CORROSION CONTROL

The rate of corrosion can be controlled by either modifying the metal or the environment. 1. Proper Designing A major factor in the corrosion failure of a component is a faulty geometrical design. Some important design principles are: 1) Avoid crevices 2) Avoid residual moisture 3) Avoid galvanic corrosion Galvanic corrosion can be prevented by the following methods, a) Use an electrical insulators b) Introduce an easily exchangeable corroding places 4) Avoid protruding parts.

2. Cathodic Protection
The principle involved in cathodic protection is to force the metal to be protected to behave like a cathode. Since, there will not be any anodic area on the metal, corrosion does not occur. There are two types of cathodic protection. Sacrificial anodic protection method Impressed current cathodic protection method.

SACRIFICIAL ANODIC PROTECTION METHOD In this method, the metallic structure to be protected is made cathode by connecting it with more active metal (anodic metal). So that all the corrosion will concentrate only on the active metal. The artificially made anode thus gradually gets corroded protecting the original metallic structure. Hence this process is otherwise known as sacrificial anodic protection.

Examples of sacrificial anode This method is used for the protection of ships and boats. Sheets of zinc and magnesium are hung around the hull of the ship. Zinc and magnesium being anodic to iron get corroded. Since they are sacrificed in the process of saving iron (anode), they are called sacrificial anodes.

Applications of Sacrificial Anode

Protection of underground pipelines and cables from soil corrosion. Magnesium rods are inserted in to domestic water boilers or tanks to prevent the formation of rusty water. Calcium metal slag's are employed to minimize engine corrosion.

IMPRESSED CURRENT CATHODIC PROTECTION

In this method, an impressed current is applied in the opposite direction to nullify the corrosion current and convert the corroding metal from anode to cathode. This can be done by connecting negative terminal of the battery to the metallic structure to be protected. Positive terminal of battery is connected to an inert anode. inert anode used for this purpose is graphite or platinised titanium.

The anode is surrounded by backfill (containing mixture of gypsum, coke, sodium sulphate) to improve the electrical contact between the anode and the surrounding soil. APPLICATION OF IMPRESSED CURRENT PROTECTION This type of cathodic protection is applied to open water-box coolers, water tanks, buried oil and water pipes, condensers, marine piers, transmission line towers, etc.,

Comparison of sacrificial anode and impressed current cathodic method

Sacrificial anodic method No external power supply is necessary. This method requires periodical replacement of sacrificial anode. Investment is low.

Impressed current method External power supply must be present. Here anodes are stable and do not disintegrate. Investment is more.

Soil corrosion effects are not taken in to account. This is most economical method especially when short-term protection is required.

Soil corrosion effects are taken in to account. This method is well suited for large structures and long term operations.

Control of corrosion by modifying the environment DEAREATION The presence of increased amount of oxygen is harmful and increase the corrosion rate. Deareation involves removal of dissolved oxygen by increase of temperature with mechanical agitation. It also removes dissolved CO2 of water.

DEHUMIDIFICATION
In this method, moisture from the air is removed by lowering the relative humidity of the surrounding air. This is done by adding silica gel (or) alumina, which adsorbs moisture preferentially on its surface.
ALKALINE NEUTRALISATION

The acidic character of the corrosive environment (due to presence of H2S, HCl, CO2, SO2, etc) can be neutralized by spraying alkaline neutralisers (like NH3, NaOH, lime etc).

CORROSION INHIBITORS DEFINITION

A corrosion inhibitors is a substance which when added in small quantities to the aqueous corrosive environment effectively decreases the rate of corrosion of the metal.

Inhibitors are classified in to three types, ANODIC CATHODIC VAPOUR PHASE

ANODIC INHIBITORS
Chromates, phosphates, nitrite, nitrate, inhibit the anodic corrosion reaction by forming sparingly soluble compound with a newly produced metal ion (at the anode). They are absorbed on the metal surface forming a protective film or barrier there- by reducing corrosion rate. This kind of corrosion rate is not fully reliable since certain areas left uncovered by the film can produce severe corrosion.

CATHODIC INHIBITORS
In acidic solution, the main cathodic reaction is evolution of hydrogen. 2H+(aq) +2e- H2 (g) In an acidic solution, the corrosion can be controlled by slowing down the diffusion of H+ ions through the cathode. This can be done by adding organic inhibitors like amines, pyridine, azoles, etc. They absorb over the cathodic metal surface and act as a protective layer.

