal sol of the powder quality 6% of drying, then mixing granulation, the minus mesh of 18 mesh and 220 purposes are carried out using sieve
Oversize is granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 21MPa
Type is made, cold isostatic compaction is then carried out using the pressure of 170MPa on cold isostatic press, obtains molding blank；500
Molding blank is heat-treated 7 hours at a temperature of DEG C and carries out dumping, then the green body after dumping is put into vacuum sintering funace,
Vacuum heating-press sintering is carried out under conditions of 1100 DEG C of temperature, pressure 25MPa, vacuum degree 5Pa 7 hours, you can simulation time actinium is made
It is nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoro that stainless steel, liner material are that the degree of polymerization is 7500
The hydrothermal reaction kettle of ethylene is as container is leached, by the liner of hydrothermal reaction kettle in the aqueous solution of nitric acid that molar concentration is 2mol/L
It is middle to impregnate 3 hours, liner is rinsed 2 times with deionized water, in the sodium hydrate aqueous solution for being then 17% in mass percent concentration
It impregnates 3 hours, liner is rinsed 2 times with deionized water；It is small that 3 are impregnated in the ethanol water for being 95% in mass percent concentration again
When, liner 2 times is rinsed with deionized water, is impregnated 4 hours in 90 DEG C of deionized waters, then 2 hours are boiled with deionized water, finally
Liner is rinsed with deionized water, until the difference of the pH value of flushing liquor is 0.3 pH unit twice in succession；By the leaching after cleaning
Container is dried for standby；The deionized water that conductivity is 50 μ S/m is taken, the pH value of deionized water is 7, and leaching agent is made；It will simulation time
Actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching of fluor-apatite ceramic solidification body
Agent volume=10m-1Leaching agent, 150 DEG C, leaching test pressure 0.828MPa of control leaching test temperature are poured into, leaching agent pH value is
7, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, tested using conductivity meter
The conductivity of leachate, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and original
Ca in the analysis means such as sub- absorption spectrum test leachate2+、Gd3+、Na+Ion concentration；With Ca in leachate2+、Gd3+、Na+
Ion concentration calculate Ca2+、Gd3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate（g/m3）,V
For leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluor-apatite ceramics
The surface area of firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, scanning electricity
Object phase change before and after mirror-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, with reference to leaching
Go out Ca in the front and rear leachate conductivity variations of experiment and leachate2+、Gd3+、Na+Normalization leaching rate variation, overall merit
Chemical stability of the simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 36：
With Ca2P2O7、CaF2、Gd2O3、Na2CO3、SiO2For raw material, according to chemical formula Ca1Gd6Na3(PO4)3(SiO4)3F2Claim
Each component raw material is taken to carry out dispensing, according to dispensing：Abrading-ball：Absolute ethyl alcohol or/and water are 65：20：15 mass percent, mixing
It is ground 5 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
Expect the polyvinyl alcohol colloidal sol of quality 10%, then mixing granulation is carried out using sieve, the minus mesh of 25 mesh and the oversize of 270 mesh are
For granulation material obtained；Granulation material is fitted into steel die, is pressed on a hydraulic press using the pressure of 35MPa,
Then cold isostatic compaction is carried out using the pressure of 260MPa on cold isostatic press, obtains molding blank；At a temperature of 600 DEG C
Molding blank is heat-treated 10 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace, in temperature
1200 DEG C, pressure 35MPa, vacuum heating-press sintering is carried out under conditions of vacuum degree 10Pa 12 hours, you can simulation time actinium series is made
Nucleic fluor-apatite ceramic solidification body；Enclosure material is used as polytetrafluoroethyl-ne that stainless steel, liner material are that the degree of polymerization is 10000
The hydrothermal reaction kettle of alkene is as leaching container, in the aqueous solution of nitric acid for being 3mol/L in molar concentration by the liner of hydrothermal reaction kettle
It impregnates 3 hours, rinses liner 2 times with deionized water, soaked in the sodium hydrate aqueous solution for being then 30% in mass percent concentration
