EP1751071A2 - NANO GLASS POWDER AND USE THEREOF, PARTICULARLY MULTICOMPONENT GLASS POWDER WITH A MEAN PARTICLE SIZE OF LESS THAN 1 µM - Google Patents

NANO GLASS POWDER AND USE THEREOF, PARTICULARLY MULTICOMPONENT GLASS POWDER WITH A MEAN PARTICLE SIZE OF LESS THAN 1 µM

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Publication number
EP1751071A2
EP1751071A2 EP05744811A EP05744811A EP1751071A2 EP 1751071 A2 EP1751071 A2 EP 1751071A2 EP 05744811 A EP05744811 A EP 05744811A EP 05744811 A EP05744811 A EP 05744811A EP 1751071 A2 EP1751071 A2 EP 1751071A2
Authority
EP
European Patent Office
Prior art keywords
glass
ceramic powder
glass ceramic
powder according
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05744811A
Other languages
German (de)
French (fr)
Inventor
José ZIMMER
Johann Daimer
Matthias Rindt
Susanne Kessler
Jörn BESINGER
Karine Seneschal-Merz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
Original Assignee
Schott AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schott AG filed Critical Schott AG
Priority to EP10000497A priority Critical patent/EP2189426A1/en
Publication of EP1751071A2 publication Critical patent/EP1751071A2/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1005—Forming solid beads
    • C03B19/102—Forming solid beads by blowing a gas onto a stream of molten glass or onto particulate materials, e.g. pulverising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing

Definitions

  • the invention relates to multi-component glasses with at least three (3) elements with an average particle size of less than 1 ⁇ m, preferably less than 0.1 ⁇ m, particularly preferably less than 10 nm. Glasses with such an average particle size are also referred to as nanopowders.
  • the application also includes processes for producing such glasses and their use.
  • Inorganic nanopowders are for non-crystalline compositions for Si0 2 and for crystalline compositions such as. B. Ti0 2 or ZnO known. Regarding SiO 2 nanopowder, reference is made to Degussa's Aerosil® product.
  • CeO nanoparticles for polishing suspensions are e.g. B. from Nanophase (USA) and Zr0 2 nanoparticles or Al 2 0 3 nanoparticles from Nanogate (Germany).
  • Metallic nanoparticles are e.g. B. known for silver and silver alloy. Such nanoparticles are used, for example, as antimicrobial agents, for. B. for polymers.
  • Powders made of metallic nanoparticles can also be used for bonding in the field of electronics. According to HD Junge, A. Möschwitz, "Elektronik”, VCH-Verlag 1993, p. 89, bonding is a welding process for contacting electronic elements, for example on an integrated circuit. The use of metallic nanopowders greatly reduces the bonding temperatures.
  • hydroxyapatite nanoparticles have also become known, for example from BASF (Germany), which are used in the field of oral care, dental hygiene, ie in the field of oral care applications.
  • Glasses with antimicrobial activity have become known from the following patent applications WO03 / 018495, WO03 / 18498, WO03 / 18499, WO03 / 050052, WO03 / 062163, WO03 / 018496.
  • the glass powders described in these documents were obtained in the form of grinding, for example in aqueous media. By grinding as described in the above documents, glass powders with an average particle size corresponding to that of nanoparticles cannot be obtained.
  • Glasses which are used in the dental field, so-called dental glasses have become known from DE 4323143, US 5,641,347, DE 4443173 and EP 0997132.
  • nanoparticles known from the prior art are used in a large number of fields.
  • the use of nanoparticles in cosmetic sun protection formulations is described in US20040067208
  • US20040042953 describes the use of nanoparticles in toilet powders, the mean particle size fluctuating between 10 and 20 nm. These nanoparticles are manufactured using gas phase reactions.
  • nanoparticles for the detection of nucleic acid is known from US20030148282.
  • US20030064532 describes the use of semiconductor nanoparticles in the field of luminance and optical data storage.
  • silver or silver alloy nanopowder is produced using PVD processes.
  • US Pat. No. 4,642,207 has disclosed a PVD plasma arc process for producing nanoparticles via evaporation and condensation.
  • a method for producing nanocrystalline material has also become known from US 5874684. Binary oxides are used as raw materials for this. Different atmospheres can be used to produce different substances.
  • the object of the invention is to provide a multi-component glass powder which is distinguished by the fact that it can be used in a large number of fields and has an improved activity compared to conventional glass powders.
  • the object is achieved by a glass powder which has multi-component glasses with at least 3 elements, the mean particle size of the
  • the glass contains more than 4, more preferably more than 5, most preferably from 'more than 6 elements.
  • the component of an oxidic glass is understood to be the oxidic component, for example SiO 2 or B 2 O 3 .
  • the element in a glass composition is understood to mean the individual element, that is to say Si or B or O.
  • a multi-component glass is therefore a glass which, for example, comprises SiO 2 and B 2 0 3 as components.
  • a glass, which comprises Si0 2 and B 2 O 3 as components, has a total of three elements. So it would be in Language usage of this application is a 2-component glass with 3 elements.
  • the glass powders with a particle size of less than 1 ⁇ m, which are also referred to as nanoglasses comprise SiO 2 and / or B 2 O 3 and / or P 2 O 5 as network formers.
  • the proportion of the network former or the sum of the network former, if the multicomponent glass comprises more than one network former, is preferably between 30-95% by weight, preferably between 30 and 80% by weight, in particular between 40 and 75% by weight, most preferably between 50 and 70% by weight.
  • the glasses can be divided into the group of silicate, borate or phosphate glasses.
  • Alkali ions e.g. B. Na, K, Li, Cs, can be used in the glass composition
  • the total concentration of the alkalis is between 0 and 50% by weight, preferably between 0 and 30% by weight.
  • the alkalis can also be used to adjust the reactivity of the glass, since the alkali can deliberately interrupt the glass network.
  • biocides such as e.g. B. Zn or Ag are more easily released.
  • the alkaline earth metal ions such as. B. Mg, Ca, Sr, Ba, in total between 0 and 50 wt .-%.
  • the alkaline earth ions also act as network converters and serve to adjust the reactivity of the glass.
  • the Ca plays a special role. In the case of special bioactive glasses, the presence of Ca allows a mineral layer to be formed on the particle surface in aqueous media, the so-called hydroxyapatite layer.
  • the multi-component glasses can further comprise aluminum oxide. Aluminum oxide significantly influences the chemical stability and the crystallization stability of the glasses.
  • the Al 2 0 3 concentration is preferably between 0% by weight and 25% by weight.
  • the glass can include zinc oxide as an essential glass component.
  • the Zn ions of the glass can be released and lead to an antimicrobial effect, which is further supported by alkali or alkaline earth ions.
  • the ZnO concentration is usually in the
  • the multi-component glasses can also comprise titanium oxide and / or zirconium oxide. With the help of these additives, the refractive index of the glass powder can be adjusted. In particular, the addition of TiO 2 can also be used for UV blocking.
  • nanopowders are glass ceramic nanopowders
  • additions of Ti0 2 or Zr0 2 can serve as nucleating agents.
  • the chemical resistance of the nanopowders can be adjusted using Ti0 2 or Zr0 2 .
  • the hydrolytic resistance can be improved in particular by the addition of Zr0 2 , which is particularly important in the case of hygroscopic nanopowders.
  • TiO 2 and ZrO 2 can also be used to adjust the modulus of elasticity.
  • the concentration of TiO 2 is preferably between 0 and 25% by weight and the concentration of ZrO 2 is between 0% and 30% by weight.
  • the nanoglass powder can include tantalum and / or tungsten oxide.
  • the concentration is from Ag2Ü, CuO, ZnO, I less than 15% by weight, preferably less than 10; more preferably less than 5% by weight.
  • Precious metals such as Au, Pt can also be present in metallic or oxidic form up to less than 10% by weight, preferably less than 5% by weight, most preferably less than 2% by weight.
  • Coloring ions such as B. Cr, Mn, Ni, V, Ce, Fe, V, Co can be present in total (oxide) up to 10% by weight.
  • Rare earth ions such as B. Eu, Ce, Sm, Nd, Er, Sm, Yb, can be introduced as doping in conventional concentrations.
  • Fluorine can be contained in the glasses as a melting aid.
  • Oxides of the elements Nb, La, Pb and Bi serve primarily to adjust the refractive index or dispersion.
  • Refining agents such as. B. SnO, As 2 0 3 , Sb 2 0 3 , can be contained in the usual concentrations in the nanoglass powders, with the exception of the nanoglass, which are used in dental, medical and cosmetic applications.
  • the aforementioned metals Au, Ag, Pt, Cu can be present in the glass matrix not only in oxidic but also in metallic form.
  • Radioactive elements can also be added.
  • nitrides or oxide nitrides can also be used as starting materials and corresponding nitride or oxynitride nanoglasses can be obtained in this way.
  • the advantage of nitride or oxynitride nanoglass is the better mechanical properties than with oxide glasses.
  • the nanopowders according to the invention have average grain sizes of less than 1 ⁇ m, preferably less than 200 nm, particularly preferably less than 100 nm, more preferably less than 50 nm, most preferably less than 20 nm. In a particular embodiment, grain sizes less than 5 nm are used. In special embodiments, the nanoparticles can be smaller than 2 nm.
  • the BET surface area of conventional inorganic fillers in dental materials is e.g. B. between 4 and 65 m 2 / g.
  • the BET Oberfumbleen the nanoparticles are larger than 50 m 2 / g, preferably greater than 100m 2 / g, more preferably greater than 500 m 2 / g, Trustzugtesten greater than 900 m 2 / g.
  • the surface properties play an increasingly important role compared to the bulk properties. Due to the high free surface area, surprisingly high reactivities, in particular a high ion release, for example in the case of glasses which are inert per se, such as antimicrobial silicate glasses, are particularly high. B. achieved in aqueous media or in organic compounds, high antimicrobial effect of the powder.
  • the particles can be used as powder and suspension.
  • Amorphous, phase-separated, crystallized glass or glass ceramic nanoparticles can be used. Different phases can be achieved in the primary manufacturing process or in post-processing.
  • organosilanes For use as a filler in the dental field, a modification of the surface with organosilanes is possible and advantageous, such as. B. methacryloxypropyl-tri-methoxy-silane.
  • the organosilanes used are particularly characterized by the fact that they can both bind to the glass surface and also bind to an organic resin via an organic functional side group. This facilitates the formulation in the organic resin matrix on the one hand and increases the mechanical stability on the other.
  • the most widespread for dental applications is 3-methacryloxypropyltrimethoxysilane, better known under the trade name MEMO from Degussa.
  • MEMO 3-methacryloxypropyltrimethoxysilane
  • Ions of the elements La, Ba, Sr, Y, Yb, Nb, Zr, Zn serve to adjust the x-ray visibility of dental glasses.
  • the nanopowders according to the invention comprising multicomponent glasses and glass ceramics can be used in the fields of cosmetics e.g. B. as a UV blocker for UV-A and / or UV-B, dental filler, oral care, optical polymers, sintered materials, antimicrobial applications, in the medical field as an active ingredient or active ingredient carrier, for water filtering, cleaning, treatment, as solder glasses; as pigments, for rapid prototyping, which describes the very rapid production of three-dimensional structures, in fuel cells, as abrasive materials, for catalysis, as UV protection, in polishing processes, in textile fibers, in thermoplastics, in paints and varnishes; in surface technology, as non-stick, anti-scratch, anti-reflective, anti-fog, easy to clean layer, for corrosion protection; in the field of ceramic technologies, as raw materials e.g.
