DE750186C - Process for making coherent films of gold - Google Patents

Description

Process for making continuous films of gold Die The invention relates to the production of interrelated films of pure gold and achieved; that in a simple, effective way such gold felts can be applied to any Can attach surface.

With the known methods it is necessary in two stages Use of strong oxidizing agents to work, being particularly disadvantageous is that no visible precipitate is obtained in the first stage of the process and that the second process stage only after a period of several days has elapsed It is also possible not to gild oil on metal surfaces.

According to the invention, contiguous gold @ lms are any Surface hanging gold films on any surface produced in that the surfaces to be treated are brought into contact with a solution. the contains a monovalent alcohol which can be oxidized directly, furthermore an alkali hydroxide or alcoholate and an organic gold compound of the formula R2Au X or R "AuX where R is a monovalent hydrocarbon radical that substitutes may be, and R 'is a divalent hydrocarbon radical. that too may be substituted, while X is a halogen atom or an organic gold compound means. dlie from one of these organic gold compounds by action derived from a silver salt; and the components of the solution in such a proportion come to use that at least 1 mole of Alkalihvdrox @ d or -alkoholät per atom Gold is contained in the organic gold compound.

The knowledge that solutions are more organic is used here Gold compounds of the formula R2AuX or R "'AuX when in contact with these surfaces decompose. With these organic gold vurbine runner eyes represents R a monovalent hydrocarbon radical that could be substituted while W 'denotes a divalent hydrocarbon radical which is also substituted can be. X represents a halogen atom or compounds selected from the above The body is drained when silver salts contain inorganic or organic acids act on it. Examples of such organic gold compounds are described in the Tournal of the Chemical Society 1907, Vol-.9r, page 2o61, 193o page 253I, I93I Page a407, I934 page 86o, I935 pages 2z9 and I024, I936 Spage 324, I937 page I69o, and itn Journal of the Adleriran Chemical Society I93z, Vol. 53, pp. 27oI and 3o53.

According to the invention is a solution containing an organic gold compound according to the above, a monohydric alcohol, which directly can be oxidized (this is a primary or secondary monohydric alcohol), and containing an alkali hydroxide or alcoholate, brought into contact with the surface; to be plated with gold. Instead of the organic gold compound can a direct derivative of it can also be taken from which the connection is made simple reaction as described in the publications cited obtained can be.

The alkali hydroxide can be used in aqueous or alcoholic solution or are only formed under the reaction conditions, e.g. B. by an alkali phenolate, which forms alkali hydroxide in the presence of water. The alkali hydroxide or alcoholate is preferably used in a ratio of at least z moles for each atom of gold in the organic gold compound applied. Albeit satisfactory fmnit alkali hydroxide can be achieved, it is in some cases more advantageous to use alkali alcoholate.

Monohydric alcohols particularly useful for practicing the invention are suitable, the primary alcohols, particularly ethyl alcohol, are examples of others suitable monohydric alcohols are methanol, tn-propanol, isopropanol, n-butanol, Benzyl alcohol. Other monohydric alcohols, aliphatic or cyclic, which also are amenable to immediate oxidation can of course also be used but the above-mentioned alcohols cannot be used as commercial products seem most appropriate. The alcohol can also be mixed with one another.

The monohydric alcohol or a mixture used to remove it of several can be diluted with vain or several indifferent fluids will, which solve the connection, z. B. with acetone, tertiary butyl alcohol, benzene: so much water can also be present that the gold compound has not yet precipitated takes place. When choosing a diluent, however, the influence is on the reaction is decisive. Namely, it has been found that the precipitation of gold by Addition of certain compounds to the reaction mixture can be reduced, in particular by glycol and glycerol.

