15. CURRENT AND METAL DISTRIB H. L. Pink Fellow Engineer, Process Engineering De Wes stinghouse Electric Cor Revised by Lawr It is scarcely necessary to emphasize the im- portance of metal distribution in eleetroplating, regardless of the purpose of the plating oper- ation. The ability to control the distribution of metal over the surface of the workpiece is the key to successful plating for corrosion resi: tance, and more especially to meeting the very exacting requirements of electroforming and other engineering uses of plating. The distribution of an electrodeposit over an object is determined by the local current density ateach point as well as by the cathode effieienc of the bath at that current density. The local current density in turn is determined by the primary current distribution and the local po- larization. The primary current distribution, 2 will be explained later, is determined com- pletely by the geometry of the plating cell. [t is independent of the properties of the solution provided they are uniform throughout the solu- tion, right up to the electrode surface. The term “polarization” combines all those phenomena, both physical and electrochemical, which oper- ate to change the properties of the solution in the vieinity of the electrode. ‘These changes result in an actual local or “secondary” current distribution which differs from the primar distribution. Many subtle variables influence the distribu- tion of electrodeposited metal, however exch may be put into one of four elasses: 461 UTION erospace Division, poration, Baltimore, Mu. ence J. Durney 1. Those governing the primary current dis- tribution ‘Those related to the plating bath and con- ditions of operation, which function to alter the primary current distribution. . Those aspects of the shape and d the workpiece which do not per the primary current distribution, yet oper ate to alter it. ‘The relation of plating bath efficiency to the current density. ign of control In most practical cases, the primary current distribution is the controlling factor in determin ing the metal distribution. When the primary current distribution is uniform or very nearly so, the cathode polarization will usually be equaily uniform, and so will the metal distribu- tion, When the primary current distribution is markedly non-uniform, the other classes of fac- tors may operate either to improve or worsen the uniformity of metal distribution over what would be expected in their absence, but in general, they cannot completely overeome the overriding influence of the primary current bution. PRIMARY CURRENT DISTRIBUTION ‘The current distribution over an electrode in the absence of polarization and other disturbing factors at the electrode is called the primary462 1 / GENERAL PROCESSING DATA current distribution. [tis determined solely and completely by the geometry of the system which includes the shape and size of the electrorles, their conductivity, in the rare ease when they are not equipotential surfaces, the spatial rela- tionships of the electrodes to each other wd to the electrolyte boundaries, the conductive nature of these boundaries, znd the shape and location of any other conductive or nonconiuctive bodies in the electrolyte. In practice, such bodies would be either thieves or shields. ‘The general theory of the potential field is of such universal seientifie interest that it at tracted the attention of mathematical physicists as soon as the concept of a potential had ap- peared. The first application to electroly made by Riemann? in 1855 and later by Weber®, but it was not until the work of Kas 1939-42 and later of Kronsbein‘ that any serious application of the theory was made to the art of electrodeposition. ‘The subject is mathemat- ically so complex that at the present time only the simplest cases of geometry can be consid- ered, and even then, cathode polarization m be assumed to be either absent or uniform Therefore it is not now of any practical use to es was pert in ss in detail the results of these theoretical investigations. However, a general grasp of the theory of the potential field and a few general rules arising from the mathematical work will be of immense help to the practical plater and will prevent many misconceptions and misinter- pretations of experiments. Whenever an electric potential, i.e, voltage is applied between two electrodes in an electro- Iyte, every point in the electrolyte assumes some potential intermediate between that of the two electrodes. Since the conductivity of the metal electrodes is usually several million times that of the electrolyte, it may be assumed with a slight margin of error that every point on the electrode surface is at the same potential, ie., it is an equipotential surface. Similarly, equi- potential surfaces will be found in the electrolyte surrounding each electrode. Close to one elee~ trode, the equipotential surface will resemble that electrode in shape; however the shape will change as one moves farther away until at last the equipotential surface close to the second electrode assumes a shape more or less conform- ing to that electrode (Fig. 1). The shape of these equipotential surfaces in this and similar simple eases may be computed mathematically’ and has been verified experimentally’. It is also possible to calculate or map experimentally the diseu: Fic. 1, Trace of equipotential surfaces in a tank of electrolyte with two line electrodes (+ and =) path that the current follows (Fig. 2). In this plot, an equal amount of current, e.g., one ampere, is flowing along each of the electrolyte paths