120007747_E-ECHP_00_00_R1_072205

1
2
Electroplating
3 E
4
Helen H. Lou
5
Department of Chemical Engineering, Lamar University, Beaumont, Texas, U.S.A.
6
7 Yinlun Huang
8 Department of Chemical Engineering and Materials Science, Wayne State University,
9 Detroit, Michigan, U.S.A.
10
11
12
13
14 INTRODUCTION and then back to the cathode constitutes the current
15 in the external circuit. The metallic ions of the salt in
16 Electroplating is an electrodeposition process for the electrolyte carry a positive charge and are thus
17 producing a dense, uniform, and adherent coating, attracted to the cathode. When they reach the nega-
18 usually of metal or alloys, upon a surface by the act tively charged workpiece, it provides electrons to
19 of electric current.[1] The coating produced is usually reduce those positively charged ions to metallic form,
20 for decorative and=or protective purposes, or enhan- and then the metal atoms will be deposited onto the
21 cing specific properties of the surface. The surface surface of the negatively charged workpiece.
22 can be conductors, such as metal, or nonconductors, Fig. 1 illustrates a typical plating unit for plating F1
23 such as plastics. Electroplating products are widely copper from a solution of the metal salt copper sulfate
24 used for many industries, such as automobile, ship, (CuSO4). The cathode, which is the workpiece to be
25 air space, machinery, electronics, jewelry, defense, plated, is charged negatively. Some of the electrons
26 and toy industries. The core part of the electroplating from the cathode bar transfer to the positively charged
27 process is the electrolytic cell (electroplating unit). In copper ions (Cu2þ), setting them free as atoms of
28 the electrolytic cell (electroplating unit) a current is copper metal. These copper atoms take their place on
29 passed through a bath containing electrolyte, the anode, the cathode surface and copper plate it. Concurrently,
30 and the cathode. In industrial production, pretreatment the same number of sulfate ions SO42
is discharged
31 and posttreatment steps are usually needed as well. on the copper anodes, thereby completing the electrical
32 circuit. In so doing, they form a new quantity of copper
33 sulfate that dissolves in the solution and restores it to
34 its original composition. This procedure is typical of
35 BACKGROUND ordinary electroplating processes with sacrificial
36 anodes; the current deposits a given amount of metal
37 The workpiece to be plated is the cathode (negative on the cathode and the anode dissolves to the same
38 terminal). The anode, however, can be one of the two extent (of the same electrical charge), maintaining the
39 types: sacrificial anode (dissolvable anode) and perma- solution more or less uniformly.
40 nent anode (inert anode).[2] The sacrificial anodes are
41 made of the metal that is to be deposited. The perma-
42 nent anodes can only complete the electrical circuit,
43 but cannot provide a source of fresh metal to replace ELECTROCHEMISTRY FUNDAMENTALS
44 what has been removed from the solution by deposi-
45 tion at the cathode. Platinum and carbon are usually When a direct electric current passes through an
46 used as inert anodes. electrolyte, chemical reactions take place at the con-
47 Electrolyte is the electrical conductor in which tacts between the circuit and the solution. This process
48 current is carried by ions rather than by free electrons is called electrolysis. Electrolysis takes place in an
49 (as in a metal). Electrolyte completes an electric circuit electrolytic cell. Electroplating is one specific type of
50 between two electrodes. Upon application of electric electrolysis. Besides electroplating, electrolysis has
51 current, the positive ions in the electrolyte will move also been widely used for preparation of halogens and
52 toward the cathode and the negatively charged ions notably chlorine, and refining of metals, such as copper
53 toward the anode. This migration of ions through the and zinc. Understanding the electrochemical principles
54 electrolyte constitutes the electric current in that part of electrodeposition is essential to the development
55 of the circuit. The migration of electrons into the of electroplating technologies. Some basic concepts
56 anode through the wiring and an electric generator are presented below.[3]
Encyclopedia of Chemical Processing DOI: 10.1081/E-ECHP-120007747
Copyright # 2006 by Taylor & Francis. All rights reserved. 1
 120007747_E-ECHP_00_00_R1_072205
2 Electroplating