The following are some examples of gold compounds which have been prepared and which have been found useful in the practice of the invention. z. Compounds of the empirical formula R2AuX Dietilononochlorogold [(C2H5) 2AuC1] 2, Diäithylmonohromogold [(C2H5) 2AuBr] 2, Diethyl monoiodogold [(C2H5) 2 AuI] 2 and their homologues, Dicyclohexylmonoclhlorogolcl [(C6H11) 2AuCl] 2, Dicyclolhexylmonobromogold ((C6HII) 2Au Br] 2, Dicyclolhexylmonoiodogold [(C6Htl) 2Au-I] 2, - Dibenzylmonochlorogold (C7H7) 2AuCl] 2, D) il) enzylnonol) romogold [C7H7) 2AuBr] 2, d) benzylmoltoiodogold ((C7H7) 2AuI] 2, Diphenylethyl) monol) ronmogol [i (C6 H5. C H2 C I2)) Att ßr] 2. a) Examples of connections. those from the above, dutrclh effect of the silver salt of an organic acid Diläthyillmonocyatl) gold [(C2II5) 3AuCN] 4t iund (his holmologists, Dillenzyl monoeyano gold [(C7 II7) 2Aut CN] 4, Dicyclohexyl monocyano gold [(C6II11) 2AuCN] 4. 1)) Examples of 'compounds which are derived from those mentioned under @r, by rin- The effect of the silver salt of an inorganic seed is made Tetraethylene sulfate sulfate gold (C2H5) 2Au ₧ SO4 ₧ Au (C2H5) 2, Tetra (plhenly1iit1) monosulphlatodigold (C6II5. C2 II4). Au.tt S O4. Autt (C2 II4. C6 II5) .2. 2. Compounds of the empirical formula R "AuX Bis (cyglopentamethylenmnoobromogold) (C5H10AuBr) 2,, Bis (cyclodecamethylene monobromo gold) (C10H20Aubr) 2. The following list shows examples that can be derived through simple reactions similar body, namely of connections, can. from which the required for the invention monoaminodiethylmnonolbromogold (C2 H5) 2 Au Br N H3, Monopyridinodiethylmonobromogold (C3H7) 2AuBrN C5H5, Monoethylenediaminodiethylgoldblromid [(C2H5) 2Auenu] Br, Monoethylene diamino di-n-propyl gold bromide ((C3H7) = Auen] Br, Monoethylenediaminodi-i-propylgoldbromid [(C3H7) 2Auen] Br, Monoethylenediaminodi-butylgoldbromid [(C4, H9) 2 atoms] Br, Monoäthylendiamninodibenzylgoldlbromid [(C7 H7) 2 Auen] Br, Monoithylenediaminotetra-n-propyldibromodigold (C.3H2) BrAtu.en.Br (C3H7) 2 ,, Monoethylenediaminotetraethyldicyanodigold (C2H5) 2 (CN) Au.en. (CN) (C2H5) 2, Monoethylene diamino tetra-n-propyl cyanodigold (C3H7) 2 (CN) Au .en. (CN) (C3H7) 2, Mionoäthylendiaminodiethylgoldaurocy-anide [(C2H5) 2Au.en] Au (CN) 2, Monoethylenediaminodi-n-propylgoldaurocyanide [(C3H7) 2Au.en] Au (CN) 2, where en, = Ethylenediamine NH2. C2 H4. NH2, Monoethyldibromogold (C2H5) 2Br.Au.AuBr3, Mono-n-propyldibromogold (C3H7) 2ßrAu.Aussr3, Monobenzyldibromogold (C7H7) 2Br Au.AuBr3, Monocyclohexyldibromogold (C6HII) 2BrAu.tBr3. The compounds used according to the invention can be prepared from the above-mentioned substances containing ammonpyridines or ethylenediamines by treatment with sufficient hydrogen chloride or hydrogen bromide or sulfuric acid to react with the basic component of the molecular shell or to neutralize it. Of the other substances, the compounds used according to the invention can be prepared either by treatment with as much hydrochloric or hydrobromic acid or alkali chloride or alkali bromide as is necessary for connection with the gold tribromide component of the molecule.

