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ELECTR PL!T"#$
Mordechay Schlesinger, Department of Physics, University of Windsor Windsor, ON N9B 3P , !anada (September, 2002) Electroplating has, over recent decades, evolved from an art to an exact science. This development is seen as responsible for the ever-increasing number and idening t!pes of applications of this branch of practical science and engineering. Some of the technological areas in hich means and methods of electroplating constitute an essential component are all aspects of electronics" macro and micro, optics, opto-electronics, and sensors of most t!pes, to name onl! a fe . #n addition a number of $e! industries such as the automobile industr! (that uses for example chrome plating to enhance the corrosion resistance of metal parts) adopt the methods even here other methods, such as evaporation, sputtering, chemical vapor deposition (%&') and the li$e are an option. That is so for reasons of econom! and convenience. (! a! of illustration it should be noted that that modern electroplating e)uips the practitioner ith the abilit! to predesign the properties of surfaces and in the case of electroforming those of the hole part. *urthermore, the abilit! to deposit ver! thin multila!ers (less than a millionth of a cm) via electroplating represents !et a ne avenue of producing ne materials.

"ig# $# Schematics of an electrolytic cell for plating metal %M% from a sol&tion of the metal salt %M'%#

Electroplating is often also called +electrodeposition+, and the t o terms are used interchangeabl!. ,s a matter of fact, +electroplating+ can be considered to occur b! the process of electrodeposition. Electrodeposition is the process of producing a coating, usuall! metallic, on a surface b! the action of electric current. The deposition of a metallic coating onto an ob-ect is achieved b! putting a negative charge on the ob-ect to be coated and immersing it into a solution hich contains a salt of the metal to be deposited (in other ords, the ob-ect to be plated is made the cathode of an electrol!tic cell). The metallic ions of the salt carr! a positive charge and are thus attracted to the ob-ect. .hen the! reach the negativel! charged ob-ect (that is to be electroplated), it provides electrons to reduce the positivel! charged ions to metallic form. *igure / is a schematic presentation of an electrol!tic cell for electroplating a metal +0+ from an a)ueous ( ater) solution of metal salt +0,+. To further illustrate the foregoing, let us assume that one has an ob-ect made of one of the common metals, li$e copper, and that it has been properl! pre-cleaned. .e should ant to plate it ith, sa!, nic$el. , ire ill have to be attached to the ob-ect hile the other end of the ire should be attached to the negative pole of a batter! (or a po er suppl!). To the positive pole of the batter! (or po er suppl!) e connect another ire ith its other end connected to a rod made of nic$el. 1ext e fill the cell ith a solution of the metal salt to be plated. #t is possible to use a molten salt and in some not so common cases, such as the deposition of tungsten, that is hat is done. #n most, more common, cases though the salt is simpl! dissolved in ater. #n our present example the nic$el chloride salt dissociates in ater to positivel! charged nic$el cations and negativel! charged chloride anions. ,s the ob-ect to be plated is negativel! charged it attracts the positivel! charged nic$el cations, and electrons flo from the ob-ect to the cations to neutrali2e them (to reduce them) to metallic form. 0ean hile the negativel! charged chloride anions are attracted to the positivel! charged nic$el rod ($no n as the anode of the electrol!tic cell). ,t the anode electrons are removed from the nic$el metal, oxidi2ing it to the nic$el cations. Thus e see that the nic$el dissolves as ions into the solution. That is ho replacement nic$el is supplied to the solution for that hich has been plated out and one retains a solution of nic$el chloride in the cell. 1ic$el chloride is used here to exemplif! the process of electroplating for a number of reasons. *irst among those is simplicit!. #t is not recommended, ho ever, that nic$el be used for, sa!, school science demonstrations because some individuals are )uite allergic to it. .e further do not recommend that chloride salts be used because those are amenable to release chlorine gas. *or school or amateur t!pe demonstration e recommend plating copper coins ith 2inc or nic$el coins ith copper.