1 Power Supply
2
3
4 _
+
5
6
7
8
9
10
11
12
13

Copper Metal
14 Cu 2+
2
H 2O Cu 2+
2

15
16 Cu 2+
2
, SO42–
2

17 Electrolyte
18 Copper Sulphate Solution
19
20 Cathode Anode
21 Fig. 1 Principle of electroplating.
22
23
24 Oxidation/Reduction the anode. The anode material can be either a sacrifi-
25 cial anode or an inert anode. For the sacrificial anode,
26 In a wider sense, all electron-transfer reactions are the anode reaction is:
27 considered oxidation=reduction. The substance gaining
28 electrons (oxidizing agent, or oxidant) oxidizes the sub- M ! Mnþ þ ne
ð2Þ
29 stance that is losing electrons (reducing agent, or
30 reductant). In the process, the oxidizing agent is itself In this case, the electrode reaction is electrodissolution
31 reduced by the reducing agent. Consequently, the that continuously supplies the metal ions.
32 reduction process is sometimes called electronation,
33 and the oxidation process is called ‘‘de-electronation.’’
34 Because a cathode is attached to the negative pole of Faraday’s Laws of Electrolysis
35 the electric source, it supplies electrons to the electro-
36 lyte. On the contrary, an anode is connected to the In 1833, the English scientist, Michael Faraday, devel-
37 positive pole of the electric source; therefore, it accepts oped Faraday’s laws of electrolysis. Faraday’s first law
38 electrons from the electrolyte. Various reactions take of electrolysis and Faraday’s second law of electrolysis
39 place at the electrodes during electrolysis. In general, state that the amount of a material deposited on an
40 reduction takes place at the cathode, and oxidation electrode is proportional to the amount of electricity
41 takes place at the anode. used. The amount of different substances liberated by
42 a given quantity of electricity is proportional to their
43 electrochemical equivalent (or chemical equivalent
44 Anode and Cathode Reactions weight).
45 In the SI system, the unit quantity of electricity
46 Electrodeposition or electrochemical deposition (of charge and the unit of electric charge are coulomb
47 metals or alloys) involves the reduction of metal ions (C); one coulomb is equivalent to one ampere flowing
48 from electrolytes. At the cathode, electrons are sup- for one second (1 C ¼ 1 A sec). The electrochemical
49 plied to cations, which migrate to the anode. In its sim- equivalent of an element is its atomic weight divided
50 plest form, the reaction in aqueous medium at the by the valence change involved in the reaction. For
51 cathode follows the equation: example, for the reaction, Fe2þ ! Fe0 , the valence
52 change is 2, and the electrochemical equivalent of iron
53 Mnþ þ ne
! M ð1Þ is 55.85=2 ¼ 27.925 in this reaction. Depending on the
54 specific reaction, one element may have different
55 with a corresponding anode reaction. At the anode, equivalent weights, although it has only one atomic
56 electrons are supplied to the anions, which migrate to weight.
 120007747_E-ECHP_00_00_R1_072205
Electroplating 3

1 In detail, to reduce one mole of a given metal from a Current Efficiency, Current Density,
2 metal ion with the valence charge of nþ, n moles of and Current Distribution
3 electrons are required. That is, the total cathodic E
4 charge used in the deposition, Q(C), is the product of Faraday’s laws give theoretical prediction of electrode-
5 the number of gram moles of the metal deposited, m, position in an ideal situation. In a real application, many
6 the number of electrons taking part in the reduction, factors influence the coating quantity and quality.[4]
7 n, Avogadro’s number, Na (the number of atoms in a
8 mole), and the electrical charge per electron, Qe(C). Current efficiency
9 Thus, the following equation gives the charge required
10 to reduce m moles of metal: It is stated in Faraday’s laws that the amount of
11 chemical charge at an electrode is exactly proportional
12 Q ¼ mnNa Qe ð3Þ to the total quantity of electricity passing. However, if
13 several reactions take place simultaneously at the elec-
14 The product of the last two terms in Eq. (3) is the trode, side reactions may consume the product. There-
15 Faraday constant, F. Therefore, the number of moles fore, inefficiencies may arise from the side reactions
16 of the metal reduced by charge Q can be obtained as: other than the intended reaction taking place at the
17 electrodes. Current efficiency is a fraction, usually
18 Q
m ¼ ð4Þ expressed as a percentage, of the current passing
19 nF through an electrolytic cell (or an electrode) that
20 The Faraday constant represents the amount of accomplishes the desired chemical reaction. Or,
21 electric charge carried by 1 mol, or the Avogadro’s
22 number of electrons. The Faraday constant can be Current efficiency ¼ 100  WAct =WTheo ð9Þ
23 derived by dividing Avogadro’s number, or the num-
24 ber of electrons per mole, by the number of electrons where WAct is the weight of metal deposited or
25 per coulomb. The former is approximately equal to dissolved, and WTheo is the corresponding weight to
26 6.02  1023 and the latter is approximately be expected from Faraday’s laws [Eq. (7)] if there is
27 6.24  1018. Therefore, no side reaction. Note that the cathode efficiency is
28 the current efficiency applied to the cathode reaction,
29 and the anode efficiency is the current efficiency
ð6:02  1023 Þ
30 F ¼ ¼ 9:65  104 C=mol ð5Þ applied to the anode reaction.
ð6:24  1018 Þ
31
32 On the other hand, the total charge used in the Current density
33 deposition can be obtained as the product of the cur-
34 rent, I (A), and the time of deposition, t (sec), if the Current density is defined as current in amperes
35 deposition current is held constant. Or, if the current per unit area of the electrode. It is a very important
36 varies during the deposition, variable in electroplating operations. It affects the
37 character of the deposit and its distribution.
38 Z
39 Q ¼ I dt ð6Þ
Current distribution
40
41 The weight of the deposit, W (g), thus can be The local current density on an electrode is a function
42 obtained by multiplying the number of moles of metal of the position on the electrode surface. The current
43 reduced with the atomic weight, Mw, of the deposited distribution over an electrode surface is complicated.
44 metal: Current will tend to concentrate at edges and points,
45 and unless the resistance of the solution is very low,
Z
46 Mw it will flow to the workpieces near the opposite elec-
47 W ¼ I dt ð7Þ
nF trode more readily than to the more distant work-
48 pieces. It is desired to operate processes with uniform
49 Ideally, the deposition thickness, d (cm), can be current distribution. That is, the current density is
50 solved by: the same at all points on the electrode surface.
51 Z
52 W Mw
d ¼ ¼ I dt ð8Þ
53 rA nFrA Potential Relationships
54
55 where r is the density of the metal (g=cm3) and A is the In electroplating, sufficient voltage should be provided
56 area of deposition (cm2). by the power source. The voltage–current relationship
 120007747_E-ECHP_00_00_R1_072205
4 Electroplating

