EP0391578B1 - Films de métal/oxyde à deux phases - Google Patents
Films de métal/oxyde à deux phases Download PDFInfo
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- EP0391578B1 EP0391578B1 EP90303077A EP90303077A EP0391578B1 EP 0391578 B1 EP0391578 B1 EP 0391578B1 EP 90303077 A EP90303077 A EP 90303077A EP 90303077 A EP90303077 A EP 90303077A EP 0391578 B1 EP0391578 B1 EP 0391578B1
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- Prior art keywords
- film
- metal
- porous
- pores
- deposited
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/34—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within the package
- B65D81/3446—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within the package specially adapted to be heated by microwaves
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/12—Anodising more than once, e.g. in different baths
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2581/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D2581/34—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within
- B65D2581/3437—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within specially adapted to be heated by microwaves
- B65D2581/3439—Means for affecting the heating or cooking properties
- B65D2581/344—Geometry or shape factors influencing the microwave heating properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2581/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D2581/34—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within
- B65D2581/3437—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within specially adapted to be heated by microwaves
- B65D2581/3463—Means for applying microwave reactive material to the package
- B65D2581/3466—Microwave reactive material applied by vacuum, sputter or vapor deposition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2581/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D2581/34—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within
- B65D2581/3437—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within specially adapted to be heated by microwaves
- B65D2581/3471—Microwave reactive substances present in the packaging material
- B65D2581/3472—Aluminium or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2581/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D2581/34—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within
- B65D2581/3437—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within specially adapted to be heated by microwaves
- B65D2581/3486—Dielectric characteristics of microwave reactive packaging
- B65D2581/3487—Reflection, Absorption and Transmission [RAT] properties of the microwave reactive package
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2581/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D2581/34—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within
- B65D2581/3437—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within specially adapted to be heated by microwaves
- B65D2581/3486—Dielectric characteristics of microwave reactive packaging
- B65D2581/3494—Microwave susceptor
Definitions
- This invention relates to two phase metal/oxide films. More particularly, the invention relates to porous oxide films supporting metal deposits.
- Oxide films supporting metal deposits can be used for a variety of purposes, e.g., as catalysts for various chemical reactions, but it is difficult to produce such films in a highly controllable manner and at reasonable economic cost.
- a process for producing a two phase metal/oxide film which comprises forming a porous oxide film on a substrate, introducing a weakened stratum into the oxide film so that at least an outer part of the film can be subsequently detached along said stratum, depositing a metal on and/or within the pores of said film in at least said outer film part, and detaching at least said outer film part from said substrate.
- a two phase metal/oxide film produced by the method of the invention comprising a porous oxide film having a metal deposited on a surface of said film and/or within the pores of said film.
- an acid e.g., phosphoric acid, sulfuric acid or oxalic acid
- Porous anodization can also be modified to introduce the required weakened stratum into the oxide film. This is achieved by a pore branching technique as disclosed in our European patent application serial number 0 178 831 published on April 23, 1986 (the disclosure of which is incorporated herein by reference) and involves a variation in the anodization voltage in a continuous or stepwise manner during the porous anodization step. This causes each pore formed during the normal anodization to branch out at its bottom part to form numerous smaller pores that collectively weaken the film.
- the anodization voltage can be reduced from the normal anodization voltage (typically in the range of 3 to 200 V, but more usually 5 to 100 V) to 0 V in 0.5 V increments. We have found that the introduction of the weakened stratum in this way can be carried out without causing the film to separate prematurely from the substrate.
- a metal can be deposited within the pores of the film and/or on the outer surface of the film by any one of a variety of techniques. Electrodeposition can be used to deposit a metal, e.g. a transition metal such as tin, copper, iron, or silver, at the pore bottoms by the procedure disclosed for example in our British patent specification no. 1,532,235 published on November 15, 1978 (the disclosure of which is incorporated herein by reference). Vacuum sputtering and similar techniques can be used to coat the surface of the film with a continuous or discontinuous layer of metal of any type. Electroless or immersion plating can be used to coat both the surface of the porous layer and the internal walls of the pores with various metals.
- a metal e.g. a transition metal such as tin, copper, iron, or silver
- a surface metal layer can also be formed by first "flash" anodizing a metal substrate to form a thin non-conductive essentially non-porous oxide layer, depositing a metal layer on the oxide layer by electroless plating and then continuing the porous anodization to grow a porous oxide film below the metal layer and forming the weakened stratum in the porous oxide film. This procedure is feasible if the metal layer is not made too thick, i.e. so that it remains discontinuous or at least porous to the electrolyte.
