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Pasquale Cavaliere

Fatigue and
Fracture
of Nanostructured
Materials
Fatigue and Fracture of Nanostructured Materials
Pasquale Cavaliere

Fatigue and Fracture of

Nanostructured Materials
Pasquale Cavaliere
Department of Innovation Engineering
University of Salento
Lecce, Italy

ISBN 978-3-030-58087-2 ISBN 978-3-030-58088-9 (eBook)

https://doi.org/10.1007/978-3-030-58088-9

© Springer Nature Switzerland AG 2021

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the
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broadcasting, reproduction on microfilms or in any other physical way, and transmission or information
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The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
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Preface

Nanostructured materials represent a possible alternative for a broader range of

applications, outperforming many of today’s engineering materials. As new
nanomaterials are rapidly developing and many applications exist, mainly within
fields such as medicine, communication, consumer goods, and engineering, it is
necessary to identify what special properties this fairly new material group can offer.
All engineering materials based on nanotechnology, involving the understanding of
physical properties and how they change with material dimensions, are to be
considered alternatives in existing products.
Metals with a grain size in the range of 100–1000 nm are classified as ultrafine
grain; grain sizes less than 100 nm are considered to be in the nanocrystalline
domain. The altered response of such properties is a direct consequence of the
nanoscale microstructural arrangements of the atoms themselves. Regarding engi-
neering design, these metals pose significant promise as next-generation structural
materials due to reported increases in ultimate strength, resistance to fatigue, and
wear resistance.
The abnormally high volume fractions of noncrystalline material exaggerate the
importance of the grain boundaries, ultimately leading to a shift in the physical
plasticity mechanisms which take place during deformation. At the smallest grain
sizes traditional intragranular dislocation-based mechanisms begin to shut off which
leads to the dominance of grain boundary-mediated mechanisms.
The main routes employed to produce UFG and NC materials are presented by
underlying the pros and cons of the application of each production from mechanical
alloying and severe plastic deformation to electrodeposition, sputtering, and surface
modification. All those mechanisms, active at the nanoscale, governing the crack
initiation and growth behavior as well as the crack-grain-microstructural features, are
theoretically described. The strength-ductility effect on the fatigue life of nanocrys-
talline materials with particular attention to cyclic plastic strain is discussed. The
effect of grain boundary strengthening through alloying with the related conse-
quences on the fatigue life and fatigue mechanisms acting during cyclic deformation
is underlined. The different behaviors due to the various mechanisms acting during

v
vi Preface

creep in nanocrystalline metals and alloys have been described. The effect of
nanostructuring on the creep and superplastic behavior of metals and alloys is also
shown. The different mechanical behavior of thin films due to the reduced thickness
and the confined deformation mechanisms is described as well. How mechanical
properties of thin films differ from those of bulk materials is underlined. The wear
behavior related to the effect of grain refinement and the consequent grain-mediated
deformation mechanisms is shown. The contact fatigue and fretting mechanisms
acting in nanostructured metals and alloys are also described. The cycle sliding-
activating fatigue mechanisms in nanostructured metals and alloys are shown too.
My special thanks to the professionalism of the editorial office manager and
assistants. I would like to dedicate this book to my son Paolo.

Lecce, Italy Pasquale Cavaliere

Contents

1 Nanostructuring of Metals, Alloys, and Composites . . . . . . . . . . . . 1

1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Nanostructured Material Synthesis . . . . . . . . . . . . . . . . . . . . . . 18
1.2.1 Mechanical Alloying . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.2.2 Severe Plastic Deformation . . . . . . . . . . . . . . . . . . . . . . 26
1.2.3 Electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
2 Cyclic Deformation of Metal Alloys and Composites . . . . . . . . . . . . 59
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.2 Elastoplastic Behavior in Nanostructured
Metals and Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.2.1 Dislocations and Plasticity . . . . . . . . . . . . . . . . . . . . . . 61
2.2.2 Cyclic Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2.3 Nanoindentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2.3.1 Cyclic Nanoindentation . . . . . . . . . . . . . . . . . . . . . . . . 95
2.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3 Crack Initiation and Growth in Metal Alloys and Composites . . . . 105
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3.1.1 Dislocation Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.1.2 GB Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.1.3 Grain Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
3.1.4 Dislocation Absorption . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.1.5 Strain Rate Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.2 Grain Deformation at the Crack Tip . . . . . . . . . . . . . . . . . . . . . 119
3.3 Mechanisms of Cracking in NC Materials . . . . . . . . . . . . . . . . . 121
3.3.1 Crack Behavior in NC Materials . . . . . . . . . . . . . . . . . . 121