1 follows Ohm’s law. The concepts of electrode poten- change; a the activity of the metal ion. In approxima-
2 tials, equilibrium electrode potential, overpotential, tion, the concentration of the metal ion can be used
3 and overvoltage are of fundamental importance. instead of the activity.
4 If numerical values are substituted for R and F, and
5 The voltage–current relationship: Ohm’s law T is at 25 C (298 K), and base 10 logarithm is used
6 instead of base e, the Nernst equation can be expressed as:
7 The current is driven by a potential difference, or
8 voltage through the conducting medium, either electro- 0:059
9 lytic or metallic. The voltage necessary to force a given E ¼ E0 þ log a ð13Þ
n
10 current through a conductor is given by Ohm’s law:
11
In the above equation, if a ¼ 1, then E ¼ E0. The
12 E ¼ IR ð10Þ
standard potential of an electrode E0 is the potential of
13
an electrode in contact with a solution of its ions of
14 where E is the voltage (V) and R the resistance of the unit activity. The standard potentials are always
15 conductor (O). expressed against the standard hydrogen electrode,
16
the potential of which is zero by definition. The stan-
17 Electrode potentials dard potentials are a function of temperature; they
18
are usually tabulated for 25 C. Standard electrode
19 The electrode potential is the electrical potential differ- potential is also called normal electrode potential.
20 ence between an electrode and a reference electrode.
21 The absolute potential of an electrode is not directly
22 measurable. Therefore, the electrode potential must Overpotential and overvoltage
23 always be referred to an arbitrary zero point that is
24 defined by the potential of the reference electrode. The equilibrium is dynamic with metal ions being
25 discharged and metal atoms being ionized, but these
26 Equilibrium electrode potential two effects cancel each other and there is no net change
27 in the system. For the realization of metal deposition
28 When a metal is immersed into a solution containing at the cathode and metal dissolution at the anode,
29 ions of that metal, equilibrium is set up between the the system must be moved away from the equilibrium
30 tendency of the metal to enter solution as ions and condition. An external potential must be provided
31 the opposing tendency of the ions to lose their charge for the useful electrode reactions to take place at a
32 and deposit on or in the metal. practical rate; this external potential may have several
33 causes.
34 M $ Mnþ þ ne
ð11Þ Overpotential is the difference in the electrode
35 potential of an electrode between its equilibrium
36 Depending on the conditions of the system, this can potential and its operating potential when a current
37 occur in either direction. At equilibrium, the driving is flowing. The overpotential represents the extra
38 forces for metal ions being discharged and metal atoms energy needed to force the electrode reaction to
39 being ionized are equal. The potential difference proceed at a required rate (or its equivalent current
40 between the metal and the solution phases under these density). Consequently, the operating potential of an
41 conditions is the equilibrium potential difference. anode is always more positive than its equilibrium
42 The equilibrium electrode potential is the electrical potential, while the operating potential of a cathode
43 potential of an electrode measured against a reference is always more negative than its equilibrium potential.
44 electrode when there is no current flowing through the The overpotential increases with increasing current
45 electrode. It is also called open circuit potential (OCP). density. The value of the overpotential also depends
46 The equilibrium potential between a metal and a solu- on the inherent speed of the electrode reaction. A slow
47 tion of its ions is given by the Nernst equation as reaction (with small exchange current density) will
48 follows: require a larger overpotential for a given current den-
49 sity than a fast reaction (with large exchange current
50 RT density). Overpotential is also referred to as polariza-
51 E ¼ E0 þ ln a ð12Þ tion of the electrode.
nF
52 An electrode reaction always occurs in more
53 where E0 is the standard electrode potential, which is a than one elementary step, and there is an overpotential
54 constant characteristic of the material of the electrode; associated with each step. Even for the simplest case,
55 R the gas constant (8.3143 J=k=mol); T the absolute the overpotential is the sum of the concentration
56 temperature (K); F the Faraday constant; n the valence overpotential and the activation overpotential.
 120007747_E-ECHP_00_00_R1_072205
Electroplating 5

