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WO2008135542A1 - Structures multicanal modifiées - Google Patents

Structures multicanal modifiées Download PDF

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Publication number
WO2008135542A1
WO2008135542A1 PCT/EP2008/055458 EP2008055458W WO2008135542A1 WO 2008135542 A1 WO2008135542 A1 WO 2008135542A1 EP 2008055458 W EP2008055458 W EP 2008055458W WO 2008135542 A1 WO2008135542 A1 WO 2008135542A1
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WIPO (PCT)
Prior art keywords
channel structure
particles
coating
precursor material
channels
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Ceased
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PCT/EP2008/055458
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German (de)
English (en)
Inventor
Jörn Volkher WOCHNOWSKI
Jürgen HECK
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Universitaet Hamburg
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Universitaet Hamburg
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Filing date
Publication date
Application filed by Universitaet Hamburg filed Critical Universitaet Hamburg
Priority to EP08750022A priority Critical patent/EP2152928A1/fr
Publication of WO2008135542A1 publication Critical patent/WO2008135542A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • 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
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0209—Pretreatment of the material to be coated by heating
    • C23C16/0218—Pretreatment of the material to be coated by heating in a reactive atmosphere
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
    • G21K1/06—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators
    • G21K1/067—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators using surface reflection, e.g. grazing incidence mirrors, gratings
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/254—Noble metals
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K2201/00—Arrangements for handling radiation or particles
    • G21K2201/06—Arrangements for handling radiation or particles using diffractive, refractive or reflecting elements
    • G21K2201/067—Construction details

Definitions

  • the invention relates to modified multi-channel structures, to processes for their production and to the use of the modified multichannel structures.
  • Channel systems such as polycapillary structures are used in a variety of technical fields.
  • polycapillary structures are known above all as op- tics for focusing X-ray and neutron radiation (MA Kumakhov, FF Komarov, Multiple Reflection from Surface X-Ray Optics, Physics Reports 191, No. 5 289-350, 1990).
  • Polycapillary structures are also increasingly used as microcontainers, separators or microreactors for medical, chemical and biological applications (Optical Technologies from Berlin and Brandenburg, Newsletter No. 7, July 2003). They are produced from regularly arranged, uncoated glass capillaries or glass rods with the help of various drawing and sintering processes.
  • the known multichannel systems are not internally coated.
  • Multi-channel structures can be produced with almost any geometrical parameters of both the inner channels and the overall structure.
  • the above-mentioned polycapillary structures are currently produced exclusively from glass, since glass is the sole material because of its unique technical-physical and chemical properties (high radiation resistance, very good moldability, optimum flow properties and ease of processing), which meets the high requirements for production fully complied with polycapillary structures (V. Arkadiev, A. Bjeouhmov, Handbook of Practical X-Ray Fluorescence Analysis, Springer, 107-111, 2006).
  • the invention also relates to a method for producing a modified multi-channel structure according to claims 9 to 31 and to the use of a modified multi-channel structure according to claims 32 and 33.
  • the modified multichannel structure according to the invention is characterized in that (a) it has at least 10, preferably at least 100, more preferably at least 1000 and most preferably at least 10000 channels (eg at least several tens of thousands such as 20,000, 30,000, 40,000, 50,000 or more) and (B) in the channels of the multi-channel structure an inner coating and / or particles are introduced.
  • multichannel structure here refers to a structure which already exists prior to the introduction according to the invention of the inner coating and / or of the particles and which consists of a plurality of channels arranged at regular intervals at regular intervals and open at the ends.
  • multi-channel structures are polycapillaries, composite lenses made of individual mono- and / or polycapillaries, monolithic lenses made of individual mono- and / or polycapillaries, photonic crystals and monolithic integral microlenses.
  • the inner diameters of the individual channels of the multi-channel structures are usually in the range of 1 nm to 10 mm. Preferably, the inner diameters are smaller than 1000 ⁇ m, in particular smaller than 100 ⁇ m.
