Cobalt Based Super Alloys
Cobalt Based Super Alloys
Cobalt Based Super Alloys
by
Alireza Khoddamzadeh
B. Eng., M.A.Sc. Materials
Doctor of Philosophy
in
Mechanical Engineering
Copyright ©2012
Alireza Khoddamzadeh
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To my mother
Abstract
This thesis reports the design and development of two classes o f new composite
materials, which are low-carbon Stellite alloy matrices, reinforced with either chopped
plain carbon fiber or chopped nickel-coated carbon fiber. The focus o f this research is on
substituting carbides as the main strengthening agent in Stellite alloys with the
aforementioned carbon fibers. Stellite 25 was selected as the matrix because o f its very
low carbon content (0.1 wt%) and thereby relatively carbide free microstructure. The
nickel coating was intended to eliminate any chance of carbide formation due to the
possible reaction between carbon fibers and the matrix alloying additions. The composite
specimens were fabricated using the designed hot isostatic pressing and sintering cycles.
The fabricated specimens were microstructurally analyzed in order to identify the main
phases present in the specimens and also to determine the possible carbide formation
from the carbon fibers. The material characterization of the specimens was achieved
conductivity tests. These novel materials exhibit superior properties compared to existing
Stellite alloys and are expected to spawn a new generation o f materials used for high
R. Liu and Professor M. Liang, for their continuous support throughout this research.
I also wish to thank Dr. M. X. Yao o f Kennametal Stellite for technical guidance
unwavering love and encouragement and my friends for their energetic support.
Table of Contents
Acknowledgements..................................................................................................................... iv
Table o f Contents..........................................................................................................................v
List o f Tables................................................................................................................................ x
List o f Figures.............................................................................................................................xii
Nomenclature........................................................................................................................... xvii
Chapter 1: Introduction................................................................................................................ 1
1.2.1 Objectives................................................................................................................... 6
2.1 Superalloys........................................................................................................................ 12
vi
3.2.1 Chemical Composition of the Com posites...........................................................41
4.1.1 O bjectives................................................................................................................. 50
4.1.3 Apparatus.................................................................................................................. 53
4.4.1 Macrohardness..........................................................................................................58
4.4.2 Microhardness...........................................................................................................59
vii
4.6 Thermal Conductivity..................................................................................................... 63
4.6.1 Background............................................................................................................... 63
4.6.2 Methodology..........................................................................................;................. 63
5.1.1 Microstructure...........................................................................................................65
5.1.2 Density...................................................................................................................... 68
5.1.4 Hardness.................................................................................................................... 70
5.2.1 Microstructure...........................................................................................................74
5.2.2 Density...................................................................................................................... 75
5.2.4 Hardness.................................................................................................................... 76
5.3.1 Microhardness...........................................................................................................79
Chapter 6: Discussion................................................................................................................ 82
viii
6.2 Beneficial Effects of Carbon Fibres...............................................................................84
7.1 Conclusions...................................................................................................................... 96
7.2 Cotributions.....................................................................................................................101
Table 3.4 Physical properties of chopped plain carbon fibre at room tem perature...... 121
Table 3.6 Physical properties o f chopped nickel-coated CF at room tem perature....... 121
Table 3.7 Mechanical properties o f chopped nickel-coated CF at room tem perature.. 122
Table 3.8 Chemical composition o f Stellite 25 and Stellite 25-based com posites....... 122
Table 5.1 Carbide volume fraction in plain CF reinforced composite specimens........ 125
Table 5.2 Specific densities o f the plain CF reinforced composite specimens.............. 125
Table 5.3 Carbide volume fraction in Ni-coated CF reinforced composite specimens 126
Table 5.6 Relative thermal properties obtained with pulsed thermography technique. 127
Table 6.1 Property comparison between the fabricated composites and PTFE based
Figure 2.1 Typical microstructure o f Tribaloy alloys: (a) T-400 and (b) T-800.......... 129
Figure 2.2 Typical microstructure o f Stellite alloys: (a) Stellite 1, (b) Stellite 6 (cast),
Figure 3.6 DSC thermograms: (a) specimen A, (b) specimen B, (c) specimen C and (d)
specimen K..........................................................................................................136
Figure 3.7 Sintering cycle for pure Stellite 25 and Stellite 25based com posites 136
(a) pure Stellite 25 (specimen A), (b) composite specimen F and (c)
Figure 5.2 SEM image of the etched composite F in an area close to carbon fibres ..145
Figure 5.3 SEM/EDX analysis o f specimen F: (a) SEM microstructural image at high
magnification, (b) EDX spectrum o f white phase, (c) EDX spectrum o f dark
Figure 5.4 Optical microstructural image of the etched pure Stellite 25 specim en.... 148
Figure 5.5 Microstructural pictures used for the evaluation of carbide volume fraction:
Figure 5.7 Rockwell hardnesses o f plain carbon fibre reinforced specimens.............. 152
Figure 5.8 Variations o f friction coefficient of plain carbon fibre reinforced specimens
Figure 5.9 Volume losses o f plain CF reinforced specimens due to sliding w ear 153
Figure 5.10 Specific wear rates o f plain CF reinforced specimens under sliding wear 154
Figure 5.11 Optical images o f worn surfaces: (a) specimen A, (b) specimen B, (c)
specimen C, (d) specimen D, (e) specimen E and (f) specimen F ............... 157
Figure 5.13 Intermittent nature o f the wear tracks in plain CF reinforced composites. 158
Figure 5.14 Worn surface analyses o f pure Stellite 25 specimen: (a) SEM morphology
Figure 5.15 Worn surface analyses o f composite specimen F: (a) SEM morphology and
Figure 5.16 Worn surface analyses o f carbon fibres in composite specimen F: (a) SEM
Figure 5.17 Microstructural images: (a) Unetched pure Stellite 25 (specimen A), (b)
Figure 5.18 Presence o f voids in the Ni-coated carbon fibre reinforced composites.... 164
Figure 5.19 Pictures used for carbide volume fraction analysis: (a) specimen A, (b)
Figure 5.20 Corrosion test results o f Ni-coated CF reinforced composite specimens.. 168
Figure 5.21 Rockwell hardness test results o f the Ni-coated carbon fibre reinforced
composite specimens.........................................................................................168
Figure 5.22 Variations o f friction coefficient for Ni-coated carbon fibre composite
xiv
Figure 5.23 Volume losses o f Ni-coated carbon fibre reinforced composite specimens
Figure 5.24 Specific wear rates of Ni-coated carbon fibre reinforced composite
Figure 5.25 Worn surfaces: (a) specimen A, (b) specimen K, (c) specimen L, (d)
Figure 5.26 Worn surface analyses o f specimen O: (a) SEM micrograph and (b) EDX
spectrum.............................................................................................................. 175
Figure 5.27 Microhardness test: (a) specimen F (100x) and (b) specimen O (100x)... 176
Figure 5.28 Microhardness test o f the carbidic phase in specimen F (500x)................. 176
Figure 5.29 Thermal conductivity study: (a) tested specimens, (b) PT thermogram at Is
Figure 6.1 Vickers hardness indentations on specimen F under load o f 60 kg: (a) close
Figure 6.2 Vickers hardness indentations on specimen O under load o f 60 kg: (a) close
Figure 6.3 Comparison of specific density between plain fibre reinforced composites
Figure 6.4 Comparison of corrosion rate between plain fibre reinforced com posites......
Figure 6.5 Comparison o f hardness between plain fibre reinforced composites and........
xv
Figure 6.6 Comparison of friction coefficient between plain fibre reinforced..................
Figure 6.7 Comparison o f wear rate between plain fibre reinforced composites a n d ......
xvi
Nomenclature
M Coefficient o f friction
Y Austenitic phase
/
Y Aluminide precipitates
f f
Y B C T N i3Nb
8 Orthorhombic N i 3 Nb
n Hexagonal NisTi
e HCP cobalt
a FCC cobalt
K Thermal conductivity
P Density
W Weight
M Mass
t Time
A Area
V Volume
F Normal force
T Temperature
Q Applied energy
xvii
Thermal effusivity
xviii
List of Acronyms
CF Carbon fibre
SA Superalloy
PAN Polyacrylonitrile
PT Pulsed thermography
IR Infra red
PTFE Polytetrafluoroethylene
XX
1
Chapter 1: Introduction
Many industrial processes such as gas turbine engine operation, oil production
and refining, chemical processing industry, and mechanical manufacturing pose high
stress, high temperature, and severe wear and corrosion environments. Therefore, it is
possess good corrosion and wear resistance as well. In response to this need, superalloys
(SAs) which are a group of high-performance alloys have been introduced to the market.
These alloys can be divided into three major classes; iron-based superalloys, nickel-based
provide the ductile matrix and to impart high-temperature strength [1,2]. Many o f the
properties o f these alloys arise from the crystallographic nature of cobalt. This element
imparts an unstable, face-centered cubic (fee) crystal structure with a very low stacking
fault energy (SFE) to its alloys. The unstable fee structure and its associated low stacking
fault energy result in high yield strength, high work-hardening rate due to the interaction
between stacking faults, limited fatigue damage under cyclic stresses due to the lack o f
2
cell walls within plastically deformed materials, and the ability to absorb stresses through
Carbon- (C) containing cobalt-based alloys can be categorized into three groups:
high-carbon alloys (1.2 wt% ~ 3 wt%) designed for wear service, low-carbon alloys (<
0.5 wt%) designed for high-temperature service, and medium (0.5 wt% ~ 1.2 wt%) to
low-carbon alloys designed to combat corrosion or simultaneous corrosion and wear [1],
Generally, the softer and tougher compositions are used for high-temperature
applications, such as gas turbine vanes and buckets, while the harder grades are used for
wear resistant materials [4,5]. Stellite alloys make up one main family o f tribocorrosion
resistant cobalt-based superalloys with various types of commercial grades that satisfy
most o f the industry requirements. It is believed that the properties o f a Stellite alloy
mostly depend upon its chemical composition and fabrication process [6],
constituents o f Stellite alloys include chromium (Cr), tungsten (W), molybdenum (Mo),
nickel (Ni), iron (Fe), Aluminum (Al), etc. Each constituent plays a different role in
Stellite alloys. For example, chromium mainly implants corrosion resistance and forms
carbides, tungsten strengthens the solid solution matrix, molybdenum functions same as
tungsten but also enhances the wear resistance. The contents of these constituents
The effects o f the main strengthening phases in Stellite alloys have been
recognized. In these alloys, carbides are considered as the primary strengthening phase
and solid-solution hardeners including chromium, tungsten, and molybdenum are known
Regarding the primary strengthening phase, one o f the key issues is the carbon
content in the alloys. In other words, the carbon content and, thus, carbide volume
fraction in the material, is considered as the main distinction among individual Stellite
alloys. In these alloys, carbides can be found in various forms, including MC, M 2 C,
Although many types of carbides can improve the mechanical and tribological properties
of Stellite alloys, the presence o f carbon in these alloys has its own problems.
Firstly, carbon existence in Stellite alloys may lead to the formation o f some types
of unwanted intermetallic compounds and/or carbides that are also detrimental with
respect to tribomechanical properties. For instance, M 2 C and MeC carbides are brittle
and decrease the mechanical strength o f Stellite alloys [7], Also, some MC carbides such
as tungsten carbide (WC) have a low heat of formation which makes them easily
Secondly, when subjected to a high-temperature cyclic stress, carbidic phases M7C3 and
MC are oxidized preferentially, which creates crack initiation sites in Stellite alloys; thus
4
Likewise, the solidifying MeC carbide degenerates over a certain concentration range o f
along with the carbide types, different sizes and shapes o f the carbide particles within
Stellite alloys may also strongly influence the properties o f the alloys. For instance, larger
carbides that usually pose higher strength provide the alloys with higher resistance to
wear [1,3].
As a result, the problems associated with the presence o f carbon in Stellite alloys
compounds and carbidic phases in Stellite alloys is inevitable and the type, size, shape,
distribution, and amount o f desired carbides cannot be easily predicted or controlled. This
is due to the fact that the carbide formation process in Stellite alloys is affected by many
factors, including alloying element types and fraction, carbon content, fabrication
casting, wrought, and powder metallurgy (P/M). Comparing these three fabrication
techniques for different materials, it is disappointing that relatively little research effort
has been made so far on the P/M fabrication o f Stellite alloys. In particular, no research in
P/M fabrication of carbon fibre reinforced Stellite alloy composites has been found.
effective fabrication process. The advantages of HIP over other P/M techniques include
properties and also improved mechanical properties [11]. It is believed that the HIP
rates, HIP maximum pressure, and HIP time length have considerable effects on the final
cycle is required to ensure that the final products meet the requirements and can be
1.2.1 Objectives
The present research was a joint project between Carleton University and the
Research and Development Grant (CRD) program with the Deloro Stellite Group as the
experimental work in this research were performed in the NRC Institute for Aerospace
Carleton University. The proposed research attempted to design and develop two classes
o f new materials, which are Stellite alloy based composites reinforced by carbon fibres
(CFs). These new materials exhibited superior properties to conventional Stellite alloys
by solving the carbide problems that exist in Stellite alloys. This can be achieved by
using carbon fibres as a novel strengthener in Stellite alloys instead o f different types o f
carbides. Thus, the fabricated composites are expected to spawn a new generation o f
materials used for high temperature, severe corrosion, and wear resistant applications in
various industries.
The new materials were fabricated by the HIP/sintering technique. To obtain the
materials in good quality, the HIP parameters and sintering cycle elements o f the
7
Stellite alloys, it was attempted to substitute carbides, which are the main strengthening
phase in Stellite alloys, with carbon fibres. Using the idea o f metal matrix composites
(MMCs) and their inherent advantages with respect to other types o f composites and
unreinforced metals, carbon fibres, which possess very useful engineering properties,
properties of carbon fibres, which make them good replacements for carbides in Stellite
alloys, include their low density, excellent thermal stability, high chemical inertness,
good mechanical properties and outstanding thermal conductivity along with their broad
commercialization. In the newly fabricated composites, a special low carbon Stellite alloy
designated as Stellite 25, with the main alloying elements o f chromium, tungsten and
nickel, was selected as the matrix material. The reinforcing elements included chopped
plain carbon fibres and chopped nickel coated carbon fibres with 3 mm and 6 mm lengths
respectively. The use o f the chopped form o f carbon fibres can promote the fabrication o f
phase, pure Stellite 25 material along with two groups o f composite materials consisting
o f eleven different Stellite 25 based composites with 0.25 to 10 wt% o f the two types of
carbon fibres were fabricated. The fabrication process included the following steps:
8
1. Material blending: Mixing Stellite 25 powder with carbon fibres using a three
2. Vacuum outgassing: Placing the blended materials in HIP containers (round tubes o f
3. Differential scanning calorimetry (DSC) testing: Studying the phase formation and
a quality control method to evaluate the purity of Stellite 25 powder and also as a
4. Designing the HEP/sintering cycles: Selecting HIP parameters and sintering cycle
elements including HEP pressure and time along with sintering peak temperature,
5. Fabricating specimens: Subjecting the sealed HIP containers to the designed P/M
route by simultaneously applying the set isostatic pressure to the containers and
consolidating the powders and reinforcements with the designed sintering cycle.
the fabrication parameters were selected properly and also to identify the main phases
1. Surface preparation: The surfaces o f the specimens were prepared in several steps
4. Energy dispersive X-ray (EDX): The EDX spectra were employed to analyze the
Vision Lite™, was employed to examine whether carbon fibres induce any carbides
described below:
1. Density test: The density o f each specimen was measured using immersion density
2. Corrosion test: Immersion testing method was used to evaluate the corrosion
resistance of the specimens according to the ASTM Standards G 1-03 [13] and G 31-
72 [14],
3. Hardness test: Overall hardness o f each specimen was determined with a Rockwell
4. Microhardness test: Hardness variation from the interface between the matrix and
carbon fibres to the matrix of each fabricated composites was measured using a fully-
10
Technologies Inc. The purpose o f this test was to investigate whether any diffusion o f
carbon from the fibres into the matrix occurred during the material fabrication
process. If the diffusion occurred, the hardness o f the interface region would increase
the wear resistance o f each specimen in accordance with ASTM Standard G 99-05
[16], The worn surfaces of all the specimens were studied using optical and SEM
microscopies and the EDX technique was used to analyze the chemical
6 . Friction test: The coefficient of friction (/u) o f each specimen was automatically
recorded throughout the wear test with the aid of a linear variable displacement
transducer.
incorporation o f carbon fibres into Stellite 25 alloy was analyzed based on the Pulsed
Thermography (PT) method using a 240x320 pixels infra red (IR) camera.
