Oxide coating method
13 claims: 6 independent, 7 dependent
- 1Patentkrav 1. Sätt att bilda en metalloxidbeläggning på ett substrat, som åtminstone delvis är glasaktigt, där en lösning omfattande åtminstone en metallförening i ett aprot lösningsmedel med en dielektricitetskonstant större än 15 och ett dipolärt moment större än 3D anbringas på substratet och föreningen eller föreningarna omvandlas in situ genom inverkan av värme, så att en beläggning bildas omfattande åtminstone en metalloxid, kännetecknat av att lösningen, som användes för att bilda beläggningen, består av en lösning av ett eller flera metallsalter, utvald ur gruppen acetater, halogenider och nitrater.
- 2Sätt enligt krav 1, kännetecknat av att substratet förvärmes till en temperatur tillräckligt hög, som räcker att leverera den erforderliga värme, som krävs för omvandlingen av metallföreningen eller -föreningarna.
- 3Sätt enligt krav 2, kännetecknat av att substratet förvärmes så att ytan som skall beläggas når en temperatur mellan 300 och 700°C.
- 4Sätt enligt något av de föregående kraven, kännetecknat av att lösningen anbringas i form av små droppar.
- 5Sätt enligt något av de föregående kraven, kännetecknat av att lösningen som anbringas på substratet omfattar en eller flera acetater, halogenider eller nitrater av en metall eller ett flertal metaller utvalda ur gruppen Mg, Zr, V, Cr, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, In, Sn, Pb, Bi, Th,.Si.
- 6Sätt enligt något av de föregående kraven, kännetecknat av att lösningen, som anbringas på substratet, innehåller en eller flera acetat, halogenider eller nitrater av en metall eller av ett flertal metaller utvalda ur gruppen angiven i kravet 7 i blandning med en eller flera acetat, halogenider eller nitrater av en metall eller ett flertal metaller utvalda ur gruppen Au, Ti, Ce, Mo, Sb, Al, As, Rh.
- 7’ Sätt enligt något av de föregående kraven, kännetecknat av att lösningen även innehåller acetylaceton. 7316705-8
- 8Sätt enligt krav 7, kännetecknat av att lösningen innehåller acetylaceton i en proportion så att mängden acetylaceton, som användes, är av storleksordningen n gånger antalet moler av använt metallsalt (där n representerar valensen eller summan av valenserna på metallkatjonerna).
- 9Sätt enligt krav 1, kännetecknat av att lösningen anbringas så att en metalloxid bildas, genomsläpplig för ljus.
- 10Sätt enligt något av de föregående kraven, känneteck n a t av att substratet utgöres av plant glas som befinner sig i tillverkning som ett kontinuerligt band.
- 11Sätt enligt krav 10, kännetecknat av att lösningen anbringas på glasbandet på ett ställe, där temperaturen på bandet ligger mellan 450 och 650°C. 17. Sätt enligt något av de föregående kraven, känneteck n a t av att lösningen, som användes, bildas helt eller delvis av en eller flera tennklorider (hydratiserad eller vattenfri).
- 1213. Sätt enligt krav 12, kännetecknat av att oxidbeläggningen, som bildas, uppvisar antistatiska egenskaper.
- 1314. Sätt enligt krav 13, kännetecknat av att lösningen anbringas så att en beläggning bildas med en tjocklek av storleksordningen 200-800 A. 7816705-8
Independent claims13
349 paragraphs in 5 sections, as filed
(54) Title: Methods of forming a metal oxide coating on a substrate (56) Published publications: SE 7208789-3, SE 297 066 (CO3C 17/22)
7316705-8
The invention relates to a method of forming an oxide coating of at least one metal on a substrate, wherein a solution comprising at least one metal compound is applied to the substrate and the compound (s) is converted in situ by the action of heat, so that a coating is formed comprising at least one metal oxide. The invention also relates to substrates on which a coating is applied by such a method.
It is well known to produce oxide coatings,
e.g. those of cobalt oxide, by spraying an aqueous solution of a hydrated metal salt, e.g. an aqueous solution of CoC 2 -GI 2 O or FeCl 2 .Gf 2 O, on the surface of a substrate which is heated to a temperature sufficiently high to cause conversion of the metal salt in situ. When this process is carried out, the coating is usually of poor quality, especially as regards the degree of uniformity of thickness and the composition of such coating. E.g. when such an aqueous solution of a cobalt salt is applied, the result is equal to a grainy deposit of irregular thickness and usually the coating has very poor adhesion to the substrate. Coatings formed in this way are easily removed in the form of dust, simply by passing a finger over the coating or by applying a piece of adhesive tape to the coating and then peeling away the tape.
One of the objects of the invention is a method whereby metallic oxide coatings of uniform and uniform thickness and composition can be readily prepared on various substrates. In particular, the invention relates to a method in which metal oxide coatings with a high degree of uniformity and uniformity can be formed on the surface of at least partially glassy substrates, such that the method can be used to form optical films on glass active bodies or articles, e.g. glazing discs, windscreens, patterned glass and lenses for sunglasses.
Another object of the invention is a method by which metal oxide coatings can be produced which exhibit antistatic or electrically conductive properties.
According to the present invention, there is provided a method of forming a metal oxide coating on a substrate which is at least partially glassy, wherein a solution comprising at least one metal compound in an aprotic solvent having a dielectric constant greater than 15 and a dipolar moment greater than 3D is applied to the substrate and the compound or the compounds are converted in situ by the action of heat, so that a coating is formed comprising at least one metal oxide, which is characterized by the solution, used to form the coating consists of a solution of one or more metal salts selected from the group of acetates, halides and nitrates.
7316705-8
Generating the method according to the invention, it is possible to produce metal oxide coatings, the thickness and thickness of which are substantially uniform and uniform as this is essential, for example, in very thin coatings, which permeate large quantities. light and in the case of coatings which are required to exhibit certain electrical properties, for example, determined electrical resistance.
Therefore, the method is suitable for forming optical films on glassy bodies or objects to modify their light transmittance and / or their light reflection, for example, to give the bodies or objects a toned appearance when viewed in continuous or reflected light. The method is also very important for forming antistatic or conductive films on substrates of non-conductive material.
