WO2017067581A1 - Batterie de cuisine à induction pour lave-vaisselle - Google Patents

Batterie de cuisine à induction pour lave-vaisselle Download PDF

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Publication number
WO2017067581A1
WO2017067581A1 PCT/EP2015/074262 EP2015074262W WO2017067581A1 WO 2017067581 A1 WO2017067581 A1 WO 2017067581A1 EP 2015074262 W EP2015074262 W EP 2015074262W WO 2017067581 A1 WO2017067581 A1 WO 2017067581A1
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WO
WIPO (PCT)
Prior art keywords
layer
tsi
coating
protective layer
stick
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PCT/EP2015/074262
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English (en)
Inventor
Jan HELSKENS
Liu XINXUE
Original Assignee
Jiangmen Anotech Cookware Manufacturing Company Ltd.
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Publication date
Application filed by Jiangmen Anotech Cookware Manufacturing Company Ltd. filed Critical Jiangmen Anotech Cookware Manufacturing Company Ltd.
Priority to PCT/EP2015/074262 priority Critical patent/WO2017067581A1/fr
Publication of WO2017067581A1 publication Critical patent/WO2017067581A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • A47J36/025—Vessels with non-stick features, e.g. coatings

Definitions

  • Aluminium Cookware items have several significant advantages compared to their cast iron or stainless steel counterparts.
  • a first advantage relates to aluminium being a lightweight material. Because of its low weight, handling aluminium cookware is much easier than handling heavier cast iron or stainless steel counterparts.
  • a second advantage relates to aluminium having a high thermal conductivity such that heat generated under the cookware item's base is more evenly distributed throughout the cookware item's body in comparison with cookware made from, for example, stainless steel. This is advantageous as it reduces the risk of local overheating and the associated burning of foodstuffs and enables more even cooking of foodstuffs.
  • Al 2 0 3 is however stable only in a relatively narrow pH range which is not too acidic nor too basic; see e.g. N. L. Sukiman et al., Durability and Corrosion of Aluminium and Its Alloys: Overview, Property Space, Techniques and Developments, Aluminium Alloys - New Trends in Fabrication and Applications, Prof. Zaki Ahmad (Ed.), ISBN: 978-953-51 -0861 -0. Aluminium is a soft metal which scratches easily. This may result in rapid deterioration of the aesthetic characteristics of bare aluminium surfaces with normal use.
  • aluminium's softness may cause traditional polymeric non-stick coatings that are based on fluoropolymers such as PTFE (polytetrafluoroethylene) to be damaged more easily during normal use.
  • fluoropolymers such as PTFE (polytetrafluoroethylene)
  • solid aluminium cookware is not compatible with induction stoves, which are gaining popularity because of their safety and energy efficiency.
  • the present invention provides a solution for, inter alia, the aforementioned challenges.
  • a first aspect of the present invention provides a method of preparing a dishwasher-safe, non-stick, induction capable cookware item having a vessel component (100) for holding food and/or liquids preferably made essentially from a metal that is aluminium or aluminium alloy and having a body (20) with an interior surface for heating and/or cooking the food and an exterior surface (120) opposing the interior surface, a base (160) and a side wall (162) extending upward from the base (160), comprising the steps:
  • thermospray induction, TSI, layer (30) containing a thermospray iron coating to at least part, preferably all of the exterior (120) of the base (160),
  • HA layer a non-stick layer (60) to the interior (120) HA layer (50), and e. applying a second protective layer (70) over the exterior (140) side wall (162) HA layer (50).
  • Applying the TSI layer (30) may further comprise the step of applying a thermospray aluminium coating onto the thermospray iron coating.
  • the TSI layer (30) may not extend beyond the base (160).
  • the non-stick layer (60) may comprise one or more ceramic nonstick coatings.
  • the non-stick layer (60) may comprise one or more PTFE non-stick coatings.
  • the first protective layer (40) comprises one or more high temperature paint (HTP) coatings.
  • the first protective layer (40) may comprise:
  • the composition of the first coating and second of the ceramic hybrid HTP may be the same.
  • the ceramic hybrid HTP may comprise 40-50 wt% ceramic-silicone resin; 10-20 wt% PMA/IPA solvent; 20-30 wt% titanium dioxide; 7-9 wt% carbon black; 10-20 wt% cobalt & Fe dioxide; 0.5-1 wt% trimethylamine; 8-15 wt% whisker filler; 0.2-1 wt% mica; and 0.5 wt% surfactants.
  • the first protective layer (40) may have a dry thickness of between 30 ⁇ and 60 ⁇ .
  • the metallic body (20) of the vessel may roughened by chemical treatment or by grit-blasting.
  • the maximum thickness of the TSI layer (30) may be 0.4 mm to 0.7 mm.
  • Step a) may be performed prior to step b), step b) may be performed prior to step c), step c) may be performed prior to step d), and step d) may be performed prior to step e) or step e) may be performed prior to step d).
  • a further aspect of the invention relates to a dishwasher-safe, non-stick, induction capable cookware item having a vessel component (100) for holding food and/or liquids preferably made essentially from a metal that is aluminium or aluminium alloy and having a body (20) with an interior surface for cooking the food and an exterior surface (120) opposing the interior surface, a base (160) and a side wall (162) extending upward from the base (160), comprising:
  • HA hard anodisation
  • HA hard anodisation
  • HA layer (50) disposed on the interior surface and exterior side wall
  • a non-stick layer (60) disposed over the HA layer (50) on the interior surface (120)
  • the cookware item may be prepared according to a method of any of methods herein.
  • FIGs. 1 and 2 show a vertical transverse cross-section of a cookware item vessel, wherein surfaces, base and side wall indicated.