The thesis consists o f seven chapters with the contents outlined as follows:
Chapter 2 is the literature review o f the previous studies related to this research.
analysis, density test, hardness test, tribological tests, and corrosion test.
The conclusions drawn from this research along with the recommendations for
2.1 Superalloys
alloys generally used when operating temperatures are beyond about 540 °C (1000 °F),
hence also known as high-performance alloys. Over the years, a large number o f
superalloys have been developed and used. The base alloying elements o f these alloys are
transition metals with consecutive positions in the periodic table of elements [1]. The
matrixes o f superalloys include the austenitic y phase with the face-centered cubic crystal
hardened alloys. While the former alloys are strengthened both by solid solution
hardening and by the presence o f carbides, the latter alloys are strengthened by the
intermetallic compounds — Laves phase [1,3,17], The secondary phase in cobalt based-
based superalloy; however, the secondary phase include various carbides, y fee
13
fatigue, and creep conditions; good surface stability, superb oxidation and corrosion
resistance, and good phase stability at high temperatures [18,19], The incipient melting
temperatures for cobalt-based superalloys are generally greater than those for nickel- and
all superalloy-based metals can be formed into a variety o f shapes such as disk, sheet,
plate, bar, shaft, tubing, airfoil, surface coating, and pressure vessel (case) [1,20]. Typical
applications o f superalloys are in aircraft, marine and industrial gas turbines, space
vessels, aircraft skins, power generation turbines, dental and orthopedic prostheses,
military electric motors, cutting tools, environmental protection applications, and heat
a volume basis, superalloys are also employed at cryogenic temperatures and at body
14
temperature. Since the application o f components fabricated from the superalloys requires
Cobalt is a tough, lustrous, silvery-gray ferrous metal that resembles iron and
nickel in appearance and in some properties. The element with atomic number 27, cobalt
(symbol Co) falls between iron and nickel in the middle o f the ferromagnetic trio, which
form the transition group VIII of the first long period o f the periodic table [2,4], Although
cobalt-based compounds had been used for many centuries for making jew elry and
paints, isolation o f the free metallic cobalt was first effected by the Swedish chemist
Georg Brandt in 1735 [21], Pure cobalt is not found as a native metal in nature; however,
it occurs in various metallic-lustered ores in a fairly widespread but dispersed form. The
main ores o f cobalt are sulfidic cobaltite (CoAsS), safflorite (C0 AS2 ), skutterudite
(CoAs 3 ), and smaltite (CoNiAss). Cobalt is not usually mined alone but is produced as a
byproduct of other more abundant or more valuable metals, particularly copper, nickel,
and platinum [ 1 ,2 1 ].
(e -cobalt) stable at room temperatures below 417 °C (783 °F), and a face-centered cubic
structure (a-cobalt) stable at higher temperatures between 417 °C (783 °F) and its melting
point o f 1493 °C (2719 °F). The phase transformation temperature depends critically on
the rate o f temperature change, experimental conditions, and cobalt purity. While
15
alloy transformation happens gradually over a temperature range with both phases present
in the intervening field. In reality, the transformation is known to be sluggish. This is due
to the fact that the structure transformation free-energy change is low, about 360 J mol' 1
for a -> e and 500 J mol' 1 for e -> a. Therefore, most cobalt-based alloys exhibit a
metastable fee structure at room temperature. Also, the grain size favors the cubic form;
thus, cobalt powders, evaporated thin films, and fibres might maintain an essentially
cubic phase at room temperature. The mechanism associated with the allotropic
planes of the cubic lattice. This accounts for the plane change from abcabc characteristic
o f the cubic form to ababab of the hexagonal form because o f the stacking sequence on
these planes [ 1 ,2 ].
Elemental cobalt has an atomic weight o f 58.9332 g-mof1. The metal has one
stable-naturally occurring isotope, Co59, and twelve other radioactive isotopes ranging in
mass from 54 to 64. The physical and mechanical properties o f cobalt may be critically
dependent on the crystal structures resulting from the sluggishness o f the cubic-to-
hexagonal transformation. These properties are also influenced markedly by the effects o f
polymorph o f cobalt [1,2]. Table 2.1 and Table 2.2 respectively quote the physical and
Massive cobalt is resistant to many mild corrosive agents and is very slowly
attacked by air or water at temperatures below about 300 °C (572 °F). However, fine
cobalt powder can be much more readily attacked and may be even pyrophoric in air.
Compared with nickel, cobalt is much less oxidation resistant over a wide temperature
range. The oxide scale, however, progressively reduces the oxidation rate as it grows in
thickness [2 ,2 1 ],
defense-related industries and the need o f industrialized nations on cobalt imports. The
pure metal has few applications such as scientific studies, particularly because of its
uniquely high Curie point, and its low stacking-fault energy. The wide range o f practical
constituent [ 1 ,2 ].
chemicals (for instance, paint pigments, catalysts for the petroleum and chemical
industries, adhesives; drying agents for paints, varnishes, and inks, soaps, and ground
coats for porcelain enamels) and electronic applications (for example, batteries and
magnetic recording media) [1,4]. Cobalt compounds are also important for metallurgical
applications, such as wear resistant, heat resistant, and corrosion resistant cobalt-based
implants [1,4].
Cobalt-based alloys were first investigated by Elwood Haynes at the turn o f the
20th century [22]. Initially, the stainless nature and high strength of the binary cobalt-
chromium alloys were discovered by him. Later, Haynes introduced the Co-Cr-Mo and
and tungsten within the cobalt-chromium system. Because o f their star-like luster, the
alloys were named Stellite after the Latin, Stella, for star. The name is now a trademark o f
the Deloro Stellite Company, Goshen, USA. During World War I, Stellite alloys were
used as cutting tool materials because o f their high strength at elevated temperatures.
Later, from about 1922 cobalt-based alloys were promoted in weld overlay form to
protect surfaces from wear. To satisfy the need for suitable high-temperature corrosion
the 1930s and early 1940s. The biocompatible, low-carbon content cobalt-based alloys
strength, good stress rupture, low creep rates, superior adhesive and abrasive wear
typically comprised o f about 50-60% cobalt, Co, 20-30% chromium, Cr, 5-15%
compared with Ni-based SAs [20], The cobalt-based superalloys gain their super strength
such as aluminide precipitates (y ] has been found for cobalt based superalloys that
results in a large strength increase with the same degree o f utility in nickel- or iron-
Many properties o f the alloys originate from the crystallographic nature o f cobalt.
In particular, the good response to stress o f this class o f materials is due to the low
stacking-fault energy of both cobalt allotropes [3], Also, the fee matrix of cobalt-based
superalloys has excellent ductility and extended solubility for some alloying additions. As
discussed before, the structure of the Co-rich matrix o f the alloys is generally fee, even at
ambient temperature, due to the sluggish nature of the phase transformation. In addition,
cobalt has a higher incipient melting temperature than nickel. Thus, amongst all types o f
superalloys, the cobalt-based SAs normally show greater resistance to softening at high
temperatures [ 1 ],
19
Tribaloy alloys and Stellite alloys are known as the two main groups of cobalt-
wear/corrosion resistant applications. Tribaloy alloys are a series of wear resistant cobalt-
(or nickel-) based alloys containing a large volume fraction of a hard, intermetallic Laves
phase dispersed in a much softer eutectic matrix (Fig. 2.1) [1], The Laves phase in cobalt-
range o f 30 ~ 70 vol% that these materials can withstand wear under dry or boundary
lubricating conditions [25], The main alloying elements in Tribaloy alloys include
but molybdenum and silicon are added at levels in excess o f their solubility limit in order
to induce the precipitation o f the Laves phase [1]. The chemical compositions o f
commonly used Tribaloy alloys are listed in Table 2.3 [1], Stellite alloys are a range o f
cobalt-chromium alloys which may also contain tungsten or molybdenum and a small (<
3 wt%) amount o f carbon [1]. These alloys are explained in more detail below.
Stellite alloys are a range o f cobalt-based materials which are derived from the
C o-C r-W -C family, first developed by Elwood Haynes, mainly for wear applications
involving elevated temperatures [3]. Stellite alloys also have non-corrosive and non
magnetic properties with astounding hardness and toughness [7], Typical applications o f
20
the alloys are cutting tools, jet engine turbine blades, poppet valves, and high corrosion
The principal constituents o f Stellite alloys belong to the quaternary systems Co-
carbides in the cobalt matrix. The compositions of various Stellite alloys are listed in
Table 2.4 [1]. The main differences among the current Stellite alloy grades are their
carbon and tungsten contents which affect the type and amount of carbide formation in
the microstructure [1]. Considering the application o f the alloys, some other elements
such as nickel, molybdenum, iron, tantalum, and niobium with different weight
percentages can be also added [27,28]. The typical microstructures o f Stellite alloys,
more ductile cobalt solid solution mainly containing chromium and tungsten or chromium
and molybdenum, are presented in Fig. 2.2. The nominal composition o f these alloys are
selected in accordance with the type of wear encountered (e.g., abrasive, adhesive, or
erosive wear) in a particular application [1]. The major alloying constituents o f Stellite
• C arbon: The density o f carbon is somewhere between 1.8 and 2.1 g/cc (0.065
and 0.075 lb/in3) and its melting temperature is about 3527 °C (6381°F). This
the amount o f carbides in the alloys. For instance, at a carbon level o f 1 wt%
(Stellite 6B), the carbides constitute about 13 wt% o f the alloy while with a
carbon content o f 2.4 wt% (Stellite 3), the carbides constitute approximately 30
wt% o f the material [1]. In general, there are four main classes o f carbides: M7C3,
M23C6, M 6C, and MC. As discussed before, in M7C3 and M23C6 carbides M
and zirconium [1,17,29], The type, size and shape of carbides in Stellite alloys are
The carbides in the quaternary system Co-Cr-W-C are mostly o f the chromium-
rich M7C3 type and in alloys with high tungsten content like Stellite 1 the
tungsten-rich MeC carbide is also present [1]. Since metal carbides are generally
wear resistant, they improve tribological properties o f the alloys and more
specifically their wear resistance. Carbides formed in Stellite alloys may also
strength [3,7,20], Alloying addition o f carbon also promotes the stability o f the
most important alloying element in the cobalt matrix [1]. The density o f Cr is 7.19
g/cc (0.259 lb/in3) where its melting point is recorded at 1907 °C (3465 °F) [22],
corrosion, oxidation and sulfidation resistances, and serves as the primary carbide
former which impart wear resistance in Stellite alloys [1,7]. The main carbide in
amongst the carbides present in the alloys. The chromium-rich CT2 3 C 6 carbide is
respectively. The density of tungsten is recorded as 19.25 g/cc (0.695 lb/in3) while
the density o f molybdenum is 10.28 g/cc (0.371 lb/in3) [22], Ranging from about
the cobalt matrix by impeding dislocation flow due to their large atomic size. If
their content in the alloys exceeds about 5 atomic percent, W and Mo also
these elements serve to enhance the general corrosion resistance o f the Stellite
alloys [1,6,11,17]. It was reported that molybdenum addition in Stellite alloys (in
adhesive wear. This is because Mo diffuses much more quickly since it has
relatively smaller and much lighter atoms than W. Therefore, under the same
conditions, the volume fraction o f carbides that imparts abrasive and adhesive
desired fee matrix. This element has a density of 7.87 g/cc (0.284 lb/in3) and a
• Nickel: The metallic element nickel is commonly used in Stellite alloys as a solid-
solution strengthener and the fee matrix stabilizer. The common range o f alloying
addition o f Ni in these alloys is between 0 and 4 %wt Nickel has a density o f 8.90
g/cc (0.249 lb/in3) and a melting temperature o f 1453 °C (2651 °F) [1,22].
The high toughness and hardness o f Stellite alloys make them and their alloy parts
very difficult to machine. Thus, Stellite products are preferred to be precisely cast so that
usually preferable to cutting. The machining tools for Stellite alloys are generally made
turbines such as buckets and vanes [3], In addition to the high-temperature usage, these
alloys find widespread applications around room temperature. These applications include
24
fracture fixation devices, orthopaedic prostheses for the shoulder, knee, and hip, dental
implants, and dental crowns. Various in vitro and in vivo tests have shown that some
Stellite alloys meet extremely high requirements with regard to mechanical, tribological
outstanding corrosion resistance to body fluids [23,32]. Considering the volume fraction
of carbides, the present-day Stellite alloys may be classified into three application areas
as follows [1]:
• Low to medium-carbon alloys (0.5 wt% ~ 1.2 wt%) designed to combat only
The largest applications for Stellite alloys are for wear and corrosion resistant
purposes. From a wear standpoint, Stellite alloys containing high levels o f carbon (more
than 1.2 wt%) exhibit high hardness and are intended for use in applications where severe
wear is involved. The several distinct types o f wear generally fall into the following three
main categories: abrasive wear, adhesive wear and erosive wear [1,33]. Abrasive wear
occurs when hard particles like carbides or hard surface asperities are forced against or
moved relative to a softer surface. The abrasive resistance of Stellite alloys which contain
a hard phase generally increases by increasing the volume fraction of the hard constituent
phase. Other factors significantly influencing the abrasion resistance include the shape
25
and the size of the hard phase precipitates in the microstructure and the shape and the size
o f the abrading counterfaces [1,29,34], Adhesive wear is often referred to the formation
friction during sliding process and hard carbide particles in the matrix o f Stellite alloys
normally reduce their adhesive wear [1,29]. Erosive wear are caused by the impingement
of small hard particles carried in a fluid stream against a surface. While ductility o f
Stellites can influence their erosive properties, the carbide volume fraction has very little
The single-phase alloys generally possess better corrosion resistance than multi
phase alloys since the latter alloys have more interfaces between their phases. Although
the high-carbon content Stellite alloys show some aqueous corrosion resistance, such
shortage of chief alloying elements imparting corrosion resistance in their matrices, and
the grain boundary carbide precipitation [1,36,37], Thus, from a corrosion standpoint,
Stellite alloys which contain low levels o f carbon (less than 0.5 wt%) are designed for
severe corrosive environment applications. Other alloying elements such as Cr, Mo, and
The prominent examples for the three major groups o f Stellite alloys include high-
carbon alloys such as Stellite 1, 3 and 720, medium-carbon alloys like Stellite 6 and 694,
and low carbon alloys including Stellite 21 and 25. Normally, the wear resistance
26
increases with the higher volume fraction o f carbides while corrosion resistance and
and average corrosion resistance for applications including pump sleeves, wear pads,
rotary seal rings, expeller screws, and bearing sleeves. Stellite 1 has a high fraction o f
hard primary tungsten-rich MgC carbides, as shown in Fig. 2.2(a). This structure provides
high hardness and exceptional wear resistance for Stellite 1. This alloy maintains its
includes its low toughness. Since this alloy is very hard and also more crack-sensitive
compared to other Stellite alloys, it should only be finished by grinding. Also, like other
high carbon Co-Cr-W-C alloys, Stellite 1 is inadequate for applications where harsh
The medium-carbon Stellite 6 alloy is one o f the most widely used wear resistant
cobalt based alloys due to its good all-round performance. Fig. 2.2(b) shows the typical
hypo-eutectic microstructure o f the cast form o f Stellite 6 which contains the hard carbide
phase dispersed in a tougher and more ductile CoCr alloy matrix. While the carbidic
phase provides exceptional wear resistance for this alloy, its CoCr matrix imparts
resistance to cavitation, galling, and corrosion. The major disadvantage o f the cast form
alloy microstructure. The wrought form of this alloy, Stellite 6B, has a completely
broken up carbides which are dispersed evenly in the CoCr alloy matrix. During the
Stellite 6 B alloy. The resulting structure avoids the brittle carbidic network to act as the
continuous crack-propagation sites in Stellite 6 B while maintains the hard carbides as the
primary wear resistant component in the wrought alloy. Thus, the mechanical properties
and toughness of Stellite 6 B are significantly superior to those o f the cast version.
