US2097630A - Plating of cadmium - Google Patents

Plating of cadmium Download PDF

Info

Publication number
US2097630A
US2097630A US45426A US4542635A US2097630A US 2097630 A US2097630 A US 2097630A US 45426 A US45426 A US 45426A US 4542635 A US4542635 A US 4542635A US 2097630 A US2097630 A US 2097630A
Authority
US
United States
Prior art keywords
cyanide
cadmium
reaction
product
hydrogenation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US45426A
Other languages
English (en)
Inventor
Lutz George
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US45426A priority Critical patent/US2097630A/en
Priority to FR816536D priority patent/FR816536A/fr
Application granted granted Critical
Publication of US2097630A publication Critical patent/US2097630A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/26—Electroplating: Baths therefor from solutions of cadmium
    • C25D3/28—Electroplating: Baths therefor from solutions of cadmium from cyanide baths

Definitions

  • This invention relates to the eleotrodeposition of cadmium from cyanide-cadmium baths, andis particularly directed to cyanide-cadmium plating compositions, plating baths, and plating processes which employ, as an addition agent, a reduced amketaldoresin whereby a bright, smooth, uniform cadmium deposit is obtained.
  • Baths containing these novel addition agents are characterized by good throwing power and by a wide bright current density range.
  • ketaldones Represented by a circle in the upper left-hand corner of the drawing are the starting materials from which my addition agents are derived. .
  • the starting materials are designated ketaldones but, as will be explained below, certain ketaldones are particularlysuitable for my purpose.
  • Mypreferred starting materials are, generally speaking, aliphatic and carbocyclic ketaldones, that is aldehydes and ketones, but, as will become apparent hereinafter, the best results are obtained by the use of certain aliphatic and carbocyclic aldehydes and ketones.
  • ketaldonyl has been applied to designate the 0 0 group as it appears in aldehydes and ketones in contradistinction to the 0:0 group as it appears in acids.
  • th carbonyl group as it appears in acids
  • ketaldonyl group as used herein is of the type tones, and the expression "ketaldonyl group is wherein R is a hydrocarbon radical and wherein R is hydrogen, in the case of an aldehyde, or R is a hydrocarbon radical, in the case of a ketone. It will also be understood that the ketones and aldehydes themselves are referred to herein as ketaldones in accordance with this terminology.
  • the starting materials which I employ are, broadly, 'ketaldones. While I may use aldoses, ketoses, heterocyclic aldehydes and ketones or any other such ketaldones, I prefer. to use allphatic and carbocyclic ketaidones which do not contain a carboxyl group, which do not contain sulfur, and which do not contain nitrogen.
  • the starting materials moreover, should contain no more than two hydroxyl groups and preferably should contain at least two carbon atoms. More specifically, I prefer to employ ketaldones which contain only carbon, hydrogen, and oxygen, which contain at least two carbon atoms, and in which the hydrogen-oxygen ratio is greater-than that of water.
  • the starting materials, the ketaldones are reacted with ammonia or an amine, in alkaline solution, to produce an amo-reaction product. It will be observed that amo is used to designate both ammonia and-an amine. As will'be noted hereinafter, the amo-reaction products of the ketaldones are very similar in their physical and chemical characteristics. They all contain nitrogen, and all are, apparently, complex mixtures. I have,
  • reaction products amketaldoresins.
  • the nature of the products and the nature of the reaction will be discussed in more detail hereinafter.
  • amketaldoresins are subsequently modified by hydrogenation to yield nitrogen-containing derivatives which are effective as addition agents.
  • These derivatives while more effective, are very similar to the amketaldoresins, ordinarily differing slightly as to color and solubility.
  • a preferred group of ketaldones the aldacets, are illustrated in the upper right-hand corner of the drawing. More will be said hereinafter regarding the members of the illustrated aldacet equilibrium. As is shown in the drawing, the aldacets, like the ketaldones generally, are reacted with ammonia, or cyanide to produce an amketaldoresin. The particular amketaldoresln produced from the aldacets are designated herein, the amaldacets.”
  • amaldacets are hydrogenated, as were the amketaldoresins .generally, to produce nitrogen-containing derivatives.
  • ketaldones which I employ as starting materials are reacted in weak alkaline solution with an amo to produce an amo-reaction product from which addition agents of my invention may be prepared.
  • cyanide is considered substantially equivalent to reacting the ketaldones with amoes in alkaline solution.
