18 JUN 2010

: M Mn+ + ne : O2 + 2H2O + 4e- 4OH-

(anode) (cathodic) () () (+)

Other reduction reaction

In an acid solution In a neutral or base solution

O2 4H 4 e 2H2 O O2 2H2 O 4 e 4OH

One metal only

Two different metal T diff t t l

Cathodic site

A Anode Cathode Pt

Anodic site

e-

e-

Gas explosion caused by charged soil (crater size: 15 m x 34 m) due to microbial corrosion of gas pipeline (Carlsbed, New Mexico, USA, Aug. 19, 2000)
Source: National Transportation Safety Board (USA) www.ntsb.gov

Cost of corrosion (1998, USA)

Highway Bridges Gas and Liquid Transm. Pipelines Waterways and Ports Hazardous Materials Storage Air Ports Railroads Gas Distribution Drinking Water and Sewer System Electrical Utilities Telecommunication Motor Vehicles Ships Aircraft Railroad Cars Hazardous Materials Transport Oil and Gas Expl. And Production Petroleum Refining Chem., Petrochem., Parm. Pulp and Paper Agricultural g Food Processing Electronics Home Appliances $1.5 $20.0 $10 $20 $30 $40 Defense Nuclear Waste Storage $0.1 $0 $2.7 $2.2 $2 2 $0.5 $0.9 $1.4 $3.7 $1.7 $6.0 $1.1 $2.1 $6.9 $6 9 $23.4 $0.3 $7.0 $8.3 $7.0

Total 276 billion $ !! 3.1% of GDP

$5.0

$36.0

g $ Mining $0.1

Corrosion Cost and Preventive Strategies in the United States, G.H. Koch, M.P.H. Brongers, N.G. Thompson, Y.P. Virmani and J.H. Payer, FHWA-RD-01-156, Office of Infrastructure Research and Development Federal Hi h F d l Highway Administration, Department of T Ad i i t ti D t t f Transportation, 2003 t ti

Cost of Corrosion Per Analyzed Economic Sector, ($ x billion)

Most common Corrosive environment evenly distributed over entire metal surface Metal: metallurgically and compositionally uniform On the basis of tonnage waste, the most important forms of corrosion waste Most readily detectable (visual) and preventable (alloying)

Atmospheric corrosion (rusting) Corrosion in acid solutions

TABLE. TABLE Galvanic Series in Seawater (or Fig. 6.1) Fig 6 1)

The galvanic series

Ordered by observed behavior in service Allows for corrosion products Can be defined for alloys Different for every environment Note that some alloys can appear twice acc ording to whether they are active or passive .

Cathodic protection (CP), sacrificial anode protection Galvanized steels; Zn is anodic to steel, act as a sacrificial metal

water-line corrosion

Crevice corrosion of Ti flange in hot seawater

Crevice corrosion of SS

Crevice corrosion of socket weld at gap formed between type 304L pipe And type 316L valve

Chloride pitting of stainless steel due to soldering flux contamination

Pitting of exterior of lead cable sheath due to stray current Carbon steel Pitting Pitti underground

Pitting of Aluminum air duct due to salt contamination Pitting of Inconel in Brine

Sensitization of Stainless Steel or Weld Decay

When grain boundary Cr carbide preci pitation has occurred, the stainless ste el is said to be sensitized. Sensitization frequently occurs in the h eat-affected zone (HAZ) during welding , and the resultant corrosion is called Weld decay.

Fig. 1.16.

Erosion-Corrosion of a 316L SS flange and pipe (This pump takes its suction about 6m below the surface of the Persian Gulf)

IGSCC of an Inconel heat exchanger tube (500X)

Chloride SCC of S31603 (316L) chemical processing piping system. It can be characterized b th multi-branched t b h t i d by the lti b h d lightning bolt TG crack pattern (300X)

Caustic SCC in a 304L SS pipe in methanol reforming service oxalic acid etch (50X)

Also called: hydrogen induced corrosion (HIC) Involves the ingress of hydrogen into the metal causing
Reduced ductility and load-bearing capacity Subsequent cracking and Catastrophic brittle failures at stresses below the yield stress of susceptible ma

terials

Most vulnerable are high-strength steels, titanium alloys and aluminu m alloys

Alloying to resist corrosion (SS, cupronickel, etc.) Metallic coatings (galvanizing) Organic coatings ( i t li i ) O i ti (paint, lining) Electrochemical protection
Cathodic protection Anodic protection

Corrosion inhibitors
Automotive cooling systems, cooling towers, boilers, etc.