In a neutral solution, the cathodic reaction is, H2O + O2 + 2e- 2OH-(aq) The formation of OH- ions is only due to the presence of oxygen. By eliminating the oxygen from the medium, the corrosion rate can be reduced. O2 can be removed by adding some reducing agents like Na2SO3 or by deaeration. Salts of Zn, Mg, Ni are employed as they form insoluble metallic hydroxide which forms impermeable self barriers.

VAPOUR PHASE INHIBITORS Vapour phase inhibitors are organic inhibitors which readily sublime and form a protective layer on the metal surface. Example : Dicyclohexyl ammonium nitrite, Benzotriazole. Vapour phase inhibitors are used in the protection of machineries, sophisticated equipments, etc. which are sent by ships. The condensed inhibitor can be easily wiped off from the metal surface.

PROTECTIVE COATING

INTRODUCTION Protective coatings are used to protect the metals from corrosion.
It acts as a physical barrier between the

coated metal surface and the environment.

They impart some special properties such

as hardness, electrical properties and thermal insulating properties to the protected surface.

Protective coatings

Inorganic coating Metallic coating Chemical Conversion

Organic coating 1. Paints 2. Varnishes 3. Enamels 4. Ceramic

Sample Preparation
Mechanical cleaning To remove loose scale and rust, using hammer, wire-brushing, grinding and polishing. Sandblasting To clean large surface areas in order to produce enough roughness for good adherence of protective coating, using sand with air stream at 25-100 atm. Solvent Cleaning To remove oil, grease, rust using organic solvents like alcohol, xylene, toluene, hydrocarbons followed by cleaning hot water or steam.
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Sample Preparation (contd..)

Alkali Cleaning To remove old paints that are soluble in alkaline medium using chemicals like NaOH, Na3PO4 etc. After cleaning, the metal is washed with 1% chromic acid solution. Acid pickling and etching Base metal is dipped inside acid solution at a higher tempt for a long duration. Acids used are HCl, H2SO4, H3PO4, HNO3, under dilute conditions.

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Metallic coatings
Anodic coating Galvanization:
It is produced by anodic coating metals (Zn, Al, Cd) on the surface of base metal (Fe) based on the relative negative electrode potential.

Cathodic coating:
It is produced by cathodic coating metals (Sn, Cr, Ni) on Fe surface based on the relative positive electrode potential of coat metal.
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Methods of application of metallic coating

Hot dipping Metal cladding Electroplating Cu, Cr, Ni, Au, Ag Vacuum metalizing Metal spraying

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Hot Dipping
It is one of the common method of applying metallic coating on the surface of base metals. Hot dipping is a process of coating the base metal by immersing it in the molten coat metal. Examples: Galvanizing and Tinning

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Galvanizing: Fe or steel is coated with a thin coat of Zn by immersing in molten Zn to prevent rusting. Fe or steel base metal is cleaned by acid pickling using dil. H2SO4 (60-90 0C) for 15-20 min. Base metal dipped in molten Zn (430 0C) and then passed through rollers to correct the thickness of the film. NH4Cl flux used to protect the surface of molten Zn from oxide formation. Annealed at 250 0C and cooled slowly Coating of Iron pipes, screws, bolts, wires, etc. Poisonous for utensils that store food stuffs
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Tinning: In this process tin is coated over mild steel sheets immersed in molten tin (Sn). The sheet is subject to acid pickling and passed through a bath of molten tin covered with a flux of ZnCl2. After coating, the sheet is passed through palm oil to protect from oxidation Finally the sheet is passed to roller to get uniform thickness. It is used for the coating of steel, Cu and brass sheets that store food stuffs.
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Metal Cladding
It is the process of sandwitching the base metal between two thin layers of coating metal by hot-rolling the composite to produce a firm bonding. The coat metals are usually metals of least reactivity (Cu, Ni, Ag, Pt, Ti) The cladding layer should be very thin and its thickness is only 5% of the total composite metal. Duraluminium sandwiched between Al sheets and hot rolled to produce Alkad composite which is free from stress corrosion
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ELECTROPLATING
PRINCIPLE Electroplating is the process in which the coating metal is deposited on the base metal by passing a direct current through an electrolytic solution containing the soluble salt of the coating metal. Electroplating is probably the most important and most frequently applied industrial method of producing metallic coatings. The metal film produced is quite uniform with little or no pinholes per unit area. When the thickness of the deposit increases, the number of pinholes decreases.
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 The base metal to be plated is made cathode of an electrolyte cell, whereas the anode is either made of the coating metal itself or an inert material of good electrical conductivity. THEORY If the anode is made of coating metal itself in the electrolytic cell, during electrolysis, the concentration of electrolytic bath remains unaltered, since the metal ions deposited from the bath on cathode are replenished continuously by the reaction of free anions with the anode.
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Objectives of electroplating: (i) To increase the resistance to corrosion and chemical attack of the plated metal. (ii) To obtain a polished surface (iii) To improve hardness and wear resistance Example: Electroplating of Cu, Au, Ag, Cr, Ni, Sn etc. Uses of electroplating: (i) It is often used in electronic industries for making printed circuit boards, edge connectors, semiconductor lead-out connection (ii) It is also used in the manufacture of jewelery, 29 refrigerator, electric iron etc.

