CN115192465A - CaF 2 @SiO 2 Method for producing nanoparticles or clusters - Google Patents
CaF 2 @SiO 2 Method for producing nanoparticles or clusters Download PDFInfo
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- CN115192465A CN115192465A CN202110378504.7A CN202110378504A CN115192465A CN 115192465 A CN115192465 A CN 115192465A CN 202110378504 A CN202110378504 A CN 202110378504A CN 115192465 A CN115192465 A CN 115192465A
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- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 127
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 98
- 229910004261 CaF 2 Inorganic materials 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 50
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000007921 spray Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 29
- 208000002925 dental caries Diseases 0.000 abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 abstract description 14
- 239000011737 fluorine Substances 0.000 abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011258 core-shell material Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 239000004851 dental resin Substances 0.000 abstract description 3
- 230000002459 sustained effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract 1
- 239000000805 composite resin Substances 0.000 description 36
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 230000008439 repair process Effects 0.000 description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 238000000016 photochemical curing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000013329 compounding Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 210000000214 mouth Anatomy 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- -1 fluoride ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003178 glass ionomer cement Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000003578 releasing effect Effects 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011350 dental composite resin Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 210000004268 dentin Anatomy 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004924 electrostatic deposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/76—Fillers comprising silicon-containing compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
- A61K6/17—Particle size
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
Abstract
The invention discloses a CaF 2 @SiO 2 A method for preparing nanoparticles or clusters, comprising the steps of: s1, dispersing calcium fluoride nano particles in deionized water, ultrasonically dispersing uniformly, adding absolute ethyl alcohol, and adding a pH regulator to regulate the pH value; s2, adding a silicon source, stirring at the temperature of 10-90 ℃ for 1-24h, carrying out suction filtration, and carrying out rotary evaporation drying to obtain CaF 2 @SiO 2 And (3) nanoparticles. The prepared nano particles are of a core-shell structure, and the average particle size is 12-23nm. And (3) drying the prepared nano particles by spraying to obtain spherical clusters with uniform appearance, narrow particle size distribution and average particle size of 3 mu m. CaF prepared by the invention 2 @SiO 2 Nanoparticles or clusters as inorganic fillersThe material can not only enhance the mechanical strength of dental resin, but also provide sustained and stable fluorine release, effectively prevent dental caries and inhibit secondary caries.
Description
Technical Field
The invention belongs to the field of dental repair resin, and particularly relates to CaF for dental repair resin 2 @SiO 2 A method for preparing nanoparticles or clusters.
Background
Secondary caries and restorative fracture are the two most common problems in dental restorations, with marginal caries repair being a common cause of replacement restorations, accounting for 50-70% of all restorations. According to the data of the world health organization, 60-90% of school-age children and most adults are suffering from dental caries in most industrialized countries. There is evidence that sustained release of fluoride ions is of substantial benefit for dental restoration, as fluorine can enrich the surrounding enamel or dentin against secondary caries. Fluoride-releasing repair materials include glass ionomers, resin-modified glass ionomers, and resin composites. However, glass ionomer and resin-modified glass ionomer materials have poor mechanical properties and are liable to cause repair fracture, and thus, the range of use thereof is greatly limited.
The resin composite consists of an organic resin matrix, a surface treated inorganic filler and an initiator system. In the mid-1960 s, polymeric dental restorative composites were first introduced to restore anterior teeth. The popularity of using light-cured resin composites has increased rapidly due to their aesthetics, biocompatibility and convenient clinical handling. The silica used as the inorganic filler can reduce the polymerization volume shrinkage of the material and improve the mechanical property of the material, thereby reducing the repairability fracture. In reducing the incidence of secondary caries, the release of fluorine promotes the re-precipitation of calcium ions in the mouth, which in turn promotes remineralization of the teeth. However, the low calcium concentration in the mouth has a limited driving force for calcium fluoride formation, and typically only very small deposits of calcium fluoride are formed after conventional fluoride rinsing, and therefore the introduction of calcium fluoride nanoparticles in the mouth repair resin is effective in inhibiting secondary caries. However, dental composite resins containing calcium fluoride have a high initial fluorine release rate and a low long-term fluorine release rate, which may result in unstable release of fluoride.
