Oil & Gas Material Selection - Basic Maetallurgy - Rev.1

An Introduction to Oilfield Metallurgy and Castings
An on line Course
September 2020
Flowserve Ltd
Presented by Dr Clayton Thomas

Lloyd-Thomas Consultancy Ltd
www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409 1

Oilfield Metallurgy and Castings
Session 1 : Oil and Gas Material Selection/ Basic Metallurgy
Session 2 : Steels and Castings
Session 3 : Mechanical Testing and Inspection
www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Lloyd-Thomas Consultancy Ltd
• Started in March 2000, based in Barnsley, South Yorkshire, UK
• Dr Clayton Thomas and Ms Lisa Lloyd
• Provide metallurgical support and consultancy
• Provide metallurgy training
www.lloydthomasmetallurgy.co.uk

Clayton Thomas
• Graduated in Metallurgy B.Sc (Eng) – Imperial College (1980 – 83)
• MMet – University of Sheffield (1983 – 84)
• Ph.D – University of Sheffield (1984 – 87)
• British Steel Technical (Rotherham) – Investigator (1987 – 90)
• Cameron (UK) – Metallurgist/ Senior Metallurgist (1990 – 2000)
• Lloyd-Thomas Consultancy Ltd – Metallurgist/ Director (2000 - )

An Introduction to Oilfield Metallurgy and Castings
Session 1
Oil and Gas Material Selection/ Basic Metallurgy

Oil and Gas Material Selection and Basic Metallurgy : 1
Which Material ?
Metals
Plastics Ref: plasticsuk.com
Ref: World Steel

Composites
Glass
Ref : Glass Five group.com

Ref: Das et al : Advanced Composites

Metal Properties
Strength Toughness Hardness
Ref: Michigan technological university Ref: technologystudent.com ref: Subtech.com

Material Selection
Using the right materials – points to consider
• Strong
Flowserve ball valve
• Tough
• Corrosion resistant
• Ease of fabrication
• Low cost

Material Applications
All of these applications require

good strength and toughness
but there are some differences.

Oiltool equipment may operate subsea or onshore
Subsea the equipment will

be exposed to seawater
which is very corrosive
Ref: Westwood Global Energy group
Onshore the environment may be very Ref: Al Mothouka Oilfield Services

hot but less corrosive

The Oilfield Environment
One of the main differences between the Oilfield and other applications is the
service environment
External environment : Atmosphere, seawater
Produced fluids : High pressure, oil and gas, water
Injection fluids : Water and gas, acids, corrosion inhibitors

Corrosion
Corrosion is defined as the degradation of Materials due to the environment.
Iron or steel reacts with water and this causes corrosion or rusting:
H 2O + O2 + Fe Fe (OH)3
Water Oxygen Iron Rust
Ref : CTS-Inc.net

Effect of Temperature on Corrosion

Variation of corrosion rate with temperature
Ref. www.engineeringtoolbox.com

Seawater Corrosion
Corrosion is caused by:
• Water and Air (oxygen)

• Made a lot worse by the salt content of seawater
Ref: Federal Highways Authority

Ref: Materialenkennis.NL

Material Corrosion Rates in Seawater
Nickel 625 0 mils/ year

Titanium 0
AISI 316 5
Nickel 400 1
Copper 3
Brass 2
Low alloy steel >10
In quiet seawater (1 mil = 0.025 mm)

Comparison of Costs
Nickel 16 GBP / Kg
Titanium 8 GBP / Kg
Aluminium 1.30 GBP / Kg
Stainless steel 2 GBP / Kg
Steel 0.4 GBP / Kg
Galvanic anodes 90 GBP / sqm

Coatings 10 – 15 GBP / sqm Ref. North West Trail
Inhibitors 20 GBP / sqm
Note these values are taken from various sources and should only be used for
comparison. Actual figures may vary depending on many factors.