- the ability to carry out further porous anodization after the deposition of a metal in the pores also opens up the possibility of depositing several metal layers within the porous film separated by strata of the oxide. This is achieved by carrying out a first porous anodization step, depositing a metal in the resulting pores, carrying out a second porous anodization to lengthen the pores, electrodepositing a metal at the pore bottoms (a procedure which turns out to be feasible despite the initial metal deposit in the pores), and repeating the procedure if desired to create further metal layers at even lower levels in the film. As a final step, the weakened stratum is introduced into the film.
- the first method involves electrodepositing a noble metal seed within the pores of the initial structure.
- Noble metals e.g. Pd
- Pd are resistant to acid electrolytes used for the subsequent porous anodization but they tend to spread up the sides of the pores as deposition proceeds and this may be disadvantageous if the deposits are desirably to have uniform heights and flat outer surfaces. Therefore, the electrodeposition is carried out just long enough to deposit a small amount of the noble metal.
- the structure is subjected to electroless plating.
- the noble metal deposit acts as a seed for the deposition of the additional metal and the deposit is thus enlarged until it reaches an adequate size for the desired application.
- the second method is similar to the first, except that the noble metal seed is enlarged by electroless plating before the anodization to lengthen the pores. This is possible because the metals deposited by electroless plating (e.g. Ni) are resistant to the acids used in the electrolytes required for porous anodization.
- the noble metal seed is enlarged by electroless plating before the anodization to lengthen the pores.
- the metals deposited by electroless plating e.g. Ni
- the acids used in the electrolytes required for porous anodization are resistant to the acids used in the electrolytes required for porous anodization.
- a third method is the most preferred. This involves first electrodepositing the normal (so called ANOLOKTM) metals. These deposits are then protected by providing them with an acid-resistant coating of a noble metal such as Pd or Au by an immersion plating technique (e.g. using a PdCl2 or AuCl2 solution). Immersion plating is somewhat similar to electroless plating but will not continue indefinitely once it has been initiated, thus plating will cease once all the surface sites of the host metal are occupied). Then further anodization can be carried out to lengthen the pores without the deposits being attacked to any substantial extent. This method is the most preferred because it relies on the electrodeposition of normal deposition metals and because it produces a very regular and uniform semi-transparent metal layer in the anodic film, which is desirable in certain applications.
- Fig. 1(a) shows a cross-section of a porous anodic film 10 formed by porous anodizing a metal substrate 11.
- Fig. 1(b) shows the same film after a pore branching step to introduce a weakened stratum 12, formed by branched pores 13, at the substrate/film interface by the collective weakening produced by continuous or stepwise voltage reduction.
- Fig. 1(c) shows the structure of 1(b) having a discontinuous metal layer 14 on the outer surface of the anodic film 10 produced, for example, by sputtering after the formation of the film or by the "flash" anodization procedure described above.
- Fig. 1(d) shows the structure of Fig. 1(b) having metal deposits 15 at the bottoms of the pores introduced, for example, by electrodeposition.
- Fig. 1(e) shows a structure similar to Fig. 1(d) having a continuous metal layer 16 on the outer surface of the film formed, for example, by sputtering for a period longer than that required for the structure of Fig. 1(c).
- Fig. 1(f) shows a structure having metal deposits 17 at intermediate levels in the pores. These deposits are formed by carrying out a first porous anodization to produce a structure similar to Fig. 1(a), electrodepositing a metal at the bottoms of the pores, carrying out a second porous anodization (after protecting the metal deposits against acid attack, if necessary) to lengthen the pores below the deposits and then carrying out a final pore branching step to create a weakened stratum 12.
- Fig. 1(g) shows a structure similar to Fig. 1(b) having metal deposits 18 coating the surface of the film and the inner walls of the pores. This can be produced by electroless or immersion plating the structure of Fig. 1(b).
- Fig. 1(h) shows a structure similar to Fig. 1(f) except that the metal electrodeposition and pore lengthening steps are carried out a second time to produce additional buried metal deposits 19 before carrying out the final pore branching step.
- the electrodeposition and pore lengthening steps could be repeated before carrying out the final pore branching step to produce even more buried metal layers, as required.
- a surface metal coating (not shown) could then be applied as in Fig. 1(c) or Fig. 1(e).
- the electrodeposits of Fig. 1(d) or Fig. 1(f) may be made to extend to the outer surface of the film by suitably prolonging the electrodeposition or the electroless plating step and may, if desired, merge with a metal surface deposit.