1 Overvoltage is the difference between the cell Alkaline Cleaning. Workpieces are immersed in tanks
2 voltage (with a current flowing) and the open-circuit of hot alkaline cleaning solutions to remove dirt and
3 voltage (OCV). The overvoltage represents the extra solid soil. A special type of alkaline cleaning is electro- E
4 energy needed to force the cell reaction to proceed at cleaning. In electrocleaning, the workpiece can be
5 a required rate. Consequently, the cell voltage of an either the cathode (namely direct cleaning) or the
6 electrolytic cell is always more than its OCV, while anode (reverse cleaning). Electrocleaning adds to the
7 the cell voltage of a galvanic cell (e.g., a rechargeable chemical action of the cleaner the mechanical action
8 battery during discharging) is always less than its caused by plentiful gas evolution at the surface of the
9 OCV. Occasionally, it is also referred to as polarization workpiece.
10 of the cell.
11 The overvoltage is the sum of the overpotentials of Acid Cleaning. Acid cleaning can move heavy scale,
12 the two electrodes of the cell and the ohmic loss of the heat-treat scale, oxide, and the like. The most com-
13 cell. Unfortunately, the terms overvoltage and overpo- monly used acids include sulfuric and hydrochloric.
14 tential are sometimes used interchangeably. Pickling can also be combined with current to be more
15 effective.
16
17
SURFACE PREPARATION Mechanical approaches
18
19
Workpieces to be plated may be put through a variety Mechanical preparations include polishing, buffing,
20
of pretreating processes, including surface cleaning, and some variations. Polishing is to remove small
21
surface modification, and rinsing.[4] A schematic flow- amounts of metal by means of abrasives. It produces
22
sheet of a typical electroplating plant, including surface a surface that is free of the larger imperfections left
23
F2 treatment and waste treatment, is depicted in Fig. 2. by grinding, and is a preliminary to buffing. Buffing
24
The purpose of surface pretreatment is to remove is similar to polishing, but uses finer abrasives to
25
contaminants, such as dust and films, from the sub- remove very little metal. Buffing can produce an extre-
26
strate surface. The surface contamination can be mely smooth surface.
27
extrinsic, composed of organic debris and mineral dust
28
from the environment or preceding processes. It can
29
also be intrinsic, such as a native oxide layer. Contami- Surface Modification
30
nants and films interfere with bonding, which can
31
cause poor adhesion and even prevent deposition. Surface modification includes change in surface attri-
32
Therefore, surface pretreatment is important to ensure butes, such as application of (metal) layer(s) and=or
33
plating quality. Most (metal) surface treatment opera- hardening.
34
tions have three basic steps: surface cleaning, surface
35
treatment, and rinsing.
36
Rinsing
37
38
Surface Cleaning In wet plating, when workpieces are transferred from
39
one treating solution to another, or when they leave
40
Cleaning methods should be able to minimize substrate the final treating solution, they carry some of the solu-
41
damage while removing the contaminants, dust, film, tion in which it has been immersed. This solution is
42
and=or debris. Cleaning processes are based on two app- called drag-out. In most cases, this residue solution
43
roaches: chemical approach and mechanical approach. should be removed from the workpieces surface by rin-
44
sing before the workpieces enter the next step in
45
Chemical approaches sequence, or come out of the final processing solution.
46
The dirty rinse water will be sent to the wastewater
47
A chemical approach usually includes solvent degreas- treatment facilities before being discharged to a public
48
ing, alkaline cleaning, (soak cleaning), and acid clean- sewage system.
49
50 ing (acid pickling).
51
52 Solvent Degreasing. Contaminants consist of oils and ELECTROLYTIC METAL DEPOSITION
53 grease of various types, waxes, and miscellaneous
54 organic materials. These contaminants can be removed There are three types of electrolytic metal deposition
55 by appropriate organic solvents, either by dipping the processes: direct current electrodeposition, pulse plat-
56 workpieces in the solvent or by vapor decreasing. ing, and laser-induced metal deposition.[2]
 120007747_E-ECHP_00_00_R1_072205
6 Electroplating