According to the invention, gold can be deposited on any surface be e.g. B. on glass, which can be concave, convex, spherical or flat, on ice glass, on silicates, on textiles, natural silk, viscose silk, acetate silk, cotton, Wool, paper, mica, on glazes, porcelain, chinaware, earthenware, on synthetic resins, z. B. formaldehyde resins, on wood, e.g. B. oak wood, on metals, e.g. B. copper, Nickel, aluminum, zinc, magnesium, on alloys, such as. B. steel, brass, Bronze, magnalium, on waxy materials such as B. solid paraffin.

The amount of precipitation depends on the different surfaces and not always the same under the given conditions. On surfaces of solid Paraffin is the amount of precipitation z. B: much less than on the others mentioned areas. This property of paraffin wax can be used to advantage be to the wider extent a gold deposit on places of the surface to restrict -which are in contact with the solution according to the invention by other areas are covered with paraffin. So can be used to attach a gold film on objects or substances that only.

can be treated by hanging m a solution, the used The inner surface of the vessel is coated with paraffin, the heavier being Gold precipitation occurs on the object to be treated. That on the paraffin Deposited gold can be recovered either mechanically or chemically will. The thickness of the gold film deposited according to the invention can be through Change in the amount of gold in the solution can be influenced.

Based on a gold compound that gives 0.1932 g of gold, an area of zöoo dm can only be formed with a gold film of o.t ic thickness. From this analysis it can be calculated what amount of any gold compound is needed to make a certain area with the desired thickness of the gold film to cover.

The method according to the invention becomes moderate with ordinary Temperature carried out, although larger amounts of precipitation will be obtained, though at increased Temperature is being worked on. It must meanwhile Care must be taken that work is carried out at temperatures at which the gold compounds do not decompose on their own. The amount of gold precipitate can also be influenced in its extent by regulating the concentration of the gold compound more dilute solutions take longer than more concentrated ones.

The following examples illustrate various embodiments the invention. The parts are given in parts by weight. Example I around a gold film Hitting the inner surface of a glass container becomes a solution of o.335 Parts of diethyl monobromo gold prepared in 40 parts of ethanol. Become this solution 0.08 parts of sodium hydroxide are added, which are dissolved in 2 parts of water. The mixture is expediently shaken well and the resulting solution is placed in a glass vessel, whose inner surface has been cleaned beforehand. The solution is left at the more ordinary one Temperature in the vessel until the gold appears as a film on the surface of the vessel that was in contact with the solution. The deposit begins in 5 to 10 minutes and is finished in about 25 to 30 minutes. After education the remaining solution is removed and the film with increasing amounts of ethanol washed or with water, ethanol and finally with ether. Then you let him dry.

Examples A flat surface of a round, flat piece of glass becomes Gilded in the following way: Then the glass plate on the side that gilded is to be cleaned, it is placed in a flat, round bowl that has something is larger than the glass plate, embedded in paraffin, so that only the cleaned one Side of the plate is exposed. The inner sides of the shell are useful as well Covered with paraffin to prevent the precipitation of gold from all other, not desired Prevent bodies.

A solution of 0.15 parts of diethyl monobronogold in 32 parts of ethanol, the sodium sodium ether dissolved in 1.1 parts of ethanol was added to the (), o73I parts is poured into the bowl on the exposed surface of the glass piece. The bowl is advantageously covered. Then it becomes about 3o with its contents Minutes wet to and fro, Wegt. During this time, the gold will be in the Mainly deposited on the exposed surface of the glass plate. The remaining solution is then poured all over and the inside of the bowl with the The glass piece was washed three times with ethanol and then dried. After that, that will Piece of glass detached from the wax.

For covering a round, flat piece of glass about 17 cm in diameter are 0.18 g of diethyl monobromo gold to achieve a film of about 0.2μ thickness needed. Example 13 There are 2 parts of diethyl monobromo gold in 160 parts of ethanol dissolved and with a solution of 0.812 parts of sodium ethylate in Io, 6 parts of ethanol mixed. The resulting solution is poured into a glass flask with a clean inner surface and the piston rotated moderately so that the entire inner surface of the piston during the Gold precipitation comes into contact with the solution. The film will begin to be discontinued in about 7 minutes and after about 40 minutes it covers the entire inner surface of the Piston terminated; then the solution is removed and the inside of the flask in the Washed out manner described above. 'Example 4 The precipitation of gold on Textile is described by the following description of the treatment of a piece Silk fabric explained.

