CORROSION RATE MEASUREMENTS

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Basic Corrosion Measurements

If a piece of metal:

corrodes to this:

How would we know how much corrosion had occurred? Clearly, we need before and after measurements Mass?
Weigh before, weigh after To be of any use, a weight loss measurement has to be scaled to the size of the specimen corrosion is a surface related phenomenon.

Basic Corrosion Measurements

Size?
Length, Length , width and/or thickness before before
What about after?

Volume before and after by y liquid q displacement p

Sensitive enough?

M Mass? ?
Weigh before, weigh after To be of any use, use a weight loss measurement has to be scaled to the size of the specimen corrosion is a surface related phenomenon.

Basic Corrosion Measurement

Because corrosion is a surface phenomenon, weight loss is related to surface area. For example: a metal coupon having a total surface area of 10 cm2 loses 1 mg when h exposed d to t a particular ti l environment i t for f a month; th

1 mg Total corrosion = 10 cm 2
which should be a characteristic amount for that metal in that environment in a month.

mg Rate = 0.1 01 cm 2 month

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Basic Corrosion Measurement

Corrosion engineers traditionally work in units of dm2, thus:
mg cm2 mg 0.1 2 10 100 = = 10 mdm 2 2 cm month dm dm month

BUT even though mdms give reasonable numbers for most corrosion situations situations, the month is a bad unit

So,

mg dm 2 day

are often used . mdd

Basic Corrosion Measurement

If we know the metal density density, we can convert the weight loss to penetration: for in g/cm3:

1g mg cm 3 dm 2 x 5 = = 10 cm / day 2 2 dm day g 1000 mg 100 cm x

Basic Corrosion Measurement

However, we note that 1 cm = 104 m, thus:

10

cm x m day d x m 0.1 365 36.5 day day yr yr

A Another th common unit it for f corrosion i penetration t ti (in (i the th US) i is the th mil or milli-inch per year (=0.001 in/year or mpy).

m
yr

z mil 25.4 yr

Basic Corrosion Measurement

NOTE: these rates are averaged over the exposure time, and are quoted as if corrosion were constant with time though it often is not

Corrosion rate 1 =

M1 T1

Corrosion rate 2 =

M2 T2
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Basic Corrosion Measurement

Often, our bit of metal ..

after exposure, looks like this

It is covered with scale. How would we assess corrosion under these conditions?

Basic Corrosion Measurement

Consider the scaling process
Weight before = Wo [g] Surface area = A [dm2]

Exposure time = [days] Find condition; weight after = W1 [g]

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Basic Corrosion Measurement

We can only be sure that the remaining metal provides an unequivocal reference, so Descale

Descaled weight = W2 [g]

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Basic Corrosion Measurement

Total corrosion amount =
(divided by for rate mdd mdd) ) We also have a measure of the weight of scale

(W0 W2 ) 1000 mg mg 2 A 1g dm

(W1 W2 ) g scale = A dm 2
If we assume the scale is composed of Fe2O3, we can calculate the iron in scale as

Fein scale Fein scale

(W1 W2 ) = fraction of Fe in scale A 1000 mg (W W2 ) ( 2 56 ) = 1 A ( 2 56 ) + ( 3 16 ) 1g

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Basic Corrosion Measurement

Fein scale (W1 W2 ) mg = 700 A dm 2

The difference between iron in scale and total amount corroded is either
Iron released to environment OR Iron deposited p from environment

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How Do We Descale?
Chemically or electrochemically usually in weak acids (See Table 1.2). BUT such descaling can also dissolve some of the remaining metal, so how h do d we account t for f thi this? ?
Employ an inhibitor Use a blank Figure 1.24. (ASTM G1)

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Summary
Simplest and most powerful technique for corrosion rate determination is the Weight Loss Technique Corrosion Rate = mass/[(exposed surface area] [time]) or = Average corrosion penetration depth/time = (mass/density/surface area/time) Common Corrosion Rate Units
gmd: grams of metal loss per square meter per day (mdd (mdd) ) mm/y: / average millimeters illi t penetration t ti per year mpy: average mils penetration per year, 1 mil = 0.001 inch)

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Basic Corrosion Measurement (Non(Non -uniform Corrosion)

NOTE: such corrosion measurements and units are useful for general or uniform corrosion but they dont work for localized corrosion (e.g. pitting or cracking). A component can fail by stress corrosion cracking (SCC) with no detectable weight loss

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Basic Corrosion Measurement

For these situations, we use concepts such as crack propagation rate o or pit p p propagation p g rate. For example:
percent

through through-wall wall for tubes tubes, pipes pipes, vessels vessels, etc etc.; ;

crack depth or pit depth usually in mil or mm;

propagation rate

m
yr

mm etc. yr

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Industrial Corrosion Measurement

How would you measure (estimate) the corrosion of plant components? p p For example:
pressure vessels or pressure tubes; f d pipes feeder i steam generator tubes; feedwater pipes and heaters; etc. etc.