  • the inner diameter of the first cylindrical body For example, in general, the inner diameter of the first cylindrical body
  • Polycapillaries are usually monolithic structures having a plurality of channels, which channels are of substantially equal length and usually have a length to internal diameter ratio of at least about 100: 1, preferably at least about 1000: 1.
  • Polycapillaries may, for example, contain more than 10 3 to more than 10 6 channels which have internal diameters of, for example, less than 1 mm to less than 1 ⁇ m.
  • Photonic crystals are artificial periodic structures of a dielectric (e.g., glass) having specific optical properties. In addition to glass, other materials can also be used. Photonic crystals are used, for example, in optical metrology, communications and life sciences and are described in VP Bykov, "Spontaneous emission in a periodic structure", Soviet Physics JETP, American Institute of Physics, New York 1972, 35, 269 and K Busch et al. (Ed.), “Photonic Crystals - Advances in Design, Fabrication, and Characterization", Wiley-VCH, 1st Edition, 2004.
  • VP Bykov "Spontaneous emission in a periodic structure”
  • Soviet Physics JETP American Institute of Physics, New York 1972, 35, 269 and K Busch et al. (Ed.)
  • Photonic Crystals - Advances in Design, Fabrication, and Characterization Wiley-VCH, 1st Edition, 2004.
  • Monolithic integral microlenses are very largely miniaturized multi-channel structures which, for example, can have channels with inner diameters of about 0.3 to 1 ⁇ m.
  • Multi-channel structures often have a relatively thin channel wall in direct comparison to their outer wall.
  • This channel wall is significantly thinner than the outer wall of monocapillaries, as it serves only for the separation of the channels and has no structure-supporting function as in monocapillaries. This is possible with multichannel structures because of their monolithic overall structure.
  • the modified multi-channel structure according to the invention has a large inner surface and a large quotient of inner surface to inner volume. As a result, it is possible, for example, to carry out catalytic reactions with high efficiency and high throughput in the presence of a suitable coating or suitable particles.
  • Modified multi-channel structures according to the invention can have a wide variety of shapes and geometries. Examples of suitable shapes are cylindrical and non-cylindrical, for example elliptical or parabolic multi-channel structures.
  • the multichannel structure according to the invention preferably consists of glass.
  • the multi-channel structure contains heat conducting wires or heat conducting wires, eg by introducing metals, in particular heat conducting wires, into the multi-channel structure during the production of the multi-channel structure (eg in the stretching process).
  • heat conducting wires or heat conducting wires eg by introducing metals, in particular heat conducting wires, into the multi-channel structure during the production of the multi-channel structure (eg in the stretching process).
  • the coating and / or the particles of the modified multi-channel structure according to the invention usually contain an element other than carbon from the second to fifth main group or a subgroup of the Periodic Table of the Elements.
  • the coating and / or the particles contain an element selected from the group consisting of Zr, V, Cr, Mo, W, Ni, Cu, Pd, Pt, Au, Fe, Al, Re, Rh, Ru and Ir, with the elements Ni, Cr, Mo, Cu, Pd, Pt, Rh, Ru and Ir being particularly preferred. Coatings and particles containing these elements are particularly suitable for catalytic applications.
  • the coating and / or the particles contain an element selected from the group consisting of Be, Ni, Pt, Cu, Pd, Ag, W, Re, Ir, Os, Au, Pb, Bi and U, wherein the elements Ni, Ag, Au, W, Pb, Pt, Bi and U are particularly preferred. Coatings and particles containing these elements are particularly suitable for optical applications and applications in the guidance of electromagnetic radiation.
  • the coating and / or particles can consist, for example, of metal layers and / or metal particles, of metal oxide layers and / or metal oxide particles or of metal carbide layers and / or metal carbide particles.
