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Mechanical
Tribology
 Mechanical
Tribology
Materials, Characterization, and Applications

edited by
George E. Totten
G. E. Totten & Associates, LLC
Seattle, Washington, U.S.A.

Hong Liang
University of Alaska
Fairbanks, Alaska, U.S.A.

MARCEL

M A R C E L DEKKER, I N C . N E W YORK • B A S E L

D E K K E R
Transferred to Digital Printing 2005

Cover: A tribology test machinefor measuring high stress traction between a crowned roller and
a disc specimen. Courtesy of L. D. Wedeven, Wedeven Associates, Inc., Edgmont, Pennsylvania.

Although great care has been taken to provide accurate and current information, neither the
author(s) nor the publisher, nor anyone else associated with this publication, shall be liable
for any loss, damage, or liability directly or indirectly caused or alleged to be caused by this
book. The material contained herein is not intended to provide specific advice or recom-
mendations for any specific situation.

Trademark notice: Product or corporate names may be trademarks or registered trademarks

and are used only for identification and explanation without intent to infringe.

Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress.

ISBN: 0-8247-4873-5

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Neither this book nor any part may be reproduced or transmitted in any form or by any
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publisher.
Preface

There are many texts and handbooks available describing surface characterization and
various aspects of tribology. However, there has been a need for a single text that combines
these subjects and integrates them into various application technologies. This book was
developed to address this need from a thorough, mechanistic perspective.
This book is divided into two parts. Part One, “Material and Tribological Character-
ization” describes surface characterization methodologies, concentrating on the chemical
structure of surfaces (Chapter 1) and the physical structure of surfaces (Chapter 2). These
two chapters provide a thorough discussion of a wide range of surface structural char-
acterization methodologies. This discussion is followed by an extensive, in-depth treatment
of the surface properties and tribology of plastics (Chapter 3), a description of a relatively
new thermal analysis surface characterization that combines microthermal surface analysis
and atomic force microscopy (AFM) for surface structural elucidation (Chapter 4). A
rigorous discussion of the macro- and micromechanical properties of ceramics is provided
in Chapter 5.
In addition to surface structural analysis, various methodologies for examining
lubrication and wear are also discussed in Part One. These chapters include: methodologies
for characterizing and scuffing and seizure wear processes (Chapter 6), characterization of
wear mechanisms by wear mapping (Chapter 7), and the measurement and characterization
of thin film lubrication (Chapter 8).
Part Two, “Tribological Applications” focuses on selected characterization method-
ologies that include: metal cutting (Chapter 9), metal forming (Chapter 10), textile manu-
facturing (Chapter 11), and biotribology (Chapter 12). These topics were selected because
they are omitted in many texts but are vitally important manufacturing technologies,
especially as they relate to a wide range of surface modification technologies. This discussion
is followed by a topic of increasing importance in the tribological community, biocompat-
ible metals and alloys (Chapter 13). Finally, Chapter 14 discusses a relatively little known
process, epilamization barrier films, which prevent oil from spreading and creeping in lubri-
cating applications.
This book will not only be useful to material scientists and engineers, mechanical
engineers, tribologists, and lubrication engineers as an invaluable addition to their collec-
iii
iv Preface

tion, but it may also be used as a textbook for advanced undergraduate or graduate courses
in tribology and wear.
We are grateful for the vital assistance of the various international experts for their
contributions. Special thanks to the staff at Marcel Dekker, Inc., and Richard Johnson for
their patience and invaluable assistance.

George E. Tot ten

Hong Liang
Contents

Preface iii
Contributors vii

Part One Material and Tribological Characterization

1. Surface Characterization of Materials 1

Paul J. Pigram, Narelle Brack, and Peter D. Hodgson

2. Surface Characterization Techniques: An Overview 33

Kazuhisa Miyoshi

3. Mechanical Behavior of Plastics: Surface Properties and Tribology 57

Nikolai K. Myshkin and Mark I. Petrokovets

4. Visualization and Characterization of Bulk and Surface Morphology

by Microthermal Analysis and Atomic Force Microscopy 95
Scott Edwards, Nguyen Duc Tran, Maria Provatas, Namita Roy
Choudhury, and Naba Dutta

5. Macromechanics and Micromechanics of Ceramics 135

Besim Ben-Nissan, Giuseppe Pezzotti, and Wolfgang H. Muller

6. Scuffing and Seizure: Characterization and Investigation 185

Tadeusz Burakowski, Marian Szczerek, and Waldemar Tuszynski

7. Wear Mapping and Wear Characterization Methodology 235

Christina Y. H. Lim and S. C. Lim

8. Measuring Technique and Characteristics of Thin Film Lubrication

at Nanoscale 257
Jianbin Luo and Shizhu Wen
V
vi Contents

Part Two Tribological Applications

9. Tribology of Metal Cutting 307

Viktor P. Astakhov

10. Tribology in Metal Forming 347

Emile van der Heide and Dirk Jan Schipper

11. Tribology in Textile Manufacturing and Use 375

Stephen Michielsen

12. Biotribology 397

Hong Liang and Bing Shi

13. Biocompatible Metals and Alloys: Properties and Degradation

Phenomena in Biological Environments 429
Alexia W. E. Hodgson, Sannakaisa Virtanen, and Heimo Wabusseg

14. Epilamization/Barrier Films 475

Zygmunt Rymuza

Index 491
Contributors

Viktor P. Astakhov, Ph.D., Dr.Sci Astakhov Tool Service Company, Rochester Hills,
Michigan, U.S.A.

Besim Ben-Nissan, Ph.D. Department of Chemistry, University of Technology, Sydney,

Sydney, Australia

Narelle Brack, Ph.D. Department of Physics, Centre for Materials and Surface Science,
La Trobe University, Bundoora, Victoria, Australia

Tadeusz Burakowski, D.Sc., Ph.D., M.Sc. Eng. Department of Mechanical Engineering,

Radom Technical University, Radom, Poland

Namita Roy Choudhury, Ph.D. Ian Wark Research Institute, University of South Aus-
traha, Mawson Lakes, South Austraha, Australia

Naba Dutta, Ph.D. Ian Wark Research Institute, University of South Austraha, Mawson
Lakes, South Austraha, Austraha

Scott Edwards, Ph.D. Ian Wark Research Institute, University of South Austraha,
Mawson Lakes, South Australia, Australia

Alexia W. E. Hodgson, Ph.D. Department of Materials, Swiss Federal Institute of Tech-

nology, Zurich, Zurich, Switzerland

Peter D. Hodgson, Ph.D. School of Engineering and Technology, Deakin University,

Geelong, Victoria, Australia

Hong Liang, Ph.D. Department of Mechanical Engineering, University of Alaska, Fair-

banks, Fairbanks, Alaska, U.S.A.

vii
viii Contributors

Christina Y. H. Lim, Ph.D. Department of Mechanical Engineering, National University

of Singapore, Singapore

S. C. Lim, Ph.D. Department of Mechanical Engineering, National University of Singa-

pore, Singapore

Jianbin Luo, Ph.D. State Key Laboratory of Tribology, Tsinghua University, Beijing,
China

Stephen Michielsen, Ph.D. Department of Textile and Apparel Technology and Manage-
ment, College of Textiles, North Carolina State University, Raleigh, North Carohna,
U.S.A.

Kazuhisa Miyoshi, Ph.D., Dr. Eng. Department of Materials, National Aeronautics and
Space Administration, Glenn Research Center, Cleveland, Ohio, U.S.A.

Wolfgang H. Müller, Dr. rer. nat. habil. Dipl.-Phys. Technische Universität, Berlin, Berlin,
Germany

Nikolai K. Myshkin, Ph.D., D.Sc. Department of Tribology, Belarus National Academy of

Sciences, Gomel, Belarus

Mark I. Petrokovets, Ph.D., D.Sc. Department of Tribology, Belarus National Academy

of Sciences, Gomel, Belarus

Giuseppe Pezzotti, Ph.D. Department of Chemistry and Material Engineering, Kyoto

Institute of Technology, Kyoto, Japan

Paul J. Pigram, Ph.D. Department of Physics, Centre for Materials and Surface Science,
La Trobe University, Bundoora, Victoria, AustraUa

Maria Provatas, B.Sc. Ian Wark Research Institute, University of South Australia,
Mawson Lakes, South Austraha, Australia

Zygmunt Rymuza, Ph.D., D.Sc., Meng. Department of Mechatronics, Institute of Micro-

mechanics and Photonics, Warsaw University of Technology, Warsaw, Poland

Dirk Jan Schipper, Dr. ir. Department of Surface Technology and Tribology, University of
Twente, Enschede, The Netherlands

Bing Shi Department of Mechanical Engineering, University of Alaska, Fairbanks, Fair-

banks, Alaska, U.S.A.

Marian Szczerek, D.Sc., Ph.D., M.Sc. Eng. Department of Tribology, Institute for
Terotechnology, Radom, Poland

Nguyen Due Tran Ian Wark Research Institute, University of South Australia, Mawson
Lakes, South Australia, Australia
Contributors ix

Waldemar Tuszynski, Ph.D, M.Sc. Eng. Department of Tribology, Institute for Terotech-
nology, Radom, Poland

Emile van der Heide, Dr. ir. Department of Tribology, TNO Industrial Technology,
Eindhoven, The Netherlands

Sannakaisa Virtanen, Ph.D. Department of Materials, Swiss Federal Institute of Technol-

ogy, Zurich, Zurich, Switzerland

Heimo Wabusseg, Ph.D. Department of Materials, Swiss Federal Institute of Technology,

Zurich, Zurich, Switzerland

Shizhu Wen, B.Sc. State Key Laboratory of Tribology, Tsinghua University, Beijing,
China
1
Surface Characterization of Materials

Paul J. Pigram and Narelle Brack

La Trobe University, Bundoora, Victoria, Australia

Peter D. Hodgson
Deakin University, Geelong, Victoria, Australia

I INTRODUCTION
A. The Nature and Importance of Surfaces
The surface of a material is the interface between the bulk and the external phase in direct
contact with the material. The external phase may be solid, liquid, or gas. The surface of a
material may be defined in a number of ways, depending principally on the interaction being
considered. In fundamental terms, the outermost layer of atoms of the material composes
the surface. The physical and chemical behavior of these atoms, however, is strongly
influenced by atomic layers in the vicinity, to a depth of the order of several nanometers into
the bulk. In practical terms, surface modification and the application of thin films, for
example, for lubrication, creates a functional surface region of the order of 100 nm thick [1].
Controlling and characterizing the behavior of surfaces is central to physical and
chemical tribology. Friction and wear processes occur at surfaces and interfaces and are a
manifestation of the physical and chemical characteristics of the materials in question.
Surface modification is the means by which these processes are controlled or mitigated. For
example, the inherent wear properties of a material depend on parameters such as hardness,
structure at the surface, and chemical reactivity. Erosion may be influenced by preferential
surface segregation of species and processes occurring at the surface such as oxidation and
degradation. Wear behavior may be controlled by the application of hard surface films, as in
plasma nitriding, and appropriate lubrication regimes.
Analytical tribology necessarily involves the determination of the chemical, electronic,
and structural characteristics of the surface and wear debris. Modern surface analytical
techniques provide a comprehensive understanding of tribological mechanisms via spectros-
copy, imaging, and depth profiling.

B. Surface Properties and Processes Occurring at Surfaces

Surface phenomena, which determine surface properties and processes, occur on scales
ranging from tenths to hundreds of nanometers. Figure 1 summarizes the characteristic
length scales of tribological phenomena and associated materials properties.
1
2 Pigram et al.

1nm 1 um 1mm 1m
1010 109 108 107 106 105 104 103 102 10 1 100

Alcmic diameter
Oxygen molecule diameter
Monolayer films
Natural oxide films
Muttilayre films
EHDfilms
Hydrodynamic films
Aspertty Sizes
Microjunctions
Macrojunctions
Siding wear particles
Rolling wear particles
Design folerances
Engineering components

Figure 1 Surface-related phenomena in tribology and associated length scales. (From Ref. 2.)