  • polymers e.g. Duromers, plastomers, monomers
  • Electronics for example as glass solders for joining or as passivation glass for semiconductor components.
  • the nanoparticles are produced, for example, in a PVD process (Physical Vapor Deposition).
  • PVD process Physical Vapor Deposition
  • the evaporated substances are deposited on a cold surface, for example a substrate surface, and reorganize in the glassy state
  • the multicomponent glass or glass ceramic nanoparticles according to the invention are produced.As described above, in addition to nanoglasses, a nanoglass ceramic or a nanoglass, which comprises a segregated system, can also be produced in this way. The production of nanoparticles using the sol-gel method is also possible.
  • CVD processes can also be used.
  • CVD (Chemical Vapor Deposition) processes describe this chemical deposition from the gas phase.
  • VDI lexicon “Material Technology” VDI-Verlag 1993, pp.139 and pp.5-6, the disclosure content of which is included in full in the disclosure content of the present application.
  • Another method for producing nanoparticles is flame pyrolysis.
  • flame pyrolysis reactive gases are led into a flame.
  • the nanoparticles are synthesized in the flame and deposited in cold regions.
  • liquid raw materials can also be used in flame pyrolysis.
  • non-oxidic carrier gas is used in the processes described, in particular in the PVD process, nitride or oxynitride nanoglasses can be produced.
  • PVD processes are particularly suitable for producing the described nanoglasses or nano-glass ceramics.
  • the plasma processes in particular plasma processes combined with high-frequency evaporation or electron evaporation, are particularly suitable.
  • the plasma process is characterized by the fact that the raw material is evaporated in a plasma.
  • Metals or metal oxides are used as starting materials in the PVD processes known in the prior art.
  • multicomponent glasses as starting materials for the production of the multicomponent glasses according to the invention with particle sizes smaller than 1 ⁇ m.
  • different multi-component glasses can be mixed in different weight fractions and particle size distributions.
  • suitable element combinations can already be put together in one raw material.
  • the PVD process local heating of the multicomponent glass as the raw material selectively evaporates this raw material and the raw materials are then deposited again as glass powder or glass ceramic powder according to the invention with particle sizes smaller than 1 ⁇ m.
  • the starting materials are introduced, for example in rod or powder form, into a recipient and evaporated there in a plasma arc and the corresponding nanoparticles are then deposited in a gas stream.
  • the advantage of the PVD process is that the rapid cooling rates mean that glasses prone to crystallization can also be deposited in amorphous form. This also applies to glasses that cannot be produced stably under standard melting conditions and from which no amorphous glass powder can be obtained by conventional melting and grinding.
  • oxidic glasses can be deposited with the aid of oxidic carrier gases, for example oxi-nitride glasses with the help of non-oxidic carrier gases.
  • the glasses according to the invention can be used to bridge gaps in bonding processes or as adhesive bonds in optical applications, for UV or IR absorption, for thermal insulation, for light reflection, as fire-resistant material, as sealant, as glossy material, as color brilliance.
  • Use fabric as well as in electrostatics.
  • porous electrodes for fuel cells hard solders for ceramic-metal connections or low-temperature solders.
  • solders in the field of glass-glass, glass-metal, glass-ceramic or glass-crystal compounds solders in the field of glass-glass, glass-metal, glass-ceramic or glass-crystal compounds.
  • glasses, ceramics, glass ceramics, crystals, metals can generally be connected to one another with such solders.
  • nanoparticles according to the invention can also be deposited electrophoretically on surfaces or in porous bodies.
  • inorganic non-metallic biocides described in the prior art can only be produced and used in relatively large particle sizes greater than 1 ⁇ m. They are therefore less effective than organic biocides.
  • the reactivity, but in particular the antimicrobial activity can be increased extraordinarily strongly by the nanoparticles according to the invention.
  • the increased surface generates a synergistic additional antimicrobial effect.
  • the metallic antimicrobial nanopowders for example silver nanopowders
  • the oxidic compounds have little tendency to discolour and the silver is already in its antimicrobial, effective, oxidized form.
  • the composition of the glass or glass ceramic nanoparticles can be adjusted so that they completely dissolve in aqueous systems.
  • nanopowders are obtained from zero expansion material according to the invention, they are particularly suitable for sintering and as a filler.
  • the nanoparticles according to the invention it is possible to lower the sintering temperature and to achieve very high final densities with very low porosity, which are characterized by low scatter and high transparency.
  • Optical glasses can also be obtained from the nanoparticles according to the invention by viscous sintering. Put together, the nano glasses form a sintered green compact.
  • the composition of the sintered green compact Due to the composition of the sintered green compact from a large number of individual nanoparticles, an extremely high surface area is introduced into the sintered green compact. Due to this extremely high surface, special structures with the smallest crystallite sizes can be created. Depending on the type of glass, the crystallization of the sintered green compact can take place either surface-controlled or volume-controlled. Another advantage of the extremely high surface area of the green compacts is that nanocrystals (both in terms of volume and surface-controlled crystallization) are generated in the sintered solid materials. This is one way of producing sintered glass ceramics with nanocrystals.
  • nano-glass powder can also be used as a sintering aid for high-melting materials.
  • Another application is the use in the melting of temperature-sensitive materials or semi-finished products.
  • soldering temperature can be reduced here.
  • Solder glasses made of nanoparticles are used to achieve the lowest possible temperature and voltage loads.
  • nanoglasses according to the invention can be adjusted in a wide range in their optical positions. This possibility of adjustment affects, for example, the transmission, refractive index, dispersion and also partial dispersion of the glass.
  • polymers By mixing polymers with nano glasses, it is possible to obtain polymer-glass composites in which the optical parameters can be set very precisely. Due to the variability of the glass chemistry and the corresponding surface modification that are carried out during and after production, properties such as dispersibility can also be adjusted. This is e.g. B. necessary if nanoparticles are dispersed in monomers.
  • nanoglass powders according to the invention is so-called rapid prototyping, i.e. the production of three-dimensional prototypes, for example in the field of tissue engineering, i.e. the production of three-dimensional implant frameworks, which serve as carrier materials for the growth of tissue cells.
  • the nano glass powder or nano glass ceramic powder can also be used as an implant material, coating material for implants or a carrier system for medication. Because of the anti-inflammatory or antimicrobial properties, the nanoglass or nanoglass powder according to the invention can also be used directly as an active ingredient. Alternatively, it is possible to introduce the active ingredients into the glass or to apply the active ingredients to the glass surface. Such systems then represent so-called “release systems”.
  • Composite materials such. B. from LGA and / or PGA or their copolymers for biomaterial in particular for tissue engineering are possible.
  • LGA and PGA are bioresorbable polymers.
  • glass and / or glass ceramic nanoparticles according to the invention with an antioxidative, anti-inflammatory, antimicrobial, remineralizing effect is also possible. If certain substances are added, it is possible to produce magnetic nanoparticles, for example, for treatments that promote blood circulation.
  • the chemical composition of the glasses can be varied, it is possible to change the mechanical properties of the nanoparticles made of glass or glass ceramic, such as. B. hardness, modulus of elasticity, density, chemical resistance (e.g. against water, lye and acids) or the electrical properties, adjust and adjust.
  • the zeta potential can also be adjusted by composition and / or surface modifications.
  • Table 1 shows compositions of glasses or starting glasses for glass ceramics in% by weight, from which nanoglass or nanoglass ceramic particles can be produced using the methods according to the invention.
  • the glass compositions given in Table 1 relate to the glass compositions of the starting glasses, which can be evaporated using, for example, an electron beam.
  • the glass composition of the nanoglass or nanoglass ceramic particles deposited in the PVD process essentially match the compositions of the starting glasses if the process is carried out appropriately.
  • customary refining agents are understood, for example, as refining agents Sn 2 0 3 , NaCl, As 2 O 3, Sb 2 0 3 , As 2 S 3 , Sb 2 S 3 , and the usual amounts of a conventional refining agent are 0 - 4% by weight of the total composition
  • Exemplary embodiments of nanoglass powder and their use are to be given below.
  • Exemplary embodiment 1 relates to a nanoglass powder which is introduced into a polymer matrix and leads to an antimicrobial effect of the polymer-nanoglass composite material.
  • nanoglass powder with a particle size of less than 1 ⁇ m according to Example 2 in Table 1 0.1% by weight of nanoglass powder with a particle size of less than 1 ⁇ m according to Example 2 in Table 1 is incorporated into a polystyrene matrix and extruded into sheets.
  • the antimicrobial effectiveness of the surface is tested according to the ASTM standard. A reduction in the test germs (E. Coli, Candida Albicans) by more than 2 log levels is determined.
  • bioactive nanoglass powder with particle sizes smaller than 1 nm according to Example 1 in Table 1 0.1% by weight of bioactive nanoglass powder with particle sizes smaller than 1 nm according to Example 1 in Table 1 is incorporated into a formulation for a deodorant. A significant sweat reduction is observed.
  • Nanoglass powder formulated in a dental resin Typical dental resins are described in EP 0475239 and the documents cited therein.
  • the nanoglass of the glass powder has a glass composition according to Example 4 in Table 1.
  • the average particle size is less than 1 ⁇ m.
  • a high-melting glass for example the Schott glass with number 8330
  • nanopowder is mixed with nanopowder as an admixture in order to lower the sintering temperature.
  • Embodiment 5 relates to a solder glass consisting of 70% by volume of nano glass powder with a composition according to Example 9 in Table 1 and a particle size of ⁇ 1 ⁇ m and 30% by volume of an inert filler (eg cordierite) for adjusting the elongation.
  • the nano-composite glass solder obtained in this way has a melting temperature which is 50 ° C. lower than that of the same mixture of the original material.
  • 5% by weight of a nanoglass powder with particle sizes smaller than 1 ⁇ m with a glass composition which comprises 2% by weight of TiO 2 is added to a sun milk formulation in order to achieve UV blocking.

Abstract

The invention relates to a glass powder or a glass-ceramic powder comprising multicomponent glasses with at least three elements, and is characterized in that the glass powder or a glass-ceramic powder has a mean particle size of less than 1 µm, preferably less than 0.1 µm, particularly preferred less than 10 nm.

Description

Nanoglaspulver und deren Verwendung, insbesondere Multikomponenten- Glaspulver mit einer mittleren Partikelgrösse kleiner 1 μm. Nanoglass powder and its use, in particular multicomponent glass powder with an average particle size of less than 1 μm.
Gegenstand der Erfindung sind Multikomponentengläser mit mindestens drei (3) Elementen mit einer mittleren Partikelgrösse kleiner 1 μm, vorzugsweise kleiner 0,1 μm, besonders bevorzugt kleiner 10 nm. Gläser mit einer derartigen mittleren Partikelgrösse werden auch als Nanopulver bezeichnet. Neben den Multikomponentengläsern umfasst die Anmeldung auch Verfahren zur Herstellung solcher Gläser sowie deren Verwendung.The invention relates to multi-component glasses with at least three (3) elements with an average particle size of less than 1 μm, preferably less than 0.1 μm, particularly preferably less than 10 nm. Glasses with such an average particle size are also referred to as nanopowders. In addition to the multi-component glasses, the application also includes processes for producing such glasses and their use.
