CN114404303A - Fluorescent glass inorganic filler and preparation method and application thereof - Google Patents
Fluorescent glass inorganic filler and preparation method and application thereof Download PDFInfo
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- CN114404303A CN114404303A CN202111653499.2A CN202111653499A CN114404303A CN 114404303 A CN114404303 A CN 114404303A CN 202111653499 A CN202111653499 A CN 202111653499A CN 114404303 A CN114404303 A CN 114404303A
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- 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
- A61K6/77—Glass
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/50—Preparations specially adapted for dental root treatment
- A61K6/54—Filling; Sealing
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
- C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
Abstract
The invention relates to the field of dental materials, in particular to a fluorescent glass inorganic filler and a preparation method and application thereof. The fluorescent glass inorganic filler comprises glass powder; an inorganic fluorescent component; the inorganic fluorescent component can emit near ultraviolet light of 200-400nm and blue light wave band of 400-450nm under the excitation of near infrared light with the wavelength of 780-3000 nm. The fluorescent glass inorganic filler contains an inorganic fluorescent component, and can emit near ultraviolet light and blue light through mild red light excitation so as to initiate resin curing. Therefore, health damage to operation personnel such as doctors and the like exposed to the blue light environment for a long time can be reduced.
Description
Technical Field
The invention relates to the field of dental materials, in particular to a fluorescent glass inorganic filler and a preparation method and application thereof.
Background
Light-curable composite resins were introduced in the dental field in the 60's of the 20 th century. The material has the advantages of beautiful color, high strength, good bonding and retention effects, good plasticity, capability of being polished and polished after curing and the like, and can be used for the defect repair of teeth by preparing mixed slurry with proper viscosity and curing after specific light irradiation. And thus has received much attention in the dental restoration field. The inorganic filler is added into the composite resin as a reinforcement, has the main functions of endowing the material with good physical and mechanical properties, and has the functions of reducing resin polymerization shrinkage, reducing thermal expansion coefficient, improving refractive property, X-ray radiation resistance and the like. Most of the resin powder for dental use is ceramic powder or glass powder. The type, the particle size distribution, the shading index, the hardness, the X-ray radiation resistance and the volume mass percentage of the inorganic filler in the composite resin all influence the performance and the clinical performance of the composite resin. The inorganic filler not only needs to meet the basic requirements of general reinforcing materials, but also needs to have good light transmittance and small absorptivity so as to reduce the loss of light energy as much as possible, thereby ensuring that the matrix has high utilization rate of light energy. In addition, in order to improve the binding force between the filler and the polymer matrix, the filler is generally subjected to silanization treatment or other surface treatment in advance to improve the interface binding between the filler and the matrix and improve the abrasion performance.
At present, blue light is commonly used for curing the composite resin as induced light, and the damage of the blue light to human eyes is mainly reflected in the pathological damage of the eyes and the rhythm damage of human bodies, which cause myopia, cataract and maculopathy. Blue light has extremely high energy and can penetrate the crystalline lens to the retina, causing atrophy and even death of retinal pigment epithelial cells. Blue light is also one of the factors that induce maculopathy and cataracts. In addition, since the blue light wavelength is short, the focus point passes through the back of the crystalline lens and is in front of the retina, and the long-time work causes visual fatigue, thereby causing low learning efficiency and low working efficiency. While red light, in terms of eye health, is more beneficial than less beneficial. In addition to the high intensity red light illumination that may burn and affect eye irritation, red light is in most cases a mild wavelength range for the eye, and is of great benefit to the eye if it is well utilized. In the field of dental material photocuring, red light can generate better curing effect due to thermal effect compared with a blue light curing material which is cured only by light.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems.
The invention firstly provides a fluorescent glass inorganic filler, which comprises: glass powder; an inorganic fluorescent component; the inorganic fluorescent component can emit near ultraviolet light of 200-400nm and blue light of 400-450nm under the excitation of near infrared light with the wavelength of 780-3000 nm.