1
Parts Flow
2
3
Alkaline
4 Cleaning
5
6 Neutralization
7 Rinsing
and Precipitation
8
9 Electro-
10 Cleaning
11
12
Rinsing
13
14 Settle
15 Acid
Fresh
16 Water Cleaning
17
18
Rinsing Precipitation
19
20
21 Chromium
Plating Treated
22 Reduction
23 Water
24 (To WWTP)
25 Rinsing Precipitation Sludge
26
27 Chromium
28 Plating
29
30 Off-Site
Rinsing/
31 Treatment/
Drying
32 Disposal
33
34 Fig. 2 Process flowsheet of a typical electroplating plant.
35
36
37
38 Direct Current Electrodeposition will tend to have thicker deposits on the outside
39 corners and thinner ones in the recessed areas. The
40 In the direct current (DC) electrodeposition, the cur- cause of this difference in the resulting layer thickness
41 rent source is. A power source in the form of a battery is that the DC current flows more densely to sharp
42 or rectifier (which converts alternating current electri- edges than to the less accessible recessed areas. In other
43 city to regulated low-voltage DC current) provides words, the current distribution is not uniform. There-
44 the necessary current. fore, a judicial placement of the anode(s) as well as
45 Electroplating is performed in a plating unit. Elec- modifications of the current density are required to
46 trodes, immersed in the electroplating bath (electro- overcome the thickness irregularity effects.
47 lyte), are connected to the output of a DC current
48 source. The workpiece that is to be plated acts as a
49 negatively charged cathode. The positively charged Pulse Plating
50 anode(s) completes the electric circuit. This type of
51 circuit arrangement directs electrons (negative charge Electrodeposition using pulsed currents is known as
52 carriers) into a path from the power supply (rectifier) pulse plating. The pulsed currents can be unipolar
53 to the cathode (the workpiece to be plated). (on–off) or bipolar (current reversal). Pulses can be
54 The geometric shape and contour of a workpiece to used along or be superimposed on a DC feed. By using
55 be plated affect the thickness of the deposited layer. In the bipolar pulse, metal deposition occurs in the catho-
56 general, workpieces with sharp corners and features dic pulse period, with a limited amount of metal being
 120007747_E-ECHP_00_00_R1_072205
Electroplating 7