- a structure similar to Fig. 1(g) may be produced with uncoated pore sections at the bottom of the film by carrying out a first porous anodization, electroless plating the resulting film, carrying out a second porous anodization to lengthen the pores (no protection of the deposited metal is usually required because electroless deposited metal is usually resistant to metal attack) and then carrying out the pore branching step.
- pore branching step is normally carried out as the final step of the electrolysis to position the weakened stratum at the substrate/oxide interface
- normal porous anodization can be carried out if desired following the pore branching step in order to separate the weakened stratum from the substrate. This is found to be possible without causing the upper part of the film to detach prematurely and without affecting the ability of the layer to detach when desired.
- the advantage of separating the weakened stratum from the substrate is that it may give a cleaner separation (fewer defects) if there are localized defects in the film due to the impurities in the substrate.
- the next step is to detach the metal-containing film 10 from the substrate 11 along the weakened stratum 12. If the film is relatively thick and self-supporting, this can be done by allowing the anodic film to stand or "soak" in the acidic electrolyte until it separates at the weakened stratum, but it is more conveniently done by attaching a flexible non-porous or porous support to the outer surface of the film and using the support to peel the film from the substrate. Alternatively, if the substrate 11 itself is flexible (e.g.
- a relatively inflexible support can be applied to the film and the substrate can be peeled away from the support and the attached metal-containing anodic film 10.
- the support can be attached to the anodic film by any suitable means.
- the support when the support is a polymer sheet it may be adhered or heat sealed (e.g. if made of polypropylene) to the anodic film or metal coating layer.
- Hot melt interfacing materials can be applied in preprogrammed patterns or designs. This provides a meltable layer between the anodic film and the support.
- iron-on interfacing normally used for stiffening fabrics, can be used to attach a membrane, such as a porous nylon mesh, to the anodic film. If a porous support is to be adhered to the anodic film and its porous nature is to be maintained, this may be done by the spot application of adhesive or polymer solution, e.g. using ink jet printing techniques, to prevent complete blocking of the pores.
- Yet another attachment technique involves so-called heat staking a porous polymeric membrane of polypropylene, if necessary facilitated by the use of a laser.
- the support may be inorganic rather than organic (e.g. the polymer mentioned above).
- the anodic film may be incorporated into a porous composite membrane of the type disclosed in our co-pending British patent application serial number 8912425.9 filed on May 31, 1989, the disclosure of which is incorporated herein by reference.
- the porous anodic film is integrally bonded to an overlying layer of partly sintered inorganic particles by one of two methods. In the first method, a slurry of inorganic particles is "tape cast" onto the film surface and then heated to partly sinter the particles together.
- a slurry of inorganic particles is tape cast onto the surface, a preformed layer of sintered particles is then applied on top and finally the coatings are heated.
- the average pore size of the ceramic layer is larger than the average minimum pore size of the metal-containing anodic film.
- the support can be used as a new substrate for the two phase film or it can be subsequently removed or replaced. Removal of the support can be carried out, for example, by sandwiching the laminate of the two-phase film and the support between a pair of fine mesh grids (made for example of TEFLON or stainless steel) and dissolving or burning away the substrate in situ . If the two phase film is sufficiently thick (e.g. greater than about 50 microns) it may not be necessary to continue to support the resulting free-standing laminate with the mesh grids. If the two phase film is very thin, on the other hand, the mesh grids can be used to form a new supporting structure even though they may not be bonded to the film, or a new support may be attached.
- a pair of fine mesh grids made for example of TEFLON or stainless steel
- pores in selected areas of the anodic film may be filled with a material (e.g. a settable liquid such as a lacquer or a polymer solution) that itself reinforces the film.
- a material e.g. a settable liquid such as a lacquer or a polymer solution
- a suitable pattern of application such as a dot or grid pattern, good support may be provided while maintaining high average porosity of the film.
- the material penetrating the pores in this way can act alone as a supporting structure after the original support has been removed or it can provide additional support in combination with a layer of material or other supporting structure.
- the exposed lower surface of the film can, if desired, be coated with a discontinuous or continuous layer of a metal, e.g. by sputtering.
- the substrate 11 used for the formation and initial support of the porous layer can be of any suitable shape, size and thickness, e.g. a plate, a shaped article, bulk metal, a foil or a thin layer itself supported by another material. If the substrate is a flexible metal foil and if low anodizing voltages are employed for the formation of the film so that the risk of "burning" the foil by heat generation is minimized, the process can be carried out continuously or semi-continuously.
- the metal foil can be unwound from a roll, passed through a first electrolysis bath to carry out initial porous anodization, passed through a metal deposition station, passed through a further electrolysis bath to introduce a weakened stratum, adhered to a flexible support unwound from a roll and then separated from the support with the separated parts being wound up or processed separately.
