HighHigh--Performance Nickel Alloys: Performance Nickel Alloys: Solving Corrosion Problems Solving Corrosion Problems

in the Process Industriesin the Process Industries

TodayToday’’s Presentations Presentation• Nickel Alloy Families• Corrosion-Resistant Alloys• Heat-Resistant Alloys• Applications• Fabrication• Question & Discussion

Processing EquipmentProcessing Equipment

Oil & Gas ExtractionOil & Gas Extraction

Oil & Gas Oil & Gas RefiningRefining

Petrochemical Petrochemical ProcessingProcessing

Chemical ProcessingChemical Processing

Marine & Shipbuilding

Air Pollution ControlAir Pollution Control

Aqueous CorrosionAqueous CorrosionGeneralPittingCrevice

IntergranularGalvanic

Erosion - CorrosionStress-Induced Corrosion

Leaching

Corrosive MediaCorrosive Media• Acids (Hydrochloric, Sulfuric, Nitric, Acetic,

Formic, Phosphoric, Mixed)

• Salts & Brines (Chlorides, Fluorides, Nitrates, Sulfates)

• Caustic (Hydroxides & Carbonates)

• Seawater (Flowing, Stagnant, Onboard, Chlorinated)

Localized Corrosion in Localized Corrosion in Acid / Halide EnvironmentsAcid / Halide Environments

Pitting Attack Crevice Attack

Nickel Alloy CRA FamiliesNickel Alloy CRA Families• Nickel - Pure Nickel (200 & 201)• MONEL - Ni-Cu (400, K-500)• INCOLOY - Fe-Ni-Cr (800)• INCOLOY - Fe-Ni-Cr-Mo (825, 28, 27-7MO)• INCONEL - Ni-Cr-Fe (600 & 601)• INCONEL - Ni-Cr-Mo (625, 22, C-276, 686)

Pure Nickel Pure Nickel CRACRA’’ss

• UNS N02200 - Nickel 200• UNS N02201 – Nickel 201

NiNi--Cu Cu CRACRA’’ss• UNS N04400 - alloy 400• UNS N04405 – alloy R-405• UNS N05500 – alloy K-500• UNS C17500 – 70/30 Cu/Ni

NiNi--CrCr--Mo Mo CRACRA’’ss

• UNS N06625 - alloy 625• UNS N07725 – alloy 725• UNS N06022 – alloy 22• UNS N10276 – alloy C-276• UNS N06686 – alloy 686

FeFe--NiNi--CrCr--Mo Mo CRACRA’’ss• UNS N08825 - alloy 825• UNS N09925 – alloy 925• UNS N09945 – alloy 945• UNS N08020 – alloy 20• UNS N08028 – alloy 28• UNS N06985 – alloy G-3• UNS N07718 – alloy 718

SuperSuper--Austenitic Stainless SteelsAustenitic Stainless Steels

• UNS N08367 - alloy 25-6HN / 6XN• UNS N08926 – alloy 25-6MO / 1925HMo• UNS S31277 – alloy 27-7MO

With all of these With all of these different alloys, different alloys, how do I decide how do I decide which one to use? which one to use?

CorrosionCorrosion--Resistant Resistant Alloys for Service in Alloys for Service in Aggressive Aqueous Aggressive Aqueous

EnvironmentsEnvironments

““PRENPREN””Pitting Resistance Equivalency NumberPitting Resistance Equivalency Number

Chemical Composition & PREN of Corrosion-Resistant Alloys

Alloy Ni Cr Mo Nb W N PREN

AISI 316 Steel 12 17 2.2 20.4 INCOLOY 825 42 21.5 3 23.7

INCOLOY 25-6HN 25 20 6.5 0.20 35.8 INCONEL 625 62 22 9 3.5 40.8

INCOLOY 27-7MO 27 22 7.2 0.34 43.0 INCONEL C-276 58 16 16 3.5 45.2

INCONEL 22 60 20.5 14 3.5 46.8 INCONEL 686 58 20.5 16.3 3.5 50.8

PREN = %Cr + 1.5 (%Mo + %W + %Nb) + 30 (%N)

Localized Corrosion Resistance Localized Corrosion Resistance Critical Pitting & Crevice TemperaturesCritical Pitting & Crevice Temperatures

ASTM G48, Methods C & DASTM G48, Methods C & D

Alloy CPT (°C) CCT (°C) PREN*

316 Stainless Steel 20 <0 20.4 alloy 25-6MO (N08926) 70 35 35.8

alloy 625 (N06625) >85 35 40.8 alloy 27-7MO (S31277) >85 45 43.0 alloy C-276 (N10276) >85 50 45.2 alloy 686 (N06686) >85 >85 50.8