  • amketaldoresins are preferably derived from the aliphatic ketaldones termed the aldacets.
  • the derivatives of the aldacets are typical of the amketaldoresins, and their preparation will be described below in some detail as illustrative of the amketaldoresins generally.
  • the aldacets comprise the aliphatic aldehydes: acetaldehyde, aldol, crotonaldehyde, and paraldol.
  • acetaldehyde acetaldehyde
  • aldol aldol
  • crotonaldehyde a crotonaldehyde
  • paraldol aliphatic aldehydes
  • the aldacets appear to exist in equilibrium, any one of the aldacets leading to the production of all at a rate of conversion apparently depending upon the specific aldacet first present.
  • the aldacet equilibrium is illustrated in the upper, right corner of the drawing.
  • the aldol may lose one molecule of water and become crotonaldehyde, thus:
  • Equation 3 is a whole number, probably 2.
  • acetaldehyde is-illustrated as converting to aldol.
  • the aldol may go toparaldol or to crotonaldehyde.
  • the aldol might also go back to acetaldehyde, but only to a small extent.
  • the paraldol may go back to aldol,'or it may lose water and go to crotonaldehyde, though this latter conversion probably takes place to a very small degree.
  • the crotonaldehyde may form from acetaldehyde, aldol, or paraldol, and, by gaining water, may revert to any of them, though it is likely that it would move largely by way of aldol.
  • the aldacets As is seen in the drawing, then, we may consider the aldacets as being in equilibrium. This equilibrium will, according to my belief, be substantially the same regardless of which of the four substances are initially added to the cyanide solution, though, as will hereinafter be noted, the aldacets are not entirely equivalent, and it is possible that some of the aldacets in dilute alkaline solution form this aldacet equilibrium rather slowly or move more rapidly in certain directions than in others.
  • Aldol, acetaldehyde, crotonaldehyde, and paraldol are the only commercially available aldacets at the present time. For practical reasons, therefore, I prefer to use as a starting material an aldehyde selected from the group consisting of acetaldehyde, aldol, crotonaldehyde, and paraldol.
  • the aldacets are those aliphatic ketaldones, such as acetaldehyde, aldol, crotonaldehyde, and paraldol, which exist in some sort of equilibrium when one of the said kctaldones is put into alkaline or alkali metal cyanide solution.
  • the aldacets are aliphatic aldehydes from the group consisting of acetaldehyde and its condensation or equilibrium products in alkaline and alkali metal cyanide solutions.
  • the aldacets are reversible equilibriumcondensation products of acetaldehyde in alkaline solution and particularly in alkaline solutions such as those of the following Examples I and X.
  • aldacets are not entirely equivalent for my purposes but'are substantially so.
  • crotonaldehyde seems to lead to slightly lower yields. This may be attributable to the fact that crotonaldehyde is but slowly converted to the necessary form, or to some other now unknown cause.
  • amketaldoresins produced from the aldacets
  • amaldacets the specific amketaldoresins produced by the reaction of the aldacets with amoes or cyanide in alkaline solutions.
  • amaldacets are almost indistinguishable from one another in physical and chemical properties though, as will be noted hereinafter, they differ slightly from one another as to their efficiency as addition agents for cyanidecadmium plating.
  • reaction is used to express whatever occurs when the ketaldones, or specifically-the aldacets, are treated in alkaline solution with cyanide or with an amo.
  • reaction is used to distinguish from "condensation as used above with reference to the aldacet equilibrium tho, in fact, the reaction probably includes both polymerizations and condensations.
  • amaldacets as well as the amketaldoresins contain nitrogen as determined by the Kjeldahl method.
  • the nitrogen is present in about the ratio of one nitrogen atom to each two molecules of aldol four of acetaldehyde, one of paraldol, etc.). I have been unable to determine how the nitrogen is located in the amaldacet molecules, and insuflicient evidence is available towarrant any assumptions.
  • amaldacets are not simple compounds, but are complex mixtures, is evidenced by the fact that portions are water-soluble, other portions chloroform-soluble, etc. It seems probable that the amaldacets are the result of many intricate polymerizations, condensations, and reactions.
  • reaction product is a mixture of separable materials. More is said of this separability hereinafter.
  • Example II A similar amaldacet was produced by reacting 'equimolecular proportions of aldol and monoethanolamine. A product exceedingly similar to the one of Example I was produced.
