WO2002088593A1 - Gasdichter behälter - Google Patents

Gasdichter behälter Download PDF

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Publication number
WO2002088593A1
WO2002088593A1 PCT/CH2002/000229 CH0200229W WO02088593A1 WO 2002088593 A1 WO2002088593 A1 WO 2002088593A1 CH 0200229 W CH0200229 W CH 0200229W WO 02088593 A1 WO02088593 A1 WO 02088593A1
Authority
WO
WIPO (PCT)
Prior art keywords
container
diffusion barrier
layer
nanoparticles
barrier layer
Prior art date
Application number
PCT/CH2002/000229
Other languages
German (de)
English (en)
French (fr)
Inventor
Eva Maria Moser
Armin Reller
Original Assignee
Eva Maria Moser
Armin Reller
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 Eva Maria Moser, Armin Reller filed Critical Eva Maria Moser
Priority to EP02712717A priority Critical patent/EP1384027A1/de
Priority to CA002445812A priority patent/CA2445812A1/en
Priority to BR0209247-6A priority patent/BR0209247A/pt
Priority to JP2002585853A priority patent/JP2004522104A/ja
Priority to US10/474,416 priority patent/US20040149759A1/en
Publication of WO2002088593A1 publication Critical patent/WO2002088593A1/de

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/10—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge with provision for protection against corrosion, e.g. due to gaseous acid
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0104—Shape cylindrical
    • F17C2201/0109—Shape cylindrical with exteriorly curved end-piece
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/056—Small (<1 m3)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/01—Reinforcing or suspension means
    • F17C2203/011—Reinforcing means
    • F17C2203/012—Reinforcing means on or in the wall, e.g. ribs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
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    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0607—Coatings
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    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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    • F17C2203/0612—Wall structures
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    • F17C2203/0619—Single wall with two layers
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    • F17C2203/0614—Single wall
    • F17C2203/0621—Single wall with three layers
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    • F17C2203/0624—Single wall with four or more layers
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    • F17C2203/00—Vessel construction, in particular walls or details thereof
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    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
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    • F17C2203/0646—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
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    • F17C2203/0648—Alloys or compositions of metals
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
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    • F17C2203/0656—Metals in form of filaments
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    • F17C2203/00—Vessel construction, in particular walls or details thereof
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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    • F17C2205/00—Vessel construction, in particular mounting arrangements, attachments or identifications means
    • F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
    • F17C2205/0302—Fittings, valves, filters, or components in connection with the gas storage device
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    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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    • F17C2205/03—Fluid connections, filters, valves, closure means or other attachments
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    • F17C2205/0394—Arrangement of valves, regulators, filters in direct contact with the pressure vessel
    • F17C2205/0397—Arrangement of valves, regulators, filters in direct contact with the pressure vessel on both sides of the pressure vessel
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    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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    • F17C2209/00—Vessel construction, in particular methods of manufacturing
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    • F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
    • F17C2223/035—High pressure (>10 bar)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
    • F17C2223/036—Very high pressure (>80 bar)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/03—Dealing with losses
    • F17C2260/035—Dealing with losses of fluid
    • F17C2260/036—Avoiding leaks
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/03—Dealing with losses
    • F17C2260/035—Dealing with losses of fluid
    • F17C2260/037—Handling leaked fluid
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/05—Improving chemical properties
    • F17C2260/053—Reducing corrosion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0165—Applications for fluid transport or storage on the road
    • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0186—Applications for fluid transport or storage in the air or in space
    • F17C2270/0189—Planes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/07—Applications for household use
    • F17C2270/079—Respiration devices for rescuing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the invention relates to a gas-tight, pressure-resistant storage and / or transport container for low-molecular, reactive filling media, in particular for hydrogen, oxygen, air, methane and / or methanol, with a high filling pressure, which container is essentially rotationally symmetrical and has at least one connection cap has a closure device.
