Sol-Gel Coating Comprising A Temperature Indicator

Abstract

The present invention relates to a sol-gel coating of the surface of a household article comprising at least two decorations (a) and (b) arranged between or in its layers, (a) being a decoration comprising at least one thermochromic pigment composition in the form of particles consisting of a (Bi1-xAx)(V1-yMy)O4-type pigment and optionally additives, where: —x is equal to 0 or x is from 0.001 to 0.999; —y is equal to 0 or y is from 0.001 to 0.999; —A and M are selected from the group consisting of nitrogen, phosphorus, an alkali metal, an alkaline earth metal, a transition metal, a poor metal, a metalloid or a lanthanide; —A and M are different from each other; (b) being a decoration comprising a temperature-indicating pigment composition.

Claims

1. A sol-gel coating of the surface of a household article comprising at least two decorations (a) and (b) arranged between or in its coats: (a) decoration comprising at least a thermochromic pigment composition in the form of particles consisting of a (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment in which x is equal to 0 or x is between 0.001 and 0.999, y is equal to 0 or y is between 0.001 and 0.999, A and M are chosen in the group consisting of nitrogen, phosphorus, an alkali metal, an alkaline earth metal, a transition metal, a poor metal, a metalloid or a lanthanide, A and M are different from one another, (b) a decoration comprising a temperature reference pigment composition.

2. The coating according to claim 1 wherein each of the two decorations (a) and (b) are present in the form of non-overlapping adjacent patterns.

3. The coating according to claim 1 wherein the two decorations (a) and (b) are partially overlapping.

4. (canceled)

5. The coating according to claim 1, wherein the ΔE* of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 pigment in said coating is greater than or equal to 11 between room temperature and 150° C., ΔE* being defined by the formula CIE1976 in the CIELAB colour space:
ΔE*=√{square root over ((L.sub.2*−L.sub.1*).sup.2+(a.sub.2*−a.sub.1*).sup.2+(b.sub.2*−b.sub.1*).sup.2)} L.sub.1*, a.sub.1* and b.sub.1* values characterising the L*a*b* values of said compound at room temperature L.sub.2*, a.sub.2* and b.sub.2* values characterising the L*a*b* values of said compound at 150° C.

6. The coating according to claim 1, wherein the ΔE* of said (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 pigment in said coating is greater than or equal to 15 between room temperature and 200° C., ΔE* being defined by the formula CIE1976 in the CIELAB colour space:
ΔE*=√{square root over ((L.sub.2*−L.sub.1*).sup.2+(a.sub.2*−a.sub.1*).sup.2+(b.sub.2*−b.sub.1*).sup.2)} L.sub.1*, a.sub.1* and b.sub.1* values characterising the L*a*b* values of said compound at room temperature L.sub.2*, a.sub.2* and b.sub.2* values characterising the L*a*b* values of said compound at 200° C.

7. The coating according to claim 1, wherein the amount of (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 in the decorative coat (a) is comprised from 0.1 to 100% by weight relative to the weight of said coat in the dry state.

8. The coating according to claim 1, wherein said coating comprises one or more finish coats.

9. The coating according to claim 1, wherein the decorations are applied by screen printing or pad printing.

10. The coating according to claim 1, wherein the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 pigment exhibits a monoclinic scheelite crystallographic form at room temperature.

11. The coating according to claim 1, where x and y equal 0.

12. The coating according to claim 1, wherein A and/or M is an alkali metal chosen from Li, Na, K, Rb and Cs, A and M being different from one another; and/or A and/or M is an alkaline earth metal chosen from Be, Mg, Ca, Sr and Ba, A and M being different from one another, and/or A and/or M is a transition metal chosen from Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Ta, W and Jr, A and M being different from one another, and/or A and/or M is a poor metal chosen from Al, Zn, Ga, In and Sn, A and M being different from one another, and/or A and/or M is a metalloid chosen from B, Si, Ge and Sb, A and M being different from one another, and/or A and/or M is a lanthanide chosen from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, A and M being different from one another.

13-17. (canceled)

18. The coating according to claim 1, wherein said coating comprises one or more primer coats applied onto the substrate of the household article.

19. The coating according to claim 18, wherein said coating comprises, in the following order from one of the faces of the substrate of the household article: one primer coat, two decorative coats and a finish coat.

20. The coating according to claim 1, wherein the decorations are directly applied onto the substrate of the household article.

21. The coating according to claim 1, wherein the sol-gel coats are obtained from a sol-gel (SG) composition comprising at least one metal oxide, and at least one precursor of metal alkoxide type.

22. A household article comprising a substrate, completely or partially covered with a coating according to claim 1.

23. The household article according to claim 22, wherein the household article is a cookware and in that the coating completely or partially covers the face of the household article receiving the food.

24-25. (canceled)

26. The household article according to claim 22, wherein the household article is a clothing iron and in that the coating completely or partially covers the soleplate of said clothing iron.

27. The household article according to claim 22, wherein the household article is a hair straightener and in that the coating completely or partially covers the plates of said hair straightener.

