TITLE: PREPARATION OF PEROXY AND PEROXYESTER TUNGSTEN DERIVATIVES TECHNICAL FIELD This invention relates to methods of converting hydrated tungsten oxides, to peroxy and peroxyester tungsten derivatives and to methods of making alcoholic solutions containing these metal derivatives. The invention also relates to methods of producing tungsten oxides from these solutions that are useful as coatings on glass surfaces in displays, solar control windows and light modulators. Further, this invention relates to the peroxy and peroxyester tungsten derivatives, to the coatings and to the devices employing such coatings The peroxy and peroxyester tungsten derivatives are useful and important precursors in the production of nanocrystalline tungsten oxide coatings. They are relatively inexpensive to produce and these colloidal dispersions incorporate only a small percentage of organic material that helps to avoid contamination of the inorganic metal oxide layers with extraneous impurities after firing. High quality tungsten oxide coatings from these derivatives can be formed at relatively low firing temperatures.

BACKGROUND TO THE INVENTION Peroxy and peroxyester tungsten derivatives have been investigated for their use in coating glass surfaces with metal oxides as alternative precursors.

Competitive materials such as metal alkoxides, metal chlorides and colloidal metal oxides all have some disadvantages related to the cost of production, incorporation of organic or inorganic impurities in the final metal oxide layer and, most importantly, solution instability. Solution instability manifests as an increase in viscosity and appearance of insoluble precipitates, rendering the solution unsuitable for application by dip-coating, spraying or spin-coating. A further advantage of peroxy or peroxyester metal derivatives is that stable solutions of concentrations between 0.5 to 1.0 molar are relatively easy to prepare thus allowing a single-dip operation for producing a suitable metal oxide layer.

Early attempts, for instance, to form colloidal tungstic acid obtained by adding hydrochloric acid to an alkaline sodium tungstate solution highlighted the different types of particles such as rectangular and hexagonal plates that can be formed. The colloidal phase, which was contaminated by sodium and chloride ions, was purified by dialysis and eventually the first-formed colloidal tungsten species produced insoluble hydrated tungsten oxide, W03. nH20 (S. N.

Chatterjee, J. Colloid Science, 1950,13,61, A. Chretien, W. Freundlich, Nouveau Traite Chim. Min., 1959,14,860). If acidification is effected by ion exchange in a proton-exchange resin, a transitory colloidal solution of tungstic acid species is formed free of contaminating ions. However, as noted before, the solution is stable for only a few hours before becoming turbid and finally yielding tungsten oxide hydrate (A. Chemseddine, M. Henry and J. Livage, Revue de Chimie Minerale, t. 21,1984,487). Acidification of tungstate anions either in the presence or absence of interfering ions leads to the establishment of complex

equilibria, consecutive and parallel reactions (D. L. Kepert and T. H. Kyle, J.

Chem. Soc., Dalton Trans., 1978,133). More stable colloidai solutions of tungstic acid could be achieved by adding solvent (J. Lemerie and J. Lefebvre, Canadian J. Chem., 55 (1977) 3758).

Amorphous W03 layers obtained from such solutions containing colloidal tungstic acid species were shown to have good electrochromic properties (A.

Chemseddine, R. Morineau, J. Livage, Brevet Francais, 1982, No. 8208934) but adhesion of the W03 layer to glass was considered to be inadequate (M. A.

Aegerter, Sol-Gel Chromogenic Materials and Devices in Structure and Bonding, Vol. 85, p. 149, Springer-Verlag, Berlin, 1996).

Precipitated hydrated tungsten oxide does not exhibit any photochromic or electrochromic properties (A. Chemseddine, R. Morineau and J. Livage, Solid State lonics, 9 and 10 (1983) 357).

An alternative method of forming stable colloidal solutions of tungsten were disclosed in U. S. Patents Nos. 4,634,585 (1987), and 5,035,478 (1991).

Methods of producing polytungstic acid from tungsten carbide and tungsten metal respectively by dissolution in hydrogen peroxide and methods of forming useful W03 coatings from such precursors were described.