1 redissolved in the anodic period. This repeated deposi- electrolytic conductance. The conductivity of an
2 tion and partial redissolution could improve the mor- electrolyte is a function of the degree of dissociation,
3 phology and the physical properties of the deposit. the mobility of the individual ions, the temperature E
4 and viscosity, and the electrolyte composition.
5
Laser-Induced Metal Deposition
6
7 Covering Power
In laser-induced metal deposition, a focused laser beam
8
is used to accelerate the metal deposition. Experiments Covering power describes the extent to which an elec-
9
have shown that the deposition rate can be increased trodeposition electrolyte can cover the entire surface of
10
by 1000 times. The plating equipment mainly consists a workpiece being plated, with reasonable uniform
11
of a laser head with focusing optics and the electrolytic thickness. Covering power is influenced by the nature
12
cell. The focused laser beam can pass through a hole in of the substrate surface, the electrolyte composition,
13
the anode through the electrolyte and impinge on the the temperature and viscosity, and the current density.
14
cathode surfaces.
15
16 Macrothrowing Power
17
ELECTROLYTE
18 Macrothrowing power predicts the ability of an elec-
19 trolyte to lay down as nearly as possible a uniformly
Different metals may need different types of electro-
20 thick deposit across the surface of a workpiece. A good
lyte. The composition and properties of the electrolyte
21 covering power is a prerequisite for good macrothrow-
is very important for the coating quality.
22 ing power. Other factors that affect macrothrowing
23 power include the current distribution and current den-
24 Types and Components sity, electrolyte composition, electrolytic conductance,
25 and electrolyte agitation.
26 Types of electrolytes include water solutions of acids,
27 bases, or metal salts, certain pure liquids, and molten
28 salts. Gases may act as electrolytes under conditions Microthrowing Power
29 of high temperature or low pressure. In addition to
30 metal salts, electrodeposition electrolytes usually con- Microthrowing power indicates the extent to which
31 tain a number of additives for various purposes. Some metal electrodeposition occurs at the outer plane of
32 agents are used to increase electrolyte conductivity the substrate or at the base of valleys or cracks. Micro-
33 (supporting electolytes). Others may be used for throwing power can be improved by activating the
34 increasing bath stability (stabilizers), activating the surfaces at the base of valleys or cracks to promote
35 surface (surfactants or wetting agents), improving electrodeposition there, while inhibiting the outer
36 leveling or metal distribution (leveling agents), or opti- surfaces by using inhibitors preferentially. In many
37 mizing the chemical, physical, or technology properties cases, microthrowing power is inversely related to
38 of the coating. These coating properties include corro- macrothrowing power.
39 sion resistance, brightness or reflectivity, hardness,
40 mechanical strength, ductility, internal stress, wear
41 resistance, or solderability.[2] TYPES OF ELECTROPLATING PROCESSES
42
43 Depending on the size and geometry of the workpieces
Properties of Electrolyte
44 to be plated, different plating processes, including mass
45 plating, rack plating, continuous plating, and in-line
The properties of electrolyte are usually characterized
46 plating, may be adopted.[2]
by electrolytic conductance, covering power, macro-
47
throwing power, and microthrowing power.[4]
48
49 Mass Plating
50 Electrolytic Conductance
51 Mass plating is used for small workpieces to be plated
52 Electrolytic conductance is different from electrical in large quantities, such as nuts and bolts, but it is not
53 conductance in metal. Electronic conductance is called used for delicate workpieces. The most widely used mass
54 a ‘‘Class I’’ conductor, while electrolytic conductance plating system is called barrel plating, where the work-
55 is a ‘‘Class II’’ conductor. Both inorganic and organic pieces are loaded into a plating barrel. Other mass plating
56 salts, acids or alkalis can be used to increase the containers include plating bells and vibratory units.
 120007747_E-ECHP_00_00_R1_072205
8 Electroplating

1 Rack Plating the surface, such as solderability, wear resistance,

2 reflectivity, and conductivity. Metals for engineering
3 Some workpieces cannot be mass plated because of purpose include precious gold (Au) and silver (Ag),
4 their size, shape, or special features. Rack plating means six platinum metals, tin, and lead (Pb). The six plati-
5 workpieces are mounted on a rack for the appropriate num metals are ruthenium (Ru), rhodium (Rh), palla-
6 pretreatment plating and posttreatments. Racks are dium (Pd), osmium (Os), iridium (Ir), and platinum
7 fixtures suitable for immersion in the plating solution. (Pt). These six metals are noble, i.e., with positive elec-
8 Rack plating is sometimes called batch plating. trode potentials and they are relatively inert.
9
10
Continuous Plating Minor Metal Coating
11
12
Continuous plating means the workpieces to be plated Minor metals here refer to iron (Fe), cobalt (Co), and
13
move continuously passing either one row or between indium (In). They are easily plated but have limited
14
two rows of anodes. Continuous plating is usually used applications in electroplating.
15
for a workpiece of simple and uniform geometry, such
16
as metal strip, wire, and tube.
17 Unusual Metal Coating
18
19 In-Line Plating The unusual metals are rarely electroplated and can be
20 divided into the following categories: 1) easily platable
21 In-line plating is used to integrate the plating and from aqueous solutions but not widely used, such as
22 finishing processes into a main production line. The arsenic (As), antimony (Sb), bismuth (Bi), manganese
23 benefit of in-line plating includes exclusion of pretreat- (Mn), and rhenium (Re); 2) platable from organic elec-
24 ment steps and a significant reduction in material, che- trolyte but not aqueous electrolyte, such as aluminum
25 mical and energy consumption, and waste discharge. (Al); and 3) platable from fused-salt electrolyte but
26 not aqueous electrolyte, including refractory metals
27 (named because of their relatively high melting points),
TYPES OF METAL COATINGS
28 such as titanium (Ti), zirconium (Zr), hafnium (Hf),
29 vanadium (V), niobium (Nb), tantalum (Ta), molybde-
Plating metals can be roughly classified into the follow-
30 num (Mo), and tungsten (W). The periodic table in
ing categories with the typical applications.[4]
31 Fig. 3 shows that the metals that can be electrodepos- F3
32 ited from aqueous solutions are those inside the frame.
33 Sacrificial Coatings
34
Alloy Coatings
35 Sacrificial coatings are primarily used for the protec-
36 tion of the base metal, usually iron and steel. Another
An alloy is a substance that has metallic properties and
37 name for sacrificial coating is anodic coating, because
is composed of two or more chemical elements, at least
38 the metal coatings are anodic to the substrate metal,
one of which is a metal. The elements composing the
39 so the coatings sacrifice themselves to protect the base
alloy are not distinguishable by the unaided eye. Exam-
40 metal from corrosion. Zinc (Zn) and cadmium (Cd)
ples of alloy coating include gold–copper–cadmium,
41 coatings can be used as sacrificial coatings. Because
zinc–cobalt, zinc–iron, zinc–nickle, brass (an alloy of
42 of high toxicity, cadmium plating is now forbidden
copper and zinc), bronze (copper–tin), tin–zinc, tin–
43 by law in many countries.
nickle, and tin–cobalt. Alloy coatings are produced
44
by plating two metals from the same solution.
45
Decorative Protective Coatings
46
47 Multilayered Coatings
Decorative protective coatings are primarily used for
48
adding an attractive appearance to some protective
49 Multilayered coatings are produced by plating differ-
qualities. Metals in this category include copper (Cu),
50 ent metals from the same solution at different poten-
nickle (Ni), chromium (Cr), zinc (Zn), and tin (Sn).
51 tials. A pulse train-shaped potential is enforced,
52 resulting in the multilayer deposition. For example,
53 Engineering Coatings multilayered coatings based on copper, nickle, chro-
54 mium, in that order, can be applied to either metal
55 Engineering coatings (sometimes called functional or plastic components for visual appearance, corrosion
56 coatings) are used for enhancing specific properties of and wear resistance, and weight saving.
 120007747_E-ECHP_00_00_R1_072205
Electroplating 9