vii
viii Contents

3.4 Crack Initiation and Growth in Nanostructured Materials . . . . . . 128

3.4.1 Fatigue Cracks in NC Materials . . . . . . . . . . . . . . . . . . 128
3.4.2 Crack Propagation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
3.4.3 Nanotwinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
3.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4 Fatigue and Crack Behavior of Nanostructured Metal
Alloys and Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
4.1.1 Effect of Strain Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
4.1.2 Dislocation-GB Interaction . . . . . . . . . . . . . . . . . . . . . . 164
4.2 Fatigue Life of NC Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 175
4.2.1 Fatigue Endurance in NC Metals and Alloys . . . . . . . . . 175
4.3 Crack Initiation and Growth in Nanocrystalline Materials . . . . . 183
4.3.1 Fracture Behavior in NC Materials . . . . . . . . . . . . . . . . 184
4.3.2 Cyclic Behavior of Graded Materials . . . . . . . . . . . . . . . 193
4.3.3 Cyclic Indentation of Graded NC Materials . . . . . . . . . . 204
4.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
5 Fatigue and Crack Behavior of Bulk Nanostructured
Metal Alloys and Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
5.1.1 Anisotropy in SPDed Materials . . . . . . . . . . . . . . . . . . . 227
5.2 Fatigue Life of UFG Materials . . . . . . . . . . . . . . . . . . . . . . . . . 228
5.2.1 Deformation Mechanisms in UFGed Materials . . . . . . . . 229
5.2.2 Fatigue Life of UFGed Materials . . . . . . . . . . . . . . . . . . 231
5.3 Damage Tolerance of UFG Materials . . . . . . . . . . . . . . . . . . . . 242
5.3.1 Crack Initiation and Growth in UFGed Materials . . . . . . 242
5.3.2 Microstructural Behavior of Deformed UFGed
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
5.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
6 Creep in Nanostructured Materials . . . . . . . . . . . . . . . . . . . . . . . . . 263
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
6.1.1 Creep Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
6.1.2 Creep Characterization of NC Materials . . . . . . . . . . . . . 268
6.1.3 Microstructural Features . . . . . . . . . . . . . . . . . . . . . . . . 272
6.2 Creep in UFG Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
6.2.1 Effect of SPD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
6.2.2 Creep Rate in UFGed Materials . . . . . . . . . . . . . . . . . . 275
6.3 Creep in NC Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
6.3.1 Creep Mechanisms in NC Materials . . . . . . . . . . . . . . . 279
6.3.2 Strain Rate Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
Contents ix

6.4 Creep in Thin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285

6.4.1 Size Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
6.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
7 Superplasticity in Nanostructured Materials . . . . . . . . . . . . . . . . . . 297
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
7.1.1 Grain Boundary Sliding . . . . . . . . . . . . . . . . . . . . . . . . 298
7.1.2 Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
7.1.3 Constitutive Relationships . . . . . . . . . . . . . . . . . . . . . . 302
7.2 Superplasticity in SPD Materials . . . . . . . . . . . . . . . . . . . . . . . 303
7.2.1 Grain Development Behavior . . . . . . . . . . . . . . . . . . . . 305
7.2.2 Uniform Elongation . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
7.2.3 Mechanisms in UFGed Materials . . . . . . . . . . . . . . . . . 310
7.3 Superplasticity in Nanocrystalline Materials . . . . . . . . . . . . . . . 313
7.3.1 Grain Size Effect on Superplastic Behavior . . . . . . . . . . 314
7.3.2 Dislocation Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . 315
7.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
8 Mechanical Properties of Thin Films and Coatings . . . . . . . . . . . . . 333
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
8.1.1 Microstructural Evolution in Thin Films . . . . . . . . . . . . 335
8.1.2 Grain Evolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
8.2 Mechanical Properties of Thin Films . . . . . . . . . . . . . . . . . . . . 338
8.2.1 Thin-Film Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
8.3 Fatigue of Nanostructured Thin Films . . . . . . . . . . . . . . . . . . . 344
8.3.1 Fatigue Mechanisms in Thin Films . . . . . . . . . . . . . . . . 344
8.3.2 Size Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
8.3.3 Fracture Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
8.3.4 Grain Boundary Structure . . . . . . . . . . . . . . . . . . . . . . . 356
8.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
9 Contact Fatigue and Crack Behavior of Nanostructured
Metal Alloys and Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
9.2 Wear Mechanisms in Nanostructured Materials . . . . . . . . . . . . . 368
9.2.1 Wear Characterization . . . . . . . . . . . . . . . . . . . . . . . . . 369
9.2.2 Scratch Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
9.3 Fretting in Nanostructured Materials . . . . . . . . . . . . . . . . . . . . . 376
9.3.1 Fretting Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . 378
9.3.2 Size Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
9.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
x Contents

