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CHEMISTRY OF NICKEL ELECTROPLATING SOLUTIONS
The Watts Nickel Plating Solution
The majority of nickel plating solutions, particularly those used for decorative plating, are based on the ‘Watts’ formulation developed by Professor Oliver P. Watts in 1916. The Watts electrolyte combines nickel sulphate, nickel chloride and boric acid. While the proportions may vary according to the application, a typical formulation together with operating parameters is given in Table 2.
Table 2
Typical formula and operating conditions for Watts nickel electroplating solutions
Function of Ingredients
Nickel Sulphate (NiSO4.6 H2O) Nickel Chloride (NiCl2.6 H2O) Boric Acid (H3BO3) Temperature
pH
Cathode Current Density
Deposition Rate
240-300gL-1
30-90g L-1
30-45g L-1
40-60°C
3.5 - 4.5
2-7A dm-2
25-85μm h-1
The nickel sulphate is the primary source of nickel ions (Ni++) with nickel chloride a contributing source. Nickel chloride has two major functions – it appreciably increases solution conductivity thereby reducing voltage requirements and it is important in obtaining satisfactory dissolution of nickel anodes.
Boric acid is a buffer and has the major function of controlling the pH of the solution. As discussed in the previous section, due to the cathode efficiency being less than 100% there is a tendency for the pH to increase as some hydrogen ions (H+) are discharged to liberate hydrogen gas. Regular additions of sulphuric acid are therefore required to adjust the pH. Boric acid limits the effect on the pH resulting from the discharge of hydrogen ions, thereby, simplifying pH control. The mechanism by which boric acid operates is complex, but it is generally understood that it exists in solution as a mixture of borate ions and non-ionised boric acid. When hydrogen is discharged some boric acid will ionise to replace the hydrogen
ions lost and so the pH change is limited. At the same time, borate ions form. When acid is added to adjust the pH, these borate ions combine with hydrogen ions to reform boric acid. Boric acid is therefore only lost through dragout or other solution losses.
The Role of Addition Agents
Watts nickel plating solutions are commonly used for functional applications as will be discussed in a later section. Deposits from Watts solutions without additives are soft and ductile but dull in appearance. The appearance and properties can however be dramatically changed by the use of addition agents. The addition agents consist of organic and certain metallic compounds selected to brighten and level the deposits. As will be discussed further in the section on decorative plating, addition agents may be used to produce semi-bright, bright or satin nickel coatings.
Bright Nickel Plating
In bright nickel plating, four main classes of addition agents are used:
‘Carriers’
(Confusingly these are sometimes also referred to as Brighteners of the First Class, Secondary Brighteners or Control Agents)
These are usually aromatic organic compounds containing sulphur. Examples are benzene sulphonic acid, 1,3,6-naphthalene sulphonic acid (sodium salt), p-toluene sulphonamide, saccharin and allyl sulphonic acid. The major function of carriers is to refine the grain structure and to provide some increased lustre compared with additive-free solutions. Many carriers, for example saccharin, also have significant stress reducing properties. Carriers introduce sulphur into the deposit and the effect of this incorporated sulphur is discussed under decorative plating. Consumption of carriers is largely by dragout as they are not consumed rapidly by electrolysis.
‘Brighteners’
(Also referred to as Brighteners of the Second Class, Primary Brighteners, Levelling Agents)
In combination with carriers, brighteners produce brilliant deposits with good ductility and levelling properties over a broad current density range. There are a wide range of brighteners used (generally supplied as proprietary mixtures). Compounds include formaldehyde chloral hydrate, o-sulpho benzaldehyde, allyl sulphonic acid, 2-butyne-1, 4-diol, thiourea, coumarin and many others. Brighteners are generally present in very low concentrations and are consumed by electrolysis. They therefore need to be replenished on a regular basis in order to maintain the desired brightness.