* PREN = %Cr + 1.5 (%Mo + %W + %Nb) + 30 (%N)

!!! BUT !!!!!! BUT !!!DonDon’’t Be Misled by t Be Misled by

Corrosion Test DataCorrosion Test Data

ASTM GASTM G--28, Method A28, Method ATypical Corrosion Rates (mm/a)Typical Corrosion Rates (mm/a)

C-276 6.4686 1.822 1.0

316L 0.5025-6MO 0.45

625 0.4027-7MO 0.38

Alloy ApplicationsAlloy ApplicationsWhat alloy do I use in a wet environment containing … ?

Reducing AcidsReducing Acids(H(H22SOSO44 & & HClHCl))

Ni-Cr-Mo and Fe-Ni-Cr-Mo AlloysMolybdenum is the Key Element

FeNiCrMo alloys 825, 20, G-3, SASSNiCrMo alloys 625, 22, C-276, 686

Weld with FM’s 625, 622, 686

NiNi--CrCr--Mo Alloys in Sulfuric AcidMo Alloys in Sulfuric Acid

The iso-corrosion lines indicate a corrosion rate of 20 mpy (0.51 mm/a)

NiNi--CrCr--Mo Alloys in Hydrochloric AcidMo Alloys in Hydrochloric Acid

The iso-corrosion lines indicate a corrosion rate of 20 mpy (0.51 mm/a)

Oxidizing AcidsOxidizing Acids(HNO(HNO33))

Ni-Cr and Fe-Ni-Cr AlloysChromium is the Key Element

FeNiCrMo alloy 825 & NiCrMo alloy 625NiCrFe alloy 690

Corrosion in Boiling 10% Nitric AcidCorrosion in Boiling 10% Nitric Acid

Oxidizing SaltsOxidizing Salts( FeCl( FeCl33, CuCl, CuCl22))

Ni-Cr-Mo and Fe-Ni-Cr-Mo AlloysChromium & Molybdenum are Key

FeNiCrMo alloy 825NiCrMo alloys 686, 22, 625

FGD Air Pollution Control SystemsSO2 abatement for coal-fired power plants create applications for super-austenitic alloys 25-6HN & 27-7MO & nickel-base CRA’s 22, C-276 & 686 for construction of new equipment & repair & upgrade of existing systems. Clad steel plate & sheet wallpaper are common construction scenarios.

Corrosion in a Simulated FGD MediumCorrosion in a Simulated FGD Medium

0

50

100

150

200

250

INCONEL alloy686

INCONEL alloyC-276

INCOLOY alloy27-7MO

VDM 31 INCONEL alloy625

INCOLOY alloy25-6MO

Cor

rosi

on R

ate

(mpy

)

168 Hour Tests in 60% H2SO4 + 2.5% HCl + 0.2% HF + 0.5% Flyash at 80oC

Hydrofluoric AcidHydrofluoric AcidNiCu alloy 400 - BestNiCrMo alloy 686 - GoodNickel 200 / 201 - GoodNiCrFe alloy 600 - Fair

Aeration, Temperature Critical - Ref: SMC-026

Hydrofluoric AcidHydrofluoric AcidIsoIso--Corrosion Chart for 20 Corrosion Chart for 20 mpympy (0.51 (0.51 mm/amm/a) )

MONEL alloy 400 in Hydrofluoric AcidMONEL alloy 400 in Hydrofluoric Acid

NiCu alloy 400 Alkylation Tower

Because of it resistance to corrosion by hydrofluoric acid, NiCu alloy 400 is the material of choice for fabrication of many components of the alkylation towers used in the production of high octane gasoline additives.

Organic AcidsOrganic AcidsFe-Ni-Cr-Mo & Ni-Cr-Mo Alloys

FeNiCrMo alloys 825 & 20NiCrMo alloys 625, 22, C-276 & 686

Aeration, Temperature Critical - Ref: SMC-026

FeNiCrMoFeNiCrMo alloy 825alloy 825Boiling 10% Organic Acid SolutionsBoiling 10% Organic Acid Solutions

Acid Corrosion Rate,mpy (mm/a)

Acetic <0.1 (<0.003)

Formic 2.5 (0.06)

Lactic 0.3 (0.008)

Melaic 0.1 (0.003)

Phthalic <0.1 (<0.003)

Oxalic 20 (0.51)

