United States Patent Office 2,791,554 Patented May 7, 1957 1 2,791,554 ‘METHOD OF ELECTRODEPOSITING ZINC John B. Winters, Westake, Ohio, assignor fo Ann F. Hull amd Adrian Medert, Cleveland, Obio, a5 cotrastces No Drawing. Application September 22, 1954, Serial No. 457,97 6 Claims, (C1. 20455) ‘This invention relates to the electrodeposition of zine, and is more particulary directed to a new and iasproved bath composition and process for producing bright zine deposits wherein the cyanide bath contains in solution bathsoluble reaction products of epishlorhydrin with ammonia of primary eines, Zine plated from cyanide baths is widely employed as a coating to protect stest base metals from corro- sion and to provide corrosion resistant undercoats for organic and other protective fishes which ae applied ‘hereover. A zine coating upon an article plated fram, 4 cyanide plating bath is dull gray or dark in color, relatively crystalline in structure, is poor in appearance, stains readily and aocordiagly such coating bas a very limited field of application. It has Tong been common’ ‘practice to obtain 2 costing of improved physical char- acteristic, particularly in appearance, by incorporating in the cyanide plating bath various organic and inor- aganie substances whieh are generally refered to as addi ton agents or brighteners, Heretofore it has heea the common practice in ob- taining bright zinc deposits from cyanide plating baths {0 use as addition agents a combination of organic and inorganic compounds, and optimam results depended. ‘on maintaining a pre-determined balance between the ‘concentrations of the organic and inorganic constituents, Accordingly the prior practico required relatively close control over a plurality of the constituents of the plat ing bath by chemical analysis, or other means if ana- lytical methods wore not feasible, “In the commercial ‘operation of plating baths employing such addition agents, numerous drawbacks were encountered by Teason of such addition agents which were in addition to those brought about by any’ unbalanced relationship between the organic and inorganic substances, For example, one of the disedvantages of the combination of organicine organic addition agents is that the inorganic constituent is a soluble metal compound, the metal of which co- deposits with the zinc, greatly to the detriment of some of its physical properties, such at ductility and corso sion resistance. Such cO-doposition causes stains. and undesirable appearance of the costed surface upon the subsequent application of surface treatments which are commonly used to passivate the zine surface or t0 pro- duce thereon a taruish of corrosion resistant fim. ‘The ppurer the zinc deposit upon the surface of the article the better it is for corrosion protection and for eccept- ing subsequent surface treatments desigued to produce passive or protective films such as the chromate type or phosphate coatings to promote lacquer adhesion. Tt is among the objects of my invention to provide an addition agent for zine cyanide plating bath eompo- sitions by means of which bright, smooth and relatively pure zine deposits can be obiained therefrom. A further object of my invention Is to provide zine plating baths and a plating process employing the same which produce bright zinc deposits that are uniformly responsive to 0 Ea 50 0 2 oxidizing bright dip, chromate type protective dips and bhosrhatiing dips. aes ‘These objects are accomplished briefly by the use of agusoos cyanide zine baths that contin, betheolbie Teaston products of eleloehydsa. ith ammonia oF With pritry amos citer sione or for some purposes incombinadoa with un aromatle aldehyde selected from the arp consisting of onphetrooylcaldhes, phen thors and’ methoxy benaadstydos Such reason prod- Ucts may be Kaown as plyepoxyamines snd will be 30 designated hereter ‘Wille my novel blhtenes are efetve in any com- mercaly operable aine cyanide plating bath, Best Te Se ae obtained withthe approximate bath’ compon- tion and operting conditions thowa ia Table 1, which can be varied as required for spec’ purposes in ac: Cordance withthe know il nthe art. Table 1 ‘Bath composition: Zine cyanide. Sodium cyanide Sodium hydroxide. NaGN (free and combined) _» Ratio of a Operating conditions: “Temperature—about____. 80° F. Cathode current densija.. 