January 21st, 2009

Robert J. Sinko

Corrosion Experts!
An expert is someone who carries a briefcase and

comes from more than 50 miles away (anonymous)

An expert is a man who has made all the mistakes

which can be made in a very narrow field (Niels Bohr)

Outline of the Talk

A Little History Corrosion Basics Top Corrosion Mechanisms Monitoring Corrosion and Obtaining Data Materials Selection Points to consider Continuing Education Questions

A Little History
Corrosion has been here since the copper age.
18th century has Luigi Galvani and Allesandro Volta

dabbling in electrochemistry. A. Volta goes to make the 1st recorded battery or voltaic pile

A Little More History

Sir Humphry Davy in early 1800s passes current through substances to decompose them (electrolysis). Concludes that the voltaic piles and electrolysis were same process.

Claims that current is generated only when the electrolyte and one of the metals was oxidized
Found that two metals are not required as

reaction proceeds with zinc and carbon. Initiated the use of zinc as a sacrificial anode for copper hulled British warships

A Little MORE History

Michael Faraday had been Sir Davys lab flunky but

outgrew the role in the 1830s he contributed by developing the theory of electrochemical action and coined the following words we use now. Electrode Electrolysis Ion Sir Davy tried to block Faradays election to the Royal Society There are countless more that have moiled in the service

Corrosion Basics/History
Man sees ore in lowest energy state

Man transforms ore in useful object

Nature wants her dirt back Nature transforms the object back to dirt. Remember J.W. Gibbs (free energy diagram)?
He really worked with the 2nd Law of Thermo in the

late 1800s.

(You cant break even - entropy)

Smelted, heated and beated, forged, ground, drilled and machined

Useful life!
Left out in the rain

Energy

Ore

Rusted away

Time

Corrosion Basics
Corrosion is electrochemical
Anode (Oxidizing losing electrons) Electrode Cathode (Reducing gaining electrons) Electrode Need Short circuit for electrons between terminals And need a medium for ion transport

Electricity and chemicals are main drivers Influenced by other factors

Corrosion Basics
Usual Textbook Equations Chemical: Zn + 2HCl = ZnCl2 + 2H Electrical: Zn Zn+2 + 2e- (anode) 2H+ + 2e2H (cathode) Note: hydrogen is atomic, not diatomic This can come back to get you Generally, the electrical part is not shown Oxygen reaction can be inserted as well

Note that atomic hydrogen forms on surface and becomes diatomic in solution. Hydrogen atoms can be absorbed into materials (Ti and carbon steel couple) Figure 2.6 Electrochemical reactions occurring during the corrosion of zinc in air-free hydrochloric acid.
Used by permission, NACE, Corrosion Basics An Introduction, NACE, 1984, pg 28.

Corrosion Basics- Other Factors

Corrosion rates are almost initially very high Polarization something to slow down reactions
Cathodic and anodic surface polarization Film thickness of corrosion product Rate of hydrogen or oxygen diffusion to and from surfaces

Rate of corrodant ion diffusion away

Areas of reaction (anode to cathode) Oxygen Content (cathodic depolarizer) Temperature every 10C = 2 x corrosion rate Velocity effects moving species to & fro

Corrosion Top Mechanisms

General
Pitting Crevice
Enviromental Cracking
Stress Corrosion Hydrogen Embrittlement Liquid metal embrittlement

Underdeposit
Dealloying Galvanic

Corrosion Fatigue
Cavitation Erosion

Corrosion Top Mechanisms General

The even removal of metal.
Allows great planning Monitoring Replacement and scheduling Unfortunately, rare in the real world.

What general corrosion might look like!

Corrosion Top Mechanisms Pitting

Most common form of localized attack
Break down of protective scale Localized attack in break Pit sets up its own environment Draws in chlorides and sulfates Can form caps over pits Low corrosion rates are deceitful

Pitting corrosion small and large

Corrosion Top Mechanisms Crevice

Much like a large area pit.
Occurs in cracks or crevices Think of flanged connections such as Piping flanges Column body flanges Trays on tray rings Car or truck doors It will also set up its own environment

Crevice attack on titanium from fluorinated o-ring

Severe crevice attack as well as general

Corrosion Top Mechanism Underdeposit

Very similar to crevice corrosion but a larger
Usually an unplanned occurrence Tools left on floor River water silt buildup in bottoms Sometimes called poultice corrosion Sometimes called oxygen concentration cell

Corrosion Top Mechanism Dealloying

Copper alloys
Brasses with >30% zinc (bath sink tap screws) Copper nickel alloys (nickel removed)

Cast iron (graphitization) Almost any alloy can have the problem Two Theories
One element is leached from solution Both elements corroded but more noble plates back.

Brass River Water Impellor suffering from dealloying and cavitation

Corrosion Mechanisms Galvanic

Think dry cell battery Carbon center cathode Zinc jacket anode MnOH (manganese hydroxide paste) Switch short circuit provided by your flashlight Galvanized water pipe to your house
Powerhouse soot blower of SS nozzle and steel pipe

Over the road trailers with Al sides and steel rivets

Your water heater with aluminum sacrificial anode

SS Nozzle

CSTL Pipe

Soot blower metallographic sample

Corrosion Top Mechanisms Environmental Cracking

Stress Corrosion Cracking Chlorides (aluminum, 300 series SS) Caustic (cstl, 300 series SS, nickel alloys) Ammonia (brass drain) Hydrogen Embrittlement
Liquid Metal Embrittlement Copper on stainless steel pipe Zinc on stainless steel pipe

Weld metal

Knife line attack Transgranular chloride SCC in 316 stainless steel

Intergranular caustic SCC in 304L stainless steel finned tube.