Corrosion in Boiling 40% Formic AcidCorrosion in Boiling 40% Formic AcidCorrosion Rate

Alloy mpy mm/a FeNiCrMo alloy 825 8.0 0.20

Nickel 200 10.4 0.26

NiCu alloy 400 2.2 0.06

NiCrFe alloy 600 10.0 0.25

NiCrMo alloy G-3 2.0 0.05

NiCrMo alloy 625 7.3 0.18

NiCrMo alloy C-276 2.8 0.07

Stress Corrosion Cracking due to Stress Corrosion Cracking due to PolythionicPolythionic & & NapthenicNapthenicAcids in Oil Refining & Petrochemical ProcessingAcids in Oil Refining & Petrochemical Processing

During downtime, polythionic & napthenic acids can form in refining & petrochemical processing systems. These acids can induce stress cracking in non-stabilized materials such as 800H and 304H. Stabilized nickel-base alloys 625, 825 & 20 are resistant to this attack.

Processing VesselsStainless steels & nickel-base CRA’s are used in the fine chemical & pharmaceutical industry because of their very low corrosion rates in a variety of aggressive media.

Heat Exchangers & CondensersHeat exchanger tubes, shells, baffles, and shells are fabricatedfrom corrosion-resistant nickel alloys, the choice being dictated by the temperature, pressure and environment.

Caustic & Strong AlkaliCaustic & Strong AlkaliMaterials with High Nickel Content

Nickel = Resistance to SCC

Nickel 200 / 201NiCu alloy 400

NiCrFe alloy 600Stress Relieve to Avoid SCC

CopsonCopson DiagramDiagramNickel vs. Stress Corrosion CrackingNickel vs. Stress Corrosion Cracking

Nickel 200 / 201 in Sodium HydroxideNickel 200 / 201 in Sodium Hydroxide

Plant Exposure TestsPlant Exposure Tests23% Caustic Soda at 22023% Caustic Soda at 220°°F (104F (104°°C)C)

Material Corrosion Rate, mpy (mm/a)

Nickel 200 0.16 (0.004)

NiCu alloy 400 0.20 (0.005)

NiCrFe alloy 600 0.17 (0.004)

Seawater & BrineSeawater & BrineNi-Cu, Ni-Cr-Mo & Fe-Ni-Cr-Mo Alloys

NiCu alloys 400 & K-500NiCrMo alloys 625, 725, 22, C-276, 686, FeNiCrMo alloys 20, 825, 925, 25-6MO,

& 27-7MO

Corrosion in Flowing Seawater Corrosion in Flowing Seawater 150 ft/sec. (45.7 m/sec.)150 ft/sec. (45.7 m/sec.)

Corrosion/Erosion Rate Material

mpy mm/a NiCrMo alloy 625 Nil Nil

FeNiCrMo alloy 825 0.3 0.008

NiCu alloys 400/K-500 0.4 0.01

Nickel 200 40 1.0

70/30 Cu/Ni 50 1.3

Carbon Steel 120 3.0

Corrosion in Stagnant Sea WaterCorrosion in Stagnant Sea Water3 Year Exposure Tests3 Year Exposure Tests

Max. pit depth Material inch mm NiCrMo alloy 625 Nil Nil FeNiCrMo alloy 825 0.00098 0.025 NiCu alloy K-500 0.034 0.864

NiCu alloy 400 0.042 1.067

316 Stainless Steel 0.052 1.575

Mild Steel 0.072 1.829

U.S. Navy Submarine “Virginia”Modern naval vessels may contain over a million pounds of nickel alloys including NiCrMo alloy 686 fasteners, NiCrMo alloy 725 forgings, NiCu alloy 400 piping, NiCrMo filler metal 625 weld overlays, & NiCu alloy K-500 chain.

Gasketed Plate Marine Heat ExchangerCoastal and on-board heat exchangers cooled with seawater are commonly used in marine service. Since the environment is hot seawater often containing chlorine for control of marine organisms, super-austenitic stainless steel & nickel-base corrosion-resistant alloys are required to combat corrosion by these aggressive conditions.

FastenersNuts, bolts, and other forms of fasteners for service in corrosive environments are manufactured from Nickel-base CRA’s including NiCrMo alloys 625, 686, 718 & 725 & NiCu alloys 400, R-405 & K-500.

Salt Evaporation VesselMONEL 400, INCONEL 625, & INCOLOY 25-6MO have excellent resistance to corrosion by sodium chloride and other chloride solutions and brines. Thus, these alloys are used for construction of salt production & evaporation equipment.