1 Group**
2
3 Period 1 18 E
4 IA VIIIA

5 1A 8A
1 2 13 14 15 16 17 2
6 1 H IIA IIIA IVA VA VIA VIIA He
7 1.0088 2A 3A 4A 5A 6A 7A 4.003
8 3 4 5 6 7 8 9 10

9 2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
10
11 11 12 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

12 3 Na Mg IIIB IVB VB VIB VIIB ------- VIII ---- IB IIB Al Si P S Cl Ar

22.99 24.31 3B 4B 5B 6B 7B --- 1B 2B 26.98 28.09 30.97 32.07 35.45 39.95
13 ------- 8 -------
14 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
15 4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
16 39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.47 58.69 63.55 65.39 69.72 72.59 74.92 78.96 79.90 83.80
17 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
18 5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
19
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
20
21
6 Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 190.2 195.1 197.0 200.5 204.4 207.2 209.0 (210) (210) (222)
22 87 88 89 104 105 106 107 108 109 110 111 112 114 116 118
23 7 Fr Ra Ac~ Rf Db Sg Bh Hs Mt --- --- --- --- --- ---
24 (223) (226) (227) (257) (260) (263) (262) (265) (266) () () () () () ()

25
26 58 59 60 61 62 63 64 65 66 67 68 69 70 71
27 Lanthanide Series* Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
28 140.1 140.9 144.2 (147) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
29 90 91 92 93 94 95 96 97 98 99 100 101 102 103

30 Actinide Series~ Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 (231) (238) (237) (242) (243) (247) (247) (249) (254) (253) (256) (254) (257)
31
32
33 Fig. 3 Periodic table (metals inside the frame can be electrodeposited from aqueous solutions). (View this art in color at
34 www.dekker.com.)
35
36 Composite Coatings salts. The chromate coatings can be applied to alumi-
37 num, zinc, cadmium, and magnesium. The coatings
38 Composite materials can be defined as coatings con- usually have good atmospheric corrosion resistance.
39 sisting of minute second-phase particles dispersed Chromate coatings are widely used in protecting common
40 throughout a metal matrix. The size of the second household products, such as screws, hinges, and many
41 phase particles may range from 10 mm down to nanoscale hardware items with the yellow-brown appearance.
42 and the particles can be inorganic, organic, or occasion-
43 ally metallic. The presence of fine particles in a metal
44 matrix generally improves its mechanical and chemical Anodized Coatings
45 properties, resulting in a wide range of applications. Com-
46 posite coatings with an electrodeposited metal matrix Anodizing is produced by electrochemical conversion.
47 and nonmetallic inclusions have excellent wear resistance In an anodizing process, the metal workpiece to be
48 and permit emergency dry running of machinery. plated is the anode in a suitable electrolyte. With the
49 electric current passing through the electrolyte, the
50 metal surface is converted to a form of its oxide. An
51 Conversion Coatings anodizing process is usually used on aluminum for pro-
52 tection and cosmetic purposes. The electrolyte provides
53 Conversion coatings are formed by a reaction of the oxygen ions that react with metal ions to form the
54 metal on the surface of the substrate with a solution.[5] oxide, and hydrogen is released at the metal or carbon
55 For example, chromate coatings are formed by the reac- cathode. Anodizing differs from electroplating in two
56 tion of water solutions of chromic acid or chromium aspects. In electroplating, the workpiece to be plated
 120007747_E-ECHP_00_00_R1_072205
10 Electroplating

