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CORROSION CONTROL METHOD

Corrosion Inhibitor Painting and Lining Cathodic Protection Designing for Corrosion Control

(Coating)


Surface Preparation

Mechanical methods Solvent cleaning Alkali cleaning Acid picking *Rinsing *Agitation: ultrasonic => physically adsorbed particle

Surface Preparation
Acid picking

Sulfuric acid process


5~20%, upto 95oC, 2-10min. Dissolves wustite(FeOx)

Chloric acid process


1~10%, 20~50iC, 1~5min. Dissolves magnetite, Hematite Recyle Whiter, brighter surface

Economics and nature of oxide

Mechanical Cleaning

Traditional typical preparation of steel


exposing the steel surface for a few months thick adherent layer of mill scale break down abraded with a wire brush primer containing red lead in linseed oil

Red lead pigment


exact mechanism remains unclear. Ecological concerns

Quality of surface cleanliness


Soluble contaminant (burrowed) Copper sulfate test Measurement of roughness


Statistical approach: centerline average Maximum peak

Residual Dust and Embedded abrasive Surface Reactivity

High Pressure Water Cleaning


Sand + inhibited water (polyphosphate)

Abrasive Wheel Cleaning

Cleaning surfaces before Coating

(Metallic Coating)


/

VIII Ni, Co, Cr

(electroplating): Sn, Cu, Cr (thermal spray coating) (hot dipping): Al, Zn (cladding) Cementation
pack, intermediate, gas spray, electroless(=chemical) plating, diffusion coating, )


(electroplating):
throwing power: (macro, micro) : Ni-Fe, Zn-Al Stress:

()

()
Potential

Reversal
per decade reduction in solution)


(60mV/30mV

Complexing activity Reversal Zinc(-0.76V,cf. Fe: Eo=0.44V)


Reversal

above 150oC

()

Potential Reversal
Reversal Tin Can (Sn: Eo= -0.136V vs. Fe: Eo = -0.44V) Fe2+ + Sn = Fe +Sn2+
Reversal

at (Sn2+/Fe2+)<10-11 Complexant (citrate, tartrate) and Hydrogen overvoltage

Aerobic and no complexant condition: Sn cathodic

, LPG stainless steel lining cladding

Trends in Coating
Low

volatile component No lead Electrostatic spray

Electrostatic Spray

Sharp protrusions get extra coating quality Increased use because of low volatiles

Factory-applied External Coatings Uncoated area at joint Field-applied coatings at joints

Conversion Coating
Coatings made by reaction of metal with the environment or chemical/electrochemical treatment Conversion coating (phosphate coating, chromate coatings, mixed oxide coating) Anodized aluminum :

Oxide Coatings on Steel


persulfates, nitrate, chlorate , Magnetite

Oxide Coatings on Aluminum


Anodizing Outer porous layer/inner barrier layer Porous outer layer Sealing in hot water or steam (hydroxide, Al2O3.H2O) Corrosion by SOx gas

Oxide Coatings on Aluminum


Sulfuric acid: common, clear, sulfate Chromic acid:


Gray, rinsing , high fatigue strength

Boric acid: dense barrier type Oxalic acid: hard

Oxide Coatings on Aluminum


Log life thickness Severe industrial atmosphere: 35 m Moderately industrial atmosphere: 16 m Severe marine: 35 m Weathering resistance Better base for painting

Chromate coatings on Anodized Aluminum

Aluminum, cadmium, copper, iron, magnesium, silver, zinc, and their alloys. Cr+6 => Cr+3 : barrier layer Cr +6 induces repassivation Cathodic oxygen reduction Chromate 6 soluble insoluble 3 , self-healing effect, Anodic inhibitor

Chromate coatings on Anodized Aluminum

Chromic acid process:


Cr +6 passivation chromate Activator: sulfate, formate, and chlorides inhibit passivation

Chromic acid-phosphoric acid process:


2H2Cr2O7 + 10H3PO4 + 12HF + 4Al CrPO4 + 4AlF3 + 3Cr(H2PO4)3 + 14H2O Greenish color: hydrated chromium phosphate with hydrated chromium oxide No hexavalent chromium compounds No self-healing

Phosphate coatings

Iron, steel, zinc, aluminum, and their alloys Phosphate coatings on steel: parkerizing, bonderizing Immersion, spraying, or other techniques Crystalline or amorphous phosphates of the substrate materials or of the metal ions in the solution Steel in zinc, iron, manganese phosphate solutions.