Bubble 3 hours rinses liner 2 times with deionized water；It is impregnated 3 hours in the ethanol water for being 99% in mass percent concentration again,
Liner is rinsed with deionized water 2 times, is impregnated 6 hours in 90 DEG C of deionized waters, then boiled 2 hours with deionized water, is finally used
Deionized water rinses liner, until the difference of the pH value of flushing liquor is 0.5 pH unit twice in succession；Leaching after cleaning is held
Device is dried for standby；The deionized water that conductivity is taken to be 150 μ S/m uses the pH value that ammonium hydroxide adjusts deionized water that leaching is made for 9
Agent；Simulation time actinium series nucleic fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to fluor-apatite ceramic solidification body
Surface area/leaching agent volume=10m-1Leaching agent is poured into, controls 200 DEG C, leaching test pressure 1.554MPa of leaching test temperature,
Leaching agent pH value 9, after 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days leaching test time, using electricity
Electrical conductivity instrument tests the conductivity of leachate, is then sent out using inductivity coupled plasma mass spectrometry, inductively coupled plasma optics
Penetrate Ca in the analysis means such as spectrum and atomic absorption spectrum test leachate2+、Gd3+、Na+Ion concentration；With Ca in leachate2 +、Gd3+、Na+Ion concentration calculate Ca2+、Gd3+、Na+Normalization leaching rate, the calculation formula for normalizing leaching rate is as follows：LR=c·V/f·A·t, wherein,LRNormalization leaching rate for element（g·m-2·d-1）,cFor the ion concentration in leachate
（g/m3）,VFor leachate volume（m3）,fMass fraction for element in fluor-apatite ceramic solidification body（wt.%）,AFor fluorine phosphorus ash
The surface area of feldspar firming body（m2）,tFor the leaching test time（d）；Using X-ray diffraction, back scattering secondary electron image, sweep
Retouch the object phase change before and after Electronic Speculum-X-ray energy spectrum analysis mode time actinium series nucleic fluor-apatite ceramic solidification body leaching test, knot
Ca in leachate conductivity variations and leachate before and after conjunction leaching test2+、Gd3+、Na+The variation of normalization leaching rate, it is comprehensive
Chemical stability of the Simulation time actinium series nucleic fluor-apatite ceramic solidification body under " heat, water, power, chemistry " coupling.
Embodiment 37~43：
A kind of chemical stability evaluation method of fluor-apatite ceramic solidification body, is completed by following steps：
A, it prepares（Simulation time actinium series nucleic）Fluor-apatite ceramic solidification body：
With Ca2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-3a/2MA a (PO4)6F2
It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤a≤3（In embodiment 37~43aRespectively：
0.001、0.01、0.05、0.1、1、2、3）；
According to the mass percent of dispensing 35~65%, abrading-ball 15~55%, absolute ethyl alcohol or/and water 5~50%, it is mixed in
It is ground 2~5 hours in planetary ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder of drying
Expect the polyvinyl alcohol colloidal sol of quality 3~10%, then mixing granulation carried out using sieve, take the minus mesh of 12~25 mesh with 170~
The oversize of 270 mesh is granulation material；Granulation material is fitted into steel die, in hydraulic press（Equipment can be that Tianjin section device is high
The 769YP-24B type hydraulic machines of New Tech S. R. L.'s production）It is upper to be pressed using the pressure of 8~35MPa, then cold etc.
Static pressure machine（Equipment can be that the LDJ100/320-300 types of Sichuan Aviation Industry Chuanxi Machine Co., Ltd.'s production are cold etc. quiet
Press）The upper pressure using 80~260MPa carries out cold isostatic compaction, obtains molding blank；It is right at a temperature of 400~600 DEG C
Molding blank is heat-treated 5~10 hours and carries out dumping, then the green body after dumping is put into vacuum sintering funace（Equipment can be
The ZT-45-20Y30T type vacuum sintering funaces of Shanghai Guan Sheng vacuum equipments Co., Ltd production）In, temperature 1000~
1200 DEG C, 15~35MPa of pressure, vacuum heating-press sintering is carried out under conditions of 1~10Pa of vacuum degree 2~12 hours, obtain（Mould
Intend time actinium series nucleic）Fluor-apatite ceramic solidification body；
Each C divides the specific mass percent dosage of raw material see the table below in each embodiment：
B, container is leached in cleaning：
Enclosure material is used as stainless steel, the hydrothermal reaction kettle that liner material is polytetrafluoroethylene (PTFE)（Equipment can be Shanghai
The YH-200 type hydrothermal reaction kettles of more experimental instruments and equipment limited productions）As container is leached, by the liner of hydrothermal reaction kettle