Mixing CaF 2 @SiO 2 The introduction of the core-shell structure particles into the dental repair resin can not only effectively control the release rate of the fluorine ions, but also simultaneously dissolveSolving the two problems of secondary caries and repairing fracture. At present, caF is not yet available 2 @SiO 2 The core-shell structure particles are used as related reports of dental repair resin fillers. In the chinese patent application publication No. CN109199873A, a method for preparing an inorganic nanoparticle cluster for dental repair resin is disclosed, in which a spray dryer is used to mix and spray dry respective modifications of a plurality of particles, so that the obtained cluster has a uniform morphology and is well monodisperse in a resin matrix. However, this method does not silica coat the particles and the particles do not have fluorine releasing properties. H.H.K.xu et al used a spray dryer (two material feeds) to prepare calcium fluoride nanoparticles for dental repair (Xu, H.H.K.; moreau, J.L.; sun, L.; chow, L.C.Novel CaF) 2 nanocomposite with high strength and fluoride ion release[J]Journal of dental Research,2010,89, 739-745) by passing a calcium hydroxide solution and an ammonium fluoride solution into a spray dryer at the same speed using a two-liquid phase nozzle, and collecting calcium fluoride generated by the reaction by electrostatic deposition, the prepared calcium fluoride composite resin having a long-term fluorine release property. However, the fluorine release rate is greatly reduced in the early stage, and the incorporation of calcium fluoride causes the mechanical properties of the composite resin to be reduced. In the Chinese invention patent application document with the publication number of CN110436942A, the preparation process of the silicon dioxide coated nano flaky calcium fluoride composite powder is disclosed, wet gel obtained after reaction is added into a mixed solution of n-butanol and distilled water, moisture is removed under an oil bath at 93 ℃, then the powder is dried under heating of the oil bath at 117 ℃, and the obtained composite powder is added into a metal or ceramic matrix, so that the mechanical property of the material can not be reduced and the lubricating property of the material can be improved.
Aiming at the existing defects, the CaF which has simple preparation process, low energy consumption, short reaction time, controllable release rate of fluorine ions and good mechanical property and can be used for dental repair needs to be provided 2 @SiO 2 And (4) filling.
Disclosure of Invention
Hair brushThe first technical problem to be solved is to provide a CaF for dental restoration resin 2 @SiO 2 A method for preparing nanoparticles. The nano particles prepared by the preparation method are used as inorganic filler, have the average particle size of 19nm, are in a core-shell structure, and are used as the oral cavity repair resin inorganic filler, so that the better mechanical strength of dental resin can be ensured, the sustained and stable fluorine release amount can be provided, the dental caries can be effectively prevented, and the secondary caries can be inhibited.
The second technical problem to be solved by the invention is to provide CaF for dental repair resin 2 @SiO 2 A method for preparing a cluster. The cluster prepared by the preparation method is uniform in appearance, spherical, narrow in particle size distribution, 3 mu m in average particle size, and free of modification in the preparation process. As an inorganic filler, it can enhance the mechanical strength of dental resins and provide a stable and sustained fluorine release amount; can effectively prevent dental caries and inhibit secondary caries, and is helpful for inhibiting two problems of repairing fracture and secondary caries commonly seen in dental repair.
In order to solve the first technical problem, the invention adopts the following technical scheme:
CaF for dental restoration 2 @SiO 2 The preparation method of the nano-particles comprises the following steps:
s1, dispersing calcium fluoride nano particles in deionized water, uniformly dispersing by ultrasonic, adding absolute ethyl alcohol, and adding a pH regulator to regulate the pH;
s2, adding a silicon source, stirring at the temperature of 10-90 ℃ for 1-24h, carrying out suction filtration, and carrying out rotary evaporation drying to obtain CaF 2 @SiO 2 And (3) nanoparticles.
As a further improvement of the technical scheme, in the step S1, the solid content of the calcium fluoride is 1-10%; preferably, the calcium fluoride has a solids content of 2 to 8%.
Preferably, in step S1, the time for ultrasonic dispersion is 20-40min.
Preferably, in step S1, the volume ratio of the deionized water to the absolute ethyl alcohol is 1; more preferably, the volume ratio of deionized water to absolute ethanol is 1.
Preferably, in step S1, the pH regulator is one or more of ammonia water, sodium hydroxide and hydrochloric acid.
Preferably, in step S1, the pH is 8-12.
Preferably, in step S2, the silicon source is selected from one or more of ethyl orthosilicate, sodium silicate and methyl orthosilicate.
As a further improvement of the technical scheme, in the step S2, the dosage of the silicon source is determined according to the coating amount of the product silicon dioxide, and the mass ratio of the silicon dioxide to the calcium fluoride is 0.06.
Preferably, in step S2, the stirring temperature is 20-70 ℃ and the stirring time is 2-13h.
Preferably, in the step S2, the rotary evaporation drying temperature is 10-90 ℃, and the time is 30-360 min; more preferably, the rotary evaporation drying temperature is 20-70 deg.C, and the time is 45-240 min.
In order to solve the second technical problem, the invention adopts the following technical scheme:
CaF for dental restoration 2 @SiO 2 The preparation method of the cluster body comprises the following steps:
s1, dispersing calcium fluoride nano particles in deionized water, ultrasonically dispersing uniformly, adding absolute ethyl alcohol, and adding a pH regulator to regulate the pH value;
s2, adding a silicon source, stirring at the temperature of 10-90 ℃ for 1-24h, carrying out suction filtration, and carrying out rotary evaporation drying to obtain CaF 2 @SiO 2 A nanoparticle;
s3, preparing CaF 2 @SiO 2 Dispersing the nanoparticles in a medium, and ultrasonically dispersing to form CaF 2 @SiO 2 A nanodispersion;
s4, preparing CaF in the step S3 2 @SiO 2 Introducing the nano dispersion into a spray dryer for spray drying to obtain CaF 2 @SiO 2 A cluster intermediate;
s5, adding the CaF prepared in the step S4 2 @SiO 2 Calcining the cluster body at the temperature of 300-900 ℃ for 1-12 ℃ to obtain CaF 2 @SiO 2 And (3) clustering bodies.