23

MATERIAL AND SERVICES Protective Coatings Organic Coatings Metallic Coatings Metals & Alloys Corrosion Inhibitors Polymers (Anodic) Cathodic Protection Services Research & Development R h D l t Education & Training

RANGE ($ x b o ) billion) 33.5-167.5 1.4 14 7.7 1.1 1.8 18 1.97-2.46 1.2 0.020 0 020 0.01 TOTAL $48.7-$183.19

AVERAGE COST ($ x b o ) billion) 100.5 1.4 14 7.7 1.1 1.8 18 2.22 1.2 0.02 0 02 0.01 $115.95 (%) 86.7 1.2 12 6.6 1.0 1.6 16 1.9 1.0 <0.1 <0 1 <0.1 100%

Resistance to chemical environment, moisture

Have Ch i l added t th coating t hi d reactions. H Chemicals dd d to the ti to hinders ti Lead & chromate inhibitive.

Usually U ll contain Zn dust as th predominant pigment t i Z d t the d i t i t Might be a sacrificial metal applied by hot-dip galvanizing or spray metallizing

28

Page x of y

29

An inhibitor is a chemical substance that, when added in small concentration to an environment, effectively decreases the corrosion rate. A minimum conc. of inhibitor must be present to maintain the inhibiting surface film. Thus, good circulation and the absence of any stagnant areas are necessary to maintain the required level of inhibitor concentration. An addition of inhibitors reduces icorr by increasing the Tafel slope and/or by reducing the exchange current density.
E E

Anodic inhibitor

log i

Cathodic inhibitor

log i

A. Adsorption-type inhibitors Organic compounds which adsorb on th metall surface and suppress metall di l ti and reduction reactions. T i l O i d hi h d b the t f d t dissolution d d ti ti Typical of this class of inhibitors are the organic amines. B. Hydrogen evolution poisons The susbstances such as As, Sb, P, and S retard hydrogen recombination reaction, thereby reducing corrosion rate of a metal in acid solutions.

C. C Scavengers These substances act by removing corrosive species from solution : Sodium sulfite : 2Na2SO3 + O2(sol.) 2Na2SO4 Hydrazine : N2H4 + O2 N2 + 2H2O D. Oxidizers or passivators - effective only in metals showing active/passive transition. : CrO42- , NO2-, MoO42- , WO42- , and ferric salt

CURRENT

ANODE

CURRENT T

Power Source

+
CUR RRENT ANODE

100 58 25.4 25 4 10 31 34.2 35.2

0.1 0.04 0 04 0.018 0.01 -1000 -800 -600 -400 (mV/CSE) -200 0 200

Seawater is highly corrosive to mild steel (3.4% salt)

Concentration (mg/L)

Species

ClNa+ Mg+2 Ca+2 SO4-2 HCO3pH p Temperature Pressure

19,000 10,700 1,300 400 2,750 150 8.0 25oC 1 atm.

3.4% Salt (nearly constant) + slightly alkaline, pH 8: good electrolyte can cause galvanic corrosion & service corrosion. l i i i i

Corrosion is affected by O2 content, velocity, temperature and biological organisms.

45

Sea water is a highly corrosive electrolyte towards mild steel. This ship has suffered severe damage in the areas which are most buffeted by waves, where the protective coating of paint has been largely removed by mechanical action. action

Corrosion of ballast water tank

Calcareous deposit reduces the demand for current:

Calcareous d C l deposits reduce th effective cathodic surfac it d the ff ti th di f e area thereby lowering demand for current. The calcareous deposit is formed when MgOH2 and CaCO3 salts precipitate on the cathode (steel surface). The following changes the composition and quality of th e calcareous layer: current density td it temperature pressure seawater quality y flow velocity

CO

H 2 O H 2 CO

H 2 CO HCO

H HCO H CO

2 3

pH (pH ) pH H CO32 + Ca+2 -> CaCO3 Mg M +2 + OH->Mg(OH)2 OH M (OH)