  • FIG. 3 shows a vertical transverse cross-section of part a cookware item vessel, wherein exemplary layers disposed according to the invention are depicted.
  • FIG. 3A show a possible detail of a rim cross-section of the cookware item of FIG. 3.
  • FIG. 4A to F shows a vertical transverse cross-section of part a cookware item vessel, and a possible sequential order of applying layers.
  • the present invention relates to lightweight cookware items, compatible with induction heating that are durable and are dishwasher safe.
  • the cookware item has a vessel component for holding food and/or liquids preferably made essentially from aluminium.
  • the vessel more in particular its body has an interior surface for cooking the food and an exterior surface opposing the interior surface, a base and a side wall extending upward from the base.
  • the vessel is disposed with a plurality of layers, namely a thermospray induction (TSI) layer, a hard anodized (HA) layer, and a first and preferably a second protective layer and a non-stick (IMS) layer.
  • TSI thermospray induction
  • HA hard anodized
  • IMS non-stick
  • thermospray induction, TSI, layer to at least part, preferably all of the exterior of the base
  • the method steps are preferably performed in the order a) to e). However, steps d) and e) may be reversed.
  • the first protective layer over the TSI layer prevents acid attack of the TSI layer during hard anodization of the aluminium vessel. The hard anodisation is thus performed on regions where the first protective layer is not disposed.
  • the second protective layer may be provided as a single coating or more preferably applied as two coatings either successively (wet-on-wet) or with an intermittent drying between such layers.
  • the cookware item is any suitable for stove-top cooking on all types of stove. It includes a pot and a pan, and variations thereof such as a saucepan, grill pan, frying pan, skillet, wok, stock pot and the like.
  • the cookware item comprises a vessel component for holding food and/or liquids, and may optionally be disposed with one or more handles adapted to carry the vessel.
  • the vessel has an interior that typically contacts the food and can be enclosed by a removable lid, and an exterior opposing the interior.
  • the vessel has a base, adapted for support by the stove top, more in particular by the hob.
  • the exterior of the base is preferably essentially planar.
  • a planar exterior base provides stability to the cookware item. It also allows even thermal contact with the hob.
  • the exterior base is typically round, though other shapes are envisaged. Extending upwards from the base is a side wall that delimits a vessel cavity around the base.
  • the side wall typically has a round profile (viewed from above), though other shapes are envisaged including rectangular or square as found for instance in a grill pan or oval as found in the case of a fish pan.
  • the side wall is typically rounded towards the base.
  • FIGs. 1 and 2 show an exemplary cross- section of a cookware item (100), more in particular the vessel component thereof, having an interior (120) and exterior (140), a base (160) and side wall (162).
  • the side wall is rounded towards the base.
  • the vessel is typically made from a single casting or by pressing or forging a sheet; the segmented appearance in FIG. 2 denotes typical fictive boundaries between the base (160) and side wall (162).
  • the vessel has a body that may be made substantially from any non-inductive material including aluminium, or aluminium alloy.
  • aluminium alloying elements include copper, magnesium, manganese, silicon, tin and zinc.
  • the vessel body is made from aluminium that may be cast or pressed or otherwise formed.
  • the surface of the vessel component Prior to applying a TSI layer to the base (prior to step a)), the surface of the vessel component may be roughened to create a surface for adhesion by the iron, non-stick layer and second protective layer. Typically the whole of the vessel surface is roughened.
  • the surface may be roughened by grit blasting, also known as sand blasting. Grit blasting has been described in the art, for instance, in CN 1052802.
  • a surface for promoting adhesion of non-stick interior coatings or exterior decorative and protective coatings may also be roughened by acid etching wherein the metallic substrate is exposed to one or more acidic etching solutions which may be different.
  • a surface may be roughened by alkali etching wherein the metallic substrate is exposed to one or more alkali etching solutions which may be different. The acid or alkali etching also serve to remove surface contaminants such as grease and oil.
  • the vessel is roughened by acid etching.
  • the acidic aluminium etching is performed in warm phosphoric acid, as described for example in “Zhou, Bo, and W. Fred Ramirez. "Kinetics and modeling of wet etching of aluminium oxide by warm phosphoric acid.” Journal of The Electrochemical Society 143, no. 2 (1996): 619-623.”
  • the vessel surface is acid etched by means of a solution consisting of 80% phosphoric acid, 5% nitric acid, 5% acetic acid, and 10% water; as described in “Williams, Kirt R., and Richard S. Muller. "Etch rates for micromachining processing.” Microelectromechanical Systems, Journal of 5, no.
  • the TSI layer may be applied. At least part, or preferably all of the exterior of the base is provided with a thermospray induction (TSI) layer.
  • the TSI layer comprises a thermospray iron coating, and optionally a thermospray aluminium coating.
  • thermospraying is known in the art and is where heated or molten metal particles (e.g. iron or aluminium) are sprayed onto a surface.
  • the particles are heated by electrical means such as plasma or an arc, or by chemical means such as a combustion flame.
  • Thermospraying is also known in the art as thermal spraying, electric arc wire thermal spraying, or arc spraying and is described in the art, for instance, in US 2,982,845, and US 5,753,313 A.
  • the thermospray iron powder may optionally contain molybdenum, copper, and boron; as disclosed, for example, in US 4,822,415.
  • the thermospray iron coating contains essentially only iron.
  • the TSI layer may comprise one or more coatings applied by the process of thermospraying.
  • the TSI layer comprises a thermospray iron coating and a thermospray aluminium coating.
  • the thermospray aluminium coating may be provided over the thermospray iron coating.
  • the thermospray aluminium coating has been found to enhance corrosion protection of the TSI layer.
  • an induction coil in the hob heats the iron base of cookware.