28. A method of using a household article according to claim 22, comprising the following steps: Heating said household article or putting it in the presence of an external heating source; Observing the colour change(s) of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment and the temperature reference pigment composition; and Using said household article when: the colours of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 pigment and the temperature reference pigment composition are identical, or the colours of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 pigment and the temperature reference pigment composition, respectively, reach the colours defined in the instructions for use of said household article.

29. The household article according to claim 22, where x and y equal 0.

Description

FIGURES

[0069] FIG. 1: The factors influencing colour

[0070] FIG. 2: Focused sphere representing CIELAB space

[0071] FIG. 3: Diagram illustrating the energy band theory

[0072] FIG. 4: Diagram illustrating the connection between the forbidden band (or gap) and the colour observed

[0073] FIG. 5: General diagram of computer vision method

[0074] FIG. 6: Production of a coating integrating a temperature indicator

[0075] FIG. 7: Diagram illustrating the different types of samples and light booth installation+camera

[0076] FIG. 8: Comparison of pigments in the form of powders

[0077] FIG. 9: diagram of the pattern distribution. 9A=non-overlapping adjacent patterns. 98=partially overlapping patterns. 9C=overlapping patterns.

DETAILED DESCRIPTION OF THE INVENTION

[0078] A first subject-matter of the invention relates to a sol-gel coating of the surface of a household article comprising at least two decorations (a) and (b) arranged between or in its coats: [0079] (a) a decoration comprising at least a thermochromic pigment composition in the form of particles consisting of a (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment, [0080] x is equal to 0 or x is between 0.001 and 0.999, [0081] y is equal to 0 or y is between 0.001 and 0.999, [0082] A and M are chosen in the group consisting of nitrogen, phosphorus, an alkali metal, an alkaline earth metal, a transition metal, a poor metal, a metalloid or a lanthanide, [0083] A and M are different from one another, [0084] (b) a decoration comprising a temperature reference pigment composition.

[0085] Preferably, the amount of (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 in decoration (a) is comprised from 0.1 to 100% by weight relative to the weight of said coat in the dry state, preferably 0.2 to 80% by weight, more preferably 0.5 to 70% by weight.

[0086] Preferably, the amount of temperature reference pigment composition in decoration (b) is comprised from 0.1 to 100% by weight relative to the weight of said coat in the dry state, preferably 0.2 to 80% by weight, more preferably 0.5 to 70% by weight.

[0087] The coating according to the invention is an organo-mineral or entirely mineral sol-gel coating. These coatings synthesised by the sol-gel pathway from precursors of the metal poly alkoxylate type have a hybrid network, generally of silica with grafted alkyl groups. A sol-gel (SG) composition comprises at least one colloidal metal oxide and at least one metal alkoxide type precursor.

[0088] The metal oxide is preferably a colloidal metal oxide chosen from colloidal silica and/or colloidal alumina.

[0089] A metal alkoxide is preferably used as a precursor chosen from the group consisting of: [0090] the precursors corresponding to the general formula M.sub.1(OR.sub.1).sub.n, [0091] the precursors corresponding to the general formula M.sub.2(OR.sub.2).sub.(n-1)R.sub.2′, and [0092] the precursors corresponding to the general formula M.sub.3(OR.sub.3).sub.(n-2)R.sub.3′.sub.2, with:
R.sub.1, R.sub.2, R.sub.3 or R.sub.3′ designating an alkyl group,
R.sub.2′ designating an alkyl or phenyl group,
n being a whole number corresponding to the maximum valence of the metals M.sub.1, M.sub.2 or M.sub.3,
M.sub.1, M.sub.2 or M.sub.3 designating a metal chosen from Si, Zr, Ti, Sn, Al, Ce, V, Nb, Hf, Mg or Ln.

[0093] Advantageously, the metal alkoxide of the sol-gel solution is an alkoxysilane.

[0094] Alkoxysilanes which can be used in the sol-gel solution of the method of the invention can particularly include methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), dimethyldimethoxysilane, and mixtures thereof.

[0095] Preferably, the alkoxysilanes MTES and TEOS will be used, because they have the advantage of not containing methoxy groups. Indeed, methoxy hydrolysis leads to the formation of methanol in the sol-gel formulation, which, given its toxic class, requires additional precautions during application. In contrast, hydrolysis of ethoxy groups only generates ethanol, having a more favourable class and therefore less restrictive using requirements for the sol-gel coating.

[0096] The formation of this sol-gel coating consists of mixing an aqueous composition A comprising the colloidal metal oxide and a solution B comprising the metal alkoxide. The mixture is advantageously done in a ratio of 40 to 75% by weight of the aqueous composition relative to the weight of the sol-gel composition (A+B), so that the quantity of colloidal metal oxide represents 5 to 30% by weight of the sol-gel composition (A+B) in the dry state.

[0097] Aqueous composition A can also comprise a solvent, in particular a solvent comprising at least one alcohol.

[0098] Aqueous composition A can also comprise at least one silicone oil.