The uniformity and uniformity of the coating possible by the invention depends not only on the choice of salt, but also on the choice of solvent.
Metal salt solutions used in the practice of the invention can be obtained at very low cost and enable metal oxide coatings to be produced very economically advantageously on an industrial scale. Furthermore, the metal salt solutions can be relatively concentrated and this is advantageous, especially as the solution needs to be applied to a substrate which moves quite rapidly with respect to a coating station. Another important factor is the safety with which such solvents can be used under very high temperature conditions. Therefore, it is possible to heat and vaporize the solvent very quickly and to achieve a rapid conversion of the metal compound (s) and this is also an important factor in the formation of coatings of uniform and uniform density.
7316705-8
The method can be used to obtain a wide range of properties relating to the coating applied, by appropriate choice of metal salts. The applied solution may contain a single metal salt or a mixture of two or more metal salts. Thus, there is a rich variety of possibilities in the way of making coatings which have certain optical or electrical properties. For example, it is possible to prepare coatings composed of cobalt, iron and chromium oxides using a solution comprising cobalt acetate, iron (III) chloride and chromium nitrate.
Preferably, the substrate is preheated to a temperature sufficiently high to provide the heat required to induce the conversion of one of the metal compound (s).
Preheating the substrate results in evaporation of the solvent and conversion of the metal compound (s) immediately, that is, as soon as the solution contacts the substrate. j
As already suggested, rapid transformation promotes uniformity and uniformity of the coating.
In order to achieve the objects which are primarily intended, the optimum temperature of the substrate is generally when the laying process is carried out in the range of 300 ° C - 700 ° C. Tempe-! the ridge is generally preferably chosen so that it is as high as possible and compatible with the avoidance of any risk of damage to the substrate. When coating glassy substrates, a temperature in the range of 450 ° C - 6pO ° C is recommended. With a temperature between these limits, very uniform and uniform coatings are obtained together with very good adhesion of the coating.
7316705-8 to the vitreous substrates, where such adhesion is also affected by the temperature of the substrate at the moment coating solvent, is applied.
The metal saline solution is preferably applied in the form of small droplets. The desired results are most easily obtained by applying the solution in such form. For example, a spray gun with internal mixture can be used and supplied with compressed air and brine separately both at the same pressure above atmospheric pressure. The salt solution itself can be of ambient temperature or of a higher temperature provided there is no undesirable premature vaporization of the solvent and no decomposition and oxidation of the metal compound or compounds and provided that the substrate is not exposed to harmful thermal shock.
As already stated, the results obtainable by the method of the invention are partly due to the choice of an aprotic solvent having a dielectric constant greater than 15 and a non-polar moment greater than> D. Examples of aprotic solvents having such properties are the following: dimethylformamide, dimethylacetamide, tetramethylurea, dimethylsulfoxide, acetonitrile, nitrobenzene, ethylene carbonate, tetramethylene sulfone, hexamethylphosphoramide.
Particular preference is given to dimethylformamide. This solvent is particularly suitable for most of the metal salts in question, so that these compounds can be applied at relatively high concentration, which means that the rate of application of the solution in a given zone of the surface of a substrate can be relatively low to produce a coating. of given thickness. Dimethylformamide can also be used to apply coatings
7316705-8 on substrate Mid very high temperatures without any risk of fire or explosion.
Priority is given to embodiments of the invention in which the solution applied to the substrate comprises one or more acetate, halides or nitrates of a metal or metal.<sup>t</sup>· Selected from the following group: lig, Zr, V, Or, W, Kn, Fe, Co, i; i, Cu, Zn, Cd, In, Sn, Pb, Bi, Th, Si.
It is advantageous to use, in admixture with one or more of the said salts, one or more acetates;
In genids or nitrates of a metal or metals selected from | group: Au, Ti, Ge, Mo, Sb, Al, As, Rh. !
It should be noted that the coating formed on the substrate is not necessarily exclusively formed of a metal; oxide or of metal oxides, but may also contain an element; for example gold in metallic condition. Generally, all of the above salts can be used in admixture with the selected solvent or solvents without any special precautions; with the exception of those well known to those skilled in the art | in technology and. intended to avoid undesirable redox or hydrolysis reactions in the solution.
When such solutions are used, it is possible to form thin very high quality metal oxide coatings which modify the light reflection and light transmittance of the substrate and metal oxides which adhere perfectly to ceramic substrates and the like. <sup>: </sup>glass and especially vitreous, for example glass crystalline or glass ceramic substrates, which are the materials which primarily require an opaque coating. It is also possible to form thin metal oxide coatings with controlled electrical resistance, which meet given specifications. In the latter case, the coatings are preferred 7
7316705-8 on non-conductive substrates such as glass, ceramic and glass crystalline or glass ceramic materials.
Advantageously, acetylacetone is also present in the saline nerve attached. The presence of acetyl acetone is generally particularly favorable when applying a solution of one or more halides or nitrates. The acetyl acetate permits optimum], filing ability of the solution and allows for better pyrolysis of: the metal compounds.
For example, it is possible to obtain coatings of improved optical quality by adding acetylacetone to solutions including vanadium chloride, chromium nitrate, iron or nickel nitrate or indium nitrate.
In some cases, the presence of acetylacetone ensures better safety in the preparation of the film-forming solution. For example, if one is to prepare a solution of anhydrous SnGl 2 in dimethylformamide, it is preferred to first mix the tin (IV) chloride with acetylacetone and pour the resulting liquid into the selected solvent to prevent the latter from igniting.
It has been found that when using acetylacetone it is preferable to use such proportions that the amount of acetylacetone used is of the order of n times the number of moles of metal salt used (where n represents the valence or suction of the valences for the metal cation (ions).
As already indicated, the invention has been found to be particularly important for forming metal oxide coatings on glassy or partially glass actuated substrates such as substrates of glass silica or glass ceramic material. This is due to the fact that the method permits bilbin combinations of inch metal oxide coatings which are high grade.
7316705-8 uniform and uniform in thickness as well as density, which are properties which are particularly desirable for optical, antistapis, or conductive films, which serve to modify the biscuits. and / or the dielectric properties of bodies or objects to which the coatings are applied.