Compared with the cast Stellite 6 , the wrought form exhibits dramatic improvements in
the aqueous corrosion resistance because o f its more uniform carbide structure. These
properties along with the good machinability o f Stellite 6 B have made the wrought alloy
a good choice for critical applications where simultaneous wear and corrosion are
involved [1,38].
strengthened by dispersed hard carbides. Due to the low volume fraction o f carbides,
molybdenum is also employed in this alloy to strengthen the solid solution. The
considered as a corrosion resistant alloy which shows high corrosion resistivity to both
reducing and oxidizing gaseous atmospheres up to 1150 °C (2100 °F). Compared with
Stellite 1 and Stellite 6 , Stellite 2 1 has higher corrosion resistance in reducing or complex
environments. This is because of the fact that the main constituents of this alloy belong to
the quaternary system o f C o-C r-M o-C rather than C o-C r-W -C . In addition, due to the
28
low carbon content in this alloy, most o f the chromium is in the solid solution matrix
prosthetics, hip and denture implants because of its biocompatible properties [1,39].
wrought, and P/M. The fabrication process o f Stellite alloys affects their microstructures
and their properties as explained before for Stellite 6B for instance. While each o f these
methods has its own advantages and disadvantages, the first two fabrication methods are
used more often in industrial production o f Stellites. This is mostly due to the fact that
these two methods are highly adaptable to the requirements o f mass production. Thus,
large numbers o f a given cast or wrought Stellite alloy may be produced very rapidly.
Despite their inherent advantages, the main disadvantage of the cast and wrought
Stellite alloys is the problems associated with the chemical partitioning in these products
[37,40], Through the years, producers o f these materials have increased the content o f
alloying elements to achieve different properties. For instance, the content level o f
chromium has been increased to obtain more corrosion resistivity. Also, more carbide
forming elements such as molybdenum and tungsten have been used to improve
properties such as wear resistance. Increasing alloying additions has led to the highly
alloyed materials which are prone to microsegregation even under careful controls [11],
in these alloys. As a result, Stellite alloys sometimes show anisotropic-like behavior due
to their nonuniform structures. This ultimately leads to the lower yield strength, lack o f
toughness, lower wear resistance, and severe cracking in the final products [6,41].
increases the production cost [5,11], One reason that Stellite alloys are normally
expensive is because o f their high machining cost due to their difficult machining
process. Also, a full density Stellite alloy is hard to obtain using the common cast and
wrought methods; thus, some properties such as corrosion resistance o f these alloys
would be affected due to the porous nature of the materials [5,32], Many o f these
problems either cannot be found in the P/M products o f Stellite alloys or exist to a much
lower extent. These advantages along with the near-net-shapemaking capability o f the
P/M fabrication method have generated more interests in the fabrication o f the P/M
Stellite alloys in the recent years. However, the start-up costs for acquiring the required
equipments for any P/M fabrication method remain as the main barrier in mass
materials between which a recognizable interface exist. The two categories o f required
30
continuous constituent that surrounds, binds together, supports, and provides form to the
principal purpose is to provide superior level o f structural properties such as strength and
stiffness to the matrix. The reinforcing materials may also impart their special electrical,
Composite materials can be classified at two distinct levels. The first level o f
classification is usually made with respect to the reinforcing constituent which include
reinforced- composites. The second level o f classification refers to the matrix constituent.
Like all composites, metal matrix composites consist o f at least two chemically
and physically distinct constituent materials; i.e., matrix and reinforcement, which are
properly distributed to supply properties not obtainable with either o f the individual
materials. The matrix constituent is a completely continuous metal or metallic alloy such
as aluminum, titanium, magnesium, beryllium, copper, silver, iron, nickel and cobalt. The
lighter weight aluminum-, titanium-, and magnesium-based MMCs are m ost widely used
such as rollers and tool dies iron-nickel, cobalt, and cobalt-nickel matrices are
common [42,43],
chemical reaction, is embedded into the matrix with a range from 1 to 70 vol. % o f the
compounds, are used to improve structural properties and/or enhance physical properties
such as wear resistance, friction coefficient, or thermal conductivity [42]. These materials
continuously aligned long fibres. Since the reinforcements are embedded into the matrix
in a certain direction, the result is an anisotropic structure in which the alignment o f the
particles, platelets, whiskers, and short fibres. Compared with the continuously reinforced
structural, wear, high temperature, electrical and thermal management applications. The
composites - CMCs and OMCs - MMCs offer many distinct advantages which
are mostly because o f the contribution o f the metal alloy matrix in these
problems [42,45],
metal matrix itself. The improved properties include hardness, strength, stiffness,
creep and fatigue resistance. However, the improvements in these properties come
at the expense o f inferior ductility and fracture resistance o f MMCs since the
ductility and toughness o f most reinforcements are very low. Also, the presence o f
advanced composites including MMCs. These materials have been used widely with the
aluminum matrix to produce low density/high strength composites which are employed in
primary structural applications and internal combustion engines for instance. However, in
these composites the reaction of carbon with the matrix material at high temperatures
during fabrication process or under service conditions (above 500 °C) generates a brittle
compound of AI4 C 3 on the surface o f the fibres that affects the strength and functionality
showed that up to 500 °C the strength o f CF/A1 composites declined slightly, while it was
composites were investigated by many researchers. Daoud [51] showed that the addition
o f CF remarkably improved the wear resistance of 2014 Al/CF over pure 2014 A1 alloy
because o f the formation o f a lubricating film on the worn surface o f the composites.
Kong et al. [52] proved that this lubricating film composed o f graphite and metal oxide.
Song et al. [47] investigated the sliding friction and wear properties of AI/AI2 O 3 /C hybrid
MMCs and concluded that their wear resistance was significantly improved over
AI/AI2 O 3 composites because o f the reduced friction force between MMCs and their
counterface material. Lee et al. [48] made the same conclusion and indicated that the
unreinforced aluminum alloy suffered from a severe complex wear regime while the wear
mechanisms in hybrid AI/AI2 O 3 /C composites included abrasive and slight adhesion. Liu
et al. [46] concluded that increasing the volume fraction o f short carbon fibres decreased
the friction coefficient and wear mass loss o f the CF reinforced aluminum matrix
composites since short carbon fibres reduced direct contact between the matrix and its
reinforced AI2 O 3 matrix composites were investigated by Jun et al. [53], The wear
properties o f the normal-oriented composites were better than that of the parallel-oriented
composites and the former composited had smoother worn surface with less microcracks
Carbon fibres are also used to reinforce copper (Cu) alloys. Xu et al. [54]
investigated the wear behavior o f Cu/CF and demonstrated that the incorporation o f
carbon fibres notably improved the wear resistance o f the reinforced composites
compared with pure copper. Xia et al. [55] compared the tribomechanical properties o f
35
Cu/Zn/Sn/CF composites and a common leaded copper alloy (Cu/Zn/Sn). The results
indicated that the composites possessed higher hardness, bending strength, wear
resistance, and antifriction properties than the unreinforced copper alloy. Jim et al. [56]
studied the effects o f the short carbon fibre volume fraction on wear performance o f the
lead free tin bronze matrix composites. As the fibre volume fraction increased, the
Two predominant factors for the wide usage o f CFs can be described as follow:
After 40 years o f fabrication and use, CFs are now on the brink o f broad
because o f their increasing availability and considerable price reduction from the
1990s [42,57],
• Second, carbon fibres have very useful engineering properties including good
conductivities, outstanding thermal stability, and low density; that can be readily
The raw material used to make carbon fibers is called the precursor. Depending
on the precursor and the processing route, carbon fibres are available in a wide range o f
forms, diameters, and lengths; having even wider types with different mechanical
36
properties such as strength and modulus. The several forms of carbon fibres can be
divided into continuous fibres and short fibres, including chopped fibres and milled fibres
[43,57], Two major types of carbon fibres based on their precursors include
polyacrylonitrile-based fibres (PAN fibres) and pitch-based fibres both o f which have
good chemical resistance to corrosive environments. PAN-based fibres, which are more
commonly used, offer low to high modulus of about 240 to 310 GPa (35 to 45 x io 6 psi)
and the highest strengths ranging from 3515 to 6380 MPa (510 to 925 ksi). The increase
carbon fibres exhibit linear stress-strain behavior to failure. Pitch-based fibres have low
strength and high to ultra-high modulus ranging up to 825 GPa (120 x 106 psi), attractive
The process for making carbon fibers involves both chemical and mechanical
operations. The majority of today carbon fibers are known to be PAN-based. Therefore,
the typical sequences o f operations to make these fibers are explained here. The process
starts with spinning operations, which include polymerization, washing, and stretching
the precursor into the desired fiber diameter. The next operation is stabilizing the fibers
by oxidation process that involves heating the fibers in air in a range from 200 °C (392
°F) to 399 °C (572 °F). The process continues by carburizing the fibers in oxygen-free
furnaces by heating the fibers in a temperature range between 700 °C and 2480 °C (1292
°F and 4500 °F). The next step is surface treatment which involves oxidizing the surface
o f the fibers to improve their bonding properties. The last operation is sizing in which the
fibers are coated to protect them from damage during handling or processing [42,43,57],
37
cobalt-chromium alloy, produced at Deloro Stellite Group. The main reason for selecting
Stellite 25 is that the microstructure o f this alloy has very small volume fraction o f
carbides (less than 4%) due to its very low carbon content (0.1 wt%). In this case, the
effect of carbides in the alloy can be kept as low as possible. Stellite 25 is the cast version
o f the wrought alloy L605 with a nominal chemical composition presented in Table 3.1.
The available forms o f this alloy include castings and welding consumables and it can be
welding. The alloy can be readily welded by both manual and automatic welding
methods, such as Gas Metal Arc (GMAW), Shielded Metal Arc (coated electrodes),
was provided by Deloro Stellite Group for this research. This alloy combines exceptional
thermal fatigue resistivity with good resistance to corrosion, oxidation and carburization
up to 1038 °C (1900 °F) for prolonged exposures. The alloy is resistant to wet chlorine at
ambient temperature and resists nitric and hydrochloric acids at certain concentrations
and temperatures. As a non-magnetic material, this alloy has been found to possess good
thermal cracking resistance and hot metal-on-metal wear resistance. However, it is not
recommended for severe wear conditions and low stress or low angle particle erosion
service. This is because the microstructure of this alloy is relatively free o f carbide
reinforcement due to the low carbon content in the alloy. The physical and mechanical
properties o f Stellite 25 alloy are presented in Tables 3.2 and 3.3 respectively. The
combination o f these properties makes this alloy suitable for a number o f component
applications in furnace hardware and metal working tools such as piercing points,
forming tools, and extrusion dies [1,58]. According to its material safety data sheet
(MSDS), Stellite 25 has few health hazards under normal handling and use. However,
performing certain processes such as machining, grinding, welding on this material can
produce dust, fumes, or particulate containing the component alloy elements [59]. Thus,
proper ventilation is required when performing these processes to control the exposure to
additives and reinforcements including particles (0-D) like graphite and fibres (1-D) such
as glass and carbon fibres was studied. Although it is impossible to theoretically predict
the precise behavior o f reinforcements in a metal matrix, the effort was to select the
reinforcing elements with higher chances o f success. Therefore, the method adopted to
39
solve the problem was empirical and evolutionary, while guided by previous experience
in the design o f MMCs. The composites properties were estimated by the rules o f
mixtures. These are mathematical expressions which are used to approximate estimation
their constituents. The usage o f fibres was preferred to particles for two reasons. First, a
fibre is inherently stronger than its bulk material since the flaw size in the fibre is limited
by its small diameter. Second, if propagation o f flaws in a fibre produces a failure in that
fibre, this failure will not propagate to the other fibres to fail the entire composite as
would normally happen in the bulk material [42], Finally, carbon fibre was selected to be
the reinforcing agent in the developed composites because of its large-scale production
and functional engineering properties, including low density, high chemical inertness,
Compared with glass fibre, carbon fibre has lower density and higher thermal
conductivity. The thermal conductivity o f carbon fibre filled composites was reported to
be 10 to 15 times more than that o f the corresponding glass fibre reinforced compounds
reinforcement material. Therefore, it was expected that the composites reinforced with
carbon fibre would possess superior structural efficiency to the pure Stellite 25 matrix
material because o f their good specific strength and specific stiffness (material strength or
stiffness divided by its density). To this end, two different types of PAN-based carbon
fibres were selected for this research to be individually mixed with the Stellite 25 powder
40
in order to make two groups of carbon fibre reinforced composites. Various properties o f
these two groups o f composites such as their tribological, mechanical and corrosion
properties were compared with each other and also with pure Stellite 25 alloy to optimize
The above fibres were obtained from Toho Tenax Company in chopped shape.
This shape allows avoiding areas with inhomogenity in the final composites, i.e. isotropic
reason for using the chopped shape o f carbon fibres is that the fabrication techniques for
discontinuously reinforced composites are usually more cost-effective than that o f the
continuous ones since the former composites can be processed using similar techniques to
The first product is a plain carbon fibre with 3 mm (1/8 in) length and 0.007 mm
(2.7 X 10*4 in) diameter. This product provides good processability and good translation
of mechanical and electrical properties [60], The second type o f carbon fibre is a nickel-
coated chopped carbon fibre with 6 mm (1/4 in) length and 0.0075 mm (2.95 x 10^ in)
filament diameter. The thickness of nickel layer is about 0.25 pm which corresponds to a
weight fraction o f 44% Ni. This product combines the excellent mechanical properties o f
carbon fibre with the properties of nickel such as high electrical conductivity.
interference (RFI) shielding, and lightning strike protection for aircraft [60], The nickel-
41
coating on the carbon fibres serves three intended functions. One is to enhance the
interface bonding between the carbon fibres and the matrix. The second is to prevent
diffusion o f carbon from the carbon fibres into the matrix, thus avoiding formation o f
carbides in the matrix. The third is to alleviate redox reactions including carbon oxidation
service. The physical and mechanical properties o f these fibres are presented in Table 3.4
to Table 3.7.
based composites, listed in Table 3.8, were prepared for specimen fabrication. In general,
reinforcements, their content level and the fibre orientation were carefully investigated
for the composites developed in this research. The specific objectives o f using carbon
addition, using the chopped form o f carbon fibres can result in fabrication o f randomly
As shown in Table 3.8, specimen A was used to measure the properties o f pure Stellite 25
and F were used to study the role of chopped carbon fibre and its content level in the
investigate the effects of the chopped Ni-coated carbon fibre and its content level on the
composites.
was performed using glass bottles, which were half filled with the constituent materials o f
the composites so that there was enough space foT blending. Stellite 25 powder and
carbon fibres were mechanically mixed for an hour in a three dimensional Turbula type
T2C mixer, shown in Fig. 3.1. This apparatus mixes the materials by rotation, translation,
and inversion. The mixing process took several cycles until enough powder mixture was
The technique used to fabricate composites has a significant effect on the final
properties o f the products [42]. In the current research, the hot isostatic pressing
technique was employed to obtain the specimens. HIP is a powder metallurgy processing
powder-to-solid, and powder-to-powder, and is adopted to remove bond line pores. These
43
materials are bonded together by using a multiplier effect of high temperature and
isostatic pressure [ 1 1 ],
distribution, loading the blended materials into containers, vacuum outgassing and
sealing the containers, applying isostatic high-pressure gas to the containers, and
the powders and/or reinforcements are plastically deformed that results in porosity
Containers for consolidation are commonly made from aluminum, mild steel, or
stainless steel depending on the HIP parameters and the blended materials. The powder-
filled containers can be designed and produced as simple geometric shapes or complex
near-net shapes [5,11]. hi the present work, round tubes o f stainless steel-grade 316
having 40 cm (15.75 in.) length and 1.5 mm (0.06 in.) wall thickness with inside
diameters o f 1.3 cm (0.51 in.) were used as consolidation containers for fabricating the
44
specimens (Fig. 3.2). The use o f the round tubes allows a uniform isostatic pressure to be
applied to the blended materials and also avoids any areas o f stress concentration.
The containers were filled with the blended materials and the tubes were sealed at
one end. The mould filling plays an important role in the quality of the final products. To
avoid contamination o f the mixture, moulds were cleaned with acetone prior to each
filling process. Care was taken to fill the moulds uniformly, since improper mould filling
could cause uneven densities, cracks, or distortions in the final products. Therefore, a
glass funnel was used in this step to uniformly pour the mixture into the moulds.
