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2006:251 CIV

M A S T ERS T H E SI S

Ageing Influence on Nickel-based


Superalloys at Intermediate
Temperatures (400600C)

SA MARTINSSON

MASTER OF SCIENCE PROGRAMME


Engineering Materials EEIGM

Lule University of Technology


Department of Applied Physics and Mechanical Engineering
Division of Engineering Materials

2006:251 CIV ISSN: 1402 - 1617 ISRN: LTU - EX - - 06/251 - - SE


ABSTRACT

Nickel-based superalloys are employed in a variety of gas turbine components


due to their excellent high-temperature properties. Unfortunately, several of
these superalloys have proved to shrink during long-term service/ageing at
intermediate temperatures (400-600C). This study comprises an investigation of
the ageing effects of two nickel-based superalloys from different classes of
material; Haynes 230 and single crystal CMSX-4. The work is divided into three
parts:
I. Literature study. Haynes 230 and CMSX-4 were studied as well as reports
and articles concerning shrinkage and microstructural changes owing to
ageing in different nickel-based superalloys.
II. Mechanical testing. The ageing effects on mechanical and physical
properties were investigated in a series of experiments. The employed
methods are tensile testing, impact testing, low cycle fatigue testing and
hardness testing.
III. Microstructural examination. The underlying causes to the property
changes were investigated in a microstructural examination including
carbide size measurements, chemical analysis of the composition and
analysis of micro images taken with scanning electron microscope and light
optical microscope.
The results from the experimental testing show that the ageing has a marked
effect on the properties of both CMSX-4 and Haynes 230. The low cycle fatigue
properties of Haynes 230 are unaffected by the ageing while the yield and tensile
strength and hardness are improved. The ductility is improved in both Haynes
230 and CMSX-4. The hardness of CMSX-4 was unaffected by the ageing while
the tensile strength was slightly impaired. It was also found that the properties
and the ageing effect depended on the single crystal direction.
The study shows that the ageing has a significant effect on the precipitation of
secondary carbides at grain boundaries in Haynes 230, which has a
strengthening effect on the material. No distinct changes of the microstructure
explaining the property changes in CMSX-4 were found.
It is reported in other studies that shrinkage in other superalloys is caused by
short and long range ordering based on Ni2Cr and Ni3Cr. The microstructural
examination neither confirms nor refutes that the shrinkage and property
changes are caused by this type of ordering. However, the results from the
examination indicate that ordering formation is possible.
SAMMANFATTNING

Nickelbaserade superlegeringar anvnds i ett antal gasturbinkomponenter p


grund av deras utmrkta hgtemperaturegenskaper. Tyvrr har ett flertal av
dessa superlegeringar visat sig krympa vid lngtidsldring/anvndning vid
medelhga temperaturer (400-600C). Denna studie omfattar en underskning av
ldringseffekterna fr tv nickelbaserade superlegeringar frn olika
materialklasser; Haynes 230 och CMSX-4. Arbetet r indelat i tre delar:
IV. Litteraturstudie. Haynes 230 och CMSX-4 studerades liksom rapporter och
artiklar om krympning och frndringar i mikrostrukturen orsakade av
ldring i olika nickelbaserade superlegeringar.
V. Mekanisk provning. ldringseffekter p mekaniska och fysikaliska
egenskaper undersktes i en serie experiment. De anvnda metoderna r
dragprovning, slagprovning, lgcykelutmattning och hrdhetsprovning.
VI. Mikrostrukturunderskning. De bakomliggande faktorerna till frndring
av egenskaperna undersktes i en mikrostrukturstudie som omfattade
mtning av karbidstorlek, kemisk analys av sammansttningen och analys
av foton tagna med svepelektronmikroskop och optiskt ljusmikroskop.
Resultaten frn den experimentella delen visar att ldringen har markant effekt
p egenskaperna fr bde CMSX-4 och Haynes 230.
Lgcykelutmattningsegenskaperna r ofrndrade efter ldring i Haynes 230
medan strck- och brottgrns samt hrdheten frbttras. Duktiliteten frbttras
i bde Haynes 230 och CMSX-4. Hrdheten i CMSX-4 pverkas inte av ldringen
medan dragbrottstyrkan frsmrades ngot. Resultaten visar ocks att
egenskaperna och ldringens pverkan beror p enkristallens riktning.
Studien visar att ldringen har en pfallande effekt p utskiljningen av
sekundra karbider i korngrnserna i Haynes 230, vilket har en strkande effekt
p materialet. Inga ptagliga ndringar i mikrostrukturen som frklarar
frndringen av egenskaperna i CMSX-4 hittades.
Det har rapporterats i andra studier att krympning i andra superlegeringar
orsakas av short and long range ordering baserad p Ni2Cr and Ni3Cr.
Mikrostrukturstudien varken bekrftar eller motbevisar att krympningen och
frndringen av egenskaperna beror p den hr typen av ordning i materialen.
Resultaten indikerar dock att den hr typen av ordning r mjlig.
PREFACE

The work presented in this Masters thesis was carried out at Siemens Industrial
Turbomachinery AB, Finspng, during the period Mars August 2006. To the
persons who made this thesis possible, I give my deepest thanks.
I would like to express my sincere gratitude to my supervisor Johan Moverare
(Division of Materials Technology, SIT AB) for his great support and all the
fruitful discussions we have had, for his encouragement and for believing in me.
A special thank goes to Carina Jansson who was a great help in the laboratory
and Ramn Nio Lopez for having an answer to all my questions. I would also
like to thank everybody at the Division of Materials Technology for making me
feel like home during my time at SIT AB.
Finally I thank Magnus Odn (Division of Engineering Materials, Lule
University of Technology) for his time and guidance.
NOMENCLATURE

A5 Elongation of waist of tensile test specimen


at% Atom percent
Bal Balance
BEI Backscattered electron image
D Diameter of waist of tensile test specimen after test
D0 Initial diameter of waist of tensile test specimen
d1 Mean diameter of primary carbides
d2 Mean diameter of secondary carbides
DS Directionally solidified
E Elastic modulus
EDS Electron dispersive spectroscopy
EDX Electron dispersive X-ray
FCC Face centred cubic
HCF High cycle fatigue
K Strength coefficient
KV Energy absorbed during impact test
L Length of waist of tensile test specimen after test
L0 Initial length of waist of tensile test specimen
LCF Low cycle fatigue
LOM Light optical microscope
LRO Long range ordering
N Number of cycles in LCF test
n Strain-hardening exponent
Nf Number of cycles to failure in LCF test, 50 % load drop or failure
Ni Number of cycles to crack initiation in LCF test, 5 % load drop
r1 Aspect ratio of primary carbides
r2 Aspect ratio of secondary carbides
ref Reference
Rm Tensile strength
Rp0.1 Yield strength, calculated at 0.1 % of plastic strain deformation
Rp0.2 Yield strength, calculated at 0.2 % of plastic strain deformation
RT Room temperature
SEI Secondary electron image
SEM Scanning electron microscope
SIT AB Siemens Industrial Turbomachinery AB
SRO Short range ordering
SX Single crystal
TBC Thermal barrier coating
TC Critical temperature
TCP Topologically close-packed
temp Temperature
vol% Volume percent
wt% Weight percent
Z Reduction of cross-section area of tensile test specimen
Gamma matrix phase
Gamma prime phase
pl Plastic strain range
Electrical resistivity
phase A specific type of topologically close-packed phase
max Maximum stress
CONTENTS

1 INTRODUCTION 9

1.1 SIEMENS INDUSTRIAL TURBOMACHINERY AB 9


1.2 BACKGROUND 9
1.3 PURPOSE 9
1.4 PRESENTATION OF THE PROBLEM 9
1.4.1 Objective 10
1.5 DELIMITATIONS 11
1.6 THEORETICAL BACKGROUND 11
1.6.1 Gas turbines 11
1.6.1.1 The compressor 12
1.6.1.2 The combustion chamber 12
1.6.1.3 The turbine 12
1.6.2 Turbine blade 13
1.6.3 Combustion chamber 14
1.6.4 Equipment 15
1.6.4.1 Tensile test equipment 15
1.6.4.2 Impact test equipment 16
1.6.4.3 Low cycle fatigue test equipment 16
1.6.4.4 Scanning electron microscope (SEM) 17
1.6.4.5 Light optical microscope 18
1.6.4.6 Stereo microscope 19
1.6.4.7 Hardness test equipment 19

2 SUPERALLOYS 20

2.1 NICKEL-BASED SUPERALLOYS 20


2.1.1 Composition 20
2.1.2 Phases and microstructure 20
2.1.2.1 Gamma matrix () phase 21
2.1.2.2 Gamma prime () phase 21
2.1.2.3 Carbides 22
2.1.2.4 Grain boundary () phase 22
2.1.2.5 Borides 23
2.1.2.6 Topologically close-packed (TCP)-type phases 23
2.1.3 Strengthening of superalloys 23
2.1.3.1 Solid-solution strengthening 23
2.1.3.2 Precipitation hardening 24
2.1.4 Rafting 24
2.2 GAS TURBINE BLADE CASTING 25
2.2.1 Directional solidification (DS) 25
2.2.2 Single crystal (SX) casting 26
2.3 SINGLE CRYSTAL SUPERALLOY CMSX-4 26
2.4 SUPERALLOY HAYNES 230 27

3 AGEING EFFECTS IN SUPERALLOYS 29

3.1 CONTRACTION IN SUPERALLOYS 29


3.2 SHORT RANGE ORDERING (SRO) AND LONG RANGE ORDERING (LRO) 32
3.3 NEGATIVE CREEP 35
3.4 CARBIDE PRECIPITATION 35

4 AGEING INFLUENCE ON MECHANICAL PROPERTIES AND


MICROSTRUCTURE OF HAYNES 230 AT INTERMEDIATE
TEMPERATURES (500-550C) 37

4.1 SPECIMEN PREPARATION AND EXPERIMENTAL PROCEDURE 37


4.1.1 LCF test 37
4.1.2 Impact test 37
4.1.3 Tensile test 37
4.1.4 Microscopic examination 38
4.1.5 Hardness test 39
4.2 TEST RESULTS 40
4.2.1 LCF test 40
4.2.2 Impact test 42
4.2.3 Tensile test 43
4.2.4 Hardness test 45
4.2.5 Carbide size measurements 47
4.2.6 Chemical analysis 48
4.3 DISCUSSION 50
4.3.1 Mechanical tests 50
4.3.2 Microstructural examination 52
4.4 CONCLUSION 55

5 AGEING INFLUENCE ON MECHANICAL PROPERTIES AND


MICROSTRUCTURE OF CMSX-4 AT INTERMEDIATE TEMPERATURES
(500-550C) 56

5.1 SPECIMEN PREPARATION AND EXPERIMENTAL PROCEDURE 56


5.1.1 Tensile test 56
5.1.2 Microscopic examination 56
5.1.3 Hardness test 57
5.2 MECHANICAL TEST RESULTS 58
5.2.1 Tensile test 58
5.2.2 Angle of slip plane 61
5.2.3 Hardness test 61
5.3 DISCUSSION 62
5.3.1 Mechanical tests 62
5.3.2 Microstructural Examination 63
5.4 CONCLUSION 65

6 FUTURE WORK 67

7 REFERENCES 68

8 ANNEXES 70

8.1 MATERIAL DATASHEET FOR HAYNES 230 COATING 70


8.2 TEST CERTIFICATE, HAYNES 230, HEAT NO 1830587801 71
8.3 DRAWINGS 72
8.3.1 Low cycle fatigue test specimen 72
8.3.2 Impact test specimen 73
8.3.3 Tensile test specimen 74
8.4 CALCULATIONS 75
8.4.1 LCF test 75
8.4.2 Tensile test 75
8.5 RESULTS 76
8.5.1 Tensile test, Haynes 230 76
8.6 MICROSCOPY PHOTOS 77
8.6.1 Haynes 230 77
8.6.2 CMSX-4 89
1 INTRODUCTION

1.1 SIEMENS INDUSTRIAL TURBOMACHINERY AB

Siemens is one of the worlds largest electrical engineering and electronics


companies. Some of the areas where the company is active are Information and
Communications, Automation and Control, Power, and Medical. Siemens is
represented in 190 countries all over the world.
Siemens Industrial Turbomachinery AB (SIT AB) is a part of the business sphere
Power Generation and is by far the largest of Siemens companies in Sweden with
a turnover of 6 billion SEK. SIT AB is located in Finspng and Trollhttan and
has over 2000 employees working to develop, produce and install gas turbines,
steam turbines and power plants for industrial application. The effect of the gas
turbines is in the area 15-50 MW and the steam turbines are in the area 60-180
MW.

1.2 BACKGROUND

The largest type of gas turbines produced in Finspng is SGT-800 with an


electrical output of 45 MW and an electrical efficiency of 37 %. The large
electrical output requires very high temperatures in operation in the combustion
chamber as well as in the turbine. The high-temperature properties of steel are
not good enough for these components, so different types of nickel-based
superalloys are used.
One of these superalloys is Haynes 230, used in the combustion chamber. The
sheets surrounding the flames can reach a temperature of over 900C as a
maximum. The outer parts of the combustion chamber, previously made of
Hastelloy X, which belongs to the same class of material as Haynes 230, reach a
temperature not higher than approximately 500C.
CMSX-4 is a nickel-based superalloy of a different class, used in the hottest part
of the turbine. The airfoil of the blade in the first turbine stage is exposed to hot
gases, heating the material to a temperature of up to 900C. On the other hand,
the temperature in the blade root is within the temperature range 400-600C.

1.3 PURPOSE

The purpose of this diploma work is to examine microstructural changes in


nickel-based superalloys due to ageing at intermediate temperatures (400-
600C). The study will also comprise an examination of mechanical and physical
properties in order to find any possible changes owing to ageing and phase
transformation.

1.4 PRESENTATION OF THE PROBLEM

The use of nickel-based superalloys isnt uncomplicated. Despite their excellent


high-temperature strength, several superalloys have proved to shrink at
intermediate temperatures, 400-600C [1]. The results from these measurements

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will be discussed in detail in chapter 3. Haynes 230 and Hastelloy X are two
examples. The affected part is the combustor mounting ring which makes it
possible to bolt the combustor chamber to the turbine casing. This ring with bolt
holes used to be made of Hastelloy X, but this material caused problems during
inspection. The ring has to be removed during inspection of the combustion
chamber and afterwards it didnt fit because of shrinkage. A short-term solution
of the problem has been to make the ring out of Cr-Mo steel instead.
The shrinkage measurements carried out at Siemens [1] proved that Haynes 230
was the superalloy in the study that exhibited the largest shrinkage and at the
shortest time during ageing. This is why it was chosen to be examined
experimentally in this study.
It is desired to understand the microstructural changes that are behind the
shrinkage phenomenon. Previous studies of simple binary Ni-Cr systems and
tertiary Ni-Cr-Fe systems prove that ageing of these materials can result in a
long range ordering of the structure [2]. Whether this ordering phenomenon
exists in more complex alloys such as commercial nickel-based superalloys isnt
established but there are indications that this could be the case.
A phase transformation is likely to affect the mechanical properties of the alloy
[2]. This could for example affect the fracture behaviour and thereby shorten the
life time of the components.
No measurements in order to determine the existence of shrinkage in CMSX-4
have been carried out so far, but the shrinkage behaviour has been observed in
similar alloys at intermediate temperatures [3]. Since the service temperature of
the blade root is within the critical temperature range, the material was included
in this study. If the shrinkage phenomenon affects the superalloy, hopefully the
results of this study will facilitate the life time assessment and the dimensioning
of the turbine blade.

1.4.1 Objective

The aim of this diploma work is to map out and analyse any changes in structure
and mechanical properties between new and aged material in order to gain a
deeper understanding of the behaviour of Ni-based superalloys. The experimental
work that ought to be done is:
1. to perform tensile test, impact test, low cycle fatigue test and hardness
test on Haynes 230
2. to perform tensile test and hardness test on CMSX-4
3. to examine the fracture surface of the tensile test specimens
4. to examine the cross-section of the tensile test specimens (scanning
electron microscope and light optical microscope)
5. to analyse the composition of the matrix and the carbides in Haynes 230
6. to measure the carbide size in Haynes 230
7. to analyse existing experimental data about negative creep from a
metallurgical perspective
The first six paragraphs are prioritised and the last one will be carried out as far
as time admits.

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1.5 DELIMITATIONS

Haynes 230 is examined in this diploma work because of its ageing behaviour.
Its the austenitic material found in a gas turbine that exhibits the largest and
fastest shrinkage when heat treated at intermediate temperatures. Hastelloy X
that is mentioned several times in the report exhibits a pronounced shrinkage as
well, but the lack of material prevented the incorporation of the alloy in the
experimental part of this study. However, Hastelloy X is very similar to Haynes
230 in composition and behaviour, and its therefore reasonable to believe that
the causes that lie behind the shrinkage phenomenon are the same for both
materials.

