CN107381613B - A kind of synthetic method of single phase cubic body fluorite - Google Patents

A kind of synthetic method of single phase cubic body fluorite Download PDF

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CN107381613B
CN107381613B CN201710732466.4A CN201710732466A CN107381613B CN 107381613 B CN107381613 B CN 107381613B CN 201710732466 A CN201710732466 A CN 201710732466A CN 107381613 B CN107381613 B CN 107381613B
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soluble
fluoride
fluorite
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certain time
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CN107381613A (en
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匡敬忠
黄哲誉
刘鹏飞
黄震
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Jiangxi University of Science and Technology
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Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/22—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention discloses a kind of preparation methods of single phase cubic body fluorite, comprising the following steps: step 1: at normal temperature, soluble fluoride and soluble calcium salt being configured to the solution of certain mole of solubility with deionized water；Step 2: enuatrol or lauryl sodium sulfate are dissolved according to a certain percentage in soluble fluoride solution；Step 3: controlling soluble calcium salt using peristaltic pump respectively and has dissolved the addition flow of the soluble fluoride of enuatrol, and certain power ultrasonic processing mixed solution certain time is used when controlling flow, reacts it under ultrasonication；Step 4: the mixed solution product after ultrasonic treatment is continued into mechanical stirring certain time, continues to react, then be aged certain time, obtains reaction precipitate；Step 5: it can be obtained fluorite after the reaction precipitate that step 4 obtains is filtered, washs and is dried.Single phase cubic body fluorite good dispersion prepared by the present invention, avoids agglomeration.

