Recent Trends of Electrodeposition of Some Selected Metals in Aqueous and Non-aqueous Media

by

Dr. Azza El-Sayed El-Shenawy

Lecturer of Physical Chemistry Chemistry Department, Faculty of Science (Girls) Al-Azhar University Presentation Jan, 2013

ecturer

Electrodeposition
Electrodeposition is the process of coating a thin layer of one metal on top of a different metal to modify its surface properties.
Objectives:

To protect and enhance the functionality of parts used in many diverse industries. Corrosion resistance. To reduce friction. To improve heat tolerance.
Applications:

Automotive parts. Printed circuitry and electrical contacts. General engineering components. Gold-silver wares and jewelry. Decorative wares. Home appliances. Special technologies such as electroless depostion,

Classification of corrosion prevention methods

An example of electroplating of Nickel

Corrosion Prevention By Change of metal Change of environment

sign improvement

V
Creation Of Surface Compressive Stresses

Change of electrode potential

Use of coatings

Ni

. Change of Operating Variables 2+

Ni

Cathodic protection Ni2+

Metallic coatings

Ni2+
Elimination Of Tensile Stresses Use of Inhibitors

Anodic protection

Ni

Non- metallic coatings

Change of Micro Structure

Removal of Corrosive Constituent

Anode (+ve electrode) Ni(s) Ni2+(aq)

Change Of Composition

Cathode (-ve electrode) Ni2+(aq) + 2e- Ni(s)

2e-

Influencing Factors in Electrodeposition

The morphology and composition of electrodeposition of metals depend on: 1- Current density. 2- Concentration of electrolyte. 3- Temperature. 4- Presence of colloidal matter. 5- pH of the solution. 6- The metal nature. 7- Solution composition.

Influencing Factors in Electrodeposition

(1) Current density

At very high current density At high current density the crystals tend to grow outward towards regions of higher concentration; the deposits, then is "treed" . porous and spongy deposits are obtained

At low current density a coarse crystalline deposit is precipitated

(2) Concentration of electrolyte

Increase of concentration of electrolyte, makes the solution conductive and greater current will be passed. The influence of concentration on the rate of nuclei formations is uncertain.

(3) Temperature Increase of temperature favours diffusion of ions to cathode. Also the hydrogen overvoltage is decreased, therefore simultaneous discharge of hydrogen metal ions will occur at cathode. (4) Presence of colloidal matters

(5) pH of the solution

The presence of small amount of colloidal metal or of certain organic compounds, often result in the production of smooth, fine grained and microcrystalline deposit. Among the material used as addition agents are gelatin, agar-agar, glue, various gums, alkaloids, dyestuffs, sugars and camphor. The action is often specific and depend on the nature of the metal and nature of electrolyte.
The preceding conventional classification of plating baths emphasize the importance of pH measurements in the control of plating operations. Recent studies have shown that the grain size, hardness, and oxide content of nickel deposits from a given bath may reach minimum values at a certain pH and increase with a pH change in either direction.

Influencing Factors in Electrodeposition

(6) Metal Nature

Metal Property Hg, Ag, T1, Pb, Bi, Cu, Zn n x 102 Co, Fe, Ni n x 101 n x 108-n x109

Cd, Sn
Overpotential, V Exchange current, 0 to n x 103

n x101-n x103 n x 104- n x

A/cm2
Mean linear dimensions of >103

105
103 to 104 <105

grains, cm

Influencing Factors in Electrodeposition

Nature of the salt anion: Usually the overpotential decreases from anion to anion in the following order: PO43-, NO3- , SO42-, ClO4- , NH2SO3-, Cl- , Br- , I The presence of different cations in the solution: - The metal overpotential rises with increasing concentration of hydrogen ions. - The overpotential increases considerably in the presence of surfaceactive cations of the tetrasubstituted ammonium type. The presence of impurities The addition of traces of molecular, ionic substances and predominantly organic substances.
(7) Solution composition

Effects of Overpotential on Surface Morphology of Sn

Smooth Sn

compact
Potential (V)

dendrite
Powdery Sn

Powdery structure is obtained at high cathodic overpotential.

powdery

Cathodic current density (A/cm2)