  • a coating and / or particles for optical applications particularly preferably consist of amorphous metal layers and / or amorphous metal particles.
  • a coating and / or particles for catalytic applications particularly preferably consist of crystalline metal oxide layers and / or crystalline metal oxides. oxide particles.
  • the thickness of the coating can be varied within wide ranges depending on the inner diameters of the individual channels. For example, a coating according to the invention may have a thickness in the range from 1 to 1000 nm (frequently in the range from 10 to 250 nm, for example about 100 nm).
  • the invention also relates to a method for producing the modified multi-channel structures according to the invention.
  • This method is characterized in that the inner coating and / or the particles by a wet chemical process
  • wet chemical impregnation, dip coating a photolytic process (for example, laser coating), an electrochemical process (for example, an electrochemical coating process), a plasma technology process or a gas phase process are introduced into the multi-channel structure.
  • a photolytic process for example, laser coating
  • an electrochemical process for example, an electrochemical coating process
  • a plasma technology process or a gas phase process are introduced into the multi-channel structure.
  • wet-chemical methods for introducing the inner coating and / or the particles into multi-channel structures are particularly applicable to multi-channel structures whose inner channels have diameters of at least 400 ⁇ m.
  • wetting agent examples include sulfates of unbranched primary C 1 -C 6 -alcohols, such as sodium lauryl sulfate, and benzenesulfonates preferably substituted with branched C 1 -C 8 -alkyl groups, such as sodium dodecylbenzenesulfonate.
  • Suitable commercially available wetting agents are, for example, wetting agents H 135 and DL from Enthone, Inc., West Haven, CT, USA.
  • Examples of gas-phase processes are chemical vapor deposition (CVD), chemical vapor infiltration
  • CVI chemical vapor deposition
  • PVD Physical Vapor Deposition
  • methods are suitable in which the interior Layering and / or the particles by chemical vapor deposition of organometallic compounds, for example chemical vapor deposition of organometallic compounds (OMCVD), chemical vapor infiltration of elemental compounds, for example chemical vapor infiltration of organometallic compounds (OMCVI), or gas phase epitaxy of organometallic compounds, for example gas phase epitaxy Organometallic compounds (OMVPE) into which multichannel structures are introduced.
  • OMCVD chemical vapor deposition of organometallic compounds
  • OMCVI chemical vapor infiltration of elemental compounds
  • OMCVI chemical vapor infiltration of organometallic compounds
  • OCVPE gas phase epitaxy Organometallic compounds
  • organometallic compounds for gas-phase processes are in particular also complex or coordination compounds which contain an organic ligand and / or carbonyl.
  • Complex or coordination compounds which contain a ligand selected from the group consisting of carbonyl, hexafluoroacetylacetonato and acetylacetonato are preferred.
  • Coating processes using high temperatures or energies can destroy the thin channel wall of multi-channel structures due to the action of energy.
  • chemical vapor deposition of organometallic compounds in particular the chemical vapor deposition of organometallic compounds (OMCVD), here a coating process is provided, can be carried out with the coatings of multi-channel structures at relatively low temperatures, without the thin channel walls of the muI tikanal Modellen damage or destroy.
  • OMCVD chemical vapor deposition of organometallic compounds
  • the invented The method according to the invention is also particularly suitable for producing modified multi-channel structures with special or complex geometries, such as elliptical multi-channel structures.
  • a method for producing the modified multi-channel structure according to the invention comprises the steps
  • the multi-channel structure is first of all connected in a gastight manner to a vacuum system by means of a temperature-stable adhesive, preferably a two-component adhesive.
  • a temperature-stable adhesive preferably a two-component adhesive.
  • a suitable vacuum system is described, for example, in DE 198 52 722 C1.
  • suitable two-component adhesives are epoxy resin adhesives, which are temperature-stable up to about 450 K, and silicone adhesives, which are temperature-stable up to about 570 K.
  • the adhesive is cured for a sufficient time.