Anorganische Nanopulver sind für nicht kristalline Zusammensetzungen für Si02 und für kristalline Zusammensetzungen wie z. B. Ti02 oder ZnO bekannt. Betreffend SiO2-Nanopulver wird auf das Produkt Aerosil® der Degussa verwiesen.Inorganic nanopowders are for non-crystalline compositions for Si0 2 and for crystalline compositions such as. B. Ti0 2 or ZnO known. Regarding SiO 2 nanopowder, reference is made to Degussa's Aerosil® product.
Des weiteren sind CeO-Nanopartikel für Poliersuspensionen z. B. von Fa. Nanophase (USA) sowie Zr02 -Nanopartikel oder Al203 Nanopartikel von der Fa. Nanogate (Deutschland) bekannt.Furthermore, CeO nanoparticles for polishing suspensions are e.g. B. from Nanophase (USA) and Zr0 2 nanoparticles or Al 2 0 3 nanoparticles from Nanogate (Germany).
Metallische Nanopartikel sind z. B. für Silber und Silberlegierung bekannt. Eingesetzt werden derartige Nanopartikel beispielsweise als antimikrobielle Wirkstoffe z. B. für Polymere.Metallic nanoparticles are e.g. B. known for silver and silver alloy. Such nanoparticles are used, for example, as antimicrobial agents, for. B. for polymers.
Pulver aus metallischen Nanopartikeln können auch zum Bonden im Bereich der Elektronik eingesetzt werden. Das Bonden ist gemäß H. D. Junge, A. Möschwitz, „Elektronik", VCH-Verlag 1993, S. 89 ein Schweißverfahren zum Kontaktieren von elektronischen Elementen beispielsweise auf einer integrierten Schaltung. Durch die Verwendung von metallischen Nanopulvern werden die Bondingtemperaturen stark herabgesetzt. Neben den oben genannten Nanopartikeln sind auch Hydroxylapatit-Nanopartikel beispielsweise von der Firma BASF (Deutschland) bekannt geworden, die im Bereich der Mundpflege, Zahnhygiene, d.h. im Bereich der Oral Care- Anwendungen verwendet werden.Powders made of metallic nanoparticles can also be used for bonding in the field of electronics. According to HD Junge, A. Möschwitz, "Elektronik", VCH-Verlag 1993, p. 89, bonding is a welding process for contacting electronic elements, for example on an integrated circuit. The use of metallic nanopowders greatly reduces the bonding temperatures. In addition to the above-mentioned nanoparticles, hydroxyapatite nanoparticles have also become known, for example from BASF (Germany), which are used in the field of oral care, dental hygiene, ie in the field of oral care applications.
Wie aus dem zuvor beschriebenen Stand der Technik hervorgeht sind vor allem keramische Nanopartikel mit 2 Elementen, bestehend in der Regel aus einem Metall und einem Sauerstoff, bekannt geworden.As can be seen from the prior art described above, ceramic nanoparticles with 2 elements, consisting generally of a metal and an oxygen, have become known.
Als Nanopartikel in der glasigen Phase sind ausschließlich Zwei-Element-Systeme bestehend aus einer einzigen Komponente, nämlich reinen SiO2-Partikeln bekannt. Nachteilig an derartigen reinen Si02-Systemen ist, dass sie auf Grund ihrer geringen chemischen Variabilität auch keine besonders breite Variation in den Materialeigenschaften aufweisen. Dies betrifft insbesondere optische, chemische, physikalische und mechanische Eigenschaften.Only two-element systems consisting of a single component, namely pure SiO 2 particles, are known as nanoparticles in the glassy phase. A disadvantage of such pure SiO 2 systems is that, owing to their low chemical variability, they do not have a particularly wide variation in the material properties. This applies in particular to optical, chemical, physical and mechanical properties.
Gläser mit bioaktiver und teilweise auch antimikröbieller Wirkung werden bei LL. Hensch, J. Wilson, An Introduction to Bioceramics, World Scientific Publ., 1993, als Bioglas beschrieben. Derartiges Bioglas zeichnet sich durch die Bildung von Hydroxylappatitschichten in wässrigen Medien aus. Schwermetallfreie Alkali- Erdalkali-Silicat-Gläser mit antimikrobiellen Eigenschaften werden in den Anmeldungen WO 01/04252 und WO 01/03650 beschrieben.Glasses with bioactive and sometimes also antimicrobial effects are used at LL. Hensch, J. Wilson, An Introduction to Bioceramics, World Scientific Publ., 1993, as Bioglas. Such bioglass is characterized by the formation of hydroxylappatite layers in aqueous media. Heavy metal-free alkali-alkaline earth silicate glasses with antimicrobial properties are described in the applications WO 01/04252 and WO 01/03650.
Gläser mit antimikröbieller Wirksamkeit sind aus den nachfolgenden Patentanmeldungen WO03/018495, WO03/18498, WO03/18499, WO03/050052, WO03/062163, WO03/018496 bekannt geworden. Die in diesen Schriften beschriebenen Glaspulver wurden in Form von Mahlung beispielsweise in wässrigen Medien erhalten. Durch eine Mahlung wie in obigen Schriften beschrieben, können keine Glaspulver mit einer mittleren Partikelgrösse, die der von Nanopartikeln entspricht, erhalten werden. Gläser, die im Dentalbereich Verwendung finden, sogenannte Dentalgläser, sind aus der DE 4323143, US 5,641,347, DE 4443173 sowie der EP 0997132 bekannt geworden.Glasses with antimicrobial activity have become known from the following patent applications WO03 / 018495, WO03 / 18498, WO03 / 18499, WO03 / 050052, WO03 / 062163, WO03 / 018496. The glass powders described in these documents were obtained in the form of grinding, for example in aqueous media. By grinding as described in the above documents, glass powders with an average particle size corresponding to that of nanoparticles cannot be obtained. Glasses which are used in the dental field, so-called dental glasses, have become known from DE 4323143, US 5,641,347, DE 4443173 and EP 0997132.
Gläser und insbesondere Glaskeramiken, die sich durch eine geringe oder sogar durch eine Nullausdehnung auszeichnen, sind in der DE 19907038 und der US 5070045 gezeigt.Glasses and in particular glass ceramics, which are characterized by little or even zero expansion, are shown in DE 19907038 and US 5070045.
Die aus dem Stand der Technik bekannten Nanopartikel werden in einer Vielzahl von Gebieten eingesetzt. So ist die Anwendung von Nanopartikeln in kosmetischen Sonnenschutzformulierungen in der US20040067208 beschriebenThe nanoparticles known from the prior art are used in a large number of fields. The use of nanoparticles in cosmetic sun protection formulations is described in US20040067208
Die Oberflächenbehandlungen von Nanopartikeln sowie deren Drucken werden in der US20040052957 beschrieben.The surface treatments of nanoparticles and their printing are described in US20040052957.
Die Herstellung von Nanopartikeln sowie kratzfeste Beschichtungen mit Nanopartikeln werden in der DE0001022009A1 beschrieben.The production of nanoparticles and scratch-resistant coatings with nanoparticles are described in DE0001022009A1.
Die DE000069600059 beschreibt die Verwendung von TiO2-Nanopartikeln in Sonnenschutzmitteln.DE000069600059 describes the use of TiO 2 nanoparticles in sunscreens.
Die US20040042953 beschreibt die Verwendung von Nanopartikeln in WC- Pulvern, wobei die mittlere Partikelgrösse zwischen 10 und 20nm schwankt. Hergestellt werden diese Nanopartikel über Gasphasenreaktionen.US20040042953 describes the use of nanoparticles in toilet powders, the mean particle size fluctuating between 10 and 20 nm. These nanoparticles are manufactured using gas phase reactions.
Aus der US20030148282 ist die Verwendung von Nanopartikeln zur Detektion von Nukleinsäure bekannt.The use of nanoparticles for the detection of nucleic acid is known from US20030148282.
Die US20030064532 beschreibt die Verwendung von Halbleiter-Nanopartikeln im Bereich Luminiszenz und der optischen Datenspeicherung. Die Herstellung beispielsweise von Silber- oder Silberlegierungsnanopulver geschieht über PVD-Verfahren. Beispielsweise ist aus der US 4642207 ein PVD Plasmabogen-Verfahren zur Herstellung von Nanopartikeln über Verdampfung und Kondensation bekannt geworden.US20030064532 describes the use of semiconductor nanoparticles in the field of luminance and optical data storage. For example, silver or silver alloy nanopowder is produced using PVD processes. For example, US Pat. No. 4,642,207 has disclosed a PVD plasma arc process for producing nanoparticles via evaporation and condensation.
Auch aus der US 5874684 ist ein Verfahren zur Herstellung von nanokristallinem Material bekannt geworden. Hierfür werden binäre Oxide als Rohmaterialien eingesetzt. Zur Herstellung unterschiedlicher Stoffe können verschiedene Atmosphären eingesetzt werden.A method for producing nanocrystalline material has also become known from US 5874684. Binary oxides are used as raw materials for this. Different atmospheres can be used to produce different substances.
Aufgabe der Erfindung ist es ein Mehrkomponenten-Glaspulver zur Verfügung zu stellen, das sich dadurch auszeichnet, dass es in einer Vielzahl von Gebieten verwandt werden kann und gegenüber herkömmlichen Glaspulvern eine verbesserte Aktivität aufweist.The object of the invention is to provide a multi-component glass powder which is distinguished by the fact that it can be used in a large number of fields and has an improved activity compared to conventional glass powders.
Gelöst wird die Aufgabe durch ein Glaspulver, welches Multikomponentengläser mit mindestens 3 Elementen aufweist, wobei die mittlere Partikelgrösse desThe object is achieved by a glass powder which has multi-component glasses with at least 3 elements, the mean particle size of the
Glaspulvers kleiner als 1 μm, bevorzugt kleiner 0,1 μm, noch bevorzugter kleiner 50 nm, besonders bevorzugt kleiner 10 nm aufweist.Glass powder smaller than 1 micron, preferably less than 0.1 microns, more preferably less than 50 nm, particularly preferably less than 10 nm.
In einer bevorzugten Ausführungsform weist das Glas mehr als 4, besonders bevorzugt mehr als 5, ganz besonders bevorzugt' mehr als 6 Elemente auf.In a preferred embodiment, the glass contains more than 4, more preferably more than 5, most preferably from 'more than 6 elements.