1.6 THEORETICAL BACKGROUND

1.6.1 Gas turbines

Gas turbines are power generating engines used for a variety of industrial
applications, such as aircraft and marine propulsion, driving generators or
pumps and electricity generation in power plants. The three main components in
a gas turbine are the compressor, the combustion chamber and the turbine. A
cross-section diagram of gas turbine SGT-800 is shown in Figure 1.

Figure 1: SGT-800 gas turbine [4].

The gas turbine cycle is usually described with help of the ideal Brayton cycle,
illustrated in Figure 2. Fresh air at atmospheric pressure flows into the
compressor. The compression is isentropic and results in a rise in temperature
and pressure. The compressed air is mixed with fuel and ignited in the
combustion chamber, causing a dramatic temperature rise. The hot gases are
then passing through the turbine where work is derived during the expansion of
the gases. [5], [6]

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Figure 2: Simplified scheme of the gas turbine system and the ideal Brayton cycle [7].

1.6.1.1 The compressor

Fresh air, holding ambient temperature and atmospheric pressure, enter the gas
turbine under free stream conditions at station 1. Ideally, an isentropic
compression takes place between station 1 and 2. The compression results in a
volume reduction and a significant increase in pressure and temperature. In
reality, the entropy isnt unaffected by the compression. The work executed on
the gas will slightly increase the entropy, making the line between station 1 and
2 in the T-s diagram in Figure 2 incline somewhat to the right. [6]
In SGT-800 the air is compressed in 15 stages before the flow exits the
compressor. The gas pressure is 19.3 atm after all stages of compression and the
temperature of the gas exiting the compressor is approximately 430C. [4], [8]
The aerodynamics of the compressor is of highest importance for the efficiency of
the gas turbine. Continuous efforts are made to improve the design of the
compressor with the intention of minimising the consumption of work required
during the compression of the air.

1.6.1.2 The combustion chamber

The hot air is mixed with fuel in the annular combustion chamber before ignition.
The pressure is remained constant during the combustion (between station 2 and
3), but the heat added in the process will cause a critical increase in temperature.
Because of the ideal gas law,

PV = nRT , Equation 1: Ideal gas law.

the volume will increase as well. The temperature of the hot exhaust depends on
the type of fuel mixed with the compressed air but also on the proportion of fuel
in the gas mixture [5], [6]. The fuel used in general is diesel oil or natural gas.
The temperature of the exhaust after combustion is approximately 1420C in
SGT-800 [8].

1.6.1.3 The turbine

In the last process, the hot gases are allowed to expand isentropically while
passing through the turbine. Between station 3 and 4, the temperature and the

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pressure decreases over several turbine stages while work is derived from the
expansion. The compressor and the turbine are mounted on the same shaft and a
part of the work obtained in the turbine is used to drive the compressor. The
exceeding work is either obtained in the form of mechanical drive used for driving
external load, such as pumps or propellers, or in the form of electrical power. [5],
[6]
The gas enters the turbine, passing by the first stage vanes. The vanes are
directing the gas in the optimal angle towards the following blades. The work
performed by the gas is forcing the blade disk to rotate, from where the electrical
power is derived. The gas continues towards the next set of vanes and the
procedure is repeated. For each stage, the volume is increasing and the
temperature is decreasing.
The turbine outlet temperature is 546C [4]. The hot gases can be used for
heating water in a combined cycle with a steam turbine, which will diminish the
energy losses and increase the efficiency notably.

1.6.2 Turbine blade

The most complex components in a gas turbine are found in the hot gas path. The
turbine blades and vanes belong to these components. The turbine blade consists
of two parts: the airfoil which is exposed to the flow of heat gases, and the root
section which attaches the blade to the turbine disk. A picture of the first stage
turbine blade from SGT-800 is found in Figure 3.
The blades are
exposed to very high Trailing
temperatures and edge
centrifugal stresses
during service, facts Leading Airfoil
that make great edge
demands on the
material and the
design of the blade.
The high
temperature and the Root
flow of contaminated Platform section
exhaust expose the
blades to oxidation
and corrosion [9]. Figure 3: First stage blade in SGT-800 [10].
The high rotational
speed of the turbine creates another problem. High centrifugal forces will affect
the blade and lead to high stress in the material, which in turn result in creep.
Other aggravating circumstances for the lifetime of the blade are the start-ups
and stops. Great changes in temperature and unequal distributed loads will
result in thermal strain in the material. [11]
The design of the blade is worked out from the thermal and mechanical
conditions in the turbine. We can take the case of the first stage blade in SGT-
800 to illustrate the design of a blade. The gas temperature after the first vane is
approximately 1180C. The material in the first stage blade is CMSX-4, which
has a melting temperature range between 1320C and 1380C [12]. In order to
avoid high metal temperature, two measures are taken. The blade is cooled

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internally with air. The air is passing via the root section and out through the
cooling holes. A thin film of cool air is then created on the outside of the blade,
protecting it from the hot gases. Furthermore, the airfoil and the platform of the
blade are covered with thermal barrier coating, TBC, in order to keep the metal
temperature down. In this specific case the blade is coated with platinum
aluminide to improve the oxidation and corrosion resistance. Its important that
the cooling doesnt provoke a thermal gradient in the material since it would
have a negative influence on the performance of the blade.
The average temperature of the surface of the first stage blade is 850-900C. The
cooling is concentrated to the load-bearing parts where the temperature can be as
low as <750C. The blade tip belongs to the hotter areas where the local
temperature can reach over 1000C. [8] The root section holds a temperature of
around 500C.
Because of the severe conditions, the lifetime of a turbine blade is today 20 000
operating hours. Continuous development of the material and the design of the
blades and the vanes is performed in order to prolong the lifetime of the
components and in that way reduce the cost.

1.6.3 Combustion chamber

The combustor section consists of three main parts: the fuel injection system, the
combustion liner and the combustion outlet. See illustration of SGT-800
combustion section in Figure 4. The combustion chamber is the first part in the
hot gas path. The components have to face loads at high temperatures when the
mixture of compressed air and fuel are burned.
The conditions in the combustion chamber are severe. The annular combustion
chamber in SGT-800 is built up by an inner and outer wall, also called
combustion liner. The combustion liner is constructed by sheets of Haynes 230,
surrounding the flames. The walls are exposed to creep and oxidation due to high
temperature and pressure in the chamber. Another influence is created by the
flames tendency to pulsate. The intensity variation of the flames creates high
cycle fatigue, HCF, vibrations in the walls. To sustain the strain, it takes a
ductile material with maintained good strength and resistance to corrosion at
high temperatures.

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Figure 4: Combustor section, SGT-800.[4].

SGT-800 is the gas turbine with the highest firing temperature manufactured at
SIT AB. The outlet gas temperature is, as mentioned before, approximately
1420C [8]. Since the melting temperature range of Haynes 230 is 1301-1371C
[13] measures have been taken to keep the metal temperature at a considerably
lower level. The sheets are coated with TBC, in this case in two layers. The bond
coat is made up of NiCoCrAlY and the top coat consists of Y2O3-stabilised ZrO2.
See Annex 8.1 for further information. Furthermore, film cooling is used to
additionally lower the metal temperature. These steps result in an average metal
temperature of the combustion liner between 800C and 850C. Near the flame
and at the outlet of the combustion chamber, local temperatures above 900C
have been measured.

1.6.4 Equipment

1.6.4.1 Tensile test equipment

The tensile tests were performed in a


Schenck-Trebel RSA 100 test machine. The
test rig is controlled digitally through an
EDC 120 controller. The test equipment
consists of a clamping system and a load cell
attached to a crosshead. The test rig has a
loading capacity of 100 kN in both traction
and compression tests. A photo of the
equipment is found in Figure 5.
An extensometer of the type Sandner with a
gauge length of 10 mm was attached to the
specimens to measure the strain during the
first part of the test.
Figure 5: Schenck-Trebel RSA 100
tensile test equipment.
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The test machine is also equipped with a furnace with a heating capacity of up to
1000C and a measuring instrument for acoustic emissions. These tools werent
used in this study.

1.6.4.2 Impact test equipment

The impact strength of Haynes 230 was


investigated by using a Charpy impact test
machine manufactured by Wolpert. The
maximum energy possible to absorb is 150 J or
300 J, depending on the applied load.
A photo of the equipment is found in Figure 6.

Figure 6: Charpy impact test


equipment.

1.6.4.3 Low cycle fatigue test equipment

The universal testing machine Instron


1275 was used to carry out the strain
controlled low cycle fatigue (LCF) tests.
Its a servo-hydraulic testing machine
which can be used for dynamic and static
tensile testing as well as for low cycle
fatigue and high cycle fatigue testing.
The test rig has a loading capacity of
100 kN. Equipped with the furnace
visible in Figure 7, testing at
temperatures up to 1000C can take
place. The test machine is controlled by
the Instron fast track 8800 equipment.
A dynamic extensometer from Instron
with catalogue number 2620-602 was
used to measure the strain. The
extensometer has a gauge length of 12.5
mm and a travel of 2.5 mm.
All the experiments in this study were
effectuated at room temperature, RT, and
in total strain control. Figure 7: Instron 1275 LCF equipment.

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1.6.4.4 Scanning electron microscope (SEM)

The scanning electron microscope (SEM) is today a common tool used in a variety
of branches in the industry. Its used to reproduce surfaces and objects at high
magnitude and to determine the composition of the material, both quantitatively
and qualitatively. [14]
A SEM consists of three main components: an electron gun, lenses and an
electron detector. A schematic image of SEM is shown in Figure 8. The electron
gun contains a filament, usually made of tungsten. When the filament is heated
with an electrical current, a
thermal emission of electrons is
created. The electron gun
accelerates the electron beam to an
energy between 2 keV and 40 keV.
Magnetic lenses are focusing the
beam to a diameter of 1-10 nm
before it reaches the sample. [14],
[16]
The scanning coils are moving the
electron beam in a rectangular set
of straight lines, also known as
raster, over the sample. When the
beam hits the sample, an
interaction occurs between the
surface of the sample and the
incident electrons, which results in
an emission of secondary electrons
from the surface. A detector counts
the number of secondary electrons.
By comparing the intensity of the
secondary electrons and the
intensity of the incident electron
beam, a topographic secondary
electron image (SEI) is created.
The magnitude of the image is
easily changed by changing the Figure 8: Schematic image of SEM [15].
size of the raster. [14], [16]
When bombarded with electrons, the surface emits not only secondary electrons
but backscattered electrons and X-rays. The detected backscattered electrons
create a backscattered electron image (BEI) which shows a view depending on
the composition of the sample. By detecting the X-ray emission the chemical
composition of the sample can be obtained. [16]
The SEM used in this study is a JSM-5800 produced by Jeol. The microscope is
equipped with an electron dispersive spectroscopy (EDS) system, Link ISIS and a
Link EDX (electron dispersive X-ray) detector, which are used for the chemical
analyses. The entire equipment is shown in Figure 9. The SEM can create images
with a resolution of 3.5 nm and high quality images can be obtained at a
magnification of up to 10 000x. The EDS system can detect elements with atomic
number 5 (boron) and higher.

17
Figure 9: Jeol JSM-5800 Scanning Electron Microscope.

1.6.4.5 Light optical microscope

The light optical microscope (LOM) Olympus


BX60M was used in the microstructural
examination. The microscope is equipped with a
video camera of the type Olympus U-TV1X
which is connected to a computer. With this
setup, shown in Figure 10, its possible to take
pictures with a magnitude of up to 500x. The
microscope has been used for taking overview
photos and for examination of the carbides in
Haynes 230 by means of the image analysis
software Image-Pro Plus.

Figure 10: Olympus BX60M light


optical microscope.

18
1.6.4.6 Stereo microscope

In order to examine the fracture surfaces of the tensile test specimens and to
measure the angle of the slip planes in CMSX-4, the stereo microscope Leica Wild
M10 was employed. The microscope is connected to a digital camera of the type
Leica DC180 and the taken photos are transferred to a computer.

1.6.4.7 Hardness test equipment

Two different types of hardness testers have been employed in this study. The
first one, a Diatestor 2N from Wolpert (see Figure 11), was used to determine the
macrohardness of the materials. It has a loading capacity of 1-250 kg.
The other one was a Leco M-400DT microhardness tester (see Figure 12)
connected to a Panasonic CCTV camera. The photos were transferred to a
computer where the measuring of the imprints was made. The microhardness
tester has a loading capacity of 10-1000 g.

Figure 11: Macrohardness tester. Figure 12: Microhardness tester.

19
2 SUPERALLOYS

The development of gas turbines has been the main driving force for the
existence of the superalloys. The metallic alloys are today used in high-
temperature and corrosion-resistant applications in a variety of industries. Not
infrequently the service temperature goes beyond 0.7 of the superalloys melting
temperature. Superalloys are divided into three classes: nickel-based, cobalt-
based and iron-nickel-based alloys. The nickel-based superalloys are the
superalloys most frequently used in gas turbine components. [17]-[20]

2.1 NICKEL-BASED SUPERALLOYS

Nickel-based superalloys can be used to a higher fraction of melting temperature


and are therefore more favourable than cobalt-based and iron-nickel-based
superalloys at service temperatures close to the melting temperature of the
materials [18].
The application areas of nickel-based superalloys in gas turbines are for instance
the turbine blades and vanes because of the alloys good corrosion and creep
resistance and retained strength at high temperatures. Furthermore, the alloys
are possible to strengthen in different ways and they are in possession of high
phase stability. More about this is found in chapter 2.1.3 and 2.1.2, respectively.

2.1.1 Composition

The composition of nickel-based superalloys is altered depending on the desired


properties. Besides nickel, the alloys contain in general 10-20 % chromium, up to
8 % aluminium together with titanium, and 5-10 % cobalt. Small amounts of
boron, zirconium and carbon are included as well. Common addition in some
alloys is for example molybdenum, tungsten, niobium, tantalum and hafnium.
There are also some tramp elements, i.e. elements which unintentionally were
included in the alloy, and these elements have to be carefully controlled.
Examples of elements belonging to this group are silicon, phosphorus, sulphur,
oxygen and nitrogen. [17]
Chromium and aluminium are desired since they improve the oxidation
resistance of the alloy. A small amount of yttrium binds the oxide layer to the
substrate. Boron and zirconium are added to the polycrystalline superalloys
where they segregate to the grain boundaries. This results in a better creep
strength and ductility. The carbides tend to precipitate at the grain boundaries
and prevent the sliding phenomenon of the boundaries. A few examples of
carbide formers are carbon, chromium, molybdenum and tungsten. Some
elements function as solid-solution strengtheners, e.g. cobalt, iron, niobium,
rhenium and molybdenum. The addition of titanium will increase the hot
corrosion resistance and the role of nickel is to give phase stability. [18], [20]

2.1.2 Phases and microstructure

Different phases are formed during the fabrication of nickel-based superalloys.


The dominating phases are the gamma matrix and the gamma prime.