Glassy or partially glassy bodies or objects of any kind can be coated by the method of giving them a predetermined tint and particularly special light reflection properties or to give them desired antistatic or conductive properties. It is very advantageous to form coatings on glassy transparent bodies and objects, such as windshields or glazing panels, as this allows metallozide coatings to be formed, which give the object or body different gradients seen in both through and reflected light. The method has not only been found to be suitable for forming a metal oxide coating directly on a glass or on a surface of partially vitreous material, but also for forming such metal oxide coatings on an already formed coating film which adheres to the glassy substrate, particularly on an already present metal oxide coating, such as, for example, a film of titanium oxide or copper oxide.
The metal oxide coating thickness selected in any given case depends on the function that the coating should perform and may vary, for example, within a range of a few hundred to a few thousand Angstroms. A coating of a given thickness can, if necessary or desirable, be formed by two or more consecutive layers. A coating thickness is best measured by interferometry, although it is also possible to dissolve the coating, analytically determine the weight of the coating per unit area and calculate the thickness, taking into account the known density of the oxide
7316705-8 and its degree of seal packing as a bottom film.
The method can be carried out particularly economically by automation of a flat glass coating film by spraying the solution on a continuous glass and during its manufacture, for example at a coating station located in the drawing chamber of a glass drawing machine or in a cooling oven. The solution is preferably applied where the glass is at temperatures in the range JOO ° G - 7GO ° G<sub>?</sub> preferably between 450 ° C - 6 ° C as indicated above. It is advantageous to direct the shower solution with coating solution perpendicular to the glass strip and to allow the device to reciprocate across the strip's direction of movement past the coating station. Advantageously, the method can also be carried out by spraying the solution on patterned glass during its preparation in the form of a continuous strip. Such a glass moves at a relatively higher rate is flat glass, but this presents no difficulty, since the prepared solution may be sufficiently concentrated to produce the coating within the time limits dictated by the manner of forming the glass.
When a mixture of two or more salts is used, the proportions of the different salts can be adjusted to regulate the coating's properties, for example, to regulate the coating's tint in continuous and / or reflected light, or to control its electrical resistance.
It is often desirable to use the metal acebates, halides or nitrates in the perfectly crystalline form. For example, one or more hydration acebate may be used as divalent cobalt acetate which crystallizes with 4 molecules of water or anhydrous acetate such as zinc acetate unless a disturbing separation involves waste of coating material.
7316705-8
In order to obtain films with selected gradients viewed in continuous and reflected light, it is possible to use mixtures of a plurality of acetates, halides or nitrates dissolved in one or more aprotic solvents having a dielectric constant greater than 15 and a dipolar moment greater than JD. For example, the coating can use mixtures of salts of cobalt, iron and chromium to obtain coatings which have a bronze tint when viewed in continuous light and which, moreover, have good resistance to external conditions even in the presence of an acid.
An advantageous application of the method is the coating of an infrared obstructing glass with a highly reflective coating without substantially increasing the energy absorption.
The light and energy transmittance for a given thickness coating can be increased without significantly modifying light or energy reflection using suitably selected metal I compounds, such as, for example, one or more acetates, nitrates or halides of one or more metals of the group: aluminum, | in
zinc, thorium, cerium, tin and magnesium. in
Generally, the presence of water in a relatively high amount in the film-forming solution is acceptable, but preferably does not exceed 10% by volume. If the amount of water is in excess, the resulting coating will have a lot of smudges in dark spots, which are often referred to as pitting. However, he should note that the extent to which such defects are visible, if axis, is in practice partly due to a number of other factors and in particular the composition and the geometry of the coated surface and the thickness of the coating. The defects are less noticeable on the stained glass, whose motifs are very much present
7316705-fc primed, on reinforced glass (glass in which wire reinforcement is included, on profiled glass, for example in the form of a U and on some glass scrib / L-illLiV. Material than on flat glass with flat surfaces.
Even when the coating is applied to flat glass, such defects tend to be less prominent as the thickness of the coating is greater. On the other hand, the thicker the coating, the more the light transmittance of the coating is reduced and in cases where this factor is important, the thickness of the coating constitutes a compromise between the absence of defects and the high light transmittance.
By way of example, it can be stated that a cobalt oxide coating applied to a flat glass surface having a thickness of 500 Å has a light transmittance of 4-7% and if not the most favorable conditions described herein are observed to produce a coating free of defects. such defects are likely to occur and be observable to the unarmed eye. If t the same solution is applied to form an oxide coating with an optical thickness of 900 Å, imperfections are difficult to see, if not completely invisible, but the light transmission is only 26%.
The hardness of the prepared coatings according to the invention is usually high using the preferred compositions. Most of the glazes thus coated can be used as simple glazes, where the coated surface is exposed to ambient conditions, since such coatings are sufficiently resistant to mechanical damage under normal conditions of use. However, if required, a protective coating such as, for example, a coating of SnOg, ZrOg or TiOp may be applied to the layer of the invention, for example, on a colored coating.
To test the hardness and adhesion of the pray
By means of a method according to the invention, it is possible to use a reciprocating friction element having a surface area of 1 cm and formed of rubber in which corundum -r articles having a diameter of 75 - 125 microns are included. The friction element is inserted into a loaded tube (weight of the aggregate 100 g) which slides vertically into a support. Thus, constant contact is ensured between the friction element and the sample. The friction element is reciprocated by a crank system. The amplitude of the movement is 3 cm and its frequency is a forward and a reverse stroke per second. After some time, the resulting wear pattern consists of scratches, which are very close to each other with undisturbed coating between them. '
In various tests performed on glass coated with oxide coatings such as Zr0<sub>2</sub>, Sn0<sub>2</sub>, Sn0<sub>2</sub> and St><sub>2</sub>0j, Ti0<sub>2</sub>, Oc ^ O ^, 0r<sub>2</sub>0p ϊ<sub>£</sub>0Th0<sub>2</sub>, 0e0<sub>2</sub>, Si0<sub>2</sub> or a mixture of these oxides, it was found that after 5 min. 5% of the surface subjected to friction was scratched. At least 1 hour was required for 95% of the surface to be scratched. IN
According to certain embodiments of the method, a layer of tin oxide is formed on a substrate. Such a coating is particularly advantageous because tin oxide gives the coating very considerable hardness. ''
It is possible, for example, to deposit on a glass substrate · coatings consisting essentially of iron oxide containing a small amount of tin oxide, ie 90% Ke<sub>2</sub>And 10% Sn0<sub>2</sub>, sor: are colored and can be used for a simple glazing, which is not the case with a colored coating consisting solely of iron oxide. A coating of this kind is readily prepared by spraying on glass a solution of iron (III) chloride, to which is added acetylacetone and anhydrous SnClg in dimethylformamide.
