What is Electroplating ?

Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the reduction of cations of that metal by means of a direct electric current. The part to be coated acts as the cathode (negative electrode) of an electrolytic cell; the electrolyte is a solution of a salt of the metal to be coated; and the anode (positive electrode) is usually either a block of that metal, or of some inert conductive material. The current is provided by an external power supply.

Electroplating is widely used in industry and decorative arts to improve the surface qualities of objects—such as resistance to abrasion and corrosion, lubricity, reflectivity, electrical conductivity, or appearance. It is used to build up thickness on undersized or worn-out parts, or to manufacture metal plates with complex shape, a process called electroforming. It is used to deposit copper and other conductors in forming printed circuit boards, and copper interconnects in integrated circuits. It is also used to purify metals such as copper.

The term “electroplating” may also be used occasionally for processes that use an electric current to achieve oxidation of anions on to a solid substrate, as in the formation of silver chloride on silver wire to make silver/silver-chloride (AgCl) electrodes.

Electropolishing, a process that uses an electric current to remove metal cations from the surface of a metal object, may be thought of as the opposite of electroplating.

Process

Simplified diagram for electroplating copper (orange) on a conductive object (the cathode, “Me”, gray). The electrolyte is a solution of copper sulfate, CuSO
₄. A copper anode is used to replenish the electrolyte with copper cations Cu²⁺
 as they are plated out at the cathode.

See also: Electrotyping and Electroforming

The electrolyte should contain positive ions (cations) of the metal to be deposited. These cations are reduced at the cathode to the metal in the zero valence state. For example, the electrolyte for copper plating can be a solution of copper(II) sulphate, which dissociates into Cu²⁺ cations and SO²⁻
₄ anions. At the cathode, the Cu²⁺ is reduced to metallic copper by gaining two electrons.

When the anode is made of the coating metal, the opposite reaction may occur there, turning it into dissolved cations. For example, copper would be oxidized at the anode to Cu²⁺ by losing two electrons. In this case, the rate at which the anode is dissolved will be equal to the rate at which the cathode is plated and thus the ions in the electrolyte bath are continuously replenished by the anode. The net result is the effective transfer of metal from the anode to the cathode.

The anode may instead be made of a material that resists electrochemical oxidation, such as lead or carbon. Oxygen, hydrogen peroxide, or some other byproducts are then produced at the anode instead. In this case, ions of the metal to be plated must be periodically replenished in the bath as they are drawn out of the solution.

The plating is most commonly a single metallic element, not an alloy. However, some alloys can be electrodeposited, notably brass and solder. Plated “alloys” are not “true alloys” (solid solutions), but rather they are tiny crystals of the elemental metals being plated. In the case of plated solder, it is sometimes deemed necessary to have a true alloy, and the plated solder is melted to allow the tin and lead to combine into a true alloy. The true alloy is more corrosion resistant than the as-plated mixture.

Many plating baths include cyanides of other metals (such as potassium cyanide) in addition to cyanides of the metal to be deposited. These free cyanides facilitate anode corrosion, help to maintain a constant metal ion level and contribute to conductivity. Additionally, non-metal chemicals such as carbonates and phosphates may be added to increase conductivity.

When plating is not desired on certain areas of the substrate, stop-offs are applied to prevent the bath from coming in contact with the substrate. Typical stop-offs include tape, foil, lacquers, and waxes.

The ability of a plating to cover uniformly is called throwing power; the better the throwing power the more uniform the coating.

Strike

Initially, a special plating deposit called a strike or flash may be used to form a very thin (typically less than 0.1 μm thick) plating with high quality and good adherence to the substrate. This serves as a foundation for subsequent plating processes. A strike uses a high current density and a bath with a low ion concentration. The process is slow, so more efficient plating processes are used once the desired strike thickness is obtained.

The striking method is also used in combination with the plating of different metals. If it is desirable to plate one type of deposit onto a metal to improve corrosion resistance but this metal has inherently poor adhesion to the substrate, a strike can be first deposited that is compatible with both. One example of this situation is the poor adhesion of electrolytic nickel on zinc alloys, in which case a copper strike is used, which has good adherence to both.^[3]

Pulse electroplating

See also: Pulse electrolysis

The pulse electroplating or pulse electrodeposition (PED) process involves the swift alternating of the electrical potential or current between two different values resulting in a series of pulses of equal amplitude, duration and polarity, separated by zero current. By changing the pulse amplitude and width, it is possible to change the deposited film’s composition and thickness.

The experimental parameters of pulse electroplating usually consist of peak current/potential, duty cycle, frequency and effective current/potential. Peak current/potential is the maximum setting of electroplating current or potential. Duty cycle is the effective portion of time in certain electroplating period with the current or potential applied. The effective current/potential is calculated by multiplying the duty cycle and peak value of current or potential. Pulse electroplating could help to improve the quality of electroplated film and release the internal stress built up during fast deposition. Combination of the short duty cycle and high frequency could decrease the surface cracks. However, in order to maintain the constant effective current or potential, a high performance power supply may be required to provide high current/potential and fast switch. Another common problem of pulse electroplating is that the anode material could get plated and contaminated during the reverse electroplating, especially for the high cost, inert electrode such as platinum.

