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By Ali Dad Chandio

Electrochemical and chemical techniques


In electrochemical (electroplating) and chemical techniques, several effects may be

utilized.
To deposit a metallic coating or to either deposit or set a non-metallic coating on

the surface of a metal, alternately, to polish or clean (pickle) a metal surface, this effect is electrochemical reduction (for electrochemical and conversion coatings, electrolytic polishing and etching) or chemical reduction (for chemical and conversion coatings, and chemical polishing and etching).
In the case of paint coatings, other chemical reactions are utilized. Coatings

obtained in this way exhibit properties that are superior to those of the coated metal. These properties include: corrosion resistance, wear resistance and some physico-chemical ones, like color, luster and reflectivity.
Coatings are most commonly produced by the bath technique, i.e. immersion in an

electrolyte, a chemical bath, paint or sol, by spraying and, less frequently, by tampons, centrifugal rinsing or spreading.

Electrolytic deposition (electroplating) enables the creation of metal or alloy coatings, as the result of reduction, by electric current at the cathode, of ions of the coating metal from electrolyte solutions. The obtained coatings may be single layered, with a thickness of 0.3300 m or multi-layered. The most frequently used coating metals (in descending order ) are: chrome, nickel,

zinc, tin, cadmium, copper, lead, silver, gold, rhodium, palladium, platinum, ruthenium, iron, cobalt, indium, as well as alloys: Sn-Pb, Sn-Ni, Sn-Cd, Zn-Ni, CuZn, Ni-Fe, Ni-Co, Ni-P, Co-P, Co-W, brasses, used single or in combination with other coatings, mainly for corrosion protection, and for decorative purposes.
In some branches of technology, e.g. repair of machine components, intermediate layers in electronics, special military applications, electroplating is complementary to tampon deposition (instead of an electrolytic bath, a fabric tampon dipped in it or a saturated solid is used).

The tampon technique allows selective deposition of microcrystalline

metal or alloy coatings on fragments of even very big objects.


With some modifications of the electrolyte (aqueous solutions of

alkalis, acids and salts) as compared to immersion techniques, this technique also enables the obtaining of coatings with special properties on both metallic and non-metallic substrates, e.g. ceramic, glass, plastics.
Besides a 10-20 times shorter deposition time, lower cost and material

as well as energy economy, the tampon technique yields coatings which are harder than those obtained in the immersion technique and have a disordered or amorphous structure with a lower hydrogen content.
Finally, the tampon technique also enables the deposition of

composite ceramic-metal coatings.

Chemical deposition (electroless) enables the obtaining of metal or alloy coatings on metals or alloys, as the result of exchange, contact or reduction with, or without the participation of a catalyst. Exchange and contact is used for the deposition of tin coatings; exchange, contact and reduction with

the utilization of a catalyst is the technique used for copper and nickel coatings.
Contact and reduction, but without the catalyst is used for the deposition of silver coatings, while gold is deposited by means of exchange and reduction

with a catalyst. In most cases deposition is by chemical reduction without a catalyst (e.g. by sodium hypophosphite) in baths or by spraying.
It is applied for the deposition of coatings, mainly nickel, on substrates which are otherwise difficult to electroplate (complex shapes, slender long holes, etc.)

and on other coating metals: Ag on Cu, brasses or non-conductors, such as glass and plastics, Au on Cu or brasses, Co and Cu on plastics; Pd, Pt, Sn on Cu or on Al; Bi on steels; Ag on glass. Layer thickness is 5-20 m. The main purpose of these applications is enhancement of corrosion resistance or creation of contact layers on cast iron and steel (Ni) prior to coating with enamel.

Conversion deposition is an artificially induced and controlled

process of metal or alloy corrosion by chemical or electrochemical treatment.


It is result is the formation on the surface of a coating which is

practically insoluble in water or in the triggering environment, tightly bound to the substrate material and exhibiting dielectric properties.
It is composed of compounds of substrate material with the reagent

solution, in which object are immersed or which is sprayed on the objects. It may be a chromate, phosphate, oxide, oxalate or a other coating.
Depending on the type of bath used and on the substrate material (e.g.

aluminum, zinc, cadmium, steel, copper and its alloys, magnesium alloys, silver, etc.) the coatings may have different compositions, color and properties.

The thickness of coatings ranges from several to several hundred micrometers. Conversion coatings are applied for corrosion resistance and:

to improve adherence of paint coatings to steel, zinc and aluminum,


to improve the properties of other coatings, to activate the diffusion of nitrogen to steel, facilitate cold deformation of

steel (broaching, extrusion, pressing), electrical insulation of substrate,


to reduce friction (lubricating coatings), to enhance esthetic value (decorative coatings). Broadest application is found by phosphate coatings (coatings of steel sheet prior to painting) and oxide (oxidizing of machine components, tools and firearms).

Polishing - finishing treatment, carried out with the purpose of

obtaining smoothness and luster of the object surface, and accomplished in an electrolyte or a chemical bath.
It consists of selective dissolution of peaks of microasperities, while

leaving microrecesses practically unchanged:


chemical polishing (electroless polishing, chemical brightening)

brightening and partial polishing, carried out by treatment of metals and alloys, most frequently aluminum and its alloys, in baths containing oxidizing agents (primarily acids, like orthophosphoric, nitric, sulfuric, acetic), in order to achieve an attractive appearance;

electrolytic (electropolishing, electrochemical polishing) - smoothing (dissolution of asperities of heights greater than 1 m) and brightening (reduction of asperities from above 1 m to below 0.01 m), carried out by treatment of metals and alloys (mainly aluminum), with appropriately selected electrolytes and current conditions. The polished object is the anode.

The treatment does not alter the state of residual stresses in the surface layer. It is used to obtain high luster or as preparation of the substrate for protective-decorative processes (e.g. electroplating).

Etching - removal of layers of scale, rust, oxides or alkaline salts from the surface of metals and alloys, carried out before final pickling and deposition of electroplated coatings. It can be carried out by:

chemical means (electroless) - by immersion in acidic solutions, reacting with metal oxides, electrolysis - in an electrolytic process, where the metal may be pickled by the anode or the cathode.

Chemical setting enables the production of paint coatings out of material deposited by any chosen technique, as the result of: oxidation at ambient or elevated temperature, upon contact with oxygen from the air by spontaneous oxidation or oxide polymerization of the filmogenic substance (drying oil or the product of its initial transformation); reticulation, without the participation of oxygen, of chemosetting resins at ambient temperature, due to polymerization, polycondensation or polyaddition, under the influence of reagents (catalysts, resinous co-reagents or other macromolecular substances).

Gelling or formation of coatings by the sol-gel technique - a low temperature synthesis of coating material by way of the sol1) colloidal solution and multiphase gel2).
In stricter terms, this is a process of formation of sol, its subsequent transformation into gel and final treatment of gel.

The sol is a homogenous solution of an easily soluble precursor (e.g. aloxyl derivatives) in an organic solvent, mixed with a reagent, e.g. with water [15, 16]. After acid treatment (e.g. by water with HCl), the sol is transformed into gel by polycondensation.