[0099] Aqueous composition A can also comprise a pigment.

[0100] Aqueous composition A can also comprise a mineral filler.

[0101] Aqueous composition A can also comprise fumed silica, whose function is to regulate the viscosity of the sol-gel composition and/or the gloss of the dry coating.

[0102] Aqueous composition A typically comprises for a primer coat: [0103] i) 5 to 30% by weight relative to the total weight of aqueous composition A of at least one colloidal metal oxide; [0104] ii) 0 to 20% by weight relative to the weight of composition A of a solvent comprising at least one alcohol; [0105] iii) optionally, 0.05 to 3% by weight relative to the total weight of said aqueous composition A of at least one silicone oil, [0106] iv) 5 to 30% of pigment, [0107] v) 2 to 30% of mineral filler.

[0108] Aqueous composition A typically comprises for a finish coat: [0109] i) 5 to 30% by weight relative to the total weight of aqueous composition A of at least one colloidal metal oxide; [0110] ii) 0 to 20% by weight relative to the weight of composition A of a solvent comprising at least one alcohol; [0111] iii) optionally, 0.05 to 3% by weight relative to the total weight of said aqueous composition A of at least one silicone oil, [0112] iv) 0.1 to 1% of metallic glitter.

[0113] Solution B can also comprise a Bronsted or Lewis acid. Advantageously, the metal alkoxide precursor of solution B is mixed with an organic or mineral Lewis acid which represents from 0.01 to 10% by weight of the total weight of solution B.

[0114] Particular examples of acids usable for mixture with the metal alkoxide precursor are acetic acid, citric acid, ethyl acetoacetate, hydrochloric acid or formic acid.

[0115] Solution B can also comprise a solvent, in particular a solvent comprising at least one alcohol.

[0116] Solution B can also comprise at least one silicone oil.

[0117] Solution B can also comprise metallic glitter.

[0118] According to an advantageous embodiment of the process of the invention, solution B can comprise a mixture of one of the alkoxysilanes such as defined above and an aluminium alcoholate.

[0119] Given that A and M are different from one another, when: [0120] A is an alkali metal, it can be chosen from Li, Na, K, Rb and Cs, [0121] M is an alkali metal, it can be chosen from Li, Na, K, Rb and Cs, [0122] A is an alkaline-earth metal, it can be chosen from Be, Mg, Ca, Sr and Ba, [0123] M is an alkaline-earth metal, it can be chosen from Be, Mg, Ca, Sr and Ba, [0124] A is a transition metal, it can be chosen from Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Ta, W and Ir, [0125] M is a transition metal, it can be chosen from Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Ta, W and Ir, [0126] A is a poor metal, it can be chosen from Al, Zn, Ga, In and Sn, [0127] M is a poor metal, it can be chosen from Al, Zn, Ga, In and Sn, [0128] A is a metalloid, it can be chosen from B, Si, Ge and Sb, [0129] M is a metalloid, it can be chosen from B, Si, Ge and Sb, [0130] A is a lanthanide, it can be chosen from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, [0131] M is a lanthanide, it can be chosen from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

[0132] Preferably, A and M different from one another are B and/or Mg.

[0133] According to one embodiment, each of the decorations (a) and (b) are present in the form of non-overlapping adjacent patterns. For example, each decoration is represented by different geometric patterns uniformly distributed over the entire surface and alternating with one another (see FIG. 9A).

[0134] According to another embodiment, the two decorations (a) and (b) are partially overlapping. For example, each decoration is represented by different geometric patterns uniformly distributed over the entire surface and partially overlapping (see FIG. 9B).

[0135] Preferably, the two decorations (a) and (b) are overlapping, either because one of the two decorations is a continuous coat and the other decoration covers it in the form of patterns, or because the two decorations (a) and (b) are present in the form of overlapping patterns (see FIG. 9C).

[0136] Preferably, the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment exhibits a monoclinic scheelite crystallographic form at room temperature.

[0137] Said decorations optionally comprise additives.

[0138] Said additives are chosen in the group consisting of solvents, thickeners, antifoaming agents, pH adjusters, wetting agents and dispersing agents.

[0139] Said solvents are preferentially chosen in the group consisting of: water, alcohols, diols, glycols and esters.

[0140] Said thickeners are preferentially chosen in the group consisting of acrylic based copolymer or polyurethane based copolymer, cellulose, fumed silica and silicone resin.

[0141] Said anti-foaming agents are preferably chosen in the group consisting of polysiloxane, modified polysiloxane, polyether-siloxane copolymer, amphiphilic polymers, silicone and aliphatic mineral oil.

[0142] Said pH adjusters are preferably chosen in the group consisting of Bronsted bases: ammonia, amines (triethyl amine, triethanolamine, etc.), hydroxides (sodium hydroxide, potash, etc.), and carbonates.

[0143] Said wetting and dispersing agents are preferably chosen in the group consisting of high molecular weight fatty acid derivatives, modified polyether, surfactants and modified polyacrylate.