In dieser Anmeldung wird als Komponente eines oxidischen Glases die oxidische Komponente verstanden, also beispielsweise SiO2 oder B2O3. Unter dem Element in einer Glaszusammensetzung wird das einzelne Element, also Si oder B oder O verstanden. Ein Mehrkomponentenglas ist also ein Glas, welches beispielsweise als Komponenten SiO2 und B203 umfasst. Ein Glas, das als Komponenten Si02 und B2O3 umfasst, weist insgesamt drei Elemente auf. Es würde sich also im Sprachgebrauch dieser Anmeldung um ein 2-Komponenten-Glas mit 3 Elementen handeln. Gemäß der Erfindung umfassen die Glaspulver mit einer Partikelgrösse kleiner 1 μm, die auch als Nanogläser bezeichnet werden, als Netzwerkbildner SiO2 und/oder B2O3 und/oder P2O5. Der Anteil des Netzwerkbildners bzw. der Summe der Netzwerkbildner, falls das Multikomponentenglas mehr als einen Netzwerkbildner umfasst, liegt bevorzugt zwischen 30-95 Gew%, vorzugsweise zwischen 30 und 80 Gew%, insbesondere zwischen 40 und 75 Gew%, am bevorzugtesten zwischen 50 und 70 Gew%. Gemäss der Hauptnetzwerkbildner können die Gläser in die Gruppe der Silikat-, Borat- oder Phosphat-Gläser eingeteilt werden.In this application, the component of an oxidic glass is understood to be the oxidic component, for example SiO 2 or B 2 O 3 . The element in a glass composition is understood to mean the individual element, that is to say Si or B or O. A multi-component glass is therefore a glass which, for example, comprises SiO 2 and B 2 0 3 as components. A glass, which comprises Si0 2 and B 2 O 3 as components, has a total of three elements. So it would be in Language usage of this application is a 2-component glass with 3 elements. According to the invention, the glass powders with a particle size of less than 1 μm, which are also referred to as nanoglasses, comprise SiO 2 and / or B 2 O 3 and / or P 2 O 5 as network formers. The proportion of the network former or the sum of the network former, if the multicomponent glass comprises more than one network former, is preferably between 30-95% by weight, preferably between 30 and 80% by weight, in particular between 40 and 75% by weight, most preferably between 50 and 70% by weight. According to the main network builder, the glasses can be divided into the group of silicate, borate or phosphate glasses.
Alkaliionen, wie z. B. Na, K, Li, Cs, können in die Glaszusammensetzung alsAlkali ions, e.g. B. Na, K, Li, Cs, can be used in the glass composition
Netzwerkwandler eingebracht werden. Die Konzentration der Alkalien liegen in der Summe zwischen 0 und 50 Gew%, bevorzugt zwischen 0 und 30 Gew%. Die Alkalien können auch der Einstellung der Reaktivität des Glases dienen, da durch die Alkalien das Glasnetzwerk gezielt unterbrochen werden kann. Beispielsweise können in die Glasmatrix eingebrachte Biozide Ionen wie z. B. Zn oder Ag leichter abgegeben werden.Network converters are introduced. The total concentration of the alkalis is between 0 and 50% by weight, preferably between 0 and 30% by weight. The alkalis can also be used to adjust the reactivity of the glass, since the alkali can deliberately interrupt the glass network. For example, biocides such as e.g. B. Zn or Ag are more easily released.
Neben oder statt den Alkalien können die Erdalkaliionen, wie z. B. Mg, Ca, Sr, Ba, in Summe zwischen 0 und 50 Gew.-% vorliegen. Auch die Erdalkaliionen wirken als Netzwerkwandler und dienen der Einstellung der Reaktivität des Glases. Das Ca nimmt eine besondere Rolle ein. Bei speziellen bioaktiven Gläsern kann durch Vorhandensein von Ca eine Mineralschicht auf der Partikeloberfläche in wässrigen Medien ausbildet werden, die sogenannte Hydroxylapatit-Schicht. Die Multikomponentengläser können des weiteren Aluminiumoxid umfassen. Aluminiumoxid beeinflusst massgeblich die chemische Stabilität sowie die Kristallisationsstabilität der Gläser. Die Al203 Konzentration liegt bevorzugt zwischen 0 Gew% und 25 Gew%. Neben den Netzwerkkomponenten kann das Glas Zinkoxid als eine wesentliche Glaskomponente umfassen. Die Zn-Ionen des Glases können freigesetzt werden und zu einer antimikrobiellen Wirkung führen, die durch Alkali- oder Erdalkaliionen noch unterstützt wird. Die ZnO-Konzentration liegt üblicherweise in derIn addition to or instead of the alkalis, the alkaline earth metal ions, such as. B. Mg, Ca, Sr, Ba, in total between 0 and 50 wt .-%. The alkaline earth ions also act as network converters and serve to adjust the reactivity of the glass. The Ca plays a special role. In the case of special bioactive glasses, the presence of Ca allows a mineral layer to be formed on the particle surface in aqueous media, the so-called hydroxyapatite layer. The multi-component glasses can further comprise aluminum oxide. Aluminum oxide significantly influences the chemical stability and the crystallization stability of the glasses. The Al 2 0 3 concentration is preferably between 0% by weight and 25% by weight. In addition to the network components, the glass can include zinc oxide as an essential glass component. The Zn ions of the glass can be released and lead to an antimicrobial effect, which is further supported by alkali or alkaline earth ions. The ZnO concentration is usually in the
Ausgangszusammensetzung der Rohstoffe zwischen 0-25 Gew%. Ausserdem kann Zink die chemische Beständigkeit der Gläser verbessern.Starting composition of the raw materials between 0-25% by weight. Zinc can also improve the chemical resistance of glasses.
Die Multikomponentenmgläser können auch Titanoxid und/oder Zirkonoxid umfassen. Mit Hilfe dieser Zusätze kann gezielt die Brechzahl des Glaspulvers eingestellt werden. Insbesondere der Zusatz von TiO2 kann auch zur UV-Blockung eingesetzt werden.The multi-component glasses can also comprise titanium oxide and / or zirconium oxide. With the help of these additives, the refractive index of the glass powder can be adjusted. In particular, the addition of TiO 2 can also be used for UV blocking.
Falls die Nanopulver Glaskeramiknanopulver sind, können Zusätze von Ti02oder Zr02 als Keimbildner dienen.If the nanopowders are glass ceramic nanopowders, additions of Ti0 2 or Zr0 2 can serve as nucleating agents.
Des Weiteren ist mit Ti02 oder Zr02 eine Einstellung der chemischen Beständigkeit der Nanopulver möglich.Furthermore, the chemical resistance of the nanopowders can be adjusted using Ti0 2 or Zr0 2 .
Die hydrolytische Beständigkeit kann insbesondere durch die Zugabe von Zr02 verbessert werden, was insbesondere bei hygroskopischen Nanopulvern von Bedeutung ist. Neben der Brechzahlanpassung können TiO2 und ZrO2 auch zur Einstellung des E-Moduls genutzt werden.The hydrolytic resistance can be improved in particular by the addition of Zr0 2 , which is particularly important in the case of hygroscopic nanopowders. In addition to the refractive index adjustment, TiO 2 and ZrO 2 can also be used to adjust the modulus of elasticity.
Bevorzugt liegt die Konzentration von TiO2 zwischen 0 und 25 Gew% und die Konzentration von ZrO2 liegt zwischen 0 Gew% und 30 Gew%.The concentration of TiO 2 is preferably between 0 and 25% by weight and the concentration of ZrO 2 is between 0% and 30% by weight.
Zur Feinanpassung der Brechzahl kann das Nanoglaspulver Tantal- und/oder Wolframoxid umfassen.For fine adjustment of the refractive index, the nanoglass powder can include tantalum and / or tungsten oxide.
Neben oder statt Zn können zur Erzielung von antimikröbieller Wirksamkeit Ag, Cu, I im Glas enthalten sein. In Summe ist die Konzentration von Ag2Ü, CuO, ZnO, I kleiner 15 Gew%, bevorzugt kleiner 10; noch bevorzugter kleiner 5 Gew %.In addition to or instead of Zn, Ag, Cu, I can be contained in the glass to achieve antimicrobial activity. In total the concentration is from Ag2Ü, CuO, ZnO, I less than 15% by weight, preferably less than 10; more preferably less than 5% by weight.
Auch Edelmetalle wie Au, Pt können in metallischer oder oxidischer Form bis kleiner 10 Gew% vorzugsweise kleiner 5 Gew% am bevorzugtesten kleiner 2 Gew % enthalten sein.Precious metals such as Au, Pt can also be present in metallic or oxidic form up to less than 10% by weight, preferably less than 5% by weight, most preferably less than 2% by weight.
Farbgebende Ionen wie z. B. Cr, Mn, Ni, V, Ce, Fe, V, Co können in Summe (Oxid) bis zu 10 Gew% vorliegen.Coloring ions such as B. Cr, Mn, Ni, V, Ce, Fe, V, Co can be present in total (oxide) up to 10% by weight.
Selten Erd Ionen wie z. B. Eu, Ce, Sm, Nd, Er, Sm, Yb, können als Dotierung in üblichen Konzentrationen eingebracht werden.Rare earth ions such as B. Eu, Ce, Sm, Nd, Er, Sm, Yb, can be introduced as doping in conventional concentrations.
Fluor kann in den Gläsern als Schmelzhilfsmittel enthalten sein.Fluorine can be contained in the glasses as a melting aid.
Oxide der Elemente Nb, La, Pb und Bi dienen in erster Linie der Brechzahl bzw. Dispersionseinstellung.Oxides of the elements Nb, La, Pb and Bi serve primarily to adjust the refractive index or dispersion.
Die Zugabe von Elemente wie z. B. Ba, Cs, La ermöglicht es eine hohe Radioopazität einzustellen.The addition of elements such as B. Ba, Cs, La makes it possible to set a high radio opacity.
Auch Läutermittel, wie z. B. SnO, As203, Sb203, können in der üblichen Konzentrationen in den Nanoglaspulvern enthalten sein, mit Ausnahme der Nanogläser, die in dentalen, medizinischen und kosmetischen Anwendungen Verwendung finden.Refining agents, such as. B. SnO, As 2 0 3 , Sb 2 0 3 , can be contained in the usual concentrations in the nanoglass powders, with the exception of the nanoglass, which are used in dental, medical and cosmetic applications.
Die zuvor erwähnten Metalle Au, Ag, Pt, Cu können nicht nur in oxidischer, sondern auch in metallischer Form in der Glasmatrix vorliegen.The aforementioned metals Au, Ag, Pt, Cu can be present in the glass matrix not only in oxidic but also in metallic form.
Radioaktive Elemente können ebenfalls zugesetzt werden. In speziellen Ausführungsformen können auch Nitride oder Oxidnitride als Ausgangsmaterialien eingesetzt werden und darüber entsprechende Nitrid oder Oxinitrid-Nanogläser erhalten werden. Der Vorteil von Nitrid- oder Oxinitridnanogläser sind die besseren mechanischen Eigenschaften als bei oxidischen Gläsern.Radioactive elements can also be added. In special embodiments, nitrides or oxide nitrides can also be used as starting materials and corresponding nitride or oxynitride nanoglasses can be obtained in this way. The advantage of nitride or oxynitride nanoglass is the better mechanical properties than with oxide glasses.
Wie oben angegeben haben die erfindungsgemäßen Nanopulver mittlere Komgrössen kleiner 1 μm, bevorzugt kleiner 200 nm, insbesondere bevorzugt kleiner 100 nm, noch bevorzugter kleiner 50 nm, am bevorzugtesten kleiner 20 nm. In einer besonderen Ausführungsform werden Komgrössen kleiner 5 nm verwendet. In speziellen Ausführungsformen können die Nanopartikel kleiner 2 nm sein.As indicated above, the nanopowders according to the invention have average grain sizes of less than 1 μm, preferably less than 200 nm, particularly preferably less than 100 nm, more preferably less than 50 nm, most preferably less than 20 nm. In a particular embodiment, grain sizes less than 5 nm are used. In special embodiments, the nanoparticles can be smaller than 2 nm.
