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.

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• 2004
  • 2004-05-29 DE DE102004026433A patent/DE102004026433A1/de not_active Withdrawn
• 2005
  • 2005-05-25 US US11/597,959 patent/US7816292B2/en not_active Expired - Fee Related
  • 2005-05-25 JP JP2007513794A patent/JP2008500935A/ja active Pending
  • 2005-05-25 WO PCT/EP2005/005633 patent/WO2005115936A2/de not_active Ceased
  • 2005-05-25 EP EP10000497A patent/EP2189426A1/de not_active Withdrawn
  • 2005-05-25 EP EP05744811A patent/EP1751071A2/de not_active Withdrawn
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