- the metal foil substrate could possibly be reused for economy. The details of the precise steps would of course have to be varied according to the particular structure being formed.
- FIGs. 2(a) to 2(m) Examples of some of the structures which can be produced in this way or on a batchwise basis are shown in Figs. 2(a) to 2(m) (omitting any support that may be present).
- the pores and deposits in these figures are shown in a similar manner to those in Figs. 1(a) to 1(h) and so detailed explanation is believed to be unnecessary as the structures represented will be self-evident.
- the two phase films produced according to the present invention can be used for a variety of applications, most of which fall into three generic areas.
- the invention makes it possible to coat substrates made of non-anodizable materials, e.g. plastic and paper, with metal-containing oxide films (for which direct deposition is problematic) by fabricating the films on anodizable metal substrates and transferring them.
- the spacings between the supported metal layers in the films are made optically thin (i.e. thin enough to create light interference, e.g. less than 3 microns and preferably less than 1 micron), the films are capable of generating optical interference effects which can be imported to various supports, e.g. transparent layers of glass or plastic.
- An example of the products which can be produced by coating two phase anodic films on a non-metallic substrate is a magnetic recording film.
- Conventional magnetic media for recording or information storage consist typically of fine magnetic particles, such as iron oxide, dispersed in a polymeric binder media which is spin coated as a thin film onto a rigid disk or applied to a flexible web for magnetic tape or floppy disks. More recently, the use of continuous thin magnetic films vacuum deposited onto a disk or flexible web has been developed.
- a third type of magnetic media for rigid disks consists of an aluminum platter anodized to provide a porous anodic film over the surface in which magnetic particles such as cobalt are electrodeposited into the pores (see S. Kawai, R. Ueda, J. Electrochem, Soc.
- the appreciably greater resistance of the web at its centre relative to the edges leads to non-uniform anodizing across the width of the web.
- the heat generated due to the resistance of the aluminum film can have a deleterious effect on the porous anodic film, which is sensitive to temperature, and hence on the magnetic properties.
- the present invention can be used to form the anodic film to the required thickness and with magnetic metal (Fe, Ni, Co) deposited in the pores, directly on an aluminum foil substrate.
- a weakened stratum is incorporated in the film below the metal deposit, as in the structure of Fig. 2(e), to allow transfer on lamination to a flexible web material.
- the adhesion of the transferred anodic film to the plastic web can be very good. There is no residual aluminum to cause stability problems.
- a section of continued anodizing film can be left below the deposit and above the weakened stratum to provide a residual porous layer on the top of the transferred structure.
- Fig. 2(e) This functions as a hard overlayer which additionally can be impregnated with lubricant.
- the metal deposit in Fig. 2(e) is preferably formed by electroless plating since electrodeposition to the required thickness may tend to block the pores and prevent continued anodization.
- Suitable packaging can be made by transferring a metal-containing anodic film, such as the one used for magnetic media described above, onto paper or plastic. Films of this type yielding sufficient magnetization may still be transparent, due to the discrete nature of the deposits, providing greater appeal as a packaging film.
- Examples of devices incorporating optical interference films are as follows. Structures such as those shown in Figs. 2(h) and 2(i) involve a plated metal layer covering one or more semi-transparent buried deposit layers within the film. If the plated layer is a metal such as Ag or Pd and the separations between the various layers are optically thin, then the structures are capable of generating interference colours.
- the structure of Fig. 2(h) gives an MOMO device (metal-oxide-metal-oxide). Due to interference of light reflected from the various layers, the structure appears coloured and the colour may be dichroic.
- Pd (opaque)/4.36 L/Pd/4.36 L/Pd where L is aluminum oxide in quarterwaves at a set point of 550 nm (i.e. 3747 Angstroms), and the Pd layers are nominally 50-100 Angstroms thick. This film exhibits a gold-to-green colour shift.
- Fig. 2(h) has an electrodeposited (versus electroless) layer which tends to plug the pores
- the fact that continued anodization can be carried out below such a deposit indicates that liquids or other materials may penetrate through the deposits and produce colour shifts due to the consequent change of effective refractive index of the film between the reflective layers.
- devices of this kind can be used in a variety of devices and sensors which produce a visible colour shift when materials enter or leave the pores. Examples of such devices include moisture sensors, freeze-thaw indicators, etc.
- the structure of Fig. 2(b) can be top-metallized by vacuum deposition while intact on the substrate and can then be transferred to yield the same structure as in Fig. 2(h).