Leveling and Throwing Power

Throwing power:
deposit

- The ability of electroplating solution to deposit almost equal thickness on both recessed and prominent areas, since it indicates the degree of plate uniforming (thickness distrbution) over the substrate surface. - Ni plating (also other acidic Cu and Zn baths) show poor throwing power. If the C.E. values are close to 100 % at low and high current density values, then the macroscopic irregularities on the cathode will lead to non-uniform deposits. - Alkaline baths have better throwing power, since the metal ions are present as complex ions.

substrate

Leveling and Throwing Power

Throwing power: - The ability of electroplating solution to deposit almost equal thickness on both recessed and prominent areas. - Ni plating (also other acidic Cu and Zn baths) show poor throwing power. If the C.E. values are close to 100 % at low and high current density values, then the macroscopic irregularities on the cathode will lead to non-uniform deposits. - Alkaline baths have better throwing power, since the metal ions are present as complex ions. Leveling: - The ability of electroplating solution to fill in defects and scratches on the surface preferentially is called leveling.
deposit substrate

Throwing Power of various electroplating

Solution Throwing Power (%)

i) Alkaline stannate & zincate solutions

50

ii) Most other cyanide solutions

25 - 50

iii) Most acid solutions

0 - 25

iv) Chromium plating

- 100 - 0

Leveling and Throwing Power

Leveling: - The ability of electroplating solution to fill in defects and scratches on the surface preferentially is called leveling. Leveling is important in metal finishing industry and in electronic industry for deposition through masks. Types of Leveling: Leveling can be achieved in solutions either in the absence or presence of leveling agents. There are two types of leveling: 1. Geometric leveling in the absence of additives. 2. True or electrochemical leveling in the presence of additives.

deposit substrate

A classical solution of an lectrolyte is obtained by issolution of a salt in a molecular solvent. uch as system consists of olvated ions, their charged or eutral combinations and .

On the other hand, a salt may melted down (liquified) by provi heat to the system, to cou balance the salt lattice energy. Such a system called molten sa ionic liquid consists of ions and combinations and is .

Aqueous media

Aqueous media
Aqueous electrolytes are the most commonly used media in electrodepostion and they have significant limitations such as narrow potential windows, gas evolution, necessity for comlexing agents and environmental impact, since all of the water must eventually be returned to the water course.
Advantages of aqueous depostion: Lower costs Thicker coatings Coating complex shapes Control and modification of deposit properties Control of residual stress

Chromium electrodeposition from Cr(III) aqueous solutions

The electrolytic deposition of chromium is widely used industrially for producing wear-resistant and protective coatings with specific mechanical properties, such as high hardness, or as a finishing process for surface decoration

Moreover, the use of formic acid as a specific complexing agent for Cr (III) enables us to identify two optimum bath compositions to obtain chromium coating from Cr(III) aqueous solutions: i) a bath composition that ensures good results concerning decorative chromium plating was developed (solution C2), although the process has a very low faradic efficiency; ii) a solution capable of depositing hard chromium from trivalent chromium aqueous solutions, with high faradic efficiency, was developed (C5 solution) although, despite the testing of various additives, it was not possible to eliminate completely the defects found in these deposits, in particular the high surface roughness.
solution Composition CrCl3 C2 C5 C5 100 200 200 H2SO4 0 0.37 0.37 HCOOH 30 30 30 Deposition time\ min. 60 60 15 Working conditions i= 0.6 A/cm2 i= 0.6 A/cm2 i= 0.6 A/cm2 (pulsed current) Section microstructure Fig 7 a Fig 7b Fig 7 a

Non-aqueous media

 Electrodeposition in non-aqueous electrolytes (such as conventional organic solvents, ionic liquids and molten salts) are the water and air stability and the wide electrochemical window of these media. The following metals have been electrodeposited and investigated for the last 15 years: aluminum, zinc, silver, palladium, tantalum, zirconium, gadolinium, plutonium, nickel, cobalt, and other alloys.

The role of non-aqueous electrolytes in technology has become more and more important. Facing serious problems concerning the environment and energy scientists have found out new possibilities in electrochemical applications using non-aqueous electrolytes.