Die BET-Oberfläche herkömmlicher anorganischer Füllstoffe bei Dentalmaterialien liegt z. B. zw. 4 und 65 m2/g.The BET surface area of conventional inorganic fillers in dental materials is e.g. B. between 4 and 65 m 2 / g.
Im Gegensatz hierzu sind die BET-Oberfächen der Nanopartikel grösser als 50 m2/g , bevorzugt grösser als 100m2/g, noch bevorzugt grösser als 500 m2/g, am bevorzugtesten grösser als 900 m2/g.In contrast, the BET Oberfächen the nanoparticles are larger than 50 m 2 / g, preferably greater than 100m 2 / g, more preferably greater than 500 m 2 / g, bevorzugtesten greater than 900 m 2 / g.
Durch das hohe Oberflächen- zu Volumenverhältnis bei den erfindungsgemäßen Nanogläsern spielen die Oberflächeneigenschaften gegen über den Bulkeigenschaften eine zunehmend starke Rolle. Durch die hohe freie Oberfläche werden für den Fachmann auch bei an sich inerten Gläsern, wie es antimikrobielle Silikatgläser sind, überraschend hohe Reaktivitäten, insbesondere eine hohe lonenabgaben z. B. in wässrigen Medien oder in organischen Verbindungen, hohe antimikrobielle Wirkung der Pulver erzielt.Due to the high surface to volume ratio in the nanoglass according to the invention, the surface properties play an increasingly important role compared to the bulk properties. Due to the high free surface area, surprisingly high reactivities, in particular a high ion release, for example in the case of glasses which are inert per se, such as antimicrobial silicate glasses, are particularly high. B. achieved in aqueous media or in organic compounds, high antimicrobial effect of the powder.
Die Partikel können als Pulver und als Suspension zum Einsatz kommen. Es können sowohl amorphe, phasenentmischte, kristallisierte Glas bzw. Glaskeramik-Nanopartikel eingesetzt werden. Unterschiedliche Phasen können bereits im primären Herstellungsprozess oder in einer Nachprozessierung erreicht werden.The particles can be used as powder and suspension. Amorphous, phase-separated, crystallized glass or glass ceramic nanoparticles can be used. Different phases can be achieved in the primary manufacturing process or in post-processing.
Für die Verwendung als Füllstoff im Dentalbereich ist eine Modifikation der Oberfläche mit Organo-Silanen möglich und vorteilhaft, wie z. B. Methacryloxypropyl-tri-methoxy-Silan. Die verwendeten Organo-Silane zeichnen sich besonders dadurch aus, dass sie sowohl an die Glasoberfläche anbinden können als auch über eine organische funktioneile Seitengruppe an ein organisches Harz binden können. Dadurch wird einerseits das Einformulieren in die organische Harzmatrix erleichtert und andererseits die mechanische Stabilität erhöht. Am weitesten verbreitet für Dentalanwendungen ist das 3-Methacryloxypropyltrimethoxysilan, besser bekannt unter dem Handelsnamen MEMO von der Degussa. Daneben gibt es eine Vielzahl weiterer funktioneller Seitengruppen, wie zum Beispiel Amino-, Glycidoxyl-, Mercapto-, Vinyl-, Alyl-Gruppen mit den entsprechenden Spacern.For use as a filler in the dental field, a modification of the surface with organosilanes is possible and advantageous, such as. B. methacryloxypropyl-tri-methoxy-silane. The organosilanes used are particularly characterized by the fact that they can both bind to the glass surface and also bind to an organic resin via an organic functional side group. This facilitates the formulation in the organic resin matrix on the one hand and increases the mechanical stability on the other. The most widespread for dental applications is 3-methacryloxypropyltrimethoxysilane, better known under the trade name MEMO from Degussa. There are also a large number of other functional side groups, such as amino, glycidoxyl, mercapto, vinyl, alyl groups with the corresponding spacers.
Ionen der Elemente La, Ba, Sr, Y, Yb, Nb, Zr, Zn, dienen der Einstellung der Röntgensichtbarkeit von Dentalgläsern.Ions of the elements La, Ba, Sr, Y, Yb, Nb, Zr, Zn serve to adjust the x-ray visibility of dental glasses.
Die erfindungsgemäßen Nanopulvern, umfassend Multikomponentengläsern und -glaskeramiken können in den Bereichen Kosmetik z. B. als UV-Blocker für UV-A unό/oder UV-B, Dentalfüller, Oral Care, optische Polymere, Sinterwerkstoffe, antimikrobielle Anwendungen, im medizinischen Bereich als Wirkstoff oder Wirkstoffträger, zur Wasserfilterung, -reinigung, aufbereitung, als Lotgläser; als Pigmente, zum Rapid Prototyping, was die sehr schnelle Herstellung von dreidimensionalen Strukturen beschreibt, in Brennstoffzellen, als Abrasivmaterialien, zur Katalyse, als UV-Schutz, in Polierprozessen, in Textilfasern, in Thermoplasten, in Farben und Lacken; in der Oberflächentechnologie, als Antihaft-, Antikratz-, Antireflex-, Antibeschlag-, einfach zu reinigende Schicht, zum Korrosionsschutz; im Bereich der keramischen Technologien, als Rohstoffe z. B. für Gläser oder als Glaskeramik, zur Kristallherstellung, zur Herstellung von optischen Glaskeramiken und optischen Keramiken sowie optischen Polymeren, in der Lasertechnologie, in der Drucktechnologie, in der Biotechnologie, als Fluoreszenzmarker, als Luminiszenzstoff, als Klebstoff, in Polymeren (z. B. Duromere, Plastomere, Monomere), als Kontaktlinsen in Folien, Druckpapier; Leuchtmittel, Kopiertechnik, Membranen verwendet werden.The nanopowders according to the invention, comprising multicomponent glasses and glass ceramics can be used in the fields of cosmetics e.g. B. as a UV blocker for UV-A and / or UV-B, dental filler, oral care, optical polymers, sintered materials, antimicrobial applications, in the medical field as an active ingredient or active ingredient carrier, for water filtering, cleaning, treatment, as solder glasses; as pigments, for rapid prototyping, which describes the very rapid production of three-dimensional structures, in fuel cells, as abrasive materials, for catalysis, as UV protection, in polishing processes, in textile fibers, in thermoplastics, in paints and varnishes; in surface technology, as non-stick, anti-scratch, anti-reflective, anti-fog, easy to clean layer, for corrosion protection; in the field of ceramic technologies, as raw materials e.g. B. for glasses or as glass ceramics, for crystal production, for the production of optical glass ceramics and optical ceramics and optical polymers, in laser technology, in printing technology, in biotechnology, as a fluorescent marker, as a luminescent substance, as an adhesive, in polymers (e.g. Duromers, plastomers, monomers), as contact lenses in foils, printing paper; Illuminants, copying technology, membranes can be used.
Eine weitere Applikation stellt die Verwendung der Nanogläser im Bereich derAnother application is the use of nanoglass in the field of
Elektronik dar, beispielsweise als Glaslote zum Fügen oder als Passivierungsglas für Halbleiterbauelemente.Electronics, for example as glass solders for joining or as passivation glass for semiconductor components.
Die Herstellung der Nanopartikel erfolgt beispielsweise in einem PVD-Verfahren (Physical Vapor Deposition). Die PVD-Verfahren beschreiben eineThe nanoparticles are produced, for example, in a PVD process (Physical Vapor Deposition). The PVD processes describe one
Aufdampftechnik. Betreffend derartige PVD-Verfahren wird auf H. D. Junge und G. Müller, VDI-Lexikon Elektrotechnik, 1994, S.26 bis 27 oder VDI-Lexikon „Werkstofftechnik" VDI-Verlag, 1993, S. 810 - 811 sowie S. 5 - 6 verwiesen. Der Offenbarungsgehalt dieser Schriften wird vollumfänglich in die vorliegende Anmeldung mitaufgenommen. Bei PVD-Verfahren werden alle Stoffe des Glases in einem Plasma verdampft. Die verdampften Stoffe werden an einer kalten Fläche, beispielsweise einer Substratoberfläche abgeschieden und organisieren sich im glasigen Zustand neu. Es entstehen die erfindungsgemäßen Mehrkomponenten-Glas- oder Glaskeramik-Nanopartikel. Wie zuvor beschrieben kann neben Nanogläsern auch eine Nanoglaskermik oder ein Nanoglas, welches ein entmischtes System umfasst, auf diesem Weg hergestellt werden. Auch ist es möglich so hergestellte Nanogläser nachträglich einer Keramisierung zu unterwerfen. Auch die Herstellung von Nanopartikel mit Hilfe von Sol Gel- Verfahren ist möglich.Vapor deposition technique. With regard to such PVD processes, HD Junge and G. Müller, VDI-Lexikon Elektrotechnik, 1994, pp. 26 to 27 or VDI-Lexikon "Werkstofftechnik" VDI-Verlag, 1993, pp. 810 - 811 and pp. 5 - 6 The disclosure content of these documents is fully incorporated into the present application. In PVD processes, all substances in the glass are evaporated in a plasma. The evaporated substances are deposited on a cold surface, for example a substrate surface, and reorganize in the glassy state The multicomponent glass or glass ceramic nanoparticles according to the invention are produced.As described above, in addition to nanoglasses, a nanoglass ceramic or a nanoglass, which comprises a segregated system, can also be produced in this way. The production of nanoparticles using the sol-gel method is also possible.
Neben den beschriebenen PVD-Verfahren können auch CVD-Verfahren verwendet werden. CVD-Verfahren (Chemical Vapor Deposition) beschreiben die chemische Abscheidung aus der Gasphase. Betreffend CVD-Verfahren wird auf das VDI-Lexikon „Werkstofftechnik" VDI-Verlag 1993, S.139 sowie S.5 - 6 verwiesen, dessen Offenbarungsgehalt vollumfänglich in den Offenbarungsgehalt der vorliegenden Anmeldung mitaufgenommen wird.In addition to the PVD processes described, CVD processes can also be used. CVD (Chemical Vapor Deposition) processes describe this chemical deposition from the gas phase. With regard to the CVD method, reference is made to the VDI lexicon "Material Technology" VDI-Verlag 1993, pp.139 and pp.5-6, the disclosure content of which is included in full in the disclosure content of the present application.
Ein weiteres Verfahren zur Herstellung von Nanopartikeln ist die Flammpyrolyse. Bei der Flammpyrolyse werden reaktive Gase in eine Flamme geleitet. In der Flamme werden die Nanopartikel synthetisiert und in kalten Regionen abgeschieden. Neben gasförmigen Rohstoffen können auch flüssige Rohmaterialien bei der Flammenpyrolyse eingesetzt werden.Another method for producing nanoparticles is flame pyrolysis. In flame pyrolysis, reactive gases are led into a flame. The nanoparticles are synthesized in the flame and deposited in cold regions. In addition to gaseous raw materials, liquid raw materials can also be used in flame pyrolysis.
Werden in den beschriebenen Verfahren, insbesondere im PVD-Verfahren nichtoxidisches Trägergas eingesetzt, so können Nitrid- oder Oxinitrid-Nanogläser hergestellt werden.If non-oxidic carrier gas is used in the processes described, in particular in the PVD process, nitride or oxynitride nanoglasses can be produced.