%urface preparation
#t is commonl! accepted and often )uoted b! electroplaters that one can ma(e a poor coating perform )ith e*cellent pretreatment, +&t one cannot ma(e an e*cellent coating perform )ith poor pretreatment. Surface pretreatment b! chemical and3or mechanical means is important not onl! in the case of preparations for electroplating but is also re)uired in preparation for painting. #n either of these, methods are designed to ensure good adhesion of the coating or paint to the surface. 0ost (metal) surface treatment and plating operations have three basic steps. Surface cleaning or preparation. 4suall! this includes emplo!ing of solvents, al$aline cleaners, acid cleaners, abrasive materials and3or ater. Surface modification. That includes change in surface attributes, such as application of (metal) la!er(s) and3or hardening. 5insing or other or$-piece finishing operations to produce3obtain the final product. Surface cleaning or preparation ill be discussed in more detail. Success of electroplating or surface conversion depends on removing contaminants and films from the substrate. 6rganic and nonmetallic films interfere ith bonding b! causing poor adhesion and even preventing deposition. The surface contamination can be extrinsic, comprised of organic debris and mineral dust from the environment or preceding processes. #t can also be intrinsic, one example being a native oxide la!er. %leaning methods are designed to minimi2e substrate damage hile removing the film or debris. #f a (metal) surface7s chemistr! and processing histor! are $no n one can anticipate cleaning needs and methods. #n practice, extrinsic organic and inorganic soils originate ith processing of the substrate before plating, as ell as from the environment. Specific residues include lubricants, phosphate coating, )uenching oils, rust proofing oils, dra ing compounds, and stamping lubricants. #n short, the mixture of potential contaminants to hich a part is exposed is t!picall! complex. ,gain in case of a metal substrate it must be remembered that all metals form oxide and inorganic films to a degree ith environmental gases and chemicals. Some of these are protective against continuing attac$ such as the aluminum oxide formed on aluminum allo!s (see also anodi,ing). That phenomenon is the reason of the usefulness of aluminum siding on some homes. 6n the other hand, some are nonprotective, such as iron oxide on steel. Some of these films can even be plated directl! ith nic$el over aluminum oxide over aluminum being an example. The cleaning and activation steps must account for the fact that surface oxide re-forms at different rates on different metals. Specificall!, in case of iron or nic$el the oxide re-forms slo l! enough that the part can be transferred from a cleaning solution to a plating bath at a normal rate. #n case of aluminum or magnesium the oxide re-forms ver! fast such that special processing steps are re)uired to preserve the metal surface hile it is being transferred to electroplating. %leaning processes are based on t o approaches. #n ph!sical cleaning, mechanical energ! is introduced to release both extrinsic and intrinsic contaminants from the (metal) surface. Examples are ultrasonic agitation and brush abrasion. #n chemical cleaning contaminant films are removed b! active materials, dissolved or emulsified in the cleaning solution. Extrinsic contaminants are removed ith surface-active chemicals hile the chemical energies involved are modest. #ntrinsic films are removed ith aggressive chemicals that dissolve the contaminant and often react ith the surface (metal) itself. The energ! involved in surface preparation is substantial.

&eposition
(! no it should be evident that electrodeposition or electroplating should be defined as the process in hich the deposit of a (usuall!) thin la!er (of metal) is formed +electrol!ticall!+ upon a substrate (that is often, but not al a!s, also a metal). The purpose of such process ma! be to enhance or change the substrate7s appearance and3or attributes (such as corrosion resistance). Examples are the deposition of gold or silver on -e elr! and utensils, and the deposition of

chrome on automobile parts. Electroplating is performed in a li)uid solution called an electrol!te, other ise referred to as the +plating bath+. The bath is a speciall! designed chemical solution that contains the desired metal (such as gold, copper, or nic$el) dissolved in a form of submicroscopic metallic particles (positivel! charged ions). #n addition, various substances (additives) are introduced in the bath to obtain smooth and bright deposits. The ob-ect that is to be plated is submerged into the electrol!te (plating bath). 8laced usuall! at the center of the bath, the ob-ect that is to be plated acts as a negativel! charged cathode. The positivel! charged anode(s) completes the electric circuit9 those ma! be at opposite edges of the plating tan$, thus causing film deposit on both sides of the cathode. , po er source in the form of a batter! or rectifier ( hich converts ac electricit! to regulated lo voltage dc current) is providing the necessar! current. This t!pe of circuit arrangement directs electrons (negative charge carriers) into a path from the po er suppl! (rectifier) to the cathode (the ob-ect to be plated). 1o , in the bath the electric current is carried largel! b! the positivel! charged ions from the anode(s) to ard the negativel! charged cathode. This movement ma$es the metal ions in the bath to migrate to ard extra electrons that are located at or near the cathode7s surface outer la!er. *inall!, b! a! of electrol!sis the metal ions are removed from the solution and are deposited on the surface of the ob-ect as a thin la!er. #t is this process to hich e refer as +electrodeposition+. *rom the above it ould appear that the thic$ness of the electroplated la!er on the substrate is determined b! the time duration of the plating. #n other ords, the longer time the ob-ect remains in the operating plating bath the thic$er the resulting electroplated la!er ill be. T!picall!, la!er thic$nesses ma! var! from 0./ to :0 microns (micron ; one millionth of a meter), though nothing prevents the deposition of thic$er or thinner la!ers, as desired. The geometric shape and contour of an ob-ect to be plated affects the thic$ness of the deposited la!er. #n general, ob-ects ith sharp corners and features ill tend to have thic$er deposits on the outside corners and thinner ones in the recessed areas. The cause of this difference in the resulting la!er thic$nesses is that dc current flo s more densel! to sharp edges than to the less accessible recessed areas, in other ords, the current distribution is not uniform. (,nother, more accurate, explanation of this phenomenon involves the geometr! of the electric field lines that exist bet een cathode and anode in the solution). #n practice, an item such as, sa!, a atch or similar item ith sharp faceted corners are difficult (almost impossible, actuall!) to plate uniforml!. ,ccording to *arada!7s la the overall amount of chemical change produced b! an! given )uantit! of electricit! can be exactl! accounted for. Thus e define the current efficienc! as the ratio bet een the actual amount of metal deposited to that expected theoreticall! from *arada!7s la . #n other ords, the ratio of the eight of metal actuall! deposited to the eight that ould have resulted if all the current had been used for depositing is called the cathode efficienc!, and it is desirable to $eep it as close to /00< as possible.