bounded by the solid lines, and some undefined current between the outer lines and the insulating boundaries. In understanding the significance of these Fis. 2. Arrangement of Fig. 1, showing equipo- tential surface traces (dotted) and traces of surfaces of force (full lines).Fis, 3, Hypothetical contour map, illustrating analogy between contour lines and equipotential lines. diagrams of equipotential lines, it may be help- ful tocompare them to the more familiar contour » used by geographers (Fig. 3), in which points of equal elevation are connected by lines. Figure 3 represents a hill and cliff along ashore ch suc econtour line (elevation zero), and e: s is 20 ft higher. It is easy to see that over equal distances AB and CD there is a consid- erable difference in the slope of the ground, and rainfall landing on the hill at A will race to the sea; whereas from (its movement will be mueh nse, this isalsoa diagram of equipotential lines, and the closer they are crowded together, the steeper is the slope. In our diagrams of electric potentials. the current density, similar to the water flow, will be great- est where the equipotential lines are crowded most closely together. Figure 1, in mapping terms, would be inter- preted as a hill with a steep cliff in front and a gradual approach at the rear. A little d away across rather level land is a spoon quarry hole with a very steep declivity on the hill side of the hole, less steep on the other side. It is a basic law of the potential field theory that the traces of the equipotential surfaces and surfaces of force in any plane form an orthogonal net, that is, they everywhere ¢ h other at right angles. Since the electrodes thems also equipotential surfaces, this r current enters or leaves the electrode at any point in a direction perpendicular to the sur! at that point. It is also fundamental in field theory tl he slower. Inavery reals CURRENT AND METAL DISTRIBUTION 463 equipotential surface may be replaced by a (perfect) conductor without disturbing the field. milarly, the substitution of an insulating boundary for any line of force does not disturb important to recognize that thi is true only if the substitute surface completely replaces the original. Conversely, when anything cuts one of the lines of the net, the field is disturbed; moreover the effect of moving one lating tank wall closer to the electrodes is shown in Fig. 4°. It follows from what has been id that the current distribution over a eylin- drical (A of Fig. 1) and plane (B-B of Fig. 1) electrode is defined by the same plot, as is the distribution between wire (+, Fig. 1) and outside eccentrie cylinder (C of Fig. 1)* Gilmont and Walton* utilized these concepts in the design of their modified Hull cell, which gives a linear current distribution over a flat electrode, the other electrode being curved, and placed along an equipotential surface. It should be observed that in these diag we are actually representing a three~timen- sional system in two dimensions, which means that to represent the actual system, the dia- ms must be moved in a direction perpendieu- lar to the paper between two insulating bound- the field. It is ms / Oy 0 Fu: 4. Arrangement of Fig. 1, with electrodes displaced from tank center line, *Mathematically this is not rigorously true in the e, be -ylinders” are not true circles, which occurs only in an unbounded (ie., infinite) field,464 1 / GENERAL PROCESSING DATA aries. Practically, this means only that the electrodes extend from the surface of the solu- tion to the bottom of the tank. What happens when these conditions are not met, as when the plane electrode stops short of the bank walls, is diseussed by Hine’. Another interesting observa- tion may be made from these diagrams. A single anode, if it is significantly separated from the cathode, will give the same current distribution as a row of anodes rather closer to the cathode, along plant B-B of Fig. 1, for instance. ‘The substitution of condueting for insulating walls has been well discussed by Kasper* and illustrated by Lukens", As would be expec the effect is profound, and in the ease of two isolated electrocles well away from the walls, as Lukens illustrated, results in a much more uniform distribution, front to back, over the electrodes. However, this is not a practical plat ing tank arrangement, and in most cases the benefit derived would be slight, if any, in the more conventional plating tank setup. The pref- erence for insulated tanks is well justified on many other grounds THE CONTROL OF PRIMARY CURRENT DISTRIBUTION Not much more can be said about the theory of current distribution without getting more involved in detail than is the intent of this chapter. Interested readers should consult the references cited. There are also numerous ref- erences" "havingamoreimmediately practi- cal value, but unfortunately some authors**!