Recently, U. S. Patent No. 5,457,218 (1995), discloses a method of producing coating solutions containing colloidal metal derivatives. In this method, transition metals are allowed to react with hydrogen peroxides in the presence of an organic acid. Heating under reflux with ethanol then esterifies the resulting metal peroxyacids and the product is isolated as a powder. The resultant metal derivatives are dissolved in alcohol to give stable colloidal dispersions of the corresponding metal.

During our investigations of the above procedure, we have found that the method affords stable solutions or peroxypolytungstate esters that produce high quality W03 layers for electrochromic applications. However, the procedure is unsuitable for production on a large scale since the reaction is extremely exothermic and it is difficult to maintain the required temperature regimen.

Elaborate controis and expensive cooling equipment would be necessary to control the reaction temperature in the specified range of-10 to 12°C. Also, long reaction times of up to 30 hours are necessary for complete digestion at those temperatures.

Finally, U. S. Patent No. 5,772,978 (1998) discloses a method of making colloidal tungsten derivatives in which a freshly produced polytungstate solution is allowed to react with hydrogen peroxide. The polytungstate solution was derived from an acidified ammonium metatungstate solution that included species having the nominal formula (NH4) 6H2W, 2040nH2O or from acidified sodium tetraoxotungstate (VI) solution.

Although the reaction between the acidified tungstate solution and hydrogen peroxide is facile and immediate, the method suffers from the disadvantage of needing to use an ion-exchange resin to remove the sodium and ammonium cations. This would be a disadvantage in large-scale industrial applications because of the inconvenience and cost of regenerating the ion-exchange resins.

Further, the use of readily available sodium tungstate for the same purpose presents problems since more concentrated solutions of polytungstic acids (e. g. 0.35M) derived from this material tend to become extremely viscous and gel within a short time. (E. Richardson, J. Inorg. Nucl. Chem., 1959,12,79).

Indeed, the above-mentioned authors of U. S. Patent No. have stated that particular care must be taken before and during the peroxide treatment to avoid the formation of intractable gels or coagulated solids and hence more dilute tungstate salt solutions are preferably used.

Unexpectedly, we have found that readily available and inexpensive hydrated tungsten oxides, are easily dissolved in hydrogen peroxide alone or in mixtures with organic acids and alcools to give stable colloidal solutions of peroxymetallic acids or peroxyester metal derivatives. These derivatives are easily dispersed in alcohol solutions that do not become excessively viscous or intractable. Although crystals of potassium oxalatooxodiperoxotungstate, K2 WO (02) 2 (C204)], have been synthesised from K2WO4, oxalic acid and H202 reaction products from tungstic acid solutions in the presence of hydrogen peroxide and lower carbon organic acids have not been isolated or characterised (R. Stomberg and S. Olson, Acta. Chem. Scand., Ser. A, 39 (1985) 79.

In particular, the novelty of dissolving a hydrated tungsten oxide, W03. nH20 and other metal precursors such as MoO3 to give stable colloidal solutions will be described.

OBJECTIVES OF THE INVENTION An object of the present invention is to provide improved methods for the production of peroxy and peroxyester tungsten derivatives, as well as to provide stable compositions of these derivatives in alcoholic solutions.

A further object of the present invention is to provide such solutions, which can be applied to glass surfaces either by dipping, spraying or spin-coating to form thin layers of the tungsten oxide coating after firing. It is also an objective of the invention to provide transparent coherent nanocrystalline layers of tungsten oxides with improved properties for use as electrodes in electrochromic devices.

OUTLINE OF THE INVENTION In one aspect, the invention relates to a process for producing a tungsten oxide precursor solution in which a peroxytungstic acid is converted to a stable peroxyester tungsten derivatives. Unlike prior-art methods, the present invention utilises readily available and relatively inexpensive hydrated metal oxides, to form peroxymetallic acids and peroxyester metal derivatives that afford colloidal solutions in ethanol. The stability of these materials is such that concentrated dispersions in alcohol solutions give good quality coatings on glass substrates after one application by one of three methods such as dipping, spraying or spin- coating. This invention is based upon the finding that relatively insoluble unreactive starting materials such as hydrated tungsten oxides, can be converted to stable colloidal dispersions of the tungsten derivatives in alcool. In particular, we have found that water-insoluble, yellow, hydrated tungsten oxide, W03. H20, or tungstic acid dissolves readily either under reflux or when stirred at temperatures below 20° C with hydrogen peroxide. Often an admixture of hydrogen peroxide and organic acids are used to give intermediates which are easily dispersed in alcool.