 Non-aqueous media Molten salts : A classical solution of an electrolyte is obtained by dissolution of a salt in a molecular solvent. Such a system consists of solvated ions, their charged or neutral combinations and solvent molecules. Ionic liquids: advantages of ILs are: non-volatility, inflammability, low toxicity, good solubility, high thermal stability, wide electrochemical windows, high polarity, high purity. organic solvents: Electrodeposition of metals and alloys from non-aqueous solutions (such as aromatic, dimethylsulfone, acetone and acetates) provides costeffective and easy to control technique to fabricate thin films and intermetallic compounds.

The electrochemical dissolution of molybdenum in non-aqueous media

Molybdenum (Mo) is a refractory metallic element used principally as an alloying agent in steels, cast irons, and super alloys to enhance hardenability, strength, toughness, wear and corrosion resistance. Moreover, molybdenum finds significant usage as a refractory metal and in numerous chemical applications, including catalysts, lubricants, and pigments. Ammonium nitrate used as electrolyte was dried for 24 h at temperature 150 C and transferred immediately into the cell after cooling the desired amount. 1.0 molar solution of NH4NO3 in liquid ammonia was prepared by the help of magnetic stirring inside the cell. A DC power supply was used for applying constant current of 100 mA.

Effects of Additives on Electrodeposition

Effects of Additives on Electrodeposition Levelers : Levelers are adsorbed on the

peaks, and more metal is deposited on the recessed areas than peaks. Grain refiner : Grain refiner is adsorbed on the surface, and suppress the lateral growth, resulting grain refinement.
substrate additive deposit

substrate

Stress reducer : Stress reducer is adsorbed in deposited layer, and reduce residual stress that occurs from cracks formed during deposition. Wetting agent : Wetting agent reduces the surface tension of H2 bubble adsorbed on the surface of cathode, and the metal is deposited more easily.

deposit

substrate

H2 substrate

Influences of Additive on Electrodeposition

additive

The effect of additives on zinc electrodeposition from deep eutectic solvents

The electrodeposition of Zn from the deep eutectic solvents 1:2 ChCl:ethylene glycol and 1:2 ChCl:urea was investigated. It is shown that the structure of the zinc deposits is controlled by double layer properties and it is proposed that the brightening effect of ethylene diamine and ammonia are caused by their ability to inhibit the adsorption of chloride at the electrode surface

Representative,scanningelectronmicrographsofZnelectrodepositedfrom0.3m oldm3 1:2 ChCl:ethyleneglycol(a),with0.3moldm3 acetonitrile (b),0.3moldm3 ethylene diamine(c)and0.3moldm3 ammonia (d).Allelectrodepositionswerecarriedoutonmildsteelplates,at50 C andataconstantcurrentdensityof2.5mAcm2 for 30min.

Representative scanningelectronmicrographsofZnelectrodepositedfrom0.3moldm3 1:2 ChCl:urea(a),with0.3moldm3 acetonitrile (b),0.3moldm3 ethylene diamine(c)and0.3moldm3 ammonia. Allelectrodepositionswerecarriedoutonmildsteelplates,at50 C andataconstantcurrentdensityof2.5mAcm2 for 30min.

The effect of additive addition on the Zn electrodeposition process in ChCl:ethylene glycol and ChCl:urea has been presented. The additives studied; acetonitrile, ammonia and ethylene diamine were shown to have varying effects on theZn deposition mechanism. Ammonia and ethylene diamine were demonstrated to be effective brighteners for Zn deposition.

When metal are mixed to form alloys there are 3 possibilities:

Completely soluble, i.e. atoms of one will fit exactly into the structure of the other without disturbing it. (e.g. copper and nickel) Partially soluble, i.e. the atoms cannot form structures together but crystals of each will mix. (e.g. copper and zinc i.e. brass) Insoluble, e.g. molten iron will float on molten lead, they will not mix

Range of non-ferrous alloys

APPLICATIONS

Electroplating
- The chemical conversion of ions in solution into a solid deposit of metal atoms with the work of a electrical power supply

Mz+ + ze- > M(0)

Cu2+ + 2e- > Cu(0)

Cu solid

Cu2+

Cu2+ 2eCu2+

Cu ions in solution

Electroplating Cell
I V

cathode Working Electrode (WE)

anode

CuSO4 dissolved in water

Counter Electrode (CE)

If using an inert Pt electrode: 2 H2O > O2 + 4H+ + 4e-

"reduction"
Cu2+ + 2e- > Cu(0) Cu(0) > Cu2+ + 2e-

"oxidation"

An example of Current vs. Potential Curve for electroplating of metal

Composition of plating solution

Three types of plating baths: a) Acid b) Neutral c) Alkaline They baths may be classified as having pH values: a) Lower than 2 b) Between 2 & 8 c) Higher than 8

The most common examples are: a) Acid copper & chromium baths. b) Nickel baths. c) Cyanide baths of various metals.