* ° who are unaware of the basie theory become frequently confused and puzzled by their results and offer untenable explanations. Even a reader with only a fair grasp of the theory can, however, extract much of value from the data they pre- sent. It is the purpose of this section to present briefly a set of generalizations about the practi- cal control of primary current distribution. Much that will be said is intuitively recognized by the experienced plater, butsome ideas may be new to him. Perfectly Uniform Current Distribution ‘There are basi rangements giving perfectly uniform current tribution": infinite parallel planes, infinite concentric cylinders, and concentric spheres. None of these arrangements has as yet been offered to any shop to be plated, but under the rules we have certain freedoms: (a) we may ly only three possible ar- replace any line or surface of current flow with an insulating boundary, or (b) we may replace any equipotential surface with an electrode. ‘Thus, we may bos in our infinite parallel planes, with three perpendicular insulating walls and an air surface to form the well-known Haring cell, To work properly, the walls must. be exucily perpendicular to the electrodes", conse- quently the Haring cell should always be placed on a truly horizontal surface ( preeaution that has not been found mentioned in the literature). A plating rack full of closely spaced flat par equidistant between two rows of anodes, in a tank just big enough to hold the rack, is an arrangement about as similar to the Haring cell as the practical plater will probably ever see. In the same way, we may eliminate a section of our infinite cylinders by means of insulating planes at right angles to the axis and obtain an arrangement for uniform primary current distribution. The central cylinder, often the anode, must be perfectly positioned except when diameter is very small with respect to the outer cylinder. Thus it is best to use the smallest anode that will adequately carry the current, but. in most eases this poses a problem because the cathode current density is perforce smaller than the anode current density, yet usually must be above some minimum value. Hammond” dis- cusses some of the problems of plating gun barrels, a modified example of coneentrie eylin- ders. An interesting property of the concentric cylinder system is that the voltage drop between the electrodes at a given current density is dependent only on the ratio of their radii, not Jue, which may be mils or miles. As Kasper" points out, radial sections of concen- trie eylinders (the radii being insulating walls) also give perfect primary current distribution. ‘The case of concentric spheres, or radial sec- tions thereof, which are equivalent, is very rare and will not be discussed. Control of Nonuniform Current Distribution It is well recognized that almost c’ p tical plating arrangement results in a nonuni- form current distribution. This is tolerable to a degree but often requires improvement to produce acceptable work. The ability to visual- ize, even if imperfectly, the potential field around the workpiece is a great aid in making favorable adjustments in the geometry of the setup. In doing this it is most important not toneglect the effect of the insulating boundaries (the tank members and the solution surface). Thus, a rack which may give good distribution over the workload when operated in a tank full of other racks will give a very different and less uniform distribution if plated alone or ina partially loaded tank. An important problem in metal distribution, with which present theory i ble to d quantitatively, is deposition into recesses, typ- ified by an angle (Fig. 5). Theory does tell us that in a perfect angle, with perfectly sharp corners, the primary current density is infinite on the sharp external corners of the angle and zero on the internal corner. Thus it is theoret- ically impossible to deposit plate on the internal corner of a true (zero-fillet) angle (even one of 179 degrees) while the deposit on the external corners of zero radius must inevitably be burnt, atements which any practical plater will find asy to believe. Many authors have discussed this problem? ". The primary current distri- bution is not influenced by the size of the angle, but only its shape, and the last two reference: cited deal with micro-angles (one outstanding case in which factors other than primary current distribution are controlling, as is ably discussed by Kardos®. A common misconception with spect to angles and rec in general is that the farther away the anode, the better is the current distribution. This is based on the false premise that the current flow is in straight lines Fic. 5, Equipotential lines between plane anode A-B and angle cathode in tank of electrolyte. CURRENT AND METAL DISTRIBUTION 465 and deducing from this, that when the anode is farther away, the distances from the anode to near and far points of the angle (or recess) are more nearly equal. However, as can be seen from Fig. 5, the anode AB could be moved up position CD without affecting the current distribution. ‘The cathode or cathodes should be arranged to present as simple a surface over-all as as close a so. possible, whether plane or curved. The anodes should be arranged to conform, not necessarily to the shape of the cathode assembly, but to the timated form of that equipotential surface which in conjunction with the boundaries will tend to give the nearest approximation to straight-line current flow. For instance, in plat- ing into a large angle (Fig. 6), the best anode arrangement is not a conforming angle (Fig. 62). A better arrangement is a wedge (Fig. 6b); still better may be a single wire (Fig. 6c) or its equivalent, adistantanode and insulating masks A-B forming a slot (Fig. 64). ‘The potential surfaces in Fig. 5 have been drawn from pure conjecture. In such a problem, Where the cost was justified, they could be actually mapped, probably most easily by the technique of Lukens*, or with more difficulty e (a) (b) (©)| Ee | (@) Fic, 6, Angle cathode with various anode ar- rangements: (a) conforming angle (1s) tapered anode (c) point (wire) anode (d) virtual anodes formed by insulating marks A-B.4661 / GENERAL PROCESSING DATA by the analog technique”, with conductive paper, using various