  • Example III One-halt mole of monoethanolamine and one mole of aldol were reacted at temperatures between 30 and 40 C. The product was not as soluble as the product of Example II and, when reduced, it was not as satisfactory an-addition agent for use in cyanide-cadmium plating.
  • Example IV Equimolecular proportions of aldol and diethanolamine were reacted at room temperatures. A product very similar to those of the above ex-' amples was produced, the productof this example, however, being slightly less soluble than the product of Examples I and II.
  • Example V Equimolecular proportions of aldol and triethanolamine were reacted at room temperatures.
  • the reaction product of this example was'somewhat less soluble than the products of Examples I and II.
  • Example VI Aldol was treated with ammonia gas by bubbling the gas through the aldol until no further reaction was noted.
  • the reaction product when reduced, was rather difilcultly soluble, and was only a moderately eflicient addition agent for cyanide-cadmium plating baths.
  • Example VII Equimolecular proportions of crotonaldehyde 7
  • Example VIII Crotonaldehyde and ammonia gas were reacted 75 at about twenty-five degrees centigrade.
  • Example IX 1 Acetaldehyde was treated with an excess of gaseous ammonia. An amaldacet similar to that of the preceding example was obtained.
  • ammonia ammonia
  • ammonium hydroxide ammonium hydroxide
  • certain amines may be used.
  • I' may, for instance, prepare the amaldacets by treating the aldacets with amines such as the glucamines, for instance, glucamine and methyl glucamine, or aliphatic amines, for instance, methyl ethylamine, methylamine, and ethylamine.
  • amines such as the glucamines, for instance, glucamine and methyl glucamine, or aliphatic amines, for instance, methyl ethylamine, methylamine, and ethylamine.
  • amaldacets may be prepared by conducting the reactions of the above examples at rather widely varied temperatures, I prefer that the reaction be performed at temperatures between about thirty and fifty degrees centigrade. If much lower temperatures be maintained, the reaction products will tend to contain insoluble or relatively inactive constituents. Similarly, the reaction temperatures should not be permitted to rise too high, because, when the reaction proceeds at high temperatures, the reaction product may contain insoluble constituents and may have none too great an eificiency as an addition agent.
  • amaldacets by the direct reaction of ammonia or amines with the aldacets, they may be prepared by reacting the aldacets with alkali cyanides.
  • the cyanides are known to hydrolyze to produce ammonia and formates according to the following illustrative reaction:
  • Example X Five parts, by weight, of technical aldol were added to a solution containing three parts, by
  • amaldacet-containing reaction mixture obtained may immediately be reduced to form one product of my invention. It is a thick, mobile liquid, dark red in color.
  • the acid treated solution was allowed to stand for several hours and a dark red fraction rose to the top. This top layer was removed and centrifuged.
  • the separated top layer which may be reduced to form apreferred product. of my invention, is a viscous liquid, dark red in color, and it has a specific gravity of about 1.20. At temperatures as low as 17 C. it remains liquid, but at the temperature produced with a freezing mixture of solid carbon dioxide and acetone (below -80 C.) a brittle solid, apparently non-crystalline, is formed.
  • This product is substantially insoluble in such solvents as ether, benzene, and petroleum ether. It is, however, completely soluble in alcohol and acetone.
  • amaldacets of this example are not. chemical' compounds, but are mixtures as is evidenced bythe fact that portions of the cyanide reaction products are water-soluble and that smaller portions of the productsare chloroformsoluble.
  • the water-soluble portion of the cyanide reaction products exhibits the property of promoting the formation of a bright finish on recessed parts of an article. The water insoluble portion seems to exercise its major in-.
  • the temperature of the reaction is relatively important as the yield of the product and its activity as an addition agent seem to be greatly influenced thereby.
  • the yield of the hydrogenation products of this invention are similarly influenced.
  • I may use temperatures from about 30 C. to about 75 C., though more specifically I prefer to keep the reaction temperature between about 45 and 50 C.so that 'hydrogenation'products of optimum characteristics may be produced from these materials.
  • sulfuric acid is employed fo removing excess sodium cyanide by converting it to sodium sulfate which then acts tosalt out being less volatile than acetaldehyde and more easily handled than paraldol which is a solid.
  • the reaction mixture is preferably concentrated by treatment with dilute sulfuric acid, as