As a further improvement of the technical scheme, in the step S1, the solid content of the calcium fluoride is 1-10%; preferably, the calcium fluoride has a solids content of 2-8%.
Preferably, in step S1, the time for ultrasonic dispersion is 20-40min.
Preferably, in step S1, the volume ratio of the deionized water to the absolute ethyl alcohol is 1; more preferably, the volume ratio of deionized water to absolute ethanol is 1.
Preferably, in step S1, the pH regulator is one or more of ammonia water, sodium hydroxide and hydrochloric acid.
Preferably, in step S1, the pH is 8 to 12.
Preferably, in step S2, the silicon source is selected from one or more of ethyl orthosilicate, sodium silicate and methyl orthosilicate.
As a further improvement of the technical scheme, in the step S2, the dosage of the silicon source is determined according to the coating amount of the product silicon dioxide, and the mass ratio of the silicon dioxide to the calcium fluoride is 0.06.
Preferably, in step S2, the stirring temperature is 20 to 70 ℃ and the stirring time is 2 to 13 hours.
Preferably, in the step S2, the rotary evaporation drying temperature is 10-90 ℃, and the time is 30-360 min; more preferably, the rotary evaporation drying temperature is 20-70 deg.C, and the time is 45-240 min.
As a further improvement of the technical solution, in step S3, the medium is selected from one or more of water, methanol, ethanol and propanol.
Preferably, in step S3, caF for spray drying 2 @SiO 2 The solid content of the nano dispersion is 1-15%; preferably, the solids content is 2-8%.
As a further improvement of the technical scheme, in step S4, caF is pumped by a peristaltic pump 2 @SiO 2 Introducing the nano dispersion into a spray dryer, wherein the feeding speed is 0.1-1L/h; preferably, the feed rate is 0.2-0.9L/h.
Preferably, in step S4, the temperature at the nozzle during spray drying is 80-160 ℃; preferably, the temperature at the nozzle is 90-140 ℃.
Preferably, in the step S4, the gas speed of the spray head in the spray drying process is 300-650L/h; preferably, the gas velocity of the spray head is 400-500L/h.
As a further improvement of the technical solution, preferably, in step S5, the temperature of the calcination is 400 to 700 ℃.
Preferably, in step S5, the calcination time is 3-9h.
Any range recited herein is intended to include any and all subranges between the endpoints and any subrange between the endpoints or any subrange between the endpoints.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention does not need high temperature and high pressure, has mild process conditions and low cost.
2. CaF prepared by the invention 2 @SiO 2 The nano particles and the cluster body do not need to be modified, so the method is safe and environment-friendly and can be applied to oral repair.
3. CaF prepared by the invention 2 @SiO 2 The nano particles and the cluster are used as fillers, and the obtained resin compound has excellent mechanical property and fluorine release slow-control property.
4. The invention has simple process, short reaction time, low energy consumption and high production efficiency.
Drawings
The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings
FIG. 1 shows CaF prepared in example 1 2 @50％SiO 2 Transmission Electron Microscopy (TEM) images of nanoparticles.
FIG. 2 shows CaF prepared in example 1 2 @50％SiO 2 X-ray diffraction pattern of the nanoparticles.
FIG. 3 shows CaF prepared in example 1 2 @50％SiO 2 Nanoparticle composite resin and CaF 2 Graph comparing the fluoride ion release rates of the nanoparticle composite resins.
FIG. 4 shows CaF prepared in example 2 2 @50％SiO 2 Scanning Electron Microscope (SEM) images of the clusters.
FIG. 5 shows a calcium fluoride cluster composite resin and CaF prepared in example 2 2 @50％SiO 2 Comparative graph of mechanical properties of the cluster composite resin.
FIG. 6 shows CaF prepared in example 2 2 @50％SiO 2 SEM cross-sectional view of the cluster composite resin.
FIG. 7 shows CaF prepared in example 3 2 @20％SiO 2 TEM images of nanoparticles.
FIG. 8 is CaF prepared in example 5 2 @60％SiO 2 TEM images of nanoparticles.
FIG. 9 is an SEM photograph of the product obtained in comparative example 4.
FIG. 10 is an SEM photograph of the product obtained in comparative example 6.
FIG. 11 is an SEM photograph of the product obtained in comparative example 7.
FIG. 12 shows CaF obtained in comparative example 11 2 @50SiO 2 SEM cross-sectional view of the cluster composite resin.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
As one aspect of the invention, the invention is a CaF for dental restoration 2 @SiO 2 The preparation method of the nano-particles comprises the following steps:
s1, dispersing calcium fluoride nano particles in deionized water, ultrasonically dispersing uniformly, adding absolute ethyl alcohol, and adding a pH regulator to regulate the pH value;
s2, adding a silicon source, stirring at the temperature of 10-90 ℃ for 1-24h, carrying out suction filtration, and carrying out rotary evaporation drying to obtain CaF 2 @SiO 2 And (3) nanoparticles.