Electroplating of Cu
For electroplating of Cu on metal surface, Electrolyte: (3-5%)H2SO4 / (15-30%) CuSO4 Anode: Pure Cu metal or Graphite (inert) Cathode: Metal to be coated Additive: Boric acid or gelatin Ionization reaction of electrolyte is observed, H2SO4 2H+ + SO42CuSO4 Cu2+ + SO42On passing current, Cu2+ + 2eSO42SO4 + 2e- (at anode) Cu (at cathode)

Due to common ion effect, the ionization rate of Cu2+ is controlled and the deposition process can also be controlled, with a current 30 density of 0.5 to 1.5 ampere/dm2.

Factors affecting electroplating

Surface cleaning for strong adherent Concentration of electrolyte Moderate conc. Is preferred for uniform coating Conductivity and stability of electrolyte - Good Thickness of the deposit for decorative purpose thin coating and for corrosion protection multiple coating. Current density (current per unit of the base metal) should be low for uniform controlled deposition Additives: Ensure strong adherence and mirror smooth coating. pH of the electrolytic bath between pH 4.0 - 5.5
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Thin-Film Coatings (m)

PVD Coating (Physical Vapor Deposition) CVD Coating (Chemical Vapor Deposition)
Physical Vapour Deposition, PVD a group of vacuum coating techniques that are used to deposit thin film coatings that enhance the properties and performance of tools and machine components. PVD coatings are used in a vast array of industries and thousands of applications as diverse as "self-cleaning" windows, medical implants, cutting tools, decorative fittings and Formula 1 racing parts.
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Classifications of thin-films based on their applications

Thin-film property category Optical Typical applications Reflective/antireflective coatings Interference filters, Decoration (colour, luster), Memory discs (CDs), Waveguides Insulation, conduction, Semiconductor devices, Piezoelectric drivers Memory discs/devices Barriers to diffusion or alloying Protecting against corrosion or oxidation Gas/liquid sensors Tribological (wear resistant) coatings Hardness, Adhesion, Micromechanics Barrier layers, Heat sinks
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Electrical Magnetic Chemical

Mechanical Thermal

Deposition techniques

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Deposition by Physical Vapour Deposition (PVD)

H2 = 50 psi N2 = 15 psi PVD Chamber

Substrate Ni film

Heater N2 (or) H2
9/13/2013 6:21 PM

Suction valve Ni Source 2000oC To vacuum pump

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Nanotechnology

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PVD is a process to produce a metal vapor that can be deposited on conductive materials as a thin highly adhered pure metal or alloy coating. The process is carried out in a vacuum chamber at high vacuum (10-6 torr). Single or multi-layer coatings can be applied during the same process cycle. Additionally the metal vapor can be reacted with various gases to deposit Oxides, Nitrides, Carbides or Carbonitrides. The coating method involves purely physical processes such as high temperature vacuum evaporation or plasma sputter bombardment rather than involving a chemical reaction at the surface to be coated.
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Titanium Nitride coated punches Aluminium Chromium Titanium Nitride coated

Aluminium Titanium Nitride coated

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Structure of TiAlCN
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Different types of PVD coating

Cathodic Arc Deposition: In which an electric arc is used to vaporize material from a cathode target. The vaporized material condenses on a substrate, forming a thin film. Evaporative deposition: In which the material to be deposited is heated to a high vapor pressure by electrically resistive heating in "low" vacuum. Sputter deposition: In which a glow plasma discharge (usually localized around the "target" by a magnet) bombards the material sputtering away as a vapor. Ion plating: In which the material is heated to a high vapor pressure and a plasma is established to ionize the evaporating species. These species physically implant 39 into the substrate producing strong coating bond.