The fluorescent glass inorganic filler contains an inorganic fluorescent component, and can emit near ultraviolet light and blue light through mild red light excitation so as to initiate resin curing. Therefore, health damage to operation personnel such as doctors and the like exposed to the blue light environment for a long time can be reduced.
Preferably, the glass powder comprises glass microcrystals, and the microcrystalline glass is prismatic or spherical particles with the particle size distribution D50 of 5nm to 3000 nm. The glass microcrystal can improve the light transmission of glass powder, is favorable for red light to enter the fluorescent glass inorganic filler deep, generates a thermocuring effect based on the heat effect of the red light, further improves the curing effect, and achieves the effect of dual curing.
Preferably, the content of the glass microcrystal in the glass powder is 90-99.99 wt%, and more preferably 98-99.97 wt%. The glass powder with the glass microcrystal within the content range can obtain better light transmittance.
According to the embodiment of the invention, the glass powder comprises the following components in percentage by weight: 20-50% of Al (aluminum), 0-20% of B (boron), 0-30% of Ba (barium) and 20-70% of Si (silicon). Aluminum and silicon are used as a composition framework of the glass body, boron is used as a fluxing component in the glass melting process, and barium is used as a component for regulating and controlling the powder density of the glass body.
According to the embodiment of the invention, the raw materials for preparing the glass powder can be oxides, acids, alkalis or salts of corresponding elements.
According to embodiments of the present invention, the fluorescent component may be a divalent, trivalent and/or tetravalent oxide, such as divalent europium or trivalent cerium, preferably EuO and Ce2O3。
According to the embodiment of the invention, the inorganic fluorescent coating can be attached by adopting a surface technology, and the fluorescent oxide can also be directly prepared.
Preferably, the morphology of the fluorescent component may be powder, lamellar, spherical or cylindrical. This results in better heat transfer properties of the glass component.
Preferably, the weight ratio of the glass powder to the inorganic fluorescent component is (1000:1) - (10:1), more preferably (500:1) - (50: 1).
According to an embodiment of the present invention, the inorganic fluorescent component is present in an amount of 0.1% to 10%, optionally 0.2% to 2%, by weight based on the total weight of the fluorescent glass inorganic filler. In order to ensure the strength and transmittance of the glass powder, the content of the fluorescent component is not higher than 10%, and in order to ensure the fluorescent characteristic of the composite powder, the content of the fluorescent component is not lower than 0.1%.
Preferably, the fluorescent glass inorganic filler further includes a bonding component. The bonding component can improve the bonding force between the glass powder and the inorganic fluorescent component. Binder components commonly used in the art may be employed. In some examples, the adhesive component may be polyacrylates and derivatives thereof (e.g., polymethyl methacrylate, polyacrylic acid, etc.), polyalcohols and derivatives thereof (e.g., polyvinyl alcohol, polyvinyl butyral, etc.), epoxies, and polyurethanes and derivatives thereof.
Preferably, the bonding component accounts for 0.01-20 wt%, optionally 8-20 wt%, and more preferably 0.01-3 wt% of the sum of the contents of the glass powder and the inorganic fluorescent component. It has surprisingly been found that the strength of the fluorescent glass inorganic filler can also be increased significantly when the content of the binding component is between 8 and 20 wt.%. In some examples, polymethyl methacrylate accounting for 10 percent of the sum of the glass powder and the inorganic fluorescent component is added as an adhesive component, the mixing ratio of the obtained fluorescent glass inorganic filler and bisphenol A glycidyl methacrylate can reach 80:20, and the strength can reach more than 300 MPa.
Preferably, the surface of the fluorescent glass inorganic filler has a modified organic group, so that good wettability and interface compatibility with resin can be realized. The organic group includes a hydroxyl group, a carboxyl group, an acrylate group, an amino group, and the like.