  • the heat induced in the base is transferred to the food via (metal surface) conduction.
  • Benefits of induction cookers include efficiency, safety (the induction cook-top is not heated itself) and speed. Both permanently installed and portable induction cookers are available. Copper-bottomed, aluminium and other non-ferrous cookware items are generally unsuitable.
  • the TSI layer provides an induction-heating functionality to cookware items otherwise rendered unsuitable for such heating. As the TSI layer is thin, it does not add significantly to the weight of the cookware item.
  • TSI layer generally does not extend to the exterior of the side wall, although it is within the scope of the invention that there may be a limited about of overspray.
  • the TSI layer may not extend to the interior of the vessel.
  • TSI layer is applied to more than 80%, more preferably more than 90%, and ideally 100% of the base exterior.
  • the TSI layer is preferably applied directly to the body of the vessel, e.g. directly onto the aluminium base.
  • the TSI layer is preferably applied directly to a body of the vessel.
  • the TSI layer is preferably applied directly to an un-anodised body of the vessel.
  • the TSI layer is preferably applied directly to the body of the vessel without using pre-treatment such as for example a primer.
  • the TSI layer 30 is applied directly to the exterior of the metallic base.
  • TSI layer may applied essentially only to the base by directing one or more thermospray guns to face the exterior base. There may be some over-spray of the TSI layer onto the exterior sidewalls. However, this is limited by alignment of the guns and their motion relative to the base of the cookware item. Typically the cookware item is in revolute alignment with the one or more thermospray guns.
  • the metallic base may be first roughened to create a surface for adhesion by the TSI layer as described above.
  • the roughened surface may not be limited to the exterior of the base of the vessel; preferably the whole surface of the vessel is roughened. Particularly, the whole surface of the vessel may be roughed when using acid etching.
  • the maximum thickness of the TSI layer may be 0.2 mm to 1 mm, preferably 0.4 to 0.7 mm.
  • the maximum thickness of the iron coating in the TSI layer may be 0.1 mm to 5 mm, preferably 0.3 to 0.5 mm.
  • the maximum thickness of the aluminium coating in the TSI layer may be 0.1 mm to 5 mm, preferably 0.1 to 0.2 mm.
  • the TSI layer (30) is applied directly to and is limited to the base of the vessel.
  • the method may include a step of base pressing to correct the concavity of the cookware item.
  • the pressing step ensures that the base is slightly concave when cold but becomes close to flat when heated to cooking temperatures. It may be performed prior to application of the non-stick layer, HA layer, first protective layer or second protective layer. Preferably it is performed after application of the TSI layer (step a) and prior to the application of further layers (e.g. prior to any of steps b), c), d) or e)).
  • the base pressing may be performed using a suitable press, such as a hydroforming press.
  • the first protective layer comprises one or more coatings of a high temperature paint (HTP).
  • HTP high temperature paint
  • the first protective layer may cover only the base.
  • the first protective layer may not extend to exterior of the side wall.
  • the first protective layer may not extend to the interior of the vessel. Where application of the first protective layer extends beyond the TSI layer, the extended part may be later removed, for instance, chemically or mechanically.
  • the first protective layer is preferably applied directly to the TSI layer.
  • the first protective layer is preferably applied directly to the TSI layer on the base of the vessel without pre- treatment using a primer.
  • the HTP is heat resistant at a temperatures encountered when the vessel is heated on a hob, such as an induction hob, gas or electric hob. Typical temperatures are equal to or below 300, 400, 450 or 500 deg C, preferably 450 deg C.
  • the HTP is also resistant to corrosion by reagents (e.g. acid) used in the application of the subsequent HA layer. By heat resistance, it is meant that thermal degradation of the HTP is resisted.
  • HTPs are commonly used as a coating for protecting the exterior surfaces of cookware and for decorative purposes, and are well known in the art.
  • the HTP may be, for instance, a Silicone Polyester, a High-Silicone HTP, a polyethersulfone (PES) coating, Ceramic Hybrid HTP or a Sol-Gel HTP.
  • the PES coating may be that commercially available, for instance, from Weilburger Coatings. High-silicone HTP types are widely commercially.
  • the sol-gel HTP may be a sol-gel coating manufactured for instance by Thermolon.
  • the ceramic hybrid HTP may be a ceramic hybrid coating as manufactured for example by Foshan Fruto Chemicals Co., Ltd. (China), for instance SP System coating.
  • the HTP typically has good adhesion to the TSI layer.
  • hybrid ceramic HTP is known in the art.
  • the term "hybrid” refers to ceramic HTPs that are inorganic-organic.
  • Such a HTP contains oligomeric or polymeric chains containing both Si and C atoms.
  • a hybrid ceramic HTP typically contains silicone type resins (binders) with a relatively high ratio of Si (i.e. inorganic part of the chain) to organic material (i.e. organic part of the chain).
  • Si-atoms may form a part of oligomer chain that comprises Si atoms backbone with organic linkages between them. These chains may or may not be silanes.
  • An example of a hybrid ceramic HTP is a polymer of tetraethoxysilane.
  • the chain of a hybrid ceramic HTP is generally pre-formed by a coating manufacturer.
  • the chemistry with a hybrid ceramic HTP has generally already been performed by the manufacturer.
  • the physical/mechanical properties of these hybrid ceramic HTPs generally speaking may be somewhere between inorganic ceramic-like and organic-like - e.g. harder and more temperature resistant than a silicone polyester coating but less hard and less temperature resistant than an inorganic ceramic coating.
  • hybrid ceramic HTP is the hybrid ceramic "SP System coating" manufactured by Foshan Fruto Chemicals Co., Ltd. (China).
