WO2008116599A1 - Revêtement d'émail d'un corps - Google Patents

Revêtement d'émail d'un corps Download PDF

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Publication number
WO2008116599A1
WO2008116599A1 PCT/EP2008/002252 EP2008002252W WO2008116599A1 WO 2008116599 A1 WO2008116599 A1 WO 2008116599A1 EP 2008002252 W EP2008002252 W EP 2008002252W WO 2008116599 A1 WO2008116599 A1 WO 2008116599A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
enamel
layer
coating according
enamel coating
Prior art date
Application number
PCT/EP2008/002252
Other languages
German (de)
English (en)
Inventor
Franz-Josef Behler
Günter Nose
Rüdiger Werner
Original Assignee
Düker Gmbh & Co. Kgaa
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 Düker Gmbh & Co. Kgaa filed Critical Düker Gmbh & Co. Kgaa
Publication of WO2008116599A1 publication Critical patent/WO2008116599A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
    • C03C2207/02—Compositions specially applicable for the manufacture of vitreous enamels containing ingredients for securing a good bond between the vitrified enamel and the metal

Definitions

  • the invention relates to an enamel coating for a body.
  • Enamel coatings for bodies are known.
  • enamel coatings with embedded silver can be detected in these no anti-microbial effect.
  • the invention is therefore based on the object to provide an enamel coating, which has a good antimicrobial effect.
  • an antimicrobial surface of the enamel coating is formed by an effective interface of a silver-containing enamel layer and that in the enamel layer at the effective interface silver-containing particles having a mean size of less than 500 nm.
  • the advantage of the solution according to the invention is that the possibility of imparting a good antimicrobial effect to the enamel coating by means of such small silver-comprising particles is the first option which also lasts for a long time.
  • the silver-comprising particles have an average size of less than 200 nm. It is particularly favorable if the silver-comprising particles have an average size of less than 100 nm.
  • the antimicrobial properties are further improved by the fact that the silver-comprising particles have an average size of less than 50 nm.
  • the silver-containing enamel layer is arranged on a body-covering base enamel layer, specifically on a side of the base enamel layer opposite the body.
  • a silver content of the base enamel layer is lower by a factor of 10 than that of the silver-containing enamel layer.
  • the silver content of the base enamel layer is lower by a factor of 100 than the silver content of the silver-containing enamel layer.
  • the base enamel layer is substantially free of silver.
  • the base enamel layer opens up further degrees of freedom in the structure of the enamel coating.
  • the base enamel layer may be the primary protective function for the body, and the silver-containing enamel layer primarily provides the antimicrobial effect of the enamel coating.
  • the base enamel layer may be substantially free of silver.
  • the silver-containing enamel layer has a thickness of less than 1000 microns.
  • the silver-containing enamel layer has a thickness of less than 500 microns.
  • a particularly cost-effective solution provides that the silver-containing enamel layer has a thickness of less than 300 microns.
  • the silver-containing enamel layer in order to maintain the antimicrobial properties over a long period of time, it is necessary for the silver-containing enamel layer to have a minimum thickness.
  • the silver-containing enamel layer has a thickness of at least 50 microns.
  • the silver-containing enamel layer has a thickness of at least 100 ⁇ m.
  • the duration of the antimicrobial effect is accompanied, as in a complete removal of the silver-containing enamel layer whose beneficial antimicrobial effects no longer apply.
  • the formation of the silver-containing enamel layer and the base enamel layer no details have yet been given. In principle, it would be conceivable to choose the composition of the silver-containing enamel layer and the base enamel layer completely differently.
  • the silver-containing enamel layer has the same enamel base constituents as the base enamel layer.
  • the silver-containing enamel layer apart from the additional silver-comprising particles, the same enamel composition as the base enamel layer, so that the silver-containing enamel layer and the base enamel layer essentially do not differ in their properties and thus a good connection between the silver-containing enamel layer and the base enamel layer is formed which prevents subsequent spalling of the silver-containing enamel layer from the base enamel layer.
  • the silver-containing particles are distributed substantially homogeneously in a matrix of the silver-containing enamel layer.
  • the silver-containing particles may be present in the silver-containing enamel layer in the form of cloud-like regions and / or streak-like regions. Such regions in the matrix of the silver-containing enamel layer are not detrimental to the antimicrobial action thereof, as long as the regions extend directly to the interface.