Unlike previous attempts to coat glass substrates with tungstic acid derived from acidified sodium tetraoxotungstate (VI) solutions, these modified tungstic acid derivatives are relatively easy to prepare, stable and adhere tenaciously to glass as well as having good electrochromic properties. The structure of these colloidal tungsten derivatives produced by these methods is unknown but they are formed under mild conditions and the starting material, W03. nH20, does not require any pretreatment. The process includes the step of treating hydrated tungsten oxide with hydrogen peroxide to form the peroxypolytungstate solution.

In preferred embodiments, the hydrated tungsten oxide is treated with hydrogen peroxide in the presence of a lower-carbon organic acid or anhydride, to form colourless solutions of peroxyester tungsten derivatives. It was found that the addition of alcohol at this stage interferred with the dissolution of the tungstic acid and hence was omitted. The amount of peroxide preferably ranges from about 10 to 50 mol of hydrogen peroxide per mol of tungsten, more preferably from about 2 to about 10 mol of hydrogen peroxide per mol of tungsten. The amount of organic acid or anhydride, ranges from about 0.5 to 10 mol of acid or anhydride per mol of tungsten, more preferably from about 1 to 5 of acid or anhydride per mol of tungsten.

In another aspect, the invention relates to a process for producing tungsten oxide coatings from the peroxyester tungsten derivatives dissolved in alcool.

An important application of this invention is the production of thin metal oxide films on glass that are used in electrochromic devices.

The invention provides a reliable and reproducible method for producing electrochromic tungsten oxide layers that are stable and can intercalate ions reversibly. It is interesting to note that, whereas the starting material is itself not

electrochromic, the tungsten oxide derived from solutions made from this material displays good electrochromic properties.

It has been found that the molar ratio of the reactants, the sequence of addition of the reactants and the conditions during the drying stage before addition of solvent alcool, all play a part in forming clear, stable and useful solutions for electrochromic purposes.

It was found, in particular, that tungsten precursors in solution can be modified by heating with catalytic amounts of strong acids such as trifluoroacetic, p- toluenesulfonic and triflic acid. Reflux periods of up to 1 hour have been used to produce satisfactory tungsten oxide precursor solutions. The solutions thus treated, give W03 layers, which are relatively thick, having good adhesion to glass and excellent electrochromic properties. Large amounts of water in precursor solutions ultimately hinders the de-intercalation of Li+ ions in the W03 coating and hence full bleaching is not achieved. Preferably, the precursor solutions are substantially free of water and at most contain from 2 to 10%.

A typical procedure for forming a transparent metal oxide coating on glass will be : (i) evaporating under controlled conditions of pressure and temperature the solvent and excess reagents from the peroxy and/or peroxyester metal derivatives to form a solid ; (ii) dissolving or dispersing the solid in a solvent alcohol to form a solution ; (iii) heating the alcoholic solution under reflux with or without the addition of catalytic amounts of strong organic acids to effect a stable, colloidal metal oxide solution.

(iv) applying the precursor solution to the glass as a thin film either by spraying or dip coating ; (v) drying the film releasing excess alcohol to form a solidifie coating (vi) baking the glass and the film to form a transparent metal oxide coating.

The heating is carried out in the range from about 100°C to about 350°C and more preferably from about 150°C to 250°C.

A number of hydrated metal acetates such as cobalt, or nickel, are useful as dopants and can be added to hydrated tungsten oxide or molybdenum oxide at the beginning of the reaction. The invention will now be described by way of the following examples.

DESCRIPTION OF EXAMPLES Example 1 Hydrogen peroxide, H202, (30% w/v, 21cm3,0.185mol) was added to tungstic acid, W03. nH20, (2.50g, 0.010mol) and the suspension heated to reflux. The intense canary yellow colour of W03. nH20 was observed to fade during the ensuing reaction, resulting in a colourless colloidal solution. After a reflux period of 30min, the excess peroxide solution was removed by heating (70°C) under reduced pressure (ca. 10mmHg) to yield a powdery lemon yellow sotid. The addition of dry ethanol (20cm3) initially resulted in the formation of a milky white suspension, however after heating under reflux for 30min, a pale yellow colloidal solution was formed.