20 amps. per sqft Apodes.. Zino of suitable purty. ‘The plating bath is prepared by dissolving the con- stituents in water, after which the bath should be puzi- fied by adding about one-half gram of sodium sulphide per liter of bath dissolved in water, or the bath may be tteated by stiting about tvo grams of zinc dust per llr of bath for a few hours, then setting and decanting or Sterne. T have found that addition agents used for cyanide inc plsting baths in accordance with the prior art are subject to certain disadvantages. For example, the use fof aromatic aldehydes requires very frequent additions because of their instability in the ath, and the same disadvantage applies to colloids such as gelatin, The use of polyvinyl alcohol is quite common, but tls mie terial is subject to the disadvantages of salting out of the bath, forming an undesirable scum on the bath sure face, produsing an undesirable yellow color to tho bright zine deposit, ad furthermore is not uaiform in its com- position. ‘The above disadvantages are entirely overcome with ‘my new and novel bath-soluble polyepoxysmines. These polyepaxamines are unusually siablo in the plating bath, {heir solubility is moze than sufficient to preclude theit being salted ont, they do not produce yellow deposits upon a plated article and they can be readily produced in batches that are uniform in effect when used in a plating bath. ‘The addition of bathsoluble polyepox- famines also greatly improves the covering power of c}- anide zine. plating baths to the extent that receses in the article which eannot be covered with'the metal under oninary operating conditions are readily covered if such addition agents are present ‘The polyepoxamines may be prepared by any one of 4 number of well known and established procedures. However, for both maximum effectiveness and bath sa bility, the preparation of the polyepoxamine in accord- ance ‘with the following procedure has been found most desirable, Using a jacketed stainless steel reaction vessel, 10 gal- ons of water and 56 pounds of aqueous ammonia (29% ) fare combined and cooled to a temperature commensi rate with the ability of the apparatus to convey away heat. ‘Thave found that a temperature of from 6 10 103 degres is the most desirable. Five gallons of opichtor- hnydrin are then added to the vessel. Cold water circu. fated within the jacket serves to convey away the heat of reaction and to maintain the substances within the vessel within a desirable temperature range. An initia, 5 very slow reaction or condensation takes place which Teads to an intermediate product. This is Inter poly- merized at a controlled rate, The evidence of such a slow reaction is continuous liberation of heat and a con- ‘tinuous drop in pH from about 12.5 to 8.0 as determined by a glass electrode, ‘Ailer the intial reaction has been completed which takes approximately 2 period of three hours, polyme zation is promoted by gradual elevation of the tempera ture to abont 101 degrees centigrade or the reflux tem- perature, After maintaining the high temperature for about three additional hours, the desired degree of poly ‘merization is seached and the resulting polyepoxyeasine ‘suitable for addition to zinc cyanide plating baths. The product made in accordance with this procedure possesses 4 relatively low degree of polymerization waich is most effective in the zine plating bath within the range of current densities from about $ to 125 amperes per square Toot Another procedure for, preparing polyepoxyamines suitable for use es an additive for zine plating baths con- sists in adding epichlorhydria slowly to the difuted am- ‘monia at higher temperatures. Using the same (ype of reaction vessel, 10 gallons of water and 56 pounds of ‘aqueous ammonia (29%) are combined and heated to about 60 degrees centigrade. Bpichlorhydrin in. the amount of 5 gallons is then slowly added to the vessel with the continued agitation ofthe mixture tetein while main taining a constant temperature by means of the circulation of cold water in the jacket uatil all of the epichlochydsin hhas been added. ‘The speed at which the epichlorhydrin is added is determined by ability of the eiculating water though the jacket of the container to convey avray the reaction heat. After the initial exothermic reaction is complete as evidenced by no further tendency toward temperature rise for a period of from 30 to 60 minutes, Ihot water under pressure is eirulated through tho jacket to slowly elevate the temperature to 101 degrees enti rade or reflux temperature as in the fist procedure. The resultant product shows a higher degree of polymerization than the first product and is particularly effective in the inc plating bath in the lower curzeat density ranges of from 2 to 40 amperes per square foot. In each of the above procedures for preparing a polyepoxyamine in lieu of aqucous ammonia a solution ‘of 32 pounds of ethylene diamine in 15 gallons of water may be used. The same amount of epichlorhydsin is used. Ta this case itis desirable to remove any excess of ethylene diamine which may be present by