The characterization of surface processes is also influenced by similar factors.

Bonding between atoms and adhesion, for example, involve atomic and molecular inter-
actions on a nanometer or subnanometer length scale. Similarly, the work function of a
material and the nature of electrical contact between different materials are determined by
the properties of a nanometer-scale interfacial or surface region. Wettability is a function of
surface chemistry, cleanliness, and roughness. Surfactants radically alter wettability
through the formation of molecular monolayers, bilayers, and aggregated structures at
the surface [3]. In catalytic processes, interactions involve the adsorption of individual
atoms or molecules at the surface, reaction of adsorbed species, and subsequent desorption
of products. Optical absorption by materials is also a function of the characteristics of the
surface region. It follows then that tribological phenomena, such as friction, wear, and
lubrication, are strongly affected by processes occurring on the nanometer or subnano-
meter scale.
Length or depth scales of the order of 10 nm are characteristic of important surface
chemical processes including preferential segregation of species, the formation of surface ox-
ides, and corrosion. Surface passivation is implemented on a similar scale via surface chem-
ical modification. Thin films applied to surfaces are often up to 100 nm in thickness. In the
tribology context, these may include thin lubricating layers applied to the surface to reduce
friction or modification of the surface region itself for the purpose of wear mitigation.
Surface coatings, functional films, sensors, and optical structures have thicknesses on this
scale. The distinction between a modified surface region and a discrete surface coating is
arbitrary. However, layer structures with thicknesses exceeding 100 nm may have both
surface and bulk properties in their own right, necessitating separate consideration from the
underlying substrate material.
Surface Characterization of Materials 3

C. Methodologies for Characterization

1. Overview of Characterization Strategy
A comprehensive physical and chemical surface characterization of a material requires the
selection of an appropriate set of analytical techniques and methodologies. Table 1 presents
an overview of the principal areas to be considered. It is important to recognize that no one
analytical technique will necessarily supply all the information required. The use of
techniques in combination provides a workable solution for characterization.

A robust characterization strategy can be constructed using the following stages:

1. Clear identification and definition of the issue/problem to be investigated
2. Identification of one or more possible hypotheses to be tested
3. Clear definition of the questions to be answered by the characterization and the
nature of the information to be obtained; for example, identification of an un-
known material via chemical and molecular surface spectroscopy, or determi-
nation of a coating layer profile via elemental depth profiling
4. Assignment of one or more analytical techniques to each question to generate
objective data by the most reliable and efficient route
5. Choice of experimental methodologies and acquisition of quality data, sufficient
to address the analytical questions. Data processing, interpretation, and
integration of results from different techniques
6. Evaluation of data and proposal of a solution or answer to the question and
testing of the validity of the outcome. Confirmation of the reproducibility of the
results and consistency of the findings from different techniques
7. Presentation of the outcome
This strategy has been adapted from a recently published, comprehensive work on surface
and interface analysis edited by Riviere and Myhra [4]. The work contains an extended
discussion of characterization strategy, properties of surface analytical techniques and case
studies and is recommended for readers seeking further information.

Table : Physical and Chemical Characteristics of

Materials and Analytical Methods

Physical characteristics Chemical characteristics

Structure Elemental composition

Morphology, topography • Spectroscopy
Mechanical properties • Imaging
Stress • Depth profiling
Chemical composition
• Spectroscopy
• Imaging
• Depth profiling
Molecular composition
• Spectroscopy
• Imaging
• Depth profiling
4 Pigram et al.

Table 2 Techniques Frequently Deployed in Characterizing the Elemental Composition

of Surfaces

Technique Properties

AES Description: An electron beam technique with elemental information obtained

by analysis of electron-induced Auger secondary electrons emitted from the
sample surface. Can detect elements from lithium in the periodic table.
Overlaying secondary electron micrographs and elemental images can be
obtained, allowing compositional analysis of topographic features. AES is
a key surface analytical technique for conducting and semiconducting
samples.
Spatial resolution: Of the order of 10 nm in a modern instrument with a field
emission electron gun. Resolution is influenced by sample features, with
rough and particulate samples returning lower-resolution images.
Depth of analysis: Of the order of 5 nm, determined by inelastic scattering of
emerging Auger electrons.
Limitations: High surface sensitivity rules out the use of conducting overlayers
on insulating samples to mitigate surface charging. Insulating samples
cannot be analyzed.
XPS Description: A photoelectron technique with elemental information obtained
by analysis of x-ray excited photoelectrons emitted from the sample
surface. Can detect elements from lithium in the periodic table. Charge
neutralization allows high-resolution spectra to be obtained from insulators
using a monochromatic x-ray source. XPS is a key surface analytical
technique for all vacuum compatible sample types.
Spatial resolution: Imaging instruments can achieve resolutions of the order
of 1 m. Resolution is influenced by sample features, with rough and
particulate samples returning lower-resolution images.
Depth of analysis: Of the order of 5 nm, determined by inelastic
scattering of emerging photoelectrons.
Limitations: Elemental detection sensitivity is limited to approximately 0.5
at.%
SIMS Description: An ion beam technique with elemental information obtained y the
massanalysis of secondary ions sputtered from the sample surface by a
primary ion beam or pulse. Mass spectra are commonly generated using
quadrupole, magnetic sector, and time-of-flight systems. Can detect all mass
fragments; this capability is particularly useful for light elements such
as hydrogen and for heavy clusters. Charge neutralization in modern
instruments allows high-resolution spectra to be obtained from insulators.
Spatial resolution: Imaging instruments can achieve resolutions better than
100 nm. Resolution is influenced by sample features, with rough and
particulate samples returning lower-resolution images.
Depth of analysis: Ranges from less than one monolayer in static SIMS
analyses to 10 m and greater in depth profiling tasks.
Limitations: SIMS produces mass spectra, and the data obtained are often
information-rich, requiring substantial analysis and interpretation. While
high mass resolution techniques such as TOF-SIMS facilitate identification
of elemental species, peak overlaps or interferences are a serious
consideration in identifying unknown materials.
Surface Characterization of Materials 5

2. Elemental Composition
Surface characterization of materials in any field starts with the elemental composition
of the surface region. The selection of a technique or techniques depends critically on the
nature of the information required. Issues such as depth of analysis or surface sensitivity are
most important in the investigation of thin film deposition, adsorption, delamination, and
segregation of species in multicomponent systems. Table 2 shows a selection of techniques
deployed in the elemental characterization of surfaces. The basic properties of each tech-
nique are listed with comments on experimental limitations.

3. Chemical and Molecular Information

Processes occurring at surfaces frequently involve chemical reactions, for example, corro-
sion, polymerization, bonding and adhesion, and the participation of a range of species with
similar elemental constituents but different chemical forms and structures. The ability to
distinguish different chemical forms of the same element and to gain information about the
structure of complex molecular species is critical in developing a complete understanding of
problems and processes. These issues arise routinely in the characterization of polymers, and
complex organic systems including lubricants and biomaterials. Distinguishing between the
different chemical states of carbon, for example, can be achieved using x-ray photoelectron
spectroscopy (XPS). Important complementary structural information is gained by analyz-
ing mass spectra from time-of-flight secondary ion mass spectrometry (TOF-SIMS). Table 3
shows a selection of techniques deployed in the chemical and molecular characterization of
surfaces. As in the previous section, the basic properties and limitations of each technique
are hsted.

4. Further Techniques for Surface and Near-Surface Characterization

The surface characterization techniques tabulated above are in common use and are well
suited for the investigation of surface-related phenomena associated with tribology. There
are many other surface characterization techniques available that are used for specific
sample types, used in studies of the fundamental electronic and structural properties of
materials, and emerging as valuable routine analytical tools. A selection of these techniques
is summarized below.
Important fundamental surface science techniques include those based around
diffraction, vibrational phenomena, and photoelectron emission. Low-energy electron
diffraction (LEED) and reflection high-energy electron diffraction (RHEED) are ultrahigh
vacuum techniques used for probing the structural properties of the outermost layers of
crystalline surfaces. For example, growing semiconductor layers can be monitored using
RHEED; LEED provides information on adsorption sites on the surface of model catalyst
materials and on the mechanisms of thin film growth at the atomic scale.
Ultraviolet photoelectron spectroscopy (UPS) is a photoelectron technique that
probes the valence band typically using 21.2 eV radiation (He I) generated by a helium
discharge source. Wavelengths between 8 and 45 eV are possible using different gases and
conditions in the discharge source. Figure 2(a) and (b) shows schematic descriptions of the
experimental arrangement for UPS and the photoelectron emission process, respectively.
UPS is generally used to investigate bonding interactions and the electronic structure of
crystalline materials. UPS is not deployed in imaging mode; the analysis area is defined by
the spot size of the photon source and electron energy analyzer acceptance area. The analysis
6 Pigram et al.

Table 3 Techniques Frequently Deployed in Characterizing the Chemical and Molecular

Composition of Surfaces

Technique Properties

AES Description: As per Sec. I.C.2. Peak positions in Auger electron

spectra are influenced by the chemical environment of the atom
in question. Analysis of these chemical shifts has not received
as extensive treatment as chemical shifts in XPS spectra. Useful
information, however, can be obtained about carbon chemical
states, metals and their corresponding oxides, and resonance
phenomena. Data interpretation may be complicated by the
three step Auger electron emission process. Data reduction
tools such as principal component analysis are now available
to aid the interpretation of more complex spectra [5].
Spatial resolution: As per Sec. I.C.2.
Depth of analysis: As per Sec. I.C.2.
Limitations: General lack of availability of reference works,
which collate and validate results from multiple sources.
XPS Description: As per Sec. I.C.2. XPS is an excellent tool for
surface chemical analysis. Chemical shifts in the elemental
peaks are often easy to interpret, with many reference works
and software packages available to aid the process.
Spatial resolution: As per Sec. I.C.2. Note that chemical shifts
are difficult to image adequately when component peaks
are closely spaced and low in intensity in comparison
with the overall peak envelope.
Depth of analysis: As per Sec. I.C.2. Angle-dependent XPS,
the acquisition of a series of spectra as a function of electron
emission angle, allows higher surface sensitivity and is well
suited to the analysis of ultrathin overlayers.
Limitations: As per Sec. I.C.2. XPS provides information
on chemical or oxidation state; analysis of materials, for
example, polymers, with identical bond types but different
bonding arrangements or structures may require input from
other techniques such as SIMS and infrared spectroscopy.
SIMS Description: As per Sec. I.C.2. TOF-SIMS is well established
as the principal technique for the molecular characterization
of surfaces. Mass spectra can be obtained with high mass
resolution and high mass range. The technique is widely
applied in the investigation of materials such as polymers,
biomaterials, pharmaceuticals, lubrication systems, and
semiconductors.
Spatial resolution: As per Sec. I.C.2.
Depth of analysis: As per Sec. I.C.2.
Limitations: As per Sec. I.C.2. While TOF-SIMS has a high
mass range, the ionization of larger molecules often results
in the production of many smaller fragment ions. Chemical
matrices are sometimes employed to enhance the yield of
high mass fragments. Alternative ion sources are also employed
for similar purposes.
Surface Characterization of Materials 7

Table 3 Continued
Technique Properties

Infrared spectroscopy Description: A widely used vibrational spectroscopy with a

and imaging number of specific adaptations for surface characterization.
The attenuated total reflection (ATR) mode of operation
provides enhanced surface sensitivity under ambient conditions,
using a prism in intimate contact with the sample to achieve
multiple bounces of the infrared beam along the sample surface.
Adsorbate studies may be undertaken using reflection-absorption
infrared spectroscopy (RAIRS) with the sample housed in a
controlled-environment cell or, in some instances, an ultrahigh
vacuum chamber.
Modern instruments use a Fourier transform signal detection
strategy, hence the acronym, FTIR.
Spatial resolution: FTIR microscopes achieve spatial resolutions
of the order of 10-20 m. The synchrotron-based infrared
spectromicroscopy variant of this technique achieves spatial
resolutions an order of magnitude better than lab-based
instruments due principally to a much brighter photon source.
Depth of analysis: The sampling depth in an ATR experiment
depends on the prism material and is typically in the range of
0.5-2 m.
Limitations: Sampling depth is suitable for thin films on surfaces;
thinner features such as adsorbed layers are often difficult to
analyze adequately due to signal-to-noise constraints.