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Corrosion Rate Measurement Technique

Corrosion coupon (weight loss measurement) Electrochemical methods
Potentiodynamic polarization (Tafel analysis) Linear p polarization resistance (LPR) ( ) Electrochemical impedance spectroscopy (EIS) Corrosion potential (EN) ) Electrochemical noise (

NonNon-electrochemical methods
Electrical resistance (ER) Hydrogen monitoring Chemical analysis Microscopy

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Corrosion Coupons
Various coupon shapes and sizes

ASTM G58

C Ring ASTM G38

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Example: Atmospheric Exposure Test

Image source: www.corrosionsource.com

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Electrochemical Techniques

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Electrochemical Polarization
Involving large perturbation
Potentiodynamic polarization ( (Tafel Tafel analysis)

Involving small perturbation

Linear polarization resistance (LPR) Electrochemical impedance spectroscopy (EIS)

Involving g no perturbation p
Corrosion potential (Ecorr) Electrochemical noise (EN)

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Electrical Resistance (ER) Method

Measures the change in electrical resistance of a corroding metal elements relative to a reference non non-corroding element sealed within ithi the th probe b body. b d

L R= A

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ER Probe Types

Image source: (1) Alabama Specialty Products, www.metalsamples.com (2) S.Y. Li et al., Mat. Chem. Phys., 103 (2007) 9

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Hydrogen Permeation Monitoring

The generation of atomic hydrogen, as part of the cathodic reaction in acidic environments, can be used for corrosion monitoring purposes. Hydrogen monitoring sensors are often attached to the outside walls of vessels and piping.

Image source: IonScience, www.ionscience.com

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Hydrogen Permeation Monitoring Principles

Pot 1

Pot 2

As hydrogen passes through the metallic wall of the vessel it enters a probe chamber attached tightly to the outside wall, leading to
Pressure increase with time within the chamber An electrochemical current resulting from the oxidation of hydrogen under an applied potential A current generated in an external circuit, as hydrogen enters a miniature fuel cell.

C harge Side + H + e -> H C athodic to p roduce H C ounter electrode

Oxidize Side
+ H + OH -> H O 2

Measure C urrent mA/cm 2

Ref elect Working electrode Samp le Memb rane Solutions NaOH 1M

Devanathan-Starchurski Technique

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Surface Analysis: Microscopy

SEM image of a cross section of a steel specimen including an iron carbonate film. Exposed for 10 hrs at T=80oC, pH 6.6, PCO2 = 0.54 bar, Fe2+ = 250 ppm, v = 1 m/s

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Surface Analysis: Microscopy

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Radiographic Inspection

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Standards for Corrosion Testing

ASTM A90/A90M Weight of Zinc Coatings A262 Practice A (Oxalic Acid Etch) A262 Practice B (Streicher Test) A262 Practice C (Huey Test) A262 Practice E (Modified Strauss Test) A380 Cleaning and Descaling Stainless Steels A923 SSAT Duplex Stainless Steels B813 Liquid and Paste Fluxes for Soldering Copper B154 Mercurous Nitrate Copper and Copper Alloys C871 Extraction of Leachable Ions D1141 Ocean Water D1193 Reagent Water D2240 Rubber Property Durometer Hardness D2583 Barcol Hardness D4340 Pressurized Hot Wall E3 Standard Metallographic Practice E45 Inclusion Content E112 Grain Size F746 Medical Implants F2129 E/C Testing of Surgical Implants G1 Preparation, Cleaning, Evaluating Test Specimens G3 Conventions Applicable to E/C Measurements NACE TM0169 Standard Immersion TM0174 Protective Coatings TM0177 Sulfide Stress Corrosion TM0284 Resistance to Hydrogen Induced Cracking (HIC) G5 Potentiostatic/Potentiodynamic Anodic Polarization G28 Method A (Ferric Sulfate/Sulfuric Acid) G28 Method B (PEMT) G31 Immersion Testing G36 Boiling Magnesium Chloride G44 Alternate Immersion Testing G47 Stress Corrosion Cracking of Aluminum G48 Method A (Ferric Chloride Pitting) G48 Method B (Ferric Chloride Crevice) G48 Method C (Ferric Chloride Critical Pitting) G48 Method D (Ferric Chloride Critical Crevice Temperature) G49 Constant Load Test G61 Cyclic Potentiodynamic G71 Galvanic Couple p Test G75 Miller Wear Test G102 Calculation of Corrosion Rates from E/C Measurements G108 E/C Reactivation for Detecting Sensitization G123 Boiling Sodium/Calcium/Lithium Chloride G150 Critical Pitting Temperature

ISO ISO 6509 Dezincification of Brass

OTHER Corrositex Assay y DuPont SW800M SSAT DuPont SW1P Ferroxyl Test

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Homework
1) What are the four component of a corrosion cell and list five different cathodic reactions DO NOT LIST FIVE METAL REDUCTION REACTIONS!!! 2) Problems 1-4 3) Problems 1 1-9 Due: Next week

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