  • a liquid composition for application it comprises ceramic-silicone resin (CAS no: 67763-03-5, 40-50 wt%); PMA/IPA solvent (CAS no: 108-65-6, 10-20 wt%); titanium dioxide (CAS no: 13463-67-7 20-30 wt%); carbon black (CAS no: 1333-86-4, 7-9 wt%, preferably 8 wt%); cobalt & Fe dioxide (10-20 wt%); trimethylamine (CAS no: 121 -44-8, 0.5-1 wt%); whisker filler (8-15 wt%); mica (CAS no: 12001 -26-2, 0.2-1 wt%); surfactants (0.5 wt%), the wt% being relative to the hybrid ceramic HTP.
  • the first protective layer may be applied by spraying.
  • HTP is applied according to a method of the art, the protocol and timings used will be dependent upon composition and nature of the chemistry.
  • the HTP e.g. Foshan Fruto exterior coating
  • HVLP high volume low pressure
  • the base is sprayed. Any over-spray may be removed from the side walls.
  • the HTP may be cured in a conventional tunnel oven.
  • the number of coatings of the HTP in the first protective layer may be 1 , 2, 3 or more, preferably 2. When there are two or more HTP coatings they are laid over each other. When there are two or more HTP coatings, all the HTPs coatings in the first protective layer may be the same. Two or more HTP coatings in the first protective layer may be different, alternatively. More than one coat is preferred to ensure coverage and avoidance or reduction in pinholes that might cause corrosion when exposed to reagents (e.g. acids) in the Hard Anodization process. The previous coat may be allowed to dry before the subsequent coat is applied or it can be applied with just a short drying period between applications or it can be applied wet-on-wet.
  • reagents e.g. acids
  • first protective layer comprises two (first and second) ceramic hybrid HTP coatings, one applied over the other. It is considered in the art that the strong acids used in the HA process would penetrate an exterior coating for instance through pinholes that form corrosion channels down to the metallic vessel body. Protecting such a rough surface as a TSI layer is considered an impractical and an unworkable notion. The inventors have found that applying a first protective layer of at least two coatings of ceramic hybrid HTP coatings is effective in preventing pinhole corrosion. In a particular embodiment, the first ceramic hybrid HTP coating is applied to the TSI layer.
  • the coating After application of the first ceramic hybrid HTP coating, the coating is subjected to a flash-off - a drying step in which volatile components are removed by flash evaporation (evaporation below the curing temperature) resulting in a coating that is dry but not yet cured. Subsequently, the second ceramic hybrid HTP coating is applied over the flashed-off first HTP coating.
  • the primary and secondary ceramic hybrid HTP coatings have the same composition.
  • the primary and secondary ceramic hybrid HTP coatings are curable.
  • the two HTP coatings i.e. the first protective layer is subsequently cured.
  • the HTP acts as a corrosion resistant barrier to protect the iron in the TSI layer from acid that is used in the subsequent HA process and to prevent corrosion during household use.
  • the HTP also provides a decorative function i.e. coloured surface that is suitable for printing thereon, for instance, marking such as a logo. Printing may be realised by any suitable technique such as stencil or pad printing.
  • the thickness of the first protective layer may be equal to or greater than 20 ⁇ , 30 ⁇ , 40 ⁇ , 50 ⁇ or 60 ⁇ , and typically no thicker than 100 ⁇ .
  • the thickness refers to the dry (e.g. cured) thickness of the first protective layer.
  • the first protective layer comprises 2 or more coatings of a HTP
  • the thickness of each coating in the first protective layer may be 15 to 30 ⁇ ; the thickness refers to the dry (e.g. cured) thickness of the HTP coating.
  • the first protective layer contains 2 coatings of a hybrid- ceramic HTP or of a sol-gel HTP, with a dry thickness of between 30 ⁇ and 60 ⁇ .
  • the first protective layer (40) is applied directly to and is limited to the TSI layer (30).
  • any first protective layer that extends beyond the base may be removed.
  • the hard anodised (HA) layer is a layer wherein a metallic body of the cookware item has been oxidised by hard anodisation.
  • the anodisation results in an increased thickness of the natural oxide layer which is hard, relatively inert, electrically insulating and can absorb or readily adhere to other layers such as the non-stick layer or the second protective layer.
  • the metallic body of the cookware item is assigned as anode in an electrolytic cell typically containing an acid such as sulphuric acid.
  • the anodising process grows a layer of aluminium oxide (Al 2 0 3 or corundum).
  • a barrier layer is formed by continuous formation and dissolution of a layer of oxide at the aluminium-aluminium oxide interface.
  • a more porous, more structured layer forms over the barrier layer making up the remainder of the HA layer.
  • the body may be treated to an alkali wash to remove grease and particles, followed by etching and desmutting baths to remove natural surface oxides.
  • Anodic oxidation may proceed with sulfuric acid as the electrolyte in which oxide crystals with a hexagonal shape are formed.
  • the pores of the oxide surface may be sealed to enhance strength and avoid discoloration. Sealing may be performed, for instance, by exposing the oxide surface to hot water, optionally containing one or more metal salts. Typically the temperature of the water is just below its boiling point. The water causes the material around the pores to swell and close up the holes. The metal salts where present aid closing of the pores and may provide better properties to the HA layer.
  • One method for aluminium hard anodisation is described in US 4,128,461.
  • anodising increases corrosion resistance and wear resistance, and provides better adhesion for paint primers and glues than does bare metal.
  • Anodic films can also be used for a number of cosmetic effects, either with thick porous coatings that can absorb dyes or with thin transparent coatings that add interference effects to reflected light.
  • mechanical properties of subsequently applied layers are superior where disposed on a HA surface compared with on a plain metal (normally sand-blasted) surface. Such properties can include hardness, scratch resistance, abrasion resistance, impact resistance, and the like.