The modification treatment can be carried out by adopting a coupling agent commonly used in the field, wherein the coupling agent can be silane, titanate, aluminate and other coupling agents; the modification method can be a soaking method, a solution method and an emulsion polymerization method. In some embodiments reference is made to the method disclosed in CN 201711444734.9.
In some examples, the coupling agent is one or a combination of gamma-methacryloxypropyltrimethoxysilane (KH-570), gamma-mercaptopropyltriethoxysilane (KH-580), and gamma-aminopropyltrimethoxysilane (JH-A111).
In some examples, the silane coupling agent is added in an amount of 1 to 20 wt% based on the sum of the contents of the glass powder and the inorganic fluorescent component.
Researches show that the fluorescent glass inorganic filler also has better thermal conductivity.
The invention also provides a preparation method of the fluorescent glass inorganic filler, which comprises the following steps: providing the glass powder; providing the inorganic fluorescent component; mixing the glass powder and the inorganic fluorescent component.
The fluorescent glass inorganic filler of the invention can be used as dental filler powder and can be widely used as inorganic filler components in the aspects of root canals, porcelain teeth and the like.
The invention also comprises the application of the fluorescent glass inorganic filler in the preparation of the light-cured composite resin.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Glass powder
In some embodiments, the glass powder is barium-aluminum-borosilicate glass powder, has high optical transmittance, and can enter deep positions when used as a filler, so that a better curing effect is achieved.
Preferably, the glass powder is produced by melting a raw material of the glass powder under a protective atmosphere or under vacuum.
Researches find that the glass powder can be beneficial to removing system air under protective atmosphere or vacuum condition and increasing the transparency of the glass powder.
The protective atmosphere may be nitrogen or hydrogen.
Specifically, after the glass frit is formed by melting, the glass powder is obtained through a quenching process and a grinding process.
The melting temperature may be above 1300 ℃, for example 1300 ℃ to 1900 ℃, with a preferred temperature of 1500 ℃ to 1700 ℃. The melting time is 1-5 h.
In some examples, the protective atmosphere has a gas supply end pressure of 0.1-2MPa, or a vacuum degree of < 10-6Pa。
The quenching process is that molten glass liquid is poured into quenching liquid quickly, and the quenching liquid can be water, quenching oil and other liquid with quick temperature reduction.
And taking out the glass fragments after cooling, and grinding the powder to 0.005-10 microns. The grinding equipment can be single equipment or a combination of multiple equipment such as a mortar grinder, a jaw crusher, a planetary ball mill, a sand mill and the like, and can grind powder to the equipment with specified size.
The grinding media may be glass grinding media containing the above-described glass powder constituents, so that the introduction of foreign phases by grinding is avoided. In some examples the grinding media are barium aluminoborosilicate glass spheres ranging from 0.5mm to 10 mm.
The maximum particle size of the glass powder raw material is not more than 30 μm, preferably not more than 5 μm, and more preferably not more than 0.7. mu.m. The smaller the particle size of the glass powder, the better the flowability of the product prepared as a filler will be maintained. The over-large granularity of the glass powder can lead to poor dispersion effect and reduced granular feeling and mechanical property of the product.
In some examples, the method also comprises the step of soaking the crushed powder in an acid solution with the pH value of 1-5. The treating agent may be hydrochloric acid, sulfuric acid, phosphoric acid or other strong and weak base salts. The soaking treatment can improve the binding force between powder materials and improve the defect degree of the surface.
In order to improve the permeability of the microcrystalline glass, a fully permeable glass medium or a semi-permeable ceramic medium is selected as a grinding medium, wherein the glass medium which has almost the same composition with a glass element is preferred, the size of the grinding medium is in a large relation with the target particle size of the powder, the grinding medium selected by the invention is Al-Si-B glass spheres, the size of the medium is 0.5mm-10mm, and the preferred diameter is 1mm-3 mm.