shapes and sizes of insu- lating shields. The use of shields is in this case preferable to a “thief” or “robber” at the outer angle corners because although the latter will protect the corners from overplating, they will still further decrease the plate deposited in the interior of the angle. Figure 6d also shows the use of an insulating shield AB to protect the outside corner. In this ease, a thief could do : well, but is more complicated and is wasteful of metal. In visualizing the probable effect of shields, it is convenient to remember that the equipotential surface formed by the slot or op- enings left by the shield becomes the effective anode as AC, BD and the outer broken lines of Fig. 6d. : Rousselot* has recently published the results of an experimental evaluation of the effects of shields, thieves and bipolar conductors on the field, using conductive paper for a two- dimensional analysis of simple configurations, that a properly placed shield is effective as a thief, whereas a thief may rob 2 to 50 per cent of the current, or more. Kronsbein"' made quantitative measurements of the effect of fillet radius in improving deposit distribution on the interior of an angle and concluded that as a general rule no further improvement was afforded by increasing the fillet radius beyond 0.010 in./in, of angle shank, No similar rule is yet available for external sharp edges or corners, but here it is obvious that the only upper limit of desirable radius is that set by other functional considerations. Hine’ and co-workers have shown that when two parallel electrodes of equal lengths are centered between and perpendicular to two in- sulating side walls at varying distances from them, with distant back walls, the proportioning, of current between the face and back of the electrodes can be ealeulated. It is, as would be expected, a function of the degree to which the electrodes fill the distance between the walls. Their rounded off figures show: He shows Primary Current. Distribution Per Ceat of Total Cathote Width, ag Per Cent of Wall-to-Watl Distance Garzeat oa Face 95 97.5 B 92 72 86.5 58 19 50. 5 Each automobile bumper ina rack of bumpers being plated back-to-back is an approximation of this arrangement, since between each two bumpers is an equipotential plane equivalent to an insulating boundary in the sense of the above example. The spacing of the bumpers than de- termines how much plate is deposited on the back Sometimes irregularities in current d stribu- tion may be overcome by rotating or oscillating the anode or cathode; thus in any problem of plating a cylinder, if it can be rotated about its axis, inequalities of anode spacing and hence of distribution around the circumference can be Tnequalities along the axis due to the smaller electrode® have to be dealt with by other means. This may require purposeful tapering of one of the electrodes. In the case where the larger electrode, because of thin wall section or material of construction, also appreciable voltage drop along its length, then by making the anode connection at one end and the eathode overcome tapering sections or high resistance i connection at the oppesite end, and choosing the anode cross section to give the same voltage drop per foot as the cathode, it is sometimes possible to cancel out the effect of the electrode resis- tance. This has been done in at least one in- stance™. In any such arrangement the anode must be insoluble or must not change in cross section enough to upset the calculations. With regard to anode-cathode spacing, there is usuaily iittie to be gained by ine! ing this beyond the 8 to 16 in. normally found in most commercial installations. There is, however, one consideration, frequently overlooked, from which arises the often-heard complaint that work on the battom or top of a rack rnt. This, condition can arise from having too much solu- tion above and below the rack. The top of the work should usually not be more than 2 to 3 ii below the surface unless there is good re: wanta concentration of currentat this point. The bottom of the work presents a more ticklish problem because m: solutions are operated with a layer of sludge at the bottom which the plater does not wish to disturb; hence work is usually kept 8 to 12in., and frequently more, off the tank bottom. A fairly simple way out of this difficulty is to e ating walls designed into the tank, or bu with plastic or loos brick, as shown in Fig. 7. The walls should be as close as practicable fo the plane of the cathode. This will effective ‘educe uhe amount of cur- rent received by the bottom of the rack without aggravating the studge problem. The common remedy of using anodes shorter than the work isFis, 7. Shielding bottom of workpiece from ex- cessive current. less effective and will not work at all in many cases where the anode-cathode distance may be great enough toallow the formation ofan equipo- tential field in the shape of a plane, whieh is equivalent to using full-length anodes much closer t6 the work. The number of anodes per foot of tank is not usually significant, since the equipotential sur- face a little distance away becomes practically. a plane and is equivalent to a sheet anode. However, if the cathodes do not cover the entire length of the tank as they should, the situation can be improved to a certain extent by making the effective width of anodes somewhat shorter than the cathode width. How mueh shorter can only be determined by experiment, and the anode-cathode distance is important as ex- plained above. The arr ment of work on a ra closeness of approach of