  • Thick-walled metal bottles made of steel have the disadvantage that they are extremely heavy compared to the stored content.
  • the replacement of steel bottles with appropriate aluminum bottles was a first important step in the right direction in terms of weight, but the above-mentioned mismatch between content and container continues to exist to a lesser extent.
  • US 4073400 A describes such a gas container made of a metal, preferably aluminum or steel, which has an outer protective layer made of a fiber-reinforced resin / polymer.
  • an anti-corrosion layer is also applied on the inside, which also consists of a fiber-reinforced resin / polymer.
  • DE 3821852 A1 also describes a pressurized gas bottle made of a metallic inner container and circumferential, glass fiber-reinforced plastic layers. This compressed gas bottle, intended as a propellant container for motor vehicles, is suitable for filling pressures up to 340 bar. Thanks to the metal bottle, there are no diffusion problems, and there are no corrosion problems when using a corrosion-resistant aluminum alloy for the inner container.
  • WO 00/66939 A1 describes the production of a two-layer gas pressure container made of plastic.
  • An inner container made of plastic is pretreated in rotation to increase the wetting and adhesion properties.
  • a fiber-reinforced wrapping tape is applied in a spiral line, which sticks very well to the inner container and forms an effective pressure reinforcement. Diffusion or corrosion problems are not described or mentioned.
  • a double-walled heat storage bottle made of plastic with respect to a gas pressure container for high pressures according to US 3921844 A has in a known manner the heat radiation reflecting silver layers, which also act as diffusion barriers.
  • the vacuum between the double walls with comparatively very thin walls can be maintained for a long time and heat convection prevented.
  • a pressure vessel such a double wall with a vacuum in between would not only be nonsensical, but counterproductive.
  • the inventors have set themselves the task of creating a gas-tight, pressure-resistant storage and / or transport container of the type mentioned at the outset, which is media-specific impermeable and / or, if necessary, corrosion-resistant with a reduced weight.
  • the container wall consists essentially of a thermoplastic with at least one diffusion barrier system or a diffusion barrier and corrosion protection system. Special and further developing embodiments of the container are the subject of dependent claims.
  • diffusion barrier layer encompasses layers deposited on the container wall as well as films placed on or into the container wall, with or without a functional layer / s.
  • a diffusion barrier layer can also be a corrosion protection layer at the same time or exclusively, without this having to be done every time All types of diffusion barrier layers preferably have approximately the same expansion coefficient as the container wall.
  • a “diffusion barrier system” or a “corrosion protection system” can comprise a compact layer and / or dispersed, passive or reactive nanoparticles. Reactive nanoparticles react chemically with a permeating gas, passive nanoparticles adsorb (store) this.
  • Plastic containers with a high filling pressure ie in the range of at least 50-100 bar, have the usual external dimensions and shapes. They are preferably essentially cylindrical and have a closure cap on one or both sides in the region of their longitudinal axis a closure of the usual type.
  • the jacket length of large containers is expediently in the usual range from 1 to 6 m, the inside diameter is up to 40 cm, in particular about 35 cm, the filling pressure is preferably at least 150 bar, in particular at least 250 bar.
  • the portable medical bottles for patients, which are also included in the invention are designed to be substantially smaller.
  • thermoplastic plastic of the container wall which consists for example of polyethylene, polypropylene, acetylbutadiene styrene, polyamide, polyvinyl acetate or a polyester, is reinforced with a tensile material, preferably with carbon, Glass or ceramic fibers, but also with steel wires.
  • a diffusion barrier layer is arranged inside and / or outside the container wall, possibly also or only in this wall itself.
  • an external diffusion barrier layer is also applied, which is also a corrosion protection layer.
  • a diffusion barrier layer can be integrated into this wall, for example by coextrusion or corresponding winding technology, both are known per se, or the wall of a hydrogen container contains dispersed, passive or reactive nanoparticles. At least one diffusion barrier layer can be applied to the container wall using two fundamentally different methods:
  • deposition from the gas phase with or without chemical reaction, also as a thin layer in the range from 10 to 600 nm, in particular up to 100 nm.