Inorganic fluorescent component
The fluorescent component is inorganic cylindrical powder or spherical powder containing the fluorescent component, and the preferred components are EuO and Ce2O3. The fluorescent powder can be the fluorescent powder itself, or the fluorescent powder is attached to the surface of other non-fluorescent powder. The fluorescent component can be inorganic spherical powder and columnar powder prepared by a hydrothermal process, a precipitation reaction and the like.
The particle size of the inorganic phosphor is not more than 30 μm, preferably not more than 5 μm, and more preferably not more than 0.7. mu.m.
The inorganic fluorescent powder can be synthesized by a hydrothermal method, a precipitation method, a sol-gel method and a sintering method, and can also be synthesized by other non-fluorescent powders by the method, and the shape of the powder can be spherical, cylindrical, prismatic and lamellar. Preferably cylindrical and spherical to increase the thermal conductivity of the material, and applying an inorganic fluorescent coating on the surface by using a surface coating technology such as PVD or magnetron sputtering.
Bonding component
The adhesive component is an additive component with certain viscosity, wherein the preferable organic component of the adhesive can be polyaldehyde, acrylic adhesive and polyvinyl alcohol adhesive. The adding mode is that after the fluorescent component powder and the glass powder are mixed and added, the diluent of the bonding component is added, the diluted solvent can be a common solvent, and is mixed into slurry in a high-speed dispersion machine, and the rotating speed range of the high-speed dispersion machine is 500 plus materials at 5000 r/min. The slurry is dried by spray drying. The addition amount of the adhesive is 0.1-20% of the addition mass of the powder, and the preferred proportion is 0.1-5%.
Coupling agent
In order to improve the affinity of the powder with the resin material during use, the dry powder needs to be subjected to surface treatment with a coupling agent, and the treatment method is a coupling agent treatment method disclosed. Adding inorganic filler, catalyst and silane coupling agent (gamma-methacryloxypropyltrimethoxysilane (KH-570) and/or gamma-mercaptopropyltriethoxysilane (KH-580) and/or gamma-aminopropyltrimethoxysilane (JH-A111)) into volatile solvent, reacting at room temperature for 30-150 min, stirring at 50-80 deg.C for 30-120min, removing solvent, and drying in a vacuum oven at 50-120 deg.C for 10-30h to obtain the silanized inorganic filler. The catalyst can be one of ammonia water, n-propylamine, acetic acid and oxalic acid; the volatile solvent can be one of toluene, cyclohexane, ethanol and acetone.
Example 1
(1) Preparation of glass powder
The raw material composition of the glass melting is 20 percent (Al (OH)3)，25％(BaCO3)，50％(SiO2)，5％(H3BO3)。
Placing the raw materials in a vacuum atmosphere furnace according to the above proportion, and opening a vacuum pump to make the vacuum degree be 10-6And Pa, opening a valve of nitrogen-hydrogen mixed gas, keeping the pressure at 0.5Mpa, ventilating for 10min, removing redundant gas, adjusting the hearth program, setting the temperature at 1600 ℃, keeping the temperature for 2h, quickly pouring the molten glass into water for cooling for 10min, taking out glass fragments, and grinding the glass blocks in a horizontal ball mill by 400-turn balls for 6 h. Ball-milled slurry of 40% solids content was obtained. The ball-milled slurry was soaked in 0.1M dilute hydrochloric acid solution for 24 h. And centrifuging the acid-treated powder to remove supernatant, adding water to wash, centrifuging to remove the supernatant, and continuously removing redundant acid components for three times. And drying the powder in an oven at 100-160 ℃ for 2-8h to obtain the glass powder.
(2) Preparation of fluorescent Components
2.1 fluorescent substrate preparation
50g of ethyl orthosilicate and 200ml of ethanol are put into a 500ml reaction kettle to react for 6 hours at 250 ℃, and silicon oxide inorganic powder is obtained after suction filtration and drying. The powder is prepared into slurry, injection molded into a ceramic raw sheet blank, and sintered into a ceramic sheet at 1300 ℃.