  • the inner surfaces of the channels of the multi-channel structure may be activated.
  • This activation of the inner surfaces can be carried out, for example, by passing molecular oxygen, preferably at a temperature in the range from 480 K to 773 K.
  • molecular oxygen preferably at a temperature in the range from 480 K to 773 K.
  • the channels of the multi-channel structure may be cleaned. This can be done for example by plasma treatment, for example by an inductively or capacitively generated plasma, chemical processes and / or evacuation with simultaneous annealing.
  • the cleaning of the inner channels of the multi-channel structure by evacuation at a pressure below 10 ⁇ 3 mbar with simultaneous annealing, preferably at a temperature in the range of 473 K to 773 K occur.
  • a pressure gradient is established between the ends of the multichannel structure.
  • the multi-channel structure is evacuated from one of its ends.
  • a minimum pressure of less than 10 -2 mbar at this end, preferably set less than 10 "mbar and most preferably less than 10 ⁇ 4 mbar.
  • the transport of the precursor material Furthermore, the multi-channel structure can also be supported by an adjustable carrier gas flow.
  • the entire multi-channel structure is set to a constant basic temperature in the range from 273 K to 2073 K, preferably 293 K to 873 K, which is 50 K to 150 K, preferably 80 K to 120 K below the decomposition temperature of the precursor material.
  • the constant basic temperature can be adjusted, for example, by heating or heating with a heater (e.g., electric heater or induction furnace) or by coupling in electromagnetic waves (e.g., microwave or infrared radiation).
  • the precursor material is vaporized and transported through the multichannel structure by the pressure gradient, optionally with the assistance of the carrier gas stream.
  • the precursor stream and optionally the carrier gas stream can be preheated to a defined temperature, this temperature being 50 K to 150 K, preferably 80 K to 120 K below the decomposition temperature of the precursor material.
  • the deposition of a coating and / or of particles from the precursor material takes place by locally limited supply of energy.
  • This energy supply locally sets a temperature which is equal to or greater than the decomposition temperature of the precursor material.
  • the supply of energy by a heat or radiant heater, an oven, a laser, microwave radiation and / or a plasma.
  • a heat or radiant heater for the controllable deposition of the inner coating and / or the particles.
  • the adjustment of the multi-channel structure according to the invention to a constant basic temperature below the decomposition temperature of the precursor material can reduce the local additional energy supply necessary for the coating.
  • the temperature which is set locally limited, can be unchanged over the duration of the coating process. In the course of the coating process, however, this temperature can also be varied. Thus, in particular in the case of an autocatalytic acceleration of the decomposition of the precursor material by its decomposition product, the locally limited temperature can be reduced in the course of the coating process.
  • Such autocatalytic growth of the coating is observed, for example, when bis (1,1,5,5,5-hexafluoro-2,4-pentanedionato) palladium (II) is used as the precursor material, in particular when hydrogen is used as the carrier gas is used.
  • a chemical, physical and / or morphological change of the coating and / or the particles can be effected.
  • suitable gases are oxygen, hydrogen or nitrogen.
  • metal coatings or metal particles can be oxidized to catalytically active metal oxides or impurities removed by combustion, for example from organic radicals to carbon dioxide.
  • the method for producing the modified multi-channel structures according to the invention may further comprise performing an in-situ process analysis and process control. This makes it possible to optimize the process. Process analysis can be carried out, for example, by optical measurement methods, by online mass spectrometry or by taking gas samples and by gas chromatography.
  • a product analysis of the modified multichannel structures produced according to the invention is also possible to carry out a product analysis of the modified multichannel structures produced according to the invention.
  • suitable preparations can be made for carrying out an analysis, for example cross-sections by means of an ultramicrotome for energy-dispersive X-ray measurements, in particular a two-dimensional X-ray mapping, as well as for trans-electron microscopic or scanning electron microscopy investigations.