  • This deposition can take place directly on the container wall and / or on a carrier film subsequently applied to or in the container wall ,
  • the outside film is applied, for example, by wrapping, preferably with a strong overlap of film strips applied in a spiral line, by longitudinally applying a film, again with a strong overlap of the side edges, or by applying a shrinking film or one that can be welded to size.
  • the inner coating or inner lining with a film for the production of the diffusion barrier layer takes place by introducing a bag cut to size with the dimensions corresponding to the inside of the container, one or two openings being provided corresponding to the container.
  • the inserted bag is fastened in the area of the filler neck, e.g. by gluing or clamping by screwing.
  • a metal foil usually an aluminum or a steel foil, is applied or extruded as a diffusion barrier layer, preferably as a composite foil.
  • LLDPE low density polyethylene with a linear structure
  • Pure plastic composite films or multi-layers can also be applied or extruded, e.g. LLDPE (100 ⁇ m) / OPP (20 ⁇ m) / PVA (14 ⁇ m) / OPP (20 ⁇ m) LLDPE (100 ⁇ m).
  • PVA polyvinyl alcohol.
  • the PVA layer can also be provided with an SiO x or DLC layer (Diamond Like Carbon).
  • a container according to the invention, or a film inserted therein, can also be protected with one or more diffusion barrier layers which are separated from the gas phase.
  • the deposition from the gas phase takes place in a manner known per se with or without a chemical reaction in the gas phase, also as co-deposition of materials. Specific examples are vaporization with an arc (Are) and cathode sputtering (sputtering). Further examples are the deposition using lasers, electron, ion or molecular beams or thermal action, in each case with or without plasma excitation and with or without magnetic field support, and plasma spraying.
  • the deposited layers form a diffusion barrier layer, which is also the corrosion protection layer where necessary.
  • a plastic container according to the invention or a film to be applied or inserted is to have a metallic or ceramic diffusion barrier layer
  • pretreatment is often advantageous in order to increase the adhesion of this diffusion barrier layer.
  • the pretreatment is expediently carried out with a plasma activation of the surface to be treated or with an extremely thin polar plasma layer of clearly ⁇ 1 ⁇ m.
  • the coating is deposited immediately after activation, in a second case the polar layer can stabilize the surface tension of the plastic surface for years to> 50 mN / m or, if necessary, even to> 70 mN / m.
  • a radio frequency discharge (RF) in a mixture of noble gases (Ar, He), oxygen-containing and / or nitrogen-containing monomer gases is supplied, for example using CO 2l O 2 , N 2 , NO x and / or NH 3 , good results achieved.
  • RF includes low frequency, radio frequency and maximum frequency.
  • Plasma activation has long been used industrially, for example as a corona discharge or low-pressure discharge.
  • mixtures e.g. B. from the monomer gases CO 2 , O 2 , N 2 , NO x , NH 3 , CH 3 OH, CH 4 , CH 3 CN and C 2 H 2 .
  • an anhydrous process gas is used for a polar coating, each containing at least one also substituted hydrocarbon compound with up to eight C atoms and one inorganic gas.
  • An apolar diffusion barrier layer ie with a barrier effect, can also be applied directly, ie without pretreatment, by means of plasma polymerization, for example as a 0.01 to 1 ⁇ m thick amorphous DLC hydrocarbon layer (diamond-like carbon).
  • This is based on carbon and hydrogen, has a content of 20 to 80 at% each of the two elements, and 0.01 to 6 at% each of at least one element of the group consisting of oxygen, nitrogen, fluorine, Contains chlorine, bromine, boron and silicon. Diesbezüg- reference is made to WO 00/32938 (table, item E).