  • the HA layer is applied to the regions of the vessel not disposed with the first protective layer.
  • the first protective layer prevents anodisation of the metal below.
  • the HA layer may not extend to the exterior of the base.
  • the HA layer may be provided on the exterior side wall and on the interior of the vessel.
  • the HA layer is preferably applied directly to the metallic body of the vessel.
  • the thickness of the HA layer may be equal to or greater than 10 ⁇ , 20 ⁇ , 30 ⁇ , 40 ⁇ , 50 ⁇ or 60 ⁇ , and typically no thicker than 100 ⁇ . Preferably, it is between 20 ⁇ and 60 ⁇ .
  • the HA layer (50) is disposed directly onto the metallic body 20 of the vessel, on the interior and on the exterior side wall.
  • the non-stick layer reduces the adhesion of food to the vessel interior during cooking.
  • the non-stick layer also protects the interior of the vessel from corrosion, particularly in dishwashers.
  • the non-stick layer comprises one or more non-stick coatings.
  • the nonstick coating may be any type of non-stick coating used in cookware.
  • the non-stick layer may further comprise one or more additional coatings such as an enamel coating or a primer coating.
  • the non-stick coating is heat resistant at temperatures encountered when the pan is heated on a hob, such as an induction hob, gas or electric hob. By heat resistant, it is meant that thermal degradation of the non-stick coating is resisted.
  • the non-stick coating may be, for instance, a fluoropolymer such as polytetrafluoroethylene (PTFE) or perfluoroalkoxy (PFA) based non-stick coating, or a ceramic such as a sol-gel non-stick coating.
  • the temperature resistance of the non-stick coating may be equal to or below 300, 400, 450 or 500, preferably 450 deg C; the temperature resistance will depend on the type of non-stick coating used. For instance, generally, a PTFE non-stick coating can withstand a maximum of 240 to 260 deg C, while a ceramic non-stick coating can generally withstand a maximum of 400 to 450 deg C.
  • the non-stick layer may be a non-stick layer of the art and applied according to methods of the art.
  • the non-stick layer may be applied by any suitable technique such as spraying or dip coating.
  • the non-stick layer typically has good adhesion to the HA layer.
  • the non- stick layer may contain a ceramic coating or a fluoropolymer coating, or another type of non-stick coating.
  • a ceramic coating is one that contains silica and is well known in the art of non-stick cookware items.
  • An exemplary ceramic coating and method of application are described, for instance, in EP 2 457 477.
  • the non-stick layer contains a sol-gel non-stick ceramic coating without any primer or enamel layer below.
  • a ceramic coating may be a sol-gel coating.
  • a sol-gel coating is one that contains an inorganic polymer (e.g. based on poly-silicon oxides, poly-Zirconium oxides, poly-titanium oxides and/or poly-aluminium oxides) and is well known in the art of non-stick cookware items.
  • An exemplary sol-gel coating and method of application are described, for instance, in US 2003/0138661 , or US 2004/0209072, or WO 2008/010639.
  • the non-stick layer may contain a fluoropolymer coating such as a PTFE or a PFA coating.
  • a PTFE coating is one that contains polytetrafluoroethylene polymer and is well known in the art of non-stick cookware items. An exemplary PTFE coating and method of application are described, for instance, in US 5,240,775.
  • a PFA coating is one that contains perfluoroalkoxy polymer.
  • the non-stick layer may contain multiple coatings. When there are two or more coatings they are laid over each other. The number of non-stick coatings in the non-stick layer may be 1 , 2, 3 or more, preferably 1 . When there are two or more non-stick coatings, all the non-stick coatings may be the same.
  • Two or more non-stick coatings may be different, alternatively.
  • the previous coating is allowed to dry before the subsequent coat is applied.
  • the non-stick layer contains 2-4 PFTE non-stick coatings.
  • the non-stick layer contains 1 -2 ceramic non-stick coatings.
  • the thickness of the non-stick layer may be equal to or greater than 10 ⁇ , 20 ⁇ , 25 ⁇ , 30 ⁇ , 40 ⁇ , 50 ⁇ , 55 ⁇ or 60 ⁇ , and typically no thicker than 60 ⁇ . Preferably, it is between 20 ⁇ and 30 ⁇ . Where the non-stick layer includes an enamel coating, the thickness of the non-stick layer may be in the range 100 ⁇ to 250 ⁇ . The thickness refers to the dry layer e.g. typically after setting, drying or curing.
  • the non-stick layer preferably does not extend to exterior of the side wall.
  • the non-stick layer may not extend to the exterior of the base.
  • the non-stick layer is preferably applied directly to the HA layer.
  • the non-stick layer is preferably applied directly to the HA layer without pre-treatment using a primer.
  • the non-stick layer (60) is applied directly to the HA layer (50) on the interior of the vessel.
  • the second protective layer comprises one or more coatings of a high temperature paint (HTP).
  • HTP high temperature paint
  • the HTP is heat resistant at temperatures encountered when the pan is heated on a hob, such as an induction hob, gas or electric hob. Typical temperatures are equal to or below 300, 400, 450, 500 deg C, preferably 450 deg C.
  • heat resistant it is meant that thermal degradation of the HTP is resisted.
  • HTPs are commonly used as a coating for protecting the exterior surfaces of cookware.
  • the HTP typically has good adhesion to the TSI layer.
  • the HTP is clear or translucent to that the hard anodised appearance of the exterior surface is retained.
  • the HTP in the second protective layer protects the exterior side wall from corrosion, particularly in dishwashers.
  • the HA layer may otherwise be attacked by alkaline detergents or other aggressive cleaning chemicals, converting the aluminium oxide in the HA layer to white aluminium salts; eventually the HA layer will dissolve away without the second protective layer.