20
2.1.2.1 Gamma matrix () phase

The foundation of all nickel-based


superalloys is the gamma matrix, . The
continuous phase is nonmagnetic and with
a face centred cubic, FCC, structure [17]-
[19]. Illustration is found in Figure 13.
Nickel by itself has neither exceptional
high elastic modulus nor low diffusivity. On
the other hand nickel, has a nearly filled
third electronic shell which allows alloying
with solid solution strengthening elements
without losses in phase stability. The alloy
elements composing the gamma matrix
mainly belong to Group V, VI and VII and
Figure 13: FCC gamma structure [20]. are cobalt, iron, chromium, molybdenum
and tungsten. [17]-[19]

2.1.2.2 Gamma prime () phase

The precipitated phase gamma prime, , wasnt identified until the 1940s [12].
It is formed from elements from Group III, IV and V. The addition of for example
aluminium and titanium, which are the essential solutes [20], results in a
reaction with nickel, precipitating the phase of the form Ni3X, where X is an
alloy element. The structure of the gamma
prime is FCC. The atom ordering is
illustrated in Figure 14. Other elements
included in the phase can be chromium,
hafnium, niobium and tantalum. [12], [17]-
[20]
The lattice parameter differs slightly
from the one of gamma matrix. The
mismatch is small, <0.2%, for spherical .
The close match makes it possible for the
to precipitate evenly in the matrix. [12], [19]
There are several benefits of the presence of
in the matrix. The coherence between
and results in a low surface energy and in
an exceptional long-time stability. The Figure 14: FCC gamma prime
phase is also the reason for the high- structure [20].
temperature strength and creep resistance
in most superalloys. [17], [19]
The strength of the alloy is strongly dependent on the volume fraction of .
Wrought alloys contain 20-45 % of . Higher fractions will make the deformation
too difficult. Cast superalloys can have a volume fraction of up to 60 %, which
will increase the alloy strength compared with the wrought alloys. [19]

21
2.1.2.3 Carbides

The addition of carbon, generally in amounts of about 0.02 to 0.2 %, will result in
a union with refractory elements such as hafnium, niobium and titanium.
Primary carbides of the type MC, where M can be one of the just previously
mentioned metals, are formed during freezing of the alloy. The structure of these
carbides is FCC. MC carbides are an essential source of carbon during heat
treatment and service. On those occasions, the carbides tend to decompose into
other, secondary, carbide variants, e.g. M23C6 and M6C. The dominating formulas
for formation of the two carbides are, according to Sims et al. [17], believed to be

MC + M 23 C 6 + ' (1)

and

MC + M 6 C + ' . (2)

In some alloys the formation of M6C from M23C6, according to the formula

M 6 C + M M 23 C 6 + M , (3)

has been observed, and in yet other alloys the reverse reaction occurs. M and M
can be replaced with chromium and cobalt, nickel or molybdenum, respectively.
[17]
The most common M element in M23C6 is chromium but also iron, tungsten and
molybdenum can be found in that position. The M elements generally found in
M6C are molybdenum and tungsten, but the carbide can contain chromium,
cobalt and tantalum as well. [19]
The existence of carbides plays an important role in polycrystalline superalloys.
Both M6C and M23C6 carbides are most likely to precipitate at grain boundaries.
When properly formed, they strengthen the boundary and restrain grain
boundary sliding [18]-[19]. When M23C6 is formed in the grain boundaries, the
chromium content in the matrix is reduced and the solubility for is augmented
in these zones [17]. The shape of the carbides is crucial for the properties.
Cellular shape of the M23C6 carbides can cause premature failure while irregular,
blocky particles will strengthen the alloy [19].
Fine, intergranular carbides will have a strengthening influence on the material.
Deleterious elements in the superalloy can be tied up by the carbides; hence
avoiding phase instability during service. [19]

2.1.2.4 Grain boundary () phase

It has been reported [17]-[18] that, in some alloys, may segregate to the grain
boundaries when exposed to heat, forming a film around the M23C6 carbides or

22
the decomposing MC carbides. The existence of these films is believed to improve
the rupture properties.

2.1.2.5 Borides

Small additions of boron have proved to have a positive influence on the creep-
rupture resistance. The boron precipitates into the form M3B2 which has a
tetragonal unit cell. Two different types of borides has been observed, where the
M represented a mixture of cobalt, chromium, molybdenum, nickel and titanium.
The borides are merely observed in grain boundaries. [17]-[19]

2.1.2.6 Topologically close-packed (TCP)-type phases

Not all phases found in the nickel-based superalloys are improving the
properties. The composition has to be carefully controlled in order to avoid
topologically close-packed (TCP) phases, for example phase, phase or Laves.
These phases can be formed under certain conditions, usually during service.
They are distinguished by their platelike or needlelike shapes. Alloys containing
transition metals, such as tantalum, niobium, chromium, tungsten or
molybdenum, are the alloys the most vulnerable to the formation of TCP phases.
[17], [19]
phase is a physically hard, platelike phase of the form (Fe,Mo)x(Ni,Co)y which
has a seriously harmful influence on the properties of the alloy. Crack initiation
caused by the shape and the hardness of the phase leads to brittle failure. Even
more crucial is the effect on the strength of the alloy. The phase is depleted of
refractory metals, resulting in a considerable loss of solution strengthening. The
phase is also responsible for shortened rupture life, since high temperature
rupture can occur along the plates. [17], [19]
Platelike has been observed [19] but the effects of the phase on superalloys
remain to be investigated. High content of Laves in the superalloy will decrease
the tensile ductility and creep properties at room temperature.
In the new generation superalloys the content of chromium is considerably
reduced, since too much chromium tends to form TCP and hence deteriorate the
properties of the alloy [20]. The subsequent reduction in corrosion protection is
compensated by coating the component in question.

2.1.3 Strengthening of superalloys

Strengthening of superalloys is required for the purpose of obtaining the


desirable high-temperature properties. It can be realised through either solid-
solution strengthening or precipitation hardening.
Creep resistance is an example of interaction between different hardening
mechanisms. In early stages of creep the largest contributor to the creep
resistance is the effects from solid-solution strengthening. The effect diminishes
with time whereas the contribution from the precipitation hardening increases.
[19]

2.1.3.1 Solid-solution strengthening

Solid solution is best described as a homogeneous crystalline structure in which


one or more types of atoms or molecules may be partly substituted for the

23
original atoms or molecules without changing the structure. This substitution
has a strengthening effect on the material. Common strengthening elements are
chromium, cobalt, iron, molybdenum, rhenium, tantalum and tungsten. [19]
As already mentioned in chapter 2.1.2.1, solid-solution strengthening takes place
in phase. The addition of for example molybdenum expands the lattice and
cobalt reduces the lattice when replacing iron in the superalloy matrix. An
expansion of the lattice creates an internal strain. The expansion affects the
mismatch with the strengthening precipitate phase. It has been shown that the
stacking fault energy is reduced in the presence of solid-solution strengtheners.
This will make it more difficult for dislocations, thus cross-slip at high
temperatures is restrained. [17]-[18]
Solid solution strengtheners can also have a beneficial influence on the corrosion
and oxidation resistance. Superalloys with sufficiently large chromium content
will form a protective oxide film that covers the surface [17].

2.1.3.2 Precipitation hardening

As described in chapter 2.1.2.2, gamma prime is formed during ageing by the


precipitation of aluminium and titanium. The slightly different lattice parameter
of creates a small misfit important for two reasons. First of all it guarantees a
low / surface energy which is essential for a stable microstructure and
improves the properties at elevated temperatures. Secondly, a negative misfit,
i.e. has a smaller lattice parameter than , will facilitate the formation of rafts
and by those means possibly reduce the creep rate. This will be discussed further
in chapter 2.1.4. The misfit is controlled by the composition of the superalloy,
particularly by altering the aluminium-titanium ratio, but also by the ageing
temperature. [11], [17], [20]

2.1.4 Rafting

Appropriate heat treatment or service


exposure can stimulate the formation of
rafts. A negative misfit between and
will result in internal stresses.
Under this stress, the particles
coalesce, forming layers in a direction
perpendicular to the applied stress.
These layers are also called rafts. [20]-
[21]
In low-stress applications, the rafts
improve the creep resistance by
preventing the dislocations to move
over the layers. On the other hand, if
the stress is large enough the
dislocations will be able to cut through
the rafts which have coarsened during
formation. In this case, the presence of Figure 15: Rafts in single crystal superalloy
rafts is deleterious. [21].

24
2.2 GAS TURBINE BLADE CASTING

Gas turbine blades are exposed to severe conditions during service, such as
elevated temperatures, high centrifugal forces and oxidation. Exceptionally good
high-temperature properties are indispensable for the blade and a complex
design is required to match these demands. Conventional casting will result in a
superalloy with insufficient high-temperature properties caused by the structure
containing equiaxed grains. Previously, gas turbine components made of
conventionally cast superalloys failed at the grain boundaries from a combination
of thermal fatigue, oxidation and creep. [19]
The two methods used today, directionally solidified (DS) and single crystal (SX)
cast superalloys, are superior to conventionally cast superalloys for two reasons.
Grain boundaries are failure initiation sites and the alignment or elimination of
these allows the to, through solution heat treatment, increase the creep
strength and ductility at elevated temperatures of the alloy. Secondly, a low-
modulus <001> orientation is created parallel to the solidification direction
during directionally solidification, which improves the thermal fatigue resistance.
[17], [19]
Casting turbine blades is a complicated process because of the complex shape.
Simplified, a mould is created by pouring a ceramic around a wax model of the
component. The wax is then removed and the mould is filled with molten metal
from the top of the blade. [20]

2.2.1 Directional solidification (DS)

The directional solidification of superalloys was not introduced


until the early sixties. In the directional solidification process,
the grain boundaries are aligned parallel to the solidification
direction, which coincide with the principal stress axis of the
component. The final structure consist of columnar grains with
their <001> orientation in the direction of the later on applied
load. [17]
As mentioned before in chapter 2.2, stresses at elevated
temperatures have a crucial effect on the grain boundary
perpendicular to the stress direction, which is the weakest link
of the chain. By aligning the grain boundaries the site of failure
initiation is removed and the influence from the stress on the
superalloy is very much reduced. [17]
DS turbine blades with the low modulus <001> orientation
parallel to the direction of the applied stress have proved [19] to
increase the thermal fatigue resistance fivefold compared to Figure 16:
conventionally cast turbine blades. Directionally
solidified
A picture of a directionally solidified turbine blade is found in columnar grains
Figure 16. turbine blade
[20].
Directionally solidified components are not employed in any of
the turbines produced by SIT AB.

25
2.2.2 Single crystal (SX) casting

A small modification of the DS process, originally made in the mid-1960s, enables


the casting of single crystal components. The principle is illustrated in Figure 17.
The process is performed in vacuum in a preheated, ceramic mould.

Figure 17: Single crystal processing [19].

By controlling the solidification in the helical mould, the


growth of all grains can be prevented; hence the presence of
grain boundaries is eliminated. As shown in Figure 17b, the
mould is chilled from the bottom. At the beginning the
solidification results in columnar grains perpendicular to the
thermal gradient. When reaching the helical channel, all
columnar grains except one are prevented from growing. At the
end of the helix, the structure of the solidifying superalloy is
single crystal. [17], [19] A single crystal turbine blade with the
helical channel is shown in Figure 18. Just as in the case of DS
superalloys, the preferential orientation parallel to the stress
axis is <001>.
One reason to why single crystal superalloys exhibit better
properties at high temperatures than DS superalloys is the
lack of grain boundary strengthening solutes, i.e. boron and
Figure 18: Single zirconium. The act of removing these elements will increase
crystal blade [20]. the incipient melting temperature of the superalloy thus
improving the elevated-temperature properties. [20]
The use of single crystal material in the gas turbines produced by SIT AB is
restricted to one single component: the first stage turbine blade in SGT-800. The
remaining components are conventionally cast.

2.3 SINGLE CRYSTAL SUPERALLOY CMSX-4

CMSX-4 is a second generation single crystal superalloy from Cannon-Muskegon


Corporation. The superalloy is characterised by a high solvus temperature and

26
a high concentration of refractory elements [12]. Due to its high-temperature
strength, oxidation resistance and creep resistance, its applied to the hottest
parts of the gas turbine, for example the first stage turbine blade in SGT-800.
CMSX-4 is developed from the first generation superalloys CMSX-2 and CMSX-3.
The tantalum/tungsten ratio is balanced to improve the castability. The addition
of 3 % rhenium improves both creep strength and thermal fatigue resistance of
CMSX-4 compared to CMSX-2 and CMSX-3 at elevated temperatures. The added
rhenium is mainly found in where it retards coarsening of , thus increases the
/ misfit. Another change is the higher volume content of compared to the
content in CMSX-2. The cause is to further improve the creep resistance. The
solid solubility is assisted by the increased cobalt content and the reduced
chromium content. Besides, this variation in composition prevents the formation
of TCP at elevated temperatures. [19] CMSX-4 melts in the temperature range
1320-1380C [12].
The material used in this study comes from two different batches, V 8508 and
V8677, provided by Cannon Muskegon Corporation. The composition of CMSX-4
is shown in Table 1, values expressed in wt%. The mixture is balanced (Bal) with
nickel.

Al Co Cr Hf Mo
V 8508 5.66 9.7 6.4 0.10 0.61
V 8677 5.66 9.6 6.4 0.10 0.60
Ni Re Ta Ti W
V 8508 Bal 2.9 6.5 1.04 6.4
V 8677 Bal 2.9 6.5 1.04 6.4
Table 1: Composition of CMSX-4 used in this study, expressed in wt% [22].

The superalloy is heat treated in three different stages. Firstly the material is
heat treated under vacuum. The heat treatment commences at 1277C 5C and
is in 7 steps increased to a temperature of 1321C 3C during 18 h in total
followed by a rapid gas fan quench in argon. Secondly the material is held under
vacuum at a temperature of 1140C 10C during 2 h and is then air cooled.
Finally the material is held under vacuum at a temperature of 870C 5C for 20
h and is then air cooled. [22]
The known, principal phases in CMSX-4 are gamma matrix and gamma prime.
The fraction of gamma prime amounts to approximately 60 vol%. The possible
formation of TCP at elevated temperatures is an unwanted occurrence to a large
extent impeded by the addition of refractory elements. [11]

2.4 SUPERALLOY HAYNES 230

Haynes 230 is a nickel-based solid-solution strengthened superalloy with


excellent creep-rupture strength at high temperatures and oxidation resistance.
The superalloy is designed to sustain long-term thermal stresses without
suffering from property degradation or grain coarsening. The melting

27
temperature range is 1301-1371C and the maximum service temperature is
1149C, i.e. >0.8Tm. [13]
Nickel-based superalloys that are solid-solution strengthened through a
significant addition of molybdenum or tungsten, such as Haynes 230, are harder
to form than alloys lacking these elements [18]. The tungsten was chosen as the
primary solid-solution strengthener because of its beneficial effect on the creep
strength and its ability of decreasing the stacking fault energy [23]. The carbon
quantity is kept low in the material since a content exceeding 0.15 % can result
in a significantly diminished ductility due to carbide precipitation [18]. The
resistance to oxidation is improved due to the addition of chromium to the alloys
composition. [23].
The exact composition of Haynes 230 used in this study is described in Table 2.
The material is provided and analysed by Haynes International. The whole of the
test certificate is shown in Annex 8.2.

Al B C Co Cr Cu Fe La
0.37 0.003 0.10 0.25 22.00 0.02 1.45 0.016
Mn Mo Ni P S Si Ti W
0.54 1.29 Bal <0.005 <0.004 0.44 <0.01 14.32
Table 2: Composition of Haynes 230 used in this study, expressed in wt% [Annex 8.2].

The superalloy can be either cast or wrought, depending on the application.


Haynes 230 is produced in a variety of forms, e.g. plates, sheets and bars [13]. In
order to form the sheets used in the combustion chamber, the superalloy is first
cast and then rolled. However, the test specimens in this study was turned from
a wrought bar.
The heat treatment is carried out at a temperature between 1177C and 1246C
and is then followed by rapid cooling [13]. The wrought superalloy consists
mainly of the matrix and primary MC carbides [17]. During long-term exposure
to heat, secondary carbides and intermetallic compounds can precipitate,
resulting in for example beneficial creep strength improvement or reduced
fracture resistance, depending on the precipitated phase [23].

28
3 AGEING EFFECTS IN SUPERALLOYS

3.1 CONTRACTION IN SUPERALLOYS

Shrinkage during service of superalloys and the underlying mechanisms have


been discussed in several studies [1]-[2], [24]-[27]. Marucco [24] measured lattice
contraction after ageing at intermediate temperatures (450-600C) in 20Cr-25Ni
steel, Sanicro 71 and Inconel 690 which amounted to 0.024, 0.040 and 0.038 %
respectively. The study did also show that small ordered areas arose in the alloys
due to the ageing.
Nath et al. have been involved in several studies [2], [25]-[26] investigating the
ageing effects on different nickel-based alloys, e.g. Nimonic 80A [26], a wrought
nickel-based precipitation-hardened superalloy used as a bolting material in
steam turbines. By use of X-ray diffractometry they proved that the lattice
parameter was reduced due to ageing at 450-565C and the kinetics of the
contraction was mapped. The maximum lattice parameter contraction was
obtained during ageing at 450C for 30 000 h and measured 0.115 %. According
to Nath et al. the lattice contraction was due to short range ordering (SRO) and
long range ordering (LRO) arisen during ageing. Electron diffraction studies
performed on Nimonic 80A corroborated the existence of SRO based on Ni2Cr and
the transformation into LRO owing to long-term ageing.
The lattice parameter
contraction depends on the
composition of the ordered
phase. Marucco and Nath
[2] have measured the
lattice parameter
contraction in Ni2Cr and
Ni3Cr after ageing at 475C
(see Figure 19). Ni3Cr
exhibited a small
contraction in the
neighbourhood of 0.05 %
after 10 000 h. The lattice
parameter contraction in
Ni2Cr under the same
conditions is almost 5 times Figure 19: Lattice contraction in () Ni2Cr and ()
larger. Ni3Cr as a function of the ageing time at 475C [2].