[0144] Preferably, the coating according to the invention comprises one or more finish coats advantageously applied over the decoration. Preferably, these finish coats are sol-gel coats such as defined above.

[0145] According to a first embodiment, the coating according to the invention comprises one or more primer coats applied onto the substrate. The decorations are then applied onto the last primer coat.

[0146] Preferably, the coating according to the invention comprises, in the following order from one of the faces of the substrate of the cookware: one primer coat, the two decorative coats (a) and (b), and a finish coat.

[0147] According to a second embodiment, the decorations are directly applied onto the substrate. This means that the decorations are in contact with the substrate.

[0148] The decoration can be applied by any method well known to the skilled person, for example, by screen printing or pad printing.

[0149] Preferably, x and y are 0, i.e. the invention relates to the use of bismuth vanadate (BiVO.sub.4). Advantageously, a BiVO.sub.4 pigment of monoclinic scheelite crystallographic form at room temperature is used.

[0150] Bismuth vanadate is an inorganic compound of yellow colour, of formula BiVO.sub.4, widely used for its colour properties and for its absence of toxicity. Recorded in the Colour Index International database as Q. I. Pigment Yellow 184, it is especially sold by the companies Heubach (Vanadur®), BASF (Sicopal®), FERRO (Lysopac) or Bruchsaler Farbenfabrik (Brufasol®).

[0151] This compound has been the subject of many studies due to its intense colour and to its thermochromism. Many synthesis pathways can be considered for producing BiVO.sub.4 nanoparticles, such as sol-gel synthesis, pyrolysis of precursors, hydrothermal and solvothermal syntheses and gas phase deposition. However, hydrothermal synthesis can be complex from the mechanistic viewpoint due to the simultaneous formation of stable and unstable phases in the event of rapid heating in a pressurised autoclave. The abundance of phases and the complexity of the phase diagram of the products obtained by hydrothermal synthesis make it difficult to form and stabilise one or the other of the crystallographic phases.

[0152] The second, more commonly used synthesis pathway is a solid phase sintering method. It has the advantage of easily obtaining large-scale powders with a high degree of crystallinity at a low cost. BiVO.sub.4 particles can thus be obtained by annealing a mixture of bismuth and vanadium salts via a high-temperature sintering process. The microstructure obtained (particle size, morphology, crystallinity) and optional doping elements may affect the band gap of BiVO.sub.4, with as a consequence, a modification of its initial colour and/or thermochromism.

[0153] The temperature reference pigment composition can be chosen in the group consisting of: [0154] Titanium rutile yellow pigments, [0155] Yellow pigments derived from bismuth, for example selected from stabilised bismuth vanadates (Py184), [0156] Red pigments, for example selected from perylene red or iron oxide, [0157] Bismuth oxyhalide orange pigments (PO85), [0158] Bismuth vanadate orange pigments (PO86), [0159] Tin titanium zinc orange pigment (PO82), [0160] Cerium sulfide orange pigment (PO75; PO78), [0161] Chrome antimony titanium yellow-orange rutile pigment (PBr24), [0162] Tin and zinc yellow-orange rutile pigment (Py216), [0163] Zinc tin sulfide niobium oxide yellow-orange pigment (Py227), [0164] Double oxides of tin and niobium yellow-orange pigment, [0165] and mixtures thereof.

[0166] Advantageously, the coating according to the invention is characterised in that the ΔE* of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment in said coating is greater than or equal to 11 between room temperature and 150° C., ΔE* being defined by the formula CIE1976 of the CIELAB colour space:

ΔE*=√{square root over ((L.sub.2*−L.sub.1*).sup.2+(a.sub.2*−a.sub.1*).sup.2+(b.sub.2*−b.sub.1*).sup.2)}

[0167] L.sub.1*, a.sub.1* and b.sub.1* characterising the L*a*b* values of said compound at room temperature

[0168] L.sub.2*, a.sub.2* and b.sub.2* characterising the L*a*b* values of said compound at 150° C.

[0169] Preferably, the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment has a ΔE* in said coating between room temperature and 150° C. greater than or equal to 13, in a particularly preferred way, greater than or equal to 15.

[0170] Advantageously, the coating according to the invention is characterised in that the ΔE* of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment in said coating is greater than or equal to 15 between room temperature and 200° C., ΔE* being defined by the formula CIE1976 of the CIELAB colour space:

ΔE*=√{square root over ((L.sub.2*−L.sub.1*).sup.2+(a.sub.2*−a.sub.1*).sup.2+(b.sub.2*−b.sub.1*).sup.2)}

[0171] L.sub.1*, a.sub.1* and b.sub.1* characterising the L*a*b* values of said compound at room temperature

[0172] L.sub.2*, a.sub.2* and b.sub.2* characterising the L*a*b* values of said compound at 200° C.

[0173] Preferably, the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment has a ΔE* in said coating between room temperature and 200° C. greater than 17, in a particularly preferred way, greater than or equal to 20.