  • an actual diffusion barrier layer e.g. B. deposited a metallic, organic metal-containing and / or ceramic layer.
  • the metallic layers also include boron and silicon.
  • the use of the plasma-supported coating processes is particularly suitable because the substrate temperature can be kept lower and good adhesion of the layer to the substrate through an adhesion-promoting interaction the plasma is reached.
  • a targeted variation of the plasma parameters, including the process gases, results in a layer structure that adequately copes with the respective expansions of the container.
  • Effective ceramic diffusion barrier layers consist, for example, of Al 2 O 3) TiN, TiC, Si 3 N 4 , SiC, ZrO 2 , Cr 2 O 3 , SiO x and / or SiO x Ny.
  • a diffusion barrier system comprises, according to a variant for a hydrogen container in the container wall, in the diffusion barrier layer and / or in a composite film with the diffusion barrier layer, finely dispersed passive nanoparticles for storing hydrogen or reactive nanoparticles for chemical reaction with hydrogen.
  • These nanoparticles preferably contain Ti, Pd, Fe, Al, Mg, Mg 2 Ni, TiC, TiO 2 , Ti 3 Al, TiN, Ti 2 Ni, LaNi 5 H 6 , graphite, silicates and / or carbon-containing nanotubes.
  • the nano Particles can also be embedded in a matrix, for example passive TiN nanoparticles or active Ti nanoparticles in an Si 3 N matrix with a grain size of at most a few ⁇ m.
  • Ti and / or TiC nanoparticles can be embedded in an SiC matrix, or Ti and / or TiO 2 nanoparticles in an SiO 2 matrix.
  • reactive gases eg oxygen
  • analog diffusion barrier systems (table, item I).
  • Reactive nanoparticles react chemically with a gas that diffuses through the container wall, eg Al nanoparticles with oxygen to form Al 2 O 3 .
  • Passive, ie non-reactive nanoparticles adsorb a gas diffusing through the container wall, eg Ti nanoparticles H 2 . They can be installed in a wide variety of geometric shapes and form a physical diffusion barrier.
  • a hydrogen-storing component must be selected so that the expansion coefficient for hydrogen absorption and the particle size are matched to the container mass and pressure variations.
  • - Functional layer system 1 container and film, barrier layer inside and / or outside
  • PVD Physical Vapor Deposition
  • PVD is carried out, for example, by cathode sputtering and / or arc evaporation inside and outside, thermal and electron beam evaporation outside. If this metal layer is subsequently oxidized using a plasma process, for example by means of RF discharge, a defined additional Al 2 O 3 protective and diffusion barrier layer forms on the
  • Functional layer system 2 container or container with film, barrier layer preferably inside
  • a DLC layer is deposited directly, without pretreatment, as a diffusion barrier layer, which also acts as a protective layer, on a plastic substrate.
  • a gradient layer from polymer-like to diamond-like or from elastic to dense is produced via the process control.
  • the electrically non-conductive substrate with the layer material enables inductive coupling of the radio frequency into the container.
  • metal-containing nanoparticles eg Al, Ti, Mg
  • metal-containing nanoparticles can be deposited finely dispersed on / into the container wall or in a film to be introduced via the gas phase with organometallic components, which absorb the diffusing hydrogen or oxygen and / or save.
  • Functional layer system 3 container and film, barrier layer inside (arc, sputtering) and / or outside (arc / sputtering / PA reactive electron beam evaporation).
  • a plastic substrate is plasma pretreated to smooth the surface if necessary and to increase the adhesion to the subsequent coating.
  • a ceramic layer made of Al 2 O 3 , SiO x , SiON, TiO 2 and / or
  • ZrO 2 can be deposited using the aforementioned PVD methods, arcing (Are), reactive cathode sputtering (Sputtem) and plasma-activated reactive electron beam evaporation.
