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Presentation on

HYDROGEN INDUCED CRACKING AND SULFIDE STRESS CRACKING


by DENZIL D SOUZA

Contents
     

What is HIC/SSC ? How it occurs? Where is occurs? Standards used by ARAMCO Test Method to check HIC resistance steel Acceptance criteria

What is HIC HIC is internal cracks caused in material by trapped nascent hydrogen atoms. Atomic hydrogen, and not the molecule, is the hydrogen, smallest atom and it is small enough to diffuse readily through a metallic structure. When the crystal lattice is in contact or is saturated with atomic hydrogen, the mechanical properties of many metals and alloys are diminished

2H(atoms)


H2 (gas)

If the formation of molecular hydrogen is suppressed, the nascent atomic hydrogen atom can diffuse into the interstices of the metal instead of being harmlessly evolved as a gaseous reaction product thus producing a crack in the material. Residual and applied tensile stress not necessary for HIC Certain chemical species poison this recombination (e.g. cyanides, arsenic, antimony, or selenium compounds). However, the most commonly encountered species is hydrogen sulfide (H2S), formed in many petrochemical process.

Sources of hydrogen In the making of steel In processing parts, In welding, In storage or containment of hydrogen gas, Hydrogen as a contaminant in the environment having low ph that is often a by-product of general corrosion by-

Hydrogen embrittlement: embrittlement: Ingress of hydrogen into a component causing brittle failures
at stresses below the yield stress of susceptible materials. Methane formation Reduce ductility Reduce load bearing Capacity Crack formation Failure below Yield stress by brittle Fracture

HIC IN WELDING


Cold cracking/ HAZ cracking Source for Hydrogen entrapment Moisture Organic Compounds Occurs 72 hrs later of welding At 450 F H diffuse at rate of 1 inch /hr At 220 1 inch / 48 hr Room temp 2 weeks Prevention  Weld surface should free of moisture  PWHT 400-450 F holding for 1 hr. will redistribute the H 400thru diffusion. thus reducing risk of H cracking

    

Hydrogen Blistering Nucleation of Hydrogen gas at internal defects Rupture of material What is sour service ? Sour service is a environment containing water and H2S( hydrogen sulfide) with pressure of 50PPM If the presence of hydrogen sulfide i.e. sour services causes entry of hydrogen into the component, the cracking phenomenon is often termed Sulfide Stress cracking (SSC) Electrochemical corrosion reactions produce H atoms

Chemical Reactions


H2S(aq) H2S(aq) + H2O(l) H2O(l) + H2O(l)

H3O+(aq) + HS-(aq) (Bisulfide) --------1 aq) aq) Bisulfide) --------1 H3O+(aq) + OH-(aq) -----------------------2 aq) aq) -----------------------2

HS-(aq) + H2O(l) <==> H2S(aq) + OH-(aq) aq) S(aq) aq) S2-(aq)( Sulfide) + H2O(l) <==> HS-(aq) + OH-(aq) --------3 aq)( Sulfide) aq) aq) --------3

The sulfide ion then combines with ferrous ions to form iron sulfide. The metal surface is dissolved. How are H atoms ions produced ?

Factors influencing SSC


Increase in acidity ( low pH)  Carbon Dioxide  Increased stress  Ambient Temperature (-7 to 49 degree C) (

Medium strength steel are more susceptible for HIC The most vulnerable are high-strength steels, titanium highalloys and aluminum alloys.

a. Blister b. HIC c. SSC (low strength steel) d. (high strength steel)

 

Non Branching Fast Growing

Standards used


SAESSAES-A-301 ( Materials Resistant to Sulfide Stress Corrosion Cracking ) replaced now ISO 15156-2003 Petroleum and natural gas industries 15156 Materials for use in H2S containing environments in oil and gas production.


It gives requirements and recommendations for the selection carbon and low alloy steels for service in equipment, used in oil and natural gas production and natural gas treatment plants in H2S containing environments This addresses the resistance of the steel to damage that may be caused by SSC and HIC

01-SAMSS01-SAMSS-016 - Qualification of Pipeline, In plant Piping and pressure Vessel Steels for Resistance to Hydrogen Induced Cracking
SCOPE


This specification is supplementary to current NACE TM0284 (Evaluation of pipeline and pressure vessel steels for resistance of hydrogen induced cracking) Not Applicable to seamless pipe

Applicable for following steel products




High Frequency welded pipeline per 01-SAMSS-332 01-SAMSSOr / 01-SAMSS-333 01-SAMSSSubmerged arc welded pipeline 01-SAMSS-035 and 01-SAMSS01-SAMSS01-SAMSS038 Pressure Vessel Plate per 32-SAMSS-004 32-SAMSS-

Mandatory requirements


The steel manufacturer shall guarantee that the pipe fabrication cold forming processes will not compromise the HIC resistance of the strip/plate. Pseudo-HIC Resistant steel shall not be used to fabricate equipment intended for sour service application. Steel that passes the HIC test, but has not been initially manufactured to be HIC resistant steel shall not be used.
Pseudo-HIC Resistant Steel : Plate/Strip that is not fabricated utilizing the quality control/assurance and fabrication measures to intentionally produce HIC resistant steel.

Form 175-010200 - Inspection and testing requirements - HIC Testing

Appendix B-Test Procedure for BEvaluating HIC in H2S Saturated Solution A




This test procedure is described in NACE TM0284-2003 TM0284Solution A- A sodium chloride, acetic acid (NaCl, ACH3COOH) solution saturated with H2S at ambient temperature and pressure Solution B- A synthetic seawater solution saturated with H2S Bat ambient temperature and pressure As per 01 SAMSS-016 test solution shall be Solution A SAMSS-

Apparatus


Procedure


Each test specimen shall be 100 1 mm long by 20 1 mm wide. The test specimen thickness shall be the full wall thickness of the pipe up to a maximum of 30 mm. 3 test specimens shall be taken from each test pipe for pipes produced by continuous casting and 6 for ingot casting

Sample 1 Plate Rolling Direction Sample 2




3 Sample 3

Plate Thickness 30<T<89mm

Plate Thickness T>88mm

pH of solution A : 2.7 0.1 Concentration of H2S measured by iodometric titration, shall be min of 2300ppm Test duration :96 hrs Temperature :25 3 C

Evaluation of Test Specimens


    

Specimen shall be Sectioned Each section shall be polished metallographically and etched All faces to be examined shall be subjected to either wet magnetic particle testing or macro etching prior to final metallographic polishing Cracks shall be measured as illustrated in Figure Definitions:

The "Crack Length Ratio"(CLR) is defined as the sum of the lengths of the individual longitudinal cracks divided by the width of the polished specimen face times 100% CLR =( a W ) x 100 %

The "Crack Thickness Ratio" (CTR) is defined as the sum of the thickness of crack arrays divided by the thickness of the polished specimen face times 100%

CTR =(

b T ) x 100 %

Reporting Test Results




The CLR and CTR results of the control sample shall be reported. Longitudinal crack Avg CLR <10% Transverse crack Avg CTR < 3% pH of H2S saturated solution before addition of H2s,at the start and end of the test. Chemical composition of material tested, including Al, B, C, Ca, Cr, Cu, Mn, Mo, Ni, Nb, N, P, Si, S, Ti and V. Results of cracking evaluation. Photomicrographs of metallographically -polished (1 micron finish) specimens  Magnifications 100x to 500x Hardness shall not exceed 250 HV. (load 5-10 kg)

 

THE END
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