area is typically several millimeters in diameter. Synchrotron implementations of this

technique use probe sizes of the order of micrometers at modern facilities. UPS is extremely
surface sensitive with a depth of analysis of the order of 1 nm, determined by inelastic
scattering of emerging photoelectrons. Hence, excellent vacuum conditions are required to
avoid surface contamination.
Synchrotron-based photoelectron spectroscopy provides additional opportunities for
characterizing the electronic properties of crystalline materials via angle-resolved photo-
electron spectroscopy and determining surface structure and the adsorption sites of
molecules on surfaces via photoelectron diffraction. Both are variants of laboratory-based
techniques that take advantage of the unique properties of synchrotron radiation including
a high-intensity, focused photon source and the ability to use a high-quality monochromator
to sweep continuously through a range of photon energies. The latter allows surface
sensitivity to be maximized, greatly enhances spectral resolution, and provides the oppor-
tunity for new types of experiments.
Synchrotron radiation XPS has the same general properties as laboratory-based XPS,
except use of a synchrotron photon source allows any wavelength to be selected as the probe.
Synchrotron beam lines can be designed to supply photons with very narrow energy spread,
thus allowing higher-resolution spectra to be acquired. Photon line width is of critical im-
portance when analyzing closely spaced chemical component peaks. The wavelength of the
incident radiation may be adjusted to achieve very high surface sensitivity by minimizing the
inelastic mean free path of emerging photoelectrons, detection of higher-energy photo-
8 Pigram et al.

(a) (b) ejected photoelectron

electron energy analyser

vacuum
incident
discharge lamp photon
Fermi level
detector valence band
2p
sample 2s

1s
ultrahigh vacuum chamber

Figure 2 (a) Experimental arrangement for UPS featuring a hemispherical sector analyzer; (b)
schematic description of the photoelectron emission process.

electron peaks inaccessible using laboratory x-ray sources, and optimization of detection
sensitivity by maximizing photoionization cross sections.
X-ray absorption spectroscopy (XAS) describes a group of synchrotron-based
techniques, which provide unique information about the surface structural and chemical
properties of materials. Extended x-ray absorption fine structure (EXAFS) is a technique
that studies the oscillatory variation in x-ray absorption with photon energy beyond the
absorption edge for a given element. Analysis of these oscillations allows structural
information to be extracted, in particular, the local order around individual types of atoms
[6]. Fine structure is also observed in the x-ray absorption spectrum in the region
immediately adjacent to the absorption edge, a narrow zone of approximately 50 eV in
width. This phenomenon is known as near edge x-ray absorption fine structure (NEXAFS).*
The near-edge structure is a function of the distribution of antibonding orbitals; hence
chemical shifts are observed. Chemical states at the surface of materials can be studied in a
similar manner to XPS. Linear polarization of the synchrotron light allows studies of
molecular orientation on surfaces to be undertaken. NEXAFS theory and appHcations are
comprehensively discussed in a recent book by Stöhr [7].
A synchrotron-based technique known as photoemission electron microscopy
(PEEM) is emerging as a most useful analytical tool. PEEM produces images of electrons
emitted from surfaces with a spatial resolution in some specialized instruments as small as a
few nanometers but generally of the order of a hundred nanometers, far higher spatial
resolution than any standard photoelectron spectrometer. The microscope can be operated
as a detector for NEXAFS experiments, thus producing surface chemical images with
submicrometer spatial resolution. High operating voltages within the microscope result in
some sample charging issues and difficulties analyzing insulators.
Ion scattering spectroscopy (ISS) is an ion beam technique with elemental information
obtained by analysis of primary ions inelastically scattered from atoms in the sample surface.
A useful surface analytical technique in principle, ISS finds most applications in funda-
mental studies of surface structure and as a complement to Auger electron spectroscopy

* This phenomenon is also described as x-ray absorption near edge structure (XANES).
Surface Characterization of Materials 9

(AES) [8]. ISS is used in macroscopic analyses only in laboratory-based instruments but is
highly surface sensitive, influenced by the submonolayer presence of adsorbates on the
surface. ISS is experimentally more complex than competing techniques such as XPS, AES,
and SIMS.
The surface wettability of liquids on solids is of central importance in a range of
industrial processes including application of coatings, adhesion and release issues, disper-
sion, and lubrication. Contact angle analyses provide a direct measure of the wetting
properties of a surface and hence an indirect measure of the surface chemical composition.
Surface energy and its relationship to surface functionalization can be investigated. Contact
angle measurements are most useful when used in conjunction with techniques such as XPS
and TOF-SIMS. Some instruments have mapping capability with a spatial resolution of the
order of a few millimeters. The contact angle is very sensitive to the outermost monolayer on
flat surfaces, surface roughness, and chemical heterogeneity. Although it does not provide a
direct chemical or molecular characterization, it is very valuable used in combination with
other techniques. Figure 3(a) and (b) shows a typical experimental configuration for contact
angle measurement using sessile drops and a schematic definition of contact angle and the
associated interfacial tensions.
Related techniques include the measurements of dynamic contact angle, surface
tension, and interfacial tension using the Du Noüy ring method, pendant drop method,
drop volume method, and Wilhelmy plate method. The reader is referred to Ref. 9 for a
comprehensive coverage of these areas and others.
Scanning probe microscopies (SPM) are built around the interaction between a fine tip
and a surface. Several groups of techniques exist, the dominant groups being electron
tunneUng techniques and tip-surface force techniques. The scanning tunneling microscope
(STM) was the first instrument to be demonstrated, emerging from the IBM Zurich research
laboratories in 1982 [10]. STM and a related technique, scanning tunneUng spectroscopy
(STS), rely on positioning a sharp tip in close proximity to the surface of interest, applying
a bias voltage and measuring an electron tunneling current. Scanning the tip produces
images related to surface topography and surface electronic properties with atomic res-
olution. Tips require very small radii of curvature to be effective and are generally prepared
using electrochemical etching of tungsten or platinum-iridium wires. Figure 4(a) and (b)

(a) (b)
dosing
syringe
LV

filtered light vapour

CCD camera source
liquid

sv SL
solid
sample
enclosure

Figure 3 (a) Schematic diagram of a typical contact angle measuring instrument; (b) sessile drop
showing solid, liquid, and vapor phases, contact angle, , and interfacial tensions, sv, SL, and LV.
10 Pigram et al.

(a) (b)
scanning, signal detection,
& feedback electronics

tip
current
tip following
corrugations

tip height
scanning via
feedback
piezoelectric tube
tip
sample surface
sample

Figure 4 (a) Schematic diagram of STM operating mode; (b) a typical configuration for control
systems required for operation and data acquisition.

shows schematic descriptions of the mode of operation and control systems of the STM,
respectively.
The atomic force microscope (AFM) followed in 1986 [11]. AFM relies on positioning
a micromachined assembly incorporating a lever arm and sharp tip in contact with the
surface or in close proximity to the surface. Scanning the tip across the surface produces
images related to topography, friction, and a variety of other surface properties depending
on tip and instrument configuration. Soft substrates may be analyzed by tapping rather than
dragging the tip during the scan.
The ability STM and AFM to image surfaces with atomic-scale resolution under
ambient conditions and under ultrahigh vacuum is a defining feature of this group of
techniques. In subsequent years, many variants of these two instruments have been devised
allowing spectroscopy and high-resolution studies of surface properties such as friction,
magnetic force, electrochemical behavior, and electrical conductance. There is extensive
literature available on scanning probe microscopies; the reader is referred to the references
for several starting points [12].

II. PHYSICAL PROPERTIES AND CHARACTERIZATION

A. Topography and Physical Characterization
1. Topography of Surfaces
For most applications of surface engineering, it is extremely important to be able to quantify
the physical shape of the surface. In metal-forming operations, the roughness of both the
stock and tool will determine the friction and wear behavior and will influence the
effectiveness of lubrication. For example, in some cold forging operations, the wire is drawn
immediately before forging. In this case, the roughness of the incoming rod must be suffi-
cient to allow effective bonding between the surface and the lubricant so that some of the
lubricant is still present on the surface after the draw for the subsequent forging operation.
In wear situations, however, the topography of the hard tool surface can damage the sur-
face of the product.
Surface Characterization of Materials 11

Hence, the main aim is to be able to understand and quantify the topography,
generally referred to as the roughness, of the surface and to then relate this to the behavior
of interest. Historically the topography characterization was mainly performed in only one
direction (2-D when considering the depth or height of the surface along that line), but
increasingly 3-D techniques are being used.
a. 2-D Roughness Measurements. The surface roughness or surface texture relates
to the change in height, or profile, of the surface along al i n eon the surface, relative to some
ordinate. Typically, this is measured using a stylus moved across the surface in a straight
line. The stylus is free to move perpendicular to the surface. The accuracy of this reading
depends on the stylus run, or cut-off length. The smoother the surface, then the shorter the
cut-off length required for an accurate measurement. More recently, laser techniques have
also been used to provide this information. It is also possible to have portable devices that
can be used in the field to provide in-service measurements of the evolving roughness.
The most common measure of surface roughness is Ra which is the average height of
peaks over a given length [13]. The typical measurement length is generally restricted to a few
millimeters, and hence it is important to realize that this is only a local measure and a number
of measurements at different parts of the surface are required to obtain a meaningful
representation of the average surface profile.
While Ra the most common measure of surface roughness, it has been found that
other parameters may be more appropriate measures of the surface topography. These
include:

Height parameters'.Rmax, the largest individual roughness depth; Rt, the difference
between the highest and lowest measurements; Rq, the geometric mean of all
values.
Waviness parameters: W, used to characterize the spacing of the peaks.
Skewness: Rsk, measures the symmetry of the profile about the mean value and is
used to distinguish between shape profiles with the same Ra,.
Slope and curvature: these are hybrid parameters that combine aspects of height and
wavelength.
The simple Ra measure for height displacements over a length of measure / is given
by:
1 ∫1
Ra y dx
l 0

where Ra can be simply viewed as the centerline average or arithmetical average and
represents a line drawn through the profile so that the area filled with material equals that
unfilled. A variation on this is the root mean square or Rq:

1 0.5
1 2
R q,rms X dx
l 0

These parameters are the most common in surface engineering studies. An example of the
evolving surface roughness for a range of tool coatings is shown in Fig. 5. Here the uncoated
tool shows a rapid increase in roughness as the number of parts stamped increases.
Experience in the plant had shown that a critical roughness value of 4.5 |im was associated
with galling and scoring. The variable coatings altered the rate of increase in R^. These
measurements were performed in the production environment using a portable device.
12 Pigram et al.