Other factors that could affect the pulse electroplating include temperature, anode-to-cathode gap and stirring. Sometimes the pulse electroplating can be performed in heated electroplating bath to increase the depositing rate since the rate of almost all the chemical reaction increases exponentially with temperature per Arrhenius law. The anode-to-cathode gap is related to the current distribution between anode and cathode. Small gap to sample area ratio may cause uneven distribution of current and affect the surface topology of plated sample. Stirring may increase the transfer/diffusion rate of metal ions from bulk solution to the electrode surface. Stirring setting varies for different metal electroplating processes.

Brush electroplating

A closely related process is brush electroplating, in which localized areas or entire items are plated using a brush saturated with plating solution. The brush, typically a stainless steel body wrapped with an absorbent cloth material that both holds the plating solution and prevents direct contact with the item being plated, is connected to the anode of a low voltage direct current power source, and the item to be plated connected to the cathode. The operator dips the brush in plating solution then applies it to the item, moving the brush continually to get an even distribution of the plating material.

Brush electroplating has several advantages over tank plating, including portability, ability to plate items that for some reason cannot be tank plated (one application was the plating of portions of very large decorative support columns in a building restoration), low or no masking requirements, and comparatively low plating solution volume requirements. Disadvantages compared to tank plating can include greater operator involvement (tank plating can frequently be done with minimal attention), and inability to achieve as great a plate thickness.

Barrel plating

Main article: Barrel plating

This technique of electroplating is one of the most common used in the industry for large numbers of small objects. The objects are placed in a barrel-shaped non-conductive cage, and then immersed in the chemical bath containing suspended atoms of the metal that is to be plated onto them. The barrel is then rotated, and electrical currents are run through the various pieces in the barrel which complete circuits as they touch one another. The result is a very uniform and efficient plating process, though the finish on the end products will likely suffer from abrasion during the plating process. It is unsuitable for highly ornamental or precisely engineered items.

Cleanliness

Cleanliness is essential to successful electroplating, since molecular layers of oil can prevent adhesion of the coating. ASTM B322 is a standard guide for cleaning metals prior to electroplating. Cleaning includes solvent cleaning, hot alkaline detergent cleaning, electrocleaning, and acid treatment etc. The most common industrial test for cleanliness is the waterbreak test, in which the surface is thoroughly rinsed and held vertical. Hydrophobic contaminants such as oils cause the water to bead and break up, allowing the water to drain rapidly. Perfectly clean metal surfaces are hydrophilic and will retain an unbroken sheet of water that does not bead up or drain off. ASTM F22 describes a version of this test. This test does not detect hydrophilic contaminants, but electroplating can displace these easily since the solutions are water-based. Surfactants such as soap reduce the sensitivity of the test and must be thoroughly rinsed off.

Effects

Electroplating changes the chemical, physical, and mechanical properties of the workpiece. An example of a chemical change is when nickel plating improves corrosion resistance. An example of a physical change is a change in the outward appearance. An example of a mechanical change is a change in tensile strength or surface hardness which is a required attribute in tooling industry.^[8] Electroplating of acid gold on underlying copper- or nickel-plated circuits reduces contact resistance as well as surface hardness. Copper-plated areas of mild steel act as a mask if case hardening of such areas are not desired. Tin-plated steel is chromium-plated to prevent dulling of the surface due to oxidation of tin.

Electroplating, or electroless plating may be used as a way to render a metal part radioactive, by using an aqueous solution prepared from nickel–phosphorus concentrates which contain radioactive hypophosphite ³²P ions.^[9]

Specific metals

Further information: Plating § Specific_cases

Alternatives to electroplating

There are a number of alternative processes to produce metallic coatings on solid substrates that do not involve electrolytic reduction:

• Electroless plating uses a bath containing metal ions and chemicals that will reduce them to the metal by redox reactions. The reaction should be autocatalytic, so that new metal will be deposited over the growing coating, rather than precipitated as a powder through the whole bath at once. Electroless processes are widely used to deposit nickel-phosphorus or nickel-boron alloys for wear and corrosion resistance, silver for mirror-making, copper for printed circuit boards, and many more. A major advantage of these processes over electroplating is that they can produce coatings of uniform thickness over surfaces of arbitrary shape, even inside holes, and the substrate need not be electrically conducting. Another major benefit is that they don’t need power sources or especially shaped anodes. Disadvantages include lower deposition speed, consumption of relatively expensive chemicals, and limited choice of coating metals.
• Immersion coating processes exploit displacement reactions in which the subtrate metal is oxidized to soluble ions while ions of the coating metal get reduced and deposited in its place. This process is limited to very thin coatings, since the reaction stops after the subtrate has been completely covered. Nevertheless, it has some important applications, such as the electroless nickel immersion gold (ENIG) process used to obtain gold-plated electrical contacts on printed circuit boards.
• Sputtering uses a strong electron beam to eject microscopic particles of the metal onto the substrate in a vacuum.
• Physical vapor deposition transfer the metal onto the subtrate by evaporating it.
• Chemical vapor deposition uses a gas containing a volatile compound of the metal, which gets deposited onto the substrate as a result of a chemical reaction.
• Gilding is a traditional way to attach a gold layer onto metals by applying a very thin sheet of gold held in place by an adhesive

References: Wikipedia