[0174] Advantageously, the evolution of the colour change ΔE* as a function of temperature is linear. Preferably, this linear evolution has a slope comprised from 0.05 to 0.1, preferably greater than or equal to 0.1.

[0175] The colour can be measured and characterised by means of a colour classification. This classification is only possible if the colours are defined by numbers and this conversion can be done by means of colour spaces.

[0176] “A colour space is a three-dimensional mathematical model representing the set of colours perceptible, usable or reproducible by a human or a device.” Numerous spaces exist with their own distribution of colours having precise coordinates (for example: the RGB space, widely used by television systems or the CIELAB space which takes into account the logarithmic response of the eye).

[0177] The CIELAB colour space serves to characterise the colours of different surfaces. This space can be represented according to a geometric model bearing 3 orthogonal axes representing the L*a*b* values (FIG. 2). Each colour thus has clearly specified and unique L*a*b* coordinates: [0178] L* represents the lightness along an axis expressed in percentage, or from black: 0 to white: 100 [0179] a* the axis ranging from green: −120 to red: +120 [0180] b* the axis ranging from blue: −120 to yellow: +120

[0181] These coordinates unique to each colour make it possible to calculate several parameters such as the lightness difference ΔL*, the hue difference ΔH* or the colour difference ΔE*.

[0182] The parameter which interests us in this invention is the colour difference ΔE* representing the measurement of the distance between two different colours located in the CIELAB space. The colour difference ΔE* does not have a unit.

TABLE-US-00001 Symbol CIELAB relation Hue angle h arctan (b*/a*) Hue angle difference Δh h.sub.2 − h.sub.1 Chroma C* {square root over (a*.sup.2 + b*.sup.2)} Chroma difference ΔC* C.sub.2* − C.sub.1* Lightness difference ΔL* L.sub.2* − L.sub.1* Hue difference ΔH* {square root over ((ΔE*).sup.2 − (ΔL*).sup.2 − (ΔC*).sup.2)} Colour difference ΔE* {square root over ((ΔL*).sup.2 + (Δa*).sup.2 + (Δb*).sup.2)} (CIE1976 formula)

Formulas of Deviations and Differences in Hue and Colour

[0183] The thermochromism phenomenon is defined as the ability of a compound to change colour as a function of the temperature to which it is subjected.

[0184] The BiVO.sub.4 compound is yellow at room temperature and changes colour continuously when the temperature increases, passing through orange to red.

[0185] BiVO.sub.4 is part of the family of semiconductor oxides: this category has a colour mechanism also responsible for their thermochromic properties.

[0186] Indeed, semiconductor materials are characterised by an energy band theory representing the interactions of atoms. It is a model in which the core electrons are assumed to be localised on the atom to which they belong and are thus present in discrete atomic orbitals and therefore do not appear on the energy bands of the model. The valence electrons, on the other hand, are able to be delocalised throughout the crystalline network of the solid; they constitute the valence band. The conduction band is the first empty energy band which can be occupied by the free electrons. The valence band and the conduction band are separated by a forbidden band whose width (also called “gap”) is equal to the energy difference present between the energy levels associated with the valence and conduction bands (FIG. 3).

[0187] The colour of semiconductor materials is related to the width of the forbidden band which separates the valence bands and the conduction bands of the material in question. It is the electronic transitions of energy equal to or greater than the width of the forbidden band which are responsible for the colour of the material. The width of a forbidden band ranging from 1.7 eV to 3 eV can create colours ranging from black to white through a colour palette extending to colours ranging from light yellow to red, thus passing through oranges (red corresponding to low energies and light yellow to high energies). (FIG. 4)

[0188] Under the influence of temperature, the interatomic anion-cation bonds expand, causing a decrease in the orbital overlap. This results in a drop of the covalence of the bonds and therefore a reduction of the gap; the transfer of electrons is then facilitated between the valence band and the conduction band between two atoms.

[0189] The semiconductor materials are therefore thermochromic due to the size change of their crystalline structure under the influence of a temperature increase. If the crystalline structure changes, the interactions within the network are not the same; the width of the forbidden band will then vary and, as a consequence, the colour changes.

[0190] The majority of semiconductor materials when they are subjected to a temperature increase, have a reduction of the width of their forbidden band. This explains the colour change of BiVO.sub.4, yellow at room temperature, to red when it is heated.

[0191] Another subject-matter of the invention concerns a household article comprising a substrate, preferably metal, completely or partially covered with a coating according to the invention.

[0192] The colour change of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 pigment allows the user to be notified, on the one hand, that the article is hot and therefore presents a risk of burns and, on the other hand, that the surface of the article has reached the appropriate temperature for its use.

[0193] Advantageously, the article support can be plastic, metal, glass, ceramic or terracotta. Metal supports usable in the context of the present invention advantageously include supports of aluminium or aluminium alloy, anodised or not, or of polished, sandblasted, chemically treated aluminium or aluminium alloy, or polished, brushed or bead-blasted stainless steel, or cast iron or aluminium, or titanium or hammered or polished copper.