  • Example X Theproduct issubstantially identical with the concentrated product of Example X described in detail above.
  • Example x1 a smaller ratio of cyanide to aldehyde was used than in Example X. This seems to lower the yield of active material somewhat. Generally,*the best results are obtained when the aldehyde and cyanide are used in substantially molecular proportions, but
  • the product will be less active, while if an excess of alkali metal cyanide be used, no particular dam'-' age results.
  • the product is concentrated by neutralizing with dilute sulfuric acid, the excess of cyanide, over that required to form the reaction product, is converted to alkali sulfate and hydrogen cyanide gas, bothof which are separated from the product.
  • the time of Example XI represents a practical minimum, and I usually prefer to employ a longer period. In general, the reaction temperature should be maintained for not less than about one-half hour, and I prefer to maintain it for not less than about four hours to obtain a product which, when reduced, yields an addition agent of the highest activity.
  • Example XII a To the cyanide reaction product of Example X .was added ten grams per liter of zinc dust. The
  • cyanide-cadmium plating baths were made up as follows:
  • This bath displayed good throwing power and ,awide bright current density range.
  • This bath was used for plating several objects at a current density of twenty amperes per square foot.
  • the deposit was extremely bright and smooth.
  • the number of grams of cadmium oxide in the above bath may be varied between fifteen and forty and good results will be obtained. If the bath be too concentrated the deposit will not be entirely satisfactory.
  • the reduced amaldacets are slightly more soluble than the untreated amaldacets, and are more active as addition agents in cyanide-cad mium plating. 7
  • Example XIII Following the procedure of the above Example 2H1, the reaction product of Example XI was hydrogenated. The resulting product and a concentrated product were somewhat more soluble in cyanide-cadmium baths and were effective as;
  • Example XIV The -crotoiialdehyde-monoethanolamine reaction productof Example I was dissolved in an alkali metal cyanide solution, and zinc dust was added to reduce the product. The product gave results comparable with those obtained in Example IHI when employed in similar cyanide-cadmium baths.
  • amaldacets shown above in Examples II, III, IV, V, VI, VII, VIII, and IX may'similarly be reduced to produce improved addition agents of my invention.
  • amaldacets such as a reduction product of theamaldacet of Example VI
  • amaldacets are not readily soluble in cyanide-cadmium plating baths, and it is desirable that they be dispersed in the baths.
  • the reduction products of the amketaldoresins generally, likewise, it is expedient to disperse the addition agent if difllculty is encountered in dissolving an optimum quantity.
  • the addition agents may be dispersed and their dissolution aided by adding them to a cyanide-cadmium bath in a suitable solvent. such as alcohol or acetone. It may sometimes be found desirable to reduce the addition agents to a finely divided state, or to use them in conjunction with such dispersing agents as saponin, gum arabic, and sulflte cellulose waste.
  • the plating baths of the said Patent 1,681,509 are modified, as shown above, only by employing my novel addition agents in lieu of the addition agents, goulac, dextrin, starch, etc., mentioned therein. While the plating processes described in the said Patent 1,681,509 lead to a bright, hard, dense, and smooth deposit of cadmium, and while the invention therein described and claimed has been widely accepted by the art because ofits merit, the substitution of my addition agents for those in the patent results in a cadmium deposit of even greater smoothness, uniformity, and brightness.
  • I may use other compounds of metals of the iron group having an atomic weight greater than fifty-eight, such as nickel, copper,
  • amaldacets are, of course, derived from certain aliphatic ketaldones: the aldacets; Below are discussed typical amketaldoresins derived from other aliphatic ketaldones and from carbocyclic ketaldones.
  • Example XV Example XVI Methyl ethyl ketone was treated at room temperature with gaseous ammonia. The resulting reaction product, when hydrogenated, displayedactivityas an addition agent in cyanide-cadmium plating baths.
  • Example XVII Five parts by weight of propionaldehyde were mixed with three parts by weight of sodium cyanide and ten parts by weight of water. The mixture was maintained at a temperature of about 50 C. for two hours and'then allowed to cool.
  • the reaction product was av homogeneous, mobile liquid, light yellow in color.