the parts and of racks in the tank will be discussed later because considerations other than 9 tribution may apply. ue, rimar: SECONDARY CURRENT DISTRIBUTION The distortion of the primary current distr bution by the second and third classes of factors mentioned in the opening of this chapter results in a secondary current distribution, which is really what does the work of depositing metal. It is the intent of this chapter merely to show how metal distribution may be controlled; hence many of these factors will be mentioned only briefly since many are not completely within the control of the plater, although inherent in the selection of the bath and operating condi- tions. The effects of the second clas under the term “polarization,” effect of the passage of current that results in are included which is any CURRENT AND METAL DISTRIBUTION 467 increased ré have the same effect, insofar as current distr bution is concerned. Thus, for example, the composition of the cathode film is changed by the action of the current, reducing the concen: tration of conducting ions and causing a rise in resistance (concentration polarization). An anode may become coated with a more resistant istance or in phenomena which film (chemical polarization) or gas discharge may decrease the effective cross section of the electrical path (gas polarization). Provided the anodes are uniformly polarized, there is no effect on the cathode current distribution; however nonuniform polarization will have an effect which, if desired, may occasionally be overcome by altering the anode arrangement to provide more uniform anode current distribution; by altering the batir composition or conditions, (including agitation) to reduce anode polariza- tion, or to make it more uniform. Gas polar tion may be reduced by agitation or reorienta- tion of the workpiece. Agitation will also reduce concentration polarization, but this is not always desirable since it may adversely affect throwing power (q..). With reference to thecathode, theelectrochem- properties which determine the secondary current distribution are the cathode polarizati and the conductivity of the solution. The prima current distribution between two points, 1 and 2, on a cathode (Fig. 8) is given by the equation i iy where i; and 7-are the current de points Land 2, respectively, at distances d, and ds from the anode measured along the lines of fo traversed by the current. The secondary current distribution is generally accepted" to be + os Mic, 8. Primary current distribution on a cath ode.468 1 / GENERAL PROCESSING DATA given by the equation dE ip tk GT where & is the solution conductivity and dE/dI is the slope of the cathode polarization curve between the current densities i; and i. The second terms in the numerator and denominator are identical and have the dimensions of a length. The combined effect of polarization and conductivity is therefore equivalent to adding an equal solution length to the path lengths «, and d,, It will thus be seen that the secondary current distribution is a/ways more or less of an improvement over the primary distribution.” It is also to be noted that the polarization and conductivity are not inherent properties of the solution alone, but are dependentas well on other outside factors such as temperature, agitation and current density. Furthermore, concentra- tion polarization can alter the conductivity of the solution in the vicinity of the cathode. The degree of improvement of secondary over pri mary current distribution becomes greater a the value of the second numerator and denom- inator terms increases, that is, there is relativel, more improvement in a solution of high condue- tivity, operating under conditions where the cathode polarization is increasing rapidly with curent density. The latter condition is usually obtained only at rather low current densities. The third group of factors affecting metal distribution comprises unusual geometry or me- tallie nature of the workpiece; thus cup-shaped workpieces or the presence of blind holes may require special positioning or even reorientation during plating. Chamfering or rounding the harp edges of blind holes will improve the primary current distribution toa certain extent. When the nature of the cathode metal electrolyte system is such that the depositing metal has a high overvoltage, recesses may not plate at all without special procedures such as striking ini- at high current density until the rec iscovered, or striking with another metal having a lower overvoltage, or using auxiliary or bipo- lar electrodes (Chapter 21). It is thus seen that the secondary current *This is true so long as the slope of the polarization-current density curve is not negative. No such case has yet been reporter distribution is controlled by a very complicated set of variables, and the effect of any one of these cannot be predicted in any general way. METAL DISTRIBUTION The rate of metal deposition at any a cathode is determined by the current density existing at that point in the secondary current distribution, and by the cathode efficiency of the bath at that current density. Since the secondary current distribution is unknown, the metal dis- tribution also cannot be predicted. With a suf- ficient knowledge of a given system, however, the direction of the effect of a certain change in variables can often be stated, so that an improvement in metal distribution can be ef- fected. It should still be remembered that the primary current distribution, which can be ma- nipulated in an empirical sort of way, usually is the controlling influence