It is impregnated 2~3 hours in the aqueous solution of nitric acid for being 0.1~3mol/L in molar concentration, rinses liner 2 times with deionized water, then
It is impregnated 2~3 hours in the sodium hydrate aqueous solution for being 5~30% in mass percent concentration, liner is rinsed 2 times with deionized water；
It is impregnated 2~3 hours in the ethanol water for being 90~99% in mass percent concentration again, liner is rinsed 2 times with deionized water,
It impregnates 3~6 hours in 90 DEG C of deionized waters, then is boiled 1~2 hour with deionized water, finally rinse liner with deionized water,
Until the difference of the pH value of flushing liquor is less than or equal to 0.5 pH unit twice in succession；Leaching container drying after cleaning is standby
With；
C, leaching agent is prepared：
The deionized water that conductivity is taken to be less than or equal to 150 μ S/m, the pH value for adjusting deionized water are 5~9（It may be used
Acetic acid adjust deionized water pH value for less than 7 and more than or equal to 5 or use ammonium hydroxide adjusting deionized water pH value for more than
7 and less than or equal to 9）, leaching agent is made；
D, leaching test and test：
It will（Simulation time actinium series nucleic）Fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, is consolidated according to fluor-apatite ceramics
Change surface area/leaching agent volume=10m of body-1Pour into leaching agent, control extraction temperature is 100~200 DEG C, pressure be 0.101~
1.554MPa leachate（Liquid i.e. in hydrothermal reaction kettle）PH value 5~9, extraction time 1 day, 3 days, 7 days, 10 days, 14
My god, 21 days, 28 days, 35 days, after 42 days, the conductivity of leachate is tested respectively using conductivity meter, then using inductive coupling
Plasma mass（Abbreviation ICP-MS）, inductively coupled plasma optical emission spectra（Abbreviation ICP-OES）And Atomic absorption
Spectrum（Abbreviation AAS）（Wait analysis means）Sm in leachate is tested respectively3+、Eu3+Or Gd3+Ion concentration；
E, it evaluates（Simulation time actinium series nucleic）The chemical stability of fluor-apatite ceramic solidification body：
With Sm in leachate3+、Eu3+Or Gd3+Ion concentration calculate the normalization leaching rate of samarium, europium or gadolinium element, normalizing
The calculation formula for changing leaching rate is as follows：LR=c·V/f·A·t, in formula：LRNormalization leaching rate for samarium, europium or gadolinium element
（Unit gm-2·d-1）,cFor Sm in leachate3+、Eu3+Or Gd3+Ion concentration（Unit g/m3）,VFor leachate volume（It is single
Position m3）,fMass percentage content for samarium, europium or gadolinium element in fluor-apatite ceramic solidification body（Unit wt.%）,AFor fluorine phosphorus
The surface area of lime stone ceramic solidification body（Unit m2）,tFor extraction time（Unit d）；Using X-ray diffraction（Abbreviation XRD）, the back of the body dissipate
Penetrate secondary electron image（Abbreviation BSE）, scanning electron microscope-X-ray energy spectrum（Abbreviation SEM-EDX）Analysis（Simulation time actinium series nucleic）Fluorine phosphorus
Object phase change before and after lime stone ceramic solidification body leaching test, with reference to the leachate conductivity variations before and after leaching test and leaching
The normalization leaching rate variation of samarium, europium or gadolinium element, overall merit in liquid（Simulation time actinium series nucleic）Fluor-apatite ceramic solidification
Chemical stability of the body under " heat, water, power, chemistry " coupling.
In above-described embodiment：The preparation method of polyvinyl alcohol colloidal sol described in step a is：By polyvinyl alcohol 8~16%, sweet
The percent mass ratio of oil 5~10%, absolute ethyl alcohol 2~5% and deionized water 77~85% takes each raw material；Deionized water is fallen
Enter in container, be heated to 90~95 DEG C, then under stiring, add in polyvinyl alcohol, after treating polyvinyl alcohol dissolving, add in sweet
Oil is stirred 10~adds absolute ethyl alcohol after twenty minutes, finally stirs 2~5 hours, that is, make at a temperature of 90~95 DEG C
Obtain polyvinyl alcohol colloidal sol.
The polyvinyl alcohol is the polyvinyl alcohol that the degree of polymerization can be 1750~2700；Polyvinyl alcohol molecule amount range can be with
It is 77000~118800, the concrete model of polyvinyl alcohol can be polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol
2499 and polyvinyl alcohol 2699；The manufacturing enterprise of polyvinyl alcohol has：Sinopharm Chemical Reagent Co., Ltd., the brilliant pure biochemistry in Shanghai
Science and Technology Co., Ltd., Sigma-Aldrich（Shanghai）Trade Co., Ltd etc..