  • the addition agent of this example was reduced and used in a cyanide-cadmium bath such as that of Example XII, bath (1), the addition agent of this example being used at a concentration of about 1.4 cc. per liter in lieu of the conand the bath was characterized by good throwing power and a relatively wide bright current density range.
  • Example XVIII Diethyl ketone was treated with sodium cyanide according to the procedure of Example. XVII, and the reaction-product permitted to' stand a few days. arated into two layers: a colorless lower layer, which is probably sodium cyanide solution, and an upper layer light yellow in color. While I may use both layers mixed together, I prefer to separate, and use, the upper layer;
  • the yellow upper layer was reduced with zinc dust and used in cyanide-cadmium baths .of the type shown in Example XII, bath (1) at an optimum concentration of 5 cc. per liter. Excellent results were obtained.
  • the colorless lower layer when reduced, displayed no appreciable activity as an addition agent.
  • Example XIX Methyl ethyl ketone was treated with sodium cyanide according to the procedure of Example XVII and. then allowed to stand a few days. The reaction mixture separated into a lower, light yellow layer, and a small upper layer, dark red in color. Again I may use the mixture, but I prefer to use the upper layer.
  • the upper, dark red layer was reduced. with zinc dust and used; at a concentration of 6 cc. per liter in a cyanide-cadmium bath of the type shown in Example XII, bath (1), with fair results.
  • the lower, light yellow layer, when reduced, was not substantially effective as an addition agent in cyanide-cadmium plating.
  • Example XX Example XXI Methyl n-propyl ketone was treated with sodium cyanide according to the procedure of Example XIX. A colorless upper layer and a colorless lower layer were obtained. Again .I may use the reaction mixture, but I prefer to use the upper layer.
  • reaction mixture septo be a good addition agent when employed at a v concentration of 6 cc. per liter in a cyanidecadmium bath of the type shown in Example showed no substantial effect asan additionagent in cyanide-cadmium baths.
  • Example XXII Acetone was treated with sodium cyanide acsomewhat effective as an addition agent in a cyanide-cadmium bath of the type shown in Example XII, bath (1).. When reduced and used as an addition agent in a bath of the same type,
  • Example XXIII B utyraldehyde was treated with sodium cyanide according to' the procedure of Example XIX.
  • the two layers which formed may both be reduced to produce addition agents, and I may use either .or the mixture.
  • the upper layer after reduction, produced even better results at 'a. concentration of only 5 cc. per liter in a cyanide-cadmium bath of the same type.
  • Example XXIV Hexadecoic aldehyde was treated with sodium cyanide according to the procedure of Example XVII, the mixture of aldehyde and cyanide being maintained at about 50 C. for four hours. Thereaction mixture was allowed to stand overnight and was found to have separated with a top layer of'nearly black cyanide reaction product. It is noted that the original aldehyde was light yellow in color.
  • the lower layer "even when reduced, had no appreciable effect as an addition agent in a cyanide-cadmium bath of the type shown in Example XII, bath (1).
  • the upper layer after reduction, was rather diflicultly soluble, but at its optimum concentration of 5 cc. per liter, it served as' an addition agent in a cyanide-cadmium bath of the same type.
  • the agent produced from the top layer being poorly soluble, it should be dispersed in the bath after the manner hereinbefore suggested.
  • a ketaldone When aliphatic ketaldones are used as starting materials, a ketaldone should be selected which contains at least two carbon atoms.
  • Formaldehyde, with but one carbon atom, stands in a unique position with respect to aldehydes generally. Its dissimilarity to the other aldehydes is, of course, generally recognized.
  • aliphatic ketaldones containing between two and nine carbon atoms This terminology includes acetaldehyde, for example, as a two carbon atom compound and citral as a nine carbon atom compound. I especially prefer to employ those aliphatic ketaldones of two to nine carbon atoms which contain no more than two hydroxyl groups.
  • the aliphatic ketaldones contain carboxyl groups.
  • the elements sulfur and nitrogen are preferably absent from the aliphatic ketaldones which I employ as starting materials for the production of amketaidoresins.
  • the allphatic keltaldones which I employ as starting materials contain no more than two hydroxyl groups, and,more specifically, that they have a higher ratio of hydrogen to oxygen than that of water, it is, nevertheless, within the scope of my present invention touse such ketaldones as ke toses and aldoses.
  • the following example illustrates the production of a reduced amketaldoresin from a-carbohydrate which contains a ketaldonyl group.