Upper section atmospheric (C5 M) (C5-M)

blades, turbine, housings & structure (0.08 0.2 mm/y), UV

Lower section splash / tidal

tower structure (0.2 0.5 mm/y) UV (0 2 0 5 mm/y), UV, erosion

Bottom section tidal/immersed/buried (Im 2) ( )

tower structure (0.1 0.2 mm/y), fouling

Splashzoneisthemostcritical

Protective coatings are used to control atmospheric, splash zone and underwater exposed surfaces. Splash zone systems are subsets of protective coatings designed to withstand the more severe conditions of the splash zone zone. Cathodic protection is used alone and in conjunction with protective coatings and splash zone systems to protect immersed surfaces.

57

Generic 15 year maintenance free systems

Coastal / offshore areas with high salinity
C5 Category 3-6 3 6 coats EP + PU t Total 300-500 microns 3-5 coats Zinc silicate + EP + PU Total 300-400 microns 1-2 coats solvent free EP Total 800 microns

sea or brackish water

Im-2 Category 1-2 1 2 coats of solvent free EP t f l tf Total 800 microns 2-3 coats high solids EP Total 800 microns 2 coats glass flake EP Total 1000 microns

Area Atmospheric Zone p

Coating Types 1: Zinc-rich primer p 2: Epoxy 3: UV durable topcoat (e.g., PU) Epoxy or polyester Epoxy

Coating System Min. 320 um (dft) in min. 3 ( ) coats. Min 600 um (dft) in min. 2 coats Min. 450 m (dft) in min. 2 coats.

Splash Zone Immersion Zone

Conventional Coatings Underwater-Curing Epoxy (UCE) Unidirectional C U idi ti l Composite S t it Systems Wax-Based Composites (WBC) Silicone Gel-Based Composites (SGBC) Gel Based Concrete Composite System (CC) Alloy Sheathing

62

Sacrificial (galvanic) anode

Al (+In+Zn) Zn

BASIC DESIGN
1. Pipeline Strength Design

Offshore Pipeline Wall Thickness Onshore Pipeline Wall Thickness p Buckle Arrestor Wall Thickness

14.3/15.9 mm 15.9/25.4 mm 21/24 mm

2. Corrosion Protection Design

Internal Epoxy coating for 36 line pipe. FBE or 3-Layer PE external coating. Installation of Sacrifial Aluminum Anodes for Offshore Pipeline. Impressed Current CP (ICCP) system for Onshore Pipeline.

65

Trailing Wire Spooling Dispenser Platform

Trailing Wire Attached to platform riser

Survey Vessel

Tow fish with Ag/AgCl Half Cell attached Pipeline

SACP

ICCP

Aluminum anodes mounted on a steel jacket structure

Protective coating + SACP

Protective coating + ICCP

Primary Shield
/ Fiberglass thermoplastic sheet g p 30-60cm

Secondary shield
Epoxy mastic coating 90-120cm

Shield

Tarret Moored

Spread Moored

Regulatory requirements Economics Metal to be t t d M t l t b protected Service requirements Total current requirements Variation in environment Protective coatings Electrical shielding Maintenance Stray current effect Temperature Wire d bl Wi and cable

Design parameter Seawater Resistivity Saline Mud Anode open circuit potential - buried Anode open circuit potential - seawater Anode Consumption Anode Utilization Factor Coating Breakdown Factor (FBE) Insulation Breakdown Factor Neoprene Breakdown factor Design current density for bare steel in seawater Design current density in sand or mud 83

Typical Value 20 25 ohm-cm 100 150 ohm-cm -1.05 V (Ag/AgCl) -0.95 V (Ag/AgCl) 1280 A hours/ pound 0.80 0.5% to 1.0% (initial) 10% (after 30 years) 0.5% to 1.0% (initial) 3% (after 30 years) 0.5% to 1.0% (initial) 5% (after 30 years) 12mA/ft2 (initial) 7mA/ft2 (after polarization) 2mA/ft2 (initial and after polarization)

Approach pp
1. 2. 3. 3 4. 5. Determine the total surface areas in seawater and mud zones which are to receive cathodic protection. Calculate the start-up (initial) and maintenance current required to protect the structure. Calculate th C l l t the minimum weight of anode material required f a i i i ht f d t i l i d for 20-year service life. Estimate effective anode to structure resistances. Determine number and size of anodes required.