In above-described embodiment 37~43：Polytetrafluoroethylene (PTFE) described in step b is that the degree of polymerization can be 5000~10000
Polytetrafluoroethylene (PTFE)；Polytetrafluoroethylene (PTFE) molecular weight ranges can be 500000~1000000, and the concrete model of polyvinyl alcohol can be
Polytetrafluoroethylene (PTFE) 5000, polytetrafluoroethylene (PTFE) 7500, polytetrafluoroethylene (PTFE) 10000；The manufacturing enterprise of polytetrafluoroethylene (PTFE) has：Shandong Eastern Mountain
High molecular material Co., Ltd, 3M China Co., Ltd., Sinopharm Chemical Reagent Co., Ltd., Sigma-Aldrich（On
Sea）Trade Co., Ltd etc..
In above-described embodiment 37~43：Acetic acid described in step c could alternatively be any one of oxalic acid, sulfuric acid, hydrochloric acid.
In above-described embodiment 37~43：With Ca described in step a2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For original
Material, according to chemical formula Ca10-3a/2MA a (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001
≤a≤3；It replaces with：With Ca2P2O7, CaF2, Na2CO3And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10- 2b MA b Na b (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤b≤3（Embodiment 37
In~43bRespectively：0.001、0.01、0.05、0.1、1、2、3）；It is other identical, it omits.
In above-described embodiment 37~43：With Ca described in step a2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For original
Material, according to chemical formula Ca10-3a/2MA a (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001
≤a≤3；It replaces with：With Ca2P2O7, CaF2, SiO2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-c MA c
(PO4)6-c (SiO4) c F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤c≤4（Embodiment 37
In~43cRespectively：0.001、0.01、0.1、1、2、3、4）；It is other identical, it omits.
With Ca described in step a in above-described embodiment 37~432P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For original
Material, according to chemical formula Ca10-3a/2MA a (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001
≤a≤3；It replaces with：With Ca2P2O7, CaF2, Na2CO3, SiO2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula
Ca10-3d MA2d Na d (PO4)6-d (SiO4) d F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤d
≤2（In embodiment 37~43dRespectively：0.001、0.01、0.05、0.1、1、1.5、2）；It is other identical, it omits.
In above-described embodiment：Used each raw material is commercial product.
In above-described embodiment：In used percentage, especially not dated, it is quality（Weight）Percentage or
Well known to a person skilled in the art percentages；The quality（Weight）Part can be gram or kilogram.
In above-described embodiment：Technological parameter (temperature, time, concentration, the degree of polymerization, molecular weight etc.) and each group in each step
It is range to divide with numerical quantity etc., and any point is applicable.
The technology contents being not specifically delineated in the content of present invention and above-described embodiment are compared with technology.
Can it implement the present invention is not limited to above-described embodiment, described in the content of present invention and with the good result.
Claims (4)
1. a kind of chemical stability evaluation method of fluor-apatite ceramic solidification body, it is characterized in that being completed by following steps：
A, fluor-apatite ceramic solidification body is prepared：
With Ca2P2O7, CaF2, Na2CO3And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-2b MA b Na b (PO4)6F2It weighs each component raw material and carries out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤b≤3；
According to the mass percent of dispensing 35~65%, abrading-ball 15~55%, absolute ethyl alcohol or/and water 5~50%, it is mixed in planet
It is ground 2~5 hours in formula ball mill, the mixture drying of acquisition, you can the powder dried adds in the powder matter of drying
The polyvinyl alcohol colloidal sol of amount 3~10%, then mixing granulation is carried out using sieve, take minus mesh and 170~270 mesh of 12~25 mesh
Oversize be granulation material；Granulation material is fitted into steel die, is suppressed on a hydraulic press using the pressure of 8~35MPa
Then molding carries out cold isostatic compaction on cold isostatic press using the pressure of 80~260MPa, obtain molding blank；
Molding blank is heat-treated 5~10 hours at a temperature of 400~600 DEG C and carries out dumping, then the green body after dumping is put into Vacuum Heat
It presses in sintering furnace, vacuum hotpressing is carried out under conditions of 1000~1200 DEG C of temperature, 15~35MPa of pressure, 1~10Pa of vacuum degree
Sintering 2~12 hours, obtains fluor-apatite ceramic solidification body；
The preparation method of the polyvinyl alcohol colloidal sol is：By polyvinyl alcohol 8~16%, glycerine 5~10%, absolute ethyl alcohol 2~5%, with
And the percent mass ratio of deionized water 77~85% takes each raw material；Deionized water is poured into container, is heated to 90~95 DEG C,
Then under stiring, polyvinyl alcohol is added in, after treating polyvinyl alcohol dissolving, adds in glycerine, it is stirred 10~after twenty minutes again