2.2PVD method of plating with fluorescent coating
Placing the ceramic wafer on a strontium titanate substrate by using an electron beam coating machine, and forming an oxide Ce on the ceramic wafer2O3Placing the crucible in a pure copper crucible, setting the current of an electron beam to be 1A, and setting the deposition time to be 1 h. And then taking down the ceramic wafer, crushing, placing in a ball mill for ball milling for 24h at 400r to obtain ball milling slurry, and then performing spray drying to obtain the fluorescent component powder. And sieved by a 200-mesh sieve.
(3) Bonding component
500g of the glass powder prepared in the step (1) and 10g of the fluorescent component prepared in the step (2) are selected, 6.3g of polyvinyl butyral (PVB) is added to be used as a dispersing agent, the rotating speed is adjusted to 2500r in a high-speed dispersing machine, and the mixture is mixed for 1 hour. And (3) after the mixed slurry is subjected to spray drying, sieving the dried slurry with a 200-mesh sieve to obtain the glass powder containing fluorescence.
(4) Powder surface modification
In order to improve the usability of the powder as a filler, it is necessary to perform silanization treatment on the surface of the composite powder to improve the bonding strength with other dental compositions such as resins.
And (4) drying the powder prepared in the step (3), soaking the powder in a KH570 ethanol solution for 2h, centrifuging the solution in a centrifuge at 2500r/min for 3min, pouring out supernatant, and firing the bottom coagulation substance in a muffle furnace at 200 ℃ for 2 h. And (3) after the powder is fired, crushing and sieving the powder by a 200-mesh sieve to obtain the fluorescent glass inorganic filler.
EXAMPLE 2 glass melting raw Material composition
(1) Preparation of glass raw material powder
The glass melting element composition is 8% (Al (OH)3，22％(Ba(OH)2〃8H2O，60％(SiO2)，10％(H3BO4)。
Placing the raw materials in a vacuum atmosphere furnace according to the above proportion, and opening a vacuum pump to make the vacuum degree be 10-6Pa, opening a valve of nitrogen-hydrogen mixed gas with the pressure of 0.5Mpa, ventilating for 10min, removing redundant gas, adjusting the furnace program, setting the temperature at 1750 ℃, preserving heat for 2h, and melting the glassThe glass liquid is rapidly poured into water for cooling for 10min, the glass fragments are taken out, and the glass blocks are subjected to 600-rotation ball milling for 30h in a horizontal ball mill. Ball-milled slurry with 20% solid content was obtained. The ball-milled slurry was soaked in 0.1M dilute hydrochloric acid solution for 24 h. And centrifuging the acid-treated powder to remove supernatant, adding water to wash, centrifuging to remove the supernatant, and continuously removing redundant acid components for three times. And drying the powder in an oven at 120 ℃ for 3h to obtain the glass powder.
(2) Preparation of fluorescent Components
5g of cerium acetate and 20ml of ethanol are put in a 50ml of polytetrafluoroethylene reaction kettle to react for 1h at 180 ℃, a vacuum suction filter is used for suction filtration under the condition that the vacuum degree is 0.1Mpa, and a suction filtered sample is put in an oven to be dried for 2h at 120 ℃ to obtain EuO columnar powder.
(3) Bonding component
200g of the glass powder prepared in the step (1) and 1g of the EuO columnar powder prepared in the step (2) are selected, 0.41g of polymethyl methacrylate (PMMA) is added to serve as a dispersing agent, and the mixture is mixed for 1 hour under the condition that the rotating speed of a high-speed disperser is 5000 r/min. And (3) after the mixed slurry is subjected to spray drying, screening by a 3000-mesh sieve to obtain the glass powder containing fluorescence.