- the structure of Fig. 2(b) can be metallized after transfer to a support. These are not preferred routes due to the additional processing but may be more useful for complex structures like those of Fig. 2(i).
- the structures of the present invention may also be used to prepare dichroic pigments, i.e. inks which (when dry) have a colour which exhibits dichroism. Inks of this type are useful for security printing applications because of the inability to copy the dichroic effect.
- dichroic structures i.e. inks which (when dry) have a colour which exhibits dichroism.
- Inks of this type are useful for security printing applications because of the inability to copy the dichroic effect.
- a problem is encountered when conventional dichroic structures are used to prepare such pigments because these structures are quite thick compared to the required diameters of particles used for ink (5-10 microns). If the colour and dichroism are to be highly visible, a large number of the particles must be in the proper orientation when the pigment is dry on a suitable substrate, but a large number of thick particles are orientated with the uncoloured side surfaces outermost and so the resulting colours are weak.
- the optical structure including any support, must be very thin.
- Fig. 3(a) shows an intermediate structure similar to that of Fig. 1(e) except for an additional layer of oxide beneath the weakened stratum 12.
- the outer part of the film can be detached without the intervention of a support by scratching the film since small particles are anyway desired.
- Fig. 3(b) which is a OMOM device capable of producing a dichroic colour if the spacings between the layers are made suitably thin. Since there is no polymer or other support, and the opaque reflective metal layer 16 is very thin (e.g. if produced by sputtering), the entire particle is very thin, i.e. in the region of 1 micron or less. Flakes having a size of 5-10 microns made from such a film consequently have the desired aspect ratio, and can thus be used to form dichroic pigments.
- the intermediate structures of the present invention incorporating a weakened stratum may also be used as dichroic hot stamp foils, i.e. foils which when transferred have a colour which exhibits dichroism.
- Hot stamp foils can be prepared by taking a dichroic structure containing a weakened zone, e.g. according to Fig. 3(a), and applying an adhesive to the metallized surface layer 16. Transfer of the dichroic foil is realized by applying pressure and heat if the adhesive is heat activating) between this structure and the surface on to which the transfer is to be made.
- the structure of Fig. 3(b) remains on the surface to be coated as the structure shears at the weakened stratum and exhibits a dichroic colour.
- All of the interference structures described above are based on reflection which takes place at a reflective lowermost layer of some kind. It is also possible to use the present invention to produce transmission optics, i.e. the structures of Figs. 2(b), (c) and (d) which approximate to interference filters of the metal/dielectric type. The latter are used routinely in precision optical elements such as lens coatings and a variety of designs with specific materials choices are available for particular pass-band or edge filters.
- the Al2O3 structure is not as sharp, nor does it have as high a peak transmittance in the visible as the conventional TiO2 structure, but it does have good performance. It is anticipated that there will be cost/performance niches for this anodic coating.
- controlled atmosphere packing refers to a method for extending the useful life of fresh food by altering the gaseous composition of the atmosphere inside the food package.
- This technology is presently based on including a packet containing active materials such as gas scavengers, emitters, scrubbers and absorbers inside the package. This approach has limited consumer appeal.
- the present invention can be used to directly incorporate such materials into the plastic of the package using a transferred anodic film as a support or receptacle for these materials.
- Non-optical structures of the types shown in Figs 2(e) and (f) are particularly suitable.
- An example of an oxygen scavenging film would be one containing iron or active iron oxide particles which transform to higher oxides or hydroxides on absorption of oxygen.
- One additional feature of the present invention in this field is the ability to activate the anodic film at point of use by peeling off the substrate foil.
- the structures of the present invention can also be used as catalysts when catalytically active metals are supported by the anodic film. Moreover, if the metal deposits are porous, the structures can be used as flow-through catalysts which allow the reagents to flow through the anodic film and to contact the catalytically active metal. Structures such as those shown in Fig. 2(a) and (f) with deposits of Pt or Pd are particularly well suited for this purpose.
- the resulting structure can be used as a two electrode filter for applying a voltage gradient across the filter.
- Optically variable flakes are prepared by chemically processing aluminum foil to create a poorly adhering porous oxide film containing a buried discontinuous metal layer and subsequently sputter depositing an opaque layer of aluminum on the surface.
- a poorly adhering porous oxide film containing a buried discontinuous metal layer
- flakes of the film pop off.
- the micrograph of Fig. 6 reveals a highly magnified cross-section of such a flake which shows a 200 nm layer of porous oxide separated from a second 150 nm layer by a 70 nm thick layer of metallic particles.