on metal distribu- tien. Control of the secondary current distribu- tion is less effective and is complicated by the fact that the controlling variables are com- pletely interrelated, e.g., a temperature change affects the resistivity and viscosity of the cathode film, the ionization constant of eomplex com- pounds, the hydration and mobility of ions the cathode efficiency, which variables may have conflicting effects on metal distribution and the net effect of their interaction is unpredictable, point on and Throwing Power “Throwing power” is a term invented to give a name to a phenomenon. [t was observed that there was usually a disparity between the pr mary current distribution and the metal distr bution, and that the degree of disparity ap- peared to vary from solution to solution, In their classic paper on the subject, Haring and Blum® defined throwing power as a number derived from the deviation of the actual! metal distribu- tion from the primary current distribution ‘They considered it a property of the solution, which it is not,* and measured it in the now familiar throwing power box. Numerous re- searches followed along the same “The concept of throwing power may properly be considered as deseribing a property of a solution, but any numerical value assigned to it has no meaning outside the apparatus in which it was measured. The throwing power number, however defined, is not a useful property as is conductivity, for example, in that no calculations can be based upon it in any practical case,lines, and many different ways of expressing throwing power as a number were developed. As practical tools these numbers, however de- fined, are useless since they apply only to the particular shape and size of box used in the investigation, and there are other limitations and objections", This should now be obvi- ous from what has been said in the preceding section, because throwing power in the case of a practical plating job actually combines the effects of the distorting variables producing secondary current distribution from the pri- mary with the current density-cathode effi- ciency relationship. In so doing. it absorbs all the unpredictable relationships of all these var- ples and their effect on the particular elec field under consideration. It has been previously stated that the second- ary current distribution is always somewhat better than the primary distribution, Whether the metal distribution is also better, i-e., positive throwing power as defined by Haringand Blum, depends entirely on the slope of the cathode efficiency-current density curve between the sities in question. [f the slope is current dei negative (efficiency decreasing with increasing. current density), the metal distribution will be even better than the secondary current distri- bution. If the slope is small and positive, the secondary current distribution, and may or may not be better than the primary current distri- a chromium bath, the metal distribution virtually certain to be poorer than the primary current distribution. About all that is practically useful in the throwing power concept is what every plater knows, namely, that the chromic acid bath has miserable “throw”; other acid baths can be expected to throw somewhat better but still not too well: a cyanide bath usually throws quite well, alkaline tin and tin alloy baths are about the best Illustrating the effect of geometry on throw- ing power, Graham*™ and co-workers first made the surprising observation that in micro-pores, acid copper, nickel and even chromium could fill the pores completely, but that they were never filled by deposits from eyanide baths. Th work was confirmed and extended by Rein- hard and Foulke and Kardos™ and elegantiy explained by Kardos'*. The latter showed thai when the dimensions of a recess approached the order of magnitude of the thickness of the CURRENT AND METAL DISTRIBUTION 469 cathode film, some unusual effects will be ob- tained, including even a complete reversal of the usual order of throwing power of various types of bath. Control of Throwing Power After all that has been said, it may seem strange to suggest control of throwing power. Although no rules are generally applicable, it is still possible to exert a degree of control over throwing power, but in an empirical fashion only. Such measures should be undertaken only after all obvious and practical methods of im- proving the primary current distribution have been exhausted to no avail. In spite of many theoretical objections to it, the cavity seale of ‘an*! is probably as practical a tool as any. Using a sample of the process bath in an experimental tank, the effect of agitation, temperature and bath composition variables can be studied. A change that produces a distinct improvement, as measured on the eavity scale, will probubly produce a somewhat similar improvement in production. The cavity scale employed should be one of the coarser scales suggested by Pan, as the finer scales tend to show capricious dif- ferences that are misteading. To obtain a mean- ingful improvement in produetion runs, the im- provement in throwing power must be very marked. Also, it is important to note that for this purpose, visual observation of the throw into the eavities at varying depths is meaningless. ‘The actual thickness must be measured; other wise the scale is only a measure of covering power (see below). The following example is actually a matter of controlling the primary current distribution rather than the throwing power, but it well illustrates how dependent throwing power is on the geometry, if the