Whats in oil and gas?
Ref: bpf.co.uk

Natural Gas
Ref: ihrdc.com
Ref: croftsystems.net

Typical Gas field analysis
Component Mole %
Nitrogen 2.15
Hydrogen Sulphide 10 ppm
Carbon Dioxide 0.64
Methane 87.4
Ethane 5.32
Propane 1.53
Iso-Butane 0.32
N-Butane 0.40
Iso-Pentane 0.20
N-Pentane 0.14
Undecanes 0.08
Dodecanes+ 0.28

Carbon dioxide
Carbon dioxide is the gas in fizzy drinks but it also causes pollution
Ref: scienceabc.com Ref: skymet weather

Carbon Dioxide in Oil and Gas

A well that contains carbon dioxide is called Sweet
Carbon dioxide reacts with water to form Carbonic acid which is a weak acid
with pH 5-6
Ref: kennedyclanscienceblogspot.com

Sweet corrosion low alloy steel
Carbonic acid reacts with Iron to form Iron carbonate and very deep pits in steels
Ref: metropolitanforensics.com

Carbon Dioxide Corrosion
API 6A states
0 – 7 psi mildly corrosive

7 – 30 psi moderate corrosion
> 30 psi highly corrosive
Ref. www.corrosion4dummies.com
This means that if the there are high levels of carbon dioxide Steel should not
be used instead use Stainless Steel or Nickel Alloys

Hydrogen Sulphide in Oil and Gas
A well that contains hydrogen sulphide is called Sour

Ref: himipex.com
Ref: draeger.com
Ref: controlequipment.com.au Ref: globalwestsafety.com

Oil Well Souring
Sulphate Reducing Bacteria

At the start of its life an oil well may
contain no hydrogen sulphide.
But it becomes contaminated with

Bacteria and these produce hydrogen
sulphide.
Hence the well becomes more sour

with time.
Ref. Metallurgical associates inc

Sulphide Stress Corrosion Cracking
Sulphide Stress Corrosion Cracking (SSCC)
• Very serious problem

• Very rapid failure
• Brittle fracture of ductile materials
• Does not need water
Ref: Subsea Pipeline Engineering

SSCC and Sour Service Standards
1975 NACE MR0175
The standard was first issued and since its use then there have been few
sour service failures of susceptible materials.
It has been updated every year, however in 2003 there was a major
change.
2003 (December) NACE MR 0175/ ISO 15156 issued
This was issued in response to concerns over limitations of the original

standard.

NACE MR0175 / ISO 15156

For sour service conditions materials have to meet NACE MR0175. This has a
number of requirements, the most important being a limiting maximum hardness.
Low alloy steel 22 HRc

Downhole steel tubulars 26 HRc#
410 S/S 22 HRc
F6NM 23 HRc
Super Duplex 34 HRc*
Nickel 718 40 HRc**
Nickel 625 35 HRc
# Depends on steel chemistry

* This is prior to 2003
** Depends on the heat treatment

Material Selection and NACE MR0175

Hardness and Yield Strength Limits of Various Grades
Grade NACE Hardness Yield strength

(HRc) (MPa)
Low alloy steel 22 approx 630 MPa (90 Ksi)
410 22 approx 630 MPa (90 Ksi)
F6NM 23 approx 650 MPa (95 Ksi)
Nickel 718 40 approx 830 MPa (120Ksi)
17-4 PH* 33 approx 725 MPa (105 Ksi)
So for very high strength sour service applications nickel 718 is used

Sour Service Material Selection
If the valve requires very high strength

- Over 90 Ksi, and to meet ISO 15156
Low alloy steels would not be suitable
as their hardness limit is 22 HRc
and this limits their strength to below
90 ksi.
So other materials with a high limit

(eg nickel alloys may be required).
Also any welding must meet ISO 15156

Typical Water Injection Analysis
Sodium 11000 ppm

Potassium 510
Calcium 420
Magnesium 1460
Barium 0
Strontium 7
Chloride 20000
Sulphate 24000
Oxygen 5 ppb (treated)
Norsok states that if the oxygen level is less than 10 ppb the fluid is not corrosive

Corrosion Resistance of Materials

Material Carbon Dioxide Hydrogen Sulphide Chloride
Low alloy steel Acceptable below Some corrosion, Wt. loss

7 psi, severe no SSCC if NACE corrosion
corrosion above is followed
7 psi
410/ F6NM No Effect Pitting if >0.1 psi Pitting,

not suitable
>100,000 ppm
316 No Effect Not suitable > 1 psi Some

pitting,
SCC >60 C
Super Duplex No Effect See NACE for Slight

acceptable levels
pitting
Nickel 625 No Effect No Effect No Effect

API 6A Material Classes (19 th edition)

Class Environment Service Pressure Pressure
Pressure Controlling Containing
pp CO2 pp H2S
AA < 7psi 0 General Low Alloy Steel Low Alloy Steel