- a 100 nm section of aluminum reflector layer can be seen coating the one side of the structure.
- the layer was prepared as follows.
- An 8.5 by 12.5 cm 60 micron thick aluminum/polyester panel was anodized in 1 M 30°C H3PO4 at 15 volts dc for 270 seconds. It was then rinsed thoroughly and immersed in a Ni ANOLOKTM solution whereupon it was given a 40 second 10 volt ac electrolytic treatment. After rinsing, the panel was immersed in a dilute palladium salt solution for a period of 120 seconds. The panel was then rinsed and re-immersed in the anodizing solution where it was re-anodized as before for 90 seconds. Subsequently, the anodizing voltage was reduced in a stepwise fashion using 300 times 0.05 volt steps each lasting 0.6 seconds. The panel was allowed to soak for 45 seconds at 0 volts potential before rinsing and drying.
- the oxide-metal-oxide film could be easily peeled off by any of the methods disclosed in the above disclosure (e.g. it could have been hot melt laminated with a flexible porous or non-porous web, etc.) and used in a variety of applications, e.g. as a flow through catalyst, heat reflecting window film, microwave susceptor, controlled atmosphere packaging film, etc.
- the flakes were optically variable, changing colour from green to red depending on the angle at which they were viewed.
- the optically variable structure could be easily coated with a heat set adhesive (e.g. Rohm & Haas product B48S) and transferred to paper, wood, plastic, etc. via hot stamping.
- a heat set adhesive e.g. Rohm & Haas product B48S
- Example 2 an optically variable transferable structure was prepared by chemically processing aluminum foil to create a poorly adhering porous oxide film containing a buried discontinuous metal layer and subsequently sputter depositing an opaque layer of aluminum on the surface.
- This Example differs in that an electroless metal deposition technique is used to form the discontinuous metal layer.
- An 8.5 by 12.5 cm 60 micron thick aluminum/polyester panel was anodized in 1 M 30°C H3PO4 at 15 volts dc for 240 seconds.
- the anodized panel was then rinsed thoroughly and immersed in a dilute palladium nitrosylsulfate solution at pH 2.0, whereupon it was given a 20 second 10 volt ac electrolytic treatment. After rinsing, the panel was immersed in an electroless Ni solution (Harshaw Chemical Co. Alpha 103) maintained at 73°C for a period of 20 seconds.
- the panel was then rinsed and re-immersed in the anodizing solution where it was re-anodized as before for 90 seconds. Subsequently, the anodizing voltage was reduced in a stepwise fashion using 300 times 0.05 volt steps each lasting 0.6 seconds. The panel was allowed to soak for 45 seconds at 0 volts potential before rinsing and drying.
- the oxide-metal-oxide film could by easily peeled off via any of the methods disclosed in the above disclosure (e.g. it could have been hot melt laminated with a flexible porous or non-porous web, etc.) and used in a variety of applications, e.g. as a flow through catalyst, heat reflecting window film, microwave susceptor, controlled atmosphere packaging film, etc.
- the flakes were optically variable, changing colour from purple to yellow depending on the angle at which they were viewed.
- a heat set adhesive e.g. Rohm & Haas product B48S
- transfer the optically variable structure to paper, wood, plastic, etc. via hot stamping.
- the buried metallic layer is prepared by first seeding the film with a metallic precursor and subsequent to re-anodizing an electroless technique is used to plate the metal at the location of the seed.
- a 4 by 12 cm 60 microm thick aluminum/polyester panel was anodized in 1 M 30°C H3PO4 at 15 volts dc for 210 seconds. It was then rinsed thoroughly and immersed in a dilute palladium nitrosyl sulfate solution whereupon it was given a 10 second 15 volt ac electrolytic treatment. The panel was then rinsed and re-immersed in the anodizing solution where it was re-anodized at 15 volts dc for 90 seconds. Subsequently, the anodizing voltage was reduced in a stepwise fashion using 300 times 0.05 volt steps each lasting 0.6 seconds. The panel was allowed to soak for 45 seconds at 0 volts. The final stage included building up the metallic seed deposit via immersion in an electroless nickel solution for a period of 15 seconds (Harshaw Chemical Co. Alpha 103) at 80°C followed by rinsing and drying.
- the oxide-metal-oxide film could be easily peeled off via any of the methods disclosed in the above disclosure (e.g. it could have been hot melt laminated with a flexible porous or non-porous web, etc.) and used in a variety of applications, e.g. as a flow through catalyst, a heat reflecting window film, a microwave susceptor, a controlled atmosphere packaging film, etc.