Zur Herstellung der beschriebenen Nanogläser oder Nano-Glaskeramiken eignen sich ganz besonders die oben beschriebenen PVD-Verfahren. Bei den PVD- Verfahren sind besonders die Plasmaverfahren, insbesondere Plasmaverfahren kombiniert mit Hochfrequenzverdampfung oder Elektronenverdampfung, geeignet. Die Plasmaverfahren zeichnen sich dadurch aus, dass die Verdampfung des Rohmaterials in einem Plasma erfolgt.The above-described PVD processes are particularly suitable for producing the described nanoglasses or nano-glass ceramics. In the case of the PVD processes, the plasma processes, in particular plasma processes combined with high-frequency evaporation or electron evaporation, are particularly suitable. The plasma process is characterized by the fact that the raw material is evaporated in a plasma.
Als Ausgangsmaterialien werden in den im Stand der Technik bekannten PVD- Verfahren Metalle oder Metalloxide werden.Metals or metal oxides are used as starting materials in the PVD processes known in the prior art.
Besonders bevorzugt ist es aber zur Herstellung der erfindungsgemäßen Multikomponentengläser mit Partikelgrössen kleiner 1 μm als Ausgangsmaterialien aber bereits Multikomponentengläser zu verwenden. Werden Multikomponentengläser als Ausgangsmaterialien eingesetzt, so können unterschiedliche Multikomponentengläser in unterschiedlichen Gewichtsanteilen und Korngrössenverteilungen gemischt werden. Durch die Verwendung von Multikomponentengläsern als Rohstoffe können bereits in einem Rohstoff geeignete Elementkombinationen zusammengestellt sein. Im PVD-Verfahren wird durch lokale Erwärmung des Multikomponentenglases als Rohstoff, dieser Rohstoff selektiv verdampft und die Rohstoffe dann als erfindungsgemäßes Glaspulver oder Glaskeramikpulver mit Partikelgrössen kleiner 1 μm wieder abgeschieden. Wie beschrieben werden die Ausgangsmaterialien beispielsweise in Stab- oder Pulverform in einen Rezipienten eingebracht und dort in einem Plasmabogen verdampft und in einem Gasstrom anschliessend die entsprechenden Nanopartikel abgeschieden.However, it is particularly preferred to use multicomponent glasses as starting materials for the production of the multicomponent glasses according to the invention with particle sizes smaller than 1 μm. If multi-component glasses are used as starting materials, different multi-component glasses can be mixed in different weight fractions and particle size distributions. By using multi-component glasses as raw materials, suitable element combinations can already be put together in one raw material. In the PVD process, local heating of the multicomponent glass as the raw material selectively evaporates this raw material and the raw materials are then deposited again as glass powder or glass ceramic powder according to the invention with particle sizes smaller than 1 μm. As described, the starting materials are introduced, for example in rod or powder form, into a recipient and evaporated there in a plasma arc and the corresponding nanoparticles are then deposited in a gas stream.
Der Vorteil des PVD-Verfahrens ist, dass durch die schnellen Abkühlraten auch kristallisationsanfällige Gläser in amorpher Form abgeschieden werden können. Dies betrifft auch Gläser die unter Standardschmelzbedingungen nicht stabil produziert werden können und von denen somit über konventionelles Schmelzen und Mahlen kein amorphes Glaspulver erhalten werden kann.The advantage of the PVD process is that the rapid cooling rates mean that glasses prone to crystallization can also be deposited in amorphous form. This also applies to glasses that cannot be produced stably under standard melting conditions and from which no amorphous glass powder can be obtained by conventional melting and grinding.
Durch Einführung unterschiedlicher Reaktionsgase können Oberflächenmodifkationen sowie Gesamtzusammensetzungsmodifkationen erzielt werden. Beispielsweise können mit Hilfe oxidischer Trägergase oxidische Gläser abgeschieden werden, mit Hilfe nicht-oxidische Trägergase beispielsweise Oxi- Nitrid-Gläser.By introducing different reaction gases, surface modifications as well as overall composition modifications can be achieved. For example, oxidic glasses can be deposited with the aid of oxidic carrier gases, for example oxi-nitride glasses with the help of non-oxidic carrier gases.
Aufgrund der sehr kleinen Partikelgrösse lassen sich die erfindungsgemäßen Gläser zur Spaltüberbrückung bei Bonding-Verfahren oder als Klebeverbindungen in optischen Applikationen, zur UV- oder IR-Absorption, zur Wärmedämmung, zur Lichtreflexion, als feuerresistenter Stoff, als Dichtstoff, als Glanzstoff, als Farbbrillianz-Stoff, sowie in der Elektrostatik verwenden.Due to the very small particle size, the glasses according to the invention can be used to bridge gaps in bonding processes or as adhesive bonds in optical applications, for UV or IR absorption, for thermal insulation, for light reflection, as fire-resistant material, as sealant, as glossy material, as color brilliance. Use fabric as well as in electrostatics.
Weitere Einsatzgebiete sind poröse Elektroden für Brennstoffzellen, Hartlote für Keramik-Metall-Verbindungen oder Tieftemperturlote. Hierbei insbesondere Lote im Bereich von Glas-Glas, Glas-Metall, Glass-Keramik oder Glas-Kristall Verbindungen. Weiterhin können allgemein jeweils Gläser, Keramiken, Glaskeramiken, Kristalle, Metalle mit solchen Loten untereinander verbunden werden.Other areas of application are porous electrodes for fuel cells, hard solders for ceramic-metal connections or low-temperature solders. In particular, solders in the field of glass-glass, glass-metal, glass-ceramic or glass-crystal compounds. Furthermore, glasses, ceramics, glass ceramics, crystals, metals can generally be connected to one another with such solders.
Auch können die erfindungsgemäßen Nanopartikel elektrophoretisch auf Oberflächen bzw. in porösen Körpern abgeschieden werden.The nanoparticles according to the invention can also be deposited electrophoretically on surfaces or in porous bodies.
Die im Stand der Technik beschrieben anorganischen nicht metallischen Biozide können nur in relativ grossen Partikelgrössen größer 1 μm hergestellt und eingesetzt werden. Sie haben daher eine geringere Wirksamkeit als organische Biozide.The inorganic non-metallic biocides described in the prior art can only be produced and used in relatively large particle sizes greater than 1 μm. They are therefore less effective than organic biocides.
Überraschenderweise kann durch die erfindungsgemäßen Nanopartikel die Reaktivität, insbesondere aber die antimikrobielle Wirksamkeit aussergewöhnlich stark gesteigert werden. Hierbei kommt nicht nur die höhere Verfügbarkeit der eingelagerten Wirkstoffe, wie z. B. Ag, Zn, Cu, zum Tragen, sondern die Glasoberfläche an sich mit einem entsprechenden Zetapotential bzw. lokal hohen pH-Werten. Die erhöhte Oberfläche generiert einen synergistischen zusätzlichen antimikrobiellen Effekt. Gegenüber den metallischen antimikrobiellen Nanopulvern beispielsweise Silber-Nanopulver ergibt sich der Vorteil dass die oxidischen Verbindungen wenig zur Verfärbung neigen und das Silber bereits in seine antimikrobielle wirksamen oxidierten Form vorliegt. Die Glas- oder Glaskeramik- Nanopartikel können von der Zusammensetzung so eingestellt werden, dass sie sich in wässrigen Systemen komplett auflösen.Surprisingly, the reactivity, but in particular the antimicrobial activity, can be increased extraordinarily strongly by the nanoparticles according to the invention. This is not only the higher availability of the stored active ingredients, such as. B. Ag, Zn, Cu, but the glass surface itself with a corresponding zeta potential or locally high pH values. The increased surface generates a synergistic additional antimicrobial effect. Compared to the metallic antimicrobial nanopowders, for example silver nanopowders, there is the advantage that the oxidic compounds have little tendency to discolour and the silver is already in its antimicrobial, effective, oxidized form. The composition of the glass or glass ceramic nanoparticles can be adjusted so that they completely dissolve in aqueous systems.
Werden Nanopulver aus Nullausdehnungsmaterial erfindungsgemäß erhalten, so eignen sich diese besonders für die Sinterung und als Füllstoff. Insbesondere ist es möglich durch Sinterung derartiger Nanopulver Nullausdehnungsformkörper über die Sinterroute herzustellen. Mit Hilfe der erfindungsgemäßen Nanopartikel ist es möglich die Sintertemperatur zu erniedrigen und sehr hohe Enddichten mit sehr geringer Porosität zu erreichen, die sich durch eine geringe Streuung und hohe Transparenz auszeichnen. Auch optische Gläser lassen sich aus den erfindungsgemäßen Nanopartikeln durch viskoses Sintern erhalten. Die Nanogläser ergeben zusammengesetzt einen Sintergrünling. Aufgrund e Zusammensetzung des Sintergrünlinges aus einer Vielzahl von einzelnen Nanopartikeln wird eine extrem hohe Oberfläche in den Sintergrünling eingebracht. Aufgrund dieser extrem hohen Oberfläche können besondere Gefüge mit kleinsten Kristallitgrössen erzeugt werden. Die Kristallisation des Sintergrünlinges kann hierbei je nach Glastyp sowohl oberflächengesteuert oder volumengesteuert ablaufen. Ein weiterer Vorteil der extrem hohen Oberfläche der Grünlinge ist, dass Nanokristalle (sowohl bei Volumen als auch bei oberflächengesteuerter Kristallisation) in den gesinteren Vollmaterialien erzeugt werden. Dies ist ein Weg, um Sinterglaskeramiken mit Nanokristallen zu erzeugen.If nanopowders are obtained from zero expansion material according to the invention, they are particularly suitable for sintering and as a filler. In particular, it is possible to produce zero-expansion shaped bodies by sintering such nanopowder over the sintering route. With the aid of the nanoparticles according to the invention it is possible to lower the sintering temperature and to achieve very high final densities with very low porosity, which are characterized by low scatter and high transparency. Optical glasses can also be obtained from the nanoparticles according to the invention by viscous sintering. Put together, the nano glasses form a sintered green compact. Due to the composition of the sintered green compact from a large number of individual nanoparticles, an extremely high surface area is introduced into the sintered green compact. Due to this extremely high surface, special structures with the smallest crystallite sizes can be created. Depending on the type of glass, the crystallization of the sintered green compact can take place either surface-controlled or volume-controlled. Another advantage of the extremely high surface area of the green compacts is that nanocrystals (both in terms of volume and surface-controlled crystallization) are generated in the sintered solid materials. This is one way of producing sintered glass ceramics with nanocrystals.
Durch die hohe Oberflächenreaktivität können Nano-Glaspulver auch als Sinterhilfsmittel für hochschmelzende Materialien eingesetzt werden. Eine andere Anwendung ist der Einsatz beim Verschmelzen temperaturempfindlicher Materialien oder Halbfertigprodukte. Mit Hilfe der früh einsetzendenDue to the high surface reactivity, nano-glass powder can also be used as a sintering aid for high-melting materials. Another application is the use in the melting of temperature-sensitive materials or semi-finished products. With the help of the early ones
Oberflächenreaktion kann hier die Löttemperatur herabgesetzt werden.Surface reaction, the soldering temperature can be reduced here.
Lotgläser aus Nanopartikeln insbesondere in Verbindung mit Lasersintern bzw. Laserlöten werden eingesetzt um möglichst niedrige Temperatur- und Spannungsbelastungen zu erzielen.Solder glasses made of nanoparticles, in particular in connection with laser sintering or laser soldering, are used to achieve the lowest possible temperature and voltage loads.