(4) Surface radical treatment
Adding KH570 with the addition of 5% of the powder prepared in the step (3), hydrolyzing in an environment with pH of 1-4, taking the powder dispersion slurry, stirring at a high speed for 3h, carrying out water bath at 80 ℃ for 12h, then placing in a centrifuge at 3000r/min, centrifuging for 2min, pouring out the supernatant, placing in an oven at 160 ℃ for drying for 3h, grinding and crushing the dried powder, and sieving with a 3000-mesh sieve to obtain the fluorescent glass inorganic filler.
Example 3
(1) Melting glass powder
The glass melting element composition is 40% (Al (OH)3，10％(Ba(OH)2〃H2O，40％(SiO2)，10％(H3BO4)。
Placing the raw materials in a vacuum atmosphere furnace according to the above proportion, and opening a vacuum pump to make the vacuum degree be 10-6Pa, opening a valve of nitrogen-hydrogen mixed gas with pressure of 0.5Mpa, introducing air for 10min, removing excessive gas, adjusting furnace program, setting temperature at 1750 deg.C, and keeping temperature at 2 deg.CAnd h, quickly pouring the melted glass liquid into water for cooling for 10min, taking out glass fragments, and performing 600-rotation ball milling on the glass blocks in a horizontal ball mill for 30 h. Ball-milled slurry with 20% solid content was obtained. And after spray drying, screening by a 3000-mesh sieve to obtain the fluorescent powder. Melting the glass in a hearth for 2h at the melting temperature of 1800 ℃, pouring the glass liquid into water for cooling for 10min, and grinding the glass blocks in a horizontal ball mill for 6h by 400-rotation balls. Ball-milled slurry of 40% solids content was obtained. The ball-milled slurry was soaked in 0.1M dilute hydrochloric acid solution for 24 h. And centrifuging the acid-treated powder to remove supernatant, adding water to wash, centrifuging to remove the supernatant, and continuously removing redundant acid components for three times. And drying the powder in an oven at 150 ℃ for 5 hours to obtain the glass powder.
(2) Preparation of fluorescent Components
Dissolving 10g of europium chloride in 100g of aqueous solution, dropwise adding 0.5M/L sodium hydroxide solution until the precipitate is not increased, filtering and drying, placing the precipitate in a 600 ℃ tube furnace, firing for two hours in a nitrogen atmosphere, and performing powder ball milling and sieving with a 200-mesh sieve to obtain the europium oxide columnar powder.
(3) Adhesive composition
500g of glass powder prepared in the step (1) and 1g of europium oxide columnar powder prepared in the step (2) are selected and soaked in 0.1M acetic acid for 5 hours, then 8.08g of polyvinyl alcohol (PVA) is added to be used as a dispersing agent, and the mixture is mixed in a homogenizer for 1 hour to obtain the glass powder containing fluorescence.
(4) Powder surface treatment
Drying the powder prepared in the step (3), soaking in KH570 ethanol solution for 2h, centrifuging at the rotation speed of 2550r/min for 2min, pouring out supernatant, and firing the bottom precipitate in a muffle furnace at 200 ℃ for 2 h. And (4) crushing the powder, and then sieving the powder with a 3000-mesh sieve to obtain the fluorescent glass inorganic filler.
Performance testing
The fluorescent glass inorganic filler prepared in the above examples 1 to 3 was mixed with Bis-GMA (bisphenol A glycidyl methacrylate) resin diluted with TEGDMA (triethylene glycol dimethacrylate) as a diluent in an amount of 40% by weight, and the amount of the fluorescent glass inorganic filler added was 70% by weight of the GMA diluted resin. Adding 4-dimethyl amino ethyl benzoate and camphorquinone as light curing initiator, and initiating curing with 980nm red light emitter.
And (3) testing mechanical properties: the flexural strength of the specimens was tested according to the flexural strength test method mentioned in 7.11 of the standard YY-1042-2011 dental polymer-based restorative material.