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- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Laminated Bodies (AREA)
- Glass Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Formation Of Insulating Films (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Compounds Of Iron (AREA)
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Claims (25)
- Procédé de production d'un film de métal/oxyde biphasique, caractérisé en ce qu'il comprend les étapes consistant :
à former un film d'oxyde poreux (10) sur un substrat (11),
à introduire une strate affaiblie (12) dans le film d'oxyde (10) de façon à ce qu'au moins une partie extérieure du film puisse être ensuite détachée le long de cette strate (12),
à déposer un métal (13,14) sur et/ou dans les pores du film (10) dans au moins ladite partie de film extérieure, et
à détacher au moins ladite partie de film extérieure à partir du substrat (11). - Procédé selon la revendication 1, caractérisé en ce que le film d'oxyde (10) est formé par anodisation à l'état poreux du substrat en un métal anodisable.
- Procédé selon la revendication 2, caractérisé en ce que la strate affaiblie est introduite dans le film par un procédé à réduction de tension au cours de l'anodisation à l'état poreux.
- Procédé selon la revendication 1, caractérisé en ce qu'au moins ladite partie de film extérieure, est détachée par liaison d'un support au film anodique, et en détachant ce support à partir du substrat avec lequel ladite partie de film extérieure est liée.
- Procédé selon la revendication 1, 2, 3 ou 4, caractérisé en ce que le métal (13) est déposé aux extrémités intérieures des pores du film (10) par électrodéposition.
- Procédé selon la revendication 1, 2, 3 ou 4, caractérisé en ce que le métal (17) est déposé entre les extrémités intérieures et extérieures en effectuant une première anodisation à l'état poreux pour former un film initial poreux, en déposant un métal aux extrémités intérieures des pores dans le film initial par électrodéposition, en effectuant une deuxième anodisation à l'état poreux pour développer une couche supplémentaire de film poreux sous le film initial et allonger les pores, et en introduisant ladite strate affaiblie (12) dans le film poreux supplémentaire aux extrémités intérieures des pores allongés.
- Procédé selon la revendication 6, caractérisé en ce que le métal (17) est protégé contre une attaque par un acide avant d'effectuer la deuxième anodisation à l'état poreux.
- Procédé selon la revendication 7, caractérisé en ce que le métal (17) est protégé par revêtement avec un métal résistant aux acides, selon un procédé choisi parmi un placage sans courant et un placage par immersion.
- Procédé selon la revendication 6, caractérisé en ce que le métal (17) déposé par électrodéposition, est sous la forme de germes résistant aux acides, et après l'introduction de ladite strate affaiblie, on accroît la taille de ces germes par placage sans courant.
- Procédé selon la revendication 6, pour former plusieurs dépôts dans les pores entre les extrémités intérieure et extérieure de ceux-ci, caractérisé en ce que le procédé comprend la répétition des opérations d'électrodéposition et d'anodisation à l'état poreux au moins une fois après la deuxième opération d'anodisation à l'état poreux, mais avant l'introduction de ladite strate affaiblie (12).
- Procédé selon la revendication 1, 2, 3 ou 4, caractérisé en ce que le métal est déposé sur une surface extérieure du film, en mettant en oeuvre un procédé choisi parmi un dépôt sans courant, une électrodéposition, un placage par immersion et une pulvérisation cathodique.
- Film de métal/oxyde biphasique, caractérisé en ce que le film est produit selon le procédé de l'une quelconque des revendications 1 à 11, et comprenant un film d'oxyde poreux comportant un métal déposé sur une surface de ce film et/ou à l'intérieur des pores du film.
- Film selon la revendication 12, caractérisé en ce que le film d'oxyde poreux est un film anodique poreux comportant des pores qui s'étendent entre leurs surfaces opposées.
- Film selon la revendication 12, caractérisé en ce que le métal est déposé dans les pores à des emplacements situés entre leurs extrémités.
- Film selon la revendication 14, caractérisé en ce que le métal est disposé selon plusieurs couches discontinues séparées par des strates du film poreux.
- Film selon la revendication 12, 13, 14 ou 15, caractérisé en ce que le métal est déposé sur au moins une des surfaces opposées du film.
- Film selon la revendication 12, 13, 14 ou 15, capable de générer une couleur d'interférence par des réflexions à partir des dépôts de métal.
- Pigment dichroïque, caractérisé en ce que le pigment comprend un film selon la revendication 12, capable de générer une couleur dichroïque.
- Pigment selon la revendication 18, caractérisé en ce que le pigment est sous la forme de particules ayant une épaisseur d'environ 1 micron ou moins, et un rapport du diamètre d'épaisseur d'au moins 5:1.