Successive partial charges and tamping to gain the designed fill height were avoided
since these could lead to the contamination problem, charge to charge interface and
After loading the blended materials into a container, it is required to minimize the
mixture adsorbed surface gases. This can be accomplished by subjecting the mixture to a
vacuum and heating the mould to remove air and adsorbed moisture [5]. Therefore, the
open end o f each tube was connected to a vacuum hose and hot outgassed at 300 °C (572
°F) for three days to a vacuum level of 10' 5 mbar using a vacuum pump, Fig. 3.3; then the
tube was sealed and welded to eliminate the possibility of trapping air in the specimens.
interaction o f many factors including shape, size, and chemical composition o f the
45
result in poor mechanical properties o f the final parts [1], As carbon fibres do not melt
during the sintering process o f the composite mixtures, since the melting point o f carbon
is about 3500 °C (6332 °F), the solid state sintering method was intended to be used in
this research. In this method, the sintering elevated temperature is below the melting
point o f the base material and usually between 50 and 90% o f the melting point o f the
constituent with the lowest temperature in the system. Most of the commercial HIP
activities with steel, nickel and cobalt alloys are typically performed between 1100 °C
the difference in the heat flow rate to the sample and to a reference sample as a function
DSC thermograms can be used as the basis o f designing sintering cycles in terms o f the
phase transformation temperatures and to evaluate the sample purity as a quality control
instrument [61,63]. Another main application of DSC is in studying the phase formation
and transformation temperatures, including melting, liquidus, solidus, and glass transition
The facility employed in this research was a Netzsch 404C Pegasus heat flux DSC
shown in Fig. 3.4. In a heat flux DSC machine, the reference and the sample are placed in
two similar crucibles. The crucibles are then placed in a single furnace on a metal disk to
46
make a low resistance heat conduction path between the two holders. The furnace then
the difference in heat flow between the reference and sample throughout the test [61].
Before starting the DSC tests, the DSC machine was carefully calibrated and the
baseline corrections were performed with empty sample and reference crucibles. The
tests were carried out in an inert gas atmosphere by repeatedly evacuating and backfilling
the furnace with argon gas. The reference material was alumina (AI2O3) powder which
did not experience any thermal events over the operating temperature range [64], The
sample and the reference material were precisely weighed and then were placed in the
crucibles. To avoid reactions between the sample and crucible, alumina crucibles were
used for the tests. Also, the sample was covered by alumina powder to improve the
Fig. 3.5 illustrates the heating/cooling cycle o f the DSC tests performed in this
research. The heating/cooling rates o f the cycle were set to 20 °C/min (6 8 °F/min) while
the initial standby temperature was 80 °C (176 °F). The maximum DSC heating
temperature o f 1500 °C (2732 °F) was selected based on the melting point o f cobalt (1493
°C). Both sample and reference crucibles were weighed again after each test to record any
possible weight change. The DSC tests on Stellite 25 and Stellite 25 based composites
were performed. To ensure accuracy o f the tests, at least two specimens were tested for
each material under the same condition. The weights o f the sample and the reference
materials before and after each test were almost constant. Fig. 3.6 presents the curves
47
obtained from the DSC tests. As presented in Fig. 3.6(a), the starting and ending points o f
melting for specimen A are 1384 °C and 1431 °C respectively. These temperatures were
close enough to the melting range between 1329 °C and 1410 °C for the pure Stellite 25
alloy, reported by the manufacturer (Table 3.2), so that the test accuracy and the sample
purity were being confirmed. The maximum sintering temperature was then determined
in terms o f the DSC curves. Since solid state sintering method was adopted, the sintering
elevated temperature should be below the lowest peak temperature o f the first phase
transformation among all the DSC curves. The results show that the peak temperature for
the pure Stellite 25 specimen, plain carbon fibre reinforced composites and Ni-coated
carbon fibre reinforced composites are respectively 1425 °C (2597 °F), 1250 °C (2282 °F)
and 1424 °C (2596 °F); thus, the maximum sintering temperature was selected to be 1150
°C (2102 °F).
The HIP process was continued by subjecting the sealed containers to a high
vessel. The pressure was transmitted to the blended materials through the flexible mould
and the mass became uniformly compacted. The elastic compression o f the mass involved
aligning the particles into the best possible packing array by slipping and sliding followed
pressure and temperature, these parameters should be selected with respect to other
sufficient to close up all pores along the bond line and to close internal pores to produce a
void-free material. However, the pressure has to be low enough to minimize internal
stress and avoid plane slippage that may generate microcracks. Superalloys are normally
hipped to full density under a pressure o f 105 to 205 MPa (15-30 ksi). An inert gas such
as argon, helium, or nitrogen is used as the pressure medium in the process, so that the
material does not chemically react with the pressurizing gas [5,11], The holding period at
the sintering elevated temperature needs to be kept to a minimum to lower the cost and to
For this research, the HIP and sintering cycle parameters including heat-up rate,
cooling rate, hold periods, and peak temperature were preliminarily determined according
to the published data for the P/M cobalt-base superalloys [1,5,8,11,23,32,65] and the
DSC test results. This design was optimized by varying these parameters in the sintering
process o f the pure Stellite 25 specimen and then evaluating the performance o f the
specimens. Finally, it was decided that all the specimens be hot isostatic pressed at the
temperature o f 1150 °C (2102 °F) under a pressure o f 150 M Pa (21.75 psi) o f argon gas
for about 2.5 h. Using the inert argon gas could eliminate the chance o f redox reactions
including oxidation of carbon and nickel to produce carbon dioxide (CO 2 ) and nickel
oxide (NiO) or the carbon reduction by hydrogen to produce methane (CH4). To avoid
49
mechanical stresses induced by the possible volume change during the sintering cycle and
hence possible cracking in the composites, both heating and cooling rates were kept low
gradients in the objects under sintering, two holding periods at 460 °C (860 °F) and 800
°C (1472 °F) were introduced in the cycle. The sintering cycle and the final sintered/cut
4.1.1 Objectives
their properties. The fabricated specimens were first examined using an optical
microscope and a SEM machine before any other material characterization tests. The
EDX technique was also used to reveal the phases present in the specimens. The purpose
(1) Confirming whether the sintering process was properly designed to render a good
(2) Identifying the main phases present in the microstructures of the specimens.
In addition, one o f the most important tasks o f this research was to investigate if
carbon fibres induced carbides in the Stellite 25 matrix. Therefore the analysis o f carbide
volume fraction was performed on the specimens using an image analysis software
(1) Cutting the metallographic specimens from the main body of the HIPed materials
handling, protect the specimen edge, and provide a uniform format for automated
mounting compound. The compound was the phenolic plastic whose general
properties are presented in Table 4.1. The hot mounting press o f Struers Co.
heating temperature, heating time, cooling time, and force was used to provide
(2) Grinding the surfaces of the specimens. The details o f this operation, which was
presented in Table 4.2. The specimen holder o f the machine is a fixed frame in
which the pressure is applied on the specimens via the central column o f the
obtain flat surfaces after grinding operation. Grinding operation was required to
reduce the surface damage caused by cutting and to achieve planar specimens due
52
carefully select the load and the speed o f the grinding operation. The silicon
carbide (SiC) abrasive paper (320 standard grit size) was used with a contact load
o f 27 N (6 Lb.) and a spindle speed o f 250 rpm, according to the ASTM Standard
E 1-01 and Buehler materials preparation guide [66,67]. Water was used as the
(3) Polishing the surfaces o f the specimens. The purpose o f the polishing operation
includes rough and final polishing steps. Rough polishing is performed to remove
specimens were roughly polished with sequentially decreasing abrasive paper grit
sizes. Final polishing was performed to eliminate any surface damage. In the
and 0.05 pm alumina suspension on two specific polishing pads. The specimens
were thoroughly cleaned in an ultrasonic bath, prior to and after each step o f the
final polishing since surface quality could be degraded by abrasion from the
(4) Etching the specimen surfaces. After polishing, the specimen surfaces were
which is the standard solution for immersion etching of cobalt-based alloys. This
solution must be aged for 1 h before use and the samples need to be immersed in
the reagent for up to 30 s [1,68]. The second reagent composition and also its
etching procedures are presented in Table 4.3. These solutions and also etching
procedures were selected because they are well known for identifying carbides in
4.1.3 Apparatus
Olympus PM-63 light microscope, shown in Fig. 4.4. The microscope is capable o f
The scanning electron microscope is one o f the most versatile instruments for
traditional optical microscope since it uses electrons instead o f visible light that is used in
optical microscopes. Also, because a SEM has a better depth of field than an optical
microscope, the sharpness o f the SEM images is much higher than that o f the optical
images. In the present research, a Hitachi S-570 model o f SEM, shown in Fig. 4.5, with
energy dispersive X-ray spectrum was used to produce the high-resolution images o f the
35x to 15000* and uses a tungsten filament thermionic emission gun as its electron beam
emission source. Once cleaned and dried, the specimens were coated prior to mounting
by a thin layer of graphite to become electrically conductive. This task was to prevent the
accumulation of static electric fields on the specimen due to the electron irradiation
required during imaging and also to improve the contrast o f the image.
the specimens, image analysis software, Clemex Vision Lite™ was employed. To obtain
accurate measurements, instrument calibration was made for each objective lens since the
width represented by a pixel would change with magnification. Then the images obtained
from the light microscopy o f specimens subjected to the aforementioned first etching
solution were loaded and the pictures went through different grey level operations to alter
the intensity values associated with each pixel in order to polish up the grey images and
produce high contrast pictures. The next step was thresholding to classify the pixels that
fell within a restricted range o f grey levels into an editable entity called a bitplane. These
bitplanes were the objects measured finally rather than the underlying image. To remove
the artifacts within one bitplane and eliminate the very small features, which should have
not been inserted in a specific bitplane, several binary operations such as trap and chord
size operations were performed. At this stage, the area percent o f all detected phases was
measured with respect to the total area covered by the field o f analysis for each picture.
The area with carbides was used to calculate the carbide volume fraction based on the
55
Delesse principle, i.e., the ratio o f the area occupied by a non-classically shaped object
relative to the entire profile area is a consistent estimate o f its volume fraction [6 j. For
each specimen, fifteen different images were captured and analyzed in three
microstructure porosity is inevitably present that undoubtedly affect the properties o f the
necessary for composite materials to determine if the part has been densified, either
overall or in a critical region, to the degree required for the intended application.
The immersion density technique was employed in accordance with the ASTM
Standard B 311-08 [12] to determine the density of the specimens. The density o f water
• Weigh the specimen in distilled water (w/) while suspended by thin wires
The following formula was used to calculate the density of the materials [12,70]:
56
p . ~ .............. :.J'--------.
Wd - (Wfl - W**» - H W J
where />* is the specific density o f the specimen, g/cm3, Wd is the mass o f the specimen in
air, g, pj 7 is the density o f distilled water, g/cm3, Wp is the weight o f the specimen in
distilled water, g, Wwires is the weight o f the Kevlar wires, g, and Wbeaker is the weight o f
beaker, g.
The basic experimental apparatus, shown in Fig. 4.6, is a Sartorius 6080 electronic
balance, which is accurate to 0 .1 mg and allows for both dry (at air) and wet (in bath)
weighing o f specimens. The setup includes a small metallic stand that fits into the
balance and a small perforated plastic beaker that is suspended from the stand with two
Kevlar wires. The beaker is submerged in a one-litre distilled water bath, allowing the
specimen to be totally immersed while being measured. Care should be taken to avoid
any contact between the beaker and wall o f the water bath.
resistance. However, these materials can corrode in several different ways. These alloys
can be attacked by various corrosive aqueous media such as mineral or organic acids,
oxidizing environment at ordinary or high temperatures, and different types o f salts in the
air necessary for combustion for instance. Also, hot corrosion might occur in gas
turbines, incinerators, and boiler tubes due to the use of sulfur- and sodium-containing
fuels [1,11]. To evaluate the corrosion resistance o f the fabricated materials, immersion
57
corrosion tests were performed on the fabricated specimens in accordance with the
ASTM Standard G 31-72 [14]. This test was intended to represent a worst-case situation
a specific condition o f exposure. Therefore, the selected test medium was the oxidizing
directly affects the results of the tests [71]. According to the ASTM Standard G 1-03 [13]
the surface o f the cylindrical specimens with 0.64 cm (0.25 in) diameter and 1 cm (0.4 in)
height, Fig. 4.7, were polished to 0.05 pm finish, cleaned in ultrasonic bath, and air-dried.
The geometric area o f each specimen was calculated to 1% accuracy and weighing o f the
specimens was accurate to 0.1 mg. The specimens were then immersed in the corrosive
solution for 72 hours and were removed afterwards for examination. Shortly after
removing from the medium, the specimens were properly cleaned by soft brushing under
warm tap water to remove bulky deposits and corrosion products without significant
removal o f the base materials. Then the specimens were dried with ethanol and a blow
dryer.
The mass loss o f each specimen due to corrosion was determined by weighing the
specimen before and after the corrosion test. To assess the corrosion damage, the average
where B is a constant equal to 3.45 * 106 for desired corrosion rates in mils per year, t is
the time o f exposure in hour, A is the area o f exposure in cm2, M is mass loss in g, and p
4.4.1 Macrohardness
indentation [72]. It is generally known that hardness of a material relates closely to its
resistance to wear. The harder the material, the more wear resistant it is [1], In order to
correlate the wear resistance with the hardness o f the fabricated materials, the hardness o f
with the ASTM Standard E 18-08b [15] in the standard laboratory atmosphere. Rockwell
materials and in quality control [73], The test determines the hardness o f a material by
indentation on the surface o f the testing specimen under specified conditions. For each
penetration as the force on the indenter is increased from a specified preliminary test
force (preload) to a specified total test force (major load) and then returns to die preload.
The test results, which are dimensionless numbers, may also correlate to some other
characteristics o f the specimens such as tensile strength, wear resistance, and ductility.
There are different scales in Rockwell hardness test; therefore, the test results should be
59
quoted as a number followed by the symbol HRX where X represents the scale
designation [15,73],
The test apparatus used in this research is a Wilson®, Norwood, USA, Series 2000
Rockwell machine shown in Fig. 4.8. In this machine the depth measurement is
automatically converted to the Rockwell hardness value. The hardness value and
Rockwell scale are then indicated by an electronic device. The test specimens, 10 mm
(0.39 in.) in thickness, were ground and polished to get smooth and flat surfaces at the
top and on the bottom. The tests were conducted using a diamond spheroconical indenter
with the preliminary test force of 10 kgf (98 N) and the total test force o f 150 kgf (1471
N) as the test parameters. For each designation, at least ten different hardness
measurements were performed and the average o f hardness values was reported as the
4.4.2 Microhardness
A Microhardness Tester Unit, Model SMT-X7 Dual Indenter, shown in Fig. 4.9,
with a load capacity o f 1 kgf (9.8 N), was also employed in this research. This instrument
allows measuring hardness in Vickers o f a material on micro level, which means that
hardness o f each phase in the microstructure can be quantified. In order to measure the
variations o f hardness in the region around carbon fibres o f the fabricated composites, a
series o f indentations were performed from the interface o f carbon fibres and the alloy
matrix gradually away to the matrix. The purpose o f this test was to further confirm if
any carbon diffusion had occurred in the fabricated composites. The carbon diffusion
60
from carbon fibres into the alloy matrix would form carbides in the region around carbon
fibres that cause alteration of the matrix hardness in the fibre-matrix interface region.
this research is for wear resistance. Therefore, the tribological behavior o f the fabricated
materials was investigated under sliding wear using a TEER-POD-2, Droitwich, UK,
Sliding or abrasive wear refers to a type o f wear generated by the sliding o f one
solid hard surface along another softer surface [74]. Therefore, in a pin-on-disk test, two
specimens are required which are known as the pin and disk. The pin used in this
research was a 5 mm diameter AISI 52100 steel ball, provided by TEER Coating
Limited, with the hardness o f 60-67 HRC, equivalent to 697-900 Vickers. The pin
specimen was positioned perpendicular to a flat surface known as disk. The disk was the
tested specimens cut from the HEPed materials with 10 mm thickness. These specimens
were polished to 0.05 pm finish, cleaned in an ultrasonic bath, and then dried. The
masses o f the polished, cleaned, and dried specimens were measured to 1 0 -4 g accuracy
with ASTM Standard G 99-05 [16], The test parameters were selected as:
• Speed: 0.1 m/s selected as the relative sliding speed between the contacting
surfaces.