  • Example XXV Glucose was treated with an. alkali metal cyanide by adding 12.3 grams of glucose to a cyanide solution made by adding 3.3 grams of sodium cyanide to 10 cubic centimeters of water. The mixture was maintained at'about to C. for eighteen hours and was agitated intermittently. During the period of treatment, a faint odor of ammonia was observed.
  • the product was a dark red-brown, viscous liquid. This product was allowed to stand for about five hours, and then four and one-half cubic centimeters of dilute sulfuric acid was added thereto. This quantity of sulfuric acid was an excess over the amount required to react with the unreacted sodium cyanide.
  • the product producedwa's reduced with zinc dust and employed as an addition agent in cyanide-cadmium baths of the type shown in Example XII in various concentrations up to ten grams per liter.
  • the addition agent effected a considerable change in the character of the cadmium deposits, but was none too satisfactory. noted that the baths containing the addition agent were reddish-yellow in color.
  • glucose was employed as an addition agent for cyanide-cadmium baths of the same type and in the same concentrations as were the products of this example.
  • Glucose itself was much less effective than its reduced cyanide-reaction product. It is noted that the baths containing glucose were light-yellow in color.
  • the reduced amketaldoresins may be prepared by the treatment of carbocyclic ketaldones with an amo or cyanide according to procedures similar to those above discussed.
  • Example XXVII Example XXV'III Benzaldehyde-was treated at 50 C. for several hours with an excess of sodium cyanide solution.
  • the cyanide solution contained three parts by weight of sodium cyanide to ten parts by weight of water.
  • Asthe benzaldehyde was added to the cyanide solution a precipitate of some relatively insoluble material formed. ,Aft'er a few hours most of this precipitate had dissolved.
  • the reaction mixture after reduction, was employed quite successfully with a cyanide-cadmium bath of the type shown in Example XII, bath (1).
  • Example XXIX Eivample XXIX and reducing, were quite satisfactory addition agents in cyanide-cadmium baths of the type shown in Example XII, bath (1)
  • Example XXX As the starting materials, benzaldehyde and benzoin, are diflicultly soluble, I added two carboxyl groups to benzoin thus:
  • ketaldones which do not contain a carboxyl group and which do not contain sulfur.
  • carbocyclic ketaldones which do not contain nitrogen are ordinarily preferred, because while Michlers ketone, for instance, responds to my broadest definition, it is none too satisfactory a starting material.
  • aromatic ketaldones are limited to a preferred group, the carbocyclic ketaldones. It will -be understood, however, that my invention in its broad aspects includes the use of cyclic ketaldones generally. I may, for instance, use heterocyclic ketaldones as starting materials for the preparation of addition agents for cyanide-cadmium plating baths.
  • Example XXXI Six and one-half grams of freshly distilled furfural was added to a sodium cyanide solution made up of 3.3 grams of sodium cyanide in 10 cubic centimeters of water. Quickly there was produced a red, heterogeneous mixture which was then maintained for six hours at 45 to 50 C. During the reaction period, a faint odor of ammonia was observed. At the end of the six hours, the mixture had reacted to form a black, tarry, lower layer and a brown, supernatant liquid. The black lower layer, after reduction, is effective as an addition agent.
  • reaction mixture obtained above before reduction, was treated with an excess of dilute sulfuric acid over that required to react with excess sodium cyanide, after the procedure of Example X.
  • acid Upon the addition of acid, a violent reaction took place, and a small amount of a black, liquid tar separated from the upper layer and joined the tar already at the bottom of the reaction receptacle.
  • Example XII The mixture of tars was employed, after reduction, as an addition agent in cyanide-cadmium baths of the type above shown in Example XII.
  • the baths were of a reddish color. Excellent results were obtained, but the agent of this example did not cause the baths to display as extended a bright current density range as did the agents of Example X.
  • agents of this example are rather diflicultly soluble, and it is preferred to add them to cyanide-cadmium baths in a suitable solvent a dark, wine color.
  • Furfural was employed as an addition agent for cyanide-cadmium baths, of the type used in.
  • Example XII in various amounts up to about ten grams per liter. After standing for several hours, the baths became very dark in color, and appeared black. By strong transmitted light, a small sample of one such bath appeared to have While furfural, in relatively large amounts, displayed some'activity as an addition agent, it was very much less efiective than the reduced furfural-cyanide products of this example.