7
Smooth
6 Hard-Cr
Uncoated
Rough
5 Uncoated
Critical Ra
Ra (microns)

4
CrCN
3

2
TiCN

0
0 5000 10000 15000 20000
No. of Cycles

Figure 5 Variation in tool roughness with part numbers during the stamping of heavy channels,
for different tool coatings. (From Ref 14.)

b. 3-D Roughness Measurements. The roughness along a line is obviously a limited

representation of the surface morphology. Many surfaces are not random and exhibit
different roughness characteristics when measurements are normal to each other. For
example, in metalworking operations the roughness in the line of metal flow will be quite
different to that normal to the flow direction. In other cases, the manufacturing operations
used to create the surface will either deliberately, or as a by-product, give quite different
surface textures in different directions.
Early methods used multiple stylus measurements of surfaces, with the data then
combined to reconstruct the surface. One issue here is in defining the reference datum for
these measurements [15]. However, with increasing use of computers, electronics, lasers, and
other technologies, it is now relatively simple to create 3-D surface maps.
Recent major developments, particularly at nanometer spatial resolution for 3-D
measurements, have been the scanning tunneUng microscope and the atomic force micro-
scope, discussed in Sec. I.C.4. Between these and the conventional stylus method, there are
the focus detection systems and those based on interferometry. The focus system uses a laser
beam that is projected onto the surface and then the lens is adjusted in the height direction
with the surface as the focal point. The movement of the lens is then the record of the height
change. A schematic diagram of such a system is given in Fig. 6.
These techniques now allow the ready construction of 3-D maps of the surface
topography of a range of materials and roughnesses. Figure 7 summarizes the relative use
of various techniques in providing roughness information as a function of the spatial
distance over which they can measure.
Stout and Blunt [15-17] have attempted to define a set of appropriate 3-D roughness
parameters (Table 4). Many of these parameters are similar to the 2-D parameters above,
although some are designed to provide information related to the anisotropy of the surface
texture, Str is specifically related to the texture anisotropy and is based on the ratio of fastest
to slowest decay in the autocorrelation function of the profile in aU directions. Stout has
stated that values less than 0.3 indicate strong anisotropy or texture, whereas values greater
Surface Characterization of Materials 13

Laser Diode

Beamsplitter

Collimator

Focus Detector

Piezo Driven
Moving Lens

Displacement
pick-up
Specimen

Figure 6 Schematic representation of laser focus instrument for 3-D topography measurements.

Stylus
mm

F ocus
SEM
m
Vertical

Pt
nm
AFM
STM
P
PI Pr Interferometer
pm.
Pb

nm m mm m
Lateral

Figure 7 Vertical and lateral resolution of different 3-D profile techniques. (From Ref. 15.)
14 Pigram et al.

Table 4 3-D Roughness Parameters

Amplitude parameters
Sq Root-mean square deviation of the surface
Sz Ten point height of the surface
Ssk Skewness of the surface
Sku Kurtosis of the surface
Spatial parameters
Sds Density of summits of the surface
Str Texture aspect ratio of the surface
Std Texture direction of the surface
Hybrid parameters
Sq Root-mean square slope of the surface
Ssc Arithmetic mean summit of the surface
Sdr Developed surface area ratio
Functional parameters characterizing bearing and oil-retention properties
Sbi Surface bearing index
Sci Core oil-retention index
Svi Valley oil-retention index
Source: Ref. 16.

than 0.5 suggest a high degree of isotropy. The actual direction of the texture is represented
by S td ; this is important only for Str. values below 0.3.
Nearly all studies of coating technologies utilize topography measures. Most still use
the simple measures of Ra and R q , partly because of a lack of systematic work to correlate the
other parameters with behavior. Increasingly, though, there is a need to use more complex
parameters for the development of surfaces, with the simple Ra measure more appropriate
for quality control or a field measurement of the change in topography.

2. Mechanical Characterization
Understanding of the behavior of the component under load requires knowledge of the
modulus of elasticity, the yield stress, and the ultimate tensile strength. Although the
thickness of the coating may often be very small compared with the bulk and, hence, is not
expected to affect the overall average properties of the component, it will have a major
impact on the local deformation behavior. Obtaining accurate and meaningful information
about the actual tensile behavior of the coating is extremely difficult. More often, the
material is simply characterized by the hardness, although new techniques such as nano-
hardness allow more information than just a single average hardness to be obtained. The
strength between the coating and the substructure is also an important mechanical
characterization of the parameter, while the friction and wear behavior have also led to
the development of a range of tests.
a. Equivalent Tensile Properties. The term “equivalent” is used here to show that
the aim of these techniques is to obtain information that would be typically measured in a
tensile test of the substrate. It is possible to perform simple tensile tests of some coating
materials. This is more common for thicker coatings that are not alloyed with the substrate.
In this case, a coating can be made separately from the component and then tested.
However, even this is extremely difficult and subject to a number of sources of error. The
coating has to be free of defects, as this will cause early failure. It must also have uniform
thickness and low levels of residual stress [18].
Surface Characterization of Materials 15

The modulus has been measured by beam bending [19]. This involves using micro-
machining techniques to remove the layers around and below a small beam of the coating.
By using a sensitive probe, such as a nanoindentor tip, it is possible to measure the deflection
of the beam as a function of the applied load and to then use standard equations to
determine the modulus. It should also be possible to use this method to measure the yield
point, as in bending this is determined from the departure from the linear elastic behavior.
However, this is very difficult and prone to a number of sources of error. Again, the
uniformity of the beam and removal of stress concentration at the coating/substructure joint
are issues.
An alternative beam method has recently been applied to determine the elastic
modulus as a function of temperature in surface coatings for hot forging dies [20]. Here
the deflection of the beam due to thermal stresses was used. The method involved heating
samples 0.25 mm thick, 8 mm wide, and 80 mm long to temperatures from room temperature
to 400°C. The strip was assumed to behave as a composite plate with known thermal
expansion values for each layer (valid only for a discrete coating on a substrate); the elastic
modulus of the substrate was also known. The elastic modulus in the surface layer was
obtained by following the deflection during heating. The values of the modulus appeared to
be close to those given by other workers for similar coatings, even though the thickness of the
coating was relatively small in comparison with the thickness of the beam (e.g., 7 jim
anodized layer on 250 m H13 tool steel).
b. Hardness. The above methods are either extremely difficult or may have limited
applicability to coating behavior. By far the most common technique to gain information
relating to the likely mechanical behavior of a surface is the hardness test. Increased hardness
of a surface will generally give greater wear resistance, as expressed by Archard's law:
W k PI H

where W is the volume of material removed by wear, l is the sliding distance, P is the load, H is
the hardness, and A: is a constant that is a function of shape and material. This is a simplistic
relationship, but it did form the basis for many early developments in wear-resistant surface
treatments.
Hardness tests involve pushing a hard indentor into the surface of a sample to measure
resistance to plastic deformation. For coatings, the preferred hardness tests are the Vickers
and Knoop tests. The Vickers hardness test uses a diamond indentor in the shape of a square
pyramid. The hardness, HV p , is given by:

HV p 1.854P d 2

where P is the load (kg) and d is the measured indentation diagonal (mm).
The Knoop test uses a blunt, elongated indentor, which can reduce the tendency for
cracking of the coating. The test can be used to highlight any anisotropy in the coating and is
useful for testing narrow grains or thin layers. In this case, the hardness, HKp, is given by:

HK p 14.2P d 2

although in this case d refers to the length of the longer diagonal.

For all hardness tests of coatings or other surface treatments the main issue is whether
the hardness measurement reflects the properties of the layer of interest alone or whether it is
also affected by subsurface layers or the bulk sample. Figure 8 shows the Vickers hardness of
a hard chrome layer on a die as a function of coating thickness for two different loads. Even
for the thickest coating, the 2.5 kg load is still increasing in hardness toward the value
16 Pigram et al.

1400
1200
Hardness (HV)

1000
800
600
400
Haixlness(2.5kgload)
200 Hardness (0.5 kg load)
0
0 20 40 60 80 100 120
Coating thickness (microns)

Figure 8 Hardness as a function of coating thickness at 2.5 and 0.5 kg indenter loads.

obtained with the 0.5 kg load. Hence, in the case of the higher load the interaction volume is
greater than the coating thickness.
The influence of the substrate on the measured properties of a coating is reduced as the
size of the indent relative to the coating is decreased. ASTM standard E 384 requires that the
depth of indentation must not exceed 10% of the sample thickness (in this case the coating).
This has led to the adoption of micro- and nanohardness tests for thin coatings. These test
methods reduce the depth of the indents to just a few micrometers or nanometers. In the case
of nanoindentations, the size of the indents is too small to be determined optically so
hardness is quantified by measuring force and displacement of the indenter during the test.
This means that there is no direct conversion between hardness values determined by
nanoindentation and those measured by conventional hardness tests where the permanent
indent is measured optically.
As mentioned earlier, one problem with thin coatings is the determination of
mechanical properties. This is a result of the samples being much smaller than those used
in conventional mechanical tests. The coatings are not always able to be removed from the
substrate without great difficulty. Force and displacement can be measured continuously as
nanoindentation is carried out. These data can be used to determine material properties such
as hardness, elastic modulus, and stress-strain curves [21]. Figure 9 shows a schematic
diagram of the load penetration curve under typical test conditions for a pointed indentor.
The total displacement is given by the sum of the elastic and plastic components, although
allowance also needs to be made for the machine compliance and the initial penetration
required before the force exceeds the background noise level. There are various assumptions
required regarding the indentor shape when determining the effective elastic modulus, which
are covered by Swain [22].
This technique has been used to determine the elastic modulus of laser-deposited
composite boride coatings on steel [23].
Nanoindentation is also used for measurement of time-dependent properties such as
stress relaxation and creep of thin films. If the deformation of the material is to be measured, it
is important to make sure that the time taken for indentation is short enough so that the results
are not affected by material flow; that is, the loading rate is much faster than the creep rate.
Another advantage of using smaller indents and lighter loads is that cracking of the
coating can be avoided or reduced. Thin, brittle coatings may crack or delaminate during
Surface Characterization of Materials 17

Total penetration
h
t
Fm
Elastic penetration he

Elastic/plastic penetration
h
P
Indenting load

Residual penetration
on unloading
hr
Loading
ng
dai
o
ni
U
0
0
Penetration

Figure 9 Schematic force-penetration curve obtained in nanohardness or other continuous

hardness measurement test. (From Ref. 22.)

indentation, particularly when the substrate is soft. While the adhesion tests described in the
next section are more popular, delamination during indentation has been used to assess
adhesion of a coating to a substrate, particularly in the case of hard films on metallic
substrates. The mechanics of the delamination have recently been modeled and the effective
adhesion energy determined for diamond-like carbon films on tool steel [24].
c. Adherence Tests. In the previous section it was shown how the hardness test often
provides some information related to the adhesion of the coating. However, the hardness
test is not designed for this purpose and the direction of loading is not that which commonly
will cause adhesion problems. Bull [25] has suggested that the experimental adhesion
strength (EA) is related to the basic adhesion strength (BA), but that there are also other
extrinsic factors related to the test conditions and intrinsic properties, such as the physical
properties mentioned above that will affect this measure.
The scratch test is the most widely used for hard coatings. The concept is simple and
relies on a hard indenter being dragged across the surface under an increasing load. For thin
coatings (less than approx. 20 m) the indentor is dragged across the coated surface. The
load can be changed during a test or between individual tests to determine the critical load
for delamination of the coating. At loads less than the critical load, the coating has damage
such as scratching, plastic deformation, and chipping of the coating. At the critical load,
delamination will occur and the coating will be removed from the substrate. The scratch test,
like most mechanical tests, is most useful for predicting performance when the types of
failure and the loading are similar to those occurring during the test, for example, coatings
that experience mild abrasive wear in-service.
A schematic description of the force trace obtained from a scratch test is given in
Fig. 10. Here there are two critical changes in the profile at C1T and C2T. These two
measurements were used in a round-robin test of equipment and gave consistent results
between the different laboratories. C1T represents the first significant change in force, while
C2T is the first substantial change in the tangential force gradient.
For thicker films such as plasma-sprayed coatings, a polished cross section is used.
In this case, a fixed load is used and the indentor travels toward the substrate/coating
18 Pigram et al.