In previous work carried out at SIT AB [1] the lattice contraction in different
nickel-based superalloys and the austenitic stainless steel X6CrNiTi18-10 was
measured. Cylindrical specimens of the length 100 mm were aged at 450, 500 and
550C and the shrinkage strain was measured after 300, 1000 and 3000 hours in
a coordinate measurement machine. The result is shown in Figure 20-Figure 22.

29
Shrinkage of Austenitic Steels and Ni-base alloys
Temperature: 450degC
0
-0,006
-0,012
-0,018 Hastelloy X

Strain, % -0,024 Haynes 230


-0,03 Inconel 718
-0,036 Haynes HR-120
-0,042 233702
-0,048
-0,054
-0,06
0 500 1000 1500 2000 2500 3000 3500
Time, h

Figure 20: Shrinkage strain at 450C [1].

Shrinkage of Austenitic Steels and Ni-base alloys


Temperature: 500degC
0

-0,01
Hastelloy X
-0,02
Strain, %

Haynes 230
-0,03 Inconel 718
Haynes HR-120
-0,04 233702
-0,05

-0,06
0 500 1000 1500 2000 2500 3000 3500
Time, h

Figure 21: Shrinkage strain at 500C [1].

Shrinkage of Austenitic Steels and Ni-base alloys


Temperature: 550degC
0

-0,01
Hastelloy X
-0,02
Strain, %

Haynes 230
-0,03 Inconel 718
Haynes HR-120
-0,04
233702
-0,05

-0,06
0 500 1000 1500 2000 2500 3000 3500
Time, h

Figure 22: Shrinkage strain at 550C [1].

30
It is obvious that the contraction of the alloys is significant already after 300 h of
ageing. Between 300 h and 1000 h the shrinkage rate is slowing down and is
almost constant between 1000 h and 3000 h. This behaviour is in accordance with
the conclusion Nath et al. made in 1984 [26] which is further discussed above
Figure 25 in chapter 3.2.
The shrinkage strain after 3000 h of ageing is plotted against the ageing
temperature in Figure 23 and the value of the maximum shrinkage strain is
presented in Table 3.

Shrinkage strain after 3000h ageing

600

500

Temperature, C
400

300
Hastelloy X
Haynes 230 200
Inconel 718
Haynes HR-120 100
233702
0
-0,06 -0,04 -0,02 0
Strain, %

Figure 23: C-curves of shrinkage strain at ageing at 3000 h [1].

Maximum Ageing
Material shrinkage temperature
strain [%] [C]
Hastelloy X -0.036 450
Haynes 230 -0.052 500
Inconel 718 -0.02 450
Haynes HR-120 -0.016 450
X6CrNiTi18-10 -0.024 550
Table 3: Maximum shrinkage strain for different
austenitic alloys after ageing for 3000 h [1].

The largest shrinkage is attributed to Haynes 230 at ageing at 500C and then
Hastelloy X at ageing at 450C.
The lattice parameter of the alloys was measured with X-ray diffraction before
and after ageing. A good correlation was found between macroscopic length
shrinkage and lattice parameter contraction.

31
3.2 SHORT RANGE ORDERING (SRO) AND LONG RANGE
ORDERING (LRO)

Short range ordering exists in all Ni-Cr alloys, irrespective of the presence of
other alloy elements. Small, ordered areas in the size of nanometres are formed
in an otherwise disordered matrix. The ordering takes place if atoms of different
types are more attracted to each other than atoms of the same type. The short
range ordered phase forms at stoichiometric compositions, e.g. AB, A2B and A3B
or at off-stoichiometric compositions but at lower kinetics. A commonly formed
ordering phase in superalloys is the orthorhombic Ni2Cr. The formation takes
place during either cooling from solution temperature or at early stages of ageing.
The degree of SRO decreases with temperature, but it is also influenced by the
composition. Studies on ternary Ni-Cr-Fe alloys [28] have shown that the
augmentation of Ni content increases the degree of SRO and the diminution of Fe
content has the opposite effect. [2], [24], [28]
Long-term ageing below a critical temperature TC will, for certain alloy
compositions, result in growth of SRO nuclei, transforming the SRO phase into
long range ordering phase [28]-[29]. TC depends on the composition of the alloy,
but is normally located between 530C and 580C [28].
Even if LRO is non-existing above TC, SRO can exist at temperatures close above
TC in stoichiometric alloys AxBy, alloys which would be long range ordered at
lower temperatures [2]. See Figure 24 for illustration.

Figure 24: The dependence of the long (S) and short () range
order parameters on temperature [2].

According to Rtishchev [29] SRO and LRO are formed in binary Ni-Cr alloys with
a chromium content of 25-37 at%. In commercial superalloys, the chromium
content in phase after the precipitation has to exceed 25 at% to make the
formation of LRO possible.
The tendency of Ni-Cr based superalloys to form LRO can be described by the Z-
criterion [29]. Z is calculated on the atom content in , after precipitation of
and minor phases, according to Equation 2:

32
Ni
Z= . Equation 2: Z-criterion, in at%at%-1 [29].
Cr + W + Mo

Rtishchev has proved experimentally that the formation of LRO occurs at


estimated values of Z<3.0.
The Ni2Cr superlattice stability is affected by the alloy elements. It has been
shown that the presence of tungsten and molybdenum stabilizes the superlattice
while the presence of cobalt has a negative effect on the stability of the structure
[29]-[30].
The degree of LRO and the kinetics depend on the ageing temperature and the
composition. If the ageing temperature is increased, the nucleation rate will
decrease while the growth rate will increase. The maximum kinetics is obtained
for the composition Ni2Cr. The larger deviation from the stoichiometry the slower
kinetics of LRO is obtained [28]. The presence of tungsten and molybdenum will
have an accelerating effect on the order kinetics. On the other hand, the kinetics
is strongly subdued by the presence of cobalt and iron. [24], [28]-[29]
Nath et al. [26] showed that the kinetics of lattice contraction depends on the
ageing time and applied strain. The results from their lattice contraction
measurements for Nimonic 80A are plotted in Figure 25. They concluded that the
contraction is divided in three stages. During the first 500 h the contraction rate
was high. During the next 15 000 h it became very slow and then it accelerated
again at longer ageing time.

Figure 25: Lattice parameters of strained and unstrained Nimonic 80A during
ageing: 500C with no strain, 500C with applied strain, 450C with
no strain, 450C with applied strain [26].

33
The lattice parameters at 450C and 500C were similar for the majority of the
ageing interval. The exception is located in the early stages of ageing where the
material with applied strain contracted faster at 450C than at 500C.
Noteworthy is also that the unstressed alloys initially contracted faster than the
stressed alloys, but after a specific ageing time the rate of lattice contraction of
the unstressed alloys slowed down, resulting in a crossover of the curves. This
crossover takes place after about 3000 h at 500C and after 25 000 h at 450C.
The ordering phenomenon affects the properties of the superalloy, mainly
through influence on the dislocation morphology. Ordering arise since the
attraction is larger between atoms of different types than between atoms of the
same type. Dislocation moving in a superalloy with such structure along one slip
plane would result in a Ni atom taking the place of a Cr atom. In this case, a
superdislocation is created. The superdislocation dissociates into two normal
dislocations and one antiphase boundary. If the ordered domains are smaller
than the width of the antiphase boundary, for example in the early stages of
LRO, the dislocation moving along one particular slip plane preclude the nearest-
neighbour bonding across the slip plane. To avoid increased disorder, successive
dislocation moving must occur along the same slip plane. This results in an
increased ease of dislocation to occur on a plane where slips already have taken
place. The dislocation is restricted to a small number of slip planes where it takes
place with coarse steps. This behaviour is also called heterogeneous deformation.
[2], [31]
The deformation is remained planar if the absorption of the dislocations, caused
by high friction stresses [30], is as fast as the emergence at grain boundaries.
Then there will be no work hardening of the alloy. If the annihilation process is
too slow a pile-up will be created and further deformation on the plane is limited.
This will result in an activation of other planes and the presence of dislocation
tangles between these planes will cause a strain hardening in the alloy. [2]
Rtishchev [29] found that the yield strength is significantly improved by the
presence of LRO. Unfortunately this leads to sharp notch sensitivity at stress
rupture and deteriorated ductility. The ordering is also responsible for an
increase in elastic modulus as well as in hardness. Marucco and Nath [2] found
that the tensile strength and ductility decreased with increasing test
temperature and that the minimum work hardening coefficient was found
between 450 and 600C. They also found high rates of work hardening at room
temperature, but at higher temperatures the dislocation-annihilation will be
faster, thus encouraging planar slip.
The ordering does also affect the electrical resistivity, . In a study made of
Marucco and Nath [2] the resistivity was measured during long-term ageing at
475C (see Figure 26). A comparison between the ordered phases Ni2Cr and
Ni3Cr shows a large difference in resistivity change. The resistivity in Ni3Cr
alloys increased with approximately 0.4 % already after 24h. was then more or
less constant during ageing up to 25 000h. The structure of the alloys remained
in the SRO state during the entire ageing time. The Ni2Cr alloys showed a
similar microstructure and resistivity at early stages of ageing. However, after a
few hundred hours the transformation of SRO into LRO begins, and the
resistivity decreases. After long-term ageing decrease in resistivity of up to 60 %
was measured.

34
Figure 26: Resistivity changes in () Ni2Cr and ()
Ni3Cr as a function of the ageing time at 475C [2].

The order-disorder transformation takes place in simple commercial nickel-based


alloys such as Nimonic 80A, but the LRO phase with Ni2Cr structure has been
found in more complex superalloys as well, such as Hastelloy [2].

3.3 NEGATIVE CREEP

The term negative creep is used for the superposition of two opposite processes.
Common plastic creep represents the positive component and lattice contraction
due to ordering represents the negative component. Negative creep in superalloys
can be observed as a contraction during creep test or as an increase in stress
during relaxation test. [2], [27]
It has been shown [2] that the ordering of Ni2Cr in the form SRO and LRO arisen
during ageing at 550C and below is responsible of lattice contraction, which
leads to dimensional instability and negative creep in Nimonic 80A and the
binary alloy Ni-20wt%Cr. It was also confirmed that the precipitation of had
no influence on the process [2], [30].

3.4 CARBIDE PRECIPITATION

In an internal report from Lincoln [32] the ageing effect on macrohardness of


Haynes 230 is investigated. The result is shown in Figure 27. The test load used
in the study was 20 kg. The report is analysing the influence of ageing
temperature (750-1050C) and ageing time (1000, 3000 and 5000 h) on the
hardness. As illustrated in the figure, ageing at lower temperatures resulted in
an improved hardness, but the hardness decreased with increasing temperature
and the higher ageing temperatures resulted in a deteriorated hardness
compared to the unaged reference.

35
Figure 27: Hardness changes due to ageing. [32]

36
4 AGEING INFLUENCE ON MECHANICAL PROPERTIES
AND MICROSTRUCTURE OF HAYNES 230 AT
INTERMEDIATE TEMPERATURES (500-550C)

4.1 SPECIMEN PREPARATION AND EXPERIMENTAL PROCEDURE

4.1.1 LCF test

Nine cylindrical LCF test specimens were turned from the same bar, all of them
following the drawing 7000 3005-1 (see Annex 8.3.1). Six specimens were aged
during 1000 h, three of them at 500C and another three at 550C. The
remaining 3 specimens were kept untreated as references (ref).
LCF tests were performed on the specimens in the universal testing machine
Instron 1275 at room temperature in agreement with ASTM E 606-92. The
nominal diameter of the specimens was 10 mm and the extensometer gauge
length was 12.5 mm. The tests were carried out in total strain control mode. The
strain rate was 6 %min-1 and the nominal strain ranges applied in the tests were
1.2 %, 1.6 % and 2.0 %. At each strain range, one reference and specimens from
500C and 550C respectively were tested, i.e. in total three specimens at each
strain range.
The number of cycles in each LCF test, N, was counted during the test. The
number of cycles to crack initiation, Ni, was defined as 5 % load drop from the
stabilised loop and the number of cycles to failure, Nf, as 50 % load drop. In those
tests where the crack initiation took place outside the extensometer range, Nf was
defined as the cycle when complete failure occurred. The maximum stress was
determined for the first cycle, max (N=1), and for midlife, max (Nf/2). The plastic
strain range, pl, was calculated for midlife. All details about the calculations
are given in Annex 8.4.1.

4.1.2 Impact test

The impact tests were performed at room temperature in Charpy impact test
equipment in agreement with the standard EN 10 045-1.
The impact test specimens were milled from a round bar into the wanted shape
according to the drawing 7000 2059-3 (see Annex 8.3.2). Ten of the fifteen V-
notched specimens were aged for 1000 h, five of them at 500C and the other five
at 550C. The last five which werent heat-treated represented the reference.

4.1.3 Tensile test

The specimens for the tensile test were turned from the same bar, following the
drawing 7000 1782-3 (see Annex 8.3.3). Out of totally twenty specimens, four
were used as references. Two were aged during 300 h, three during 1000 h and
another three during 2500 h, all at 500C. This procedure was repeated with
another set of specimens at 550C (see Table 4).
To carry out the tensile test in room temperature, Schenck-Trebel RSA 100 test
machine was used. All tests were performed within the standard EN 10 002-1.
The strain was measured by an extensometer up to 5.0 %.

37
Specimen Ageing Ageing Specimen Ageing Ageing
marking temp [C] time [h] marking temp [C] time [h]
HY21 500 1000 HY31 550 2500
HY22 500 1000 HY32 550 2500
HY23 500 1000 HY33 500 300
HY24 500 2500 HY34 500 300
HY25 500 2500 HY35 550 300
HY26 500 2500 HY36 550 300
HY27 550 1000 HY37 - -
HY28 550 1000 HY38 - -
HY29 550 1000 HY39 - -
HY30 550 2500 HY40 - -
Table 4: Ageing temperature (temp) and time for Haynes 230 tensile test specimens.

The specimens dimensions were measured before and after the test and the
elongation, A5, was calculated as well as the reduction of the cross-section area, Z
and the yield strength at 0.1 % plastic strain deformation, Rp0.1. The tensile
strength, Rm, and the yield strength at 0.2 % plastic strain deformation, Rp0.2,
were determined by the employed software during the test. No conclusions were
drawn from the elastic modulus, E, calculated by the software, since the
determination of E from tensile test curves is difficult and the result can be
unreliable. All details concerning the calculations are given in Annex 8.4.2.
All specimens aged under the same conditions, time and temperature, form a
group. Since each group contain several curves, a graph with all curves aged at
for example 500C would be undecipherable. In order to make the graphs clear,
an attempt was made to use the Ramberg-Osgood equation

1
n
= + Equation 3: Ramberg-Osgood equation.
E K

to produce a fitted curve representing an average for each set of curves. In this
expression K is the strength coefficient and n the strain-hardening exponent.
However, the fitted curve matched up poorly to the original curves, so this
adjustment was inapplicable. Instead, one curve from each group which best
described the behaviour of the group was distinguished and plotted in Figure 34
and Figure 35, found in chapter 4.2.3.

4.1.4 Microscopic examination

The cut-ups prepared for microscopic examination contain a cross-section of the


tensile test specimens or the 2.0 % strain range LCF test specimens along the
test load axis. The chosen specimens were cut perpendicular to the test load axis
using a slitting wheel. Approximately 3 cm of the specimens were cut off,

38
including the fracture surface, and the samples were then mounted. Cut-ups
containing tensile specimens were grinded roughly on a stone down to the core of
the specimens. LCF specimens were sectioned along the test load axis in the
slitting machine before the mounting. All cut-ups were then ground, starting
with 120 grade paper finish down to 1000 in five steps. The cut-ups were then
polished with diamond suspension, first with the diamond size 6 m and finally
with the size 1 m. The last act was electrolytic etching in 10 % oxalic acid at 6 V
for 25-30 s. These etching conditions were excellent for the entire area of the
specimens except for the edges. After microscopic examination of the cut-ups, the
grinding and polishing procedure was repeated from 600 grade paper finish and
completed with electrolytic etching for 5 s to enable examination of the edges.
The fracture surfaces of the tensile specimens were photographed in the
stereomicroscope before mounting. The cut-ups were examined in both optical
microscope and SEM. The examination focused on any possible difference
between new and aged material, such as carbide size and distribution, growth of
secondary carbides, deformation, new phases and composition of both matrix and
carbides.
The carbide size was measured by means of the software Image-Pro Plus. The
mean diameter, d1, and the aspect ratio, r1, were determined for primary
carbides, and also the diameter and aspect ratio for secondary carbides, d2 and r2.
Around 100 carbides were dimensioned in each sample. In the case where the
carbides in the tensile test specimens were measured, the photos in question
were taken approximately 3 cm from the fracture surface. When it comes to the
untested specimens, the photos were taken in the middle of the sample.