1 is the cathode, and the metallic coatings are deposited Electroforming

2 on the workpiece. In anodizing, the workpiece is the
3 anode, and its surface is converted to a form of its oxide. Electroforming is to produce or reproduce a metal
4 workpiece by electrodeposition in a plating bath over
5 a base form (mold) or mandrel, which is subsequently
6 RELATED PROCESSES removed. In some cases, the mandrel or mold may
7 remain within the finished metal workpiece. A mandrel
8 The related processes for metal deposition include is a form used as a cathode in electroplating.
9 electroless deposition, immersion plating, and electro- The advantage of the process is that it faithfully
10 forming.[4] They follow the basic principles of electro- reproduces a form of mandrel exactly, to within one
11 chemistry. micrometer, without shrinkage and distortion asso-
12 ciated with other metal forming techniques, such as
13 casting, stamping, and drawing. Because the mandrel
14 Electroless Deposition (Autocatalytic Plating) is machined as an outside surface, close dimensional
15 tolerances and high surface finishes can be held and
16 A special type of electroplating is called electroless maintained on complex interior configurations. The
17 deposition, autocatalytic plating, or ‘‘chemical deposi- disadvantage of electroforming includes slow produc-
18 tion.’’ In electroless plating, there is no external power tion, relatively high cost, design limitations of the geo-
19 source. The deposited metal is reduced from its ionic state metry, and the separation of workpieces from the mold
20 in solution by a chemical reducing agent. The reducing or mandrel.
21 agent supplies the electrons for the following reaction:
22
23 Mnþ þ ne
! M ð14Þ
CONCLUSIONS
24
This reaction takes place only on a catalytic surface.
25 The electroplating industry has been experiencing
Therefore, once deposition is initiated, the metal
26 continuous innovations and also facing significant
deposited must itself be catalytic for the deposition
27 challenges from economic and environmental perspec-
to continue.
28 tives. The purpose of electroplating is to produce a
Not all metals can be plated autocatalytically. The
29 qualified coating with the desirable attributes. Based
reducing agents are usually more expensive electron
30 on the specifications of the coating and the substrate,
sources as compared with the electric current. The major
31 one may select a specific electroplating process for a
advantages of electroless deposition are as follows:
32 given application.
33
1. It can be used to deposit metal on nonconduc-
34
tive surfaces, such as plastics, glass, or ceramics.
35
Some proper pretreatment steps are needed to ACKNOWLEDGMENTS
36
activate these surfaces. The metallizing of
37
printed circuit board is one such example. This work is in part supported by NSF (DMI-0225843
38
2. The throwing power is perfect. Deposits are laid and DMI-0225844) and EPA (R824732-01).
39
down on the surface with no excess buildup on
40
projections or edges.
41
42 REFERENCES
43 Immersion Plating
44 1. ASTM International. In B374-96 (2003) Standard
45 Immersion plating is the deposition of a metallic coat- Terminology Relating to Electroplating; ASTM
46 ing on a substrate by chemical replacement from a International: West Conshohocken, PA, 2003.
47 solution of salt of the coating metal. It requires no elec- 2. Kanani, N. Electroplating: Basic Principles,
48 tric circuitry or source of power, but it differs from Processes and Practice; Elsevier Advanced Tech-
49 autocatalytic plating in not requiring a chemical redu- nology: Oxford, U.K., 2004.
50 cing agent to reduce the metal ions to metal. Immer- 3. Schlesinger, M. Electroplating. In Electrochemistry
51 sion deposition stops when the substrate is Encyclopedia; http:==electrochem.cwru.edu=ed=
52 completely covered by a layer of coating. encycl= (accessed December 2004).
53 The major advantages of immersion plating include 4. Lowenheim, F.A. Electroplating; State Mutual
54 simplicity, minor capital expense, and the ability to Book & Periodical Service: New York, 1997.
55 deposit in recesses and on the inside of the tubing. 5. http:==www.efunda.com=processes=surface=
56 But, the applicability of immersion plating is limited. conversion_coatings.cfm (accessed Dec 2004).