Tangential
Force

LC2T

C1T

Sliding Distance

Figure 10 Schematic description of the results from a scratch test. (From Ref. 26.)

interface from the substrate. The load is increased between successive scratches until, at
a critical load, the indentor pulls the coating from the substrate, creating an interfacial
crack (Fig. 11).
d. Friction and Wear. The above sections have dealt largely with properties that
have a simple physical meaning. There are other physical characteristics that are not true
material properties per se, but which depend on the actual service conditions. Of particular
relevance to surface-treated materials are the friction and wear. The friction behavior is a
function of a number of parameters such as load, sHding velocity, geometry, and the nature

Crack Diameter
L
Scratch
Direction

Track
Substrate

Coating
Cone

Figure 11 Schematic description of scratch adhesion test for thick coatings. (From Ref. 25.)
Surface Characterization of Materials 19

of the object the surface is in contact with, including the lubricant. The same is also true
for wear. Hence, there are now myriads of tests that are used to quantify these parameters.
Even for one simple deformation process there may be many tests used. For example, in
sheet metal forming there are tests to handle the different types of deformation conditions
that may exist around the die, from the flat faced friction test for the blankholder [27] to the
drawbead simulator for the drawbeads [28] to actual draw tests for other regions [27,29].
The objectives of the test need to be clearly understood before choosing one test
over another. In the case of friction tests there is an increasing need to be able to provide
accurate friction values for numerical modeling. The aim then is to obtain a very accurate
and hence representative test where the full range of inputs can be examined and the speed
of testing is not an issue because only a few tests will be performed for a given condition.
However, wear tests are often designed to provide accelerated information so that materials
or other factors can be ranked. Here months or years of service must be simulated in hours
or days.
Under deformation conditions the friction coefficient [30] is a function of the
following:

• Workpiece
• Tool
• Lubricant
• Process
• Surroundings

One way to group metal forming focused tribology tests is given in Table 5. These cover both
friction and wear tests. They have been divided into process and simulative tests, where the
former refers to tests where the basic process conditions are maintained, whereas in the latter
case there can be marked deviations from the actual process kinematics. In each case, it is
possible to have direct tests where the friction parameter is actually measured, or indirect
tests where another parameter is measured and then related back to the friction parameter,
often through modeling. An example of this is force in compression, where the measured
load is converted into a force and then finite element methods, or analytical modeling, is
used to predict the force as a function of the friction coefficient. From this prediction the
“average”friction coefficient is obtained, assuming all other parameters in the model are
accurately known.
Obviously, the process tests are the most representative of actual service conditions.
However, it is also clear that it would be extremely difficult and time-consuming to evaluate

Table 5 Grouping of Tribology Tests

Process tests Simulative tests

A. Upsetting G. Global plastic deformation

B. Forging H. Local plastic deformation
C. Extrusion I. Elastic deformation
D. Drawing of rod/wire
E. Rolling
F. Drawing of sheet/strip. Ironing
Source: Ref. 30.
20 Pigram et al.

the full range of parameters that should be considered when developing a new coating. For
example, there are often strong interactions between a number of parameters so that it is not
a simple case of testing for an effect in isolation from other changes. One example is that the
effectiveness of a lubricant can be a function of the load, the surface roughness, the
composition of the surface(s) and the temperature. Hence, it is more common to use simu-
lative tests in the initial development stage and then to use a cut-down number of process
tests for final validation and performance ranking. The actual comparison between
laboratory and field performance is still quite limited [30], although the general rankings
and trends are maintained where appropriate simulative tests have been used.
The most common simulative test for wear is the pin on disc test (Fig. 12), particularly
for basic wear information of surface-treated metals [31,32]. This is suitable for simulating
sliding wear conditions and the load and environment conditions are easily adjusted. The
test is relatively simple and widely used in the surface engineering industry. Other variants
that are commonly used to evaluate coatings are the ball on disc and the pin on ring (or
plate). There are some issues with this test that limit the application to bulk forming
operations. In a forging or rolling operation, for example, the tool is constantly exposed to
fresh material that is being plastically deformed during the operation. In the pin on disc test,
this is not the case and there is only elastic loading of the tool and workpiece. However, for
simple sliding conditions this test and the various modifications can provide a quick ranking.
It should be noted that there have been different results depending on which material was the
pin or the disc [31]. For abrasive wear, there are also a number of simple tests and associated
issues [33].
The measurement of wear can be as simple as following weight loss, through to more
precise measurements of the topography, depth of wear, or changes in other features, such as
the acoustic emission during testing.

3. Secondary Electron Microscopy

In scanning electron microscopy (SEM), a focused electron beam is scanned across the
surface of a sample resulting in the emission and/or reflection of electrons and x-rays. From
the collection of these radiations, it is possible to gain information on surface topography,
composition, phase constitution, and crystallographic orientation; all of which are of

Pin on Disc

Figure 12 Schematic description of the pin on disc tribology test.

Surface Characterization of Materials 21

considerable interest to the surface scientist. In many instances, the measurements are
conveniently plotted as images in gray scale or color contrast that are readily converted into
appropriate numerical quantities by either raw data or image analysis.
The radiation emitted from the material can be traced to an interaction volume
immediately beneath the point of incidence of the narrow (1-100 nm) electron beam. The
size of this volume determines the resolution and is characteristic of the radiation type.
Figure 13 shows a schematic diagram of the relative interaction volumes for the various
radiations. The smallest volume examinable by standard SEM equipment is that from
which secondary electrons emanate while characteristic x-rays are emitted from the largest
volume. The absolute volume of interaction is determined by the material (i.e., atomic
number), probe diameter, and accelerating voltage.
Secondary electrons are generated when incident electrons ionize atoms in the surface
layer. More than one secondary electron may be generated from an incident electron. The
low energy of these electrons means that they only escape the sample if they are generated
close to the surface. The number of secondary electrons reaching the detector is therefore
very sensitive to the topography of the surface.
Backscattered electrons are "reflected" back out of the surface after collision with
constituent atoms of the sample. The greater the atomic number, the higher the intensity of
backscattered electrons. These electrons therefore carry information on the atomic compo-
sition of the sample. Regions of higher average atomic number appear brighter on images
generated from backscattered electrons. Importantly, under suitable conditions backscat-
tered electron images can also display crystallographic orientation contrast. This arises from
the different density of atoms per unit surface area for different crystallographic orientations.
Characteristic x-rays are generated by atoms following the emission of a secondary
electron. The x-ray energy emitted is characteristic of the atom and can be analyzed using
energy dispersive spectrometry (EDS) or wavelength dispersive spectrometry (WDS) to
yield quantitative elemental composition.
Secondary electron microscopes (see Fig. 14), in common with most advanced surface
analytical tools, require a high vacuum or, in some cases, ultrahigh vacuum environment for
operation. Vacuum compatibility imposes some restrictions on sample types and sample-
handling protocols. However, recently, so-called environmental or variable-pressure SEMs
have become readily available. These instruments operate at high pressures and constitute a
considerable technical achievement, as it is necessary to segment the electron gun column

c
y ri sti
Ba r
el c Incident Electrons da ct e
©e ks
ctr ca econ ons ara ys
Ons tter
S ectr Ch ra
e el X
d

Specimen

Figure 13 Schematic diagram of the interaction volume of incident electrons.

22 Pigram et al.

Figure 14 A scanning electron microscope incorporating a cold stage for imaging samples with
poor vacuum compatibility (Jeol JSM-6340F FESEM).

into a number of regions of significantly varying pressure. Along with a number of other
innovations, these instruments also make use of the ionization of the atmospheric gases to
reduce sample charging and thereby permit examination of nonconducting samples. Dirty
and wet samples are readily examined in an environmental SEM.
Irrespective of the vacuum in the sample chamber, the electron gun must be in an
ultrahigh vacuum environment. Traditional electron sources comprise thermionic tungsten
or LaB6-type filaments. A filament current heats the filament and “boils” off electrons,
which are then accelerated and filtered through a negatively charged Whenelt cap, which
aids in collimating the beam, and a small hole in the accelerating anode. So-called field
emission gun (FEG) sources involve the extraction of electrons from the very sharp tip of a
tungsten/zirconium oxide emitter using the phenomenon of quantum tunneling in the
presence of a strong electric field. The tip may (hot or Schottky FEG) or may not (cold PEG).
be heated. The electron beam generated from these guns is typically smaller and brighter
than those generated from thermionic emitters. A comparison of some of the main attributes
of the different electron sources is presented in Table 6.
The electron beam is directed onto the sample surface through a series of electro-
magnetic lenses and often also through one or more apertures. The beam is then scanned
over the sample in a raster, or held in a single location, depending on the application. The
detection of secondary electrons is often performed by an Everhart-Thornley detector,
which comprises a Paraday cage with an adjustable potential positioned in front of a
scintillator followed by a light pipe and a photomultiplier tube. The output of the photo-
multiplier tube is proportional to the total number of electrons collected. These detectors are
typically mounted to the side of the sample. There are a number of different types of
backscattered electron detectors. Some are similar to the Everhart-Thornley detector but
without the Paraday cage. Others are composed of diodes (semiconductors) that are
Surface Characterization of Materials 23

Table 6 Comparison of Electron Sources

Emitter type Thermionic Thermionic Cold FE Schottky FE

Cathode material W LaB6 W ZrO/W

Operating temperature 2800 1900 300 1800
(K)
Effective source 15.000 5000 2.5 15
radius (nm)
Emission current 3 30 17,000 5300
density (A cm - 2 )
Total emission 200 80 5 200
current ( A)
Normalized brightness 1 X 104 1 X 105 2 X 107 1 X 107
(A/cm - 2 sr-1 kV - 1 )
Maximum probe 1000 1000 0.2 10
current (nA)
Beam noise (%) 1 1 5-10 1
Emission current 0.1 0.2 5 <0.5
drift (% hr - 1 )
Operating vacuum (hPa) ≤1 X 10-5 ≤1 X 10-6 ≤1 X 10-10 ≤1 X 1 0 - 8
Cathode regeneration Not required Every 6 to
Not required 8 hr Not required
Sensitivity to external Minimal High
influence Minimal Low

Data courtesy of LEO Electron Microscopes Ltd.

positioned adjacent to the incident beam, immediately above the sample. Energy dispersive
spectroscopy employs x-ray detectors, which are also based on the interaction of the emitted
radiation with a semiconductor. Only in the case of these detectors, the semiconductor is
chilled with liquid nitrogen to reduce the thermionic creation of charge carriers. Wavelength
dispersive detectors rely on diffraction and therefore require considerably more space than
EDS detectors. WDS, however, is more suitable for analyzing the presence of low-
concentration elements. Backscattered electrons from an inclined sample can also be used
to generate a projection of Kikuchi lines, which comprise a pattern that in most cases can be
used to uniquely identify the crystallographic orientation. These lines are formed by the
diffraction of electrons and are detected using a phosphor screen in combination with a
charge-coupled device (CCD) camera.
The uses of secondary electron imaging in surface engineering are almost as broad as
optical imaging. However, the maximum magnification is much greater (up to 3 million
times) as is the depth of field. The latter is particularly useful in the examination of wear
surfaces, which are typically quite rough. Figure 15 shows examples of SEM images of a
galvanneal-type zinc coating on a steel substrate. The needlelike structure is typical of the
zinc-rich zeta phase.

4. Transmission Electron Microscopy

In contrast to scanning electron microscopy, transmission electron microscopy (TEM)
hinges on forming images using a magnified electron signal obtained from incident electrons
that travel through a thin (~200 nm) specimen. This technique enables very high lateral
24 Pigram et al.

(a)

m
32 'J x4 2 0m
b

Figure 15 Secondary electron image of a galvanneal surface coating on steel, (a) view normal to
the surface and (b) view perpendicular to the surface normal. These coatings are employed widely on
automotive steels. (Images courtesy of D. Haynes and B. Perrot, BHP Billiton Ltd.)

resolution (~0.2 nm) but necessitates onerous destructive sample preparation [34]. It is not
a tool employed often by the surface scientist and will only be considered here in passing.
Electron guns similar in principle to those employed in SEMs are also incorporated in
TEM instruments. In the case of TEM, the beam energy is typically much higher (100-600
keV compared with ~20 keV). The beam is finely focused onto the specimen through a series
of apertures. In the case of scanning transmission electron microscopy (STEM) the beam is
scanned in a raster across the sample. The transmitted signal is magnified through a series of
electromagnetic objective and projector lenses and, in some cases, filtered to remove
inelastically scattered electrons. The image is typically generated on a phosphor screen,
which is viewed through a vacuum-sealed viewing window.
Surface Characterization of Materials 25

In surface science, TEM is employed in the examination and identification of very

fine precipitates/particles that may have formed in surface regions following diffusion heat
treatments. Another example is the detection of small amorphous regions and 5 nm
crystallites in Ni-P coatings [35].