4.1.5 Hardness test

Hardness test was performed on the cut-ups used in the microscopic examination
before the re-etching. The macrohardness was measured in Vickers scale (HV10)
in a macrohardness test machine from Wolpert Probat of the type Dia testor 2N.
Four imprints were made on each specimen. The minimal distance between two
imprints was at least three times the width of an imprint. The applied load was
10 kg.
The test was carried out on the LCF test specimens as well as on a set of
untested specimens. One of the untested specimens was a virgin bar and the
other two were aged at 550 C for 1000 h and 3000 h respectively.
The size of each imprint was measured manually and the value of the Vickers
hardness was then obtained from a table.
Leco M-400 DT was employed to measure the microhardness of the untested
specimens. The imprint had to be the largest possible to secure the reliability of
the imprint measurement and yet small enough to enable the avoidance of the
carbides. Experiments showed that 50 g was the optimal load. The distance
between the imprints followed the same rules as for macrohardness testing.
Imprints were made at two different areas: close to grain boundary and in the
middle of the grain. Ten imprints were made in the matrix at each area and
sample, avoiding the primary carbides.
The size of the imprints was measured by means of the software Image Access
Hardness and the value of Vickers hardness was calculated automatically.

39
4.2 TEST RESULTS

4.2.1 LCF test

Nine LCF tests were performed. The results from the LCF tests are summarised
in Table 5.

Specimen Ageing Strain Ni Nf max (N=1) max(Nf/2) pl(Nf/2)


marking temp range [MPa] [MPa]
[C] [%]
L9 - 1.2 8093 8122 427 511 0.734
L5 500 1.2 7142 7193 430 538 0.718
L4 550 1.2 6748 6849 439 554 0.715
L13 - 1.6 2737 2771 435 563 1.058
L6 500 1.6 3035 3068 442 610 1.046
L8 550 1.6 3889 3889 428 585 1.042
L14 - 2.0 1783 1793 455 598 1.419
L7 500 2.0 1670 1684 446 654 1.387
L12 550 2.0 1982 1982 441 633 1.377
Table 5: Summary of result from LCF test.

Figure 28 and Figure 29 show the evolution of maximum stress and plastic strain
range plotted versus the number of cycles.

750

700

650

600
M a x str e ss
[M P a ]
550

500

450

400
1 10 100 1000 10000
C y c le

n e w - 1 .2 % 5 0 0 C - 1 .2 % 5 5 0 C - 1 .2 %
n e w - 1 .6 % 5 0 0 C - 1 .6 % 5 5 0 C - 1 .6 %
n e w - 2 .0 % 5 0 0 C - 2 .0 % 5 5 0 C - 2 .0 %

Figure 28: Max stress versus number of cycles.

40
1 ,6

1 ,4

P l a s ti c 1 ,2
str a i n
r a n g e [% ]
1

0 ,8

0 ,6
1 10 100 1000 10000

C y c le

n e w - 1 .2 % 5 0 0 C - 1 .2 % 5 5 0 C - 1 .2 %
n e w - 1 .6 % 5 0 0 C - 1 .6 % 5 5 0 C - 1 .6 %
n e w - 2 .0 % 5 0 0 C - 2 .0 % 5 5 0 C - 2 .0 %

Figure 29: Plastic strain range versus cycle.

The maximum stress, the inelastic strain and the total strain range at midlife is
plotted against the number of cycles, one curve for each ageing condition. The
curves are found in Figure 30-Figure 32.

M a x im u m s tr e s s v e r s u s c y c le a t m id life

700

650

600 re f
m ax
500C
[M P a ]
550 550C

500

450
100 1000 10000
C y c le

Figure 30: Maximum stress versus cycle at midlife.

41
In e la s tic s tr a in v e r s u s c y c le a t m id life

1 ,5
1 ,4
1 ,3
1 ,2
re f
p l 1 ,1
500C
[% ] 1
550C
0 ,9
0 ,8
0 ,7
0 ,6
100 1000 10000
C y c le

Figure 31: Inelastic strain versus cycle at midlife.

S tr a in r a n g e v e r s u s c y c le a t m id life

2 ,2
2
1 ,8
1 ,6 re f
to t
1 ,4 500C
[% ]
1 ,2 550C
1
0 ,8
0 ,6
100 1000 10000
C y c le

Figure 32: Total strain range versus cycle at midlife.

4.2.2 Impact test

The impact test was carried out on 15 specimens, 5 from each group: new
material, aged at 500C and aged at 550C, respectively. The result is shown in a
chart in Figure 33 together with the values of the absorbed energy. Each column
represents an average from the 5 specimens prepared under the same conditions.

42
2 0 0 ,0

1 3 9 ,2
1 6 0 ,0
1 2 1 ,0
1 0 6 ,3
1 2 0 ,0
A b so rb e d
e n e r g y [J ]
8 0 ,0

4 0 ,0

0 ,0
new Aged at Aged at
5 0 0 C 5 5 0 C

Figure 33: Result from impact test of Haynes 230.

The absorbed energy, KV, and the standard deviation are found in Table 6.

Ageing KV Standard
temp [C] [J] deviation
- 106.3 4.28
500 121.0 10.44
550 139.2 13.05
Table 6: Impact test results from
specimens aged for 1000 h.

4.2.3 Tensile test

The total number of tensile tests performed was 20, of which one test was
stopped prematurely by accident. Since the stop occurred close upon the expected
failure, the test data was still of use, tensile strength excepted.
The results from the tensile testing are shown in Table 7. All values are
calculated averages from each group of specimens prepared under the same
conditions, each group comprising 2-4 specimens. The results from the testing of
the aged material are shown as the difference between new and aged material,
written in percentages. The complete table with all original test results is found
in Annex 8.5.1, Table 18.

43
Ref 300 h 1000 h 2500 h
500C 550C 500C 550C 500C 550C
[%] [%] [%] [%] [%] [%]
Rm 862 MPa 1.0 0.9 1.0 1.3 1.7 1.2
Rp0.1 366 MPa 9.5 9.5 8.7 9.6 10.3 13.3
Rp0.2 379 MPa 4.0 3.2 3.9 4.7 5.5 5.6
A5 47.8 % 6.1 12.3 5.9 6.0 9.8 8.4
Z 48.0 % 16.2 20.0 13.2 4.6 16.4 16.3
Table 7: The percentage increase of tensile properties compared with the reference.

The stress-strain curves plotted up to 5 % strain are displayed in Figure 34 and


Figure 35.

T e n s ile t e s t , a g e d 5 0 0 C

600

500

400

S tr e ss
300
[M P a ]

200

100

0
0 1 2 3 4 5 6
S tr a in [% ]

H Y 4 0 - re f HY 33 - aged 300h
HY 21 - aged 1000h HY 26 - aged 2500h

Figure 34: Stress-strain curves from tensile test, ageing temperature 500C.

44
T e n s ile t e s t , a g e d 5 5 0 C

600

500

400

S tr e ss
300
[M P a ]

200

100

0
0 1 2 3 4 5 6
S tr a in [% ]

H Y 4 0 - re f HY 36 - aged 300h
HY 28 - aged 1000h HY 30 - aged 2500h

Figure 35: Stress-strain curves from tensile test, ageing temperature 550C.

4.2.4 Hardness test

The results from the macrohardness testing are visualised in Table 8. The
column of Vickers hardness contains the calculated averages from all imprints
made on each sample. The last column shows the increase or decrease in Vickers
hardness for the aged specimens compared with the unaged reference of the same
type, i.e. untested or LCF tested, expressed in percentages.

Specimen Ageing Ageing Vickers Standard Difference


type temp time hardness deviation compared
[C] [h] [HV10] to ref [%]
Untested - - 202.8 4.03
Untested 550 1000 211.8 4.86 4.4
Untested 550 3000 219.3 4.65 8.1
LCF tested - - 280.0 5.23
LCF tested 500 1000 280.3 5.74 0.1
LCF tested 550 1000 275.0 7.35 -1.8
Table 8: Summary of results from macrohardness tests.

45
The results from the macrohardness testing for the, until then, untested
specimens are shown in Figure 36 and the result from the previously LCF tested
specimens are shown in Figure 37.

2 3 0 ,0
+ 8 .1 %
2 2 5 ,0
+ 4 .4 %
2 2 0 ,0
V ic k e r s 2 1 5 ,0
h ard n e ss 2 1 0 ,0
[H V 1 0 ] 2 0 5 ,0
2 0 0 ,0
1 9 5 ,0
1 9 0 ,0
1 8 5 ,0
0 1000 3000

a g e in g t im e [ h ]

Figure 36: Results from macrohardness test, untested


specimens aged at 550C.

2 9 0 ,0
+ 0 .1 % - 1 .8 %
2 8 5 ,0

2 8 0 ,0

V i c k e r s 2 7 5 ,0
h a r d n e s s 2 7 0 ,0
[H V 1 0 ]
2 6 5 ,0
2 6 0 ,0

2 5 5 ,0
2 5 0 ,0
0 500 550

a g e in g t e m p [ C ]

Figure 37: Results from macrohardness test, LCF specimens


aged for 1000 h.

The microhardness testing was only performed on the untested samples. The
results are shown in Table 9 and in a chart in Figure 38. The given values of
Vickers hardness is the calculated average from the ten imprints on each sample.

46
Specimen Ageing Tested Vickers Standard Difference
type time area hardness deviation compared
[h] [HV0.05] to ref [%]
Untested - Close to grain 222.3 12.07
boundary
Untested 1000 Close to grain 264.1 9.49 18.8
boundary
Untested 3000 Close to grain 244.6 12.63 10.0
boundary
Untested - Middle of 228.9 13.04
the grain
Untested 1000 Middle of 252.4 12.14 10.3
the grain
Untested 3000 Middle of 236.7 10.23 3.4
the grain
Table 9: Summary of results from microhardness test, specimens aged at 550C.

3 0 5 ,0

2 9 0 ,0
+ 1 8 .8 %
2 7 5 ,0
+ 1 0 .3 % + 1 0 .0 %
V i c k e r s 2 6 0 ,0
h ard n e ss + 3 .4 %
2 4 5 ,0
[ H V 0 .0 5 ]
2 3 0 ,0

2 1 5 ,0

2 0 0 ,0
0 1000 3000

A g e in g t im e [ h ]
n e a r g ra in b o u n d a ry m i d d l e o f th e g r a i n

Figure 38: Results from microhardness test, untested specimens aged


at 550C.

4.2.5 Carbide size measurements

The estimated aspect ratio and mean diameter of the primary carbides are listed
in Table 10 together with their min and max values and also the standard
deviation, std. dev.
The determination of the secondary carbides dimensions turned out to be very
hazardous because of the inadequate photo resolution and limitations in the
software. These results are therefore not included in the report.

47
Test Ageing Ageing r1 Std. Min Max d1 Std. Min Max
type time temp dev. [m] dev. [m] [m]
[h] [C]
- - 1.71 0.64 1.02 4.51 1.84 1.86 0.20 9.05
300 500 1.50 0.40 1.00 3.20 2.20 1.69 0.28 8.60
Tensile
300 550 2.55 1.97 1.00 10.29 2.06 2.04 0.28 8.90
test
1000 500 1.39 0.36 1.00 2.96 2.51 1.93 0.28 9.20
1000 550 1.89 1.20 1.00 7.57 1.62 1.55 0.28 7.39
- - 1.49 0.45 1.00 3.57 2.72 1.94 0.28 10.24
Untested 1000 550 1.58 0.73 1.01 4.76 2.55 1.45 0.34 8.38
3000 550 1.46 0.61 1.04 5.51 2.62 1.75 0.34 11.38
Table 10: Dimensions of primary carbides in Haynes 230.

An example of a LOM image used to measure the carbide size is found in Figure
39.

Figure 39: LOM image of carbides in material aged


300 h at 550C.

4.2.6 Chemical analysis

The results from the chemical analysis are shown below. Several analyses were
carried out for each specimen and area. The results presented in the following
tables are representing the average result from each specimen and specific
testing area. The analysed areas are the matrix (Table 11), primary carbides
(Table 12) and secondary carbides (Table 13).

48
Ageing Ageing C Al Ti Cr Mn Fe Co Ni Mo W
time [h] temp. [C]
- - - 0.4 - 22.0 0.5 1.3 0.3 60.1 1.2 14.2
300 500 - 0.4 - 22.0 0.5 1.3 0.3 60.6 1.4 13.7
300 550 2.2 0.5 0.1 21.5 0.4 1.3 0.3 58.9 1.2 13.6
1000 500 - 0.3 - 22.0 0.6 1.3 0.3 60.2 1.3 13.9
1000 550 - 0.3 - 22.0 0.5 1.4 0.4 60.6 1.2 13.7
- - - 0.4 - 22.1 0.5 1.4 0.4 60.1 1.2 13.9
1000 550 - 0.4 - 22.5 0.6 1.4 - 61.0 1.0 13.0
3000 550 - 0.4 - 22.0 0.5 1.3 0.3 60.5 1.3 13.7
Table 11: Chemical analysis of the matrix in different specimens. The first five specimens
are from the tensile test and the last three specimens are untested.

Ageing Ageing Al Cr Mn Fe Co Ni Mo W
time [h] temp. [C]
- - 0.2 13.5 - 0.3 0.2 20.5 4.3 60.9
300 500 0.2 13.5 - 0.5 - 20.3 4.0 61.6
300 550 0.3 13.5 - 0.4 - 20.0 4.3 61.5
1000 500 0.1 13.4 0.2 0.4 0.4 20.0 4.3 61.1
1000 550 0.2 13.5 - 0.4 0.2 20.8 4.1 60.8
- - 0.4 13.7 - 0.4 0.2 21.0 3.9 60.4
1000 550 0.4 13.5 - 0.5 0.2 20.2 4.1 61.1
3000 550 0.3 13.5 - 0.5 - 20.3 4.4 61.0
Table 12: Chemical analysis of primary carbides in different specimens. The first five
specimens are from the tensile test and the last three specimens are untested.

Ageing Ageing C Al Ti Cr Mn Fe Co Ni Mo W
time [h] temp. [C]
- - - 0.2 0.1 24.5 0.7 1.4 0.4 66.0 0.6 6.2
300 500 - 0.2 - 23.1 0.5 1.4 0.3 65.0 0.7 8.7
300 550 - 0.5 - 21.7 0.5 1.4 0.3 59.3 1.3 15.1
1000 500 0.6 0.2 0.1 23.0 0.5 1.3 0.3 65.7 0.7 7.5
1000 550 7.0 0.5 0.2 20.8 0.4 1.2 0.4 52.8 1.5 15.3
- - - 0.4 - 21.9 0.6 1.3 0.4 59.4 1.3 14.7
1000 550 0.4 0.5 - 22.8 0.5 1.3 0.3 57.0 1.5 15.6
3000 550 2.4 0.5 - 22.5 0.4 1.2 0.3 53.7 1.7 17.6
Table 13: Chemical analysis of secondary carbides from grain boundaries in different
specimens. The first five specimens are from the tensile test and the last three specimens
are untested.

49
4.3 DISCUSSION

4.3.1 Mechanical tests

The ageing has an interesting effect on the LCF properties. As shown in Table 5
and Figure 28-Figure 29, the maximum stress at midlife is visually affected by
the ageing. At the lowest strain range, 1.2 %, the maximum stress increases with
the ageing temperature, but at 1.6 and 2.0 % strain range the maximum stress is
larger after ageing at 500C than after ageing at 550C. However the stress is
still lower in the unaged material. The better illustration of the ageing influence
is found in Figure 30. The graph clearly shows that the maximum stress is
increased due to ageing.
On the other hand, the total strain and inelastic strain is unaffected by the
ageing. Figure 31 and Figure 32 show that the LCF properties for the aged
specimens are equal to the behaviour of the unaged reference.
The LCF properties are favoured by a fine grain size [23]. The grain size in
Haynes 230 is controlled by the existence of primary carbides since the carbides
resist solution during heat-treatment. By controlling the grain size the
degradation of LCF properties due to ageing is prevented.
As expected, the lifetime of the specimens, i.e. the number of cycles until failure,
will shorten when the strain range is increased. However the lifetime is not
affected appreciably by the ageing. The lifetime of the specimens exposed to the
same nominal strain range is approximately the same, whether the material has
been aged or not.
Ageing of Haynes 230 does not only increase the resistance to plastic
deformation, it increases the ductility as well. The experiments show that the
impact resistance increases with increasing ageing temperature (see chapter
4.2.2). The absorbed energy increased with 14 % after ageing at 500C for 1000 h
and with 31 % after ageing at 550C for 1000 h.
The results from the tensile test (see Table 7) show that the ageing has a
significant influence on the tensile properties. The yield strength is improved for
specimens aged at both 500 and 550C. The yield strength at 0.1 % plastic strain
is around 10 % larger than the reference for all ageing times and temperatures.
At 0.2 % plastic strain the yield strength has increased about 5 % compared to
the unaged material. The tensile strength increases after ageing as well, by 1-2
%. The increase in tensile strength and yield strength is in good correlation with
the results from the LCF test, where it was shown that the ageing results in an
increased maximum stress in the material.
The ageing time doesnt seem to have any affect on the tensile properties; the
results are more or less the same for each group of specimens aged at 300, 1000
and 2500 h. However, an interesting remark is the knee formation on the stress-
strain curves representing the aged materials (see Figure 34-Figure 35). This
knee is not present on the curve representing the reference material. The reason
could be that the ageing has increased the sensitivity to variation in strain rate.
The moment the tensile specimen begins to plasticise, its difficult to keep the
strain rate absolutely constant because of the reaction in the material. A
material sensitive to changes in strain rate could then exhibit this knee
formation on the stress-strain curve.