• Distance: ~ 500 m, the accumulated sliding distance within the period o f wear test,
• Atmosphere: The tests were conducted in the standard laboratory atmosphere with
Dining the test the pin (ball) was wearing the disk (specimen) surface which was
min without lubrication. As a result, a wear track was formed in the specimen surface.
• Wear loss: After the test, the disk specimens were cleaned by soft-brushing under
warm tap water to remove debris generated dining the wear test, dried, and
weighed to 0.000lg accuracy. Assuming that there is no significant pin wear, the
following equation was used to calculate the volume losses o f the specimens due
A V = — xlOOO, (4-3)
P
where A V is volume loss, mm3, m is mass loss, g, and p is the density o f the specimen,
7
g/cm '.
• Wear factor: Using the formula expressed below, the wear factor or the specific
(4-4)
where k is wear factor, mm 3/N.m, A V is volume loss, mm3, F is normal force, N, and
As is sliding distance, m.
automatically throughout the test with the aid of a linear variable displacement
transducer so that the variation o f the friction coefficient with time could be
obtained.
the enhancement effect o f the reinforcements on the friction and wear behavior o f the
63
composites, the worn surfaces of all the specimens were examined using optical
microscopy and SEM along with the EDX spectroscopy for elemental analysis.
4.6.1 Background
Friction heat is generated at the rubbing surfaces o f materials during wear. The
produced heat causes adhesion o f the contact surfaces and thereby speeds up the wear
loss o f the materials, hi addition to their excellent wear resistance, carbon fibres possess
good thermal conductivity, which helps dissipate the friction heat when they are added to
the materials exposed to wear conditions. The reduction o f friction heat would mitigate
adhesive wear damage and thus enhances the overall wear resistance o f materials. In
order to confirm the beneficial effect o f carbon fibres on friction heat dissipation, thermal
camera, shown in Fig. 4.11, which has a thermal sensitivity o f 20 mK at 303 K and a
4.6.2 Methodology
transferring energy through vibration between the material’s adjacent atoms and
molecules. Higher rates o f heat transfer occur across the materials with high thermal
conductivities than across materials with low thermal conductivities [4,75], The variation
o f thermal conductivity between different materials can be analyzed using the pulsed
thermography method. This method is known as an active thermographic inspection in
which energy sources (flash lamps) are required to apply energy to the specimen o f
interest using a pulsed excitation in order to produce a thermal contrast between the
specimen’s front and back surfaces. Dining the cool down process, the temperature at the
2400 J power supply, were used as energy sources. Each sample was inspected from both
the front and back surfaces. Each thermogram contained 740 frames that were acquired at
60 Hz and the last frame in the acquisition was obtained at 8.15 s [75].
The following formulas were used to calculate the thermal conductivity o f the
materials [75]:
Ar = -2_, (4-5)
2e^jTrt
CK = —- , (4-6)
P
where ATisthe temperature difference between the frontand back surfaces, K, Q is the
energydensity applied at the surface, J/m , t is the frame acquisition time, s, e is the
thermal effusivity, J-m~2-K~1s~1/2, p is the density, g/cm3, C is the specific heat capacity,
J, and K is the thermal conductivity, W m '1k '1. From pulsed thermography experiments
on an aluminum plate (A1 2024-T3) and the theoretical e value calculated from literature
5.1.1 Microstructure
Fig. 5.1(a). The microstructure of this specimen looks well alloyed and dense with no
obvious porosity and cracking. This confirmed that the processing parameters were
properly selected. Fig. 5.1(b) shows the typical unetched microstructure o f the composite
specimens (specimen F) with the carbon fibres embedded in the Stellite 25 matrix. By
closely examining the microstructures of the composite specimens, a few small voids can
be found, as shown in Fig. 5.1 (c) for specimen C. The presence of voids is common in
properties from the matrix material [65], Also, the sintering process normally causes
some voids in the matrix o f composite materials because o f the point contacts between
the necked particles [65]. However, due to the low amount o f porosity in the composites’
microstructures, it can be inferred that the fabrication parameters were selected properly.
they were first subjected to the etching procedure given in Table 4.3 and then examined
66
by scanning electron microscopy. It was observed that the matrices o f the composite
specimens are similar to that of the pure Stellite 25 specimen. Fig. 5.2 shows the SEM
micrograph o f the matrix o f the etched composite F in an area close to carbon fibres. The
phases present in the matrices o f the fabricated specimens include a primary Co solid
solution matrix, an intermetallic phase, and two types o f carbides: W-rich carbide in
white and Cr-rich carbide in black. Due to the large content o f W in Stellite 25 alloy, the
amount o f W-rich carbide (WeC) is much more than that o f Cr-rich carbide (Cr?C 3
and/or Cr2 3 C 6 ). Thus, the main carbide in the matrices of the fabricated specimens is the
tungsten-rich carbide WeC. The existing phases in the matrices o f the fabricated
specimens were further examined using the EDX technique. Fig. 5.3 shows the SEM
image o f the specimen F at high magnification together with the EDX spectra for phase
identification. Firstly, the light grey area in Fig. 5.3(a) represents the fee Co solid
solution. Secondly, with the EDX major pick of W, the white phase is the tungsten-rich
carbide. Thus, tungsten not only serves as a solid solution strengthener, but owing to the
high content, also forms WgC in the matrix alloy. Thirdly, the dark grey phase in Fig.
5.3(a) represents the intermetallic phase containing Co, W and Cr, as identified in the
EDX spectrum in Fig. 5.3(c). Finally, the black phase in Fig. 5.3(a) represents the Cr-rich
carbide with the major picks o f Cr and C as seen in its EDX spectrum in Fig. 5.3(d).
One main interest o f this research is to investigate whether carbon fibres induce
carbides in the composite specimens during the P/M process. In order to measure the
volume fraction o f carbides in each specimen, the specimens were etched with the
standard cobalt-based alloys’ etching solution mentioned before in Chapter 4. The optical
67
microstructure o f the pure Stellite 25 specimen in the etched condition is shown in Fig.
5.4. The carbides (W-rich and Cr-rich) are identified in black in the cobalt-solid solution
matrix after etching with this solution. After etching, the specimens were analyzed
utilizing an optical microscope and the image analysis software Clemex Vision Lite™.
The microstructures o f all the specimens and some o f the pictures used for the evaluation
of carbide volume fraction are presented in Fig. 5.5, which shows the matrices of the
developed materials in the vicinity of carbon fibres. In this carbide volume fraction
analysis, the small carbides were neglected and only the large-size carbides were taken
into consideration.
Table 5.1. It is demonstrated that the carbide volume fractions in the composite
specimens are slightly more than that in the pure Stellite 25 specimen. Also, the
comparison in carbide volume fraction between the composite specimens suggests that
the volume fraction o f carbides increases with increasing the carbon fibre content in the
specimens. These two observations indicate that the diffusion o f carbon from the carbon
fibres occurred at the high temperatures during the sintering process. However, the
carbide volume fraction increment is very small since the maximum carbide volume
fraction in specimen F (with 5 wt% o f carbon fibre) is only 6.4 vol.%. It is worth
comparing the carbide volume fraction between Stellite alloys and the carbon fibre
reinforced Stellite alloy composites. The volume fraction o f carbides in the former varies
between 3% ~ 50% while the carbon content varies between 0.1 to 3.3 wt% [1,22,76],
However, the volume fraction o f carbides in the latter varies only between 3.8% ~ 6.4%
68
while the carbon content varies between 0.1 wt% in specimen A to about 5.1 wt% in
specimen F (0.1 wt% carbon in Stellite 25 plus 5 wt% carbon fibre). This implies that
employing carbon fibre in Stellite alloys is superior to adding carbon, as viewed from the
volume fraction o f carbides in the alloys. Therefore, it is reasonable to conclude that the
carbon diffusion from the carbon fibres during the sintering process does not significantly
5.1.2 Density
The results o f the density test are presented in Table 5.2. The density o f specimen
A is about 18% higher than the reported value for Stellite 25 alloy in literature [58], This
implies that the HEP densification process employed in this research for fabricating the
Stellite 25 specimen was well designed and the Stellite 25 powder was densified with a
combination o f high pressure and high temperature applied in the consolidation process.
This process led to a dense microstructure with very low porosity, which can be seen in
Fig. 5.1(a). The pure alloy specimen has higher specific density than the composite
specimens. This is because carbon fibre is a lightweight material with a lower density
composites would technically have more voids compared with the matrix material due to
the presence o f fibres. As a result, the density of specimen F that has the highest carbon
The corrosion rates o f the specimens, represented in mils per year, are shown in
69
Fig. 5.6. It is demonstrated that the corrosion rate o f Stellite 25 increases when reinforced
with carbon fibres and the corrosion rate o f the Stellite 25 composite increases with the
carbon fibre content as well. It should be noted that the low-carbon Stellite alloys, Stellite
25 for instance, are mainly designed to combat corrosion while some other properties o f
these alloys such as wear resistance are sacrificed to some degree. However, the
corrosion resistance o f the fabricated composites is still quite high compared with high-
and medium-carbon Stellite alloys. Even specimen F, which has the lowest corrosion
resistance among all the specimens, exhibits higher corrosion resistance than the
carbon) showed a corrosion rate greater than 985 mils/yr [76], whereas composite F
(containing 5 wt% carbon fibre) exhibited a corrosion rate o f only about 192 mils/yr, one
fifth lower than that o f Stellite 6B. It is well known that the corrosion resistance o f
Stellite alloys decreases with the increased carbon content because the presence o f
carbides initiates the interfaces in the alloys, which tends to aggravate the corrosion of
the alloys [1,76]. In addition, Stellite alloys with more carbon content suffer more from
the chemical segregation in their matrices and lack o f chief alloying elements imparting
corrosion resistance in their microstructures [1,36,77], The comparison indicates that the
alloys. This result is attractive since it implies that with a same amount o f carbon content,
the alloy containing carbon fibre is much more corrosion resistant than the alloy
containing carbon element. Therefore, it can be concluded that carbon fibre is superior to
70
show the high corrosion resistivity of the fabricated composites. The reason lies in the
fact that corrosion is a complex process that is simultaneously affected by the chemical
5.1.4 Hardness
About ten readings o f hardness at different positions on each specimen were taken
and the average o f these measurements was reported as the Rockwell hardness o f the
specimen. As presented in Fig. 5.7, pure Stellite 25 (specimen A), has the lowest
hardness among the specimens. Compared with the hardness value o f cast Stellite 25
alloy, provided by the manufacturer in Table 3.3, specimen A which was fabricated by
the P/M route shows about 41% increase in hardness. This increase was owing to the use
o f HIP process as the fabrication method, which naturally results in a material with lower
porosity and higher density [11]. The hardness of specimen A increases with addition o f
carbon fibres. It can be observed that the hardness o f Stellite 25 can be enhanced up to
49% by incorporating 5 wt% carbon fibre (specimen F). This improvement in the
hardness is due to the fact that these fibres are inherently harder than the matrix material.
The hardness values o f Stellite 25 based composites can also be influenced by the
presence o f slightly increased carbides due to diffusion of carbon fibres in these materials
as well.
71
The evolution o f the friction coefficients of the test materials during the wear test
are presented in Fig. 5.8. As illustrated, the friction coefficients for each specimen go up
at the initial stage until reaching a narrow peak. The coefficients of friction then drop to
lower values and become more or less constant afterwards. While the constant values o f
friction coefficient for all the composite specimens vary in a range o f 0.13 < / / < 0.16
after about 35 min sliding, the coefficient o f friction for the pure Stellite specimen is 0.31
after 55 min sliding. The significant reduction in friction coefficients o f the composites
can be attributed to the generation o f a thin transfer film o f graphite from the carbon
fibres on the counter surfaces. This behavior is in agreement with the analyses carried out
by other researchers [42,46,47,48,51], Under the cyclic load occurring during the wear
process, the surface o f the specimen experienced plastic deformation [78]. The removal
o f the surface layer of the specimen caused the carbon fibres to expose to wear. Under the
contact force, the carbon fibres were partially milled into fine graphite particles. The
particles o f graphite, which is known as a good solid lubricant, produced the thin films on
the wear surfaces o f the specimen and its counterface. It is believed that the friction for
all the composite specimens is reduced due to the presence o f this film, which prevents
The wear losses o f the specimens, represented by the volume losses, in the wear
tests are illustrated in Fig. 5.9. The corresponding specific wear rates are illustrated in
Fig. 5.10. The wear rate of pure Stellite 25 is reduced drastically (up to one order o f
carbon fibre among the specimens, exhibits the highest wear resistance with a low
specific wear rate about 0.86 x 10'5 mm3/N m . The wear resistance o f this specimen is
improved by about 12 times compared with the pure Stellite 25 specimen. Interestingly,
the tribological properties o f specimen F are also better than those of Stellite 694
(medium-carbon) and comparable to those o f Stellite 712 (high-carbon), which are all
fabricated by the sintering/HIPing process and tribologically tested under the same
To further study the tribological behaviour o f these new materials, the worn
surfaces o f the tested specimens were examined using optical and SEM microscopy
techniques and the chemical characterization o f the worn surfaces were performed by the
EDX technique. The images o f the wear tracks obtained by optical microscopy are
presented in Fig. 5.11. It can be observed that the width o f the wear track in the pure
Stellite 25 specimen surface is much larger than those of the composite specimens, which
is consistent with the high wear rate of pure Stellite 25. It is also noted that the width o f
the wear track decreases with the increase o f the carbon fibre content in the specimen,
which agrees with the wear rate results. In addition, severe wear scars and deep grooves
are observed on the surface o f this specimen, as shown in the surface image at high
magnification (Fig. 5.12). It is also interesting to note that the wear tracks in the
composite specimens are intermittent, as shown in Fig. 5.11(b) to Fig. 5.11(f). Compared
with the worn surface o f pure Stellite 25 specimen in Fig. 5.12, mild and shallow wear
scars can be observed in the wear track o f the composite specimen at high magnification
in Fig. 5.13. The intermittent wear tracks o f the composite specimens is definitely
73
attributed to the presence of carbon fibres since the friction behavior o f Stellite 25 matrix
with the counterface differs from that o f carbon fibre with the counterface, which results
The SEM micrographs and the corresponding EDX spectra of the wear tracks o f
the pure Stellite 25, specimen A, and the composite specimen F are respectively provided
in Fig. 5.14 and Fig. 5.15. While pure Stellite 25 shows severe wear scars on its wear
track, as observed in Fig. 5.14(a), the worn surface of specimen F in Fig. 5.15(a) is
smooth and the wear track is discontinuous. Also, comparing the EDX spectra in Fig.
5.14(b) and Fig. 5.15(b), in addition to large amounts of Co, Cr and W identified in both
surfaces, there is a peak of carbon in the EDX spectrum of specimen F wear track. This
verifies that the carbon content on the wear track of specimen F is much higher than that
of specimen A. This proves the presence o f the carbon-rich film on the wear track o f the
composite specimens. In addition, the presence of slightly more iron on the wear tracks o f
the fabricated composites (Fe peak in Fig. 5.15(b)) is due to the transferred debris from
the counterpart material (AISI 52100 steel ball). The worn surface of the carbon fibre in
the composite specimens was also examined and the corresponding SEM image and EDX
spectrum are given in Fig. 5.16. No obvious wear damage other than fibre milling is
observed on the carbon fibre surface in Fig. 5.16(a). This very smooth surface further
proves the beneficial effect o f the carbon fibres on the wear resistance o f the reinforced
Stellite 25 based composites. The corresponding EDX spectrum in Fig. 5.16(b) indicates
5.2.1 Microstructure
along with the microstructure of the pure Stellite 25 specimen are presented in Fig. 5.17.
Similar analyses made on the plain carbon fibre reinforced composites apply to the Ni-
coated carbon fibre reinforced composites. Again, it is observed that the pure Stellite 25
specimen and all the fabricated composites exhibit a very similar fine grayish matrix
microstructure in the unetched condition. The presence of porosity in the matrices o f the
fabricated composites is visible, as seen in Fig. 5.18. However, as the amounts o f voids
are very small, it is reasonable to conclude that the fabrication parameters were selected
properly.