HeatHeat--Resistant Alloys Resistant Alloys for Service at Elevated for Service at Elevated

TemperaturesTemperatures

High Temperature CorrosionHigh Temperature CorrosionOxidationSulfidationNitridation

Chlorination Carburization

Molten Salt CorrosionLiquid Metal Embrittlement

Oil Refining & Petrochemical ProcessingNickel-base corrosion-resistant alloys are widely used in the refining and processing of petroleum & petroleum-derived products because of their resistance to stress corrosion cracking.

INCOLOY 800HT Ethylene Furnace

HeaderThe furnace header disperses the feedstock into the ethylene pyrolysis tubes where the formation of ethylene takes place. Ethylene is the major monomer used to form most of the polymers that are widely used in today’s society.

Ethylene Pyrolysis FurnacesTubes, hangers, and other assorted hardware in ethylene furnaces are fabricated from INCOLOY alloys 800HT and 803. These alloys provide high temperature strength, resistance to creep & carburization, and thermal stability for long term service.

I.D. Finned Ethylene Furnace TubesSpiral finned INCOLOY alloy 800HT & 803 ethylene tubes provide dependable, long term service. The finning greatly increases the efficiency of the ethylene pyrolysis process.

Chemical CompositionChemical CompositionINCOLOY AlloysINCOLOY Alloys

---0.50.50.321320.08INCOLOY alloy 800HT

---0.50.50.725360.09INCOLOY alloy 803

0.250.41.50.40.151.825440.1INCOLOY alloy 890

TaNbMoTiAlSiCrNiC

Oxidation ResistanceOxidation ResistanceMass Change in Air + 5% Water Vapor at 1000°C

-30

-25

-20

-15

-10

-5

0

5

10

0 2000 4000 6000 8000 10000

Exposure Time, Hours

Mas

s C

hang

e, m

g/cm

2

890803800HT

AlloyAlloyEvolutionEvolution

Alloy EvolutionAlloy EvolutionINCONEL alloy 600

(Ni – 16Cr)

INCONEL alloy 601 (Ni – 22Cr – 1.3Al)

INCONEL alloy 625 (Ni – 22Cr – 9Mo)

INCONEL alloy 690 (Ni – 30Cr)

INCONEL alloy 617 (Ni – 22Cr – 12Co – 9Mo - 1.3Al)

INCONEL alloy 693 (Ni – 30Cr – 3Al)

Alloy ApplicationsAlloy ApplicationsWhat alloy do I use to resist … ?

OxidationOxidationHigh Temperature Oxidizing

Environment

Cr & Al are Beneficial

INCONEL alloys 601, 617, 693INCOLOY alloy 803

Oxidation in Air @ 1100Oxidation in Air @ 1100°°C (2012C (2012°°F)F)

-40

-35

-30

-25

-20

-15

-10

-5

0

5

0 1000 2000 3000 4000 5000 6000

Time, Hours

Mas

s C

hang

e , m

g/c

m2

693

617

601

CarburizationCarburizationCr & Al are Beneficial

Good - INCOLOY 330, 800HT, & 803Best - INCONEL 601, 617, & 693

CarburizationCarburization ResistanceResistance

Metal DustingMetal DustingReducing / Carburizing Environment

INCONEL alloys 693INCONEL alloy 690INCONEL alloy 601

Metal Dusting ResistanceMetal Dusting ResistanceCO-20% H2 at 621°C

120-Grit Ground Samples

0

5

10

15

20

25

30

0 2000 4000 6000 8000 10000 12000 14000 16000

Exposure Time, Hours

Pit D

epth

, Mils

800

601

602CA

690

671

693-2

693-4

617

693-1

693-3

693-4 sample contains matching filler

NitridationNitridationNi is Beneficial; Al is Detrimental

High-Nickel INCONEL alloys

INCONEL alloy 600

SulfidationSulfidationCr is Beneficial / Ni is Detrimental

INCOLOY 800HT & 803INCONEL alloys 671, 690, & 693

Fabrication TipsFabrication Tips

““OverOver--MatchingMatching””Welding ProductsWelding Products

Plan as Carefully for Plan as Carefully for Welding as for Alloy Welding as for Alloy Selection in GeneralSelection in General

Use Overmatching Composition Use Overmatching Composition Welding Products to:Welding Products to:

• Offset Elemental Segregation in NiCrMo alloy Weldments

• Offset Iron Dilution when Welding Clad Steel or Cladding Steel

Preferential Corrosive Attack Preferential Corrosive Attack of Filler Metal Cof Filler Metal C--276 Weldments276 Weldments