According to certain embodiments of the present invention, in step S1, the calcium fluoride has a solid content of 1 to 10%; preferably, the calcium fluoride has a solids content of 2 to 8%.
According to certain embodiments of the present invention, in step S1, the volume ratio of the deionized water to the absolute ethanol is 1; more preferably, the volume ratio of deionized water to absolute ethyl alcohol is 1.
According to some embodiments of the invention, in step S1, the pH adjusting agent is one or more of ammonia, sodium hydroxide, and hydrochloric acid.
According to certain embodiments of the invention, in step S1, the pH is 8-12.
According to certain embodiments of the present invention, in step S2, the silicon source is selected from one or more of ethyl orthosilicate, sodium silicate, and methyl orthosilicate.
According to some embodiments of the invention, in step S2, the silicon source is used according to the coating amount of the product silica, and the mass ratio of the silica to the calcium fluoride is 0.06.
According to some embodiments of the invention, in step S2, the stirring temperature is 20 to 70 ℃ and the stirring time is 2 to 13 hours.
According to some embodiments of the invention, in the step S2, the rotary evaporation drying temperature is 10-90 ℃ and the time is 30-360 min; more preferably, the rotary evaporation drying temperature is 20-70 deg.C, and the time is 45-240 min.
As another aspect of the invention, the invention is a CaF for dental restoration 2 @SiO 2 The preparation method of the cluster body comprises the following steps:
s1, dispersing calcium fluoride nano particles in deionized water, uniformly dispersing by ultrasonic, adding absolute ethyl alcohol, and adding a pH regulator to regulate the pH;
s2, adding a silicon source, stirring at the temperature of 10-90 ℃ for 1-24h, carrying out suction filtration, and carrying out rotary evaporation drying to obtain CaF 2 @SiO 2 A nanoparticle;
s3, preparing CaF 2 @SiO 2 Dispersing the nanoparticles in a medium, and ultrasonically dispersing to form CaF 2 @SiO 2 A nanodispersion;
s4, the CaF prepared in the step S3 2 @SiO 2 Introducing the nano dispersion into a spray dryer for spray drying to obtain CaF 2 @SiO 2 A cluster intermediate;
s5, adding the CaF prepared in the step S4 2 @SiO 2 Calcining the cluster body at the temperature of 300-900 ℃ for 1-12 ℃ to obtain CaF 2 @SiO 2 And (3) clustering bodies.
In the present invention, caF 2 @SiO 2 When the nano particles and the clusters are applied to the dental repair process, the nano particles and the clusters need to be compounded with resin, so that the mechanical property and the fluorine release property of the nano particles and the clusters are examined. Therefore, in order to better combine the inorganic particles with the composite resin, the CaF to be obtained needs to be combined with the composite resin 2 @SiO 2 Modifying the nanoparticles (or clusters) and then modifying the modified CaF 2 @SiO 2 Mixing the nano particles (or clusters) with resin and carrying out photocuring on the mixture to obtain composite resin; for CaF 2 @SiO 2 The purpose of the nanoparticle (or cluster) modification is to make it bind better to the resin, and photocuring is the process of polymerization of the photoinitiator with the organic resin and inorganic nanoparticles to form an organic composite resin.
According to certain embodiments of the present invention, in step S1, the calcium fluoride has a solid content of 1 to 10%; preferably, the calcium fluoride has a solids content of 2 to 8%. If the solid content is too low, the water content is high, so that the subsequent pumping filtration workload is large, the production efficiency is reduced, and if the solid content is too high, the calcium fluoride is easily agglomerated in the coating process, so that the coating effect is influenced.
According to some embodiments of the invention, in step S1, the time of the ultrasonic dispersion is 20-40min. The sonication dispersed the calcium fluoride nanoparticles well in the deionized water.
According to certain embodiments of the present invention, in step S1, the volume ratio of the deionized water to the absolute ethanol is 1; more preferably, the volume ratio of deionized water to absolute ethanol is 1. The hydrolysis rate of TEOS is accelerated due to the overhigh water content, and the formation of silicon dioxide is influenced; the higher the ethanol contentThe higher the homogeneous nucleation rate of silica, the less favorable the formation of CaF 2 @SiO 2 A core-shell structure.
According to certain embodiments of the invention, in step S1, the pH is 8-12. The proper pH regulator is helpful for the hydrolysis of the silicon source, so that the shape of the silicon dioxide coated on the surface of the calcium fluoride is regular.
According to some embodiments of the invention, in step S2, the silicon source is used in a mass ratio of 0.06. When the silicon source content is low, calcium fluoride cannot be completely coated with silica formed by hydrolysis.
According to some embodiments of the invention, in step S2, the stirring temperature is 20 to 70 ℃ and the stirring time is 2 to 13 hours. The temperature is too high or the stirring time is too long, the molecular collision is violent, and the particle agglomeration is easy to cause; the temperature is too low or the stirring time is too short, and the hydrolysis of the silicon source is insufficient.