- Encre dichroïque caractérisée en ce que l'encre comprend un véhicule liquide et un pigment dichroïque selon la revendication 18 ou 19.
- Dispositif à interférence optique, caractérisé en ce que ce dispositif comprend un film selon la revendication 12, ce film étant optiquement mince.
- Matériau d'emballage caractérisé en ce qu'il comprend une feuille de polymère ou de papier comportant un film selon la revendication 12, recouvrant au moins une surface de celui-ci.
- Matériau magnétique, caractérisé en ce que ce matériau comprend un film selon la revendication 12 dans lequel un métal magnétique est déposé dans les pores du film.
- Catalyseur caractérisé en ce que ce catalyseur comprend un film selon la revendication 12, le métal étant un métal catalytiquement actif.
- Catalyseur selon la revendication 24, caractérisé en ce que ce métal et le film d'oxyde, sont poreux de façon à ce que des réactifs puissent s'écouler à travers le film et venir en contact avec le métal.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA594495 | 1989-03-22 | ||
CA594495 | 1989-03-22 | ||
CA 614985 CA1337980C (fr) | 1989-09-29 | 1989-09-29 | Pellicules biphasiques metal/oxyde |
CA614985 | 1989-09-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0391578A1 EP0391578A1 (fr) | 1990-10-10 |
EP0391578B1 true EP0391578B1 (fr) | 1994-06-01 |
Family
ID=25672545
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90303077A Expired - Lifetime EP0391578B1 (fr) | 1989-03-22 | 1990-03-22 | Films de métal/oxyde à deux phases |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0391578B1 (fr) |
JP (1) | JPH0356690A (fr) |
AT (1) | ATE106460T1 (fr) |
AU (1) | AU5211390A (fr) |
BR (1) | BR9001348A (fr) |
DE (1) | DE69009278T2 (fr) |
ES (1) | ES2054242T3 (fr) |
NO (1) | NO901332L (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO901331L (no) * | 1989-03-22 | 1990-09-24 | Alcan Int Ltd | Interferens-struktur, samt fremgangsmaate ved fremstillingderav. |
GB8922069D0 (en) * | 1989-09-29 | 1989-11-15 | Alcan Int Ltd | Separation devices incorporating porous anodic films |
ATE267646T1 (de) * | 1999-10-06 | 2004-06-15 | Infineon Technologies Ag | Substrat mit mindestens einer pore |
JP4730842B2 (ja) * | 2007-03-05 | 2011-07-20 | 株式会社島津製作所 | 二酸化炭素の吸着要素および吸着装置 |
US20090095740A1 (en) * | 2007-10-15 | 2009-04-16 | Silberline Manufacturing Company, Inc. | Ir reflective material for cooking |
US20150140340A1 (en) * | 2013-11-21 | 2015-05-21 | Nano And Advanced Materials Institute Limited | Thermal resistant mirror-like coating |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR208421A1 (es) * | 1975-07-16 | 1976-12-27 | Alcan Res & Dev | Articulo de aluminio electroliticamente anodizado y coloreado y un metodo para producir el mismo |
GB8426264D0 (en) * | 1984-10-17 | 1984-11-21 | Alcan Int Ltd | Porous films |
-
1990
- 1990-03-22 JP JP2075368A patent/JPH0356690A/ja active Pending
- 1990-03-22 ES ES90303077T patent/ES2054242T3/es not_active Expired - Lifetime
- 1990-03-22 DE DE69009278T patent/DE69009278T2/de not_active Expired - Fee Related
- 1990-03-22 BR BR909001348A patent/BR9001348A/pt unknown
- 1990-03-22 AT AT90303077T patent/ATE106460T1/de not_active IP Right Cessation
- 1990-03-22 NO NO90901332A patent/NO901332L/no unknown
- 1990-03-22 AU AU52113/90A patent/AU5211390A/en not_active Abandoned
- 1990-03-22 EP EP90303077A patent/EP0391578B1/fr not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
NO901332D0 (no) | 1990-03-22 |
NO901332L (no) | 1990-09-24 |
ATE106460T1 (de) | 1994-06-15 |
BR9001348A (pt) | 1991-04-02 |
DE69009278T2 (de) | 1994-09-08 |
ES2054242T3 (es) | 1994-08-01 |
JPH0356690A (ja) | 1991-03-12 |
DE69009278D1 (de) | 1994-07-07 |
AU5211390A (en) | 1990-09-27 |
EP0391578A1 (fr) | 1990-10-10 |
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