  • a sandwich-like structure of the diffusion barrier layer which is completely gas-impermeable overall, but still survives the expansion of the mechanically loaded container without damage, can be achieved by varying the process parameters, eg a dense, hard layer or a soft, stretchable layer.
  • Metal-containing (elementary) nanoparticles can be incorporated into the layer by co-deposition or by additional use of a molecular beam.
  • a thin diffusion barrier layer namely a DLC layer with or without passive / active nanoparticles or a thin ceramic layer, for example made of SiO 2 , Al 2 O 3 and / or Si 3 N 4 , with or without passive / active nanoparticles, on the
  • Plastic substrate to be deposited Plastic substrate to be deposited.
  • DLC layers of submicron thickness with metallic nanoparticles i.e. Particles in the nm range of a size corresponding to at most 50% of the layer thickness are referred to WO 01/55489 and the following FIG. 9 despite the other function.
  • - Functional layer system 4 container and film, barrier layer inside and / or outside
  • a barrier layer comprises a sandwich-like to seven-layer one
  • polymer - metal - polymer - metal oxide - polymer namely: UV-hardened polyacrylate (1-5 ⁇ m) / AI (10-1000 nm) / polyacrylate (0.5 ⁇ m) / TiO 2 (10 -100 nm) / polyacrylate (0.5 ⁇ m).
  • the metal and metal oxide layers are evaporated.
  • a DLC, SiON and / or Al 2 O 3 can also be deposited.
  • Thicker layers could e.g. be deposited with plasma spraying (table, item H).
  • a polymer layer is applied as a pretreatment, for example Made of polypropylene, one or a few ⁇ m thick, to smooth the surface if necessary, which can also be plasma-activated to increase the adhesion to the following coating.
  • a number of metallic and / or ceramic “brick-like” structural layers are then applied, for example sheet silicates.
  • a polymer-like protective layer which is finally applied ensures the freedom of movement of the brick-like structure.
  • liquid-crystalline polyesters (LCP) can also be stretched biaxially and thereby produce a sheet-like structure.
  • a combination of two different deposition processes leads to a composite diffusion barrier layer consisting of an inorganic and an organic Material or from various inorganic materials.
  • the inorganic component is a metal (for example aluminum or titanium) or a ceramic (for example Si 3 N 4 or Al 2 O 3 ), the organic component
  • a measuring transition i. H. a gradient can be achieved by varying the process parameters or with incorporated particles.
  • gas-tight tank systems are created for low molecular weight, reactive media, in particular for hydrogen, oxygen, methane and / or methanol.
  • a pressure-resistant plastic container with a weight that is significantly lower for vehicles is lined on the inside and / or outside with a highly effective diffusion barrier layer, which prevents even the smallest quantities of the filling medium from escaping and stores it under legal safety specifications is guaranteed.
  • suitable metal foils plastic foils and coatings
  • a dimensionally independent functional adjustment of the high barrier film system to the respective specifications of the filling medium is required.
  • the most suitable film combination can be inserted for each filling medium, a layer can be deposited or the most suitable nanoparticles can be integrated into the container wall.
  • the coating process can be scaled up to the respective dimension.
  • the type and combination of the layers can be adapted accordingly.
  • a further layer can be applied if methanol is used as the filling medium.
  • the diffusion barrier layer can be separated, consists of an equivalent material as the container or has such a low mass fraction that it is of no importance for recycling.
  • FIG. 1 shows an axial section through a container
  • FIG. 2 shows a radial section according to II-II in FIG. 1
  • FIG. 10 shows a reaction chamber for plasma activation and the production of diffusion barrier layers.
  • gas-tight, pressure-resistant storage and / or transport container hereinafter referred to as container 10, has the internationally customary standard dimensions.
  • the container wall 12 equipped with a non-visible diffusion barrier layer consists exclusively of plastic, this wall being produced, for example, using a winding technique known per se.
  • metallic connecting caps 14 are formed, which narrow to a much smaller diameter and coaxially merge into a closure device 16, which is only shown in block form and which can be held in the region of the longitudinal axis L.