With the use o f the aforementioned first etching solution, W-rich and Cr-rich
carbides can be easily identified in the microstructures due to their blackish colour
compared with the matrix colour. In general, there is not much difference in the matrix
microstructure o f the plain carbon fibre reinforced composites and the Ni-coated carbon
fibre reinforced composites. Fig. 5.19 presents some pictures used for carbide fraction
analysis o f the Ni-coated carbon fibre reinforced composite specimens. The results o f
carbide volume fraction measurement are shown in Table 5.3. It is shown that the carbide
volume fractions in all the specimens are very close. In other words, addition o f Ni-
coated carbon fibres has no significant influence on the carbide volume fraction in the
Stellite 25 matrix o f the composite specimens. This implies that the nickel coating o f the
fibres inhibited carbon diffusion at the high temperature during the sintering process.
75
5.2.2 Density
specimens are presented in Table 5.4, together with the density value o f the pure Stellite
25 specimen for comparison. As expected, the densities of the composites are lower than
that o f the pure Stellite 25 specimen because the fillers are lighter than the matrix. Also,
compared to the pure Stellite 25 specimen due to the incorporation of fibres in the matrix
material. Therefore, the density o f specimen P containing the highest fibre content is the
lowest among the specimens and about 18.5% less than that o f specimen A.
The corrosion rates of the Ni-coated carbon fibre reinforced composite specimens
expressed in mils per year are illustrated in Fig. 5.20, together with the corrosion rate
value o f the pure Stellite 25 specimen for comparison. The results show that the corrosion
rate o f the pure Stellite 25 specimen is the lowest among the specimens. This behavior is
similar to that o f the plain carbon fibre reinforced composite specimens. Among the
composites, specimen P that contains the highest carbon fibre content shows the highest
corrosion rate with a value of 597 mils/yr. However, compared with the corrosion-
resistant medium-carbon Stellite alloy, Stellite 6B, which has a corrosion rate value o f
985 mils/yr for the same test condition [76], specimen P shows better corrosion
resistance. Considering the fact that the relationship between the corrosion resistance o f
Stellite alloys and their carbon content is normally inverse [76], this behavior is more
interesting when the carbon contents in Stellite alloys and in the Ni-coated carbon fibre
76
reinforced composites are compared. For instance, composite P contains 10 wt% carbon
fibre (carbon) while Stellite 6B contains only 1 wt% carbon. At 1 wt% carbon (Stellite
6B), the carbides constitute approximately 13 wt% o f the material, these being
predominantly chromium-rich eutectic carbides o f the M7C3 type [79], Therefore, the
carbon in the alloy forms carbides with the alloy elements which deteriorate the corrosion
resistance whereas the Ni-coated carbon fibres in the composite do not induce carbides.
As presented in Table 5.3, the Ni-coated carbon fibres induce nearly no carbides
in the alloy when they are added into the alloy as the reinforcement even with a high
content. Thus, the composites exhibit better corrosion resistance, compared with the
Stellite alloys that contain a much lower content o f carbon than the content o f carbon
fibre in the composites, for example, comparing carbon content and corrosion resistance
between Stellite 6B and composite specimen P. In addition, the good corrosion resistance
o f the composites may be attributed to the high corrosion resistance o f both Stellite 25
and carbon fibres. It should be again mentioned that the intention for the use o f such
highly corrosive environment was not to duplicate a practical condition o f exposure but
because corrosion is a complicated process which depends not only on the environment
o f the exposure but also on the chemical composition o f the exposed material.
5.2.4 Hardness
The hardness test results o f the Ni-coated carbon fibre reinforced composite
specimens are illustrated in Fig. 5.21, together with the hardness value o f the pure Stellite
77
25 specimen for comparison. The hardness of the pure Stellite alloy specimen is
enhanced (up to 57%) by the addition o f Ni-coated carbon fibres. As the fibre content
increases the hardness o f the composite increases. In particular, composite P, with the
largest amount o f carbon fibre, exhibits the highest hardness (53.3 HRC). This
improvement can be explained by the highest proportion o f the fibre which has higher
The variations o f friction coefficients with the sliding time for the Ni-coated
carbon fibre reinforced composite specimens are presented in Fig. 5.22. The friction
coefficient value for the pure Stellite 25 specimen is also presented in the figure for
comparison. For each specimen the coefficient o f friction increases initially and then
decreases until it reaches a nearly constant level, as observed for the plain carbon fibre
reinforced composite specimens as well. The constant value o f friction coefficient for the
pure Stellite specimen is about 0.31 after 55 min sliding, whereas those o f the composites
vary in a range o f 0.14 < fi < 0.2. It is clear that adding carbon fibres in the Stellite alloy
greatly reduces the friction. This may be attributed to the formation o f a thin solid
lubricating film consisting o f graphite and metal oxides on the counter surfaces. This
as a good solid lubricant. Under the repeating operation o f friction force during the
sliding process, carbon fibres are milled into fine graphite particles which generate the
thin film on the moving surfaces. This film prevents direct metal-to-metal-contact
78
between the two counterfaces. The difference in the generation of the thin graphite film
between the plain carbon fibre reinforced composites and the Ni-coated reinforced ones is
noteworthy. In the latter composites, the graphite particles are exposed and milled only
after the Ni-coatings are worn out. Therefore, the graphite films are generated gradually
The wear losses represented by the volume losses of the Ni-coated carbon fibre
reinforced composite specimens in the pin-on-disc wear tests are illustrated in Fig. 5.23.
The corresponding specific wear rates are reported in Fig. 5.24. The wear values for the
pure Stellite 25 specimen are also presented in these figures for comparison. It is shown
that addition of Ni-coated carbon fibres can make a remarkable improvement (up to one
order o f magnitude) in the wear resistance o f Stellite 25. Composite P with the highest
amount o f carbon fibre exhibits the highest wear resistance among all the composites
with a specific wear rate of 0.65 x 10' mm /N.m. The wear resistance o f Stellite 25 is
increased by about sixteen times due to addition o f Ni-coated carbon fibres up to 10 wt%
in specimen P. With the same wear test parameters, the specific wear rate o f composite P
is less than that of the sintered Stellite 694 (medium-carbon alloy) and comparable with
the specific wear rate o f the sintered Stellite 712 (high-carbon alloy) [23]. The
micrographs o f the worn surfaces of the Ni-coated carbon fibre reinforced composite
specimens, obtained by optical microscopy, are shown in Fig. 5.25. The micrograph o f
the wear track o f pure Stellite 25 is also presented for comparison. It can be seen that the
widths o f the wear tracks o f the composite specimens are much less than that o f the pure
Stellite 25 specimen, which correspond to the results o f wear loss and specific wear rate.
It is also observed that the worn surfaces of the composite specimens exhibit obviously
less damage than that of the pure Stellite 25 specimen in Fig. 5.25(a). The SEM
micrograph and the worn track EDX spectrum o f one o f the Ni-coated carbon fibre
reinforced composite specimens, specimen O, are presented in Fig. 5.26. Compared with
the EDX spectrum o f specimen A, shown in Fig. 5.14(b), it can be concluded that the
concentration of carbon on the wear track o f specimen O is much higher than that o f
specimen A. This would be considered as a proof for the generation o f the thin graphite
film on the wear track o f the composite specimens due to the presence o f the nickel
5.3.1 Microhardness
In order to further investigate the diffusion o f carbon from the carbon fibres into
the alloy matrix, microhardness test was conducted on the composite specimens.
Specimen F and specimen O were selected for these tests since the former contains the
highest carbon fibre content among the plain carbon fibre reinforced composite group,
while the latter contains the same weight fraction o f carbon fibre with specimen F in the
Ni-coated carbon fibre reinforced composite group. Four indentations were made at the
interface o f carbon fibres and the alloy matrix and gradually away to the matrix, as shown
in Fig. 5.27. Also, the microhardness o f the black carbidic phase in the composite
specimens subjected to the standard cobalt-based alloys’ etching solution was measured,
as shown in Fig. 5.28. The mean microhardness values are presented in Table 5.5. No
significant change was observed in the microhardness values obtained at the fibre/matrix
80
interface area. Since carbides are much harder than their matrix solid solution, as reported
also in literature [1], the test results imply that no major carbide formation occurred in the
The wear test results demonstrate that carbon fibre has beneficial effects on the
improved heat transfer, owing to the good thermal conductivity of carbon fibres [57], To
wt% plain carbon fibre reinforced composite and 5 wt% Ni-coated carbon fibre
method. Although the actual thermal conductivity values o f the specimens cannot be
measured with this method, the results can be used as an indication for the heat
conduction properties o f the specimens. The specimens prepared for this study are shown
in Fig. 5.29(a). The PT thermograms o f the specimens at 1 s and 8.15 s (last frame in the
acquisition) are presented in Fig. 5.29(b) and Fig. 5.29(c), respectively. The experimental
results are reported in Table 5.6. The C x K values represent the relative thermal
conductivity among the three tested specimens, where the specific heat capacity (C) is
assumed to be identical for the three specimens because their base materials are the same.
It is shown that specimen O has the largest value o f C x K among the three
specimens. The values o f C * K are improved 19.3% and 21.8% respectively for
specimens F and O compared with that o f specimen A. Thus, it can be inferred that
adding carbon fibres improves the thermal conductivity o f Stellite 25. Comparing
composite specimens F and O, the C * K value o f the latter is 2% better than the former.
Although there are no data about the thermal conductivities o f the two different types o f
coated carbon fibres which have better electrical conductivity than the plain carbon fibres
[60] possess better thermal conductivity as well. The results of the PT test prove the
hypothesis that improving the heat dissipation properties o f the composite specimens has
Chapter 6: Discussion
play the most significant role in the wear resistance o f Stellite alloys. However, the
alloys. Considering these problems associated with the presence of carbon in Stellite
alloys, the present research attempted to design and develop new materials, which are
Stellite alloy based composites reinforced with carbon fibres. Because o f the nature o f
carbon fibre, the carbon fibre reinforced composites demonstrated their superior
tribological properties (lower friction coefficient and higher wear resistance) to Stellite
alloys with lower carbon contents but higher carbide volume fractions.
It is worth making the following comparison; for Stellite alloys, at 1 wt% carbon
level (Stellite 6B), the carbides constitute approximately 13 wt% or 16 vol.% o f the
material. Also, at a carbon level o f 2.4 wt% (Stellite 3), the carbides constitute about 30
wt% or 35 vol.% o f the material [1]. However, this research showed that the carbide
volume fraction is only 6.4% for the composite containing 5 wt% plain carbon fibre plus
0.1 wt% carbon in its Stellite 25 matrix alloy. In addition, for the composite containing 5
wt% Ni-coated carbon fibre plus 0.1 wt% carbon in the matrix alloy, the carbide volume
fraction is even less, only 3.7%. Furthermore, considering composite specimens D and
M, which contain 1 wt% carbon fibre, the carbide volume fractions are 5.2% and 3.9%
respectively. Therefore, with the same amount of carbon, the carbide volume fraction in
the carbon fibre reinforced Stellite alloy composite is much less than that in Stellite
alloys. One important feature of the carbon fibre reinforced Stellite alloy composite is
that even with much less carbide volume fraction their wear resistance is superior or
respectively [23]. Therefore, in terms of the undesirable effects of carbides, carbon fibre
reinforced Stellite alloy composites are much more favorable than the conventional
Stellite alloys.
The above comparison reveals that, unlike carbon element, carbon fibre is much
more stable at high temperatures in terms o f formation o f carbides with the alloying
elements o f Stellite alloys. This is because carbon fibres are chemically inert or
unreactive materials [57], The inertness o f carbon fibres makes them stable when they are
incorporated with other materials. However, the carbide volume fraction analysis
indicated minor increase in carbide volume fraction when plain carbon fibres were added
to Stellite 25. This implied that carbon diffusion from the carbon fibres into the Stellite
alloy matrix did occur during the P/M process. However, the amount o f increase in
high-carbon Stellite alloys. Nickel coating on the carbon fibres prohibited the carbon
84
diffusion even further and made the use o f carbon fibres more attractive in consideration
o f carbide formation.
lower than that o f the pure Stellite 25 specimen since carbon fibres are much lighter than
the Stellite 25 alloy matrix. In particular, specimens F and P are respectively 14% and
18.5% lighter than specimen A that might be interpreted as higher structural efficiency
Carbon fibre is known as a reinforcing material that can induce good mechanical
carbides in Stellite alloys in terms o f these properties while the drawbacks o f the
carbides, as mentioned earlier, could be eliminated. The corrosion and wear tests in this
research demonstrated that the carbon fibre reinforced Stellite alloy composites possess
The corrosion test showed that both the plain carbon fibre reinforced and the Ni-
coated carbon fibre reinforced composites had better corrosion resistance than medium-
carbon and high-carbon Stellite alloys. The reason lies in the fact that the key factor
affecting the corrosion behaviour of Stellite alloys is the carbides precipitated in the alloy
and also shortage o f vital corrosion resistant alloying elements such as chromium in the
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matrix of Stellite alloys after formation of carbides. Therefore, the amount of carbides
present in the alloys controls their corrosion performance. Owing to the homogeneous
microstructure o f their composite matrices with minor carbides and more chromium in
the solid solution, the fabricated carbon fibre reinforced materials exhibited better
corrosion and aqueous corrosion (surface oxidation). Galvanic corrosion happens because
dissimilar materials possessing different surface potential are electrically coupled in the
conductive corrosive media [46]. While the conductive corrosive media is the dilute
boiling nitric acid, the dissimilar materials include the matrix alloy, conducting non-metal
o f carbon fibres and the nickel coating on the carbon fibres. Since graphite (carbon fibre)
is placed almost at the top o f the galvanic series as one o f the noblest materials, the
that is caused by electrochemical reactions between the corrosive media o f dilute boiling
nitric acid, the matrix material and the fibres resulting in a form of degradation in the
composites. It can be observed in Fig. 5.6 and Fig. 5.20 that the corrosion rate increases
with increasing the fibre content. This can be explained by the increased contact area
between the corrosive media and the composite materials due to the higher void content
in the composites. Also, raising the carbon fibre content increases the interface area
particular, hardness is used quite often in the field o f wear resistance as a qualitative
indicator for judging alloys, coatings, hardfacings and overlays. It was shown in this
research that adding carbon fibres enhanced the hardness o f Stellite 25 and the hardness
increased with the increase o f carbon fibre content in the composite. This is
understandable because the hardness of the reinforcing elements is a leading factor that
affects the hardness of the composites. It is interesting to compare hardness between the
Stellite alloys or high-carbon Stellite alloys. For instance, high-carbon Stellite alloys such
as Stellite 1, Stellite 3, Stellite 20 and Stellite 720 that contain a similar amount o f carbon
(about 2.5 wt%) have a hardness value around HRC 60, and medium-carbon Stellite
alloys such as Stellite 6, Stellite 694 and Stellite 706 with 1 wt% ~ 1.2 wt% carbon have
a hardness value between HRC 40 and HRC 50 [1], However, from the hardness test
results in Fig. 5.7, specimen F containing 5 wt% carbon fibre has a hardness value o f
HRC 50.5, and specimen D and specimen E containing 1 wt% and 2 wt% carbon fibre,
respectively, have the corresponding hardness values of HRC 44.6 and HRC 49.4,
accordingly.