Ein weiterer Vorteile der erfindungsgemäßen Nanogläser liegt darin, dass im Gegensatz zu kristallinen keramischen Nanopartikeln Gläser in einem grossen Bereich in ihren optischen Lagen eingestellt werden können. Diese Möglichkeit der Einstellung betrifft beispielsweise die Transmission, Brechzahl, Dispersion und auch Teildispersion des Glases. Durch Mischungen von Polymeren mit Nanogläsern ist es möglich, Polymer-Glas-Komposite zu erhalten, bei denen die optischen Parameter sehr präzise eingestellt werden können. Durch die Variabilität der Glaschemie und entsprechender Oberflächenmodifikation die während und nach der Herstellung durchgeführt werden, können auch Eigenschaften wie die Dispergierfähigkeit eingestellt werden. Dies ist z. B. notwendig, wenn Nanopatikel in Monomeren dispergiert werden.Another advantage of the nanoglasses according to the invention is that, in contrast to crystalline ceramic nanoparticles, glasses can be adjusted in a wide range in their optical positions. This possibility of adjustment affects, for example, the transmission, refractive index, dispersion and also partial dispersion of the glass. By mixing polymers with nano glasses, it is possible to obtain polymer-glass composites in which the optical parameters can be set very precisely. Due to the variability of the glass chemistry and the corresponding surface modification that are carried out during and after production, properties such as dispersibility can also be adjusted. This is e.g. B. necessary if nanoparticles are dispersed in monomers.
Da aufgrund der geringen Partikelgrösse der Nanopartikel ein sehr hoher Füllgrad bis über 50 Gew% in die Monomere eingebracht werden kann, ohne die Viskosität des Monomers zu beeinflussen, kann durch den Einsatz von Nanopulvern aus Glas, welches beispielsweise im Brechungsindex an die Anwendung angepasst wird, ein hochgefülltes Polymeres mit geringem Polymerisationsschrumpf erzeugt werden. In den hochgefüllten Polymeren können dann optische Effekte, beispielsweise ein Tyndall-Effekt gezielt erzeugt oder auch vermieden werden.Since, due to the small particle size of the nanoparticles, a very high degree of filling up to over 50% by weight can be introduced into the monomers without affecting the viscosity of the monomer, the use of glass nanopowders, which are adapted to the application, for example, in the refractive index, a highly filled polymer with low polymerization shrinkage. Optical effects, for example a Tyndall effect, can then be selectively generated or avoided in the highly filled polymers.
Beim Einsatz farbiger Gläser ist es möglich, Polymere auch dann einzufärben, wenn handelsübliche keramische Pigmente nicht verwendet werden können und organische Farbstoffe aus Gründen der Toxikologie oder der chemischen, thermischen oder UV-Beständigkeit nicht eingesetzt werden sollen.When using colored glasses, it is possible to color polymers even when commercially available ceramic pigments cannot be used and organic dyes should not be used for reasons of toxicology or chemical, thermal or UV resistance.
Ein weiteres Einsatzgebiet der erfindungsgemäßen Nanoglaspulver ist das sogenannte Rapid Prototyping, d.h. die Herstellung dreidimensionaler Prototypen beispielsweise auf dem Gebiet des Tissue Engineering also der Herstellung dreidimensionaler Implantatgerüste, die als Trägermaterialien für das Wachstum von Gewebezellen dienen.Another area of application of the nanoglass powders according to the invention is so-called rapid prototyping, i.e. the production of three-dimensional prototypes, for example in the field of tissue engineering, i.e. the production of three-dimensional implant frameworks, which serve as carrier materials for the growth of tissue cells.
Die Nanoglaspulver bzw. Nanoglaskeramikpulver sind wegen der hohen Biokompatibilität auch als Implantatmaterial, Beschichtungsmaterial für Implantate oder Trägersystem für Medikamente einsetzbar. Wegen der entzündungshemmenden bzw. antimikrobiellen Eigenschaften sind die erfindungsgemäßen Nanogläser oder Nanoglaspulver auch direkt als Wirkstoff einsetzbar. Alternativ ist es möglich, die Wirkstoffe in das Glas einzubringen oder die Wirkstoffe auf die Glasoberfläche aufzubringen. Derartige Systeme stellen dann sogenannte „Releasesysteme" dar.Because of their high biocompatibility, the nano glass powder or nano glass ceramic powder can also be used as an implant material, coating material for implants or a carrier system for medication. Because of the anti-inflammatory or antimicrobial properties, the nanoglass or nanoglass powder according to the invention can also be used directly as an active ingredient. Alternatively, it is possible to introduce the active ingredients into the glass or to apply the active ingredients to the glass surface. Such systems then represent so-called “release systems”.
Auch Komposit-Materialien z. B. aus LGA und/oder PGA bzw. deren Copolymere für Biomaterial insbesondere für Tissue engineering sind möglich. LGA und PGA sind bioresorbierbare Polymere.Composite materials such. B. from LGA and / or PGA or their copolymers for biomaterial in particular for tissue engineering are possible. LGA and PGA are bioresorbable polymers.
Eine Verwendung im kosmetischen Bereich der erfindungsgemäßen Nanopartikel ist möglich. Insbesondere kann bei Anwendung im kosmetischen Bereich eine UV- blockende und/oder lichtstreuende Wirkung hervorgerufen werden.Use in the cosmetic field of the nanoparticles according to the invention is possible. In particular, when used in the cosmetic field, a UV blocking and / or light scattering effect can be produced.
Auch die Herstellung von erfindungsgemäßen Glas- und/oder Glaskeramiknanopartikel mit antioxidativer, entzündungshemmender, antimikröbieller, remineralisierender Wirkung ist möglich. Werden bestimmte Stoffe zugegeben, so ist es möglich magnetische Nanopartikel beispielsweise für durchblutungsfördernde Behandlungen herzustellen.The production of glass and / or glass ceramic nanoparticles according to the invention with an antioxidative, anti-inflammatory, antimicrobial, remineralizing effect is also possible. If certain substances are added, it is possible to produce magnetic nanoparticles, for example, for treatments that promote blood circulation.
Da die chemische Zusammensetzung der Gläser variiert werden kann, ist es möglich die mechanischen Eigenschaften der Nanopartikel aus Glas- oder Glaskeramik, wie z. B. Härte, E-Modul, Dichte, chemische Beständigkeit (z. B. gegen Wasser, Lauge u. Säuren) oder die elektrischen Eigenschaften, einzustellen und anzupassen. Neben der Partikelgrösse kann auch das Zetapotential durch Zusammensetzungs- und/oder Oberflächenmodifikationen angepasst werden.Since the chemical composition of the glasses can be varied, it is possible to change the mechanical properties of the nanoparticles made of glass or glass ceramic, such as. B. hardness, modulus of elasticity, density, chemical resistance (e.g. against water, lye and acids) or the electrical properties, adjust and adjust. In addition to the particle size, the zeta potential can also be adjusted by composition and / or surface modifications.
Nachfolgend soll die Erfindung anhand von Ausführungsbeispielen näher beschrieben werden.The invention will be described in more detail below on the basis of exemplary embodiments.
In Tabelle 1 sind Zusammensetzungen von Gläsern oder Ausgangsgläsern für Glaskeramiken in Gew.-% angegeben, aus denen mit den erfindungsgemäßen Verfahren Nanoglas- oder Nanoglaskeramikpartikel hergestellt werden können. Beispielsweise beziehen sich bei PVD-Verfahren die angegebenen Glaszusammensetzungen gemäß Tabelle 1 auf die Glaszusammensetzungen der Ausgangsgläser, die mit Hilfe beispielsweise eines Elektronenstrahles verdampft werden können. Die Glaszusammensetzung der im PVD-Verfahren abgeschiedenen Nanoglas- oder der Nanoglaskeramikpartikel, stimmen bei entsprechender Verfahrensführung im wesentlichen mit den Zusammensetzungen der Ausgangsgläser überein. Table 1 shows compositions of glasses or starting glasses for glass ceramics in% by weight, from which nanoglass or nanoglass ceramic particles can be produced using the methods according to the invention. For example, in the case of PVD processes, the glass compositions given in Table 1 relate to the glass compositions of the starting glasses, which can be evaporated using, for example, an electron beam. The glass composition of the nanoglass or nanoglass ceramic particles deposited in the PVD process essentially match the compositions of the starting glasses if the process is carried out appropriately.
Tabelle 1 : GlaszusammensetzungenTable 1: Glass compositions
Unter üblichen Läutermittel werden in dieser Anmeldung beispielsweise als Läutermittel Sn203,NaCI,As2θ3, Sb203 , As2S3 , Sb2S3 verstanden, als übliche Mengen eines üblichen Läutermittels werden 0 - 4 Gew% der Gesamtzusammensetzung verstanden. Im nachfolgenden sollen Ausführungsbeispiele für Nanoglaspulver und deren Verwendung gegeben werden. Ausführungsbeispiel 1 bezieht sich auf ein Nanoglaspulver, das in eine Polymermatrix eingebracht und zu einer antimikrobiellen Wirkung des Polymer- Nanoglas-Komposit-Werkstoffes führt. Gemäß Ausführungsbeispiel 1 werden 0,1 Gew% Nanoglaspulver mit einer Partikelgrösse kleiner 1 μm gemäß Beispiel 2 in Tabelle 1 in eine Polystyrolmatrix eingearbeitet und zu Platten extrudiert. Die antimikrobielle Wirksamkeit der Oberfläche wird nach ASTM-Standard getestet. Es wird eine Reduktion der Testkeime (E. Coli, Candida Albicans) um mehr als 2 log- Stufen bestimmt.In this application, customary refining agents are understood, for example, as refining agents Sn 2 0 3 , NaCl, As 2 O 3, Sb 2 0 3 , As 2 S 3 , Sb 2 S 3 , and the usual amounts of a conventional refining agent are 0 - 4% by weight of the total composition , Exemplary embodiments of nanoglass powder and their use are to be given below. Exemplary embodiment 1 relates to a nanoglass powder which is introduced into a polymer matrix and leads to an antimicrobial effect of the polymer-nanoglass composite material. According to embodiment 1, 0.1% by weight of nanoglass powder with a particle size of less than 1 μm according to Example 2 in Table 1 is incorporated into a polystyrene matrix and extruded into sheets. The antimicrobial effectiveness of the surface is tested according to the ASTM standard. A reduction in the test germs (E. Coli, Candida Albicans) by more than 2 log levels is determined.
Gemäß Ausführungsbeispiel 2 werden 0,1 Gew.-% bioaktives Nanoglaspulver mit Partikelgrößen kleiner 1nm gemäß Beispiel 1 in Tabelle 1, um eine Formulierung für ein Deodorant eingearbeitet. Eine signifikante Schweißreduktion wird beobachtet.According to embodiment 2, 0.1% by weight of bioactive nanoglass powder with particle sizes smaller than 1 nm according to Example 1 in Table 1 is incorporated into a formulation for a deodorant. A significant sweat reduction is observed.