Description

A kind of synthetic method of single phase cubic body fluorite
Technical field
The invention belongs to inorganic compounds and mineral preparation technical field, and in particular to a kind of conjunction of single phase cubic body fluorite At method.
Background technique
Fluorite is a kind of excellent optical material, has good chemical stability and optical clarity.Calcirm-fluoride it is saturating Optical range is wide, and from deep ultraviolet until near-infrared (0.125~10 μm), low phonon energy can inhibit the noradiative transition of electronics It moves, therefore is very suitable to do the basis material of various optical devices and solid state laser.
Fluorite is to apply and study very extensive alkali earth metal fluoride, there is superior optical property, the company of can be used as The buffer layer of semiconductor is connect, and has good F-Ionic conductivity.CaF2It is the F- ionic conduction Journal of Sex Research for carrying out nano fluoride Main material, the method for synthetising nanometre powder body mainly has at present: 1) chemical vapour deposition technique；2) vapor condensation method；3) colloidal sol Gel method；4) microemulsion method；5) hydro-thermal method etc..
The CaF of the minimum 60nm of average grain diameter has been made with microemulsion method for stone Chun-shan Mountain etc.2Nano-powder, Li Yadong etc. is with first The method of precipitating and then hydro-thermal process is prepared for CaF2, obtain the precipitating that partial size is greater than 100 nanometers, the grain of two methods preparation Diameter is relatively large.S.tark is prepared for CaF with flame method2Etc. a variety of alkali earth metal fluoride nano-powders.Ye Jin etc. is used CTAB/ water/hexamethylene/n-amyl alcohol microemulsion system is prepared for SrF2:Eu3+ nano-powder.Aubry P and Bensalah A etc. is used Reverse microemulsion process has synthesized average grain diameter in the CaF of 20nm or so2Nano-powder.Wang Jianshe etc. uses formaldehyde conduct Solvent has synthesized Eu3+, Tb3+ doping CaF2Nanocrystal.
The fluorite of existing method preparation is mostly spherical shape, and characteristic parameter is difficult to the problems such as meeting industrial requirement, and production technology Complexity, condition are harsh, it is difficult to industrialized production and application.There is presently no mild condition, strong operability, the systems of favorable repeatability The maturation method of standby cube fluorite.
Summary of the invention
The invention aims to solve the preparation of cube fluorite and easily aggregation, and provide a kind of single-phase The preparation method of cube fluorite.
The present invention is for cube fluorite synthesis technology complexity, condition harshness, high production cost, the mostly skills such as spheric granules Deficiency in art is proposed one kind using soluble fluoride and soluble calcium salt as raw material, is synthesized using ultrasonic chemical process vertical The method of cube fluorite.It is synthesis technology simple possible, environmentally protective, there is preferable environmental benefit and economic benefit.
To reach above-mentioned technical effect, the present invention provides following technical scheme, the specific steps are as follows:
A kind of preparation method of single phase cubic body fluorite, comprising the following steps:
Step 1: at normal temperature, with deionized water by soluble fluoride and soluble calcium salt be configured to certain mole it is molten The solution of degree；
Step 2: enuatrol or lauryl sodium sulfate are dissolved according to a certain percentage in soluble fluoride solution；
Step 3: controlling soluble calcium salt using peristaltic pump respectively and has dissolved the addition of the soluble fluoride of enuatrol Flow uses certain power ultrasonic processing mixed solution certain time when controlling flow, carries out it under ultrasonication instead It answers；
Step 4: continuing mechanical stirring certain time for the mixed solution product after ultrasonic treatment, continue to react, then It is aged certain time, obtains reaction precipitate；
Step 5: it can be obtained fluorite after the reaction precipitate that step 4 obtains is filtered, washs and is dried.
According to the above scheme, soluble fluoride described in step 1 are as follows: sodium fluoride, potassium fluoride and ammonium fluoride etc.；It is solvable Property calcium salt are as follows: calcium chloride and calcium nitrate, certain mole of solubility are as follows: sodium fluoride, potassium fluoride, ammonium fluoride, calcium chloride and calcium nitrate are 0.1mol/L-1.0mol/L, mole solubility of fluorine ion are 2 times of calcium ion mole solubility；
According to the above scheme, enuatrol described in step 2 or lauryl sodium sulfate be according to a certain percentage are as follows: 0.1%- The quality percentage solubility of 6%wt fluorine.
According to the above scheme, certain power is being used in coutroi velocity described in step 3 are as follows: 500-1800w, ultrasonic wave Processing mixed solution certain time is 10min-60min；Soluble calcium salt and soluble carbonate salt are controlled using peristaltic pump respectively Flow be 6ml/min-60ml/min；It with ultrasonication mixed solution certain time is being 1min- in coutroi velocity 30min；
According to the above scheme, mechanical stirring certain time described in step 4 are as follows: 10min-180min；
According to the above scheme, it is aged certain time again described in step 4 are as follows: 10min-60min；
The beneficial effects of the present invention are: 1), the present invention pass through the flow of control soluble calcium salt and soluble fluoride, Being added simultaneously has peptizaiton, the enuatrol of chelation and lauryl sodium sulfate, and fluorite crystals is made to obtain stablizing sufficiently Growth, avoid agglomeration.It can be very good the pattern of control fluorite simultaneously, obtain the fluorite of single phase cubic bodily form looks, and And its characteristic parameter is uniform, purity is high.2) present invention process process is short, environmentally protective, environmental benefit and remarkable in economical benefits, fits Close large-scale industrial production.
Detailed description of the invention
The XRD diagram of fluorite prepared by Fig. 1 embodiment of the present invention 1；