A solution of o, II parts of diethyl monobromo gold in 32 parts of ethanol is well mixed with a solution of o, o447 parts of sodium ethylate in 1.5 parts Ethanol added. This solution is placed in a container that will hold the piece of silk is adapted, wherein the inner surface of the container has been coated with paraffin. The piece of silk remains covered by the solution and is hung so that it Side wall of the container not touched. It stays in the solution for about 2 hours, either at rest or weakly agitated. The container is advantageous with a loose Cover covered. The gold is mainly deposited on the silk, which is then washed with Ethanol and then dried. Example15 Off 0.I parts diethvlmonolbrotogold, which are dissolved in 16 parts ethanol, and o.on4o (61 file sodium methylate. which are dissolved in 1.2 parts of ethanol, as in the Describing the previous examples, a solution was created. This solution will filled into a synthetic resin vessel. the z.13 from one of the rin sich hukannteil 1 # orn lal <lchvdproduhte ordered. I: iii Part of the floor area is with paraffin off-mind. The covered vessel remains .1; \ iiiititrii leave greed to rest. While (reads-i-time the gold beats itself in one contiguous Film on the container, ethanol dissolved. The solution becomes with the answer when it comes to the solution cool on contact to ordinary temperature cloudy. is come down. on Your wax will be o.184 parts of Na gold only to a small extent Lower trium ethylate was added, which was beaten in 0.8 parts, where it passed through easily weak ethanol are contained, whereupon the solution rubbing can be removed again can. becomes clear after mixing. The solution is then in a clean Glass example 6 poured into a container and at normal temperature. A piece of freshly planed, dried out temperature left. Gradually, thick wood begins with a surface a gold film is deposited on what is un-4o.5 square centimeters, which forms the basis of a small one Cell; progresses for about 3 hours.

the side walls of which are made of glass, which is covered with paraffin on the inside is. For example, 1 g, 0.04 parts of diethyl monobromo gold are used in a similar one Result, as in Example 9 8 parts of ethanol dissolved and this solution described, is obtained if, among other things, 0.162 parts of sodium ethylate in 0.4 parts Conditions instead of sodium contain ethanol are added. The ethylate In ethanol, sodium hydroxide in a water solution mixture is poured over the wooden surface The solution was poured in equivalent amounts and left in it for about 45 minutes will. 'serene. The solution is then poured off Example 9 b 'and that Wood in the previously described way, 2 parts of the compound according to Example 9 washed. It has been dissolved in 2.6 parts of gasoline and this is more coherent Film on the wood. Solution 0.088 parts of sodium ethylate, which forms in. Example7 2.9 parts of ethanol are included, added.

The mixed solution is turned into a clean piece of aluminum with a bent Upper glass vessel is done and at an ordinary temperature surface is done immediately before use temperature left in it. Slowly it sets in by rubbing it gently with pure Tree gold film settled down during 4 hours that hold and very much diluted further developed.

Sodium hydroxide solution would be dipped, cleaned - and then washed. For example, 0.05 part of diethyl monobromogold becomes 0.5 part of tetraethylnonosulphatodigold dissolved in 8o parts of ethanol and this solution is dissolved in B parts of ethanol and 0.023 part of sodium ethylate was added to this, and 0.224 part of sodium ethylate in solution added, o, 6 parts of ethanol are included. This contained in 0.8 parts of ethanol are. The mixed solution is made into a suitable mixture in a clean glass vessel ge container, whose inner surface is tan, on the sides of which, in 2o to 3o is covered with a layer of paraffin. The aluminum groove where the solution with the Glass in miniumstückl is hung in it and long-touch is a gold film forms.

sam rotated in the solution for about 1 hour, then it is taken out and in the manner described above with ethanol ge o, I part Diethyl monobromo gold is in I6 wash. The surface of the aluminum is parts n-butyl alcohol dissolved and with o, o4o6 now with a coherent gold part Sodium ethylate mixed, which is covered in 2 parts. len ethanol in a glass jar included B3example S are. The solution becomes dark, and the 0.05 part of diethyl monobromo gold, those in places where the surface is dissolved with the Lö-20 parts of ethanol and is in contact with o; 0203 Teisang begins in about len sodium ethylate, the 0.4 parts of ethanol 13 minutes a film to precipitate. contains, are mixed, are in a clean, round bowl for a few hours cast in smooth steel. The long gone.