  • one solution provides that the silver-comprising particles are formed from a silver compound.
  • one embodiment provides that the silver compound is silver oxide.
  • the silver-comprising particles have precipitated silver.
  • this precipitated silver is crystallized silver, which is precipitated, for example, during firing of the silver-containing enamel layer and then crystallized out in the form of silver-comprising particles.
  • the silver content of the silver-containing enamel layer itself, no further details have been given so far. On the one hand, the lowest possible silver content is desirable for the most cost-effective solution possible. On the other hand, it is also necessary to be able to deliver a sufficiently large number of silver atoms or silver ions across the interface. For this reason, an advantageous solution provides that the silver-containing enamel layer has a silver content of at least 0.2 percent by weight based on the remaining constituents of the silver-containing enamel layer.
  • the silver-containing enamel layer has a silver content of at least about 0.3 or better at least about 0.5 percent by weight based on the remaining constituents of the silver-containing enamel layer.
  • Very good antimicrobial effect occurs when the silver-containing enamel layer has a silver content of at least about 0.8, more preferably at least about 1 weight percent, based on the remaining constituents of the silver-containing enamel layer.
  • the silver-containing enamel layer will have a silver content of less than about 5 weight percent, more preferably less than about 3 weight percent.
  • the silver-comprising particles in the silver-containing enamel layer are formed from silver introduced into them before firing.
  • the advantage of this solution is the fact that it the silver-containing particles are integrated into the matrix of the silver-containing enamel layer, thus form an integral part of the same, wherein only the silver-containing particles can contribute to the release of silver or silver ions, which lie directly at the interface.
  • This has the advantage that the release of silver over a very long period of time, for example many years or many tens of years, can be determined by the extent of wear of the enamel layer itself and thus the release of silver from the wear of the silver-containing enamel layer, in particular the removal of the same, is dependent.
  • a particularly favorable solution provides that the silver-comprising particles are formed during firing in the course of the enamel production, since in this case a temperature is reached at which both the constituents of the matrix of the enamel layer and then the silver are in the liquid state.
  • compositions of enamel coatings there is the problem that forms on the silver-containing enamel layer, a thin cover layer, such as a glass layer, which arises due to segregation of provided for the silver-containing enamel layer components.
  • this cover layer or glass layer is often low in silver.
  • an advantageous solution provides that the boundary surface of the silver-containing enamel layer is formed by removal of a thin cover layer formed during the production of the silver-containing enamel layer thereon. Ablation of the overcoat thus eliminates the problems encountered by demixing and interfacial effects and causes the silver-containing enamel layer to fully develop the antimicrobial properties.
  • the removal of the cover layer can be done in a variety of ways.
  • the thin cover layer is worn away by an aging process.
  • Another possibility provides that the thin cover layer is removed by autoclaving.
  • the thin cover layer has been removed by an abrasive process.
  • Another solution provides that the thin cover layer is removed by a chemical etching process.
  • the invention relates not only to an enamel coating, but also to a device with a body for receiving a medium, wherein it is provided according to the invention that the body is provided on its side facing the medium with an enamel coating according to one or more of the embodiments described above.
  • the advantages of this device are the same as the advantages of the coating according to the invention, namely that the medium is limited and guided by surfaces of the enamel coating, which have antimicrobial activity, so that in particular so-called biofilms formed on these in a reduced extent or advantageously not at all ,
  • An embodiment of such a device provides that the device is designed as a conduit for the medium.
  • the device is designed as a pipeline for the medium.
  • Another solution provides that the device is designed as a fitting for the medium.
  • the device is designed as a container for the medium or as a heat exchanger.
  • the device represents the entire conduit system for the medium, wherein the conduit system may comprise lines, fittings, containers, heat exchangers or other components whose sides carrying the medium all substantially support the enamel coating.
  • the antimicrobial properties of the enamel coating have a particularly favorable effect if the device is a device for receiving or guiding water, in particular if the water is drinking water.