The presence of tin oxide in a coating, which. also contains one or more colored oxides making it possible to b regulate and weaken the tone seen in transmitted and reflected light.
The presence of the tin oxide is also very advantageous when making coatings having antistatic or electrically conductive properties.
To form such coatings, solutions which preferably contain one or more tin chlorides are used, such as. may or may not be anhydrous, i.e. SnCl 2, SnCH 2 .SH 2 O, SnCl 2.
To form coatings that exhibit the desired electrical resistance, the thickness and composition of the coating are controlled. For example, to prepare an antistatic coating on a glassy substrate, it is preferred to use a tin oxide coating having a thickness between 200 and 300 Å.
To obtain a resistance equivalent to an anti-static. or a conductive coating, it is possible to use coatings containing small amounts of antimony in addition to tinozide. In order to obtain a conductive coating, it is preferred to a. use a saline solution containing a tin (II) salt as the main ingredient to form the coating.
The invention will be better understood and its advantages will be nitrated by the following non-limiting examples and examples. attached figure, to which Example 8 below joins, showing the results obtained with a particular embodiment of the invention. The curve of the figure Ί denotes light
7316705-8 through the patching of an oxide film. extensive SnOg and. Sogo. in different proportions while curve 2 represents the electrical resistance of the same film relative to the amount of antimony salt present in the film-forming solution.
Example 1
A film-forming solution was prepared by apu in dissolving 199 g of divalent cobalt acetate which crystallized with 4 L molecules of water and 73 g of anhydrous zinc acetate per liter of solvent. The solvent selected was dimethylformamide
The solution thus prepared; · lane-I contained 65% by weight CoO and 55% by weight ZnO. IN
This solution, whose temperature was maintained at 70 ° C,;
was sprayed onto a glass band during its continuous preparation by a drawing process in which the glass band goes up through a cooling surface, the spraying taking place at a place where the glass is disturbed; j had a temperature of 590 ° C.
A spray gun with. internal mixture was used, which I fed with the solution and compressed air both at a pressure of 5.5 l<sub>:</sub>'/ b in addition to atmospheric pressure.
t
The distance between the spray gun nozzle and the glass was 25 cm. The gun was continuously moved back and forth across the belt's direction of movement, where the belt's movement! curing rate was 1.5<sup>m</sup> P<sup>your</sup> ininut. The reciprocating movement of the gun had a stroke back and forth that took 6 seconds (glass band width: 5m).
Pistols, delivered 12.7 liters of solution per hour,
2 which corresponded to a solution flow of 47 cm per m glass band. The solution was sprayed to obtain a film with a thickness of 650 Å.
7316705-8
After the cooling of the glass, an optical film son was obtained which had a green tint in the through light and was highly reflective. The properties of the product obtained were as follows:
<td>Light transmittance</td><td>70, n</td>
<td>Light reflection on the coating side Light reflection on the glass side</td><td>1C</td>
<td>An orgasmic transferability</td><td> 69,7%</td>
<td>Energy reflection on the coating side</td><td> 1>,7%</td>
<td>Energy reflection on the glass side</td><td> 1 >, //</td>
<td>Energy absorption on the coating side</td><td>16, b / Z</td>
<td>Energy absorption on the glass side</td><td>1 island, h / u</td>
The film had uniform and uniform thickness and was free from pitting.
A similar result was obtained by replacing the dimethylformamide with another solvent such as dimethylacetamide, tetramethylurea, dimethylsulfoxide, acetonitrile, nitrobenzene, ethylene carbonate, tetramethylsulfone or hexamethylphosphoramide.
Example 2 g of chromium nitrate CrCl 2
dimethylformamide. 58.5 ml of acetylacetone was then added. The mixture was heated for 10-20 minutes at a temperature of 10 ° C. The heating was then discontinued and during the cooling of the solution, 52 µg of iron (III) chloride FeCl 2
1, 69 g of divalent cobalt acetate CoCCH 2 COO then the resulting solution was added. The hydrogen superoxide served to convert the divalent cobalt into trivalent cobalt. The solution was stirred under
7316705-8 cooling for about 15 minutes. Dimethylformamide was added to a volume of 1 liter solution. The solution obtained had a total oxide concentration of 85.1 g / liter of solution divided as shown by the following weight percent distribution:
64,1%
18.4% egg<sub>2</sub>O<sub>5</sub>
17.5% Cr<sub>2</sub>0<sub>5</sub>
This solution was then sprayed onto a glass band 4 mm thick manufactured in the same manner as in Example 1. Glassh's temperature during the spraying was 600 ° C.
The equipment used was the same as in Example 1.
The gun delivered 15.8 liters of solution per hour.
The deposited coating had a uniform and uniform thickness of 800 Å and had a bronze tone when viewed in continuous light.
The oxide composition in the coating was in parts by weight,
12% Pe<sub>2</sub>0<sub>5</sub>
18% Cr<sub>9</sub>0<sub>7</sub>
5 in
70% Co<sub>5</sub>0<sub>4</sub> IN
The light transmittance was 47.1%. The energy permeability was 51 »3%.
As the thickness of the coating was increased to 1200 Å, a more yellowish tint was obtained when considering the coating in continuous light.
In the latter case, the light transmittance was 56.7% and the energy transmittance was 42.6%.
The resulting coating had sufficient hardness;
7316705-8 to be used in single glazing and also had excellent resistance to external conditions, including acids.
The same operation was repeated on printed glass while it was at a temperature of 640 ° G during manufacture. A coating of oxides having a thickness of 540 Å was deposited on this glass using identical spraying equipment as described above. The solution output was 16.1 liters per hour and. the velocity of movement of the glass was 5.15 m / nin. (bandwidth 2 ra).