throwing power is measured on a particular workpiece in a tank instead of in a box. Shaefer and Pochapsky" have shown the effect of the spacing of parts over the rack on the current distribution in different solutions. If parts with central recesses are widely spaced on the rack in a solution of poor throwing power such as nickel, the edges will draw excessive current, thus distorting the electric field some- at as shown in Fig. 9a. By moving the pieces ogether (Fig. 9b), the equipotential line: ‘avoring deposition s than the arrange- become more nearly planar, ve metal in the cavities neni of Fig. 9a An interesting illustration of the effeetof these factors in a zine plating solution was developedTh] pi Hp ie Ue (b) Fic, 9, Effect of spacing of parts on a rack on the equipotential lines, by Swalheim and Jackson", Using panels plated ina Hull cell, the expected thickness was caleu- lated, and the actual thickness measured. The were expressed in terms of the apparent solution efficiency, although they actually com- bine the effects of the current density/efficieney curve, and the eurrent density/polarization curve. The figures obtained can be summarized: results ‘Theoretical C.D. Apparent Eftieieney 8 Ajdm* 48% 4 A/dm (40 A/ 70% fe) 2 A/dm* (20 A/ 100% ft) 05 A/dm? (5 A/fe) 137% It is important to point out that this effect can be highly variable. Aside from the effects of variation in solution composition, temperature and agitation, the final steady state of the sys tem, and therefore the magnitude of the change in plate distribution, is a function of the average current density. Had the panels been run at different applied currents, the results would have been somewhat different in magnitude, although, in general, the results would be the same. Experienced platers often manipulate solu- tion compositions to alter either the polarization or efficiency relationships to improve throwing power. Thus in cyanide zines, it is quite possible to improve throwing power at the expense of efficiency, or improve efficiency at the expense of throwing power. Even in baths with high efficiencies, and a relatively flat current density/efficiency curve, control of the current dens tion curve y/ pola} can result in an improvement of throwing power. Many of the newer bright plating s tems take advantage of this approach. Some sacrifice in the maximum allowable current density generally will have to be made in order to accomplish this, however. Barrel plating represents a special case of controlled geometry. Rather than measuring throwing power, the spread of observed thick. nesses around the nominal thickness is consid- ered. Variables include the dimension of the arrel, the speed of rotation of the barrel, the method of contacting the parts, and the compo- ition characteristies of the plating solution. In for the American Electroplaters So- ciety research program, Craig and Harr estab- lished the effect of some of these variables.* The spread in general follows the general bell curve for distribution. However, the spread factors for a6 X 6 in. barrel average 55% larger than those tor a 4 X 6 in. barrel at the same rotational speed. ‘Thus it appears that the spread factor is almost directly proportional to the barre! diameter. The effect of rotational speed is related to the barrel geometry combination of barrel geometry and rotational speed that determines the mixing of the load, and therefore the spread factor. For loads that slide easily and mix properly, the spread is approximately inversely proportional to the square root of the rotational speed. Parts which tangle or nest can produce gross deviations in the spread factor, since mixing will be nonuni- form. This problem often can be corrected by changing the method of contacting the load to produce better mixing: e.g., changing from a dangler contact to a bar contact. work don also of course ‘ince it is the Covering Power One aspect of metal distribution has to do with the ability of a bath to deposit metal at very low current densities, as in deep eavities or holes. This is termed “covering power” and is best demonstrated by the cavity scale of Pan". The covering power is governed first by the bath composition, which determines the decompos tion potential, i.e., the lowest voltage at which metal can be deposited from the solution, secondly, by the cathode metal and its surface condition, which determines the overvoltage of *Craigand Harr, AES Research Projeets #34 and #14. Reports available from AES, 1201 Louisiana Ave. Winter Park, Fla, 32789,metal deposition, ie., the voltage in excess of the decomposition voltage necessary to produce discernible deposit. This is quite different from throwing power, which determines how thick the deposit in a recess will be; whereas covering power is con- cerned simply with whether any deposit at all can be obtained in the recess. In using the cavity scale to measure relative covering power under different conditions, a simple visual observation suffices to determine the dee pest cavity in which a deposit is obtained Many metals ean be deposited at extremely low current densities, which means that in these the decomposition potential is readily attained and the metal overvoltage is insignif- icant Nickel, and more especialy chromium, have appreciable decomposition potentials; further- more chromium requires a rather high mini- mum current density to produce any deposit, under the most favorable conditions. At least 10 to 12 asf are required to deposit chromium, and the threshold current density is usually much higher. Nickel and chromium are also more