B. Stresses and Stress Measurement

1. Nature of Stresses
Residual stress refers to the stress that exists in a component after a manufacturing
operation or in service when the external forces are removed. These may be induced by
thermal stresses such as quenching, or mechanical action such as peening, or chemical
reactions such as those involving phase transformation where there is a volume change. The
residual stress can act at three levels [36]:
Type 1: macrostresses that operate on a larger scale than the grain size and which
can vary over considerable distances
Type 2: microstresses that act on the scale of an individual grain in the microstructure
Type 3: atomic-scale defects, such as those that arise due to lattice mismatch or other
highly local factors
By definition, surface treatments are altering the state of the bulk material. Most of these
treatments will produce a structure that will have quite different properties from the bulk. In
most cases, these differences extend beyond simple chemical/composition differences to
differences in the mechanical and physical properties. These can lead to residual stresses in or
near the surface, either through the formation of the coating or later through different
responses to external factors. From the above discussion, it is clear that the residual stresses
in surface engineering are typically Type 1 and operate on the scale of the coating and an
interaction volume within the substrate.
Examples of the stress-inducing processes involved in surface treatment include direct
processes, such as shot peening, through to indirect processes such as diffusion techniques,
which lead to differences in phases, through the coating interaction region. In some
processes, thermal treatment will also introduce residual stresses, such as quenching in heat
treatment. Even if these are not present or they are eliminated through subsequent heat
treatment, the difference in the properties between the surface layers and the bulk of the
sample can give rise to stress differences in service. For example, large differences in the
elastic limit between the surface and the substrate could mean that one would plastically
deform before the other, which on unloading could lead to residual stresses.
The effect of the residual stress on the performance of the component can vary,
depending upon the application. Shot peening is a simple surface treatment that introduces
compressive residual stresses. These are extremely beneficial to the fatigue life of the com-
ponent. Tensile stresses increase the likelihood of premature failure and can activate certain
chemical processes (e.g., stress corrosion cracking).

2. Stress Measurement
The various techniques can be broadly divided into destructive and nondestructive, and it is
clear that no single technique currently provides appropriate coverage and accuracy for the
range of situations where the residual stress is to be measured. Tables 7-9 from Ref. 36
summarize the current techniques that are suitable for surface engineering types of
 26

Table 7 Practical Issues for Residual Stress Measurement Methods Used for Coatings

Practical issues

Level of
Key Contact or Lab-based Availability Standards Cost of expertise
techniques noncontact Destructive? or portable of equipment Speed available equipment required

Hole Contact Semi Both Widespread Fast/Med ASTM Low Low/Med

4
drilling E837-99
X-ray Noncontact No—unless Both Generally Fast/Med No4 Med Med
diffraction depth available
profiling
Synchrotron Noncontact No Laboratory Specialist Fast No Strategic/ High
government
facility
Curvature Contact Yes Laboratory Generally Med No Low Low/Med
and layer available
removal
Raman Noncontact No Both Specialist Fast No Low Med
Pigram et al.
Surface Characterization of Materials 27

Table 8 Materials and Preparation Requirements

Technique Material type Surface preparation Surface condition

Hole drilling Metals, plastics, Light abrasion-strain Flat—preparation must

ceramics gauge not affect stresses
X-ray Metals, ceramics Important Important
diffraction
Synchrotron Metals, ceramics Important Not critical
Curvature and All Not critical Not critical
layer removal
Raman Metals, ceramics Not critical Not critical

problems; this reference also summarizes other techniques that are more suited to bulk
residual stress measurements. For coating-related residual stress measurements, by far the
most common technique is x-ray, with hole drilling and curvature also commonly used.
Other recent overviews can be found in the literature [37-40].
Synchrotron radiation techniques are typically used for fundamental studies of sur-
face properties rather than stress. They are more generally used for bulk analysis of resid-
ual stresses, whereas Raman has only been used in limited application, to date. Most of this
work is drawn from a recent study by the National Physical Laboratory in the United King-
dom, which is reviewing residual stress measurement techniques and aiming to estabhsh
future guidelines [36].
a. Hole Drilling. The hole drilling method has been extensively used for larger
components. The principle is quite simple and relies on measuring the local relaxation of
the structure through the introduction of the hole. This local strain change can then be
transformed into a stress. The hole drilhng method is generally considered as destructive,
although in some cases small holes can be introduced and then repaired without affecting the
life of the component. Because of the long history of this test, there is an ASTM standard
[41],
Figure 16 shows one arrangement for this test. Strain gauges are fixed to the sample
surface and then a hole is introduced. The residual strain, r, which can then be converted to
a stress, can be calculated from:

r max min
A max min
B cos 2

where m a x and min are the maximum and mmimum prmcipal stresses, respectively, is
the angle from the x axis to the direction of the maximum principal stress and A and B are
material constants (see the ASTM standard referenced above for further details).
An obvious drawback of this method is that it provides an average for the depth of the
hole. To obtain information about the residual stress profile away from the surface, which is
of most interest in surface engineering, it is necessary to take measurements at a range of
depths. Other limitations are that the technique is only accurate as long as the depth is less
than the diameter of the hole. It has a relatively low strain sensitivity compared with other
methods and there are potential errors from surface preparation and the dimensions of the
hole. The technique has been applied to coatings, but is not suitable for very thin coatings
because the stress will change sharply over very small distances and material removal to that
level of accuracy is not practical with most methods [38].
 28

Table 9 Physical Characteristics of Residual Stress Test Methods

Physical characteristics

Key Stress Stress Stress Sampling

techniques Resolution Penetration type state gradient Uncertainty area/volume

Hole 50-100 m = hole Macro Uniaxial, Yes—difficult Varies with 1-2 mm diameter
drilling diameter Biaxial to interpret depth 1-2 mm deep

X-ray 20 m depth 5 m—Ti Macro Uniaxial, Yes—with Limited by 0.1-1 mm2

diffraction 1 mm laterally 50 m—A1 Micro Biaxial layer removal several factors 0.05-0.1 mm
1 mm—layer
removal

Synchrotron 20 m lateral to > 500 m Macro Uniaxial, Yes Limited by 0.1 mm3
incident beam 100 mm—A1 Micro Biaxial grain sampling
1 mm parallel Triaxial

Curvature Depends on Not Macro Uniaxial, Yes

and layer material and applicable Biaxial
removal measurement
method

Raman/ 0.5 m Surface Macro Uniaxial, No

fluorescence Biaxial
Pigram et al.
Surface Characterization of Materials 29

Figure 16 Schematic diagram of standard (Type A) strain gauge arrangement for residual stress
measurement using the hole drilling technique.

The NPL study (referenced above) has identified a number of issues that need to be
considered in the hole drilling method, including:
• Drilhng method and wear
• Drill speed and feed
• Operator skill
• Strain gauge (factor, quality, installation)
• Location
• Instrumentation
These are particularly important for engineering applications, but are obviously less
relevant for laboratory- and small-scale-based studies of coatings.
The main advantages of the hole drilhng method are that it is a quick and inexpensive
method and will generally identify general trends in the residual stress profile.
b. Curvature Method. This involves measuring the curvature of a strip of material
as the coating (or substrate) is removed [38]. This destructive method is well suited to
laboratory investigations of the effects of various parameters on the coating. However, there
are a number of difficulties with this approach. It is limited to very simple shapes and has
mostly been apphed to strip or plate samples. Also, there have been problems in interpreting
the outcomes from this technique because of the difficulty in relating the shape after etching
to the residual stress profile.
The analysis of thin films is based on the Stoney formula [42]:

Et 20 K K 0
film
6 1 v t

where E is Young's modulus, to is the substrate thickness, t is the film thickness, K is the
curvature of the substrate, K0 is the curvature of the substrate without the coating, and v is
Poisson's ratio.
The curvature can be measured by a variety of methods depending on the require-
ments. These include profilometry, strain gauges, laser scanning, and optical microscopy.
c. X-Ray. The x-ray method is probably the most widely used within the surface
engineering field. Generally, it is a destructive method, as samples have to be prepared
30 Pigram et al.

for laboratory examination. However, there are a number of modern instruments that
promise in situ measurements, which are highly suited to examination of the field residual
stress. It would appear, though, that most of the field-based measurements are really suited
only for crude quahty control due to the likely errors arising from both instrumentation
and operators.
The basic principle of the x-ray methods is that the interplane spacing in the crystal in
the stressed state differs from the unstressed state. By taking one measurement with the beam
normal to the surface and another at an angle to the normal, the normal stress in the
direction ø is given by:
2
oø E 1 V d d n d0 sin
where dn, is the spacing in the stressed state at the normal angle, d0 is the spacing in the
unstressed state at the normal angle, d is the spacing in the stressed state from the
measurement at angle to the normal, E is Young's modulus, and v is Poisson's ratio.
This is the basis of the two-tilt technique where the measurements are taken rela-
tive to some arbitrary angle using two exposures. If this is repeated for two further values
of ø then the biaxial stress state is obtained. The more common method is the sin2
method, which follows from the observation that a plot of lattice spacing against this
parameter measured over a number of angles will give the stress. There are several issues
that need to be considered in this method and these are covered in more detail in the
literature [36-40].
d. Synchrotron. This method uses high-energy x-rays and so gives much higher
penetration. It can also provide much greater spatial resolution than laboratory-based x-ray
instrumentation through control of the much narrower beams. It is not really suited to the
types of problems mentioned above and is very expensive. However, there may be some
limited applications with advances in analytical technology.
e. Raman Spectroscopy. Raman spectroscopy rehes on the interaction between a
laser light source and atoms. The Raman lines are sensitive to changes in hydrostatic stress
and so can measure changes in the surface strain. It has not been used extensively in these
types of studies but has some application for these types of problems.

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2
Surface Characterization Techniques:
An Overview

Kazuhisa Miyoshi
National Aeronautics and Space Administration, Glenn Research Center,
Cleveland, Ohio, U.S.A.

1. INTRODUCTION

As soon as one is confronted with a system where surface properties are involved, one is in
trouble. The difficulty with surfaces in most practical situations is that conditions above, at,
and below the engineering surface are extremely complex.
The properties of modified engineering surfaces in practical applications can be de-
termined by material and surface analytical techniques [1]. Material and surface analyses are
evolutionary disciplines. A number of analysis techniques are available for studying mod-
ified surfaces, thin films, and coatings from the atomic and electronic levels to macroscopical
engineering component levels. Such techniques include a variety of physical, chemical, ma-
terial, and mechanical characterizations. They can provide information that will allow one
to select the materials, surface treatments (surface modification techniques and conditions),
thin films and coatings, and environments best suited for a particular technical application.
Most materials used in high-technology applications, ranging from high-temperature
oxidation, corrosion, thermal insulation, erosion, and wear to hydrophobicity, low adhesion
(no stick), and low friction, have a near-surface region with properties differing greatly from
those of the bulk material. In general, surface modifications or protective surface coatings
(thermal barrier coatings, environmental barrier coatings, and mechanical barrier coatings)
are desirable, or may even be necessary for a variety of reasons, including unique properties,
light weight, engineering and design flexibility, materials conversion, or economics. These
objectives can be attained by separating the surface properties from the bulk material prop-
erties [2,3].
Surface characterization (diagnostic) techniques are now available for measuring the
shape; chemical, physical, and micromechanical properties; composition; and chemical
states of any solid surface [1,4-10]. Because the surface plays a crucial role in many thermal,
chemical, physical, and mechanical processes, such as oxidation, corrosion, adhesion, fric-
tion, wear, and erosion, these characterization techniques have established their importance
in a number of scientific, industrial, and commercial fields [1,4-10].
This chapter deals with the application of surface characterization techniques to the
development of advanced surface modification technology and processes of tribological
33
34 Miyoshi

coatings and films. These techniques can probe complex surfaces and clarify their inter-
actions in mechanical systems and processes. The primary emphases are on the use of these
techniques as they relate to surface modifications, thin films and coatings, and tribological
engineering surfaces, and on the implications rather than the instrumentation. Finally, a
case study describes the methodologies used for surface property measurements and
diagnostics of chemical vapor-deposited (CVD) diamond films and coatings.

