High-Performance Nickel Alloys: Solving Corrosion Problems in the Process Industries

Todays Presentation
Nickel Alloy Families Corrosion-Resistant Alloys Heat-Resistant Alloys Applications Fabrication Question & Discussion

Processing Equipment

Oil & Gas Extraction

Oil & Gas Refining

Petrochemical Processing

Chemical Processing

Marine & Shipbuilding

Air Pollution Control

Aqueous Corrosion
General Pitting Crevice Intergranular Galvanic Erosion - Corrosion Stress-Induced Corrosion Leaching

Corrosive 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 Acid / Halide Environments

Pitting Attack

Crevice Attack

Nickel 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 CRAs

UNS N02200 - Nickel 200 UNS N02201 Nickel 201

Ni-Cu CRAs
UNS N04400 - alloy 400 UNS N04405 alloy R-405 UNS N05500 alloy K-500 UNS C17500 70/30 Cu/Ni

Ni-Cr-Mo CRAs
UNS N06625 - alloy 625 UNS N07725 alloy 725 UNS N06022 alloy 22 UNS N10276 alloy C-276 UNS N06686 alloy 686

Fe-Ni-Cr-Mo CRAs
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

Super-Austenitic Stainless Steels

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

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

Corrosion-Resistant Alloys for Service in Aggressive Aqueous Environments

PREN
Pitting Resistance Equivalency Number
Chemical Composition & PREN of Corrosion-Resistant Alloys
Alloy AISI 316 Steel INCOLOY 825 INCOLOY 25-6HN INCONEL 625 INCOLOY 27-7MO INCONEL C-276 INCONEL 22 INCONEL 686 Ni 12 42 25 62 27 58 60 58 Cr 17 21.5 20 22 22 16 20.5 20.5 Mo 2.2 3 6.5 9 7.2 16 14 16.3 Nb W N PREN 20.4 23.7 35.8 40.8 43.0 45.2 46.8 50.8

0.20 3.5 0.34 3.5 3.5 3.5

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

Localized Corrosion Resistance Critical Pitting & Crevice Temperatures ASTM G48, Methods C & D
Alloy
316 Stainless Steel alloy 25-6MO (N08926) alloy 625 (N06625) alloy 27-7MO (S31277) alloy C-276 (N10276) alloy 686 (N06686)

CPT (C)
20 70 >85 >85 >85 >85

CCT (C)
<0 35 35 45 50 >85

PREN*
20.4 35.8 40.8 43.0 45.2 50.8

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

!!! BUT !!!

Dont Be Misled by Corrosion Test Data

ASTM G-28, Method A

Typical Corrosion Rates (mm/a)

C-276 686 22 316L 25-6MO 625 27-7MO

6.4 1.8 1.0 0.50 0.45 0.40 0.38

Alloy Applications
What alloy do I use in a wet environment containing ?

Reducing Acids
(H2SO4 & HCl) Ni-Cr-Mo and Fe-Ni-Cr-Mo Alloys
Molybdenum is the Key Element FeNiCrMo alloys 825, 20, G-3, SASS NiCrMo alloys 625, 22, C-276, 686 Weld with FMs 625, 622, 686

Ni-Cr-Mo Alloys in Sulfuric Acid

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

Ni-Cr-Mo Alloys in Hydrochloric Acid

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

Oxidizing Acids
(HNO3) Ni-Cr and Fe-Ni-Cr Alloys
Chromium is the Key Element FeNiCrMo alloy 825 & NiCrMo alloy 625 NiCrFe alloy 690

Corrosion in Boiling 10% Nitric Acid

Oxidizing Salts
( FeCl3, CuCl2) Ni-Cr-Mo and Fe-Ni-Cr-Mo Alloys
Chromium & Molybdenum are Key FeNiCrMo alloy 825 NiCrMo alloys 686, 22, 625

FGD Air Pollution Control Systems

SO2 abatement for coal-fired power plants create applications for super-austenitic alloys 25-6HN & 27-7MO & nickel-base CRAs 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 Medium

250 200 Corrosion Rate (mpy)

150

100

50

0
INCONEL alloy INCONEL alloy INCOLOY alloy 686 C-276 27-7MO VDM 31 INCONEL alloy INCOLOY alloy 625 25-6MO

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

Hydrofluoric Acid
NiCu alloy 400 - Best NiCrMo alloy 686 - Good Nickel 200 / 201 - Good NiCrFe alloy 600 - Fair
Aeration, Temperature Critical - Ref: SMC-026