According to some embodiments of the invention, in the step S2, the rotary evaporation drying temperature is 10-90 ℃ and the time is 30-360 min; more preferably, the rotary evaporation drying temperature is 20-70 deg.C, and the time is 45-240 min. in. Too high drying temperature of the rotary evaporation easily causes particle agglomeration, while too low temperature requires longer drying time, and the consumption of energy and time is large.
According to some embodiments of the invention, in step S3, the medium is selected from one or more of water, methanol, ethanol, propanol.
According to certain embodiments of the invention, in step S3, caF is used for spray drying 2 @SiO 2 The solid content of the nano dispersion is 1-15%; preferably, the solids content is 2-8%. If the solid content is too low, the cluster bodies obtained by spray drying are few and the spray drying efficiency is low under the same dispersion dosage; the nozzle is easily blocked due to too high solid content, so that the nano particles are scattered and cannot form spherical clusters.
According to some embodiments of the invention, in step S4, caF is pumped using a peristaltic pump 2 @SiO 2 Introducing the nano dispersion into a spray dryer, wherein the feeding speed is 0.1-1L/h; preferably, the feed rate is 0.2-0.9L/h.
According to certain embodiments of the present invention, the temperature at the nozzle during spray drying is 80-160 ℃ in step S4; preferably, the temperature at the nozzle is 90-140 ℃.
According to some embodiments of the invention, in step S4, the gas velocity of the spray head during spray drying is 300-650L/h; preferably, the gas velocity of the spray head is 400-500L/h.
According to certain embodiments of the present invention, preferably, in step S5, the temperature of the calcination is 400 to 700 ℃. The purpose of the calcination is to compact the structure of the clusters so that they are not easily crushed when mixed with the resin, but the calcination temperature must not exceed the decomposition temperature of the calcium fluoride or silica.
According to certain embodiments of the invention, in step S5, the calcination is carried out for a time ranging from 3 to 9 hours.
In the preparation method, all parameters are selected to form an integral technical scheme, and the CaF for dental restoration can be obtained only by matching 2 @SiO 2 Nanoparticles and clusters. The overstepping of any condition will cause the object of the present invention to be impossible.
Example 1
CaF 2 @50％SiO 2 The preparation method of the nanoparticle composite resin comprises the following steps:
step 1CaF 2 @50％SiO 2 Preparing nano particles:
dispersing 2.16g of calcium fluoride in 108ml of deionized water, adding 324ml of absolute ethyl alcohol, and adding ammonia water to adjust the pH value to about 10.5; 4.13ml of ethyl orthosilicate was added, stirred at 25 ℃ for 4 hours, the resulting slurry was suction filtered and rotary evaporated at 45 ℃ for 1 hour.
Step 2CaF prepared as described above 2 @50％SiO 2 Application of nanoparticles in dental repair:
KH570 was added to the CaF obtained above 2 @50％SiO 2 Modifying nano particles, compounding the modified particles with resin, and photocuring to obtain CaF 2 @50％SiO 2 A nanoparticle composite resin.
FIG. 1 is a schematic view of an embodimentCaF prepared in example 1 2 @50％SiO 2 Transmission electron microscopy of nanoparticles. As can be seen from the figure, the particles have a core-shell structure and an average particle diameter of 19nm
Fig. 2 shows an XRD pattern, and the peak around 25 ° is an amorphous peak of silica.
FIG. 3 shows CaF prepared in example 1 2 @50％SiO 2 Nanoparticle composite resin and CaF 2 Graph comparing the fluoride ion release rates of nanoparticle composite resins. With CaF 2 Fast and unstable fluoride ion release phase ratio of nanoparticle composite resin, caF 2 @50％SiO 2 The fluorine ion release rate of the nanoparticle composite resin is more stable.
Example 2
CaF 2 @50％SiO 2 The preparation and application of the cluster composite resin comprise the following steps:
step 1: caF 2 @50％SiO 2 Preparation of the nanodispersion:
200ml of CaF with a solids content of 2% 2 @50％SiO 2 Nanodispersions of CaF in said dispersion 2 @50％SiO 2 Nanoparticles were prepared as in example 1 and the dispersion medium was deionized water.
Step 2: caF 2 @50％SiO 2 Preparing a cluster body:
the temperature of the spray dryer nozzle is 110 ℃, the gas velocity of the spray head is 450L/h, and the peristaltic pump is used for pumping the CaF at the velocity of 0.4L/h 2 @50％SiO 2 The nanodispersion is passed into a spray dryer.
And step 3: caF 2 @50％SiO 2 Calcining the cluster body:
the CaF prepared in the step 2 2 @50％SiO 2 The clusters were calcined at 500 ℃ for 3h.
And 4, step 4: caF 2 @50％SiO 2 Application of the cluster:
KH570 is used for the CaF calcined in the step 3 2 @50％SiO 2 Modifying the cluster, compounding the modified cluster with resin, and photocuring to obtain CaF 2 @50％SiO 2 A cluster composite resin.