  • a cyanide-cadmium plating composition containing a hydrogenated amketaldoresin derived from a carbocyclic ketaldone, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the amketaldoresin in alkaline solution, an amketaldoresin being, as herein set forth, a pre-reacted compound prepared by reacting a ketaldone with an amo in alkaline solution.
  • a cyanide-cadmium plating composition containing a hydrogenated amketaldoresin derived from an aliphatic ketaldone which contains only carbon, hydrogen, and oxygen, which has no less than two and no more than nine carbon atoms, and in which the ratio of hydrogen to oxygen is greater than that of water, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the amketaldoresin in alkaline solution, an amketaldoresin being, as herein set forth, a pre-reacted compound prepared by reacting a ketaldone withan amo in alkaline solution.
  • a cyanide-cadmium plating composition containing a hydrogenated reaction product of an amo with an aliphatic aldehyde selected from the group consisting of aldol, acetaldehyde, croto. aldehyde, and paraldol,-the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product in alkaline solution.
  • a cyanide-cadmium plating composition containing a hydrogenated reaction product of an alkali metal cyanide with a carbocyclic ketaldone, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product in alkaline solution.
  • a cyanide-cadmium plating composition containing a hydrogenated reaction product of an alkali metal cyanide with an aliphatic ketaldone, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product in alkaline solution.
  • a cyanide-cadmium plating composition containing a hydrogenated reaction product of an alkali metal cyanide with an aliphatic ketaldone which contains only carbon, hydrogen, and oxygen, which has no less than two and no more than nine carbon atoms, and in which the ratio of hydrogen to oxygen is greater than that of water, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product in alkaline solution.
  • a cyanide-cadmium plating composition containing a hydrogenated reaction product of an alkali metal cyanide with an aldacet, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product, an aldacet being, as herein set forth, one of the aldehyde equilibrium products which result when acetaldehyde is put in alkali metal cyanide solution.
  • a cyanide-cadmium plating composition containing a hydrogenated reaction product of an alkali metal cyanide with an aliphatic aldehyde selected from the group consisting of aldol, acetaldehyde, crotonaldehyde, and paraldol, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product in alkaline solution.
  • a cyanide-cadmium plating composition containing a hydrogenated reaction product of an alkali metal cyanide with aldol, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product in alkaline solution.
  • a cyanide-cadmium plating composition containing a hydrogenated amketaldoresin and a small amount of a metal of the iron group having an atomic weight greater than fifty-eight, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the amketaldoresin in alkaline solution, an amketaldoresin being, as herein set forth, a pro-reacted compound prepared by reacting a ketaldone with an amo in alkaline solution.
  • a process for the electrodeposition of cadmium comprising depositing cadmium from a cyanide-cadmium bath in the presence of an addition agent comprising a hydrogenated amketaldoresin, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the amketaldoresin in alkaline solution, an amketaldoresin being, as herein set forth, a pre-reacted compound prepared by reacting a ketaldone with an amo in alkaline solution.
  • the step comprising depositing cadmium from a cyanide-cadmium bath in the presence of an addition agent comprising a hydrogenated reaction product of an alkali metal cyanide with a ketaldone, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product in alkaline solution.
  • a process for the electrodeposition of cadmium comprising depositing cadmium from a cyanide-cadmium bath in the presence of an addition agent comprising a hydrogenated reaction product of an alkali metal cyanide of an aliphatic aldehyde selected from the group consisting of aldol, acetaldehyde, crotonaldehyde, and paraldol, the extent of hydrogenation being of the magnitude of the hydrogenation obtainable by the addition of zinc dust to the reaction product in alkaline solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US45426A 1935-10-17 1935-10-17 Plating of cadmium Expired - Lifetime US2097630A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US45426A US2097630A (en) 1935-10-17 1935-10-17 Plating of cadmium
FR816536D FR816536A (fr) 1935-10-17 1936-10-17 Produit et procédé pour le dépôt électrolytique de cadmium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US45426A US2097630A (en) 1935-10-17 1935-10-17 Plating of cadmium