Hydrofluoric Acid
Iso-Corrosion Chart for 20 mpy (0.51 mm/a)

MONEL 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 Acids
Fe-Ni-Cr-Mo & Ni-Cr-Mo Alloys
FeNiCrMo alloys 825 & 20 NiCrMo alloys 625, 22, C-276 & 686
Aeration, Temperature Critical - Ref: SMC-026

FeNiCrMo alloy 825

Boiling 10% Organic Acid Solutions
Acid
Acetic Formic Lactic Melaic Phthalic Oxalic

Corrosion Rate, mpy (mm/a)

<0.1 (<0.003) 2.5 (0.06) 0.3 (0.008) 0.1 (0.003) <0.1 (<0.003) 20 (0.51)

Corrosion in Boiling 40% Formic Acid

Alloy
FeNiCrMo alloy 825 Nickel 200 NiCu alloy 400 NiCrFe alloy 600 NiCrMo alloy G-3 NiCrMo alloy 625 NiCrMo alloy C-276

Corrosion Rate mpy mm/a

8.0 10.4 2.2 10.0 2.0 7.3 2.8 0.20 0.26 0.06 0.25 0.05 0.18 0.07

Stress Corrosion Cracking due to Polythionic & Napthenic Acids 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 Vessels
Stainless steels & nickel-base CRAs are used in the fine chemical & pharmaceutical industry because of their very low corrosion rates in a variety of aggressive media.

Heat Exchangers & Condensers

Heat exchanger tubes, shells, baffles, and shells are fabricated from corrosion-resistant nickel alloys, the choice being dictated by the temperature, pressure and environment.

Caustic & Strong Alkali

Materials with High Nickel Content
Nickel = Resistance to SCC Nickel 200 / 201 NiCu alloy 400 NiCrFe alloy 600 Stress Relieve to Avoid SCC

Copson Diagram Nickel vs. Stress Corrosion Cracking

Nickel 200 / 201 in Sodium Hydroxide

Plant Exposure Tests

23% Caustic Soda at 220F (104C)
Material
Nickel 200 NiCu alloy 400 NiCrFe alloy 600

Corrosion Rate, mpy (mm/a)

0.16 (0.004) 0.20 (0.005) 0.17 (0.004)

Seawater & Brine

Ni-Cu, Ni-Cr-Mo & Fe-Ni-Cr-Mo Alloys NiCu alloys 400 & K-500 NiCrMo alloys 625, 725, 22, C-276, 686, FeNiCrMo alloys 20, 825, 925, 25-6MO, & 27-7MO

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

Material
NiCrMo alloy 625 FeNiCrMo alloy 825 NiCu alloys 400/K-500 Nickel 200 70/30 Cu/Ni Carbon Steel

Corrosion/Erosion Rate mpy mm/a

Nil 0.3 0.4 40 50 120 Nil 0.008 0.01 1.0 1.3 3.0

Corrosion in Stagnant Sea Water

3 Year Exposure Tests
Material
NiCrMo alloy 625 FeNiCrMo alloy 825 NiCu alloy K-500 NiCu alloy 400 316 Stainless Steel Mild Steel

Max. pit depth inch mm

Nil 0.00098 0.034 0.042 0.052 0.072 Nil 0.025 0.864 1.067 1.575 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 Exchanger

Coastal 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.

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

Salt Evaporation Vessel

MONEL 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.

Heat-Resistant Alloys for Service at Elevated Temperatures

High Temperature Corrosion

Oxidation Sulfidation Nitridation Chlorination Carburization Molten Salt Corrosion Liquid Metal Embrittlement

Oil Refining & Petrochemical Processing

Nickel-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 Header

The 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 todays society.

Ethylene Pyrolysis Furnaces

Tubes, 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 Tubes

Spiral finned INCOLOY alloy 800HT & 803 ethylene tubes provide dependable, long term service. The finning greatly increases the efficiency of the ethylene pyrolysis process.