FIG. 4 shows CaF prepared in example 2 2 @50％SiO 2 SEM image of clusters. The nano particles have a balling rate of more than 80 percent and an average particle diameter of 3 mu m, and the nano particles forming the cluster body are combined tightly.
FIG. 5 shows a calcium fluoride cluster composite resin and CaF prepared in example 2 2 @50％SiO 2 Comparative graph of mechanical properties of the cluster composite resin. CaF 2 @50％SiO 2 The bending property and the compressive strength of the cluster composite resin are both superior to those of the calcium fluoride cluster composite resin.
FIG. 6 shows CaF prepared in example 2 2 @50％SiO 2 The cross-sectional view of the cluster composite resin shows the completed clusters.
Example 3
CaF 2 @20％SiO 2 The preparation and application of the nano-particle composite resin comprise the following steps:
step 1: caF 2 @20％SiO 2 Preparing nano particles:
dispersing 3.6g of calcium fluoride in 180ml of deionized water, adding 540ml of absolute ethyl alcohol, and adding ammonia water to adjust the pH value to about 10.5; 2.75ml of ethyl orthosilicate was added, stirred at 25 ℃ for 4 hours, the resulting slurry was suction filtered and rotary evaporated at 45 ℃ for 1 hour.
And 2, step: caF 2 @20％SiO 2 Application of the nanoparticles:
KH570 is used for the CaF obtained in the step 2 2 @20％SiO 2 Modifying nano particles, compounding the modified particles with resin, and photocuring to obtain CaF 2 @20％SiO 2 A nanoparticle composite resin.
FIG. 7 shows CaF prepared in example 3 2 @20％SiO 2 TEM images of nanoparticles. As can be seen from the figure, part of the calcium fluoride particles were not coated with silica.
Example 4
CaF 2 @40％SiO 2 Preparation and application of nanoparticle composite resinThe method comprises the following steps:
step 1: caF 2 @40％SiO 2 Preparation of nanoparticles
Dispersing 3g of calcium fluoride in 150ml of deionized water, adding 600ml of absolute ethyl alcohol, and adding ammonia water to adjust the pH value to about 10; 5.7ml of tetraethoxysilane is added, stirred for 5 hours at 30 ℃, and after the obtained slurry is filtered by suction, rotary evaporation is carried out for 1 hour at 45 ℃.
Step 2: caF 2 @40％SiO 2 Application of nanoparticles
KH570 is used for the CaF obtained in the step 2 2 @40％SiO 2 Modifying nano particles, compounding the modified particles with resin, and photocuring to obtain CaF 2 @40％SiO 2 The effect of the nanoparticle composite resin was similar to that of example 3.
Example 5
CaF 2 @60％SiO 2 The preparation and application of the nano-particle composite resin comprise the following steps:
step 1CaF 2 @60％SiO 2 Preparing nano particles:
dispersing 2.5g of calcium fluoride in 83ml of deionized water, adding 415ml of absolute ethyl alcohol, and adding ammonia water to adjust the pH value to about 10.5; 4.8ml of tetraethoxysilane is added, stirred for 4 hours at 25 ℃, and after the obtained slurry is filtered by suction, rotary evaporation is carried out for 1 hour at 45 ℃.
Step 2CaF 2 @60％SiO 2 Application of the nanoparticles:
KH570 is used for the CaF obtained in the step 2 2 @60％SiO 2 Modifying nano particles, compounding the modified particles with resin, and photocuring to obtain CaF 2 @60％SiO 2 A nanoparticle composite resin.
FIG. 8 shows CaF prepared in example 5 2 @60％SiO 2 TEM images of nanoparticles. It can be seen from the figure that all calcium fluoride particles are coated with silica particles.
Example 6
Example 5 was repeated with the difference that: in step 1, 2.5g of calcium fluoride was dispersed in 125ml of deionized water, 3g of sodium silicate solution was added while adjusting the pH to about 11 with hydrochloric acid, and stirred at 40 ℃ for 3 hours, the effect being similar to that of example 5.
Example 7
CaF 2 @80％SiO 2 The preparation and application of the nano-particle composite resin comprise the following steps:
step 1: caF 2 @80％SiO 2 Preparation of nanoparticles
Dispersing 2.9g of calcium fluoride in 144ml of deionized water, adding 432ml of absolute ethyl alcohol, and adding ammonia water to adjust the pH value to about 10.5; 8.8ml of tetraethoxysilane is added, stirred for 4 hours at 25 ℃, and after the obtained slurry is filtered by suction, rotary evaporation is carried out for 1.5 hours at 45 ℃.
Step 2: caF 2 @80％SiO 2 Application of nanoparticles
KH570 is used for the CaF obtained in the step 2 2 @80％SiO 2 Modifying nano particles, compounding the modified particles with resin, and photocuring to obtain CaF 2 @80％SiO 2 A nanoparticle composite resin. The effect is similar to that of example 5.