  • the HTP may be, for instance, a silicone polyester, a high-silicone HTP, PES coating, ceramic hybrid HTP or a sol-gel HTP.
  • the HTP used in the second protective layer may be the same as that used in the first protective layer, however, it would not be necessary to have any pigments present.
  • the PES coating may be that commercially available, for instance, from Weilburger Coatings. High-silicone HTP types are widely commercially.
  • the Sol-Gel HTP may be an un-pigmented exterior coating manufactured for instance by Thermolon.
  • the ceramic hybrid HTP may be an un-pigmented ceramic hybrid coating as manufactured for example by Foshan Fruto Chemicals Co., Ltd. (China).
  • the HTP typically has good adhesion to the HA layer.
  • hybrid ceramic HTP is known in the art.
  • the term "hybrid” refers to ceramic HTPs that are inorganic-organic.
  • Such a HTP contains oligomeric or polymeric chains containing both Si and C atoms.
  • a hybrid ceramic HTP typically contains silicone type resins (binders) with a relatively high ratio of Si (i.e. inorganic part of the chain) to organic material (i.e. organic part of the chain).
  • Si-atoms may form a part of oligomer chain that comprises Si atoms backbone with organic linkages between them. These chains may or may not be silanes.
  • An example of a hybrid ceramic HTP is a polymer of tetraethoxysilane.
  • the chain of a hybrid ceramic HTP is generally pre-formed by a coating manufacturer.
  • the chemistry with a hybrid ceramic HTP has generally already been performed by the manufacturer.
  • the physical/mechanical properties of these hybrid ceramic HTPs generally speaking may be somewhere between inorganic ceramic-like and organic-like - e.g. harder and more temperature resistant than a silicone polyester coating but less hard and less temperature resistant than an inorganic ceramic coating.
  • An example of a hybrid ceramic HTP is the hybrid ceramic "SP System coating" manufactured by Foshan Fruto Chemicals Co., Ltd. (China).
  • liquid composition for application it comprises ceramic-silicone resin (CAS no: 67763-03-5, 40-50 wt%); PMA/IPA solvent (CAS no: 108-65-6, 10-20 wt%); titanium dioxide (CAS no: 13463-67-7 20-30 wt%); carbon black (CAS no: 1333-86-4, 7-9 wt%, preferably 8 wt%); cobalt & FE dioxide (CAS no: 13463-67-7, 10-20 wt%); trimethylamine (CAS no: 121 -44-8, 0.5-1 wt%); whisker filler (8-15 wt%); mica (CAS no: 12001 -26-2, 0.2-1 wt%); surfactants (0.5 wt%), the wt% being relative to the hybrid ceramic HTP.
  • ceramic-silicone resin CAS no: 67763-03-5, 40-50 wt%)
  • PMA/IPA solvent CAS no: 108-65-6, 10-20 wt%)
  • titanium dioxide CAS no: 134
  • the second protective layer may be applied by spraying.
  • HTP is applied according to method of the art, the protocol and timings used will be dependent upon composition and nature of the chemistry.
  • the HTP is applied by using one or more air-assisted spray guns.
  • one or more high volume low pressure (HVLP) spray guns may be employed.
  • the exterior side wall is sprayed. Any over-spray may be removed from the base.
  • the HTP may be cured in a conventional tunnel oven.
  • the second protective layer comprises one or more coatings of a high temperature paint (HTP).
  • the number of coatings of the HTP in the second protective layer may be 1 , 2, 3 or more, preferably 1. When there are two or more HTP coatings they are laid over each other. When there are two or more coatings, all the HTPs coatings in the second protective layer may be the same. Two or more HTP coatings in the second protective layer may be different, alternatively. More than one coat is preferred to ensure coverage and avoidance or reduction in pinholes that might cause corrosion during the application of subsequent layers.
  • the previous coat may be allowed to dry before the subsequent coat is applied or it can be applied with just a short drying period between applications or it can be applied wet-on-wet
  • the thickness of the second protective layer may be equal to or greater than 5 ⁇ , 10 ⁇ , 20 ⁇ , 30 ⁇ , 40 ⁇ , 50 ⁇ or 60 ⁇ , and typically no thicker than 100 ⁇ . Preferably, it is between 10 ⁇ and 20 ⁇ .
  • the thickness refers to the dry (e.g. cured) thickness of the second protective layer.
  • the second protective layer contains 1 coating of a hybrid- ceramic HTP or of a sol-gel HTP, with a thickness of between 10 ⁇ and 20 ⁇ .
  • only the HA layer on the exterior of the side wall is provided with the second protective layer.
  • the second protective layer may not extend to the exterior of the base.
  • the second protective layer may not extend to the interior of the vessel.
  • the second protective layer is preferably applied directly to the HA layer.
  • the second protective layer is preferably applied directly to the HA layer on the exterior side wall of the vessel without pre-treatment using a primer.
  • the second protective layer (70) is applied directly to and is limited to the HA layer (50) of the exterior side wall.
  • the method steps are preferably performed in the order a) to e). However, steps d) and e) may be reversed. According to one aspect, step a) is performed prior to step b), step b) is performed prior to step c), step c) is performed prior to step d), and either step d) is performed prior to step e) or step e) is performed prior to step d).
  • the body of the vessel may be first formed by forging, followed by burr removal and edge trimming.
  • the rim may be polished, the interior and exterior surfaces cleaned with detergent, followed by a polishing thereof.
  • the body of the vessel may then proceed according to a method of the invention.
  • the base may be ground and any iron particles removed; these steps may arise prior to the optional base-pressing step.
  • the first protective layer may be polished. One or more holes may be punched in the vessel to support a handle prior to the hard anodisation step.
  • the curing step is performed prior to hard anodisation (step c).