Chemical Composition INCOLOY Alloys

C INCOLOY alloy 890 INCOLOY alloy 803 INCOLOY alloy 800HT Ni Cr Si Al
Ti

Mo

Nb

Ta

0.1

44

25

1.8

0.15

0.4

1.5

0.4

0.25

0.09

36

25

0.7

0.5

0.5

0.08

32

21

0.3

0.5

0.5

Oxidation Resistance
Mass Change in Air + 5% Water Vapor at 1000C
10 Mass Change, mg/cm2 5 0 -5 -10 -15 -20 -25 -30 0 2000 4000 6000 8000 10000 Exposure Time, Hours 890 803 800HT

Alloy Evolution

Alloy Evolution
INCONEL alloy 600 (Ni 16Cr) INCONEL alloy 625 (Ni 22Cr 9Mo) INCONEL alloy 601 (Ni 22Cr 1.3Al) INCONEL alloy 690 (Ni 30Cr)

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

INCONEL alloy 693 (Ni 30Cr 3Al)

Alloy Applications
What alloy do I use to resist ?

Oxidation
High Temperature Oxidizing Environment Cr & Al are Beneficial

INCONEL alloys 601, 617, 693 INCOLOY alloy 803

Oxidation in Air @ 1100C (2012F)

5 0
2

Mas s Change , m g/c m

-5 - 10 - 15 - 20 - 25 - 30 - 35 - 40 0 1000 2000 3000 4000 5000 6000 Tim e, Hours 693 617 601

Carburization
Cr & Al are Beneficial Good - INCOLOY 330, 800HT, & 803 Best - INCONEL 601, 617, & 693

Carburization Resistance

Metal Dusting
Reducing / Carburizing Environment

INCONEL alloys 693 INCONEL alloy 690 INCONEL alloy 601

Metal Dusting Resistance

CO-20% H2 at 621C 120-Grit Ground Samples
30
602CA 800 601

25 Pit Depth, Mils

690

20
671

15 10 5 0
0 2000 4000 6000 8000 10000 12000 14000 16000

693-2 693-4 617 693-1 693-3

Exposure Time, Hours

693-4 sample contains matching filler

Nitridation
Ni is Beneficial; Al is Detrimental High-Nickel INCONEL alloys

INCONEL alloy 600

Sulfidation
Cr is Beneficial / Ni is Detrimental

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

Fabrication Tips

Over-Matching Welding Products

Plan as Carefully for Welding as for Alloy Selection in General

Use Overmatching Composition Welding Products to:

Offset Elemental Segregation in NiCrMo alloy Weldments Offset Iron Dilution when Welding Clad Steel or Cladding Steel

Preferential Corrosive Attack of Filler Metal C-276 Weldments

INCO-WELD 686CPT Weldments After Six Months Exposure

Welded Samples in Boiling (103C) Green Death

(11.9% H2SO4 + 1.3% HCl + 1% FeCl3 + 1% CuCl2
Hastelloy alloy C-2000
w/ matchin g filler metal

Hastelloy alloy C-2000

w/ INCO-WEL D Filler Metal 686 CP T

VDM alloy 59
w/ matchin g filler metal

VDM alloy 59
w/ INCO-WEL D Filler Metal 686 CP T

INCONEL alloy C-276

w/ matchin g filler metal

INCONEL alloy 686

w/ INCO-WELD Filler Metal 686CPT

INCONEL alloy C-276

w/ INCO-WEL D Filler Metal 6 86CPT

INCONEL alloy 622

w/ matchin g filler metal

INCONEL alloy 622

w/ INCO-WEL D Filler Metal 6 86CPT

Hastelloy alloy C-22

w/ matchin g filler metal

Hastelloy alloy C-22

w/ INCO-WEL D Filler Metal 6 86CPT

Overmatching Composition Welding 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 Welding 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 more corrosion-resistance than a heavier section of a lower alloy

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

Conclusions 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 Roll-Clad Alloy Steel Plate

Pressure & Storage Vessel Construction Corrosion Resistance = Solid Alloy Plate Economical - 1/2 Solid Alloy Plate Cost Established Forming & Welding Procedures Long History of Successful Usage ASTM & ASME Standards

Roll-Bonding Clad Packet Assembly

Roll-Bonding Clad Packet Assembly

Steel Boiler Tube Weld Clad with INCONEL Filler Metal 625
Boilers 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, whats new from SMC R&D?

INCONEL alloys 945 & 945X

Fe-46Ni-22Cr-3Mo-2Cu-3Nb-2Ti
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 740H

Ni - 24Cr - 20Co - 1.5Nb - I.7Ti - 1.1Al
An Age Hardenable, High Temperature Superalloy for Ultra-Supercritical Power Production Excellent Heat Resistance High Strength to 800C Excellent Stability, Fabricability, & Weldability

Available Product Forms

Plate, Sheet, & Strip Seamless Tube & Pipe Rod, Bar, & Wire Rod Forging Stock Welding Products

Thank You !!!