[0194] Examples of household articles usable in the context of the present invention can notably include deep fryer bowls, fondue or raclette pans or pots, the bowl of a deep fryer or bread machine, the jar of a blender, the plates of a straightening iron and the iron soleplates.

[0195] For a better adhesion of the coating, the surface of the support can be treated so as to increase its specific surface, for example by sandblasting, brushing or chemical treatment; for aluminium, this treatment can be done by anodization (creation of a tubular alumina structure), by chemical etching, by sandblasting, etc. The other metal substrates can also be polished, sandblasted, brushed or bead-blasted.

[0196] Advantageously, the article according to the invention is a cookware and the coating according to the invention completely or partially covers the substrate on the face receiving the food.

[0197] Advantageously, the article according to the invention is a hair straightener and the coating according to the invention completely or partially covers its plates.

[0198] Advantageously, the article according to the invention is a clothing iron and the coating according to the invention completely or partially covers its soleplate.

[0199] Advantageously, the article is a cookware of which one of the faces of the support is a concave inner face intended to be in contact with the food placed inside said cookware and the other support face of the cookware is a convex outer face intended to be in contact with a heat source.

[0200] Preferably, said household appliance is an article of cookware, preferably chosen in the group consisting of saucepan, frying pan, stew pot, wok, sauté pan, crepe maker, grill, plancha grill, raclette grill, marmite pot or casserole dish, and said coating is intended to come into contact with food.

[0201] In the fields of application considered for the present invention, an article to be heated of the cookware type or a heating article of the iron type is typically used in a range of temperatures comprised from 10° C. to 300° C.

[0202] Another subject-matter of the invention relates to a process for use of a household article according to the invention, characterised by the following steps: [0203] Heating said household article or putting it in the presence of an external heating source, [0204] Observing the colour change(s) of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment and the temperature reference pigment composition, [0205] Using said household article when: [0206] the colours of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 pigment and the temperature reference pigment composition are identical, or [0207] the colours of the (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 pigment and the temperature reference pigment composition, respectively, reach the colours defined in the instructions for use of said household article.

[0208] The coating according to the invention comprises at least two pigments including (Bi.sub.1-xA.sub.x)(V.sub.1-yM.sub.y)O.sub.4 type pigment and the temperature reference pigment composition.

[0209] The optimal conditions of use can be reached when their colours are visually identical to the naked eye for the user at the standard distance for use of the article according to the invention. If we take one example, the coating according to the invention can comprise BiVO.sub.4 which changes from yellow to orange between room temperature and the optimal use temperature, and orange thermostable bismuth oxyhalide.

[0210] The usage instructions may indicate to the user the colours at which he may begin to use the household article according to the invention under optimal conditions. This indication will be present, for example, in the form of geometric patterns filled with ad hoc colours or a gradient colour bar (see, for example, in FIG. 4). This pattern or this bar serves as a comparative reference to the user who can bring it close to the coated surface of the article according to the invention.

[0211] Preferably, in the case of cookware, the optimal conditions are attained when the coating reaches a temperature suitable for cooking food, preferably comprised between 100 and 250° C.

EXAMPLES OF EMBODIMENT

Example 1: Pigment Selection

[0212] The pigments used are inorganic compound powders:

[0213] Thermochromic pigments: [0214] BiVO.sub.4, process described in Example 2, batches 2b and 2d [0215] Bi.sub.2O.sub.3, Varistor Fine grade, sold by the company 5N Plus [0216] Sicopal® Yellow K1120FG pigment, sold by the company BASF [0217] Bayferrox® 130 pigment, sold by the company Bayferrox

[0218] Thermostable pigments (temperature reference pigments): [0219] Yellow 10C242 pigment, sold by the Shepherd Color Company [0220] Yellow 6716B pigment, sold by the company FERRO

[0221] These compounds may be used singly or in mixture.

Example 2: Process for Synthesising a BiVO.SUB.4 .Pigment Compound According to the Invention

[0222] Process 2.1

[0223] To a solution of bismuth nitrate (0.1 M) in 1 M nitric acid is added stoichiometrically a solution of ammonium vanadate (0.1 M) in 1 M nitric acid. The mixture is stirred overnight, filtered, washed with water and then dried. The powder is then annealed at 450° C. for 3 hours.

[0224] The bismuth vanadate is then obtained in the form of a bright yellow powder of monoclinic scheelite structure characterised by X-ray diffraction analysis.

[0225] The process takes place at pH<1 with no addition of alkaline agent.

[0226] Process 2.2

[0227] To a solution of bismuth nitrate (0.4 M) in 1 M nitric acid is added a stoichiometric quantity of sodium metavanadate in the powder form. The mixture is stirred for 2 hours at 80° C. The precipitate is then filtered and washed with water to obtain a yellow BiVO.sub.4 powder in the monoclinic scheelite form. The powder is then annealed at 500° C. for 3 hours.

[0228] The process takes place at pH<1 with no addition of alkaline agent.

[0229] The monoclinic scheelite BiVO.sub.4 thus has a ΔE=40 between room temperature and 200° C.