If your sink at home is a nice shiny chromium plated brass, do not pour your ammonia down this drain and let it sit overnight. It will stress corrosion crack!

PVC/galvanized steel trap drains go ahead no problem with ammonia.

Corrosion Top Mechanism Corrosion Fatigue

Starts with an alternating stress state
Protective oxide breaks open Corrosive species attack and form products Next cycle repeats: crack growth more corrosion product accelerated fatigue failure Seen in rotating shafts

Corrosion fatigue, cracks can be oriented the other direction depending on stress state of shaft.

Corrosion Top Mechanisms Cavitation

Mostly found at

Pump impellor tips Boat propellers Constriction in fast fluids

Caused by formation of low pressure bubble Bubble is a vacuum Collapse of bubble slams the metal

Breaking protective oxide Causing great mechanical damage

Piece of pump impellor with tip cavitation

Valve trim diffuser with cavitation

Centrifuge feed nozzle

Corrosion Top Mechanism Erosion

Can be from Gaseous vapor (steam cuts on flanges) Liquid Solids (Coal slurry) Removes the protective oxide layer faster than it can

heal

Look for comet tails! Water was flowing from right to left in copper water pipe.

Monitoring Corrosion
Visual examination for leaks Lab testing Field testing (Corrosion racks with coupons) Corrosion probes ER (electrical resistance) LPR (linear polarization resistance) New technology Metals analysis in process fluids

Coupons
All kinds of materials and shapes Metals Plastics Fiber reinforced plastics Ceramics Elastomers Glass Homemade or store bought coupons Welds Heat treatments

Corrosion Lab Testing

Coupons
Lab testing at many temps but low pressure Heat flux testing to simulate exchangers

High pressure labs

Ingenious bench scale or pilot plant testing Key question - What do you want to know?

Agitator blades as corrosion coupons

Weld wires as coupons

Field Corrosion Tools

Corrosion racks

Electrical resistance probes

Linear polarization resistance probes New technology Using electrical noise LPRs ERs Metals analysis in solutions

Typical field corrosion rack for insertion through a nozzle.

V = I*R

Electrical resistance probe

R = *l/A

Linear Polarization Resistance Probe

Gives instantaneous corrosion rates
Only used in conductive solutions Based on the current flow between two or more electrodes Requires the surface to become passivated (or polarized) and current resistance is measured. Sometimes probe has a reference electrode as well.

Honeywells SmartCET uses a sensor for background electrochemical noise to detect pitting along with LPR probe and a sophisticated computer program.
http://hpsweb.honeywell.com/NR/rdonlyres/8418C7B6EBB9-4948-8441C3803B06BA2E/44686/ChemEngJune07.pdf

Newer Technology

Other Tools of the Trade

Electron Microscopy
Elemental analysis

Surface features

FTIR for identification X-ray Diffraction

X-ray Fluorescence Looking for clues by

Metals in fluids

Fluids in plastics
Corrosion products

Materials Selection
Basic Groups
Metals Plastics Ceramics Elastomers Coatings Linings

Balance of +s and -s
Corrosion Resistance Availability Mechanical Properties Cost Code Compliance Fabricability Repair options

Materials Selection Metals

Carbon steels Aluminum (3000, 5000 and 6000 series) Coppers, brasses, and bronzes Stainless steels
Austenitic (200 and 300 series)

Martensitic (400 series)

Precipitation hardening (17-4 PH) Duplex (2101, 2205, 255, and 2507)

Nickel Alloys (600 series, C, B, X, Inconel, Hastelloy)

Titanium alloys (common grades 2, 5, 7, and 11) Zirconium

Materials Selection - Plastics

HDPE and Polypropylene (low end)

PVC and CPVC

Resins epoxy, vinyl esters Fluoropolymers PTFE, PFA, FEP, ETFE, PVDF PEEK (high end) Can be used as monolithic or composite pieces in

equipment

Material Selection - Coatings

Coatings (thin or thick films) Many different technologies Always have holidays With or without reinforcement? Linings (how to anchor) Whats your permeation rate? Differences in thermal expansion rates How do you clean?

Materials Selection - Ceramics

Concrete
Acid proof bricks and mortar Refractory Glass lined steel Alumina Silicon carbide Silicon nitride

Materials Selection -Elastomers

Natural Rubbers
Nitriles Neoprenes

Compatibility
Temperature limit Mechanical properties

Polyurethanes
EPDM Silicones

Availability
Supply Chain Identification

Viton
Kalrez or Chemraz

Specifications

Gaskets & Sealing

Gasketing has many options

CNA Fiber sheet gaskets (250F limit) Rubber sheet goods (250F to 350F limits) PTFE sheets and composites (350F limit) Expanded PTFE products (600F limit) Graphite gaskets (600F limit) Spiral wounds (rings, windings and fillers) Ring joints (for high T & P) Specialty materials (Thermiculite, Cogebi)

Know Your Service

Know your process conditions?
What are the upset conditions? What are your projected lives for process? What external/environmental factors? How are you going to clean your equipment?

Corrosion Classes
Continuing Education
NACE has Basic Corrosion classes in Houston, TX.
www.nace.org is the homepage, direct link is,
http://web.nace.org/departments/education/Program.aspx?id=403af18b-

d51c-db11-953d-001438c08dca

ASM International has Corrosion Courses in Metals

Park OH.
www.asminternational.org is the hompage, direct link is,
http://asmcommunity.asminternational.org/portal/site/www/Education/C

ourseCalendar/

Last quote that sums it up for Corrosion!

..until you return to the ground from which you were

taken, for you are dirt and to dirt you shall return (Genesis 3:19)