Loosely covered bowl with its contents is moved in Example IIa for about 30 minutes, the 0.1 part of diethyl monobromo gold is poured into solution and the bowl is dissolved in the 16 parts of n-butyl alcohol and washed in the manner described. It has solution in a glass vessel, o, o573 parts of a gold film on the surface, which, with. Trutt-n-butylate, which has come into contact in 2 parts of n-butylallic solution, are contained in gel. It takes in the educate. "Compared with your previous example, Example 9 longer until the film begins to separate, 0.35 parts of Di-n-1> i-opylinonocvanogold but after about 50.5 minutes it is still chewed under heat at f 50 ° C in: 8, o parts - to determine a difference. Example 12, o, I part of diethylmonol) romogold is dissolved in 2o parts of benzyl alcohol in a safer glass container and the solution is mixed with 0.04 parts of sodium ethylate, which is contained in 2 parts of ethyl alcohol The mixture turns dark almost immediately, and within 2 minutes a gold film begins to form on the glass where the solution is in contact. EXAMPLE 13 0.25 parts of diethyl monobromo gold are dissolved in 40 parts of i-propanol, which is dissolved in To this solution are added 0.06 parts of sodium hydroxide, which are contained in 3 parts of water. When the solution is mixed, it immediately becomes dark, and it begins on the surface that is in contact with the solution before a gold mirror is formed, which is complete within 1 hour. EXAMPLE 14 0.1 part of diethyl monobromo gold is dissolved in 16 parts of ethanol, and 0.07 parts of sodium phenate, which are contained in a mixture of 2 g parts of ethanol with 0.7 parts of water, are added to this solution. The solution mixture is placed in a clean glass container in which a gold film slowly begins to develop on the glass where the solution is in contact with it. The formation lasts for several hours. -The gold films produced according to the invention are beautifully luminous, yellow) in reflected light and show the usual color of gold films in transmitted light.

Claims (7)

PATENT CLAIMS: I. Method for making a coherent Gold film on any oil surface, characterized in that the to be treated Surfaces are brought into contact with a solution containing a monohydric alcohol contains, which can be oxidized immediately, also an allalil hydroxide or alcoholate and an organic gold compound of the formula R2AuX- or IR "AuX, where R is a represents monovalent hydrocarbon radical which may be substituted and R "is a divalent hydrocarbon radical, which can also be substituted, while X is a halogen atom or an organic gold compound. from one of these organic gold compounds derived from the action of a silver salt and the components of the solution are used in such proportions that that at least 1 mole of alkali metal hydroxide or alcoholate per atom of gold in the organic Gold compound is included. 2. The method according to claim I, characterized in that that the alcohol used is a pure alcohol. 3. Procedure according to claim 2, characterized in that methanol, ethanol, n-propanol, n-butanol or benzyl alcohol is used. Method according to one of the preceding Claims, characterized in that the solution is an indifferent diluent Contains liquid that is miscible with the alcohol used. 5. Procedure according to one of the preceding claims, characterized in that diethyl monob) romogold is used as a gold compound. 6. The method according to any one of the preceding claims, characterized in that any surface is exposed to the solution and that the places where a gold deposit is not wanted, with a Fabric, such as Paraffin, on which the gold deposits more slowly than on the surfaces that are to be gilded. 7. The method according to claim 6, characterized in that the gold deposited approximately on the cover material is then removed mechanically and / or chemically. To delimit the subject of the announcement The prior art is shown in the following publication in the division procedure been: Austrian patent specification,. \ Tr. 17 3R5.