  • a measurement of the inner surfaces of the channels e.g. by means of BET or mercury porosimetry, as well as a determination of the channel internal diameter distribution and the change in the corresponding parameters brought about by the modifications made.
  • precursor materials can be used in the process according to the invention. It is advantageous if the precursor material is a sublimable material, with an easily sublimable material being preferred.
  • the precursor material may be an organometallic compound having at least one metal-carbon bond, or a complex or coordination compound containing an organic ligand and / or carbonyl.
  • Complex or coordination compounds which contain a ligand selected from the group consisting of carbonyl, hexafluoroacetylacetonato and acetylacetonato are preferred.
  • the Precursorma- material contains an element which is selected from the group consisting of Zr, V, Cr, Mo, W, Ni, Cu, Pd, Pt, Au, Fe, Al, Re, Rh, Ru and Ir, with the elements Ni, Cr, Mo, Cu, Pd, Pt, Rh, Ru and Ir being particularly preferred.
  • a precursor material which is selected from the group consisting of
  • the precursor material includes an element selected from the group consisting of Be, Ni, Pt, Cu, Pd, Ag, W, Re, Ir, Os, Au, Pb,
  • Precursor material selected from the group consisting of
  • Precursor material selected from the group consisting of
  • TEOS Tetraethyl orthosilicate
  • TMOS Tetramethyl orthosilicate
  • Tetrabutoxysilane triethoxyphenylsilane, methyltripropoxysilane, 1, 2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane,
  • the method according to the invention may also include destroying the multi-channel structure, preferably by chemical dissolution of the multi-channel structure.
  • the choice of the agent for the chemical dissolution of the multichannel structure depends on the material of the multichannel structure.
  • a suitable means for dissolving a multi-channel structure consisting of glass is, for example, hydrofluoric acid.
  • the method according to the invention also offers the possibility of producing special solid-state structures.
  • Solid-state structures with very small dimensions for example nanostructured solid-state structures, can have significantly different mechanical, optical, electrical and magnetic properties compared to corresponding macroscopic systems. Technologies that enable controlled, locally defined growth of such structures will be of considerable importance in the future.
  • the process according to the invention therefore also makes available a technology which makes it possible to produce particles-in particular metallic particles-with very narrow size distributions in relatively large quantities.
  • an agglomeration of the particles is avoided by their fixation on the inner surface of the channels of the multi-channel structures.
  • the maximum diameter of the individual particles is limited by the diameter of the channels.
  • tubes and rods can be produced by a uniform inner coating, the diameter of which is determined by the diameter of the channels.
  • nanotubes eg carbon nanotubes, CNTs
  • nanorods and nanowires eg nanopillars, nanorods, nanowires, nanofibers or nanofilaments
  • the type of growth can be controlled by selecting the material of the multi-channel structures, the precursor material and the coating parameters (eg temperature or temperature gradient, pressure, residence time or contact time).
  • coatings with high surface area, in particular rough layers and / or particles are particularly suitable for catalytic applications.
  • smooth coatings are advantageous for applications in guiding electromagnetic waves.
  • the invention also relates to the use of the modified multi-channel structures according to the invention.
  • the invention relates to the use of the modified multi-channel structures according to the invention for carrying out catalytic reactions (microreactors), for separation processes, e.g. as a membrane, separator, (molecular) sieve or as a (molecular) filter, as a memory (microcontainer) or for shaping, guiding, focusing and amplifying electromagnetic waves or particle radiation.
  • Modified multi-channel structures according to the invention can be used both for homogeneous catalytic and heterogeneous catalytic applications, e.g. catalytic gas phase reactions are used.
  • Modified multi-channel structures for catalytic applications preferably contain particles, particularly preferably nanoparticles with a narrow size distribution. Examples of catalytic gas phase reactions are C, C bond-forming reactions, oligomerization reactions and oxidation reactions.