  • both the container 10 for numerous filling media 20 and its production are known on a broad basis.
  • the container wall 12 has a diffusion barrier layer 18 on the inside, which is also corrosion protection in the case of an aggressive filling medium 20.
  • the diffusion barrier layer 18 is applied, for example, by inserting a bag made of a metal-plastic composite film or by deposition from the gas phase.
  • passive and reactive nanoparticles 19, which act as a diffusion barrier system are finely dispersed in the container wall 12 of a hydrogen container. These particles in the nm range are usually designed as clusters, platelets (eg graphite, layered silicates) or tubes based on carbon.
  • the outside atmosphere 24 is also not aggressive, and no corrosion protection is necessary.
  • the container wall 12 according to FIG. 3b limits a filling 20 with an aggressive component, which is why a diffusion barrier layer 18 is inserted or deposited in addition to FIG. 3a.
  • the passive nanoparticles are drawn so greatly enlarged that their geometric shape can be seen.
  • the diffusion barrier layer 18 is applied to the outside of the container wall 12. This is inert to the filling medium 20.
  • tensile fibers 22 are indicated, in the present case it is steel fibers, in other cases fibers 22 made of carbon, glass or ceramic.
  • the container wall 12 made of plastic is usually reinforced with tensile fibers 22, but for the sake of simplicity these are only shown in FIG. 4.
  • the outside diffusion barrier layer 18 also acts as a protection against corrosion.
  • the barrier is shrunk, for example, as an organic diffusion barrier film based on plastic polymers, welded to size or deposited as a layer from the gas phase.
  • a diffusion barrier layer 18 is applied to the inside and outside of the container wall 12, as shown in FIG. 5.
  • At least one diffusion barrier layer 18 can be applied as in FIGS. 3 to 5. As shown in FIG. 6, the diffusion barrier layer 18 can, however, also be integrated into the container wall 12 so that it is formed in two parts.
  • FIG. 7 shows a prefabricated diffusion barrier layer 18, which consists of a metal foil 26, the actual barrier, and one plastic film 28 laminated on one side. This composite film gives the metal film 26 the mechanical tear resistance required in the application process.
  • a metal foil 26 or a PVA film with a high barrier effect is protected on both sides with an extruded plastic film 28.
  • Finely dispersed, passive and reactive nanoparticles 19 are embedded in one plastic film 28 and, depending on their constitution, absorb the hydrogen and / or oxygen that diffuses through.
  • FIG. 9 shows in section a diffusion barrier layer 18 with a submicron thickness d, which can be arranged on the inside or outside of the container wall 12.
  • the container wall 12 appears flat, although in practice it is cylindrical in shape.
  • An organic or inorganic layer matrix 30 forming the diffusion barrier layer 18 contains, as shown in FIGS. 3a, 3b and 8, finely dispersed incorporated passive or reactive nanoparticles 19, which have a grain size substantially below the layer thickness d, e.g. B. ⁇ (0.1 to 0.2) .d.
  • This diffusion barrier layer 18 is produced from at least one, also substituted hydrocarbon and / or a metal-containing component (PVD, PE-CVD process).
  • a metallic intermediate layer 34 is arranged between the container wall 12 and the diffusion barrier layer 18 and acts as a further diffusion barrier layer.
  • a microwave source 38 is arranged in the peripheral region of the essentially cylindrical reaction chamber 36 and is supplied with a radio frequency by a generator 64RF.
  • the microwave discharge (GHz) 38 or a radio frequency discharge (kHz, MHz) 66 can be coupled in the central area of the reaction chamber 36, with both sources inside and / or outside treatments of the container wall 12 can be carried out.
  • a cathodic sputtering source 40, 40 ' is arranged in the central and in the peripheral region of the reaction chamber 36, which can easily be converted into an arc source 42, 42' if required.