50
As mentioned in chapter 3.2, the ordering effect leads to increased yield strength
in nickel-based alloys while the ductility is deteriorated [29]. The results
obtained in this study dont reflect that behaviour. On the contrary, the yield
strength is improved as well as the ductility after ageing. It was also reported [2]
that the tensile strength and the ductility decreased with increasing ageing
temperature due to ordering in Ni2Cr and Ni3Cr. That behaviour does not match
the results in this study either.
That the ductility is improved is also shown by the increased elongation and the
larger area reduction of the tensile specimens. This result is in good agreement
with the impact test results, even though the difference between material aged at
500C and material aged at 550C are not as pronounced as in the impact test.
Hardness test was performed on samples on which no mechanical test was
performed as well as the specimens from the LCF test. The specimens from the
LCF test were included in the hardness testing in order to give some idea about
how much the strain hardening, caused by the mechanical test, can affect the
hardness of the material, but also the effect of the ageing temperature. The
results from the macrohardness tests are found in Table 8.
As expected, the strain hardening which occurs during the LCF test is strongly
affecting the hardness in the unaged material, which increases with almost 40 %
compared to the virgin bar. On the other hand, the hardness doesnt seem to be
affected appreciably by the ageing temperature in the strain hardened LCF
specimens (see Figure 37).
However, the untested specimens are affected by the ageing. As seen in Figure
36, the hardness increases with the ageing time. The hardness in Haynes 230 is
generally attributed to the presence of carbides. An increase in hardness due to
ageing could indicate on a precipitation of carbides during the heat treatment.
This assumption agrees with the results from the microhardness test (see Figure
38) where the hardness near the grain boundaries increases due to ageing. It can
be assumed that the precipitation of secondary carbides at grain boundaries
occurring during ageing (for further discussion, see chapter 4.3.2) is at least
partially responsible for this improvement. Since the microhardness test imprints
were made in the matrix, the presence of primary carbides should not influence
on the results. However, the microhardness test also showed that the hardness
increases in the matrix in the middle of the grain as well, in an area where no
precipitation of secondary carbides has been observed. Another interesting aspect
is that the microhardness has its maximum after 1000 h of ageing both near
grain boundaries and in the middle of the grain. The fraction of secondary
carbides is not smaller after ageing at 550C than at 500C; its rather the
opposite situation. These results give reason to believe that the hardness
improvement is not only due to carbide precipitation. Whether the improvement
after 1000 h of ageing depends on a hardening of the matrix, which is then
reduced by continuous ageing, or if there are other factors responsible for this
significant hardness variation is impossible to establish without further
investigation.
The fact that the material is harder after ageing for 1000 h than after 3000 h is
in good agreement with the previous study on Haynes 230 carried out at SIT AB
in Lincoln (see Figure 27 in chapter 3.2), although the ageing temperatures are
lower in this study.
When measuring the microhardness, the purpose was to avoid the visible
carbides. Unfortunately it is impossible to locate the carbides under the surface,

51
which makes it probable that some of the performed imprints by accident have
hit underlying carbides. These imprints are likely to have given a higher value of
the hardness than expected. This is a likely reason to why the distribution of the
results is larger in the microhardness test than in the macrohardness test. The
higher test load applied the wider and deeper will the imprint be, which
increases the risk of hitting underlying carbides.

4.3.2 Microstructural examination

The microstructural examination is based on an evaluation of images which are


taken with LOM and SEM, chemical analyses measured by SEM and finally
carbide size measurements. All images are found in Annex 8.6.1.
An attempt was made to measure the carbide size in the aged and unaged
Haynes 230 tensile test specimens. The result is given in Table 10. The
measurements were made on micro photos taken with LOM at 500x
magnification with Image-Pro Plus software. Because of limitations in the
software and a resolution of the images which was inadequate, a large part of the
carbides were excluded from the size measurement, which makes the result too
unreliable to permit any conclusions about carbide size changes due to ageing.
What can be established through a visual evaluation of the images together with
the results in Table 10, without jumping to conclusions, is that the primary
carbides are cellular to the shape and the average diameter is in the range of a
few micrometers.
The SEM was used to carry out the chemical analysis. Despite the fact that this
SEM should be able to detect atoms with atomic number 5 and higher, including
carbon, this is in reality not entirely true. The quantitative analysis of carbon is
not done properly and a false value is returned. This error will of course affect
the total composition measurement as well, to a small extent. More important is
that the carbide composition determined by this SEM is unreliable since, in most
cases, the returned value of the carbon content was equal to zero. This is of
course wrong. Despite the chemical analysis, the exact carbon content in the
matrix and the carbides is unknown.
Another problem arose during the analysis of the secondary carbides. The depth
of the impact of the electron beam in the material was greater than the depth of
the secondary carbides. This implied that a part of the analysed material
belonged to the matrix, which resulted in a composition that did not agree with
the true composition of the secondary carbides. This is the reason why the
conclusions from these results have been drawn with great cautious.
The chemical analysis of the matrix is found in Table 11. No deviations from the
references can be found. The exactness of the measurements isnt good enough to
make the decimals reliable. This explains the presence of titanium in the matrix
of the specimen aged at 300 h at 550C and the absence of cobalt in the untested
specimen aged at 1000 h. As mentioned before, no attention should be paid to the
2.2 % of carbon either. No depletion of the matrix is discernable, not even after
the longest ageing time or at any ageing temperature.
Table 12 lists the results from the analysis of the primary carbides. The analysis
is mainly performed on large carbides since the small ones had a tendency of
being smaller than the depth of the electron beam impact, hence a part of the
analysed volume belonged to the matrix. Just like the matrix, the composition of
the primary carbides seems to be unaffected by the ageing at intermediate

52
temperatures. The dominating elements in the primary carbides are tungsten,
nickel, chromium and molybdenum. Principally the primary carbides contain
more tungsten and molybdenum than the matrix and less nickel, chromium, iron
and manganese. As mentioned in chapter 2.1.2.3 the primary carbides are
generally formed by a union between carbon and refractory elements [17], which
in the case of Haynes 230 can be for example tungsten, molybdenum or
chromium.
The results from the analysis of secondary carbides are shown in Table 13. In
general the composition is comparable to the composition of the matrix. However,
the content of nickel, molybdenum and tungsten varies for the different
specimens. Unfortunately it is difficult to find a tendency. Some specimens
contain a larger part of nickel than the matrix, some contain less. The same
pattern is repeated for the content of molybdenum and tungsten. Consequently it
is impossible to decide the composition of secondary carbides based on these
results.
Figure 47 in Annex 8.6.1 is a survey image at low magnification of tensile tested,
unaged Haynes 230. All the expected components are visible in Figure 48. The
primary carbides are situated either at grain boundaries or intragranular. A
selection of them is pointed out with white arrows. Twin boundaries, which
frequently exist in Haynes 230, are pointed out with black arrows.
Unfortunately, small areas are overetched, preferentially the grain boundaries
which are extra vulnerable. An example is pointed out by the thick, white arrow.
Some of the primary carbides break during tensile test (see Figure 49), creating a
void around or between the carbide parts. It is desirable to avoid large void
formations since they are causing fracture initiation. An edge fracture is visible
in Figure 50. It looks like the crack propagation is prevented by the presence of
the carbide. Overall there is no precipitation of secondary carbides in the unaged
material.
Figure 51 shows the microstructure of the specimen aged for 300 h at 500C. The
grain boundaries are more or less free from secondary carbides. Figure 52 shows
that the majority of the grain boundaries are unaffected by the ageing, even
though secondary carbides have precipitated at a small part of the boundaries.
The twin boundaries on the other hand are not visually affected. In Figure 53 a
slightly larger extent of the grain boundaries contain precipitated secondary
carbides. Besides, there is a lot of void formation around the broken primary
carbides. Figure 54 shows a crack at the fracture surface where the primary
carbides are holding the crack together. The only visible ageing effect after 300 h
at 500C is a small extent of secondary carbides precipitated at grain boundaries.
The effect of the ageing is slightly increased at 550C. Figure 55 shows grains
with unaffected boundaries while there are precipitated secondary carbides at
the grain boundaries in Figure 56. Voids are formed around primary carbides
just like for the reference. Figure 57 shows grain boundaries partially covered
with secondary carbides. These three images illustrates a distribution of the
primary carbides where all the large carbides are formed at grain boundaries or
twin boundaries, while it is common to find the small carbides inside the grains.
The effects of ageing at 500C are larger after 1000 h than after 300, which is
visible in Figure 58. The precipitation of secondary carbides is well distributed
over the boundaries. The huge void formation around primary carbides visible at
the image is probably created during preparation of the cut-up. Since the carbide
probably was broken into pieces during tensile test, there is a risk that some of

53
the parts fell off during grinding and polishing of the cut-up. Figure 59 shows
that there are grain boundaries free from precipitated secondary carbides in this
specimen as well. The size of the primary carbides can influence on the fracture
properties. Large primary carbides, as in Figure 60, run a greater risk of
breaking when a load is applied than smaller carbides do. The larger the carbide
is the larger will the void formation be. These internal microfractures can impair
the rupture resistance. Figure 61 shows an edge crack restrained by primary
carbide. Due to the hardness the carbide possesses, the propagation has to go
around the carbide rather than through it. This will make the way longer for the
crack and increase the energy absorbed during the crack propagation, which is
positive.
Figure 62 and Figure 63 shows the microstructure of the tensile test specimen
aged at 1000 h at 550C. There is a significant increase of secondary carbides
compared to both the specimen with shorter ageing time and the specimen with
lower ageing temperature. It is also visible that the void formation is present
around medium carbides as well. Figure 64 shows a fracture that has propagated
around the primary carbide.
An increased amount of secondary carbides can, if they are properly formed,
strengthen the grain boundaries and restrain grain boundary sliding [18]-[19].
The increased tensile strength of the specimen aged at 550C for 1000 h can
probably be at least partially attributed to the large amount of secondary
carbides precipitated at grain boundaries. However the specimens aged at 500C
improved their tensile properties as well, so there is most likely yet another
reason for the property change.
Figure 65 and Figure 66 shows the microstructure of the virgin bar. Here its
even more obvious that the grain boundaries are free from precipitations and
that the large primary carbides are found at grain boundaries. It is also possible
to look at the original shape of the primary carbides. The most frequent type is
the cellular-shaped carbide which often is of small or medium size. The larger
carbides are commonly of irregular shape (see Figure 67-Figure 68).
Figure 69-Figure 70 represents the microstructure of untested specimen aged at
1000 h at 550C. The first image shows no secondary carbides whatsoever but
they are visible at the grain boundaries in the second image. An interesting
observation was discovered when comparing this untested specimen with the
tensile test specimen exposed to the same ageing conditions. The precipitation of
secondary carbides has occurred to a much greater extent in the tensile test
specimen than in the untested specimen. This observation indicates that the
precipitation of secondary carbides can either be stimulated under an applied
load or is simply easier to see after tensile testing. Figure 71 and Figure 72
shows that the larger primary carbides are located at the grain boundaries and
that the intragranular carbides are much smaller to the size.
Figure 73 and Figure 74 are from the untested specimen aged for 3000 h at 550
C. They show that the precipitation of secondary carbides has increased due to
the prolonged ageing time. There are no other visible effects of the ageing. In
Figure 75 we can see that there are occasional large carbides at intragranular
sites.
The micro photos of the LCF tested specimens showed one unexpected
phenomenon that distinguished these images from the rest. This phenomenon
was discovered in specimens from all the different ageing conditions. Primary
carbides, with what looks like holes in them, are shown in Figure 76 to Figure 81.

54
The study has not given any explanation to why these carbides are present in
only the LCF tested specimens. Neither has it been established if the areas really
are holes in the carbides or for example precipitations of a different phase. The
samples where sent to Leicaster University in England for further investigations.
The microstructural evaluation shows that the ageing at intermediate
temperatures influences mainly on the precipitation of secondary carbides. It is
shown that the precipitation was stimulated by prolonged ageing time but mainly
by increased ageing temperature. These results correlate with the results from
the study carried out at SIT in Lincoln [32], except that no precipitation at twin
boundaries was visible at these intermediate ageing temperatures.
The matrix composition measured in the virgin bar was utilised to calculate the
Z-criterion. The obtained value was 1.62, which is smaller than 3.0, hence the
LRO formation is possible according to the theory.

4.4 CONCLUSION

The ageing of Haynes 230 has a positive effect on the properties. The LCF
properties proved to be unaffected, except for the maximum stress which is
higher in the aged material. The same behaviour is found in the tensile test
where the yield strength and tensile strength was improved due to ageing. The
impact test and the elongation in the tensile test showed that the material
became more ductile after the ageing. The macrohardness increased with the
ageing temperature. The strain hardening of Haynes 230 highly improved the
macrohardness and the ageing influence on the material decreased
simultaneously.
The microstructural examination neither confirmed nor refuted a growth of
primary carbides. Neither could the composition of the secondary carbides be
determined. The image analysis showed that the ageing has a positive effect on
the precipitation of secondary carbides at grain boundaries, which normally leads
to strengthened boundaries and restrained grain boundary sliding. The ageing
temperature has a larger effect on the microstructure than the ageing time.
The Z-criterion indicates that the existence of LRO in Haynes 230 is probable.
The fact that the material has proved to shrink during ageing is another
indication. Haynes 230 has many similarities to Hastelloy in which the LRO has
been observed [2]. These indications are enough convincing to justify further
research in this matter.

55
5 AGEING INFLUENCE ON MECHANICAL PROPERTIES
AND MICROSTRUCTURE OF CMSX-4 AT
INTERMEDIATE TEMPERATURES (500-550C)

5.1 SPECIMEN PREPARATION AND EXPERIMENTAL PROCEDURE

5.1.1 Tensile test

Ten tensile test specimens were cut out from 5 different bars, two specimens from
each bar. Each pair had the same single crystal direction. The dimensions of the
bars followed the drawing 7000 1782-3 which is found in Annex 8.3.3. One
specimen from each pair was aged at 500C during 1150 h. Data for each
specimen showing direction and angles for the single crystal bar, together with
ageing time and temperature, are listed in Table 14.

Specimen SX Theta Rho Ageing Ageing


marking direction temp [C] time [h]
114a Off angle 25.9 4.5 500 1150
114b Off angle 25.9 4.5 - -
122a Off angle 19.8 11.3 500 1150
122b Off angle 19.8 11.3 - -
124a <011> 42 0.2 500 1150
124b <011> 42 0.2 - -
126a <011> 41.9 7.6 500 1150
126b <011> 41.9 7.6 - -
143a <111> 53.8 43.8 500 1150
143b <111> 53.8 43.8 - -
Table 14: Specimen data for CMSX-4.

The tensile tests were performed in the tensile test machine Schenck-Trebel RSA
100 on all specimens in agreement with EN 10 002-1. The strain was measured
by an extensometer up to 2.0 %.
The diameter of the specimens was measured before and after the testing.
Tensile strength was obtained from the software calculations. The elongation of
the bar and the reduction of the cross-section area were calculated together with
the yield strength at 0.1 % and 0.2 % plastic strain deformation. All details are
given in Annex 8.4.2.

5.1.2 Microscopic examination

After the tensile test, the specimens were photographed in order to document the
fracture surfaces and determine the angle between the slip planes and the test
load axis. How to obtain the angle is illustrated in Figure 40.

56
Afterwards, cut-ups containing the tensile test specimens were prepared,
exposing the cross-section along the test load axis. The same procedure was
employed as in the case of Haynes 230 (see chapter 4.1.4) except for the etching.
For this purpose, a mixture containing MoO3, HCl, HNO3 and H2O was used. The
CMSX-4 cut-ups were etched for approximately 25 s.
The cut-ups were examined in both optical microscope and SEM. The focus was
set on any differences between new and aged material, for example on the
appearance of active slip planes and the distance between them.