10 Effect of Environment on Microstructure and Mechanical

Properties of Nanostructured Metal Alloys and Composites . . . . . . 387
10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
10.2 Corrosion of Nanostructured Materials . . . . . . . . . . . . . . . . . . . 389
10.3 SCC in Nanostructured Materials . . . . . . . . . . . . . . . . . . . . . . . 401
10.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
Abbreviations

AA Aluminum alloy
AD Axial direction
AGG Abnormal grain growth
AIF Amorphous intergranular film
ALD Atomic layer deposition
ALG Abnormally large grain
AM AMorphous
ARB Accumulative roll-bonding
C/T Compression/tension
CCC Cylinder-covered compression
CF Corrosion fatigue
CGB Clean grain boundary
CGBS Cooperative grain boundary sliding
CGP Constrained groove pressing
CIP Cold isostatic pressure
CO Coble
CR Cold rolling
CRSS Critical resolved shear stress
CSL Coincidence site lattice
CSS Cyclic stress strain
CTB Coherent twin boundaries
CVD Chemical vapor deposition
DLC Diamond-like carbon
DSC Displacement shift complete
DSI Depth-sensing indentation
DUFG Deformed ultrafine grain
EAC Environmentally assisted cracking
ECAP Equal-channel angular pressing
EIS Electrochemical impedance spectroscopy
F Ferrite

xi
xii Abbreviations

FCB Fatigue crack behavior

FCG Fatigue crack growth
FEM Finite element modeling
FGM Functionally graded materials
FSP Friction stir processing
GA Grain agglomerates
GB Grain boundary
GBAZ Grain boundary-affected zone
GBCD Grain boundary character distribution
GBD Grain boundary dislocation
GBP Grain boundary process
GBS Grain boundary sliding
GNB Geometrically necessary boundary
GNC Gradient nanocrystalline
GND Geometrically necessary dislocations
H Hardness
HAGB High-angle grain boundary
HCF High-cycle fatigue
HE Hydrogen embrittlement
HEA High-entropy alloy
HESP High-energy shot peening
HIP Hot isostatic pressure
HNM Heterogeneous nanostructured materials
H-P Hall-Petch
HPT High-pressure torsion
HSR High strain rate
IDB Incidental dislocation boundary
IGSCC Intergranular stress corrosion cracking
IHPE Inverse Hall-Petch effect
II Ion implantation
ISE Indentation size effect
ITB Incoherent twin boundary
LAGB Low-angle grain boundary
LBQ Laser beam quenching
LCF Low-cycle fatigue
LEDS Low-energy dislocation structures
LP Leading partial
LSNT Large spacing nanotwinned
LSP Laser shock peening
M Martensite
MC Microcrystalline
MD Molecular dynamic
MDS Molecular dynamic simulation
MEMS Microelectromechanical systems
Abbreviations xiii

nc Nanocrystalline
NEMS Nanoelectromechanical systems
NH Nabarro–Herring
NRD Nanoscale rotational deformation
NS Nanostructured
NT Nanotwinned
OGBC Ordered grain boundary complexion
PD Partial dislocations
PGM Plastically graded material
PIII Plasma immersion ion implantation
P-N Peierls–Nabarro
PN Plasma nitriding
PSB Persistent slip band
PZ Plastic zone
RCS Repetitive corrugation and straightening
RD Radial direction
RHAGB Random high-angle grain boundary
ROM Rule of mixture
RPZ Reversible plastic zone
S2PD Surface severe plastic deformation
SB Slip bands
SCC Stress corrosion cracking
SF Stacking fault
SFE Stacking fault energy
SFSP Submerged friction stir processing
SIF Stress intensity factor
SMAT Surface mechanical attrition treatment
SMC Submicrocrystalline
SMGT Surface mechanical grinding treatment
SNH Surface nano-crystallization and hardening
SP Shot peening
SPD Severe plastic deformation
SPS Spark plasma sintering
SRS Strain rate sensitivity
SS Stainless steel
SSNT Small spacing nanotwinned
SSP Severe shot peening
STZ Shear transformation zone
TB Twin boundary
TD Tangential directions
TJ Triple junction
TL Triple line
TP Twin plane
TTS Tribologically transformed structure
xiv Abbreviations