  • the non-stick layer and the second protective layer require curing, the non-stick layer is preferably applied (step d) and cured after the application (step e) and curing of the second protective layer.
  • the non-stick layer may be applied (step d) and cured step prior to application (step e) and curing of the second protective layer.
  • curing step of non-stick layer and the second protective layer may be performed simultaneously after the application of the nonstick layer (step d) and of the second protective layer (step f).
  • the TSI layer, a HA layer, and a first and second protective layer and a non-stick (NS) layer are disposed on the metallic body of the vessel according to the arrangement described herein.
  • the TSI layer is provided essentially only on the exterior base and the first protective layer is provided essentially over the TSI layer and does not extend beyond the exterior base.
  • the HA layer is provided over the parts not covered by the first protective layer, namely, over the interior and the exterior side wall of the vessel.
  • the NS layer is disposed over the interior of the vessel, and over the HA layer.
  • the second protective layer is disposed over the exterior side wall of the vessel, and over the HA layer. Where there is a flat rim, it is disposed with the HA layer and the non-stick layer extending from the interior.
  • the second protective layer may meet an outer edge of the rim and may abut or overlap the non-stick layer.
  • FIG. 3A shows a particular arrangement of a flat rim (80) disposed with the HA layer (50) and the non-stick layer (60) extending from the vessel interior; the second protective layer (70) abuts the non-stick layer (60).
  • the first and second protective layers may abut or overlap.
  • the exterior HA layer and the TSI layer may abut or overlap.
  • the unique combination of layers and the location in which they are disposed provide a cookware item that is lightweight, inductive, and dishwasher safe.
  • the method relates to the manufacture of the cookware as defined herein.
  • FIG. 3 depicts a cookware item, in particular the vessel component (100) according to the invention having a body (20), provided with the thermospray induction (TSI) layer (30) on the base that is covered with the first protective layer (40).
  • the body is also disposed with the hard anodised (HA) layer (50) on the interior and exterior side wall.
  • the non-stick layer (60) is provided on the interior over the HA layer (50).
  • a second protective layer is disposed over the HA layer (50).
  • FIG. 4 depicts a possible order of applying the layers, and depicts their location.
  • the metallic body (40) (A) is first provided with the thermospray induction (TSI) layer (30) on the base (B). Subsequently, the first protective layer (40) is applied over the TSI layer (30) (C).
  • the cookware item is hard anodised (D); those area not protected by the first protective layer (40) receive the hard anodized (HA) layer (50).
  • the non-stick layer (60) is applied over the HA layer (50 (E) on the interior of the vessel.
  • the second protective layer (70) is applied over the HA layer (70) (F) on the exterior side wall.
  • the second protective layer (70) may be applied over the HA layer (70) (F) on the exterior side wall and subsequently the non-stick layer (60) may be applied over the HA layer (50) (E) on the interior of the vessel.
  • the present invention relates to a cookware item prepared according to a method of the invention.
  • the present invention further relates to a method as described herein for the preparation of an item of cookware.
  • the present invention further relates to a use of hard anodisation and TSI for preparing a lightweight, dish-washer safe induction cookware item.
  • the inventors have found a combination of layers and their locations that provide an item of non-stick cookware that is dish-washer safe and induction capable. For the first time, the inventors have devised a superior cookware item and a method of manufacture thereof that provides non-stick, dish-washer safe, induction capable features in a durable and lightweight form.
  • the HA process produces a superior surface for the adhesion of subsequent layers, and the TSI layer reduces the weight and construction steps. Yet in the art the combination of HA and TSI is avoided because the strong acids used in the HA process destroy the TSI layer.
  • the inventors have found that the first protective layer provides a barrier to the acids for a sufficient period that the remainder of the vessel can be treated by HA leaving the TSI layer intact.
  • the TSI layer makes the impact bonding of disc of ferromagnetic material redundant.
  • the resulting base is more stable without the differential in thermal expansion as the pan is heated. This also places less stress on the interior ceramic non-stick coating thus reducing the tendency towards micro- cracking.
  • Example 1 dish washer safe testing
  • a 24 cm forged aluminium frying pan was treated to surface roughening treatment, after which a TSI layer was applied of an iron coating and a subsequent aluminium coating to a thickness of 0.2 mm.
  • a first protective layer of a hybrid HTP that was two coatings of Foshan Fruto SP System coating (SPG-8300/SPG-9105) was applied by spraying over the TSI layer and the pan was baked at 280 deg C so as to cure the first protective layer.
  • the thickness of the first protective layer was 74 ⁇ after curing.
  • the pan was treated by hard anodisation in a sulphuric acid bath.
  • a ceramic non-stick layer was applied onto the hard anodised layer by spraying the interior of the pan with a sol-gel non-stick ceramic coating.
  • the pan was baked at 320 deg C metal temperature so as to cure the non-stick layer.
  • the thickness of the non-stick layer was 30 ⁇ after curing.
  • the second protective layer being one coating of Foshan Fruto SP System coating (SPG-8300/SPG-9105) was applied to exterior of the side wall.
  • the pan was baked at 280 deg C so as to cure the second protective layer.
  • the thickness of the second protective layer was 25-30 ⁇ after curing. After cleaning and polishing the pan was subjected to testing.
  • the frying pan was subjected to cycles of cooking and washing in a dish washer.
  • a Haier Dishwasher was employed for performing the dish-washing. Prior to washing in the dishwasher, water was boiled in the pan for 1 hour on a gas stove. Standard detergent agent and rinse agent were used, and the feed water was softened using a cation exchanger. The original appearance of the pan was checked. A standard mode (Program no. 1 "normal", cycle time 80 min, temperature 65-70°C, dry at 70°C, disinfection. 12.5g of detergent and 3ml of rinse agent was used for each cycle. The amount water used for each cycle: 2.5L for washing, 2.5L for rinsing with water, 2.5L for rinsing with agent.