BB 7- 30 psi 0 General Stainless Steel Low Alloy Steel
CC > 30psi 0 General Stainless Steel Stainless Steel
DD < 7 psi >0.05 psi Sour Low Alloy Steel* Low Alloy Steel*
EE 7 - 30 psi >0.05 psi Sour Stainless Steel* Low Alloy Steel*
FF > 30 psi > 0.05 psi Sour Stainless Steel* Stainless Steel*
HH >> 30 psi >> 0.05 psi Sour CRA* CRA*
* Materials must meet NACE MR0175 or NACE MR0175/ ISO 15156

CRA Corrosion Resistant Alloys (Nickel base alloys)

Summary
• Oil and gas is made of hydrocarbons but the hydrogen sulphide and
carbon dioxide levels determines what materials to use.
• When carbon dioxide is present then its called sweet oil or gas and if
the levels are high then you cannot use steel, you must use stainless
steels or nickel alloys.
• If hydrogen sulphide is present the oil or gas is called sour (even if

carbon dioxide is present). This causes sulphide stress corrosion
cracking which causes rapid failure at lower than expected loads.
NACE MR0175/ ISO 15156 must be applied to prevent this and this
has hardness limits which that must be met.
• For very high strength then nickel 718 is used as it has a very high
NACE hardness limit.

Metallurgy
Metallurgy is the science and technology of metals.
Structure
Metallurgy
Process Property

Metals and Alloys

Alloys are a mixture of elements in which the main constituent is a metal
- Steel (Iron, Carbon)
- Magnesium alloys
AZ series (Magnesium, Aluminium, Zinc)
WE series (Magnesium, Yttrium, Rare Earths)
- Aluminium alloys
2000 series (Aluminium, Copper)
5000 series (Aluminium, Magnesium)

Metallic Materials - Classes
Metals and alloys are normally sub divided into two categories:
- Ferrous metals and alloys that contain a large percentage of iron such as steels
and cast irons
- Non-ferrous metals and alloys that do not contain iron (or a relatively small
amount of iron), examples of these are the non ferrous metals such as
Aluminium, copper, zinc, titanium and nickel.

Annual Use Metals
1200
1200
1000 Annual use of alloys in

Millions of metric tons
800
600
400
200
23 18 0.1
0
steel aluminium copper titanium

What is steel ?
➢ Steel is an alloy of Iron + carbon - up to ~ 2 wt %
➢ Iron + carbon > ~ 2 wt% are cast irons
➢ < 5 wt% alloy (Mn, Cr, Mo, Ni) are low alloy steels
➢ > 5 wt% alloy (Mn, Cr, Mo, Ni) are high alloy steels
➢ Stainless steels contain minimum 11.0 wt% Chromium (Cr)


Effect of Carbon
Variation of
properties
with carbon
Ref. Properties of Engineering Materials

What is the Metal Microstructure and why is it important?
Ref: sheff.ac.uk
Looking very closely at
a metal under a
microscope shows the
small “microstructure”
of the metal.
This consists of metal

grains
Sir Henry Sorby was the first

person to look down a
microscope at a metal in 1863

Metal Grains
Metal grains are just metal crystals that form when a metal is cooled down
Ref: thoughtco.uk
Ref: wikipedia

Dendrites
Ref: nde-ed.org
Ref: wikipedia

Grain Size and Properties
Small grain size increases

Strength and Toughness

Grain Size measurement

Ref : ASTM E112
Many commonly used steels

have an ASTM nos between 4
and 7.
Some oil tool standards specify a
grain size
eg API 6A CRA
Nickel 718 , grain size 2 or finer


Changing the Grain Size
• Heating the metal up and holding at high temperature (for steel over
800oC) increases the grain size.
• Cooling a metal very rapidly produces a small grain size compared to slow cooling.
• Adding elements such as aluminium and niobium reduces the grain size
• Forging and mechanical working reduces the grain size
• Grain size control in castings is very important as they tend to have a larger grain
size

Castings and Forgings
Ref: mech4study.com
Ref: edcast.ca
Ref: ironfoundry.com

Forging and Mechanical Working
Ref: scotforge.com
Ref: camforge.com
Ref: sciencedirect.com

Forgings have:
• A grain flow
• Smaller grain size
• Higher strength
Ref: forgemag.com