Figure 40: Angle of slip plane, specimen 126a.

5.1.3 Hardness test

Because of the structure of CMSX-4, it wasnt suitable to perform the hardness


test on the cut-ups. The reason is that it was impossible to confirm that the SX
direction in the hardness test loading direction was the same for both specimens
in a pair. Rotation of the cylindrical specimen would alter the SX direction
perpendicular to the ground and polished cross-section. Since CMSX-4 isnt
isotropic, a comparison between the two specimens in a pair would in that case be
pointless. The macrohardness test was therefore performed on the cross-section
of the piece that was cut off during the preparation of the cut-up. This was the
only way to guarantee the same SX direction for both specimens in a pair and
thus be able to compare the results of new and aged material.
The equipment used for macrohardness test for CMSX-4 is the same used in the
previous case of Haynes 230 (see chapter 4.1.5). The applied load was 10 kg and
the hardness was measured in Vickers scale (HV10). The distance between the
imprints followed the same rules used in the macrohardness testing of Haynes
230. See chapter 4.1.5 for more details.

57
5.2 MECHANICAL TEST RESULTS

5.2.1 Tensile test

Nine of the tests were successful and one test (specimen 114a) was stopped before
fracture. The results from the tensile tests are shown in Table 15. The difference
between new and aged material is calculated for each pair and property.

Aged at New Rm Rp0.1 Rp0.2 A5 Z


1150h at material [MPa] [MPa] [MPa] [%] [%]
500C (ref)
114b 833 810 817 6.8 30.2
114a 756 742 747 - -
Difference [%] -9.2 -8.4 -8.6 - -
122b 873 872 871 11.7 28.3
122a 796 783 783 13.2 31.3
Difference [%] -8.9 -10.2 -10.1 12.8 10.6
124b 1000 1000 1000 3.5 -
124a 885 869 869 15.0 33.0
Difference [%] -11.5 -13.1 -13.1 329 -
126b 924 924 924 12.2 29.0
126a 867 858 858 10.4 34.4
Difference [%] -6.1 -7.1 -7.1 -14.8 18.6
143b 1465 1146 1156 9.6 6.4
143a 1490 1154 1155 - 10.4
Difference [%] 1.8 0.7 -0.1 - 62.5
Table 15: Tensile test result for CMSX-4.

The stress-strain curves plotted up to 2 % strain, or until failure if it occurred at


lower strain, are presented in Figure 41 to Figure 45.

58
1000

800

600
S tr e ss
(M P a )
400

200

0
0 0 ,2 0 ,4 0 ,6 0 ,8 1 1 ,2
S tr a i n (% )

114a - aged 1150h 114b

Figure 41: Stress-strain curves from tensile test, specimen pair 114.

1000

800

600
S tr e ss
(M P a )
400

200

0
0 0 ,1 0 ,2 0 ,3 0 ,4 0 ,5 0 ,6
S tr a i n (% )

122a - aged 1150h 122b

Figure 42: Stress-strain curves from tensile test, specimen pair 122.

1200

1000

800
S tr e ss
600
(M P a )
400

200

0
0 0 ,1 0 ,2 0 ,3 0 ,4 0 ,5
S tr a i n (% )

124a - aged 1150h 124b

Figure 43: Stress-strain curves from tensile test, specimen pair 124.

59
1000

800

600
S tr e ss
(M P a )
400

200

0
0 0 ,1 0 ,2 0 ,3 0 ,4 0 ,5
S tr a i n (% )

126a - aged 1150h 126b

Figure 44: Stress-strain curves from tensile test, specimen pair 126.

1400
1200
1000

S tr e ss 800
(M P a ) 600
400
200
0
0 0 ,5 1 1 ,5 2 2 ,5
S tr a i n (% )

143a - aged 1150h 143b

Figure 45: Stress-strain curves from tensile test, specimen pair 143.

60
5.2.2 Angle of slip plane

The angle of the slip planes is presented in Table 16.

Specimen SX Theta [] Angle of


marking direction slip plane
114a Off angle 25.9 No fracture
114b Off angle 25.9 42.5
122a Off angle 19.8 45
122b Off angle 19.8 42
124a <011> 42 45.5
124b <011> 42 44.5
126a <011> 41.9 50.5
126b <011> 41.9 35
143a <111> 53.8 -
143b <111> 53.8 -
Table 16: Angle of slip planes after tensile test.

The determination of the angle of the slip planes of pair 143 and 114a was
impossible, because of the lack of visible marks on the specimen surface.

5.2.3 Hardness test

The results from the macrohardness testing are shown in a chart in Figure 46
together with the difference between new and aged material.

M a c ro h a rd n e s s

600
6 .0 %
550

500
H a rd n e ss -2 . 7 % 3 .2 %
-6 . 8 % -0 .6 % new
[H V 1 0 ] 4 5 0
aged
400

350

300
114 122 124 126 143

S p e c im e n N o

Figure 46: Results from macrohardness test for CMSX-4.

61
All data from the macrohardness tests are visualised in Table 17.

Specimen Status Vickers Standard Difference


Pair No hardness deviation compared
[HV10] to ref [%]
New 424 8.87
114
Aged 395 4.09 -6.8
New 444 10.9
122
Aged 432 17.5 -2.7
New 434 3.83
124
Aged 431 8.73 -0.6
New 423 5.16
126
Aged 437 9.40 3.2
New 516 8.57
143
Aged 547 17.4 6.0
Table 17: Data from macrohardness testing for CMSX-4.

5.3 DISCUSSION

5.3.1 Mechanical tests

Drawing conclusions from tensile tests performed on single crystal material is


always a bit hazardous. The deformation is concentrated to a few active slip
planes and whether these slip planes occur within the extensometer range or not
have a crucial effect on the deformation curves, i.e. the stress-strain curves (see
Figure 41-Figure 45). If the crack initiation takes place outside the extensometer
range the deformation is concentrated to that area and the strain measured by
the extensometer will be much smaller than the accurate value, i.e. the curve is
not appropriate. This is the reason why tensile test is not an appropriate method
to determine neither the elastic modulus nor the tensile strength at failure, and
these results are therefore not discussed in this study. The value of the
elongation at break is not taken from the curves. Instead the specimen bars were
measured after finished test.
A distinct trend in comparison between new and aged material is the reduction in
yield strength and tensile strength (see Table 15). After being aged during 1150
h, the decrease of Rp0.1 and Rp0.2, which followed each other very well, was found
to be between 7 and 13 %. The reduction in tensile strength as well was found to
bee in good correlation with these results. The only exception among the
specimens is the specimen pair in direction <111>, where the change due to
ageing was very small or negligible.
The deformation of the specimens developed during tensile loading depends on
the direction of the single crystal. The specimens in direction <111> (pair 143)
developed no neck during loading. On the contrary, the active slip planes were
uniformly distributed over the whole length of the bar, resulting in a slightly
elliptic cross-section of the bar. The tensile tests with the specimens in direction

62
<011> or off angle resulted in elliptic cross-sections as well, but these were far
more flattened. Furthermore, the slip planes were concentrated to a small part of
the bar, resulting in a neck formation in this area. Common for all the specimens
was that the larger diameter of the elliptic cross-section was not affected by the
tensile test.
The effect of the ageing phenomenon on the deformation is palpable. The overall
result is that the aged specimens show a larger elongation and a greater
reduction in cross-section than the specimens which were not aged. One
exception is found for specimen pair 126 where the ageing resulted in a smaller
elongation of the specimen. The magnitude of the deformation values varies a lot.
One reason could be that the measuring was made manually with help of a slide
calliper, a fact that can have a negative effect on the accuracy of the
measurements. Another possible reason is the lack of statistical basic data. An
average from a number of tensile tests carried out under the same ageing and
testing conditions would probably give a result more faithful to the true value.
Its difficult to find a trend in the hardness results (see chapter 5.2.3) due to
ageing. Pair 114 (theta = 25.9) shows a decrease in hardness with 6.8 % while
pair 143 (SX direction <111>) shows an increase of 6.0 % due to ageing. The other
results are well distributed between those values. However, noteworthy is that
the hardness seems to depend on the SX direction. The pairs off direction or in
the direction <011> have an average between 400 and 450 HV10. Pair 143 on the
other hand has an average closer to 550 HV10.
The slip plane angle was impossible to determine for three of the specimens due
to difficulties to see the marks from the slip planes on the surface of the
specimens. The results from the remaining three pairs reveal no distinct trend
(see Table 16). The slip plane angle is 3 degrees larger after ageing for pair 122
(theta = 19.8). The difference for pair 124 (theta = 42) is only 1 degree. In pair
126 (theta = 41.9) the difference is approximately 15 degrees. Specimens 124
and 126 have more or less the same SX direction. Therefore a similar slip plane
angle for these specimens was expected. However, specimen 126b measured a
much smaller slip plane angle compared to the other ones.
Some of the results for specimen 126b are quite unexpected, such as the small
elongation in tensile test and the angle of the slip plane. Due to the deviation
from the expected results the conclusions regarding the performance of specimen
pair 126 should be drawn with cautiousness.
The high temperature properties of CMSX-4 are thoroughly investigated in a
great number of studies. However, there is no documentation of the behaviour at
intermediate temperatures, which makes it difficult to estimate the accuracy of
the results obtained in this study.

5.3.2 Microstructural Examination

The microstructural examination is based on images which are taken with LOM
and SEM. All images are found in Annex 8.6.2. No microstructural examination
is performed on pair 114. Since the tensile test of specimen 114a was stopped
prematurely, hardly any deformation had time to occur. A comparison of the pair
would consequently be pointless since the conditions werent the same for both
specimens.
Figure 82 shows the microstructure of CMSX-4. The image is taken from
specimen 122a, which was aged before the tensile test. The dark zones are

63
particles. They are embedded in the matrix which appears as a white check
pattern on the SEM photos. The image is taken at 4000x magnitude.
The slip planes activated during the tensile test are recognised as light stripes in
the material. Figure 83 and Figure 84 from specimen 122a shows that there are
two different types of distribution of active slip planes. The first case is when
single slip planes are activated and they are distributed with a smaller or larger
distance to the next slip plane. The second case is when one slip plane is
activated and the adjacent slip planes follow after. This behaviour results in a
band of activated slip planes. An enlargement of the slip planes (see Figure 85
and Figure 86) reveals that not only the matrix is deformed during the tensile
test but also the gamma primes. The images show slip planes where the gamma
primes have been strongly prolonged. Figure 87 shows an enlarged image of a
band of activated slip planes.
The aged specimen 122a had a rather large number of activated slip planes
compared to the unaged specimen in the pair, 122b. The only slip planes found
for that specimen are shown on a LOM image in Figure 88. Figure 89 shows the
same area reproduced by the SEM. The lower surface is the edge of the specimen
and the left surface is the fracture surface in Figure 89. An interesting remark is
that the deformation in the material preferably occurs as atom planes sliding
against each other and not as crack propagation. Figure 90 shows crack
initiations on the edge of the specimens, which have not led to fracture. In Figure
91 an enlargement of single slip plane with deformed gamma prime is visible and
in Figure 92 a narrow band of slip planes shows how the material is deformed
under traction.
The difference between 122a and b is that the amount of activated slip planes is
larger for the aged specimen. It also contains more bands of slip planes while the
unaged specimen mostly contains single slip planes separated from each others.
No favourable distance between the slip planes was discerned. On the contrary,
the distribution of the slip planes seems arbitrary.
Specimen 124a contained only a few activated slip planes, all widely separated
from each other. Figure 93 shows some feeble marks from single slip planes, but
also a few unwanted inclusions of unknown kind. In Figure 94 and Figure 95
some single slip planes are visible. The enlargements in Figure 96 and Figure 97
does not show any deformed gamma primes that were visible in pair 122.
The microstructure of specimen 124b was more or less the same. Some feeble
marks of slip planes are visible in Figure 98, and the enlargement in Figure 99
doesnt show any distinct deformation. The microstructure is slightly more
affected around a crack tip (see Figure 100), but there is no sharp contrast
between deformed and unaffected regions.
There are no large differences between new and aged material in pair 124. They
both exhibit only a few separate activate slip planes and the deformation doesnt
seem to affect the form of the gamma primes appreciably. There doesnt seem to
be any tendency concerning the distance between the slip planes in any of the
specimens.
The deformation is creating both separated slip planes and bands of slip planes
in the aged specimen 126a (see Figure 101-Figure 103). The enlargements in
Figure 104 and Figure 105 show that its rather the matrix than the gamma
primes that is affected and deformed due to the glide. It is also shown in Figure
106 and Figure 107 that slip planes are possible crack initiators.

64
The images of unaged 126b (see Figure 108 and Figure 109) show a similar
behaviour. Single slip planes are found next to deformed bands. The activated
slip planes are well distributed over the specimen. Looking at Figure 110, the
gamma primes seems unaffected by the deformation.
Both specimens in pair 126 contain a lot of activated slip planes, both separated
and in bands. The deformation seems to be concentrated to the matrix and there
are no visible differences between new and aged material.
The microstructure in pair 143 is, because of the SX direction, not at all like the
microstructure of the other pairs. Since the loading axis is in the <111> direction,
there are no natural slip planes where the gliding can occur. Thats why the
behaviour seen in Figure 111 occurs. The crack propagation in the aged specimen
143a suddenly changes direction and continues along another path. An
enlargement of the crack tip (see Figure 112) shows that the microstructure
around the tip is more or less homogeneous, which makes it impossible to divine
the direction of further propagation. The few visible slip planes (see Figure 113)
resulted either in an internal fracture along the slip plane (Figure 114) or in a
deformation of the matrix (Figure 115) comparable to the behaviour of pair 126
(see Figure 104).
The unaged specimen 143b shows the same behaviour as the previously
discussed specimen. Cracks, which changed propagation direction during the test
(see Figure 116), were found in this specimen as well and the microstructure
around the crack tip seemed homogeneous and without defaults (Figure 117).
The traction resulted in internal fracture where the matrix was the weakest link
in the chain and broke down (see Figure 118 and Figure 119), but also in
deformation where the glide of atom planes deformed the matrix (see Figure 120
and Figure 121) as for the aged specimen in the pair.
Once again its difficult to find any differences between new and aged material.
The deformation expresses itself in the same ways in both specimens and the
crack propagation is hazardous and unpredictable.
The composition of the gamma matrix after precipitation of gamma prime has to
be known to determine the Z-criterion. No chemical analysis of the specific
material used in this study has been performed. Rothov et al. [33] have listed
the chemical composition of and in CMSX-4 with 60 vol% . According to
them, the formula of gamma matrix after precipitation of gamma prime is
Ni50Cr22Co20Re8. This composition renders in a Z-criterion equal to 2.27, which
would imply that the LRO formation in CMSX-4 is probable.

5.4 CONCLUSION

No obvious differences in microstructure between new and aged material have


been found that can explain the change in mechanical properties. A conceivable
cause is the amount of gamma prime before and after the heat treatment. It is
know that a too large fraction of gamma prime will deteriorate for example the
ductility and the thermo mechanical fatigue properties. Simultaneously a too
small fraction of gamma prime can result in a reduction in high temperature
strength and creep resistance. Since no measurement of gamma prime fraction
has been carried out within this study, no certain conclusions about whether it
has changed or not can be drawn.

65
It is clear that ageing at 500C influences on the mechanical properties.
Generally the ageing results in a deteriorated tensile strength and an improved
ductility. However, the impact the ageing has on the material is depending on the
SX direction. The specimen pair in <111> direction had originally significantly
higher tensile strength compared to the other specimens, and it was hardly
affected by the ageing. The remaining specimens were all influenced by the
ageing.
This study has not brought out any proof of the existence of SRO/LRO in CMSX-
4, even if the obtained Z-criterion indicates that the LRO formation is possible. It
has been proved that the ageing has influence on the properties, but whether the
material shrinks as a result of the ageing or not hasnt yet been examined.
However, nothing that tells against that the ordering phenomenon could occur in
CMSX-4 has been found either.

66
6 FUTURE WORK

There is no statistical basis for the mechanical tests performed on CMSX-4.


Testing of tensile properties and hardness with an enlarged number of specimens
would give a more reliable result.
In other studies the variation of the carbide size in Haynes 230 has been
correlated to property changes. A successful measuring of the carbide size would
facilitate the investigation of microstructural changes and its impact on the
mechanical properties. Hopefully it would result in a better understanding of
optimal heat treatment temperatures and times for Haynes 230.
An increased volume fraction of gamma prime in CMSX-4 is a possible
explanation to the property changes after ageing. By measuring the volume
fraction the understanding of the role gamma prime plays in CMSX-4 would be
ameliorated.
Until today, no measurements of shrinkage in CMSX-4 have been performed. A
negative result from such test could probably dismiss the ordering phenomenon
theory as an underlying cause to the property changes in the single crystal
material.
The presence of LRO in the materials can be proved by finding Ni2Cr superlattice
reflections in electron diffraction and an accompanying decrease in electrical
resistivity.