  • a 24 cm forged aluminium frying pan was treated to surface roughening treatment, after which a TSI layer was applied of an iron coating to a thickness of 0.2 mm.
  • a first protective layer of a hybrid HTP that was two coatings of Foshan Fruto SP System coating (SPG-8300/SPG-9105) was applied by spraying over the TSI layer and the pan was baked at 280deg C so as to cure the first protective layer.
  • the thickness of the first protective layer was 74 ⁇ after curing.
  • the pan was treated by hard anodisation in a sulphuric acid bath.
  • a ceramic non-stick layer was applied onto the hard anodised layer by spraying the interior of the pan with a sol-gel non-stick ceramic coating.
  • the pan was baked at 320 deg C metal temperature so as to cure the non-stick layer.
  • the thickness of the non-stick layer was 30 ⁇ after curing.
  • the second protective layer being one coating of Foshan Fruto SP System coating (SPG-8300/SPG-9105) was applied to exterior of the side wall.
  • the pan was baked at 280 deg C so as to cure the second protective layer.
  • the thickness of the second protective layer was 25-30 ⁇ after curing. After cleaning and polishing the pan was subjected to testing.
  • the pan was rinsed thoroughly in tap water.
  • a container was filled with tap water at room temperature. Approximately 90% of the base surface of the pan was immersed in the water in vertical position in the container; a small area above the waterline was not immersed in order to see the difference easily. After every 6 hours of immersion, the pan was removed for inspection, for a total of 24 hours. The results show no evidence of corrosion or any other defect in the pan.
  • a 28 cm forged aluminium frying pan was treated to surface roughening treatment, after which a TSI layer was applied of two thermospray iron coatings and a subsequent thermospray aluminium coating to a thickness of 0.2 mm.
  • a first protective layer of a hybrid HTP that was two coatings of Foshan Fruto SP System coating (SPG-8300/SPG- 9105) was applied by spraying over the TSI layer and the pan was baked at 280deg C so as to cure the first protective layer.
  • the thickness of the first protective layer was 50 ⁇ after curing.
  • the pan was treated by hard anodisation in a sulphuric acid bath.
  • a ceramic non-stick layer was applied onto the hard anodised layer by spraying the interior of the pan with a sol-gel nonstick ceramic coating.
  • the pan was baked at 320 deg C metal temperature so as to cure the non-stick layer.
  • the thickness of the non-stick layer was 30 ⁇ after curing.
  • the second protective layer being one coating of Foshan Fruto SP System coating (SPG-8300/SPG-9105) was applied to exterior of the side wall.
  • the pan was baked at 280 deg C so as to cure the second protective layer.
  • the thickness of the second protective layer was 25-30 ⁇ after curing. After cleaning and polishing the pan was subjected to testing.
  • the pan was rinsed thoroughly in tap water. A container was filled with tap water at room temperature. Approximately 90% of the base surface of the pan was immersed in the water in vertical position; a small area above the waterline was not immersed in order to see the difference easily. After 6 hours of immersion, the pan was removed, dried and stored at room temperature for 24 hours. Subsequently, the pan was immersed in water for a further 12 hours, removed, dried and stored at room temperature for 24 hours. The pan was removed for inspection. The procedure was performed on two separate pans. The results show no evidence of corrosion of any other defect in either pan.

Abstract

La présente invention concerne un procédé de préparation d'un ustensile de cuisine à induction, non collant, pour lave-vaisselle ayant un élément de récipient (100) pour contenir des aliments et/ou des liquides, de préférence constitué essentiellement d'un métal qui est l'aluminium ou un alliage d'aluminium, consistant à appliquer une couche d'induction à pulvérisation thermique (TSI) (30), une première couche de protection (40), une anodisation dure pour former une couche HA (50), une couche non collante (60) et une seconde couche de protection (70) dans certaines configurations. L'invention concerne également une batterie de cuisine préparée selon le procédé.
PCT/EP2015/074262 2015-10-20 2015-10-20 Batterie de cuisine à induction pour lave-vaisselle WO2017067581A1 (fr)

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CN109770696A (zh) * 2018-12-10 2019-05-21 九阳股份有限公司 一种保温锅
KR102267254B1 (ko) * 2020-12-30 2021-06-18 김구환 세라믹 소재를 이용한 구이용 타공판 및 이를 포함하는 구이용 가마
US20220218178A1 (en) * 2020-06-23 2022-07-14 Kitchen Robotics Ltd Apparatus, Method and System of Washing Induction Cookware using Induction Heating and High-Pressure Water Jet
US20220225822A1 (en) * 2019-05-23 2022-07-21 Seb S.A. Cooking Utensil Comprising An Aluminum Shell

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Publication number Priority date Publication date Assignee Title
CN109770696A (zh) * 2018-12-10 2019-05-21 九阳股份有限公司 一种保温锅
US20220225822A1 (en) * 2019-05-23 2022-07-21 Seb S.A. Cooking Utensil Comprising An Aluminum Shell
US20220218178A1 (en) * 2020-06-23 2022-07-14 Kitchen Robotics Ltd Apparatus, Method and System of Washing Induction Cookware using Induction Heating and High-Pressure Water Jet
US11730338B2 (en) * 2020-06-23 2023-08-22 Kitchen Robotics Ltd Apparatus, method and system of washing induction cookware using induction heating and high-pressure water jet
KR102267254B1 (ko) * 2020-12-30 2021-06-18 김구환 세라믹 소재를 이용한 구이용 타공판 및 이를 포함하는 구이용 가마

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