Publications (1)

Publication Number Publication Date
US2097630A true US2097630A (en) 1937-11-02

Family

ID=21937814

Family Applications (1)

Application Number Title Priority Date Filing Date
US45426A Expired - Lifetime US2097630A (en) 1935-10-17 1935-10-17 Plating of cadmium

Country Status (2)

Country Link
US (1) US2097630A (fr)
FR (1) FR816536A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2420584A (en) * 1945-06-09 1947-05-13 Eastman Kodak Co Process for preparing n-butyraldimine
US2495629A (en) * 1944-06-02 1950-01-24 Poor & Co Zinc electroplating
US3030281A (en) * 1961-07-17 1962-04-17 Harshaw Chem Corp Chromium reducer for cyanide plating baths
US3505184A (en) * 1966-02-07 1970-04-07 Enthone Acid zinc electrodepositing
US4265715A (en) * 1979-07-13 1981-05-05 Oxy Metal Industries Corporation Silver electrodeposition process
US4792383A (en) * 1987-10-27 1988-12-20 Mcgean-Rohco, Inc. Polymer compositions and alkaline zinc electroplating baths and processes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120928882B (zh) * 2025-08-15 2026-02-27 汨罗市紫航金属表面处理有限公司 一种镀镉产线的水洗干燥恒温控制方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2495629A (en) * 1944-06-02 1950-01-24 Poor & Co Zinc electroplating
US2420584A (en) * 1945-06-09 1947-05-13 Eastman Kodak Co Process for preparing n-butyraldimine
US3030281A (en) * 1961-07-17 1962-04-17 Harshaw Chem Corp Chromium reducer for cyanide plating baths
US3505184A (en) * 1966-02-07 1970-04-07 Enthone Acid zinc electrodepositing
US4265715A (en) * 1979-07-13 1981-05-05 Oxy Metal Industries Corporation Silver electrodeposition process
US4792383A (en) * 1987-10-27 1988-12-20 Mcgean-Rohco, Inc. Polymer compositions and alkaline zinc electroplating baths and processes

Also Published As

Publication number Publication date
FR816536A (fr) 1937-08-10

Similar Documents

Publication Publication Date Title
US2171842A (en) Electroplating
US2097630A (en) Plating of cadmium
US2451426A (en) Bright zinc plating
US2428356A (en) Chromium aldonate compositions and method for the preparation thereof
US2733198A (en) Acid copper plating bath
US3755096A (en) Bright acid tin plating
US2828252A (en) Electrodeposition of bright zinc, copper, or nickel
US3288690A (en) Electrodeposition of copper from acidic baths
US3360446A (en) Electrodepositing a tin-bismuth alloy and additives therefor
US3598706A (en) Acid gold plating baths
US2090049A (en) Cadmium plating
US2287654A (en) Copper plating
US2085750A (en) Electrodeposition of cadmium
US2814590A (en) Electrodeposition of copper
US2836549A (en) Nickel plating bath containing acetylenic polyamines
US3580821A (en) Bright silver electroplating
US570554A (en) Eduard jordis
US3429790A (en) Acidic tin depositing bath
US3367854A (en) Nickel plating
US2085754A (en) Addition agents for nickel plating
US2085776A (en) Cadmium electrodeposition
US2870069A (en) Bath for electroplating nickel
US3556959A (en) Nickel plating
US2485149A (en) Bright nickel plating compositions and process
US2401428A (en) Electrodeposition of nickel