Reactions performed using larger or smaller quantities of H202 were also successful, although there was some variance in the turbidity of the resulting solutions.

Example 2 To a colloidal solution formed as in example 1 was added p-toluenesulfonic acid CH3C6H4SO3. H20 (0.04g, 0.2mmol) and the mixture heated under reflux for 1 h.

The resulting solution was darker in colour and more turbid than the original solution. Increased turbidity was also observed on addition of other acids such as actetic trifluoroacetic or triflic acid.

Example 3 To W03. nH20 (2.50g, 0.010mol) was added H202, (30% w/v, 21cm3,0.185mol) and acetic acid, CH3COOH 010mol) and the suspension heated under reflux for 30min. Volatile material was then removed by heating under vacuum to yield a powdery lemon yellow solid. The milky white suspension formed on addition of ethanol (20cm3) was transformed to a pale yellow coloured colloidal solution after heating under reflux for 30min.

Example 4 To W03. nH20 (2.50g, 0.010moi) was added H202, (30% w/v, 21cm3,0.185mol), CH3COOH 010mol) and ethanol (1 Ocm3,0.1 Omol) and the mixture heated under reflux for 30min. The resulting colourless solution was more turbid than those of the previous examples. Increasing the reflux period did little to improve this. Excess reactants were removed by heating under vacuum to yield a lemon-coloured residue. The addition of dry ethanol (20cm3) initially resulted in the formation of a milky white suspension, however after heating under reflux for

30min, a cloudy paie yeilow solution was formed. Reactions performed with varying mol ratios of reactants were also successful, although there was some variance in the turbidity of the resulting solutions.

Example 5 To W03. nH20 (2.50g, 0.010mol) was added H202, (30% w/v, 21cm3,0.184mol) and acetic anhydride, (CH3CO2) 20, (1cm3,0.010mol) and the suspension heated to reflux. Volatile material was then removed by heating under vacuum to yield a iemon-coloured residue. The addition of dry ethanol (20cm3) initially resulted in the formation of a milky white suspension, however after heating under reflux for 30min, a pale yellow colloidal solution was observed.

Example 6 To white molybdenum oxide, Mo03 (1.4g, 0.01 mol) was added 95% ethanol (20cm3), H202 (30% w/v, 10cm3,0.09mol) and acetic acid (3.0g, 0.05mol) and the mixture was heated under reflux for about 1 h to give a strongly yellow coloured solution with traces of undissolved white MoO3. Only partial dissolution was achieved if less acetic acid was used.

Example 7 Nickel acetate tetrahydrate (2.48g, 0.01 mol) was dissolved in H202 (30% w/v, 10g, 0.09mol) and 95% ethanol (20cm3) added. On gentle heating, an evolution of gas took place and a clear light green solution formed. To this solution was added W03nH20 (2.50g, 0.01mol) and heating was continued under reflux for 30min, the volatile material was removed under vacuum to give a pale green solid that dissolves readily in wet alcool.

Example 8 To hydrated tungsten oxide (2.5g, 0.01mol) was added nickel acetate tetrahydrate (0.74g, 0.003moi) and H202 (30% w/v, 21cm3,0.185mol). A reaction took place to give a green transparent solution which was slightly turbid.

Example 9 To W03. H20 (10g, 0.04mol) was added H202 (30% w/v, 120 cm3,1.06moi) and acetic anhydride (1.4g, 0.01mol) and the suspension was stirred at 15°C in a controlled-temperature water bath for about 50 hours. A clear solution with a trace of insoluble white material was filtered through"Celite"to give a clear colourless solution. On evaporation of excess peroxide and water a yellow powder was formed. Heating the yellow powder under reflux with ethanol (100cm3) for about 30 minutes resulted in a clear yellow coloured colloidal alcohol solution. This solution was used for coating glass to form tungsten oxide layers after heating to 250°C. The results show that satisfactory iayers are produced in which the contrast ratio is about 3.0. (The contrast ratio is the ratio of the light transmittance of the W03 layer between its bleached and charged state. The wavelength of radiation employed was 670A and the applied charge was 15mC).