UDUFG Undeformed ultrafine grain

UHP Ultrahigh pressures
UNSM Ultrasonic nanocrystal surface modification
UP Ultrasonic peening
USP Ultrasonic shot peening
USRP Ultrasonic surface rolling processing
WIF Wear induced by fretting
Chapter 1
Nanostructuring of Metals, Alloys,
and Composites

1.1 Introduction

Nanostructured materials are the most potential and exciting candidates in many
fields for revolutionizing traditional material designs. Nanostructured metals and
alloys are a class of materials exhibiting novel characteristics across a wide range of
properties including increased hardness, superplasticity, and electrical conductivity
(Schaefer 2010). Here, the difference between ultrafine and nanocrystalline metals
needs a special mention. Conventionally, metals with a grain size in the range of
100–1000 nm are classified as ultrafine grain; grain sizes less than 100 nm are
considered to be in the nanocrystalline domain (Gleiter 1989, 1993).
The altered response of such properties is a direct consequence of the nanoscale
microstructural arrangements of the atoms themselves (Murr 2015). Regarding
engineering design, these metals pose significant promise as next-generation struc-
tural materials due to reported increases in ultimate strength, resistance to fatigue,
and wear resistance (Mittemeijer 2010).
Nanostructured materials represent a possible alternative for a broader range of
applications, outperforming many of today’s engineering materials. As new
nanomaterials are rapidly developing and many applications exist, mainly within
fields such as medicine, communication, consumer goods, and engineering, it is
necessary to identify what special properties this fairly new material group can offer.
All engineering materials based on nanotechnology, involving the understanding of
physical properties and how they change with material dimensions, are to be
considered alternatives in existing products.
Through following the Hall-Petch equation

ky
σ y ¼ σ 0 þ pffiffiffiffi
D

© Springer Nature Switzerland AG 2021 1

P. Cavaliere, Fatigue and Fracture of Nanostructured Materials,
https://doi.org/10.1007/978-3-030-58088-9_1
2 1 Nanostructuring of Metals, Alloys, and Composites

where σ y is the yield strength, σ 0 is a material constant (i.e., 25 for Cu, 70 for Fe, and
80 for Ti), ky represents the resistance of grain boundaries to dislocation mobility
(transmission through grain boundaries) giving the quantification of the grain
boundary strengthening (i.e., 0.11 for Cu, 0.74 for Fe, and 0.4 for Ti), and D is the
mean grain size. A high density of grain boundaries limits the length of dislocation
pileups and, due to restricted dislocation motion, extraordinarily high yield stress
values can be observed (Gutkin and Ovid’ko 2004). However, the extraordinary
mechanical properties of NC metals are limited by mechanisms related to the
competing length scales (Anderson et al. 2014; Mohamed 2016).
The Hall-Petch relationship essentially describes grain boundary strengthening, a
process by which grain boundaries, or regions between crystallites of different lattice
orientation, act as physical barriers for continued dislocation movement within the
material (Armstrong 2014). For more traditional, course-grained materials consisting
of average grain sizes ranging from 100 nm upwards of several microns, gliding
dislocations act as the main carriers of plasticity. For this reason, as grain size is
decreased, significant strengthening can be expected (Brandl 2019). The core of this
idea is that grain boundaries hinder dislocations, which accumulate and cause stress
concentrations (Suryanarayana and Koch 2000). This resistance is thought to be
proportional to the misalignment between the meeting slip systems and the magni-
tude of the burger’s vector of the residual grain boundary dislocation that is created
by transmission. The reliance on a planar dislocation pileup arrangement has led to
criticism of this theory. In fact, it was revealed that the length of these pileups has not
been correlated with grain size, nor are they likely to form in materials where cross-
slip to other planes is relatively easy. Instead, a different explanation was proposed
in which grain boundaries serve as nucleation sites for dislocations. The idea is that a
greater grain boundary area will provide more dislocation sources and lead to a
higher dislocation content at a given strain. Strength is known to depend on the
square root of dislocation density. Another alternate explanation of the Hall-Petch
effect has been offered by proposing that strain gradients imposed by compatibility
requirements between grains increase the dislocation density. These strain gradients
become larger as grain size decreases, and so does the number of geometrically
necessary dislocation needed to support them.
A strong effort has been devoted to metal and alloy nanostructuring in order to
reach the material’s theoretical maximum strength (G/10). The pioneering view of
Gleiter (1989) pushed the research on nanostructured metals in the recent decades. In
the paper, nanocrystalline materials are defined as single- or multiphase polycrystals
with nanoscale grain size (1–250 nm). As upper limit, “ultrafine grain” is used to
indicate grain size in the range of 250–1000 nm. First of all, the properties of these
materials are related to the increase of the grain boundary volume fraction as the
mean grain size decreases. The abnormally high volume fractions of noncrystalline
material exaggerate the importance of the grain boundaries, ultimately leading to a
shift in the physical plasticity mechanisms which take place during deformation
(Meyers et al. 2006a). At the smallest grain sizes traditional intragranular disloca-
tion-based mechanisms begin to shut off which leads to the dominance of grain
boundary-mediated mechanisms.
1.1 Introduction 3