And (3) testing the transmittance: after initiation and curing by a 980nm red light emitter, a 2mm thick 3cm diameter raw sheet was prepared and placed in a Saimer fly GENESYS 50 UV spectrophotometer, and absorbance was measured as a transmittance characteristic in the absorbance mode at a wavelength of 546 nm.
Fluorescence property test:
the excitation spectrum (PLE) and emission spectrum (PL) of the material were analyzed using a fluorescence spectrophotometer, model F-4600, Hitachi high and New technology, Japan.
1) And placing the fluorescent glass inorganic filler powder into a clamp, and flattening the powder in the groove of the clamp by using a glass sheet to be tested.
2) The jig was placed in a fluorescence spectrophotometer.
3) The emission spectrum was tested. A 980nm laser was used as an excitation light source, and the interval was set to 300nm to 750 nm. The peak position of the emission spectrum was recorded.
The test results are shown in the following table.
| Example 1 | Example 2 | Example 3 | |
| Fluorescent glass inorganic filler particle size | 3 micron | 3 micron | 0.7 micron |
| Peak position of fluorescence emission spectrum | 338nm | 428nm | 422nm |
| Resin curing time | 40s | 60s | 80s |
| Degree of resin permeability | 2.41A | 2.33A | 2.02A |
| Flexural Strength | 142Mpa | 121Mpa | 132Mpa |
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A fluorescent glass inorganic filler, comprising:
glass powder;
an inorganic fluorescent component;
the inorganic fluorescent component can emit near ultraviolet light of 200-400nm and blue light of 400-450nm under the excitation of near infrared light with the wavelength of 780-3000 nm.
2. The fluorescent glass inorganic filler according to claim 1, wherein the glass powder comprises glass crystallites, and the glass crystallites are prismatic or spherical particles having a particle size distribution D50 of 5nm to 3000 nm.
3. The fluorescent glass inorganic filler according to claim 2, wherein the glass crystallites are present in the glass powder in an amount of 90 to 99.99% by weight, preferably 98 to 99.97% by weight.
4. A fluorescent glass inorganic filler according to any of claims 1 to 3, characterized in that the glass powder contains, in weight percent: 20-50% of Al (aluminum), 0-20% of B (boron), 0-30% of Ba (barium) and 20-70% of Si (silicon).
5. A fluorescent glass inorganic filler according to any of claims 1 to 4, characterized in that the fluorescent component is a divalent, trivalent and/or tetravalent oxide, preferably EuO, Ce2O3。
6. A fluorescent glass inorganic filler according to any of claims 1 to 5, characterized in that the weight ratio of glass powder to inorganic fluorescent component is (1000:1) - (10:1), preferably (500:1) - (50: 1).
7. The fluorescent glass inorganic filler according to any one of claims 1 to 6, further comprising a bonding component;
the bonding component is preferably one or more of polyacrylate and derivatives thereof, polyalcohols and derivatives thereof, epoxy resins, polyurethanes and derivatives thereof;
further preferably, the bonding component accounts for 0.01-20 wt%, optionally 8-20 wt%, and more preferably 0.01-3 wt% of the sum of the contents of the glass powder and the inorganic fluorescent component.
8. The fluorescent glass inorganic filler according to any of claims 1 to 7, wherein the surface of the fluorescent glass inorganic filler has a modified organic group; the inorganic filler of the fluorescent glass is preferably modified by a silane coupling agent.
9. The method for preparing the fluorescent glass inorganic filler of any one of claims 1 to 8, comprising:
providing the glass powder;
providing the inorganic fluorescent component;
mixing the glass powder and the inorganic fluorescent component.
10. Use of the fluorescent glass inorganic filler according to any one of claims 1 to 9 for preparing a photocurable composite resin.
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| CN202111653499.2A Active CN114404303B (en) | 2021-12-30 | 2021-12-30 | Fluorescent glass inorganic filler and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115124248A (en) * | 2022-06-23 | 2022-09-30 | 辽宁爱尔创生物材料有限公司 | Glass powder and preparation method thereof |
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