Example 5
113.5 g of zirconium chloride ZrCl 3 was dissolved in 0.8 liters of dimethylformamide. The solution was then given a volume of 1 liter, c-1, to obtain a concentration = 60 g ZrC 2 per liter of solution. This solution had a yellowish tint and. was something milky.
This solution was then sprayed onto a glass plate at a temperature of 600 ° G. The resulting coating had gray tint and a number of small bright spots.
The same sample was repeated but with the addition of acetylacetone to the starting solution, the proportion of acetylacetone being 4 moles on one mole of ZrGl 2. The amount of acetylacetone added was 195 cm 2. After heating to 50 ° G for about 15 minutes, the solution became completely clear.
When this solution was sprayed onto the glass plate, the resulting film was completely uniform and uniform and gray when viewed in continuous and reflected light.
The properties of the product obtained were as follows:
Light transmittance 75,3) 5
Energy permeability 7%
7316705-8
Coating side light reflection 22.8%
Coating side energy reflection 18.2%
The. the resulting coating was very hard.
Example 4
A number of film-forming solutions were prepared by dissolving the metal salt corresponding to the desired oxide in a suitable solvent. The solutions shown in the table below were sprayed onto a glass plate of 4 mm thickness which was heated to a temperature of 600 ° C. The properties of the product obtained are shown in the table.
7316705-8
Initial salt Solvents The properties of the film The film's properties in the composition of the thickness of the product
<img file="SE435170B_D0001.tif" />
• A o
<td colspan="2">M</td>
<td>ra fl</td><td>Φ</td>
<td>fl Ή</td><td>al</td>
<td>* Γφ fl</td><td>al</td>
<td>h ra</td><td>• rl</td>
<td>CD</td><td></td>
<td>Φ H</td><td>"IAP</td>
<td><5 ώ «</td><td>-Φ</td>
fl flKOOA'Cl '' · 'φ: o -ua -P • cö cp O- »cö Φ Μ η ua -ρ ρ, ra g Φ φ d O fl P il fl H fl fl> Φ Md M Φ fl AH fl ΜΆ ΜΗ 'Ό Φ • H Pi fl fl • Η Η Ρι Ο -PP <: d fl -P
Φ P | H d h> <sub>m</sub>
-P ___ Φ fl> nJ Φ Mfl j> Η q (C • d tri —.....
-p cö η g fl A -P ra ο cd 'fl' ο aa φ
M: d cö fl • P Φ
H -P fl Φ H cd fl Ή · η> fl Pi -P Ö I *, · • A
O o Cx
<td></td><td>XO ox C UA</td><td>XO ox o ir \</td>
<td></td><td>KA O</td><td>uA</td>
<td>O</td><td>OH</td><td>O</td>
<td>M</td><td>Ή</td><td>rj</td>
<td> 3</td><td>A</td><td></td>
O
<img file="SE435170B_D0002.tif" />
d • ra H
<img file="SE435170B_D0003.tif" />
<img file="SE435170B_D0004.tif" />
<img file="SE435170B_D0005.tif" />
rn
<img file="SE435170B_D0006.tif" />
t
KAO-Οχ cn Ο - Ρ φ • Ρ Α Φ Α · Η ΜΗ • Η Ρι Η Ρι ρ, πί PtH - ma ο fl φ Μ • Η: tö H ra ao φ .. mm ra fl d ®
<img file="SE435170B_D0007.tif" />
<img file="SE435170B_D0008.tif" />
<img file="SE435170B_D0009.tif" />
OJ zx ooo
<img file="SE435170B_D0010.tif" />
nJ O · <£.) £. · 0-0
-O ΟΚΟ P Φ PA Φ hD Λ · Η ΜΗ φ nJ fl Φ • d
M ao. fl ra h Pi Φ d H Pi Μ · π> p <: d HP | H • H: d “Ρ H
Md ra fl fl a • Η Φ O fl − P fl Ο Φ −Ρ Φ MHW • d <n fl Φ ’ra fl Al ra ao α <υ & o
Φ X Ό ΚΑ Οοδ. Φ Ο-ν • Φ -ΟΜθaKO-p Ο Φ α-ρ α φ Φ Μ ΜΑ Η ΜΗ • Η · Η Ρι Η Ρι
Ρ ΡιΑ • Η: ttf fl ο “Pi fl PiH · ~ ί ra a ο fl φ
Μ fl A oo ua
<img file="SE435170B_D0011.tif" />
<img file="SE435170B_D0012.tif" />
• rl fl O • P
<img file="SE435170B_D0013.tif" />
<img file="SE435170B_D0014.tif" />
O
Φ
M • H dp ra • da φ. UNLOAD Ο fl - 'aj-i η A fl ο K ο pppp> ra fl
Φ. - -P d η <Ά A — t Φ HM o AA cd -ρ nJ · h '' ~: d fl Φ dg Pi.
Ο H g: o * $ Φ cR.
OH
M fl • rl fl W cd
ΟΚΑ ko
UA i £ -P <£
-P '<& -A Φ OJ CO IM A -OJ Η V Mt> - H ·· Η V fl Pi fl fl Η O p | O ra ..
fl H „. . -, -, τφ hO Φ ft fl «Hied · Η tn o β _ Φ -rl MM ra fl d φ fl
ή ..