Fig. 1.1 2-D model of nanostructured materials

The altered response of NC material properties is a direct consequence of the

nanoscale microstructural arrangements of the atoms themselves. The atoms in the
crystal interior are closely packed in an ordered configuration; those in the grain
boundaries are in a more chaotic high-energy configuration with a different spacing
(Fig. 1.1).
As the grain size decreases, the nanocrystalline material interfaces contain higher
atom fractions. For grain size in the order of magnitude of 5 nm the fraction is in the
order of 50%; for 10 nm, the grain boundary volume fraction is around 30%; for
ultrafine-grained materials it is around 2% while for microcrystalline metals and
alloys it is orders of magnitude lower (Fig. 1.2).
Unfortunately, due to the high volume fractions of grain boundaries, the driving
force for nanocrystalline grain growth is amplified (Andrievski and Khatchoyan
2016). Therefore, minimizing grain growth and maintaining their beneficial proper-
ties prove extremely challenging.
In nanocrystalline materials, the intercrystalline volume fraction is found to
comprise as much as 50% of the total crystal volume. These solids are assumed to
have a different kind of atomic structure: a crystalline structure with long-range order
for all the atoms far from the grain boundaries and a disordered structure with some
short-range order at the interfacial region. Hence, the mechanical properties of these
nanocrystalline materials are expected to be different as compared to their equal
polycrystalline material. There are two main strategies that have garnered the most
4 1 Nanostructuring of Metals, Alloys, and Composites

Fig. 1.2 MD model of nanocrystalline Ni-Fe with 5 nm grain size

attention. The first strategy utilizes kinetic mechanisms that decrease grain boundary
mobility, such as solute drag, reduced diffusivity, particle drag, and chemical
ordering. The second strategy utilizes solute segregation to reduce the grain bound-
ary energy and consequently the driving force (Razumov 2014).
The grain boundary energy is given by the following equation:

γ ¼ γ 0  ΓðΔH seg þ RT ln X Þ

where γ is the grain boundary energy, γ 0 is the original grain boundary energy of the
pure metal, Γ is the grain boundary solute excess, ΔHseg is the enthalpy of segrega-
tion, R is the Boltzmann constant, T is the temperature, and X is the global dopant
composition. The equation ultimately means that segregation of dopant to grain
1.1 Introduction 5