Where: IReq iis th t t l current demand (A the total td d (Amps) ) Idesign is the design current density Apipe is the total area of the pipeline i FCoating is the coating breakdown factor

IReq =Idesign*Apipe*FCoating/1000

(1)

4/16/2004

85

total anode weight required is then: Wanodes = (Ireq * 8760 h / hr/year * expected lif ) / (C t d life) (Consumption rate * ti t efficiency) (2) Where: Wanodes is the total anode weight need to provide the current requirement Ireq is the required current calculated in equation (1).

86

The number of anodes then is calculated as: Ntotal = Wanodes/ W bracelet Where: (3)

Ntotal is the total number of bracelet anodes requires Wanodes is the total weight calculated in equation (2). W bracelet is the weight of each individual bracelet

4/16/2004

87

NACE Standard RP0176, Corrosion Control of Steel Fixed Offshore Platforms Associated with Petroleum, is the most common criterion for d t i i f determining whether a structure iis receiving adequate cathodic h th t t i i d t th di protection. A negative (cathodic) voltage of at least 0.800 volts measured between the platform surface and a silver-silver chloride (Ag/AgCl) reference electrode contacting the water.

SACP

ICCP

Structures
Similar to rigs, platforms and ships

Difference
Unmanned Difficult to monitor/assess

Requirements
Long term performance Suitable for fabrication process Suitable for range of environment Ease of repair

Needs
Care in selection Quality application

Upper section atmospheric (C5 M) (C5-M)

blades, turbine, housings & structure (0.08 0.2 mm/y), UV Coating - durable, anti-corrosive anti corrosive

Lower section splash / tidal

tower structure (0.2 0.5 mm/y) UV (0 2 0 5 mm/y), UV, erosion Coating - durable, anti-corrosive

Bottom section tidal/immersed/buried (Im 2) ( )

tower structure (0.1 0.2 mm/y), fouling Coating - anti-corrosive, anti-fouling

Splashzoneisthemostcritical

CostProblemAccesstorepairthecoatedsurface CostProblemAccesstorepairthecoateds rface

Stagingdifficulttoerect&dismantle S i diffi l &di l

PhotoMuehlhan GmbH

Series of blasting & coating cells Auto blasting / more consistent Rz and surface cleanliness Some robot painting / internals Two component spray equipment Dust free environment Climate & temperature regulation Relative Humidity control y

Spray application epoxy / p/urethane multi layer systems or topcoats

PhotoMuehlhan GmbH

Thermal spraying Zn / Al alloy

metallization

Photo Muehlhan GmbH

Finishpaintinginternalareas

Photo Muehlhan GmbH

Coating performance failures can occur because of one or more of the following:
D i Design Product specification/selection Product quality q y Management processes Preparation/application Maintenance Repairs Climate/environmental control Worker skill

Bad spray application

Sharp edges

PhotosABS,Houston

Stress cracking in dry film

sagging

undercutting

holiday

chalking

discoloration

Disbonding

Blistering

Metallization has now achieved 30 40 years low maintenance protection on offshore oil & gas structures
The cost and application speed for systems which include this process are now close to or the same as for multi layer organic coating systems The reasons are a combination of New alloy materials New technology spray equipment Contractors improved ability to control the application environment The current trend in Europe is to thermally spray Zn / Al (first coat) 60 100 mic dft + sealer coat + 2 x EP topcoats Full exterior surface and internally 6-8 m up from bottom

UKRound3Windfarmzones

UK target 2020 15% of energy from renewables Estimated that the UK has 33% wind resources in Europe Offshore to be primary expansion zone. Wind is more constant and p predictable Jan 2010 UK govt awards Round 3 wind g farm zones / 9 successful bidders 75bn programme for offshore wind farm projects

Source:BWEA

MW Capacity Operational p Under construction & planned Zones awarded Number of turbine towers ( est )

2010

( Feb )

2015

2020

688 6,000 33,000 228 2,000 2 000 11 000 11,000

Source RenewableUK

Total Operational Capacity 10 year plan 40,000 MW Largest Offshore Capacity Plan in Europe

This is a major growth business sector.