Example 8
Example 2 was repeated with the difference that: caF used in step 1 and step 2 2 @50％SiO 2 Modification of nanoparticles and nanodispersions to CaF 2 @60％SiO 2 Nanoparticles and nanodispersions, preparation of CaF 2 @60％SiO 2 The effect of the cluster was similar to that of example 2.
Example 9
Example 2 was repeated with the difference that: caF used in step 1 and step 2 2 @50％SiO 2 Modification of nanoparticles and nanodispersions to CaF 2 @80％SiO 2 Nanoparticles and nanodispersions, preparation of CaF 2 @80％SiO 2 The effect of the cluster was similar to that of example 2.
Example 10
Example 2 was repeated with the difference that: step by stepIn step 3, caF 2 @50％SiO 2 The effect of calcining the clusters at 400 ℃ for 6h was similar to that of example 2.
Comparative example 1
Example 1 was repeated with the difference that: in step 1, the pH is adjusted to about 12. The results show that CaF is not obtained 2 @SiO 2 Core-shell structure, and the particles are seriously agglomerated.
Comparative example 2
Example 1 was repeated with the difference that: in step 1, 860ml of absolute ethanol was added. The results show that CaF is not obtained 2 @SiO 2 Core-shell structured nanoparticles, and self-nucleated silica nanoparticles are present.
Comparative example 3
Example 1 was repeated with the difference that: in the step 1, the stirring temperature is 80 ℃, and the stirring time is 0.5h. The results show that the particles are strongly agglomerated and CaF cannot be obtained 2 @SiO 2 And (3) nanoparticles.
Comparative example 4
Example 1 and example 2 were repeated except that in step 1, the slurry obtained was spray dried as it was without any treatment in example 2.
FIG. 9 is an SEM photograph of the product obtained in comparative example 4. As can be seen from the figure, the particles are agglomerated and have non-uniform morphology, and spherical clusters cannot be formed.
Comparative example 5
Example 2 was repeated, except that acetone was used as the dispersion medium in step 1. The results show that the particles cannot be dispersed in acetone.
Comparative example 6
Example 2 was repeated, except that 200ml of CaF having a solids content of 10% were taken in step 1 2 @50％SiO 2 A nanodispersion.
FIG. 10 is an SEM photograph of the product obtained in comparative example 6. As can be seen from the figure, the obtained cluster has non-uniform particle size and low balling rate.
Comparative example 7
Example 2 was repeated, except that in step 1, the CaF was treated with KH570 2 @50％SiO 2 After the nanoparticles are modified, the nanoparticles are dispersed in deionized water, and spray-dried in step 2.
FIG. 11 is an SEM photograph of the product obtained in comparative example 7. It can be seen that the surface of the cluster particles is uneven, and the balling rate is 0%.
Comparative example 8
Example 8 was repeated, except that in step 2, the feed rate of the peristaltic pump was 1.3L/h. The result shows that the nano particles are scattered greatly, and the balling rate of the cluster body is lower than 50 percent.
Comparative example 9
Example 8 was repeated, except that in step 2, the temperature at the nozzle was 50 ℃. The results showed that a large number of water droplets adhered to the inside of the apparatus, and the dispersion was not spray dried, and no clusters could be obtained.
Comparative example 10
Example 8 was repeated, except that in step 2, the showerhead gas velocity was 800L/h. The results show that a large amount of nanoparticles are scattered and there are few shaped clusters.
Comparative example 11
Example 2 was repeated except that the calcination of step 3 was not performed.
FIG. 12 shows CaF obtained in comparative example 11 2 @50SiO 2 Cross-sectional view of the cluster composite resin. As can be seen from the figure, the cluster structure was broken and no complete clusters could be observed.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (9)
1.CaF 2 @SiO 2 The preparation method of the nano-particles is characterized by comprising the following steps:
s1, dispersing calcium fluoride nano particles in deionized water, ultrasonically dispersing uniformly, adding absolute ethyl alcohol, and adding a pH regulator to regulate the pH value;
s2, adding a silicon source, stirring at the temperature of 10-90 ℃ for 1-24h, carrying out suction filtration, and carrying out rotary evaporation drying to obtain CaF 2 @SiO 2 And (3) nanoparticles.
2. CaF according to claim 1 2 @SiO 2 The preparation method of the nano-particles is characterized by comprising the following steps: in the step S1, the solid content of the calcium fluoride is 1-10%; preferably, the calcium fluoride has a solid content of 2-8%;
preferably, in the step S1, the time of the ultrasonic dispersion is 20-40min;
preferably, in step S1, the volume ratio of the deionized water to the absolute ethyl alcohol is 1; more preferably, the volume ratio of the deionized water to the absolute ethyl alcohol is 1;
preferably, in step S1, the pH regulator is one or more of ammonia water, sodium hydroxide and hydrochloric acid;
preferably, in step S1, the pH is 8-12;
preferably, in step S2, the silicon source is selected from one or more of ethyl orthosilicate, sodium silicate and methyl orthosilicate.