• * d
OO UA
<img file="SE435170B_D0015.tif" />
<img file="SE435170B_D0016.tif" />
<td>g</td><td>al</td>
<td>P</td><td>Φ P</td>
<td></td><td>• rl</td>
<td>zx</td><td>hrs</td>
<td>O</td><td>II</td>
<td>td «Η</td><td>hrs</td>
<td>X</td><td></td>
<td>KA (- *</td><td>M</td>
<td>δ</td><td></td>
<td>UA</td><td></td>
<td> + <sup>:</sup></td><td>O</td>
<td>XZ</td><td>CAJ</td>
<td></td><td>w</td>
<td>OH</td><td>COW</td>
<td>zx</td><td> •</td>
<td>O</td><td>CXJ</td>
<td>O</td><td></td>
<td>Ό</td><td>IRS</td>
<td>KA</td><td>O</td>
<td>M</td><td></td>
<td>O</td><td></td>
<td>O</td><td></td>
<td>s</td><td>g</td>
fl EH fl nJ PiO-PH-P
Co H: o fl: d -H pi ra. A d ä åi · ό ri> 'ra il ö δ h: d fl φ g φ ra fl <fl S &. --- A φ d fl A <i φ l> -P fl fl -P: o '' d H
- -. fl: d -rl Pi CQ and raHracHidH-pflgra · · '-14 oo. ι φ α φ M · «d Α nJ
H Η Α Φ Φ fl H d M fl
O UA ω
M fl fl Φ Η Η H g nJ cd Mfl MMM O 'rara W fl fl fl fl gH fl fl φ Φ Φ Φ o: O'ra'rad and fl MranAAMNA
<img file="SE435170B_D0017.tif" />
<img file="SE435170B_D0018.tif" />
<-x zx o O
.. dd
<td></td><td> 3 +</td><td>o <1 +</td>
<td>Τ '</td><td> 4-</td><td>d-</td>
<td>r4 -</td><td>rH</td><td>hrs</td>
<td>O</td><td>O</td><td>O</td>
<td>al</td><td></td><td>• rl</td>
<td></td><td>E4</td><td>E4</td>
<img file="SE435170B_D0019.tif" />
7316705-8
<img file="SE435170B_D0020.tif" />
-Ρ γΗ CÖ ω w b0 «cti h0
Ρ ί =)
<td>03 .i • Γ3 1 <-i 404-1 ς> χ</td><td>m ? · Π> 1</td><td>XI</td><td></td><td>ώ P • ro</td><td></td>
<td>Ö CO <0</td><td>H A-</td><td>ο</td><td></td><td>rH</td><td>. V</td>
<td>O fl —-</td><td>ivv * -</td><td>ο</td><td>r. ·> -</td><td colspan="2">ϊίϊ. -.</td>
<td>fl Φ LAfl-</td><td>Φ A- LA</td><td></td><td>CM CM</td><td colspan="2">Φ 00 OX</td>
<td>Φ + □ -LA</td><td>nJ - LO</td><td>φ</td><td>►Α-</td><td>nJ</td><td>-ω</td>
<td>h C + CM</td><td>qvo</td><td>Ό</td><td>τ ~</td><td colspan="2">fl V</td>
<td>ΦιΑ-Ρ</td><td>Φ LA APE.</td><td>q</td><td>CS-P</td><td colspan="2">Φ A - P</td>
<td>• r4 H 0)</td><td>• Cd. A ® _</td><td>φ</td><td>φ</td><td>efif</td><td>φ</td>
<td>CH P Xi</td><td>60-ΡΪ & -Χ1Ϊ &</td><td>• d</td><td>• ΡΧΙ</td><td colspan="2">60-P xl</td>
<td>to Φ Φ 40</td><td>S Φ lA-d- hOCM</td><td> 60</td><td>Φ 60</td><td>A</td><td>Φ 60</td>
<td>fl fl Xl -H</td><td>O xj -v · Η CM</td><td>A</td><td>χ! · Η</td><td>O</td><td>Xl Ή</td>
<td>• rl tOH</td><td>q 60 CA H</td><td>ο</td><td>60Η</td><td>al</td><td>60H</td>
<td>fl · Η · Η Pi</td><td>φ · η cm q p <q</td><td>q</td><td>Μ.Η ft</td><td>Φ</td><td>• H Pi</td>
<td>Ο Η ρ.</td><td>60 HO Pi O</td><td>φ</td><td>PH Ρ,</td><td colspan="2">ι bOH Pj</td>
<td>• Ρ Η Wd</td><td>Pi q · η: d · η</td><td colspan="2">οΟ'γό Cbicö</td><td></td><td>Pitd</td>
<td>. Ρ "9<sup>, γ4</sup></td><td>Η Ρ, Ο -Ρ Η -P</td><td></td><td>Η PiH</td><td>•HRS</td><td>PIH</td>
<td>Η 60: αί οι</td><td>: d · γ | p, 03 ΛΙ</td><td>• Η</td><td>: d «</td><td></td><td>: d ra</td>
<td>Ρ Η 0</td><td>60H -P fla Φ</td><td></td><td>• ph s</td><td colspan="2">mh a</td>
<td>60 -σι Ο</td><td>q 03 rM Ο O rH</td><td colspan="2">60 d to ο</td><td>A</td><td>03 O</td>
<td>ra ra ä fl</td><td>• ha φ ra q <h</td><td colspan="2">aaaq</td><td>•HRS</td><td>et al</td>
<td>öbo®</td><td>q ο η χ> φ φ</td><td>• Η</td><td>Φ O Φ</td><td>al</td><td>Ο Φ</td>
<td><D -ro q 60</td><td>ο q <M tö 60 fl</td><td>al</td><td>-P fl 60</td><td>O</td><td>fl 60</td>
<td>4 ° Η Φ · γ4</td><td>Χ> Φ Φ · Η · Η · Η</td><td>ο</td><td>S Φ · Η</td><td>-P</td><td>Φ -H</td>
<td>ra 60 60</td><td>60 fl 60 60 60</td><td>-Ρ</td><td>Φ 60 60</td><td></td><td>60 hO</td>
<td>q φ ra fl</td><td>q ra w fl fl A</td><td></td><td>HWA</td><td>al</td><td>ra fl</td>
<td>fl Ό ρ Φ</td><td>pqq φ φ φ</td><td colspan="2">• CD <Η φ</td><td>d</td><td>Ρ φ</td>
<td>: d q-ro qq orlw</td><td></td><td colspan="2"></td><td colspan="2">Λ4 · π> fl ra AW</td>
<td> ~=4</td><td> •=4</td><td>«ή</td><td></td><td> •<4</td><td></td>
<td>O</td><td>Ο</td><td>ο</td><td></td><td>O</td><td></td>
<td>LA</td><td>Ο</td><td>ο</td><td></td><td>O</td><td></td>
<td>LA</td><td>ω</td><td> 4·</td><td></td><td>A</td><td></td>
<td>XO SS ϋ \ ΰχ</td><td>rjX <ϊϊ.</td><td></td><td> <£. </td><td></td><td></td>
<td>ΙΑ LA</td><td>Ο Ο Ο</td><td>LA</td><td>O</td><td>O</td><td>O</td>
<td>A- Al</td><td>L0 V LA</td><td>C0</td><td>V</td><td>OX</td><td>V</td>
<td>LA LA</td><td></td><td colspan="2">κ \ κ></td><td></td><td>LA</td>
<td>OO</td><td>CM</td><td>ο</td><td>O</td><td colspan="2">CM O.</td>
<td>Al CM</td><td>Ο Ο Ο</td><td colspan="2">CM CM</td><td>O</td><td>GJ</td>