  • both sources 40, 42 and 40 ', 42' can be used with target material 41 for the outside, as for the inside coating of the container 10 used as the substrate.
  • a filter 60 is installed for the outer coating with the arc source 42 '.
  • An electron beam source or a thermal evaporation source can also be used as further energy sources, not shown in FIG. 10, for the deposition of metal-containing components, boron and silicon, which are oxidized to metal oxides in the reactive gas phase. Preferably all methods are additionally stimulated with plasma.
  • the reaction chamber 36 can be evacuated via a pump connection 52.
  • a vacuum line leads to a high-performance vacuum pump 50 via a vacuum valve 48.
  • an inner pump device 54 is arranged.
  • the gas supply to the reaction chamber 36 takes place via a plurality of gas inlets 44, each of which via a gas regulating valve 46 to the microwave source 38, into the container 10 itself, into the central and peripheral region of the reaction chamber 36, also behind the arc filter 60 and into the atomization source 40 'or into the arc source 42 ', which is opposite the microwave source 38 are arranged, lead.
  • the internal pressure of the reaction chamber 36 is regulated in cooperation with a vacuum measuring device 56.
  • Strong coils 58 for generating a magnetic field are arranged outside the reaction chamber 36, in the area of the pump connection 52 and opposite.
  • Several generators 64 serve as current sources, which supply the reaction chamber 36 with alternating current in the radio frequency range RF, from low frequency to maximum frequency, and / or with direct current DC.
  • the desired position can be controlled or set manually via two process selector switches 62.
  • An upper process selector switch 42 acting on the target material 41 has a position for a radio frequency generator 64 RF and a direct current generator 64 D c.
  • a lower process selector switch 62 connected to the container 10 has a position B for a direct current radio frequency generator 64DC / RF.
  • the container 10, the substrate can thus be placed on earth E, supply voltage B or open F (floating point).
  • the coating of a substrate can be carried out in a reaction chamber 36 according to FIG. 10 or in any other reaction chamber, for example by arc, cathode sputtering, plasma-activated evaporation, ion plating, plasma spraying and / or radio frequency discharge. All of these processes can be enhanced with a reactive gas phase and / or with magnetic fields.
  • the possible uses of the container according to the invention are extremely diverse. For large containers, gas-tight tank systems, especially hydrogen tanks in automotive vehicles, are of particular importance. Small containers are particularly suitable for ventilation of patients or stationary or mobile rooms closed by occupants, for example of aircraft passengers.
  • the following table lists the permeability of coated films and film composites. The last three examples relate to commercially available, uncoated films and are listed shaded.
  • Humidity c Water vapor permeability [g / m 2 -d]: ASTM F1249-90 Standard Test Method at 23 ° C and
  • PET PETP polyethylene terephthalate, polyethylene glycol terephthalate, polyester
  • PVAL PVA polyvinyl acetate, polyvinyl alcohol, polyvinyl ether
  • Hybrid polymer Inorganic-organic hydride polymer e.g. ORMOCER®

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Laminated Bodies (AREA)
  • Chemical Vapour Deposition (AREA)
  • Packages (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
PCT/CH2002/000229 2001-04-25 2002-04-25 Gasdichter behälter WO2002088593A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP02712717A EP1384027A1 (de) 2001-04-25 2002-04-25 Gasdichter behälter
CA002445812A CA2445812A1 (en) 2001-04-25 2002-04-25 Gastight container
BR0209247-6A BR0209247A (pt) 2001-04-25 2002-04-25 Recipiente à prova de gás
JP2002585853A JP2004522104A (ja) 2001-04-25 2002-04-25 気密容器
US10/474,416 US20040149759A1 (en) 2001-04-25 2002-04-25 Gastight container

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH00753/01A CH695222A5 (de) 2001-04-25 2001-04-25 Gasdichter Behälter.