3. CaF according to claim 1 2 @SiO 2 The preparation method of the nano-particles is characterized by comprising the following steps: in the step S2, the dosage of the silicon source is determined according to the coating amount of the product silicon dioxide, and the mass ratio of the silicon dioxide to the calcium fluoride is 0.06;
preferably, in the step S2, the stirring temperature is 20-70 ℃, and the stirring time is 2-13h;
preferably, in the step S2, the rotary evaporation drying temperature is 10-90 ℃, and the time is 30-360 min; more preferably, the rotary evaporation drying temperature is 20-70 deg.C, and the time is 45-240 min.
4.CaF 2 @SiO 2 The method for preparing the cluster body is characterized by comprising the following steps:
s1, dispersing calcium fluoride nano particles in deionized water, uniformly dispersing by ultrasonic, adding absolute ethyl alcohol, and adding a pH regulator to regulate the pH;
s2, adding a silicon source, stirring at the temperature of 10-90 ℃ for 1-24h, carrying out suction filtration, and carrying out rotary evaporation drying to obtain CaF 2 @SiO 2 A nanoparticle;
s3, preparing CaF 2 @SiO 2 Dispersing the nanoparticles in a medium, and ultrasonically dispersing to form CaF 2 @SiO 2 A nanodispersion;
s4, the CaF prepared in the step S3 2 @SiO 2 Introducing the nano dispersion into a spray dryer for spray drying to obtain CaF 2 @SiO 2 A cluster intermediate;
s5, adding CaF prepared in the step S4 2 @SiO 2 Calcining the cluster body at the temperature of 300-900 ℃ for 1-12 ℃ to obtain CaF 2 @SiO 2 A cluster body.
5. CaF according to claim 4 2 @SiO 2 A method for producing a cluster, characterized by comprising: in the step S1, the solid content of the calcium fluoride is 1-10%; preferably, the calcium fluoride has a solid content of 2-8%;
preferably, in the step S1, the time for ultrasonic dispersion is 20-40min;
preferably, in step S1, the volume ratio of the deionized water to the absolute ethyl alcohol is 1; more preferably, the volume ratio of the deionized water to the absolute ethyl alcohol is 1;
preferably, in step S1, the pH regulator is one or more of ammonia water, sodium hydroxide and hydrochloric acid;
preferably, in step S1, the pH is 8-12;
preferably, in step S2, the silicon source is selected from one or more of ethyl orthosilicate, sodium silicate and methyl orthosilicate.
6. CaF according to claim 4 2 @SiO 2 A method for producing a cluster, characterized by comprising: in the step S2, the mass ratio of the ethyl orthosilicate to the calcium fluoride is 0.2;
preferably, in the step S2, the silicon source is used according to the coating amount of the product silicon dioxide, and the mass ratio of the silicon dioxide to the calcium fluoride is 0.06;
preferably, in the step S2, the stirring temperature is 20-70 ℃, and the stirring time is 2-13h;
preferably, in the step S2, the rotary evaporation drying temperature is 10-90 ℃, and the time is 30-360 min; more preferably, the rotary evaporation drying temperature is 20-70 deg.C, and the time is 45-240 min.
7. CaF according to claim 4 2 @SiO 2 A method for producing a cluster, characterized by comprising: in step S3, the medium is selected from one or more of water, methanol, ethanol and propanol;
preferably, in step S3, caF for spray drying 2 @SiO 2 The solid content of the nano dispersion is 1-15%; preferably, the solids content is 2-8%.
8. CaF according to claim 4 2 @SiO 2 A method for producing a cluster, characterized by comprising: in step S4, the CaF is pumped by a peristaltic pump 2 @SiO 2 Introducing the nano dispersion into a spray dryer, wherein the feeding speed is 0.1-1L/h; preferably, the feed rate is 0.2-0.9L/h;
preferably, in step S4, the temperature at the nozzle during spray drying is 80-160 ℃; preferably, the temperature at the nozzle is 90-140 ℃;
preferably, in the step S4, the gas velocity of the spray head in the spray drying process is 300-650L/h; preferably, the gas velocity of the spray head is 400-500L/h.
9. CaF according to claim 4 2 @SiO 2 A method for producing a cluster, characterized by comprising: in the step S5, the calcining temperature is 400-700 ℃;
preferably, in step S5, the calcination time is 3-9h.
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| 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 |
| CN110436942A (en) * | 2019-08-28 | 2019-11-12 | 齐鲁工业大学 | The preparation method of silicon dioxide coated nano sheet calcirm-fluoride composite granule |
| CN111892388A (en) * | 2020-08-21 | 2020-11-06 | 齐鲁工业大学 | Ceramic cutter added with coating powder and preparation method and application thereof |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549317A (en) * | 1967-08-12 | 1970-12-22 | Bayer Ag | Process for utilizing fluorosilicic acid |
| 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 |
| CN110436942A (en) * | 2019-08-28 | 2019-11-12 | 齐鲁工业大学 | The preparation method of silicon dioxide coated nano sheet calcirm-fluoride composite granule |
| CN111892388A (en) * | 2020-08-21 | 2020-11-06 | 齐鲁工业大学 | Ceramic cutter added with coating powder and preparation method and application thereof |
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