The SEM figure of fluorite prepared by Fig. 2 embodiment of the present invention 1；
The XRD diagram of fluorite prepared by Fig. 3 embodiment of the present invention 2；
The SEM figure of fluorite prepared by Fig. 4 embodiment of the present invention 2；
The XRD diagram of fluorite prepared by Fig. 5 embodiment of the present invention 3；
The SEM figure of fluorite prepared by Fig. 6 embodiment of the present invention 5；
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
At normal temperature, with ultrapure water compound concentration is 0.8mol/L respectively NaF and 0.4mol/LCa (NO3)2Solution, will The enuatrol of 1%wt is dissolved into Fluorinse, controls NaF solution and Ca (NO respectively with peristaltic pump3)2The flow of solution adds Enter into reactor, carried out in the reactor in coutroi velocity ultrasonication certain time, the flow of two kinds of solution is 6ml/min, ultrasonic treatment time 17.5min, operating power 900w, after ultrasonication stops, subsequent solution is with same Flow is added in reactor, until all adding, then with 10min is aged again after magnetic stirrer 2h, by reaction product mistake Sediment is put into air dry oven drying, drying temperature is 100 DEG C, drying time with milli-Q water repeatedly to neutrality by filter 12h finally obtains required product.
Fig. 3 is the XRD diagram of product synthesized by the present embodiment, and as seen from the figure, 2 θ of the angle of diffraction is located at 2 θ of the angle of diffraction and is located at 28.36 °, 47.08 °, 55.86 °, 68.76 °, 75.92 ° there is apparent diffraction maximum, this and fluorite standard Pdf card (NO.77-2094) data result is consistent.Occur in figure without miscellaneous peak, shows to synthesize fluorite purity is high.Peak height and sharp, it is shown that Fluorite crystallinity is good.
Fig. 4 is the SEM figure of product prepared by the present embodiment, and fluorite is cube as seen from the figure, and cube side length is 100- 300nm, although crystal size is not very uniformly, good dispersion, plane of crystal is smooth, and few surface defects illustrate fluorite crystals It grows sufficiently complete.
Embodiment 2
At normal temperature, with the ultrapure water NaF and 0.4mol/L Ca (NO that compound concentration is 0.8mol/L respectively3)2Solution, will The lauryl sodium sulfate of 1%wt is dissolved into Fluorinse, controls NaF solution and Ca (NO respectively with peristaltic pump3)2Solution Flow be added in reactor, carried out in the reactor in coutroi velocity ultrasonication certain time, two kinds of solution Flow is 6ml/min, ultrasonic treatment time 17.5min, operating power 900w.After ultrasonication stops, subsequent solution It is added in reactor with same flow, until all adding, then with 10min is aged again after magnetic stirrer 2h, will be reacted Sediment is put into air dry oven drying, drying temperature is 100 DEG C, is done with milli-Q water repeatedly to neutrality by product filtering Dry time 12h, finally obtains required product.
Fig. 3 be the present embodiment synthesized by product XRD diagram, as seen from the figure, 2 θ of the angle of diffraction be located at 28.36 °, 47.08 °, 55.86 °, 68.76 °, 75.92 ° nearby there is apparent diffraction maximum, this and fluorite standard Pdf card (NO.77-2094) count It is consistent according to result.No miscellaneous peak occurs, and shows fluorite purity is high, peak height and sharp, it is shown that fluorite crystallinity is good.
Fig. 4 is the SEM figure of product prepared by the present embodiment, and fluorite is cube as seen from the figure, and cube side length is 50- 500nm, crystal size is uneven, but good dispersion, and plane of crystal is smooth, few surface defects, and fluorite crystals growth is abundant.
Embodiment 3
At normal temperature, with the ultrapure water NaF and 0.4mol/L Ca (NO that compound concentration is 0.8mol/L respectively3)2Solution, will The enuatrol of 5%wt is dissolved into Fluorinse, controls NaF solution and Ca (NO respectively with peristaltic pump3)2The flow of solution adds Enter into reactor, carried out in the reactor in coutroi velocity ultrasonication certain time, the flow of two kinds of solution is 3ml/min, ultrasonic treatment time 34min, operating power 600w.After ultrasonication stops, subsequent solution is equally to flow Amount is added in reactor, until all adding, then with 10min is aged again after magnetic stirrer 2h, reaction product is filtered, With milli-Q water repeatedly to neutrality, sediment is put into air dry oven drying, drying temperature is 100 DEG C, drying time 12h finally obtains required product.
Embodiment 4
At normal temperature, with the ultrapure water NaF and 0.1mol/L Ca (NO that compound concentration is 0.2mol/L respectively3)2Solution, will The lauryl sodium sulfate of 3%wt is dissolved into Fluorinse, controls NaF solution and Ca (NO respectively with peristaltic pump3)2Solution Flow be added in reactor, carried out in the reactor in coutroi velocity ultrasonication certain time, two kinds of solution Flow is 12ml/min, ultrasonic treatment time 18min, operating power 1800w.After ultrasonication stops, subsequent solution It is added in reactor with same flow, until all adding, then with 10min is aged again after magnetic stirrer 2h, will be reacted Sediment is put into air dry oven drying, drying temperature is 100 DEG C, is done with milli-Q water repeatedly to neutrality by product filtering Dry time 12h, finally obtains required product.
Embodiment 5
At normal temperature, with the ultrapure water KF and 0.5mol/L Ca (NO that compound concentration is 1.0mol/L respectively3)2Solution, will The enuatrol of 6%wt is dissolved into potassium fluoride solution, controls KF solution and Ca (NO respectively with peristaltic pump3)2The flow of solution is added It into reactor, is carried out in the reactor in coutroi velocity ultrasonication certain time, the flow of two kinds of solution is 3ml/ Min, ultrasonic treatment time 50min, operating power 500w.After ultrasonication stops, subsequent solution is added with same flow Enter in reactor, until all adding, then with 20min is aged again after magnetic stirrer 2h, reaction product is filtered, with super Sediment repeatedly to neutrality, is put into air dry oven drying, drying temperature is 100 DEG C, drying time 12h, most by pure water Required product is obtained eventually.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description, And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.