  • the advantageous properties according to the invention also occur, in particular, when the device is designed to receive and / or guide air as a medium.
  • the advantageous properties according to the invention are particularly favorable if the medium is a medium used in medical facilities.
  • Figure 1 is a schematic sectional view of a tube as a body according to the invention with an enamel coating on an inner side, wherein in the tube, a medium, such as water, is guided.
  • FIG. 2 shows a micrograph of a first exemplary embodiment of an enamel coating according to the invention with a base enamel layer and a silver-containing enamel layer;
  • Fig. 3 is an enlarged section of the enamel coating according to
  • FIG. 4 shows a micrograph of a second exemplary embodiment of an enamel coating according to the invention through the silver-containing enamel layer
  • Fig. 5 is an enlarged section of the second embodiment; 6 is a further enlarged section of the second embodiment;
  • FIG. 7 is a further enlarged section of the second embodiment
  • FIG 8 is a further enlarged section of the second embodiment showing silver-containing particles both in the surface of the microsection and deeper silver-containing particles.
  • FIG. 9 shows a representation of the microsection of FIG. 8 with only the silver-enclosing particles lying in the surface of the microsection;
  • FIG. 11 shows a micrograph of a third exemplary embodiment of an enamel coating according to the invention.
  • Fig. 12 is an enlarged view of the third embodiment of the coating according to the invention.
  • Fig. 13 is a further enlarged view of the microsection of the third embodiment of the enamel coating according to the invention.
  • An illustrated in Fig. 1 embodiment of a body according to the invention 10 for example, a pipe for receiving and guiding a medium 12, such as drinking water, carries on its the media 12 facing inside 14 a designated as a whole with 20 enamel coating, the inside 14th Covered over the entire surface and has an adjacent to the medium 12 surface 22.
  • the enamel coating 20 preferably has a thickness of at least 200 ⁇ m, more preferably at least 500 ⁇ m.
  • the enamel coating 20 includes a base layer 30 disposed directly on the surface 22 of the body 10 and adhered to the surface 22.
  • a silver-containing enamel layer 40 is arranged which adjoins the medium 12 with a boundary layer 42, the boundary layer 42 of the silver-containing enamel layer 40 forms the surface 22 of the enamel coating 20.
  • the silver-containing enamel layer 40 As shown in particular in FIG. 3, a plurality of silver-containing regions 44a, 44b and 44c are provided, in which the silver is in the form of silver-comprising particles 46, wherein the silver-comprising particles 46 either in cloud-like regions 48 or schlieren-like areas 49 are present in the silver-containing enamel layer 40, the enamel matrix 50 has an enamel composition having an enamel matrix 52 of the base enamel layer 30 - except for the silver-containing particles 46 - a substantially similar material composition.
  • the material composition is a common material composition, as used in a known manner for coating media-carrying bodies 10, such as pipes, use.
  • the silver-containing enamel layer 40 is thus described as containing silver thus does not require that a homogeneous distribution of silver-comprising particles 46 is present, but the silver-comprising particles 46 may well be present in cloud-like regions 48 or striae-like regions 49, so that also in the Substantially silver-free regions 54 of the matrix 50 exist.
  • the cloud-like regions 48 or at least a part thereof extend to the interface 42 of the enamel layer 20, so that at least partially exposed silver-containing particles 46 exist in the interface 42 itself towards the medium 12, which in are able to donate silver ions or silver atoms to the medium 12 to a small extent.
  • silver-containing enamel layer 40 has a thickness of approximately 200 .mu.m, while the underlying base enamel layer 30 has a thickness of at least likewise 200 .mu.m, preferably at least 500 .mu.m.
  • the silver-containing enamel layer 40 is also shown, which extends to the interface 42, wherein with increasing increase of the resolution, for example, already in Fig. 5, the silver-enclosing particles 46 can be seen, which are present in the matrix 50 in cloud-like regions 48 near the interface 42, wherein already in the enlarged view according to FIG. 7 the individual silver-comprising particles 46 can be seen, which can be estimated, for example, from FIG. it can be seen in the magnification according to FIGS. 9 and 10 that the silver-comprising particles 46 in the estimation have an average diameter in the range from approximately 30 to approximately 100 nm.
  • the base enamel layer 30 is likewise recognizable on the one hand and the silver-containing enamel layer 40 extending to the medium 12 forming the surface 22 on the other hand.
  • the cloud-like region 48 with the silver-comprising particles 46 does not extend directly to the surface 22, and thus to the interface 42, but the surface 22 is formed by a glass layer 54 which is produced during the firing of the enamel coating 20 is formed, and thus initially has a silver-poor region 56 which is immediately adjacent to the interface.