II. SURFACE CHARACTERIZATION TECHNIQUES

Although a wide range of physical and chemical surface analysis techniques is available,
certain traits common to many of them can be classified from two viewpoints. Most tech-
niques involve electrons, photons (light), x-rays, neutral species, or ions as a probe beam
striking the material to be analyzed. The beam interacts with the material in some way. In
some techniques, the changes induced by the beam (energy, intensity, and angular
distribution) are monitored after the interaction, and analytical information is derived
from observing these changes. In other techniques, the information used for analysis comes
from electrons, photons, x-rays, neutral species, or ions that are ejected from the specimen
under the stimulation of the probe beam. In many situations, several connected processes
may be going on more or less simultaneously, with a particular analytical technique picking
out only one aspect (e.g., the extent of incident Ught absorption, or the kinetic energy
distribution of ejected electrons).
Furthermore, many mechanical techniques are available for assessing the surface
roughness and micromechanical properties of material surfaces. Most techniques in this
category involve mechanical contacts between a probe and a material surface.
Table 1 briefly summarizes the popular analytical techniques available today for
studying the properties and behaviors of solid surfaces:
1. Profilometry and quantitative measurements of film thickness, plastic deforma-
tion, and fracture damage
2. Surface microprobes for hardness and mechanical strength measurements
3. Elemental composition and chemical state measurements
4. Microstructure, crystallography, phase, and defect measurements.
The table allows quick access to what types of information are provided by these
analytical techniques. In addition, it provides typical vertical resolution (or depth probed),
typical lateral resolution, typical types of solid specimen, and popularity. The reader will
find the basic principles and instrumentation details for a wide range of analytical techniques
in the literature (e.g., Refs. 4-10). However, the analytical instrumentation field is moving
rapidly, and within a year, current spatial resolutions, sensitivities, imaging and mapping
capabilities, accuracies, and instrument costs and sizes are likely to be out of date. Therefore,
these references should be viewed with caution. This table should be used as a quick
reference guide only.

III. ELEMENTAL COMPOSITION AND CHEMICAL STATE OF SOLID

SURFACES

Elemental composition is perhaps the most basic information about materials, followed by
chemical state information, phase identification, determination of structure (bond structure.
Surface Characterization Techniques 35

atomic sites, bond lengths, and angles), and defects (Table 1(c) and (d)). The elemental and
chemical states, phase, microstructure, and defects of a solid often vary as a function of
depth into the material, or spatially across the material. Many techniques specialize in
addressing these variations down to extremely fine dimensions, as small as on the order of
angstroms in some cases (refer to Fig. 1). Requests are made for physical and chemical
information as a function of depth, to depths of 1 mm or so (materials have about 3 milhon
atomic layers per millimeter of depth). This upper region at the material surface affects a
broad spectrum of properties: elemental composition, contamination, adhesion, bonding,
corrosion, surface strength and toughness, hardness, chemical activity, friction, wear, and
lubrication. Knowing these variations is of great importance when selecting and using
coatings, modified surfaces, and materials.
For surfaces, interfaces, and thin films, there is often little material to analyze—hence
the need for many microanalytical methods such as those hsted in Table 1. Within
microanalysis, it is often necessary to identify trace components down to extremely low
concentrations (parts per trillion in some cases), and a number of techniques specialize in
this aspect. In other cases, a high degree of accuracy in measuring the presence of major
components may be of interest. Usually, the techniques that are good for trace identification
do not accurately quantify major components: Most complete analyses require the use of
multiple techniques, the selection of which depends on the nature of the specimen and the
desired information.
It is important to know the sampling (information) depth of the analytical tool to be
used. For example, let us compare the analysis of two different specimens. The first has an
atomic layer of one or more impurities on the surface; the other has these atoms distributed
homogeneously within the specimen. When a conventional x-ray microprobe with a
samphng depth of about 1000 nm is used, the specimens produce signals of equal intensity
and it is not possible to differentiate between them. One can sometimes get an indication of
whether there is a bulk impurity or a surface segregation (or a thin film) by lowering the
electron beam voltage or by measuring at grazing incidence. However, this is not possible
with only a few atomic layers. On the other hand, because of their insufficient detection
limits, Auger electron spectroscopy (AES) or x-ray photoelectron spectroscopy (XPS) will
produce two quite different spectra: in the first specimen, a strong signal from the impurity
layer caused by the low sampling depth; in the second specimen, only the spectrum of the
pure bulk material with no indication of impurities.
Ion scattering spectroscopy (ISS) and secondary ion mass spectrometry (SIMS) are
extremely surface-sensitive characterization tools, followed by AES and XPS [or electron
spectroscopy for chemical analysis (ESCA)]. Electron probe microanalysis (EPMA) and
energy-dispersive x-ray spectroscopy (EDS) analysis are bulk characterization tools. Thus,
knowing both the structure of real surfaces and the capabihties of the various character-
ization techniques is of great importance.
It was during the 1960s that the amazing growth and diversification of surface
analytical techniques began and evolved with the development of two types of ultra-high-
vacuum electron spectroscopy—AES closely followed by XPS. The combination of the all-
encompassing definition of surface engineering and tribology with these surface analytical
techniques, including a variety of electronic, photonic, and ionic spectroscopies and
microscopies, reflects the trend of surface engineering and tribology today.
A number of techniques are now available for measuring the composition of any solid
surface. The most widely used techniques for surface analysis are AES, XPS (or ESCA), and
SIMS (Table 1(c)). These techniques are well suited for examining extremely thin layers,
including contaminant layers and oxide layers.
 36

Table 1 Popular Analytical Techniques for Surface, Thin Film, Interface, and Bulk Analysis of Coatings, Modified Surface Layers, and Materials
Vertical resolution Lateral resolution Types of solid Use
Technique Main information (depth probed, typical) a (typical) specimen (typical) (popularity)

(a) Profilometry and quantitative measurements of film thickness, plastic deformation, and fracture damage
Optical profiler 3D and 2D imaging, morphology, - 0 . 1 nm A few submicrons All Medium
and laser interferometry profilometry, topographical to a few tens
mapping, film thickness, of microns
wear volume, scar and crater
depth, defects
Confocal microscopy 3D and 2 D imaging, morphology, Variable; f r o m a Optical, 0.5-4 m; Almost all Medium
profilometry, topographical few nanometers SEM, 1-50 m
imaging, film thickness, to a few microns
wear volume, scar and
crater depth, defects
Optical scatterometry Profilometry, topographical ≥0.1 nm A few submicrons to Almost all N o t common
imaging/mapping, periodical a few tens of microns;
structure, morphology, defects ≥laser wavelength,
/2 for topography
Light microscopy (general) Imaging, morphology, damages, Variable Variable All Extensive
defects
Stylus profilometry Profilometry, topographical 0.5 n m 100 n m Almost all; flat Extensive
tracing, film thickness, smooth films
morphology, scar and crater
depth, wear volume
Scanning tunneling Topographical imaging, <0.03-0.05 nm Atomic Conductors Medium
microscopy (STM) compositional mapping,
morphology, profilometry,
film thickness, spectroscopy,
structure, defects
A F M or scanning force Topographical imaging. < 0.03-0.05 n m Atomic to 1 n m All Medium
microscopy (SFM) friction force mapping,
morphology, profilometry,
film thickness, wear volume,
scar and crater depth,
Miyoshi

structure, defects
Variable-angle spectroscopical Film thickness, microstructure, Tens of nanometers Millimeter Planar surface and Medium
ellipsometry (VASE) optical properties to microns interface
X-ray fluorescence (XRF) Film thickness (1-10 4 nm), 10 m 10-150 m All but low-Z elements: Extensive
element composition H, He, and Li
(qualitative mapping)

(b) Surface microprobes for hardness and mechanical strength measurements

Mechanical strength Microscale hardness, creep 0.3 nm Variable; atomic to All Extensive
microprobe deformation, plastic a few tens of microns
(microhardness deformation, fracture using STM, SFM,
measurements) toughness, strength, AFM, or optical
anisotropy microscopy
Mechanical strength Nanoscale hardness, 0.3 nm Atomic to 1 nm using All Medium
microprobe (nanohardness) Young's modulus, creep STM, SFM, or AFM
deformation, fracture
Surface Characterization Techniques

toughness, strength, anisotropy

Micrometer and nanometer Adhesion failure of thin films 0.3 nm Variable; atomic to a All Medium
scratch hardness and coatings, abrasion few tens of microns
measurements resistance, scratch hardness, using STM, SFM, AFM,
deformation, friction, fracture, or optical microscopy
strength, anisotropy

(c) Elemental composition and chemical state measurements.