Claims (1)

1. a kind of preparation method of single phase cubic body fluorite, which comprises the following steps:
Step 1: at normal temperature, soluble fluoride and soluble calcium salt are configured to certain mole of solubility with deionized water Solution；The soluble fluoride are as follows: sodium fluoride, potassium fluoride and ammonium fluoride；Soluble calcium salt are as follows: calcium chloride and calcium nitrate, Certain mole of solubility are as follows: sodium fluoride, potassium fluoride, ammonium fluoride, calcium chloride and calcium nitrate are 0.1mol/L-1.0mol/L, fluorine ion Mole solubility be 2 times of calcium ion mole solubility；
Step 2: enuatrol or lauryl sodium sulfate are dissolved according to a certain percentage in soluble fluoride solution；It is described Enuatrol or lauryl sodium sulfate according to a certain percentage are as follows: the quality percentage solubility of 0.1%-6%wt fluorine；
Step 3: controlling soluble calcium salt using peristaltic pump respectively and has dissolved the addition stream of the soluble fluoride of enuatrol Amount uses certain power ultrasonic processing mixed solution certain time when controlling flow, reacts it under ultrasonication； Described is using certain power in coutroi velocity are as follows: 500-1800W, ultrasonication mixed solution certain time are 10min- 60min；Peristaltic pump is used to control the flow of soluble calcium salt and soluble carbonate salt respectively as 6mL/min-60mL/min；On side Coutroi velocity side is 1min-30min with ultrasonication mixed solution certain time；
Step 4: the mixed solution product after ultrasonic treatment is continued into mechanical stirring certain time, continues to react, then be aged Certain time obtains reaction precipitate；The mechanical stirring certain time are as follows: 10min-180min；Described is aged one again It fixes time are as follows: 10min-60min；
Step 5: it can be obtained fluorite after the reaction precipitate that step 4 obtains is filtered, washs and is dried.
CN201710732466.4A 2017-08-24 2017-08-24 A kind of synthetic method of single phase cubic body fluorite Active CN107381613B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2349147A (en) * 1999-04-19 2000-10-25 Univ Sheffield Doped calcium fluoride precipitate
JP2009057250A (en) * 2007-08-31 2009-03-19 Univ Of Tokyo Purification method of fluorite
CN101885505A (en) * 2010-08-18 2010-11-17 中国科学院长春应用化学研究所 Method for preparing calcium fluoride hollow nanospheres
CN102583486A (en) * 2012-03-09 2012-07-18 山东轻工业学院 Preparation method of nano calcium fluoride for self-lubricating tool material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2349147A (en) * 1999-04-19 2000-10-25 Univ Sheffield Doped calcium fluoride precipitate
JP2009057250A (en) * 2007-08-31 2009-03-19 Univ Of Tokyo Purification method of fluorite
CN101885505A (en) * 2010-08-18 2010-11-17 中国科学院长春应用化学研究所 Method for preparing calcium fluoride hollow nanospheres
CN102583486A (en) * 2012-03-09 2012-07-18 山东轻工业学院 Preparation method of nano calcium fluoride for self-lubricating tool material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"超声化学法制备不同形貌的CaF2微米晶";王淼等;《无机化学学报》;20120131;第28卷(第1期);第185-190页

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