  • a possible process is a conventional aging process, which takes place in that, for example, the surface 22 is constantly streamed by the medium and thus already takes place by a long-lasting influx of the surface 22, a detachment of the glass layer 54.
  • the glass layer 54 can also be acceleratedly removed by autoclaving the enamel coating or it is conceivable to remove the glass layer 54 either by an abrasive process or by a chemical etching process, so that subsequently the interface 42 no longer passes through the glass layer 54 with the silver-poor
  • the boundary layer 42 then extends approximately in the region of a line 58, so that immediately adjacent, for example, the cloud-like region 48 to the boundary layer and thus in the boundary layer 42 sufficient silver-containing particles 46 are present, which are suitable and capable Superficially release silver ions or silver atoms.
  • the enamel coating 20 according to the invention is particularly suitable for water-bearing lines in the medical field or in medical devices, which are inevitably colonized with bacteria due to the normal contamination of drinking water with water germs.
  • Such bacterial colonization usually forms extracellular mucus substances which embed the water germs in a so-called biofilm forming on the surface, whereby the germs in the biofilm can be largely protected, for example by a chlorination of the drinking water.
  • the replacement of parts of such biofilms can then lead intermittently to an increased bacterial count in drinking water and cause infections, at least in vulnerable people.
  • the silver contained in the enamel coating 20 according to the invention in the form of the silver-comprising particles 46 is now released by the enamel coating 20 according to the invention in the region of the interface 42 in the smallest amounts and causes an antimicrobial effect, which manifests itself in that the colonization of the surface 22 by microorganisms at least is reduced, if can not be avoided, and in particular the silver released in small amounts reduces or suppresses the multiplication of the microorganisms in the biofilm.
  • the silver-containing enamel layer 40 with the silver-containing particles 46 can preferably be prepared by adding silver having a particle size between about 100 nm and about 200 nm, ie in the form of so-called nannoparticles of an enamel frit, that is, a dry mixture of base material of the enamel the addition to the enamel frit for producing the silver-containing enamel layer 40 with a weight fraction of at least 0.3% based on the enamel frit, so that ultimately in the silver-containing enamel layer is a proportion of silver in the amount of slightly less than at least 0.3 weight percent.
  • Particularly favorable values are additions of approximately 1% by weight of silver to the enamel frit, which then lead in the silver-containing enamel layer 40 to a proportion by weight of somewhat less than 1% of silver, based on the remaining constituents of the silver-containing enamel layer.
  • silver-containing enamel layers 40 by other methods, for example by ion exchange processes on the surface of enameled bodies, ion exchange processes on the enamel frit itself and subsequent introduction into the mill offset, melting of silver into the enamel frit and then introduction into the mill offset, addition of silver salt in the mill offset of the enamel slip or admixture of nanosilver in the enamel slip.
  • the material of the enamel frit intended for the enamel coating is a conventional enamel material which has conventional enamel components which are processed into an enamel slip.
  • an enamel slip for the base enamel layer 30 is first prepared and applied to the body and fired. Subsequently, the enamel slurry for the silver-containing enamel layer 40 is applied to the ember slip layer 30 of the body 10, for example likewise in a dipping process, and subsequently fired.
  • the subsequent firing of the silver-containing enamel layer 40 leads to a further melting of the base enamel layer 30 and thus intimately connect both layers, namely the base enamel layer 30 and the silver-containing enamel layer 40, especially since the constituents of the matrix 50 of the silver-containing enamel layer 40 are preferably identical are with the components of the base enamel layer 30.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un revêtement d'émail d'un corps. En vue d'obtenir un tel revêtement d'émail présentant une excellente action antimicrobienne, l'invention est caractérisée en ce qu'une surface active antimicrobienne du revêtement d'émail est formée par une surface limite active d'une couche d'émail contenant de l'argent, et en ce que des particules comprenant de l'argent, d'une granulométrie moyenne inférieure à 500 nm sont présentes dans la couche d'émail sur la surface limite active.
PCT/EP2008/002252 2007-03-26 2008-03-20 Revêtement d'émail d'un corps WO2008116599A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007016500A DE102007016500A1 (de) 2007-03-26 2007-03-26 Emailbeschichtung für einen Körper
DE102007016500.7 2007-03-26