Types of electrolytic metal deposition

There are three types of electrolytic metal deposition processes: direct current electrodeposition, pulse plating, and laser-induced metal deposition. Direct Current Electrodeposition In the direct current (DC) electrodeposition, the current source is power source in the form of a battery. Pulse Plating Electrodeposition using pulsed currents is known as pulse plating. The pulsed currents can be unipolar (onoff) or bipolar (current reversal). Laser-Induced Metal Deposition In laser-induced metal deposition, a focused laser beam is used to accelerate the metal deposition. Experiments have shown that the deposition rate can be increased by 1000 times.

Nickel plating

 The electrodeposition of Ni and its alloys is important to functionalize surfaces for corrosion-resistance, electrocatalysis and magnetic applications; with the electrodeposition of these materials widely practiced in aqueous solutions.

Nickel plating

Heavy nickel plating:

In heavy nickel plating, thick Ni coating is deposited direct on to the basis metal in an adherent form.

Applications for heavy Ni plating:

Aircraft production. Marine engine production. Building up of warm tools and machine components. Rolls and cylinders for the paper, textile and leather industries.

Nickel plating
Bright Nickel baths: Bright Nickel baths are basically watts baths to which addition agents are added to produce plated lustrous surface. Addition agents for bright Ni plating are generally distinguished according to the following classification: 1) Carrier brighteners or softeners (primary). 2) Brightness formers (secondary).

Tailoring nickel coatings via electrodeposition from a eutectic-based ionic liquid doped with nicotinic acid
Pure nickel (Ni) was electrodeposited onto a copper (Cu) substrate from choline chlorideurea (1:2 molar ratio) eutectic-based ionic liquid (1:2 ChClurea IL) with 01200 mg/L additions of nicotinic acid (NA). The resultant surface morphologies and microstructures of the Ni coatings were revealed by SEM/EDXS, XRD and TEM, demonstrating that NA can inhibit, hence tailor, the Ni deposition and serve as a very effective brightener producing highly uniform and smooth Ni deposits. The nucleation/growth process of Ni was not affected by the presence of NA.

Fig. 8. (ae) The microscopic morphologies of the Ni deposited samples prepared from 1:2 ChClurea containing 0.2 M NiCl26H2O with (a) 0 mg/L, (b) 200 mg/L, (c) 400 mg/L (d) 800 mg/L, and (e) 1200 mg/L nicotine acid additive, and (f) cross-sectional morphology of Ni-coated Cu sample from1:2 ChClurea containing 0.2 M NiCl26H2O with 800 mg/L nicotinic acid at 65 C.

CONCLUSION

 Electrodeposition of Some Selected Metals in Aqueous and Non-aqueous Media is very important for various applications. Electroplating is an electrodeposition process for producing a dense, uniform, and adherent coating, usually of metal or alloys, upon a surface by the act of electric current. Electroplating products are widely used for many industries, such as automobile, ship, air space, machinery, electronics, jewelry, and toy industries.

Applications for heavy Ni plating:

Aircraft production. Marine engine production. Building up of warm tools and machine components. Rolls and cylinders for the paper, textile and leather industries. The application of non-aqueous solutions makes possible obtaining the cathodic deposits of metals or metallic alloys that cannot be deposited by the traditional electrolysis of aqueous solutions. It is due to the potential of their liberation, much lower than the potential of hydrogen liberation, when the hydrogen overpotential is relatively low.

 The application of non-aqueous solutions in the electrodeposition of metals is definitely more economic than the formation of coatings with methods such as plasma spray.

The electrodeposition of Ni and its alloys is important to functionalize surfaces for corrosion-resistance, electrocatalysis and magnetic applications; with the electrodeposition of these materials widely practiced in aqueous solutions.

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