apt to be sensitive to the basis metal. Chromium usually covers nickel better than it brass, although the preparation of the brass is an important factor; the co buffed and conventionally cleaned br: poorer than over buffed brass that has simply been degreased. As another example in the author's experience, lead c¢ 's tin much better than it does copper. A cavity ina copper easting that could not be covered at all if plated directly in lead readily accepted a deposit after the piece had been plated in alkaline tin, which com- pletely coated the cavity. The lead “followed” the tin, and a deposit of reasonable thickness could be obtained. A well-known case illustrat- ing this phenomenon is the reluctance of a cast- iron surface to uccept a deposit of zine from the usual cyanide bath; whereas the same casting can readily be plated in other eyanide bat! in an acid zine bath. This is because the hydro- gen overvoltage on east iron is lower than the deposition potential of zine from a cyanide bath; thus under normal conditions only hydrogen is obtained. Special measures" ean be taken to enable a zine deposit to be obtained under such conditions. These involve either raising the hy drogen overvoltage, as by omitting the acid- pickling operation in the preplating treatment, or altering the bath slightly so thata good initial deposit of zine can be obtained by striking at ens ‘age on ismuch CURRENT AND METAL DISTRIBUTION 471 high voltage, i.e., above the deposition potential of zinc, after: which plating can proceed normally. ‘The discussion thus far has been based on theory, which presupposes that all conditions are ideal. Pi ns that all contacts in the electri e perfect; that the tank bus and rack members are adequate to carry the current without appreciable voltage drop: and that the electrol trically isotropic, that is, the conductivity is equal everywhere in the solution, which requires that there be no stratification with respect either to temperature or concentration, A final and very important condition is that all the current must pass through the solution directly from one electrode to the other without following other accidental haphazard paths, or “leaking” out of the system altogether, ie., there must be no stray currents, Since these conditions will normally be met in good plating practice, one may justifiably apply the precepts of this chapter to a practical prob- lem with some confidence. Stray Currents It is appropriate at this point to consider the effects of one form of deviation from the ideal conditions set fort of stray current. ‘Two types of stray current should be recog- nized. In the first, a portion of the current takes some path other than the intended one through the solution, and in the most common ease this is through the tank walls or bottom when an unlined tank is used, or when the lining is perforated in several places. Other than the obvious fact that the desired eurrent distribu- above, namely, the presence tion is upset, there are side effects which may sometimes be more serious. Thus, the tank be- comes in effect a series or intermediate electrode and will tend to plate up on areas near the anode, whereas the areas near the work act as anodes, ‘Phe plating build-up may eventually short the tank ont solidly to one or more anodes and greatly increase the magnitude of the stray current. The seriousness of the anodic tank areas, aside from the effect on current distri- bution, which will depend on the nature of the solution, will usually be detrimental. Another stray current phenomenon of this class is asso- ciated with the placing of metallic elements such as heating coils or thermostat bulbs, etc., in the path of the current where they may act as intermediate anodes with similar results14. Schaefer, R. A., and Mohler, J. B., Trans. Electrochem. Soc., 85, 431-440 (1944). 15. Schaefer, R. A., and Pochapsky, H., Proc, Am. Etectroplaters’ Soe., 88, 155-166 (1951). 16. Krosbein, J.,.J. Electrodepositors’ Teck. Soe., 17, 3-104 (1942), 17. Gardam, G. E., Proc. Am. Electroplaters’ Soe., 27, 16-23 (1939). 18. Watson, and Edwards, J., Trans. Fut. et. in, 34, 167-198 (1957). 19. Barnartt, S., Trans. Electrochem. Soc, 98, 311-317 (1951). 20. Tope, N. A., J. Hlectrodepositors’ Tech. Sot, 7, 3-90 (1932), 21. Burt-Gerrans, J. T., Proc. Am. Blectroplaters’ Soe., 27, (1939). 22. Haring, H nd Blum, W., chem, Soe., 44, 3 3. Heatley, A. H. rans. Blectro- i, 2), ,S.,and Weill, A. D., “Electroplating,” 4th Ed, 1943. 27. Hammond, R. A. F., Treens. Inst 83-105 (1957). 28. Weisselberg, A.,and Staff, Trans. Soe., 90, 235-245 (1946). 29. Unpublished data of author's laboratory. Met. Fin., 34, ‘lectrochem. CURRENT AND METAL DISTRIBUTION 473 30. Pan, L. C., Trans, Electrochem. Soc., 58, 423-434 (1930). 31. Pan, L. C., Metal Ind. (N.Y.), 28, 271-274 (1930). 22. Pinner, R., Electroplating, 7, 9-15, 49-58, 59 Jelinek, R. V.,and David, H. P.,.J. Electrochem, Soe., 104, 279-281 (1957) 35. Hoar, T. P., and Agar, J. N., Dise. Faraday Soc., 1, 159-162 (1947) blotter, M., and Korpiun, J., Trans. Eleetro- chem. Sov., 62, 129 (1932). 37. Graham, A. K., Anderson, E. A., Pinkerton, H. L., and Reinhard, C. E., Plating, 36, 702-709 (1949). 38. Reinhard, C. E., Proc. Am, Electroplater 37, 171-188 (1950), 39. Rousselot, R. H., Metal Finishing, 57, No. 10, 56-61 (1959) Tucker, W. M., and Flint, R. L., Trans. Blectro- hem. Sov., 88, 358 (19.45). 41. Diggin, M. D., Metal Finishing, 41, 277-281 ). selot, R. H., Metal Finishing, 59, No. 3, (1961). 40, theim, D. A. Hull Cell or Quality Plating Wustrated Lecture, American Electroplaters Society.