Publications (1)

Publication Number Publication Date
WO2008116599A1 true WO2008116599A1 (fr) 2008-10-02

Family

ID=39622248

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/002252 WO2008116599A1 (fr) 2007-03-26 2008-03-20 Revêtement d'émail d'un corps

Country Status (2)

Country Link
DE (1) DE102007016500A1 (fr)
WO (1) WO2008116599A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202017107123U1 (de) * 2017-11-23 2017-12-04 Christian Benzing Bioaktiver Filter

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0808570A1 (fr) * 1995-02-02 1997-11-26 Toto Ltd. Procede pour produire un email antibacterien, article portant cet email antibacterien et procede pour le produire
US20020001604A1 (en) * 1998-04-01 2002-01-03 Keijiro Shigeru Antibacterial, antifungal or antialgal article and process for producing same
EP1842525A2 (fr) * 2006-03-22 2007-10-10 Kiss Nail Products Inc. Recouvrement gel antibactérien et spa pour pédicure avec fonction antibactérienne

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5807641A (en) * 1993-05-31 1998-09-15 Sumitomo Osaka Cement Co., Ltd. Anti-bacterial and anti-fungal glaze composition for ceramic products
CN100357228C (zh) * 2002-07-24 2007-12-26 唐山惠达陶瓷(集团)股份有限公司 一种具有自洁釉面的卫生洁具
DE10308039B3 (de) * 2003-02-26 2004-05-06 Silit-Werke Gmbh & Co Kg Verwendung eines Verbundwerkstoffes bei einem Kochgeschirr und Verfahren zum Herstellen eines Verbundstoffes
WO2005115151A1 (fr) * 2004-05-25 2005-12-08 Etc Products Gmbh Agents de revetement sol-gel fonctionnels

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0808570A1 (fr) * 1995-02-02 1997-11-26 Toto Ltd. Procede pour produire un email antibacterien, article portant cet email antibacterien et procede pour le produire
US20020001604A1 (en) * 1998-04-01 2002-01-03 Keijiro Shigeru Antibacterial, antifungal or antialgal article and process for producing same
EP1842525A2 (fr) * 2006-03-22 2007-10-10 Kiss Nail Products Inc. Recouvrement gel antibactérien et spa pour pédicure avec fonction antibactérienne

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANKE DUTSCHKE: "Characterization of Silver-Modified Materials for the Development of Biofilm-Inhibiting Surfaces", FRAUNHOFER ISC ANNUAL REPORT, 2006 - 2006, Würzburg, pages 52 - 53, XP002492927, Retrieved from the Internet <URL:http://www.isc.fraunhofer.de/german/improfil/presse/publikationen/jb_2005/media/52-53_2005.pdf> *

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