Absolute ethyl alcohol is added in, is finally stirred 2~5 hours at a temperature of 90~95 DEG C, obtains polyvinyl alcohol colloidal sol；
The polyvinyl alcohol is the polyvinyl alcohol that the degree of polymerization is 1750~2700；
B, container is leached in cleaning：
Enclosure material is used to be used as stainless steel, the hydrothermal reaction kettle that liner material is polytetrafluoroethylene (PTFE) and leach container, by hydro-thermal
It impregnates 2~3 hours in the aqueous solution of nitric acid that the liner of reaction kettle is 0.1~3mol/L in molar concentration, is rinsed with deionized water
Then liner 2 times impregnates 2~3 hours in sodium hydrate aqueous solution of the mass percent concentration for 5~30%, uses deionized water
Rinse liner 2 times；It is impregnated 2~3 hours in the ethanol water for being 90~99% in mass percent concentration again, uses deionized water
Rinse liner 2 times, impregnated 3~6 hours in 90 DEG C of deionized waters, then boiled 1~2 hour with deionized water, finally spend from
Sub- water rinses liner, until the difference of the pH value of flushing liquor is less than or equal to 0.5 pH unit twice in succession；By the leaching after cleaning
Go out container to be dried for standby；
The polytetrafluoroethylene (PTFE) is the polytetrafluoroethylene (PTFE) that the degree of polymerization is 5000~10000；
C, leaching agent is prepared：
The deionized water that conductivity is taken to be less than or equal to 150 μ S/m, the pH value for adjusting deionized water are 5~9, and leaching agent is made；
D, leaching test and test：
Fluorine phosphorus ash ceramic solidification body is put into hydrothermal reaction kettle, according to surface area/leaching agent of fluor-apatite ceramic solidification body
Volume=10m-1Pour into leaching agent, control extraction temperature is 100~200 DEG C, pressure is 0.101~1.554MPa, pH of leaching solution
5~9, after extraction time 1 day, 3 days, 7 days, 10 days, 14 days, 21 days, 28 days, 35 days, 42 days, surveyed respectively using conductivity meter
Try leachate conductivity, then using inductivity coupled plasma mass spectrometry, inductively coupled plasma optical emission spectra and
Atomic absorption spectrum tests Sm in leachate respectively3+、Eu3+Or Gd3+Ion concentration；
E, the chemical stability of fluor-apatite ceramic solidification body is evaluated：
With Sm in leachate3+、Eu3+Or Gd3+Ion concentration calculate the normalization leaching rate of samarium, europium or gadolinium element, normalization leaching
The calculation formula of extracting rate is as follows：LR=c·V/f·A·t, in formula：LRFor the normalization leaching rate of samarium, europium or gadolinium element,cFor leaching
Go out Sm in liquid3+、Eu3+Or Gd3+Ion concentration,VFor leachate volume,fFor samarium, europium or gadolinium in fluor-apatite ceramic solidification body
The mass percentage content of element,AFor the surface area of fluor-apatite ceramic solidification body,tFor extraction time；Using X-ray diffraction,
Object phase transformation before and after back scattering secondary electron image, scanned topographic map fluor-apatite ceramic solidification body leaching test
Change, become with reference to the normalization leaching rate of samarium, europium or gadolinium element in the leachate conductivity variations before and after leaching test and leachate
Change, chemical stability of the overall merit fluor-apatite ceramic solidification body under heat, water, power, chemical coupling effect.
2. the chemical stability evaluation method of fluor-apatite ceramic solidification body as described in claim 1, it is characterized in that：In step c
The acid of the pH value for adjusting deionized water is any one of acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, adjusts the pH of deionized water
The alkali of value is ammonium hydroxide.
3. the chemical stability evaluation method of fluor-apatite ceramic solidification body as described in claims 1 or 2, it is characterized in that：Step a
Described in Ca2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-3a/2MA a (PO4)6F2Claim
Each component raw material is taken to carry out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤a≤3；It replaces with：With Ca2P2O7, CaF2, SiO2,
And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-c MA c (PO4)6-c (SiO4) c F2Weigh the progress of each component raw material
Dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤c≤4。
4. the chemical stability evaluation method of fluor-apatite ceramic solidification body as described in claims 1 or 2, it is characterized in that：Step a
Described in Ca2P2O7, CaF2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-3a/2MA a (PO4)6F2Claim
Each component raw material is taken to carry out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤a≤3；It replaces with：With Ca2P2O7, CaF2,
Na2CO3, SiO2And Sm2O3、Eu2O3Or Gd2O3For raw material, according to chemical formula Ca10-3d MA2d Na d (PO4)6-d (SiO4) d F2Claim
Each component raw material is taken to carry out dispensing, in formula：MA be Sm, Eu or Gd, 0.001≤d≤2。
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