In Ausführungsbeispiel 3 werden 50 Gew.-% des erfindungsgemäßenIn embodiment 3 50 wt .-% of the invention
Nanoglaspulver in ein Dentalharz einformuliert. Typische Dentalharze sind in der EP 0475239 und darin zitierten Schriften beschrieben. Das Nanoglas des Glaspulvers hat eine Glaszusammensetzung gemäß Beispiel 4 in Tabelle 1. Die mittlere Partikelgröße ist kleiner als 1 μm.Nanoglass powder formulated in a dental resin. Typical dental resins are described in EP 0475239 and the documents cited therein. The nanoglass of the glass powder has a glass composition according to Example 4 in Table 1. The average particle size is less than 1 μm.
In Ausführungsbeispiel 4 wird ein hochschmelzendes Glas (z. B. das Schott Glas mit Nummer 8330) mit Nanopulver als Beimischung gemischt, um die Sintertemperatur herabzusetzen.In exemplary embodiment 4, a high-melting glass (for example the Schott glass with number 8330) is mixed with nanopowder as an admixture in order to lower the sintering temperature.
Ausführungsbeispiel 5 betrifft ein Lotglas, bestehend aus 70 Vol% Nanoglaspulver mit einer Zusammensetzung gemäß Beispiel 9 in Tabelle 1 und einer Partikelgröße < 1 μm und 30 Vol% eines inerten Füllstoffes (z. B. Cordierit) zur Dehnungsanpassung. Das so erhaltene Nano-Kompositglaslot weist eine um 50°C geringere Einschmelztemperatur auf verglichen mit der gleichen Mischung des Ursprungsmaterials. Ausführungsbeispiel 6 betrifft ein Polymer - Glaskomposit, bei dem ein Fluorpolymer jeweils mit 5,10,20 Gew% eines Nanopulvers, das die Glaszusammensetzung eines Bleisilikatglases mit einer Brechzahl n = 1 ,9 aufweist, versetzt wird. Je nach Anteil des Nanopulvers im Fluorpolymeren verschiebt sich die Brechzahl des Kompositwerkstoffes zu höheren Werten.Embodiment 5 relates to a solder glass consisting of 70% by volume of nano glass powder with a composition according to Example 9 in Table 1 and a particle size of <1 μm and 30% by volume of an inert filler (eg cordierite) for adjusting the elongation. The nano-composite glass solder obtained in this way has a melting temperature which is 50 ° C. lower than that of the same mixture of the original material. Embodiment 6 relates to a polymer-glass composite, in which 5.10.20% by weight of a nanopowder, which has the glass composition of a lead silicate glass with a refractive index n = 1.9, is added to each fluoropolymer. Depending on the proportion of nanopowder in the fluoropolymer, the refractive index of the composite material shifts to higher values.
In Ausführungsbeispiel 7 wird 5 Gew.-% eines Nanoglaspulver mit Partikelgrößen kleiner 1 μm mit einer Glaszusammensetzung, die 2 Gew.-% Ti02 umfasst, einer Sonnenmilch-Formulierung zugegeben, um eine UV-Blockung zu erreichen. In exemplary embodiment 7, 5% by weight of a nanoglass powder with particle sizes smaller than 1 μm with a glass composition which comprises 2% by weight of TiO 2 is added to a sun milk formulation in order to achieve UV blocking.

Claims

Patentansprüche claims
1. Glas- oder Glaskeramikpulver umfassend Multikomponentengläser mit mindestens drei Elementen, dadurch gekennzeichnet, dass das Glas- oder Glaskeramikpulver eine mittlere Partikelgrösse kleiner 1 μm, vorzugsweise kleiner 0,1 μm, besonders bevorzugt kleiner 10 nm aufweist.1. Glass or glass ceramic powder comprising multi-component glasses with at least three elements, characterized in that the glass or glass ceramic powder has an average particle size of less than 1 μm, preferably less than 0.1 μm, particularly preferably less than 10 nm.
2. Glas- oder Glaskeramikpulver gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Glas- oder Glaskeramikpulver mehr als drei Elemente umfasst.2. Glass or glass ceramic powder according to claim 1, characterized in that the glass or glass ceramic powder comprises more than three elements.
3. Glas- oder Glaskeramikpulver gemäß einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass das Glas- oder Glaskeramikpulver mehr als vier Elemente umfasst.3. Glass or glass ceramic powder according to one of claims 1 to 2, characterized in that the glass or glass ceramic powder comprises more than four elements.
4. Glas- oder Glaskeramikpulver gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Glas- oder Glaskeramikpulver mehr als fünf Elemente umfasst.4. Glass or glass ceramic powder according to one of claims 1 to 3, characterized in that the glass or glass ceramic powder comprises more than five elements.
5. Glas- oder Glaskeramikpulver gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Ausgangsmaterial zur Herstellung, der Glas- oder Glaskeramikpartikel oder die Glas- oder Glaskeramikpulvernanopartikel selbst die nachfolgende Zusammensetzung (in Gew.-% auf Oxidbasis) umfasst:5. Glass or glass ceramic powder according to one of claims 1 to 4, characterized in that the starting material for production, the glass or glass ceramic particles or the glass or glass ceramic powder nanoparticles themselves comprises the following composition (in% by weight on an oxide basis):
Si02 0-90 B2O30-90 P205 0-90 Na20 0-30 Li20 0-30 K20 0-30 CaO 0-30 MgO 0-40 CsO 0-40 BaO 0-40 SrO 0-40 AI203 0-30 Ti02 0-20 ZnO 0-30 Nb203 0 - 40 La2O3 0 - 40 PbO 0 - 70 Bi203 0 - 70 W03 0-30 Zr02 0-40 Yb2O3 0-40 Y2O30-40 F 0-10 Ag20 0-5 Gew% CuO 0-10 Gew% wobei die Summe Si02+ B203+P205 grösser 25 Gew% istSi0 2 0-90 B 2 O 3 0-90 P 2 0 5 0-90 Na 2 0 0-30 Li 2 0 0-30 K 2 0 0-30 CaO 0-30 MgO 0-40 CsO 0-40 BaO 0-40 SrO 0-40 AI20 3 0-30 Ti0 2 0-20 ZnO 0-30 Nb 2 0 3 0 - 40 La 2 O 3 0 - 40 PbO 0 - 70 Bi 2 0 3 0 - 70 W0 3 0-30 Zr0 2 0-40 Yb 2 O 3 0-40 Y 2 O 3 0-40 F 0-10 Ag 2 0 0-5 wt% CuO 0-10 wt % where the sum Si0 2 + B 2 0 3 + P 2 0 5 is greater than 25% by weight
6. Glas- oder Glaskeramikpulver nach Anspruch 5, dadurch gekennzeichnet, dass die Zusammensetzung (in Gew.-% auf Oxidbasis) umfasst:6. Glass or glass ceramic powder according to claim 5, characterized in that the composition (in wt .-% on an oxide basis) comprises:
Si02 50-80 B2O30-15 P205 0-20 Na20 0-10 Li20 1-15 K2O 0-15 CaO 0-15 MgO 0-15 BaO 0-5 SrO 0-5 Al203 0-30 TiO2 0-10 ZnO 0-10 ZrO2 0-10 F 0-10 sowie übliche Läutermittel in üblichen Mengen.Si0 2 50-80 B 2 O 3 0-15 P 2 0 5 0-20 Na 2 0 0-10 Li 2 0 1-15 K 2 O 0-15 CaO 0-15 MgO 0-15 BaO 0-5 SrO 0-5 Al 2 0 3 0-30 TiO 2 0-10 ZnO 0-10 ZrO 2 0-10 F 0-10 as well as usual refining agents in usual amounts.
7. Glas- oder Glaskeramikpulver gemäß Anspruch 5, dadurch gekennzeichnet, dass die Glaszusammensetzung 40 - 80 Gew% P205 enthält.7. Glass or glass ceramic powder according to claim 5, characterized in that the glass composition contains 40-80% by weight of P 2 0 5 .
8. Glas- oder Glaskeramipulver gemäss Anspruch 5, dadurch gekennzeichnet, dass die Glaszusammensetzung 30-80 Gew% B203 enthält.8. Glass or glass ceramic powder according to claim 5, characterized in that the glass composition contains 30-80% by weight of B 2 0 3 .
9. Glas- oder Glaskeramikpulver nach Anspruch 5, dadurch gekennzeichnet, dass die Glaszusammensetzung 20 - 95 Gew% Si02 enthält.9. Glass or glass ceramic powder according to claim 5, characterized in that the glass composition contains 20-95% by weight Si0 2 .
10. Glas- oder Glaskeramikpulver nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, dass die Glaszusammensetzung 4 - 30 Gew% CaO enthält.10. Glass or glass ceramic powder according to one of claims 5 to 9, characterized in that the glass composition contains 4 - 30 wt% CaO.
11. Glas- oder Glaskeramikpulver nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, dass die Glaszusammensetzung 4 - 30 Gew% Na20 enthält.11. Glass or glass ceramic powder according to one of claims 5 to 9, characterized in that the glass composition contains 4 - 30 wt% Na 2 0.
12. Glas- oder Glaskeramikpulver nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, dass die Glaszusammensetzung 40 - 80 Gew.-% Si02 und 5 - 50 Gew.-% B203 enthält.12. Glass or glass ceramic powder according to one of claims 5 to 9, characterized in that the glass composition contains 40-80% by weight Si0 2 and 5-50% by weight B 2 0 3 .
13. Glas- oder Glaskeramikpulver nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Glaszusammensetzung Ag, Cu, Zn, I enthält.13. Glass or glass ceramic powder according to one of claims 1 to 12, characterized in that the glass composition contains Ag, Cu, Zn, I.
14. Glas- oder Glaskeramikpulver nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass das Glas- oder Glaskeramikpulver entzündungshemmende Wirkung aufweist.14. Glass or glass ceramic powder according to one of claims 1 to 13, characterized in that the glass or glass ceramic powder has an anti-inflammatory effect.
15. Glas- oder Glaskeramikpulver nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass das Glas- oder Glaskeramikpulver mittels PVD-Verfahren hergestellt wird.15. Glass or glass ceramic powder according to one of claims 1 to 14, characterized in that the glass or glass ceramic powder is produced by means of the PVD process.
16. Verwendung von Glas- oder Glaskeramikpulvern nach einem der Ansprüche 1 bis 15 in einem oder mehreren der nachfolgenden Gebiete: im Bereich Oral Care im Bereich Dentalfüllstoffe in medizinischen Produkten in der Sintertechnologie als antimikrobielle Wirkstoffe als Füllstoff für Polymere im Bereich Kosmetika im Bereich Lotgläser im Bereich Oberflächen im Bereich Dentalkeramiken im Bereich Medizinprodukte als Passivierungsmittel mit Passivierungseigenschaften mit einer organofunktionalisierten Oberfläche im Bereich Infiltrationsgläser oder im Bereich Photokatalyse. 16. Use of glass or glass ceramic powders according to one of claims 1 to 15 in one or more of the following areas: in the field of oral care in the field of dental fillers in medical products in sintering technology as antimicrobial agents as filler for polymers in the field of cosmetics in the field of solder glasses in Surfaces in the field of dental ceramics in the field of medical products as passivating agents with passivation properties with an organofunctionalized surface in the area of infiltration glasses or in the area of photocatalysis.
EP05744811A 2004-05-29 2005-05-25 NANO GLASS POWDER AND USE THEREOF, PARTICULARLY MULTICOMPONENT GLASS POWDER WITH A MEAN PARTICLE SIZE OF LESS THAN 1 µM Withdrawn EP1751071A2 (en)

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US20080044488A1 (en) 2008-02-21
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