Example 3: Integration of the Compounds into a Sol-gel Coating

[0230] In order to offer the consumer a cookware with an inner non-stick coating provided with a decoration guiding him during its cooking, compounds with improved thermochromic properties are introduced into a non-stick coating having several coats: [0231] The sol-gel primer coat(s), [0232] The thermochromic compound integrated into a decoration, [0233] The thermostable compound integrated into a second decoration, [0234] The sol-gel finish coat(s).

[0235] i. Preparation of Primer Coats and Finish Coats

Formula for the Primer Coat with Silicone Oil: Cl1

[0236]

TABLE-US-00002 Mass (grams) Aqueous composition A 30% colloidal silica 27.5 Distilled water 7 Isopropanol 3 Silicone oil 1 TiO.sub.2 12 Alumina 14 Acid solution B MTES 35.1 Formic acid 0.4 TOTAL 100

Formula for the Finish Coat with Silicone Oil: F1

[0237]

TABLE-US-00003 Mass (grams) Aqueous composition A 40% colloidal silica 31 Distilled water 8.5 Acetic acid 1.6 Isopropanol 4 Silicone oil 1 Acid solution B MTES 40.5 Butyl glycol 12.9 Pearl glitter 0.5 TOTAL 100

Formula for the Primer Coat without Silicone Oil: Cl2

[0238]

TABLE-US-00004 Mass (grams) Aqueous composition A 30% colloidal silica 27.5 Distilled water 7 Isopropanol 3 TiO.sub.2 13 Alumina 14 Acid solution B MTES 35.1 Formic acid 0.4 TOTAL 100

Formula for the Finish Coat without Silicone Oil: F2

[0239]

TABLE-US-00005 Mass (grams) Aqueous composition A 40% colloidal silica 32 Distilled water 8.5 Acetic acid 1.6 Isopropanol 4 Acid solution B MTES 40.5 Butyl glycol 12.9 Pearl glitter 0.5 TOTAL 100

[0240] ii. Preparation of a Thermochromic Decoration

[0241] A pad printing paste containing a thermochromic pigment such as described in Example 1 is prepared according to the formulation described below.

Thermochromic Decoration Formula: DT1

[0242]

TABLE-US-00006 Mass Composition (grams) Thermochromic 30 pigment Butyl glycol 25.7 Colloidal silica 15.4 Water 4 Acetic acid 0.7 Isopropanol 1.6 MTES 20.6 Byk 410 additive 2 Sum 100

Thermochromic Decoration Formula: DT2

[0243]

TABLE-US-00007 Composition Mass grams Thermochromic 30.0 pigment Additive 4.7 Water 50.0 Propylene glycol 9.5 Acrylic thickener 3.8 ammonia 2.0 Total 100

[0244] iii. Preparation of a Thermostable Reference Decoration

[0245] A pad printing paste containing a thermostable pigment such as described in Example 1 is prepared according to the formulation described below.

Formula of a Reference Decoration: DR1

[0246]

TABLE-US-00008 Composition Mass (grams) Thermostable 26 pigment Butyl glycol 28.2 Cl2 43.8 Byk 410 2 additive total 100

Formula of a Reference Decoration: DR2

[0247]

TABLE-US-00009 Composition Mass (grams) Thermostable 24.0 pigment Additive 4.7 Water 52.0 Propylene glycol 12.5 Acrylic thickener 4.0 ammonia 2.8 Total 100

[0248] iv. Production of a Cookware Integrating the Temperature Indicator

[0249] A preformed aluminium cap is previously degreased and dusted. For a better adhesion of the coating, the support surface is treated by sandblasting so as to increase its specific surface. A primer coat is then coated onto the surface of the cap by spraying. This coat can optionally be dried. A thermochromic decoration resulting from the formula described above is then applied onto the primer coat by pad printing then dried. The reference decoration is applied onto the thermochromic decoration in the pattern form by pad printing. After drying, a finish coat is applied by spray onto the three previous coats. The entire article is then cured at 250° C. for 30 minutes.

Example 4: Method for Characterising Sample Colours

[0250] A light booth consisting of a closed enclosure equipped with controlled lighting is used. A camera is directly installed above the booth and is connected to a photo processing software making it possible to obtain the colour-related characteristics of the samples analysed. The light booth is lit with a D50 illuminant (corresponding to daylight).

[0251] The principle of this characterisation is to position the material to be analysed in the booth, to take a photo of it and to extract colour data from the photo using appropriate software.

[0252] By means of the L*a*b* values obtained, a colour difference (or colour variation) ΔE* is obtained at each temperature relative to the reference temperature (RT=25° C.) for a given sample, ΔE* being defined by the formula CIE1976 of the CIELAB colour space:

ΔE*=√{square root over ((L.sub.2*−L.sub.1*).sup.2+(a.sub.2*−a.sub.1*).sup.2+(b.sub.2*−b.sub.1*).sup.2)}

with: [0253] L.sub.1*, a.sub.1*, b.sub.1*: coordinates of the pigment colour at the standard temperature (25° C. or RT) or of the reference pigment. [0254] L.sub.2*, a.sub.2*, b.sub.2*: coordinates of the pigment colour at a chosen temperature (25° C./100° C./150° C./180° C./200° C./250° C.) or of the chosen pigment.