This comparison shows that the influence o f carbon fibre content on the hardness
for the composites is not as significant as carbon content on the hardness for Stellite
alloys. This is not surprising if the carbide amount in Stellite alloys is considered. As was
well known, the hardness o f Stellite alloys is predominated by the amount o f carbides
precipitated in the solid solution matrix, except for low-carbon Stellite alloys [1]. For the
87
Stellite alloys containing about 2.5 wt% carbon, the carbides constitute about 30 wt% o f
the materials, corresponding to the volume fraction between 30% ~ 40% [1], which is
much larger than the volume fraction of the carbon fibres in specimen F (19.6% shown in
Table 3.8). However, from the above comparison, it is worth noting that the composite
containing the same amount o f carbon fibre as the amount o f carbon in Stellite alloys has
comparable hardness to the Stellite alloys, while the carbide volume fraction in the
The repair and replacement of damaged parts caused by the dimensional size loss
because o f wear are very costly in industry. The tribological tests demonstrated that
adding carbon fibres reduced the friction coefficient and significantly increased the wear
resistance o f Stellite 25. Also, compared with conventional Stellite alloys, the carbon
fibre reinforced Stellite alloy composites containing 5 wt% plain carbon fibre and 10
wt% Ni-coated carbon fibre possess better wear resistance than those o f medium-carbon
Stellite alloys and comparable to those o f high carbon Stellite alloys. The factors
Friction is known as the force resisting the sliding o f one solid body over or along
another body. The resistant force tends to oppose the relative motion o f the two
moving surfaces in mechanical contact [26,28,74], The causes for the formation o f
conditions. When two surfaces are in contact with each other, the actual mechanical
contact area comprises a number of small local asperities. Thus, the actual contact
area is much smaller than the nominal contact area that leads to an undesirable wear
and surface damage caused by the friction force [26,28,74]. Therefore, various liquid
lubricants including water, oil, and grease are used to reduce the friction and
Although they could efficiently control the system friction, liquid lubricants have
usage constraints for many reasons including complicated housing design problems
considerations, and operational problems [26], To this end, there is a strong desire
lessen friction without employing any external liquid lubricants. Self-lubricants are
any solid materials that show low friction in motion without application o f liquid
lubricants. These materials are introduced between two rubbing surfaces for the
purpose of reducing friction and providing protection from damages that happen
o f conservation o f energy, in the rubbing process of the sliding surfaces some o f the
energy is transformed into heat, which can deteriorate the strength o f the surface
materials, thus the wear resistance of the surfaces. The formation o f the graphite film
on the carbon fibre reinforced Stellite alloy composites and their mating surfaces, as
proved by the worn surface analysis, not only reduces the friction by increasing the
real contact moving area and providing solid lubrication but also lowers the friction
heat generated in the rubbing process by providing easier sliding where metal-to-
metal contact is avoided. Thus, adhesive wear due to the localized bonding between
the contacting asperities is mitigated in the composites. In addition, the graphite film
on the composite surfaces also inhibits abrasive wear since the friction force is not
large enough to pull out the fibres from the Stellite alloy matrix. Therefore,
compared with pure Stellite 25 alloy, it can be concluded that due to the presence o f
the carbon fibres the wear resistance o f the fabricated composites is enhanced while
The increase in wear resistance o f the composites can be also attributed to the
abrasion reducing role o f carbon fibres. Since the dominant wear mechanism o f
sliding wear is abrasion, the contact surfaces are normally damaged by groove
ploughing, as shown in Fig. 5.11(a) and Fig. 5.25(a). Without carbon fibre
numerous long and deep grooves which corresponded to a large volume o f material
being scratched out from the surface, as shown in Fig. 5.12. This type o f abrasion is
promoted in Stellite alloys due to the entrapment o f carbide particles between contact
surfaces in relative motion. When removed by micro cutting from the matrix o f
Stellite alloys, carbides, which are super hard particles, can plough both the matrix
and their opposing moving surfaces. The produced debris can even further aggravate
the abrasive wear between the two metallic surfaces as a third body.
On the contrary, the detached small particles o f carbon fibres are milled into soft
graphite powder during the sliding process. In this case, the new reinforcing elements
(carbon fibres) not only improve surface abrasion resistance by eliminating carbides,
but also provide surface lubrication. Both result in less groove ploughing, less
with pure Stellite 25 alloy, which can be clearly observed in Fig. 5.11(b) to Fig.
5.11(f) and Fig. 5.25(b) to 5.25(g). Therefore, in light o f the much lower wear rates
offered by the fibres, it can be concluded that the fibres might have a wear-
preventive role by acting as hard barriers to control the size and the shape o f the wear
fragments in the composites. In addition, no abrasive wear due to the pulled out fibre
from the matrix, caused by the mechanical attack during the sliding process, was
observed in the wear test. This implies that the interface bonding between the matrix
The interface bonding between the reinforcement and the matrix is always a major
consideration for composite materials, because the failure o f the interface results in
spallation of the reinforcement from the matrix under mechanical attack. For wear
resistance applications, the spallation o f the reinforcement from the matrix under the
wear load greatly increases the wear loss o f the material. For the composites
fabricated in this research, no carbon fibre spallation is observed from the worn
indentations were made with the sharp comer diamond pyramid indenter o f the tester
in the locations close to and at the fibre-matrix interface. If the interface is weak,
under the indentation load the sharp indent would initiate cracks at the interface or in
the matrix. A load level o f 60 kg was used for this purpose; however, no cracking
was observed on any o f the composite specimens. The samples o f the indentation
images are presented in Fig. 6.1 and Fig. 6.2. Although this test did not provide a
The HEP/sintering process employed for fabricating the specimens and the
compatibility o f the matrix material with the reinforcing elements m ay be the main
contributing factor to the strong interface bonding o f the composites. The term
not only reduce the matrix to reinforcement load transferring capability o f MMCs but
also act as crack nucleation sites [42]. The microhardness test results on the
composite specimens in Table 5.5 show that hardness is fairly constant around the
interface and identical to the overall matrix hardness. This also indicates indirectly
composites in the fabrication process. The two experiments mentioned in this section
support the wear test observation that the interface of the composites is strong
enough to avoid the carbon fibre pull-out from the matrix under the wear load.
believed that the wear resistance o f a material is affected by its hardness. In general,
increasing the hardness of a material enhances its wear resistance since with the
higher hardness the material is the less prone to deform plastically [1,3,9,28,48]. The
experimental results show that the hardness o f Stellite 25 is enhanced by the addition
o f carbon fibres. It is evident that the hardness induced by carbon fibres contributes
to the high wear resistance of the carbon fibre reinforced Stellite alloy composites.
93
If the heat generated due to friction during the sliding process is not properly
dissipated, the temperature rise can change the surface property o f the rubbing
reason that the carbon fibre reinforced composites exhibited better tribological
properties than their matrix materials might lie in the improved thermal conductivity
o f the composites. Due to their excellent thermal conductivity, carbon fibres can
serve not only as reinforcement, but also as an additive to improve the thermal
conductivity o f the composites [57]. Since these fibres have higher thermal
conductivity than the alloy matrix [22,42,46,57,58,60], the presence o f the fibres can
reduce the surface temperature during wear and thus enhance the resistance to wear.
This is more evident knowing that increasing the content level o f carbon fibres
results in escalating their wear resistance. Such hypothesis was also discussed by
The comparison study o f thermal conductivity of pure Stellite 25, plain carbon
fibre reinforced composite and Ni-coated carbon fibre reinforced composite was
performed in this research. The results, presented in Table 5.6, showed that the
relative thermal conductivity o f pure Stellite 25 was improved by 19.3% and 21.8%
with addition of plain carbon fibre and Ni-coated carbon fibre, respectively.
Therefore, it can be concluded that carbon fibres also improve the thermal
94
conductivity o f the composites, thus reducing the friction heat in the wear process
this research: plain carbon fibre and Ni-coated carbon fibre. The purpose o f using these
two different carbon fibres was to investigate if nickel coating would benefit the
The carbide volume fraction analysis indicated that Ni coating on the carbon
fibres, as an isolator between the carbon fibre and the alloy matrix, did prohibit carbon
diffusion, which avoided formation o f carbides. In other words, the Ni-coating on carbon
fibres can lead to elimination o f the detrimental effects o f carbides in Stellite alloys,
(2) Density:
As shown in Fig. 6.3, with the same weight content of carbon fibre, the composite
reinforced with Ni-coated carbon fibres has higher specific density than that reinforced
with plain carbon fibres. This difference may exist because o f two reasons: firstly, the
density of Ni-coated carbon fibre is much higher than that o f plain carbon fibre (about
50%), as presented in Table 3.4 and Table 3.6. Secondly, the Ni-coating on carbon fibre
may have reduced porosity o f the composites which usually develops during the sintering
95
process. The less porous structure o f the Ni-coated fibre reinforced composites can be
explained by the presence o f the Ni-coating which acts as the interface between the alloy
matrix and the carbon fibre. Since nickel is more cohesive to Stellite 25 than carbon fibre,
the cohesion o f the two dissimilar constituent materials (carbon fibre and Stellite 25) in
The comparison of corrosion resistance between the plain carbon fibre reinforced
composites and the Ni-coated carbon fibre reinforced composites is illustrated in Fig. 6.4.
The results show that the plain carbon fibre reinforced composites possess better
corrosion resistance than the Ni-coated reinforced composites. The rate o f galvanic
galvanic series, nickel is placed lower than graphite (carbon fibre). Therefore, the nickel
coating becomes anodic to the fibres. Also, between the nickel coating and Stellite 25
alloy, the matrix material becomes cathodic. Thus, nickel coating takes the form o f
galvanic anode to control the corrosion o f the matrix by means of cathodic protection.
Therefore, the galvanic corrosion o f Stellite 25 only happens after the nickel coating
decays. The high corrosion rates in the Ni-coated composites compared with the plain
carbon fibre composites can be explained by the virtue o f the more galvanic corrosion o f
(4) Hardness:
The hardness values o f the two groups of composites are compared in Fig. 6.5.
With the same content o f carbon fibre, the hardness values o f the composites reinforced
with plain carbon fibres are higher than those of the composites reinforced with Ni-
coated carbon fibres. The most pronounced reason for such difference is that the Ni-
coating prohibited carbon diffusion from the carbon fibres into the Stellite alloy matrix
during the specimen fabrication process so that the formation of new carbides was
suppressed. Therefore, the overall volume fraction of hard carbidic compounds in the
plain carbon fibre reinforced composites is relatively higher than that in the Ni-coated
carbon fibre reinforced composites which results in higher hardness values in these
composites.
The comparisons of friction and wear resistance between the two groups o f
composites are illustrated in Fig. 6.6 and Fig. 6.7, respectively. It is shown that the plain
the friction coefficient o f the plain carbon fibre reinforced composites varies in a range o f
0.13 < p < 0.16, while that o f the Ni-coated carbon fibre reinforced composites varies in a
range of 0.14 < /i < 0.2. The higher friction force in the latter composites is due to the
fact that the lubricating graphite film is generated gradually on their moving counterfaces
during the wear process only after the Ni-coating is worn out and the graphite particles
the fabricated composites, it can be noticed that even though the Ni-coated reinforced
composites possess relatively better thermal conductivity, they have some downsides
including higher friction coefficient values due to the delay in formation o f graphite film
layer on the specimen surface, lower overall hardness, and higher abrasive wear rate
because of the presence of the milled nickel coating particles. The reduction in wear
resistance o f the composites reinforced with Ni-coated carbon fibres compared with those
reinforced with plain carbon fibres may have two other reasons. Firstly, the carbide
volume fraction in the former is less than that in the latter when their carbon fibre
contents are the same. The less carbide in the Ni-coated carbon fibre reinforced
composites results in the reduction in wear resistance o f the matrix that eventually leads
to the increased wear rate o f the composites. Secondly, the higher friction coefficient o f
the Ni-coated carbon fibre reinforced composites is another reason for their higher wear
rate.
The thermal conductivity test showed that the C * K product for composite
specimen O (with Ni-coated carbon fibre) is 2% higher than that for the composite
specimen F (with plain carbon fibre). Therefore, it can be inferred that the relative
thermal conductivity o f the Ni-coated carbon fibre reinforced composites is better than
that o f the plain carbon fibre reinforced composites. Considering that the volume fraction
of carbon fibres in composite O (13.9 vol.%) is lower than that in composite F (19.6
vol.%), it can be inferred that the nickel coating increases the thermal conductivity o f
98
carbon fibres. This statement is in agreement with the general behavior o f metallic
materials for which the best electrical conductors are the best thermal conductors as well
[4,42].
composites for any specific application, it is worth comparing the properties o f these
composites with self-lubricating slider bearing materials. Under the same conditions o f
exposure, the fabricated composites show better tribological properties and corrosion
resistances than PTFE based sliding bearing materials [28], As presented in Table 6.1,
while maintaining the super low coefficient o f friction of PTFE because o f the lubricating
effect o f the thin transfer film o f graphite, the fabricated composites possess superior
corrosion and wear resistance than those o f PTFE based composites. Therefore, one main
application for the fabricated composites can be in the bearing industry. The formation o f
graphite film on the composites and their sliding counterfaces can ensure the workability
7.1 Conclusions
Two groups o f carbon fibre reinforced Stellite alloy composites have been
designed and developed in this research. Conventional Stellite 25 was selected as the
matrix of the fabricated composites because it contains very low carbon content. The
reinforcing elements included plain carbon fibres and nickel-coated carbon fibres. The
Based on the experimental results and the discussion, the following conclusions can be
1. The pure Stellite 25 specimen and all the composite specimens have a very
phases include the cobalt solid solution, the tungsten-rich carbide and the
chromium-rich carbide.
2. The presence o f carbon fibres increases slightly the carbide volume fraction o f
the plain carbon fibre reinforced composites compared with that o f pure
Stellite 25 alloy. This implies that carbon fibres are stable at high
temperatures and differ from carbon which forms carbides with metallic
100
3. The carbide volume fractions in all the Ni-coated carbon fibre reinforced
group specimens are nearly equal, which indicates that the carbon did not
diffuse from the fibres into the alloy matrix to induce carbides at the high
attributed to both the high-temperature stability o f carbon fibres and the nickel
coating.
produced the specimens with low porosity, thus achieving fairly high density.
However, the composite specimens have lower density than that o f the pure
5. Addition o f carbon fibre into the low-carbon Stellite alloy, Stellite 25,
Both the hardness and wear resistance o f the fabricated composites increase
carbon fibre on these alloys: (1) increased hardness, (2) reduced friction due
101
to the formation o f graphite film on the composite surface during wear, and
7.2 Contributions
The novel manufactured composites solve the main problems caused by the
carbides in Stellite alloys and exhibit superior tribocorrossion properties to these alloys.
1. The fabricated composites, even the specimens with the highest content o f
alloys, for example, Stellite 6B. This is attributed to the beneficial feature o f
2. The tribological properties of the composite with 5 wt% plain carbon fibre and
the composite with 10 wt% Ni-coated carbon fibre are better than those o f
alloys.
3. The newly fabricated carbon fibre reinforced composite materials avoid the
such as pumps and impellers must withstand the simultaneous wear and
corrosion.
1. The newly fabricated materials should also be fabricated with casting techniques.
3. The effects of the shape, size and aspect ratio o f the filler (carbon fibre) on the
fibres.
carbon Stellite 25 alloy as the matrix in order to eliminate the influences o f the
carbides in Stellite alloys on the final properties o f the composites or to mitigate
environments.
104
References
[1] ASM Handbook Committee, “Nickel, Cobalt, and Their Alloys”, ASM
[2] W. Betteridge, “Cobalt and its Alloys”, Ellis Horwood Ltd., Cambridge, England,
1982.
[3] R. Liu, M.X. Yao, and X. Wu, “Influence o f Carbon Content in Cobalt-Based
[4] J.R. Davis, “Metals Handbook Desk Edition”, 2nd Edition, ASM International,
[6] J. Shin, J. Doh, J. Yoon, D. Lee, and J. Kim, “Effect of Molybdenum on the
[9] W.H. Jiang, X.D. Yao, H.R. Guan, and Z. Q. Hu, “Carbide Behavior during High
[12] ASTM Standard Committee, “Standard Test M ethod for Density o f Powder
[13] ASTM Standard Committee, “Standard Practice for Preparing, Cleaning, and
USA, 2007.
[15] ASTM Standard Committee, “Standard Test Methods for Rockwell Hardness o f
[16] ASTM Standard Committee, “Standard Test Method, for W ear Testing with a
Materials”, Elsevier Science and Technology Books, St. Louis, USA, 2006.
[18] R.C. Reed, “The Superalloys Fundamentals and Applications”, 1st Edition,
[21] R.S. Young, “Cobalt, Its Chemistry, Metallurgy, and Uses”, Reinhold
[22] ASM Handbook Committee, “Properties and Selection: Nonferrous Alloys and
USA, 1990.