Electrodeposition or electrochemical deposition (of metals or allo!s) involves the reduction of metal ions from a)ueous, organic, or fused salt electrol!tes. #n it7s simplest form the reaction in a)ueous medium at the cathode follo s the e)uation =/> 0?n ? ne- ;;@ 0

ith a corresponding anodic reaction. The anode material can either be the metal to be deposited (in this case the electrode reaction is electrodissolution that continuousl! supplies the metal ions) or the anode can be an inert material and the anodic reaction is ox!gen evolution (in this case the plating solution is eventuall! depleted of metal ions). The deposition ma!, in principle, be accomplished via t o different paths"

,n electrodeposition process in hich electrons are provided b! an external po er suppl!. ,n electroless (autocatal!tic) deposition process in hich a reducing agent in solution is the electron source.

The deposition reaction presented in E)uation =/> is a reaction of charged particles at the interface bet een a solid (metal) electrode and a li)uid solution. The t o t!pes of charged particles that can cross the interface are metal ions +0?n+ and electrons +e-+. The deposition reaction involves four t!pes of issues. The! are"

0etal-solution interface as the locus of the deposition process. Ainetics and mechanism of the deposition process. 1ucleation and gro th process of the metal lattice (0 lattice). Structure and properties of the deposits.

The reduction of a metal, hich occurs during the plating process, has been generali2ed as E)uation =/> for a single metallic ion. 6bviousl!, to reduce one mole of a given metal +n+ moles of electrons are re)uired. That is, the total cathodic charge used in the deposition +B+ (coulomb) is the product of the number of gram moles of the metal deposited +m+, the number of electrons ta$ing part in the reduction +n+, ,vogadro7s number +1 a+ (the number of atoms in a mole), and the electrical charge per electron +Be+ (coulomb). Thus, the follo ing e)uation gives the charge re)uired to reduce +m+ mole of metal" =2> B ; m n 1a Be 1o , the product of the last t o terms in this e)uation is the +*arada! constant+ +*+. Therefore, the number of moles of metal reduced b! charge +B+ can be obtained as" =:> m ; B 3 (n *) 6n the other hand, the total charge used in the deposition can be obtained as the product of the current +#+ (ampere) and the time of deposition +t+ (second) if the deposition current is held constant. 6r, if the current varies during the deposition"

=C> So, the number of moles deposited can be calculated as"

=D> The eight of the deposit + + (gram) can no be obtained b! multipl!ing E)uation =D> ith the atomic eight +0 + of the deposited metal. *inall!, to calculate the thic$ness of the deposit, e have to use the densit! of the metal +'+ (gram3cm:)" =E> ' ; 3&; 3 (, T)

here +&+ is the volume of the deposited metal in cm:, +,+ is the area of the deposit in cm2, and +T+ is its thic$ness in cm. Solving for thic$ness, using E)uations =D> and =E> e have the useful practical expression"

=F> ,s mentioned above, if the current as held constant during the deposition, the integral in E)uation =F>, can be replaced b! the simple product of current and time +"'t(.