Sputtering
Coating can be done for both conductive (dc) and nonconductive (RF sputtering) materials DC sputtering the workpiece and substance to be coated are connected to high voltage dc power supply. Vacuum chamber is filled with controlled amount of argon gas to establish a pressure of 10-4 torr. The supplied direct current energizes the chamber creating a plasma between the workpiece and the material to be coated. The argon atoms get ionized and accelerated to bombard on the workpiece resulting in the sputtering of atoms, which are transported and coated on the substance
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PVD Process
The parts to be coated are first cleaned. The cleaning process varies depending on the level of quality from the electroplater, substrate material and geometry. The parts are loaded into the vacuum chamber on custom fixtures designed to optimize the chamber load size and ensure coating uniformity. The vacuum chamber is evacuated to 10-6 torr (high vacuum) to remove any contaminants in the system. The vacuum chamber is backfilled with an inert gas argon and ionized, resulting in a glow discharge (plasma). This is the gas cleaning stage and prepares the parts for the initial 41 metal deposition.

A high current, low voltage arc is initiated on the target (solid material used for deposition). The metal is evaporated and instantaneously ionized. These metal ions are accelerated at high energies into the vacuum through an inert gas or reactive gas and subsequently deposited on the part. The basic properties of the metal being evaporated (target) remain unchanged during the metal deposition cycle. Changing the volume of gas and type of gas during the reactive deposition cycle changes the nature of the coating.
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Zirconium nitride (ZrN) is a hard, yellow-gold colored coating with exceptional wear and corrosion resistance, used in plumbing and door hardware industry. Introducing measured amounts of nitrogen into the chamber during the zirconium deposition cycle produces zirconium nitride. Chromium nitride is produced in much the same way. Simply by adding an additional gas such as acetylene (C2H2), you can create chromium carbonitride. This is a gray to black color.
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TiN 2900 HV Gold ZrN 2800 HV Gold TiAlN 2600 HV Brown TiCN 4000 HV Silver CrN 2500 HV Silver DLC 1000 to 5000 HV - Black

Coating processes are performed at 300 0C or upto 2800 0C. The higher temperature processes usually produce optimum coating properties but sometimes results in softening of substrates especially steel. Thickness usually in the range of 1 to 2 m.
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CVD process
CVD involves the formation of a solid film on a surface of a heated substrate by means of a chemical reaction in a gas or in the vapor phase. The complex molecule in the vapor state impinges on the hot substrate, decomposes and forms a thin film. These reactions are promoted by resistance, RF or infrared radiation heating. Example: Monds Process
Ni(CO)4
150C

Ni + 4CO

Requirements for a CVD process 1. Vacumised chamber (10-3 mbar) connected to a rotary pump 2. Complex chamber with heating facility 3. Vapour transport SS tubes ( quarter inch) 4. Substrate holder inside the chamber with heater (flat heater 900oC)
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Deposition by Chemical Vapour Deposition (CVD)

H2 = 50 mm Hg N2 = 15 mm Hg CVD Chamber

Ni film HTV

Substrate Pre Vap N2 (or) H2 Heater Suction valve

Solid complex

400oC
Nanotechnology

To vacuum pump
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9/13/2013 6:21 PM

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CVD Process steps

Step 1: The vapor source of the film-forming material may be a solid, liquid, vapor or gas. Solid materials, having sufficient vapor pressures, need to be vaporized to transport them at moderate temperature to the deposition zone where the substrate is placed, and this is normally achieved by heating. Step 2: Another issue is the uniformity of arrival rate of vapor sources by transport to the hot substrates. This uniformity in transporting the vapor source varies with the transport medium used to transport the source to the destination (i.e. either by high vacuum or fluid (gaseous fluid).
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Step 3: Deposition is the third step in a process of developing thin-films, in which the actual growth of film over the surface occurs. Deposition pattern is determined by the source, transport of vapor and conditions of deposition zone.

Step 4: Once the deposition is over, the next step is the analysis of coated thin-films by various techniques. Analysis of thin-films can be thought of as the final stage process of monitoring but it is important in all steps of thin-film deposition.
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