[0255] The protocols described below have been developed and make it possible to control at best the following elements: no possible heating directly in the booth (so as not to disrupt the atmosphere and the camera) but taking photo at a target temperature, using timing of the transfer phases.

[0256] i. Equipment [0257] Thermometer with contact sensor [0258] Stopwatch [0259] Hotplate [0260] Photo light booth [0261] CANON EOS 13000D camera (Canon 28-mm wide-angle lens) [0262] Glass slides [0263] Data acquisition softwares: Capture One and Photoshop

[0264] ii. Protocol for Samples in the Form of Powder (FIG. 7) [0265] Make 3 separate heaps of different powders in a frying pan (about a teaspoon). [0266] Flatten the powder heaps with a glass plate in order to have smooth, homogenous surfaces with the same thicknesses. [0267] Then, perform the same protocol as previously.

Example 5: Exploitation of Results

[0268] i. Calculations of the ΔE* of a Sample at Several Temperatures

[0269] Take, for the example, the pigment Fe.sub.2O.sub.3 in the powder form.

[0270] The L*a*b* coordinates and ΔE* results for Fe.sub.2O.sub.3 for each temperature appear below:

TABLE-US-00010 Lens T° C. Room temperature = 100° C. 150° C. 25° C. ΔE* ΔE* Coordinates L* a* b* L* a* b* (RT) L* a b* (RT) Fe.sub.2O.sub.3 35.9 34.2 23.1 32.5 30.4 18.8 6.7 29.2 26.4 15.5 12.8 180° C. 200° C. 250° C. ΔE* ΔE* ΔE* Coordinates L* a* b* (RT) L* a* b* (RT) L* a* b* (RT) Fe.sub.2O.sub.3 30.0 25.4 14.6 13.5 30.0 24.2 13.9 14.8 28.7 21.9 12.2 18.0

[0271] Example at 100° C.:

ΔE*.sub.100° C.=√{square root over ((L.sub.100−L.sub.25*).sup.2+(a.sub.100*−a.sub.25*).sup.2+(b.sub.100*−b.sub.25*).sup.2 )}

ΔE*.sub.100° C.=√{square root over ((32.5−35.9).sup.2+(30.4−34.2).sup.2+(18.8−23.1).sup.2)}=6.7104

TABLE-US-00011 ΔE* values calculated for each sample at given temperatures Powders T° C. 25 100 150 180 200 250 BiVO.sub.4 2d ΔE* (RT) 0 14.3 31.4 39.2 43.6 59.5 BiVO.sub.4 2b 0 21.2 37 41.8 45.2 53.4 Bi.sub.2O.sub.3 0 18.3 30 37 42.1 52.2 Sicopal Yellow 0 12.6 19.9 20.9 19.1 23.6 K1120FG Bayferrox 130 0 6.7 12.8 13.5 14.8 18 Yellow 10C242 0 1.7 3.2 3.6 5.3 6.4 Yellow 6716B 0 1.7 3.9 4.3 5.6 6.7 Frying pans with pad printed decoration T° C. 25 100 150 180 200 250 BiVO.sub.4 2d ΔE* (RT) 0 9 17.6 22.8 25.4 34.9 BiVO.sub.4 2b 0 9 15.6 20.8 23.4 32.1 Bayferrox 130 0 6.1 9.4 12 14.1 18.4 Yellow 10C242 0 1.7 2.3 2.8 3.2 4.2

[0272] ii. Graphic Interpretations

[0273] The ΔE* values calculated for each sample at different temperatures make it possible to visualise by means of graphs (ΔE*=f (Temperature ° C.)) the evolution of the colour difference relative to the colour at room temperature.

[0274] The graph (FIG. 8) shows the colour variations of each pigment in the powder form.

[0275] The pigments studied in this case all have a fairly linear colour change as a function of temperature.

[0276] The “very good” thermochromic pigments have a colour difference ΔE* between 25° C. and 200° C. greater than or equal to 40 and a linear change in the colour difference ΔE* as a function of temperature with a slope greater than or equal to 0.2.

[0277] The “good” thermochromic pigments have a colour difference ΔE* between 25° C. and 200° C. comprised from 30 to 40 and a linear change in the colour difference ΔE* as a function of temperature with a slope greater than or equal to 0.2.

[0278] The “average” thermochromic pigments have a colour difference ΔE* between 25° C. and 200° C. comprised from 10 to 30 and a linear change in the colour difference ΔE* as a function of temperature with a slope comprised from 0.05 to 0.2.

[0279] The “thermostable” pigments have a colour difference ΔE* between 25° C. and 200° C. less than or equal to 10 and a linear change in the colour difference ΔE* as a function of temperature with a slope less than or equal to 0.05.