Phosphate coatings

Iron and Steel in zinc phosphate solution


Dissolution of base metal
Fe + 2H3PO4 Fe(H2PO4)2 + H2 Promotion by the activator 2Fe + 2H2PO4- + 2H+ + 3NO2 2FePO4 + 3H2O + 3NO 4Fe + 3Zn2+ + 6H2PO- + 6NO2 4HePO4 + Zn3(PO4)2 + 6H2O + 6NO 2ZnFe(PO4)2 + Fe(H2PO4)2 + 4H2O Zn2Fe(PO4)2.4H2O + 4H3PO4 (phosphopyllite) 3ZnFe(PO4)2 + 4H2O => Zn3(PO4)2.4H2O + 4H3PO4 (hopeite)

Precipitation of phosphate films:

Phosphate-chromate coatings
Lacquer :

Paint-phosphate couple Solubility: depend on pH, density, kind of compound Fe: Phosphopyllite , low solubility Zn: Hopeite , solubility increase at high pH Carbon contamination(from lubricant) lower corrosion resistance.

Polymeric coatings
Varnish: resin (spirit varnish) or oil + resin in solvent Lacquer: nitrocellulose, cellulose acetate-butyrate, ethyl cellulose, acrylic resin Paint:

Polymeric coatings

( ): , , , : , , : , , 2 : , , : , , : , , , , : , , : , , , / : , , , , : , , , , : , ,

COATING SYSTEM

Electrodeposition Primer

Component Function

Vehicle
Primary Resin(Binder): , Secondary Resin: Solvent: Plasticizers or Modifier

Pigment ()
Inhibitive Pigment (primer only) Inert and Reinforcing Pigments Color Pigment

Drying
Physical

drying Chemical drying


Cross linking: At high temperature high cross-link density

The Mechanism of Adhesion


Area of Contact Theory Mechanical inkpot Theory Weak Bond Formation The Weak Boundary Layer Electrostatic effects Water and Adhesion Residual Stress

The ideal adhesive strength

If the force between two semi-infinite blocks of differing material is computed, the value calculated is far in excess of the real values for the strength of adhesive joints. During the rupture process if the force is not purely tensile, then peeling will take place, Interfacial defects can lead to flaws and stress concentrations

Adhesion Measurements

Adhesion measurement
Application of a force of increasing magnitude to the paint substrate interface until the joint breaks.

To get the force at the interface, however, the application is via the coating film, which being viscoelastic, will be strain rate and temperature dependent. Further, if there is some degree of shear during the testing then "peeling" will occur which "allows the molecular interactions to be disrupted individually and sequentially" (Cherry 1981).

Corrosion at the pin hole

Effect of anodic and cathodic reaction

Blistering and Disbonding


Definition

of a Blister

Local defects in a paint film usually at the paint/ metal interface formed by an accumulation of water or aqueous solution together with a loss in adhesion and stretching of the coating.

Blistering and Disbonding


Corrosion

and Blistering

It is usually thought that the corrosion process follows the blistering process and does not precede it. However, this may not always be the case.

Blistering and Disbonding


Mechanisms

of Blistering

Swelling causing volume expansion Gas inclusion or bubble formation Osmotic Blistering Electro-osmotic blistering Phase Separation During film formation

Blistering and Disbonding


Wet adhesion Osmotic process

Filiform Corrosion

Causes
Paint on contaminated metal Stored as wrapped in plastic wrapping Relative humidity (RH) of around 80%

Remedies
Good housekeeping before painting Avoiding damage