  • Modified multi-channel structures according to the invention can also be used, in particular, for the shaping, guiding, focusing and amplification of electromagnetic waves or particle radiation, in particular of microwaves, the wavelength range from 100 cm to 1 mm, of visible light, the wavelength range of 380 to 750 nm being particularly preferred, of UV radiation, the wavelength ranges being from 50 to about 190 nm (VUV range) and 1 to 50 nm (EUV range) are particularly preferred, of laser radiation, X-rays and particle radiation ( ⁇ -radiation and neutron radiation) can be used.
  • the hard X-radiation in particular the discrete wavelengths of the CuK ⁇ radiation (8 keV) and the MoKa radiation (17 keV), as well as the high-energy range of the hard X-radiation with an energy greater than 15 KeV.
  • the use for X-ray lithographic applications such as Soft X-ray Lithography (SXRL) at 1-2 keV or deep X-ray lithography such as Deep X-ray Lithography (DXRL) at 4 to 10 keV.
  • SXRL Soft X-ray Lithography
  • DXRL Deep X-ray Lithography
  • X-ray microscopic applications in the spectral range of about 2 to about 4 nm (water window).
  • a particular advantage of the modified multi-channel structures according to the invention is their improved long-term stability when used for shaping, guiding, focusing and amplifying electromagnetic waves or particle radiation.
  • energy recordings for example by X-ray exposure, lead in the long term to material damage to the multi-channel structures and thus to loss of intensity and the unusability of the structures.
  • material damage can be at least partially avoided.
  • multichannel structures modified according to the invention for focusing EUV radiation or X-radiation for (X-ray) lithographic applications, for example in mask exposure for semiconductor production, is also particularly preferred.
  • the invention also relates to the use of the modified multi-channel structures according to the invention as a matrix for the production of nanoparticles and other nanoparticles by deposition of appropriate coatings and / or particles and subsequent destruction of the glass structure.
  • nanoparticles are nanotubes (eg carbon nanotubes (CNTs), nanorods and nanowires (eg nanopillars, nanorods, nanowires, nanofibers or nanofilaments) for nanotechnological and medical applications, for example as contrast agents (nanoparticles) or as nanoparticles Stents (microrods, ie micro hollow rods), cosmetic applications, eg titanium oxide particles as UV filters, nanomechanical or optical applications, eg as anisotropic components of system elements or as non-linear optical components.
  • CNTs carbon nanotubes
  • nanorods and nanowires eg nanopillars, nanorods, nanowires, nanofibers or nanofilaments
  • cosmetic applications eg titanium oxide particles as UV filters
  • nanomechanical or optical applications eg as anisotropic components of system elements or as non-linear optical components.
  • a glass polycapillary structure having a length of 50 mm and a maximum outside diameter of 7.20 mm was used which contained about 40,000 channels with a channel internal diameter of 29.5 ⁇ m.
  • This polycapillary structure was connected in a gastight manner by means of a two-component adhesive to a vacuum system according to the apparatus described in DE 198 52 722 C1 and cleaned from the inside by simultaneous heating to 650 K and passing 1000 mbar of molecular oxygen. Subsequently, a constant basic temperature of the polycapillary structure of 296 K was set.
  • Bis (1, 1, 1, 5, 5, 5-hexafluoro-2, 4-pentanedionato) palladium (II) was used as pre cursor.
  • the pressure gradient used was 10 " mbar vs. 10 ⁇ 5 mbar, a localized temperature of 600 K was set in sections in a first phase over a period of 240 minutes in a second phase and in a second phase the local temperature set via the furnace system gradually over a time cavities of 300 minutes to about 380 K reduced.
  • 5000 mbar oxygen to 10 -5 mbar by the inner channels of the Polykapillar Vietnamese Subsequently, at about 678 K conducted in semi-continuous operation. by this step, an oxidation of the metallic palladium carried on of the catalytically active species in the oxidation state + II.