<td>Φ fl</td><td>α · η ρ</td><td>Φ</td><td>hrs</td><td>al</td><td>CQ</td>
<td>Pi O</td><td>Ν JZ, Ο</td><td>ο</td><td> <!</td><td>m</td><td> -=4</td>
<td>1 Ό</td><td></td><td></td><td></td><td></td><td></td>
<td>Η · γ4</td><td></td><td></td><td></td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td>+5 d</td><td></td><td></td><td></td><td></td><td></td>
<td>Φ -P</td><td></td><td></td><td></td><td></td><td></td>
<td>S ®</td><td>Ρ |</td><td>βυ</td><td></td><td>jX |</td><td></td>
<td>• Η O</td><td></td><td> *>·*</td><td></td><td>Sr. ·</td><td></td>
<td>Q d</td><td></td><td>R</td><td></td><td>O</td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td>υ - ^ χ</td><td></td><td></td><td></td><td></td>
<td></td><td>d ο</td><td></td><td>O</td><td></td><td></td>
<td></td><td>ο d</td><td></td><td>d</td><td></td><td></td>
<td></td><td><4 ο</td><td></td><td>O</td><td></td><td></td>
<td></td><td> 4- <4</td><td></td><td> <4</td><td></td><td></td>
<td></td><td>χ- ^ 4-</td><td></td><td> +</td><td></td><td></td>
<td></td><td>Χ ^ τ</td><td></td><td>x_ +</td><td></td><td></td>
<td></td><td>Ο Ο</td><td></td><td></td><td></td><td></td>
<td></td><td>CM Ο CM</td><td>/ -χ</td><td>O</td><td></td><td></td>
<td>SS</td><td>Μ CM Ifl</td><td>Ο</td><td>CM</td><td></td><td></td>
<td>O</td><td>ΙΑ Μ</td><td>CÖ</td><td>M</td><td></td><td></td>
<td>Φ</td><td>• Ιθ r-Χ</td><td>ο</td><td>ox</td><td>O</td><td></td>
<td>O</td><td>if · Ο</td><td> *4</td><td> •</td><td colspan="2">CM</td>
<td>"S</td><td>^ χ CM Ο</td><td> +</td><td>K \</td><td>ifl</td><td></td>
<td> +</td><td>ΙΑ ^ χ Ο</td><td>ο</td><td>z S</td><td>LA</td><td></td>
<td>x_></td><td>_> LA ΙΑ</td><td></td><td>m</td><td> •</td><td></td>
<td>LA</td><td>«Ο ifl</td><td colspan="2">ΝΑ Ο</td><td> 4·</td><td>LA</td>
<td>la fl</td><td></td><td>rH</td><td></td><td>hrs</td><td>hrs</td>
<td>Pi pq</td><td>'ΜΜ'</td><td>ο</td><td>NMT</td><td>Ό</td><td>O</td>
<td>Φ fl</td><td>Α · Η Ρ</td><td>φ</td><td>hrs</td><td> al</td><td>m</td>
<td>& i o</td><td>ν ζα ο</td><td>ο</td><td></td><td>m</td><td> -=4</td>
DMSO = dime tylsulph oxy d DKF = dimethylformamide Acac = acetylacetone
7316705-8
Example 5
Tin oxide coatings were prepared for injecting the tin chloride solutions into dimethylformamide.
solutions were prepared by dissolving
SnO2, SnCl2.22 O, SnCl2.2 HgO in dimethylformamide.
A fourth solution was prepared by dissolving Sn01 at the beginning<sub>z</sub>in acetylacetone to give a very viscous red liquid which was then dissolved in dimethylformamide.
These four solutions had identical tin content and were sprayed onto a glass plate at a temperature of 58G ° C. The coatings obtained from the four solutions were optically identical. Their tuning was green in reflected light in all four cases.
Example 6
A film-forming solution was prepared by dissolving 400 g of tin (II) chloride SnClg 2 IL 2 O and a small amount of antimony chloride, ie 7.5 g SbCl
The solution was sprayed at a flow rate of
15.8 liters per hour on the even surface of a printed glass band moving at a rate of 5.5 m / min. just before the cooling furnace in a place where the temperature of the glass was of the order of 680 ° C. The total width of the strap was 1.57 m · The gun was moved back and forth at a distance of 1.27<sup>m</sup>· The number of sweeping periods was 25 per minute.
A coating that exhibited a uniform and uniform purple tone was obtained over a width of 1.10 m. The thickness of the coating was 2700 Å. The electrical resistance of the coating amounted to 60 /ρ / ρ · piece of glass 30 x 30 cm cut from this band and subjected to thermal curing. Silver Fern7316705-8.
electrodes were then applied. When applying a voltage of 220 V, the temperature a few millimeters above the glass was 92 ° G. If a coating of lesser thickness is deposited, ie 200 - 800 Å, the same starting solution gives an antistatic coating, which is no longer electrically conductive.
It was also possible to obtain antistatic coatings by spraying on the glass a film-forming solution containing from 70-90% by weight SnG1 and 50-10% by weight Sn01<sub>2</sub>.
Example 7
Tin (IV) chloride, SnCl ^, was dissolved in acetylacetone and the resulting liquid was dissolved in dimethylformamide and iron (III) chloride J? ECly6H<sub>2</sub>0 was added.
Various solutions containing different proportions of quaternary tin salt and trivalent iron salt were sprayed on a glass that was heated to 55 ° C.
The oxide concentrations were always 60 g / liter and the film thickness was of the order of 500 Å.