INCOINCO--WELD 686CPT Weldments WELD 686CPT Weldments After Six Months ExposureAfter Six Months Exposure

Hastelloyalloy C-2000w/ matching fillermetal

VDM alloy 59w/ matching fillermetal

VDM alloy 59w/ INCO-WELD

Filler Metal 686CPT

Hastelloyalloy C-2000w/ INCO-WELD

Filler Metal 686CPT

Hastelloyalloy C-22w/ matching fillermetal

INCONELalloy 622w/ matching fillermetal

INCONELalloy C-276w/ matching fillermetal

Hastelloy alloyC-22

w/ INCO-WELD FillerMetal 686CPT

INCONEL alloy622

w/ INCO-WELD FillerMetal 686CPT

INCONEL alloyC-276

w/ INCO-WELD FillerMetal 686CPT

INCONEL alloy686

w/ INCO-WELD FillerMetal 686CPT

Welded Samples in Boiling Welded Samples in Boiling ((103103°°CC)) Green Death Green Death (11.9% H(11.9% H22SOSO44 + 1.3% + 1.3% HClHCl + 1% FeCl+ 1% FeCl33 + 1% CuCl+ 1% CuCl22

Overmatching Composition Overmatching Composition Welding ProductsWelding Products

Use INCONEL alloy 625 or 622 Welding Products for Joining 316 & 317 Stainless Steels, INCOLOY alloys 25-6MO & 825, & Alloys with 7% Molybdenum or Less

Overmatching Composition Overmatching Composition Welding ProductsWelding Products

Use INCO-WELD 686CPT Welding Products for Joining Alloys with Over 7% Molybdenum (e.g; INCONEL alloys 22, 625, C-276, & 686) & Alloy Clad Steel Plate

A thin section of a high alloy offers A thin section of a high alloy offers more corrosionmore corrosion--resistance than a resistance than a heavier section of a lower alloyheavier section of a lower alloy

FourFour--Alloy Test Panel After Six Alloy Test Panel After Six Month Exposure in a FGD Outlet DuctMonth Exposure in a FGD Outlet Duct

Conclusions from Test PanelConclusions from Test Panel• Components built from 1/4” austenitic or

super-austenitic stainless steel plate and exposed to these conditions would have a life expectancy of less than 6 months.

• Components built of 1/16” NiCrMo alloy 686 clad steel plate or lined with 1/16”NiCrMo alloy 686 sheet (“wallpaper”) and exposed to these conditions would have a long (“unlimited”) life with no “end-of-life”event indicated.

Cost Savings Cost Savings RollRoll--Clad Alloy Steel PlateClad Alloy Steel Plate

Pressure & Storage Vessel ConstructionCorrosion Resistance = Solid Alloy Plate Economical - 1/2 Solid Alloy Plate Cost

Established Forming & Welding ProceduresLong History of Successful Usage

ASTM & ASME Standards

““RollRoll--BondingBonding””Clad Packet AssemblyClad Packet Assembly

““RollRoll--BondingBonding””Clad Packet AssemblyClad Packet Assembly

Steel Boiler Tube Weld Clad with INCONEL Filler Metal 625Boilers in coal-fired & waste-to-energy power production use alloy steel superheater tubes with a protective cladding deposited with INCONEL 52, 72, 72M, 622, 625, & 686 welding products.

So, whatSo, what’’s new s new from SMC R&D?from SMC R&D?

INCONEL alloys 945 & 945XINCONEL alloys 945 & 945XFeFe--46Ni46Ni--22Cr22Cr--3Mo3Mo--2Cu2Cu--3Nb3Nb--2Ti2Ti

• “Do-it-all” alloys for the Oilfield• Strength + Corrosion Resistance at an

Economical Price• NACE MR0175 Level VII• Replacements for alloys 718, 725, 925,

625-Plus, K-500, etc.• Lower Cost than alloys 718 & 725

INCONEL alloy 740HINCONEL alloy 740HNi Ni -- 24Cr 24Cr -- 20Co 20Co -- 1.5Nb 1.5Nb -- I.7Ti I.7Ti -- 1.1Al1.1Al

• An Age Hardenable, High Temperature Superalloy for Ultra-Supercritical Power Production

• Excellent Heat Resistance• High Strength to 800°C • Excellent Stability, Fabricability, &

Weldability

Available Product FormsAvailable Product Forms

Plate, Sheet, & Strip Seamless Tube & PipeRod, Bar, & Wire RodForging StockWelding Products

Thank You !!!Thank You !!!