SEM Imaging, morphology, elemental Variable; from a 1-50 nm in secondary Conductors and Extensive
composition, damages, defects, few nanometers electron mode coated insulators
crystallography, grain to a few microns
structure, magnetical domains
EPMA Elemental composition, SEM 1 m 0.5-1 m All Medium
imaging, compositional
mapping
EDS or WDS Elemental composition 0.02-1 m 0.5-1 m for bulk All Medium
(Z ≥ 5; boron to uranium), specimens; as small
spectroscopy, imaging as 1 nm for thin
and mapping specimens
High-resolution electron Elemental composition, 2 nm 1 mm 2 Ultra-high-vacuum- Not common
energy loss spectroscopy chemical state, bonding compatible solids
(EELS) state, imaging
(Continued on next page)
37
Another random document with
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of rounds, many of which were found to be of the explosive
character condemned by the Hague Conference, arrived from the
Amir’s agents in England. Since it never had been intended that the
right to import munitions of war accorded to the late Amir of
Afghanistan implied the power to amass an unlimited amount of war
matériel in Kabul, no other course was open to the Viceroy of India
than to see that these other stores were likewise detained by the
frontier authorities.
Something more important than considerations of prestige,
therefore, was embroiled in the indifference which the Amir of
Afghanistan displayed towards India as the paramount state, making
it incumbent upon the Government to repeat their earlier
representations. There was no need, indeed the occasion had hardly
arisen, for any violent coercion. The situation required merely such
tightening of the reins as would bring to the ruler of Kabul a proper
comprehension of the actual ties between his country and India. In
the correspondence which ensued, the Amir claimed the right to
import munitions of war under the treaty which had given similar
powers to Abdur Rahman. Unfortunately Habib Ullah had no such
right; nor was any moral obligation to honour the debit notes which
Habib Ullah had drawn every month against the Indian Treasury
attaching to the Government of India. These points were made clear
to the Amir who had neither the funds to pay for nor the authority to
order the armaments which were then waiting at the frontier. The
lesson had been driven home, and the loftiness of tone, which the
Amir of Afghanistan had adopted in the initiatory letter, was hardly
discernible in his concluding statement. Since there was no malice in
the attitude of the Government of India, the Amir of Afghanistan was
again invited to visit India for purposes of a conference with the
Viceroy. A visitation of cholera, which swept through Kabul and
North-eastern Afghanistan in 1903, the worst since the epidemic of
1879, permitted an excuse to be offered at which no exception could
be taken. Before the scourge had subsided Russia had repeated her
designs against Afghanistan. This, in view of the explicit
denouncement of her treaty requirements, implied by the
communique of January 1903, was not perhaps surprising. Their
renewal was denied by Lord Cranbourne in the House of Commons
both in the spring and autumn sessions of 1903. Nevertheless, in the
middle of February, Sirdar Ali Khan, the governor of Afghan
Turkestan, had sent to Kabul four Russian spies whom he had
arrested near Mazar-i-Sharif; but the most flagrant of these insidious
encroachments upon a British preserve occurred in the following
August, when the governor of Russian Turkestan sent back some
deserters from the Afghan army who had escaped into Russian
territory. Obviously the note of defiance in the message which
accompanied them was addressed to the suzerain power.
 It ran:
As the Tsar and the Amir are amicably disposed the one to
the other, His Imperial Majesty has given orders that every
effort shall be made to continue the friendly relations existing
between Russia and Afghanistan.
As representative of the Tsar I am directed to send back all
refugees and evil-doers who come to my territory from
Afghanistan. This is the reason why I send back to you these
eleven soldiers with their arms.
Please be kind enough to communicate this to the Amir.
In spite of these persistent endeavours to establish friendly
relations with Kabul there is little reason to believe that Habib Ullah
offered any encouragement to the Russian frontier officers.
Inveterate suspicion of foreign influence characterises every aspect
of his external policy and Russia and Great Britain are made to feel
impartially the effect of this attitude. Abdur Rahman accepted the
good faith of the Indian Government unquestioningly and
understood his northern neighbour sufficiently to realise that it was
less a wish for the friendship of Afghanistan than a desire to pin-
prick India which prompted her overtures. Habib Ullah has yet to
learn how to stand where his father strode with perfect confidence,
a foolish mistrust sapping the strength of the son. Under a less
skilful statesman than Lord Curzon it is conceivable that the patience
of the Government of India would long since have been exhausted.
That exceptional familiarity with the affairs of Asia, which
preeminently distinguishes the late Viceroy, enabling him to tread
Oriental labyrinths with wise discrimination, permitted him upon this
occasion to bridge once more a crisis between Afghanistan and
India. Almost in defiance of Kabul obstruction, he proceeded to the
solution of difficulties which did not require any personal discussion
with a refractory potentate. Early in the winter of 1903-04, the
Government of India took up for consideration those sections of the
Afghan boundary which, ever since the withdrawal of the Udny
Mission eight years previously, had required demarcation. Surprised
into ruffled acquiescence, the Amir in January 1904 began to make
extensive preparations for a meeting between Major Roos-Keppel,
the chief of the British Commission, and his own representative.
Through the brief absence of Lord Curzon from the helm of state,
the vacillation of the Amir precipitated a collapse of these plans at
the last moment. Wilfully stupid, too, only a little later—in July 1904
—was Habib Ullah’s order to Nasr Ullah Khan to select twenty-four
officers who were to be detailed as envoys to England, France,
Germany, Russia, Persia, China, Japan, Turkey and Egypt in the Old
World, and America in the New World.
If the break-down in the negotiations anent the Mohmand
boundary had increased the tension between Kabul and Calcutta, it
was certainly impossible to tolerate this more direct perversion of
the principles out of which the fabric of our relations with
Afghanistan had been woven. Concerned at the rupture which was
threatening between India and Afghanistan at a moment when Lord
Curzon was absent from India and too timid to insist upon the Amir’s
acceptance of the Viceroy’s invitation to a conference, the Imperial
Government, as the only means of renewing the Agreements upon
which they were set which remained to them, decided to despatch a
Mission to Kabul. At the instance of the Secretary of State for India,
Mr. St. John Brodrick, the acting Viceroy of India, Lord Ampthill,
acquainted Habib Ullah with the wishes of His Majesty’s Government.
In reply His Highness, with the hope of improving his position when
the time came for diplomatic discussion and as an act of conciliation
towards the Viceroy, intimated his willingness to send his son Inayat
Ullah Khan—a charming, intelligent boy of sixteen and a remarkable
instance of that youthful precocity which attains so abnormal a
development in the Oriental—to meet Lord Curzon upon his return to
India. However pressing may have been the questions outstanding
between the Government of India and the Amir of Afghanistan, the
visit of a British Mission to Kabul—no doubt desirable and in that
sense opportune—was derogatory in a Government whose
invitations to the head of the country, which it was proposed to
honour in such an emphatic fashion, had been treated with
contumacy. Lord Curzon’s opposition to the project is well-known;
but with the exception of this distinguished statesman few were
prepared for the unfortunate set back which the mission received. A
grievous miscalculation undoubtedly was made. But the blunder,
which determined its existence and brought about a complete
miscarriage of Anglo-Indian policy, lay not so much in sending the
mission as in His Majesty’s Government not having decided, if the
Amir proved recalcitrant, how far and upon what ground the Cabinet
should stand firm.

festival in honour of the dane mission

As constituted, the Mission comprised Mr., now Sir, Louis Dane,

Foreign Secretary at Simla, Mr. H. R. Dobbs—who, together with
Major Wanliss, had recently returned from replacing the boundary
pillars on the Perso-Afghan border—Major W. Malleson, R.A., Captain
Victor Brooke, 9th Lancers, and a British doctor. Leaving Peshawar
on November 27, the mission reached Dakka on November 29, and
was met at Lundi Khana by 200 Afghan cavalry under the Sipah
Salar Ghulam Hussein, the Sarhang of Dakka, and Mahommed
Hasan Khan. Major Roos-Keppel, political agent for the Khyber,
accompanied the party for a few miles beyond Lundi Khana to
Torkhana, where a guard of honour of the Khyber Rifles was drawn
up, the mission ultimately arriving at Kabul on December 10.
Elaborate gifts were conveyed by Mr. Dane for presentation to the
Amir, among many others a £700 motor-car and several cases of
sporting equipment. As a compliment to the ladies of the harem the
Government of India thoughtfully included a cinematograph,
providing at the same time the necessary operator. Among the
presents to the Mission from his Highness were a gold watch and a
set of gold cuff links which Habib Ullah had offered to Mr. Dane. The
note struck by the negotiations was scarcely in the same pitch as the
festivities by which the withdrawal of the Mission was celebrated,
when seven gramophones simultaneously discharged bursts of
discordant revelry. Nevertheless, the din of these instruments fell on
the ears of those who had every cause to be relieved at the peaceful
termination of their labours, since the clouds had hung low over
Kabul throughout the Anglo-Afghan conferences of 1904-05.
Many things in our buffer state of course required to be improved
as much for the enhancement of its own interests as for the
advantage of India. There was the Amir’s perpetuation of Abdur
Rahman’s objection to Afghan subjects using the northern extremity
of the Quetta-Chaman railway to be discussed, as well as the
projection of railways from Chaman to Kandahar and from Peshawar
to Kabul. Besides these important subjects there were the
prolongation of the Indian system of telegraphs to Kabul and
Kandahar; the provision of telegraphic communication between
Kabul, Mazar-i-Sharif and Herat; Kabul and Kandahar; Kandahar and
Herat. The re-organisation of the Afghan army had also to be
considered, while the demarcation of the Mohmand boundary and
the Seistan border, the definition of the Amir’s control over border
tribes, the question of the subsidy and Habib Ullah’s powers in
respect of the importation of munitions of war were topics, the
examination of which would be, it was expected, to the mutual
benefit of the contracting parties in an Anglo-Afghan alliance. In
India it was understood that there might be a difficulty in the
arrangement of the terms which were to be secured from the Amir;
but that ultimately, and after protracted negotiations, our demands
would be conceded. To this end the chief of the Mission was
provided with a treaty, drawn up under the personal supervision of
Lord Curzon during his brief residence in London in 1904, which was
designed to bring about a discussion of every aspect of the old
agreements with a view to removing previous difficulties and arriving
at a clear understanding for the future.

scene of the audiences between habib ullah and sir louis dane

This treaty comprised three clauses, but Habib Ullah, simulating

annoyance at the terms of the clause which attempted to restrict the
importation of arms, would not enter into any discussion over it.
After the Mission had passed four months in the Afghan capital, the
limit, to which the Amir of Afghanistan would permit himself to go,
reproduced simply the formal renewal on both sides of the
engagements entered into between Abdur Rahman, the late Amir of
Afghanistan, and the Government of India.
The Dane Treaty therefore was as follows:
He is God, Extolled be His perfection,
His Majesty Siraj-ul-millat-wa-ud-din, Amir Habib Ullah
Khan, Independent King of the State of Afghanistan and its
Dependencies, on the one part, and the Honourable Mr. Louis
William Dane, C.S.I., Foreign Secretary of the Mighty
Government of India and the Representative of the Exalted
British Government on the other part.
His said Majesty doth hereby agree to this, that in the
principles and in the matters of subsidiary importance of the
Treaty regarding internal and external affairs, and of the
engagements which his Highness my late father, that is, Zia-
ul-millatwaud-Din, who has found mercy, may God enlighten
his tomb! Concluded and acted upon with the Exalted British
Government, I also have acted, am acting, and will act upon
the same agreement and compact, and I will not contravene
them in any dealings or in any promise.
The said Honourable Mr. Louis William Dane does hereby
agree to this, that as to the very agreement and engagement
which the Exalted British Government concluded and acted
upon with the noble father of his Majesty Siraj-ul-millatwaud-
Din, that is, his Highness Zia-ul-millatwaud-Din, who has
found mercy, regarding internal and external affairs of
principle or subsidiary importance, I confirm them and write
that they (the British Government) will not act contrary to
those agreements and engagements in any way or at any
time.
Made on Tuesday, the 14th day of Muharram-ul-haram of
the year 1323 Hijri, corresponding to the 21st day of March of
the year 1905 a.d. (Persian Seal of Amir Habib Ullah Khan.)
This is correct. I have sealed and signed.
Amir Habib Ullah,
Louis W. Dane, Foreign Secretary,
Representing the Government of India.
 Thus the situation upon the arrival of Mr. Dane from Kabul
differed in no way from that which had preceded his departure for
the Afghan capital, save that substantial concessions had been
awarded to the Amir of Afghanistan who, in return, had conceded
nothing. In addition to an astonishing and entirely unnecessary
elevation in the style and title of the ruler of Afghanistan—conveyed
in the charge “Independent King of the State of Afghanistan and its
Dependencies,” and the reference to “His Majesty,” which the
precious instrument reveals—inevitable corollaries of the transaction
were the continuation of the annual subsidy of eighteen lakhs to
Abdur Rahman’s successor, the release of the arrears—approximately
amounting to £400,000—which had been accumulating since a little
previous to the demise of the late Amir, and the right to an
unrestricted importation of arms.

escort outside the gate of the quarters occupied by the dane mission

It must not be supposed that the mere ratification of the

engagements was sufficient for the purposes of British policy in
Central Asia. Much more was needed; and, since facilities were
deliberately withheld and the Amir rejected consideration of our
pledged responsibility, it is evident that the subjugation of
Afghanistan to the interests of India is incomplete. It is of value
perhaps to have ascertained that the Amir is disaffected and
untrustworthy. There was always a doubt but it was hoped that the
affront, which he offered so sedulously to the British Government,
was due to his own conspicuous vanity rather than the manifestation
of actual ill-will. The Kabul conference made that point clear; but, as
the Imperial Government have elected to observe an impressive
reticence upon the circumstances of this unfortunate episode, it is
no less incumbent upon others to do likewise. Nothing can be gained
by revealing to the world the details of a rebuff without parallel in
the history of Indian politics, unless such acknowledgment were
made to assist public opinion in appreciating the issues involved in
the absence of any satisfactory understanding between Kabul and
Calcutta. That this course formed no part of the late Government’s
policy was disclosed on June 21, 1905, by the debate in Parliament
upon the Indian budget and, at a later date, upon Mr. Balfour’s
speech on Imperial Defence. The Ministers, who spoke on these
occasions, concealed the truth rather than stated it, and their
utterances cannot be accepted as either correct or adequate. Mr.
Balfour’s statement that the construction “of strategic railways by
Russia in Afghanistan” would provoke Great Britain to war does not
render the character of Anglo-Afghan policy more intelligible, nor
remove the disadvantages from our position. On the contrary, the
utterance was most misleading since no such contingency, as the
construction of Russian railways in Afghanistan itself, is likely to
occur until Russia is prepared to strike with all her strength in Persia
and Afghanistan. The question of Anglo-Afghan relations, therefore,
remains for solution, having given rise to a situation which was
regarded by the late Viceroy and every member of his Council with
the gravest apprehension.