The following arrangement gives the properties of the obtained films and of the solutions used:
<td>PERCENTAGE</td><td>in</td><td>snow</td><td> . 0</td><td> 10</td><td> 20</td><td> 50</td><td> 40</td><td> 100</td>
<td>solution</td><td></td><td> ^<sup>e</sup>2°5</td><td> 100</td><td> 90</td><td> 80</td><td> 70</td><td> 60</td><td> 0</td>
<td>PERCENTAGE</td><td>in</td><td>Sn0<sub>2</sub></td><td> 0</td><td> 25</td><td> 41</td><td> 64</td><td> 79</td><td>1C0</td>
<td>film</td><td></td><td>J? E<sub>2</sub>O<sub>5</sub></td><td> 100</td><td> 75</td><td> 59</td><td> 56</td><td> 21</td><td> 0</td>
<td>Light transmittance</td><td> (%)</td><td></td><td> 50.5</td><td> 55,2</td><td> 60,1</td><td> 65,6</td><td> 71,1</td><td> 76,6</td>
<td>toning</td><td></td><td></td><td>Pronounced childish</td><td>Bärnstensgrå</td><td>Amber</td><td>Yellowish gray</td><td>Gray</td><td>Pale gray</td>
stensgul
2.5 7316705-8
Example 8
75.5 g of anhydrous SnClp and 15 g of SbCl were dissolved in 1 liter of dimethylformamide. The solution was sprayed onto a glass slab to form a coating of a thickness of size; 2000 Å.
The coating had a very intense blue tint seen in continuous light. The light transmittance was of the order of 21%.
Light reflection 5% ·
It is possible to vary the intensity of the blue gradient and also the resistance of the coating to the concentration of SbCl 2. This is shown in Fig. 1, where curve 1 represents the light transmittance of the film relative to the amount of SbCl 3 present in the film-forming solution and curve 2 represents the resistance of the film to the amount of SbCl 2 present in the solution.
Curves 1 and 2 were plotted from the following data; the lightness of the film with a thickness of 700 Å (percentage) was deposited on the left ordinate and the electrical resistance in XL./D deposited on a logarithmic scale on the right ordinate. The abscissa represents the number Φ<sup>7</sup>® SbCl<sub>3</sub> added to 1 1. solution containing 75.5 g of anhydrous SnClg »
Example 9
127 g of indium chloride InCl ^ was dissolved in 1 liter of dimethylformamide. 1.58 g of SnCl<sub>2</sub> was added (so as to obtain 2% metallic Sn with respect to the metallic In content).
The solution was sprayed on a glass heated billet 500 ° C to obtain a coating of the order of 1200 Å.
J
7316705-8
A coating of this kind had blue tonirp in reflected light and light yellow in through light.
Light transmission 87.2%
Energy throughput 79.5%
Electrical resistance 70 1Y / O
A coating of this kind can be used as a glazing for heating purposes. It was found that the addition of a small amount of acetylacetone to the film-forming solution (ie, 1/3 mol of acetylacetone to 1 mol of InCl / o and even less. ii
Example 10;
A spray solution was prepared by diluting silica chloride SiG1 to which acetylacetone was added in dimethylformamide.
The solution was sprayed onto a glass slab heated to 500 ° 0 to form a very thin film of SiO2 with a thick layer of the order of 150 Å.ί
An indium oxide coating identical to that indicated in Example 9 was then deposited on the glass coated in this manner.
The optical and electrical properties of the coating were similar to those obtained in Example 9, the quality and uniformity of the coating being particularly high.
Solvents can be classified as prota (or acidic) and aprot (or basic). Solvent solvents are hydrogen sensors. Solvents with a dielectric constant greater than 15, although they may contain hydrogen atoms which are not in the ground
7316705-8 to form strong bonds can also be called dipolar, aprotic solvents (compare PARKER, AJ) The effects of solvation on the properties of anions in dipolar aprotic solvents
Quarterly Reviews, 16, p. 16J (1962).
7316705-8 <16
Contents5
21 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21
31 members in 20 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 66730 | Luxembourg | A | |
| 66730 | Luxembourg | A | |
| 66730 | – | – | – |
| LU19720066730 | – | – | – |
Members31
| Document | Office | Kind | |
|---|---|---|---|
| IL43809A0 | Israel | A0 | |
| IL43809D0 | Israel | D0 | |
| BE808532A | Belgium | A | |
| IE38645L | Ireland | L | |
| NL7317280A | Netherlands (Kingdom of the) | A | |
| DE2363319A1 | Germany | A1 | |
| JPS4990313A | Japan | A | |
| ZA739479B | South Africa | B | |
| AU6368273A | Australia | A | |
| NO133032B | Norway | B | |
| IT996924B | Italy | B | |
| ATA1047273A | Austria | A | |
| NO133032C | Norway | C | |
| ES421729A1 | Spain | A1 | |
| AT332022B | Austria | B | |
| US3984591A | United States of America | A | |
| GB1455148A | United Kingdom | A | |
| IL43809A | Israel | A | |
| FR2327207A1 | France | A1 | |
| CA1014803A | Canada | A | |
| CH592585A5 | Switzerland | A5 | |
| FR2327207B1 | France | B1 | |
| IE38645B1 | Ireland | B1 | |
| FI56365B | Finland | B | |
| FI56365C | Finland | C | |
| JPS586695B2 | Japan | B2 | |
| SE435170BThis record | Sweden | B | |
| DE2363319C2 | Germany | C2 | |
| NL179364C | Netherlands (Kingdom of the) | C | |
| DK155515B | Denmark | B | |
| DK155515C | Denmark | C |
Numbers
- Publication, DOCDB
- 435170
- Publication, EPODOC
- SE435170
- Application
- 7316705
- Application, DOCDB
- 7316705
- Application, EPODOC
- SE19730016705
Titles2
- Swedish
- SETT ATT BILDA EN METALLOXIDBELEGGNING PA ETT SUBSTRAT
- English
- PUT TO PICTURE A METAL OXIDE COATING ON A SUBSTRATE
Classification
- CPC, 6
- C03C17/25
- C03C2217/229
- C03C2217/23
- C03C2218/112
- C09C3/063
- C01P2006/42
- IPC, 3
- C03C17 25
- C04B41 87
- C09C3 06