67
7 REFERENCES

[1]. Moverare, J., (2005). Shrinkage and ageing of Ni-base alloys at intermediate
temperatures (400-600C).
Finspng: Siemens Industrial Turbomachinery AB.
Internal technical report 1CS51497.
[2]. Marucco, A., Nath, B., (1988). Effects of ordering on the properties of Ni-Cr alloys.
J. Mat. Sci., 23, 21072114.
[3]. Granacher, J., Pfenning, A., (1994). Optimierung und Verifizierung von
Kriechgleichungen fr Hochtemperaturwerkstoffe.
Darmstadt: Institut fr Werkstoffkunde der Technischen Hockschule Darmstadt
Technical report 523.
[4]. SGT-800 presentation from SIT AB.
[5]. General Electric Reference Document: Gas Turbine Design Philosophy.
GER-3434D.
[6]. http://www.grc.nasa.gov/WWW/K-12/airplane/brayton.html
[7]. http://en.wikipedia.org/wiki/Gas_turbine
[8]. Annerfeldt, M., et al, (2004). Result from the thermo-crystal test performed in
B520 Helsingborg Blades and Vanes temperature and SAS pressure.
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Internal technical report RT T10C 50/03.
[9]. General Electric Reference Document: Advanced Gas Turbine Materials and
Coatings.
GER-3569G.
[10]. Shukin, S., Bjrkman, M. SGT-800 Vertion A+. Turbine Blade 1 Design, 3D
Thermal & MI analysis.
Finspng: Siemens Industrial Turbomachinery AB.
Internal technical report RT GRC 249/05.
[11]. Orakzai, K., (2004). Effect of Carbon Content on the Properties of CMSX-4.
Finspng: Siemens Industrial Turbomachinery AB.
Internal technical report 1CS41538.
[12]. Chapman, L.A., (2004). Application of high temperature DSC technique to nickel
based superalloys. J. Mat. Sci., 39, (24) 72297236.
[13]. Haynes 230 alloy Product Brochure H-3000H.
[14]. Hogmark, S., Jacobson, S., Kassman-Rudolphi, ., (1998). Elektronmikroskopi i
praktik och teori. Uppsala: Uppsala universitet, ngstrmslaboratoriet.
[15]. http://www.rpi.edu/dept/materials/COURSES/NANO/shaw/Page5.html
[16]. Goodhew, P.J., Humphreys, F.J., (1988). Electron Microscopy and Analysis.
2nd edition. London: Taylor & Francis.
[17]. Sims, C.T., Stoloff, N.S., Hagel, W.C., (1987). Superalloys II.
New York: Wiley-Interscience.
[18]. Donachie, M.J., Donachie, S.J., (2002). Superalloys. A Technical Guide.
2nd edition. Materials Park: ASM International.
[19]. Davis, J.R., (1997). Heat Resistant Materials.
Materials Park: ASM International.
[20]. http://www.msm.cam.ac.uk/phase-trans/2003/Superalloys/superalloys.html

68
[21]. http://www.msm.cam.ac.uk/phase-trans/2003/Superalloys/rafting.html
[22]. Material certificate from Cannon-Muskegon, Heat No: V 8508 and V 8677.
[23]. Johnsson, A., (2001). A LTA/LTE study on the thermal characteristics of Haynes
alloy 230.
Finspng: Siemens Industrial Turbomachinery AB.
Internal technical report RT TRM 54/98.
[24]. Marucco, (1989). Materials Architecture. 10th Ris International Symposium on
Metallurgy and Materials Science
[25]. Marucco, A., Nath, B., (1991). Effects of volume fraction on ordering behaviour
and rupture properties of Alloy 80A. Proc. 6th International Conference on
Mechanical Behaviour of Materials (ICM6), Kyoto, Japan.
[26]. Metcalfe, E., Nath, B., Wickens, A., (1984). Some Effects of the Ordering
Transformation in Nimonic 80A on Stress Relaxation Behaviour. Mat. Sci. Eng.,
67, (2), 157162.
[27]. Reppich, B., (1994). Negatives Kriechen und Mikrogefge langzeitexponierter
Gasturbinenwerkstoffe. Z. Metallkd., 85, (1).
[28]. Marucco, A., (1995). Phase transformations during long-term ageing of Ni-Fe-Cr
alloys in the temperature range 450-600 C. Mat. Sci. Eng., A194, (2), 225233.
[29]. Rtishchev, V.V., (1994). Structure transformations and property changes of Ni-
base superalloys on ageing. Mat. Adv. Power Eng., (1), 889898.
[30]. Pettinari, F., Prem, M., Krexner, G., Caron, P., Coujou, A., Kirchner, H.O.K.,
Clment, N., (2001). Local order in industrial and model phases of superalloys.
Acta Mat., 49, 25492556.
[31]. http://www.cmse.ed.ac.uk/AdvMat45/SuperMicro.pdf
[32]. Marchant, G., (2005). Microstructural degradation of combustor alloy Haynes
230.
Lincoln: Siemens Industrial Turbomachinery AB.
Internal technical report 05-LAB-211
[33]. Rothov, V., Stloukal, I., ermk, J., (2000). Permeation of hydrogen in Ni-based
superalloy CMSX-4. Acta Mat., 48, 827833.

69
8 ANNEXES

8.1 MATERIAL DATASHEET FOR HAYNES 230 COATING

70
8.2 TEST CERTIFICATE, HAYNES 230, HEAT NO 1830587801

71
8.3 DRAWINGS

8.3.1 Low cycle fatigue test specimen

72
8.3.2 Impact test specimen

73
8.3.3 Tensile test specimen

74
8.4 CALCULATIONS

8.4.1 LCF test

Ni and Nf Number of cycles to crack initiation and failure


Ni is defined as 5 % load drop from the stabilised loop. A linear interpolation
of the loop between 30 % and 70 % of the total amount of cycles was compared
to the actual stress in each point. Ni was obtained when the drop exceeded 5
%. The same method was used to calculate Nf, which is defined as 50 % load
drop.
max (N = 1) Maximum stress at first cycle
The maximum stress at the first cycle was read off during the test.
max (Nf / 2) Maximum stress at midlife
The maximum stress at midlife was obtained from the graph where maximum
stress was plotted against the number of cycles.
pl (Nf / 2) Plastic strain range at midlife
pl was read off the graph where plastic strain was plotted against the
number of cycles.

8.4.2 Tensile test

A5 Elongation of waist of specimen


L L0
A5 = 100 Equation 4: Elongation of waist of test specimen.
L0
L0 is the initial length between two fixed points at the waist of the specimen
and L is the length between the two points after tensile test.
Z Reduction of cross-section area of specimen
D02 D 2

Z= 4 4 100 Equation 5: Reduction of cross-section area of specimen.
D 2
0

4
D is the diameter of the waist after tensile test and D0 is the initial diameter.
Rp0.1 Yield strength at 0.1 % plastic strain deformation
A linear curve with the same slope as the stress-strain curve and with an
offset of 0.1 % strain was plotted. The point where the stress-strain curve and
the linear curve intersected was defined as the yield point at 0.1 % plastic
strain deformation. The stress read off in the graph at this point is defined as
the yield strength.

75
8.5 RESULTS

8.5.1 Tensile test, Haynes 230

Ref 300 h 1000 h 2500 h


500C 550C 500C 550C 500C 550C
Rm [MPa] 862 871 869 871 873 876 873
Rp0.1 [MPa] 366 400 400 398 401 403 415
Rp0.2 [MPa] 379 395 392 394 397 400 400
A5 [%] 47.8 50.7 53.7 50.6 50.7 52.5 51.8
Z [%] 48.0 55.7 57.6 54.3 50.1 55.8 55.8
Table 18: Result from tensile test, Haynes 230.

76
8.6 MICROSCOPY PHOTOS

8.6.1 Haynes 230

Figure 47: Tensile test specimen ref survey image taken with LOM. Marker size: 100
m.

Figure 48: Tensile test specimen ref SEM photo of twin boundaries (black arrows) and
primary carbides (white arrows). The thick white arrow shows an overetched area.
Marker size: 50 m.

77
Figure 49: Tensile test specimen ref SEM photo of void formation around broken
primary carbides (black arrows). Marker size: 50 m.

Figure 50: Tensile test specimen ref SEM photo of edge fracture stopped by primary
carbide (black arrow). Marker size: 20 m.

Figure 51: Tensile test specimen, aged 300 h at 500C SEM photo of grain boundaries
free from secondary carbides. Marker size: 50 m.

78
Figure 52: Tensile test specimen, aged 300 h at 500C SEM photo of twinning and grain
boundaries partially free from secondary carbides. Marker size: 50 m.

Figure 53: Tensile test specimen, aged 300 h at 500C SEM photo of grain boundaries
with secondary carbides (black arrow) and void formation around broken primary
carbides (white arrows). Marker size: 50 m.

Figure 54: Tensile test specimen, aged 300 h at 500C SEM photo of fracture kept
together by primary carbides (black arrows). Marker size: 50 m.

79
Figure 55: Tensile test specimen, aged 300 h at 550C SEM photo of grain boundaries
without secondary carbides. Marker size: 50 m.

Figure 56: Tensile test specimen, aged 300 h at 550C SEM photo of secondary carbides
precipitated at grain boundaries (black arrow). Marker size: 50 m.

Figure 57: Tensile test specimen, aged 300 h at 550C SEM photo of void formation
around broken primary carbides (black arrows) and precipitated secondary carbides
(white arrows). Marker size: 50 m.

80
Figure 58: Tensile test specimen, aged 1000 h at 500C SEM photo of large void
formations around primary carbides (black arrows) and secondary carbides precipitated
at grain boundaries (white arrows). Marker size: 50 m.

Figure 59: Tensile test specimen, aged 1000 h at 500C SEM photo of grain boundaries
with (black arrow) and without (white arrow) secondary carbides. Marker size: 50 m.

Figure 60: Tensile test specimen, aged 1000 h at 500C SEM photo of large void
formation around broken primary carbides (black arrows). Marker size: 50 m.

81
Figure 61: Tensile test specimen, aged 1000 h at 500C SEM photo of primary carbide
preventing crack propagation. Marker size: 20 m.

Figure 62: Tensile test specimen, aged 1000 h at 550C SEM photo of an advanced
stage of precipitation of secondary carbides at grain boundaries. Marker size: 100 m.

Figure 63: Tensile test specimen, aged 1000 h at 550C SEM photo of void formation
around primary carbides at grain boundaries. Marker size: 50 m.

82
Figure 64: Tensile test specimen, aged 1000 h at 550C SEM photo of crack propagation
without the presence of primary carbides (black arrow). Marker size: 50 m.

Figure 65: Untested specimen, ref SEM photo of grain boundaries without secondary
carbides and large primary carbides at grain boundaries. Marker size: 50 m.

Figure 66: Untested specimen, ref SEM photo of small, intragranular primary carbides
(black arrows) and twinning (white arrows). Marker size: 50 m.

83
Figure 67: Untested specimen, ref SEM photo of large, primary carbides at grain
boundaries. Marker size: 50 m.

Figure 68: Untested specimen, ref SEM photo of distribution of primary carbides.
Marker size: 50 m.

Figure 69: Untested specimen, aged 1000 h at 550C SEM photo of twinning and grain
boundaries without secondary carbides. Marker size: 20 m.

84
Figure 70: Untested specimen, aged 1000 h at 550C SEM photo of precipitation of
secondary carbides at grain boundaries (black arrows). Marker size: 50 m.

Figure 71: Untested specimen, aged 1000 h at 550C SEM photo of distribution of
primary carbides. Marker size: 50 m.

Figure 72: Untested specimen, aged 1000 h at 550C SEM photo of small, intragranular
primary carbides. Marker size: 50 m.

85
Figure 73: Untested specimen, aged 3000 h at 550C SEM photo of small, intragranular
primary carbides and twinning. Marker size: 50 m.

Figure 74: Untested specimen, aged 3000 h at 550C SEM photo of precipitation of
secondary carbides at grain boundaries. Marker size: 50 m.

Figure 75: Untested specimen, aged 3000 h at 550C SEM photo of larger intragranular
primary carbides. Marker size: 50 m.

86
Figure 76: LCF tested specimen, ref SEM photo of primary carbide with holes? Marker
size: 10 m.

Figure 77: LCF tested specimen, ref SEM photo of primary carbides with holes? Marker
size: 20 m.

Figure 78: LCF tested specimen, aged 1000 h at 500C SEM photo of primary carbides
with holes? Marker size: 10 m.

87
Figure 79: LCF tested specimen, aged 1000 h at 500C SEM photo of primary carbides
with holes? Marker size: 10 m.

Figure 80: LCF tested specimen, aged 1000 h at 550C SEM photo of primary carbides
with holes? Marker size: 10 m.

Figure 81: LCF tested specimen, aged 1000 h at 550C SEM photo of primary carbides
with holes? Marker size: 10 m.

88
8.6.2 CMSX-4

Figure 82: 122a SEM photo of CMSX-4 structure. Marker size: 10 m.

Figure 83: 122a SEM photo of slip plane. Marker size: 100 m.

Band of activated
slip planes.

Single slip
plane

Figure 84: 122a SEM photo of slip plane. Marker size: 100 m.

89
Figure 85: 122a SEM photo of band of activated slip planes with deformed gamma
prime. Marker size: 10 m.

Figure 86: 122a SEM photo of slip plane with deformed gamma prime. Marker size: 10
m.

Figure 87: 122a SEM photo of band of activated slip planes with deformed gamma
prime. Marker size: 10 m.

90
Figure 88: 122b LOM photo of the specimen edge near fracture surface. Marker size: 20
m.

Figure 89: 122b SEM photo of separate slip planes at fracture surface. Marker size: 100
m.

Figure 90: 122b SEM photo of crack initiations. Marker size: 100 m.

91
Figure 91: 122b SEM photo of slip plane. Marker size: 10 m.

Figure 92: 122b SEM photo of band of activated slip planes with deformed gamma
prime. Marker size: 10 m.

Figure 93: 124a SEM photo of microstructure with enclosures. Marker size: 100 m.

92
Figure 94: 124a SEM photo of single slip plane. Marker size: 50 m.

Figure 95: 124a SEM photo of separate slip planes. Marker size: 50 m.

Figure 96: 124a SEM photo of single slip plane. Marker size: 10 m.

93
Figure 97: 124a SEM photo of separate slip planes. Marker size: 20 m.

Figure 98: 124b SEM photo of feeble marks of slip planes. Marker size: 100 m.

Figure 99: 124b SEM photo of single slip plane. Marker size: 10 m.

94
Figure 100: 124b SEM photo of structure around a crack. Marker size: 10 m.

Figure 101: 126a LOM photo of separate slip planes. Marker size: 50 m.

Figure 102: 126a LOM photo of separate and bands of activated slip planes. Marker
size: 100 m.

95
Figure 103: 126a LOM photo of band of activated slip planes. Marker size: 50 m.

Figure 104: 126a SEM photo of single slip plane. Marker size: 10 m.

Figure 105: 126a SEM photo of single slip plane. Marker size: 10 m.

96
Figure 106: 126a SEM photo of fracture caused by gliding. Marker size: 50 m.

Figure 107: 126a Enlargement of deformation around crack tip in Figure 106. Marker
size: 10 m.

Figure 108: 126b LOM photo of separate slip planes. Marker size: 100 m.

97
Figure 109: 126b LOM photo of band of activated slip planes. Marker size: 50 m.

Figure 110: 126b SEM photo of slip plane. Marker size: 20 m.

Figure 111: 143a SEM photo of crack which changed direction during propagation.
Marker size: 50 m.

98
Figure 112: 143a SEM photo of structure around crack tip. Marker size: 10 m.

Figure 113: 143a SEM photo of separate slip planes. Marker size: 10 m.

Figure 114: 143a SEM photo of internal fracture by slip plane. Marker size: 10 m.

99
Figure 115: 143a SEM photo of single slip plane. Marker size: 10 m.

Figure 116: 143b SEM photo of crack which changed direction during propagation.
Marker size: 50 m.

Figure 117: 143b SEM photo of structure around crack tip. Marker size: 10 m.

100
Figure 118: 143b SEM photo of internal fracture by slip plane. Marker size: 10 m.

Figure 119: 143b SEM photo of internal fracture. Marker size: 10 m.

Figure 120: 143b SEM photo of deformation due to activated slip planes. Marker size:
10 m.

101
Figure 121: 143b SEM photo of deformation due to activated slip planes. Marker size:
10 m.

102