distillation prior to final polymerization. ‘The amount or concentration of my novel adkltion agents will depend upon various conditions such as hath composition, degree of brightness of deposit desired and degree of covering power. A desirable range of elfective- ness has been found through the use of from 0.25 to 4.0 stam per liter of cyanide zine plating bath. The pre- ferred range of concentration is from 0.5 to 2 grams per Titer of eyanide zinc plating bath Zin eyanide plating baths containing my novel bright- ceners prodice bright zine deposits direct from the plating. baths.” The zinc is relatively pure as it contains no co deposited brightener metal and its normal ductility has ‘ot been materially impaired. If under some conditions fof operation a light yellow film occurs over the bright zine surface, such film ean be removed by dipping in any of the commercially used bright dips such as dilute nitric acid (approximately 4% , dilute acidified hydrogen per- oxide, etc, all of which are well known in the art, with- ‘out staining the bright zinc surface. Bright zinc deposits from my novel beth composi 10 0 “0 9,791,564 4 can be subjected to any of the many chromate type dips for producing passive surfaces or protective costings with uniform and satisfactory results. Likewise such bright inc deposits will take a uniform phosphatizing teal- ment by any of the widely used commercial processes {or producing undercoats on zine for organie finishes and the like. ‘My novel brighteners greatly improve the plating char- acteristic ofthe zinc cyanide bath in which they are used by increasing both its covering power and throwing power, and by providing a broad range of current deasitiee over which bright deposits can be plated. While my novel Drighteners are self-suficient in producing bright, smooth, ‘relatively pure zine elestrodeposits from zine cyanide plst- jing baths containing them in solution, there are certain conditions encoustered, for example, in barrel plating, where the use of an aromatic aldehyde such as anise aldehyde or heliotopin, in conjunction with my novel brighteners produces superior results mainly from the standpoint of coverage on low current density areas with improvement in brightness thereon. Accordingly, undet such condition I find it advantageous to add about Yo t0 1 gram of such aromatic aldehyde per liter of zine eva aide bath containing my novel brightener. Experi. ‘ments have proven that the action of my novel ‘brighteners with such compounds is syaergistc as identi- cal results can not be obtained by tho use of either alone. ‘Similarly if desired for some applications, a metal bre ening agent such as a compound of molybdenum ot chromiam or others given in United States Patent No. 2,080,520, may be employed with my polyepoxyamines, Having thus described my invention so that thos skilled in the art may understand and practice the same, what T by Letters Patent ig embodied in the appended 1. An aqueous zine cyanide electroplating bath con- taining a bath soluble polyeposyamine resulting from the condensation reaction of epichlorkydrin with 2 primary Amine in sufficient amouat to provide bright zine de post. 2,” An aqueous zine cyanide electroplating bath contin ing from 0.25 to 4.0 grams per Iter of a bath-soluble polyepoxyamine resulting fram the condensation reaction of epichloshydvin with a primacy amine, 3. In the process for electrodeposting zinc, the step ‘comprising depositing zine from an aqueous zine eysnide bath containing in solution from 0.25 to 4.0 grams per liter of bath of a bath soluble polyepoxyamine resulting from the condensation reaction of epichioriyrin with & Primary amine 4a the process for electrodepositing zinc, the step ‘comprising depositing zine from an aqueous zine eyanide bath containing insolation fom 0.29 to. 40 grams per liter of a bath soluble polyenoxyamine resulting from the ‘condensation reaction of epichlorhydrin with a primary amine and an oxyheterocycic aldehyde 5. In the process for electrodeposting zinc, the step comprising depositing zinc from an aqueous zine cyanide bath containing in solution from 0.25 to 40 grams por liter of bath soluble polyepoxyamine resulting from the condensation reaction of epichlorhydtin with a pri- ‘mary amine and a phenyl ether. 6. In the process for electrodepositing zinc, the step ‘comprising depositing zin: from an aqueous zine cyanide ‘ath containing in solution from 0.25 to 4.0 grams pe liter of a bath soluble polyepoxyamine resulting from the condensation reaction of epiehlorhydrin with a primary amine and a methoxy benzaldchyde References Cited inthe file of this patent UNITED STATES PATENTS Hoffman Dee. 28, 1948 Ellis Dee. 15, 1953 2,457,152 21662,853