Cast v Forged Mechanical Properties
➢ Cast steels – A352: LCC

Yield Strength 275 MPa
Impact Properties 20J @ - 460C
➢ Forged steels – A350: LF2

Yield Strength 359 MPa
Impact Properties 54J @ - 460C

Alloying and Grain Size
CMn steel CMn Nb steel
The addition of niobium to steel results in the formation of niobium carbide

and niobium carbo nitride. Both of these pin the grain boundaries and inhibit
grain growth

Casting and Grain Size

When a hot metal is poured into a mould, lots of small crystals form on the
cooler mould wall and these results in a small grain size next to the wall
Ref: researchgate.net
Ref: diva-portal.com
Ref: DoITPoMS.ac.uk

Castings and grain size
• In a casting the grain size is larger

• More uneven
• So castings are not as strong as forgings
• There is no grain flow
Ref: trans.msm.cam.ac.uk
Ref: substech.com
Cast Structures of Metals
(a) pure metals
(b) solid-solution alloys
(c) structure obtained by

using nucleating agents.
Ref: slideshare.com

Cast Structure of Metal with Inoculants
Grains form on an inoculant (nucleating agents)
Grains form on the mould wall

Ref: slideshare.net

Effect of inoculants on steel
Ref: semanticscholar.com

Cooling Rate and Grain Size
Ref: sciencedirect.com

Castings and Grain Size
Ref: semanticscholar.com
Ref: B. Niroumand

Grain size and wall thickness and cooling rate
Ref: sheffieldforgemasters.com
Ref: astm

Grain Flow
Compared to a forging there is little grain flow shown in a casting

Summary
• The microstructure of a metal is very important, in particular the grain
size, which helps to determine its properties.
• Small grain size gives better strength and toughness.
• Forgings have smaller grain size compared to castings.
• The grain size can be controlled by temperature, composition and

mechanical working
• Grain size control in castings is important as they tend to have a larger

and more uneven grain size.
• By adding inoculants the grain size can be controlled.
• By controlling the pouring temperature and cooling rates the grain

size may be altered.

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An Introduction to Oilfield Metallurgy and Castings

Presented by Dr Clayton Thomas

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409 1

Session 1 : Oil and Gas Material Selection/ Basic Metallurgy

Session 2 : Steels and Castings

Session 3 : Mechanical Testing and Inspection

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

• Started in March 2000, based in Barnsley, South Yorkshire, UK

• Dr Clayton Thomas and Ms Lisa Lloyd

• Provide metallurgical support and consultancy

• Provide metallurgy training

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409 3

• Graduated in Metallurgy B.Sc (Eng) – Imperial College (1980 – 83)

• MMet – University of Sheffield (1983 – 84)

• Ph.D – University of Sheffield (1984 – 87)

• British Steel Technical (Rotherham) – Investigator (1987 – 90)

• Cameron (UK) – Metallurgist/ Senior Metallurgist (1990 – 2000)

• Lloyd-Thomas Consultancy Ltd – Metallurgist/ Director (2000 - )

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409 4

Oil and Gas Material Selection/ Basic Metallurgy

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Ref: World Steel

Ref : Glass Five group.com

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Strength Toughness Hardness

Ref: Michigan technological university Ref: technologystudent.com ref: Subtech.com

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

All of these applications require

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Oiltool equipment may operate subsea or onshore

Subsea the equipment will

Ref: Westwood Global Energy group

Onshore the environment may be very Ref: Al Mothouka Oilfield Services

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

The Oilfield Environment

External environment : Atmosphere, seawater

Produced fluids : High pressure, oil and gas, water

Injection fluids : Water and gas, acids, corrosion inhibitors

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409 12

Effect of Temperature on Corrosion

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

• Water and Air (oxygen)

Ref: Federal Highways Authority

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Material Corrosion Rates in Seawater

Nickel 625 0 mils/ year

In quiet seawater (1 mil = 0.025 mm)

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Galvanic anodes 90 GBP / sqm

Inhibitors 20 GBP / sqm

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409 16

Whats in oil and gas?

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Typical Gas field analysis

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Ref: scienceabc.com Ref: skymet weather

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409

Carbon Dioxide in Oil and Gas

www.lloydthomasconsultancy.co.uk email : info@lloydthomasmetallurgy.co.uk tel : 0794 0047409