[24] Y.Q. Wang and B.L. Zhou, “Behavior o f Coating on Reinforcements in Some
[29] M.X. Yao, J. Wu, and Y. Xie, “Wear, Corrosion and Cracking Resistance o f
[30] C. Sims, N. Stoloff, and W. Hagel, “Superalloys It: High Temperature Materials
for Aerospace and Industrial Power”, John Wiley & Sons, Toronto, Canada,
1987.
[34] A. Frenk and W. Kurz, “Microstructural Effects on the Sliding Wear Resistance
Resistant Alloys for Use in Aqueous Media”, Cobalt Journal, Vol. 52, 1971, pp.
160-1.
[40] G. Y. Lai, J. J. Barnes, and J. E. Bames, “A Burner Rig Investigation o f the Hot
[43] N. Chawla and K. Chawla, “Metal Matrix Composites”, Springer, New York,
USA, 2006.
[44] B. Ralph, H.C. Yuen, and W. B. Lee, “The Processing o f Metal Matrix
[46] L. Liu, T. Ping, and S. Bin, “Friction and W ear Properties of Short Carbon Fibre
[47] J. Song and K. Had, “Effect o f Volume Fraction o f Carbon Fibres on W ear
Friction and Wear Properties o f AI2 O 3 and Carbon Short Fibres Reinforced
AlSinCuMgNi Hybrid Composites”, Wear Journal, Vol. 254, 2003, pp. 164—
72.
[52] L. Kong, Y. Lu, and B. Yang, “Investigation of Friction and W ear Behaviour o f
[53] C.S. Lee, Y.H. Kim, and K.S. Han, “Wear Behaviour of Aluminium Matrix
[54] J. Xu, H. Yu, L. Xia, and H. Yang, “Effects o f Some Factors on the Tribological
[55] L. Xia, B. Jia, J. Zeng, and J. Xu, “Wear and Mechanical Properties o f Carbon
[56] Z. Jun, X. Jincheng, H. Wei, and L. Lei, “Wear Performance o f the Lead Free
[57] Zoltek Committee, “User’s Guide for Short Carbon Fibre Composites”, Zoltek
[59] J. Davies, “Cobalt Base Alloys MSDS”, Deloro Stellite Company, Goshen,
USA, 2007.
[60] Toho Tenax Committee, “Tenax Chopped Products Technical Data”, Toho
[64] ASTM Standard Committee, “Standard Test Method for Enthalpies of Fusion
[67] “The Science Behind Materials Preparation”, Buehler Ltd., Lake Bluff, USA,
2004.
[69] J.W. Weeton and R.A. Signorelli, “Effect o f Heat Treatment upon
Alloy”, Trans. Am. Soc. Met., Vol. 47, 1955, pp. 815-52.
[70] Y. Ning, “Effects o f Sintering Process and the Coating of the Reinforcements
[78] R. Liu and D.Y. Li, “A Finite Element Model Study on W ear Resistance o f
pp. 169-175.
116
[79] R. Liu R, M.X. Yao, X. Wu, and P.C. Patnaik, “An Improved Wear-Resistant
Hardness(a) HV 140-250
MPa 800-875
Tensile Strength^5
(ksi) (116-127)
Elongation^ % 15-30
MPa 305-345
0.2 % yield strength^
(ksi) (44-50)
GPa 211
Yoimg’s Modulus
(psi) (30.6 x 106)
GPa 82
Shear Modulus (11.9 x 106)
(psi)
GPa 183
Compressive Modulus
(psi) (26.5 x 106)
Note: (a) At 20 °C, (b) Annealed high purity (99.5 %) vacuum-melted cobalt
119
Alloy Co Cr W C Fe Ni Si Mn/Mo
Stellite 3
Bal. 20 15 0.1 10 1 1.5
25 (max)
Hardness HRC 24
MPa 925
Tensile Strength
(ksi) (134)
Elongation A% 5
MPa 895
0.2 % yield strength
(ksi) (130)
GPa 207
Young’s Modulus
(psi) (30.0 x 106)
121
Table 3.4 Physical properties o f chopped plain carbon fibre at room temperature [60]
Elongation % 1.7
GPa >207
Young’s Modulus
(psi) (30.0 x 106)
Elongation % 1.7
GPa 238
Young’s Modulus
(psi) (34.5 x 106)
Form - Granular
Clarity - None
Cost - Low
Base
Load N (Lb.)/ Time
Surface Abrasive/Size Speed(rpm)/
Specimen Direction (min:sec)
CarbiMet® 320 - (P400)
Grit SiC Until
Abrasive Grinding 27(6) 2 5 0 /Contra8
Plane
Discs Water Cooled
3 pm MetaDi®
TexMet® 1000
Supreme
Polishing Pad 27(6) 1 0 0 /Contra8 5:00
Diamond
Suspension
1pm MetaDi®
TexMet® 1000
Supreme
Polishing Pad 27 (6) 100 / Contra8 3:00
Diamond
Suspension
0.05 pm
Microcloth MasterPrep®
27 (6) 100 / Contra8 3:00
Polishing Pad Alumina
Suspension
Note:
(a) Contra = platen and specimen holder rotate in opposite directions
(b) Comp. = Complementary (platen and specimen holder both rotate in the same direction)
Carbide
Standard
Designation Fraction
Deviation
(vol.%)
A 3.8 0.1
B 4.2 0.1
C 4.8 0.3
D 5.2 0.2
E 5.8 0.2
F 6.4 0.4
Specific Density
Designation
g/cm3 (lb/in3)
A 9.823 (0.3549)
B 8.769(0.3175)
C 8.751 (0.3161)
D 8.716(0.3149)
E 8.647(0.3124)
F 8.437 (0.3048)
126
Carbide
Designation Fraction
(vol.%)
A 3.8
K 3.9
L 3.8
M 3.9
N 3.9
0 3.7
P 3.8
Specific density
Designation
g/cm3 (lb/in.3)
A 9.823 (0.3549)
K 9.744 (0.3520)
L 9.709 (0.3507)
M 9.609 (0.3471)
N 9.403 (0.3397)
O 8.833(0.3191)
P 8.001 (0.2890)
127
Standard
Indentation HRC (HV)
Deviation
F, 482 (48) 22
f2 520 (50) 16
f3 580 (54) 19
f4 566 (53) 25
0, 434 (44) 13
o2 483 (48) 26
o3 494 (49) 39
o4 518 (50) 7
Carbide 1510 (-) 45
Table 6.1 Property comparison between the developed composites and PTFE
based sliding bearing materials
Laves phase
Eutectic Co
solid solution
L. 48731 £ 8 KV K588
(a)
f- ' ,
v:'‘ S
8 0 9 813 K j
(b)
Fig. 2.1. Typical microstructure o f Tribaloy alloys: (a) T-400 and (b) T-800.
130
m 6c
Carbides
(a)
1|!, Semi-continuous
carbidic phase
Cobalt solid solution
(b)
131
f
^ & ‘S
Broken up
carbides
Cobalt solid solution!
V ,
#
\
fc
IP
'J
0
7 4
*20 utm ■kif
r.-f , / v
(C)
Cr23C6
Co solid solution
Eutectic Cr?C3 I
(d)
Fig. 2.2. Typical microstructure o f Stellite alloys: (a) Stellite 1, (b) Stellite 6 (cast), (c)
Stellite 6B (wrought), and (d) Stellite 21 [70]
Fig. 3.1. Three dimensional Turbula type T2C mixer.
1600
(80,1500) (140,1500)
1400
1200
1000
20 °C/min
S> 800
600
(190,500)
400
200
(10, 100)
DSC /(uV/mg)
I exo
1.00
P«fc 1425.1 *C
0.50
0.0
- 1.00
Peak: 1303.0'C
-1.50
(a)
135
DSC /(uV/m g)
P e a t 1247.1 *C
0.60
1244.1 *C End: 1251.3 *C
- 0.20
6G0 700 800 900 1000 1100 1200 1300 1400 1500
T em p eratu re / X
(b)
DSC /(uV/mg)
P e a t 1373.8*0
O nset 13673 *C
0.60 End 1403.7 *C
Onset 1249.6 *C
0.40
End 1272.0*0
P eat 933.4 *C
0.0
Onset: 13335*C End 13735 *C
0.20
-
Peak 1227.9 *C
Peak 1366.2 *C
-0.40
(c)
136
DSC /(UV/mg)
I exo
100
0.50
0.0
- 1.00
-1.50
800 900 1000 1100 1200 1300 1400 1500
Tem perature / X
(d)
Fig. 3.6. DSC thermograms: (a) specimen A, (b) specimen B, (c) specimen C and (d)
specimen K.
1400
1200 (1 3 0 ,1 1 5 0 ) (280,1150)
1000
800 (3 1 5 ,8 0 0 ) (3 3 0 ,8 0 0 )
600
(4 5 ,4 6 0 )* _ * t6 0 ,460)
400
1 0 °C /m ln
200
(410, 0)
0
0 50 100 150 200 250 30 0 350 400 450
T im e (m in)
Fig. 3.7. Sintering cycle for pure Stellite 25 and Stellite 25 based composites.
G
sisi ti
wry \
/ cm .
^ ■
2 0 |jm
(a)
Stellite 25
matrix
Carbon fibre
(b)
144
Voids
(C)
Fig. 5.1. Optical microstructural images o f the specimens in an unetched condition: (a) pure
Stellite 25 (specimen A), (b) composite specimen F and (c) presence of voids in the
composite specimen (specimen C).
145
| Cr-rich
Carbide
, *; £*:f a- ’r :& C*
■'•• * ? ' , ' - / ' ? * • - ' . V I '-2 ' ' * " - '- * V * - •'■ “■* ' ' • ' > • ‘n ’ l ’ ' »•* • V . ‘ ' ■ A i ' V v . ' i i ' * ' : f . *>. . V ; > .»> . * .• ;• * ’ • — s.
-i '■-••- •;.-!--,»t :-,,:.->'.v- a :-_-. '•■.-■ ' • W-rich Carbide
Acc.V Spot Magn Det WD I------------------------1 50 pm i?;
20.0 kV 3.0 1000x BSE 6.0 Sample F £1
Fig. 5.2. SEM image o f the etched composite F in an area close to carbon fibres.
W6C Carbide
■Co Solid
(Solution (fee)
Intermetallic
Compound |Cr-rich
ICarbide
(a)
146
Co
Co Mo W
W
Mn Co W
(b)
Co
W
W
W
W ________
(C)
147
Cr
Mn Co
Mn
W
Mo
Co W
W
(d)
Fig. 5.3. SEM/EDX analysis o f specimen F: (a) SEM microstructural image at high
magnification, (b) EDX spectrum of white phase, (c) EDX spectrum of dark
grey phase and (d) EDX spectrum o f black phase.
148
Carbides
Solid Solution
Matrix
Fig. 5.4. Optical microstructural image of the etched pure Stellite 25 specimen.
(q)
00
6P1
150
r*j£$?5ioo|jnfc
(d)
^
Fig. 5.5. Micro structural pictures used for the evaluation o f carbide volume fraction: (a)
specimen A, (b) specimen B, (c) specimen C, (d) specimen D, (e) specimen E
and (f) specimen F.
152
Specimen
Fig. 5 .6. Corrosion resistances o f plain carbon fibre reinforced specimens in oxidizing acid
65% HNO 3 at boiling temperature.
■ H a rd u e ss a S ta n d a r d deviatio n
Specimen
0.4
0.35
| 0.25
is 0.2
0
a 0.15
1 0.1
u
fa
0.05
0 20 40 60 80
Duration time (m in)
Fig. 5.8. Variations o f friction coefficient o f plain carbon fibre reinforced specimens
with sliding time.
I
Specimen
Fig. 5.9. Volume losses o f plain CF reinforced specimens due to sliding wear.
154
8.56
1.93
0.86
I 0.1
Specimen
Fig. 5.10. Specific wear rates o f plain CF reinforced specimens under sliding wear.
(a)
156
(e)
157
789pm
200|J m
Fig. 5.11. Optical images o f worn surfaces: (a) specimen A, (b) specimen B, (c) specimen C,
(d) specimen D, (e) specimen E and (f) specimen F.
Fig. 5.12. Severe wear scars in the specimen A surface
Fig. 5.13. Intermittent nature o f the wear tracks in plain CF reinforced composites.
159
:s>
o .-
Co Co
Co
Mn
W W
Mo
W
W w
W
(b)
Fig. 5.14. Worn surface analyses of pure Stellite 25 specimen: (a) SEM morphology and (b)
EDX spectrum.
160
(a)
W
W
W
W
■Jffai
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
(b)
Fig. 5.15. Worn surface analyses o f composite specimen F: (a) SEM morphology and (b) EDX
spectrum.
161
Carbon Fibre
(a)
Co
Fe
Fe Co
(b)
Fig. 5.16. Worn surface analyses of carbon fibres in composite specimen F: (a) SEM
morphology and (b) EDX spectrum.
162
iiii
(b)
163
(d)
Fig. 5.17. Microstructural images: (a) Unetched pure Stellite 25 (specimen A), (b) unetched Ni-
coated CF reinforced composite (specimen P), (c) unetched specimen P at higher
magnification and (d) the matrix of etched specimen P in an area close to the fibres.
164
(c)
166
ilOOjim,
(d)
(e)
167
(g)
Fig. 5.19. Pictures used for carbide volume fraction analysis: (a) specimen A, (b) specimen K,
(c) specimen L, (d) specimen M, (e) specimen N, (f) specimen O and (g) specimen P.
168
£ 500 -
I 400 ^
300 -I 269.19
Specimen
Fig. 5.21. Rockwell hardness test results of the Ni-coated carbon fibre reinforced composite
specimens.
169
0.35
0.25
0.15
0.05
Time (min)
Fig. 5.22. Variations o f friction coefficient for Ni-coated carbon fibre composite
specimens with sliding time.
A£
0.51
III...
0.5 -
% 0.4 -
J 0.3 -
2
1 0.2 -
0.1 -
0 - ^ ^ ^ ^ ^ ----- 1
A K L M N O P
Specimen
Fig. 5.23. Volume losses o f Ni-coated carbon fibre reinforced composite specimens
under pin-on-disc wear.
170
Specimen
Fig. 5.24. Specific wear rates of Ni-coated carbon fibre reinforced composite specimens under
pin-on-disc wear.
171
(b)
172
1,081 jjnd
(d)
(})
turlg28
uirigeg
ez.i
174
(g)
Fig. 5.25. Worn surfaces: (a) specimen A, (b) specimen K, (c) specimen L, (d) specimen M, (e)
specimen N, (f) specimen O and (g) specimen P.
s r. • •»
(a)
Sam ple O', w ear track
Co
Fe
do
S_T1
w w
w
w
Z.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
(b)
Fig. 5.26. Worn surface analyses of specimen O: (a) SEM micrograph and (b) EDX spectrum.
(b)
Fig. 5.27. Microhardness test: (a) specimen F (100x) and (b) specimen O (100x).
(a)
(b)
O
(c)
Fig. 5.29. Thermal conductivity study: (a) tested specimens, (b) PT thermogram at 1 s and (c)
PT thermogram at 8.15 s.
178
(b)
Fig. 6.1. Vickers hardness indentations on specimen F under load of 60 kg: (a) close to the
interface and (b) at the interface.
179
(b)
Fig. 6.2. Vickers hardness indentations on specimen O under load of 60 kg: (a) close to the
interface and (b) at the interface.
180
■ Ni-coated fiber
0.25% 0.50% 1% 2%
Carbon fiber content
Fig. 6.3. Comparison of specific density between plain fibre reinforced composites
and Ni-coated fibre reinforced composites.
300
250
•£ ?
t/i*
200
9)
150
■
■Plain fiber
100 ■ Ni-coated fiber
o
U 50
1
0.25% 0.50% 1% 2% 5%
Carbon fiber content
Fig. 6.4. Comparison o f corrosion rate between plain fibre reinforced composites
and Ni-coated fibre reinforced composites.
181
■ Plain fiber
■ Ni-coated fiber
Fig. 6.5. Comparison of hardness between plain fibre reinforced composites and
Ni-coated fibre reinforced composites.
■Ni-coated fiber
0.25% 0.50% 1% 2%
Carbon fiber content
8999999995
IPlain fiber
59901
IN i-coated fiber
■
0.25% 0.50% 1% 2% 5%
C arb on fib er con ten t
Fig. 6.7. Comparison of wear rate between plain fibre reinforced composites and
Ni-coated fibre reinforced composites.