CH753/01 2001-04-25

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WO2002088593A1 true WO2002088593A1 (de) 2002-11-07

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US (1) US20040149759A1 (ja)
EP (1) EP1384027A1 (ja)
JP (1) JP2004522104A (ja)
CN (1) CN1520500A (ja)
BR (1) BR0209247A (ja)
CA (1) CA2445812A1 (ja)
CH (1) CH695222A5 (ja)
RU (1) RU2298724C2 (ja)
WO (1) WO2002088593A1 (ja)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1286831A1 (en) * 2000-05-12 2003-03-05 Pechiney Emballage Flexible Europe Squeezable containers for flowable products having improved barrier and mechanical properties
DE10247504A1 (de) * 2002-10-11 2004-04-22 Bayerische Motoren Werke Ag Druckbehälter für kondensierte Gase, insbesondere Kryotank für ein Kraftfahrzeug
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DE10231856C5 (de) * 2002-07-12 2014-06-12 Krones Ag Beschichteter Hohlkörper, Verfahren zu seiner Herstellung und die Verwendung einer Nanopartikel enthaltenden Zusammensetzung
DE10247504A1 (de) * 2002-10-11 2004-04-22 Bayerische Motoren Werke Ag Druckbehälter für kondensierte Gase, insbesondere Kryotank für ein Kraftfahrzeug
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DE102005055321B4 (de) * 2005-11-21 2019-02-07 Bayerische Motoren Werke Aktiengesellschaft Behälter zur Speicherung von Kraftstoff
WO2008072046A1 (en) * 2006-12-13 2008-06-19 Toyota Jidosha Kabushiki Kaisha Pressure container
US8087537B2 (en) 2006-12-13 2012-01-03 Toyota Jidosha Kabushiki Kaisha Pressure container
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WO2012107581A1 (de) * 2011-02-11 2012-08-16 Martin Markert Druckbehälter für helium
DE102011106576A1 (de) * 2011-06-16 2012-12-20 Gaby Traute Reinhardt Druck-Speichereinrichtung
DE102011107883A1 (de) * 2011-07-18 2013-01-24 Gaby Traute Reinhardt Druck-Speichereinrichtung
EP2573446A1 (de) 2011-09-22 2013-03-27 Frauenthal Deutschland GmbH Verfahren und Anlage zur Herstellung eines Druckbehälters und damit hergestellter Druckbehälter, insbesondere Druckluftbehälter
EP2592327A1 (de) * 2011-11-10 2013-05-15 Roth Werke GmbH Speicherbehälter für ein fluides Medium, insbesondere Wasser, Flüssiggas oder dergleichen
AT515917A4 (de) * 2014-11-24 2016-01-15 Mario Paul Stojec Verfahren und vorrichtung zur innenbeschichtung von druckbehältern
AT515917B1 (de) * 2014-11-24 2016-01-15 Mario Paul Stojec Verfahren und vorrichtung zur innenbeschichtung von druckbehältern
WO2020109438A1 (de) * 2018-11-30 2020-06-04 Robert Bosch Gmbh Herstellungsverfahren für einen wasserstoff-druckbehälter, druckbehälter sowie kraftfahrzeug mit einem wasserstoff-druckbehälter
CN113056631A (zh) * 2018-11-30 2021-06-29 罗伯特·博世有限公司 用于氢压力容器的制造方法、压力容器以及具有氢压力容器的机动车
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FR3129386A1 (fr) * 2021-11-25 2023-05-26 Airbus Réservoir à hydrogène pourvu d’un système de capture d’hydrogène gazeux.
EP4187141A1 (fr) * 2021-11-25 2023-05-31 Airbus SAS Réservoir a hydrogène pourvu d'un système de capture d'hydrogène gazeux

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CN1520500A (zh) 2004-08-11
EP1384027A1 (de) 2004-01-28
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BR0209247A (pt) 2004-06-08
CH695222A5 (de) 2006-01-31

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