  • the modified polycapillary structure thus prepared was used in a heterogeneous catalytic process. Ethene was passed through the modified polycapillary structure in a continuous procedure. Gaseous products were separated by a specially designed cooling trap system and the unreacted ethene was recycled. The resulting products were analyzed by GC / MS coupling and separated by distillation or chromatography. It could be shown that by catalytic ethenoligomeri- (analogous to the SHOP process) ⁇ -terminal olefins were formed.
  • a polycapillary structure was connected to a vacuum system as in Example 1 and cleaned from the inside. Subsequently, a constant basic temperature of the polycapillary structure of 296 K was set. Bis (1,1,1,5,5-hexafluoro-2,4-pentanedionato) palladium (II) was used as precursor. The pressure gradient used was 10 ⁇ 3 mbar against 10 ⁇ 5 mbar.
  • a locally limited temperature of 600 K was set in sections in a first phase over a period of 120 minutes. In a second phase, the local temperature set via the kiln system was continuously reduced to about 380 K over a period of 500 minutes.
  • a polycapillary structure was connected to a vacuum system as in Example 1 and cleaned from the inside. Subsequently, a constant basic temperature of the polycapillary structure of 296 K was set. Bis (1,1,1,5,5-hexafluoro-2,4-pentanedionato) palladium (II) was used as precursor. The used pressure gradient was 10 ⁇ 4 mbar against 10 ⁇ 5 mbar.
  • a locally limited temperature of 435 K was set in sections in a first phase over a period of 360 minutes by means of a mobile furnace system.
  • the local temperature set via the furnace system was continuously reduced to about 380 K over a period of 1200 minutes.
  • the polycapillary structure was removed and placed completely in hydrofluoric acid in a bowl for 48 hours. To improve internal wetting, surfactants were added to the hydrofluoric acid. Additionally, the hydrofluoric acid was warmed cautiously to about 320 K to accelerate the kinetics. Upon complete decomposition of the polycapillary structure, the hydrofluoric acid was removed and the microtubes were supported on a scanning electron microscopic slide. The microtubes were examined by scanning electron microscopy (LEO 1525, 5 kV acceleration voltage) and by transelectron microscopy.

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Abstract

L'invention concerne une structure multicanal modifiée, ladite structure multicanal comprenant 10, de préférence, au moins 100, plus avantageusement, au moins 1000, et au mieux, au moins 10000 canaux, un revêtement intérieur et/ou des particules étant introduit dans les canaux de la structure multicanal. L'invention concerne en outre un procédé de production de la structure multicanal modifiée et son utilisation.
PCT/EP2008/055458 2007-05-03 2008-05-05 Structures multicanal modifiées Ceased WO2008135542A1 (fr)

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DE102021005684A1 (de) 2021-11-16 2023-05-17 Jörn Volkher Wochnowski STED-Verfahren mit Hohllichtwellenleitern

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DE102022004934A1 (de) 2021-12-30 2023-07-06 Jörn Volkher Wochnowski Anwendungsmodifizierte Glasfaser- (Hohl)Lichtwellenleiter zum Beispiel mit durch Femtosekunden-Laser erzeugte(n) und bearbeitete(n) Schicht(en)
DE102021215134B4 (de) 2021-12-31 2024-04-25 Jörn Volkher Wochnowski Hohllichtleiteranordnungen
DE102021215135B4 (de) 2021-12-31 2024-05-29 Jörn Volkher Wochnowski Additives Fertigungsverfahren und Vorrichtung zur Durchführung eines additiven Fertigungsverfahrens
DE102023001827A1 (de) 2023-04-19 2024-10-24 Horst Wochnowski Verfahren und dazugehörige Vorrichtung zum Züchten von in Gewässern Mikroplastik zersetzenden und abbauenden Mikroorganismenstämme durch einen künstlich herbeigeführten und beschleunigten Evolutions- und Selektionsprozess

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