Painting Offshore Wind Towers

Typical 3 MW Tower structure Painting area Painting cost g per tower p per tower 6250 31,250 6250 31,250 12,500 60 70,000 per tower External m2 1250 Internal m2 1250 Total m2 2500

EP / PU multi layer @ 5 / m2 Total cost Paint + Application up to 25 / m2 *

* Source JPCL / Muhlberg March 2010

Typical Wind Tower Structure

Installation cost per MW Installation cost per tower / 3MW Painting cost ( P+A ) per tower Paint + Application
as % tower installation cost

3.3 mill 10 mill 60 70,000 0.6 0.7%

Factory painting + site erection painting less than 1% of installed cost

Overview:Paintingareas&costs
Tower structures No. of Tower structures Painting P i ti areas 2500 m2 per 100m tower Painting costs Paint + Application 60 70,000 per tower 14-16 mill 120-140 mill 660-770 mill 0.57 mill m2 5 mill m2 27.5 mill m2 2010
( Feb )

2015 2,000

2020 11,000

228

If the build specification fails to perform f failure repetition can multiply by the number of towers in the f p py y f field

Tower structures No. No of Tower structures Total Painting area 2500 m2 per 100m tower p Total Painting cost Paint + Application 60 70,000 per tower Assume 3% area failure Offshore repair cost up to 1000/ m2

2010

( Feb )

2015 2,000 2 000 5 mill m2 120-140 mill 150,000 m2 150 mill

2020 11,000 11 000 27.5 mill m2 660-770 mill 825,000 m2 825 mill

228 0.57 mill m2 14-16 mill 17,100 m2 17 mill

Torepaironly3%areafailure couldcostmorethanthetotalinitialcostofpainting

To improve application efficiency and tolerance, possibly of existing basic technologies. T develop new i h To d l inherently more stable and durable chemistries, whi tl t bl d d bl h i t i hi ch meet all application requirements and give longer lifetimes. To develop coating systems that provide benefits to the wind tower f abricator, e.g., speed of cure (steel through put), lower VOC (solvent ) emissions

Standard/Specification
ISO 20340 O ti 1 Option
72 hours Salt spray 5% NaCl pH 7 (ISO 7253) 24 hours Dry out at -20C 72 hours Condensation/UV (ASTM G53) 4 hours UV at 60C, 4 hours condensation at 50C 72 hours Salt spray 5% NaCl pH 7 (ISO 7253) 24 hours Dry out at +23 C 72 hours Condensation/UV (ASTM G53) ( ) 4 hours UV at 60C, 4 hours condensation at 50C

ISO 20340 Cyclic Testing: Option 2

NORSOK M501

The submerged area (Monopod Type)

This can be protected by the application of a coating of two-part epoxy

compound, compound being applied at the construction yard. yard A method of cathodic protection using zinc anodes should also be used to compliment the epoxy coating. The anodes can be either fitted at the construction phase or an underwater sledge arrangement used. Both methods have their merits, the onshore fixing of the anodes to the structure being quicker and more economical, economical but difficult to replace under water water. An underwater sledge consists of a frame which contains numerous anodes welded into it. The frame is then positioned close to the support on the seabed and connected to the structure by heavy copper wire cables This method cables. allows for easy replacement of anodes but is expensive due to its installation to the location and, connection to the structure which requires underwater welding by divers divers.

LIFT TRIPOD JACKET

Areas sq. meters 205 350 806 318 1118 423 1849 646 2167 1055 1971 1572 5005 Mud Six Wells -150 Mud Line -120 -60 Elevation (M) Water Line 0

-30

-90 90

Elevation

Area Sq. Meters

Relative Fraction of Area

Number of Anodes

Meters 0 to 14 14 14 to 38 38 38 to 69 38 69 69 69 to 105 105 105 to 143 143 143 143 to 160 160 Totals 350 205 806 318 1118 423 1849 646 2167 1055 1971 1572 12,480 0.028 0.016 0.065 0.025 0.090 0.034 0.148 0.052 0.174 0.085 0.158 0.126 1.000 8 4 18 7 25 9 41 14 48 24 44 35 + 6 = 41 283

Coatings
Offshore wind tower (dry docking)

CP

, / ,

/ /

syli@correltech.com