Fig. 1.3 Ideal tetrakaidecahedron grains with a grain boundary thickness of 1 nm

boundaries can lower the grain boundary energy and consequently change its
behavior.
By analyzing this aspect through the employment of an ideal tetrakaidecahedron
grain structure with a grain boundary thickness of 1 nm (Fig. 1.3), it is possible to
plot the relationship between the grain size and the volume fraction.
So, both the volume fraction and the triple junctions increase as the mean grain
size decreases (Fig. 1.4).
The dotted lines show the evolution of grain boundary thickness and its effect as a
function of grain size (range 1–0.1 nm).
Experimental evidences show that GB size is around 0.5 nm for NC materials
with FCC crystal structure and 1 nm for NC BCC crystal structure. From Fig. 1.5 it
can be observed that for a grain size of 5 nm approximately 40% of the atoms lie in
the grain boundary (Siegel and Thomas 1992; Spearot and McDowell 2009).
The volume fraction as a function of grain size distribution was measured for
many Ni and Ni-Fe electrodeposited nanostructured materials (Fig. 1.6).
So, the overall behavior of nanocrystalline materials is dependent on not only the
grain size but also the nature of grain boundary structures. Generally, these interfaces
are responsible for the strength behavior of metals and alloys. The atom orientation
6 1 Nanostructuring of Metals, Alloys, and Composites

Fig. 1.4 Volume fraction and triple junctions as a function of the grain size

Fig. 1.5 Brain boundary vs. grain interior volume fraction

1.1 Introduction 7

Fig. 1.6 Volume fraction vs. grain size distribution for different Ni and Ni-Fe

in adjacent grain is different; in addition, the atoms in the grain boundaries are in a
disordered state. These factors lead to a difficulty for a dislocation to continuously
slip in all the material volume because it must overcome the grain boundaries with a
change in the slip direction (Fig. 1.7).
This hinders the material plasticity with a direct effect on the yield strength
increase of the material (Sun 2014). The stress applied to the crystal (σ) generates
a shear stress (τa); the crystal opposes a resistance (τ0) to the generated shear stress
(Fig. 1.8).
So, the effective stress (τeff) for the dislocation sliding is

τeff ¼ τa  τ0

This is the model describing the situation in the grain interior. By approaching the
grain boundary, the dislocation must have sufficient energy to overcome the grain
boundary; otherwise it is pinned by the grain boundary. In this model the shear stress
at grain boundary (τgb) is given by
8 1 Nanostructuring of Metals, Alloys, and Composites

Fig. 1.7 Dislocation-grain boundary interaction

Fig. 1.8 Stress leading to dislocation sliding inside the grain

rffiffiffiffiffi rffiffiffiffiffi
D D
τbg ¼ τeff ¼ τa  τ0
4r 4r

where r is the distance from the point of dislocation generation and the grain
boundary. Finally, the shear stress necessary for the dislocation movement taking
into account the crystal interior and the grain boundary resistances is given by
1.1 Introduction 9

rffiffiffiffiffi
4r
τa ¼ τ0 þ τbg
D

that is the Hall-Petch relationship in terms of shear.

Some researchers observed that the capacity of generating dislocations inside the
grain is related to the parameter

emitted dislocation length

μ¼
grain area

that is related to the dislocation density (ρ) by

3μ
ρ¼
D

Finally, the Hall-Petch relationship can be expressed by

rffiffiffiffiffi
3μ
τ ¼ τ0 þ αGb ¼ τ0 þ k0y D1=2
D

where α is a parameter depending on the crystal structure, G is the shear modulus,

and b is the Burgers vector.
Now, the most common dislocation generation mechanism in the grain interior is
given by the Frank-Read source. By reducing the grain size the dislocation loop
dimension is reduced up to disappearance for nanosized grains (Fig. 1.9).
So, by decreasing the grain size, the material strength increases because of the
limited dislocation generation and the limited space for sliding before the interaction
with the grain boundary (Fig. 1.10).

Fig. 1.9 Dislocation generation inside the grains

10 1 Nanostructuring of Metals, Alloys, and Composites

Fig. 1.10 Strength variation vs. grain size in pure Cu

Dislocation activity is grain size dependent. Full dislocation activity may be

inhibited at very small grain sizes as partial dislocation activity becomes more
favorable. In terms of the Orowan relation, the resolved shear stress required for
expansion of a dislocation loop with a diameter of D is

μb
τRSS ¼
D

where μ is the shear modulus and b is the Burgers vector of dislocation. Full
dislocation multiplication requires that Frank-Read-type sources have a minimum
grain size (D*) at the yield strength (σ y) of

μb
D ¼ σ D
m

where 1/m is the average Schmid factor for polycrystals (m ¼ 3). This would mean
that as grain size becomes smaller than D* full dislocation is inhibited and partial
dislocation activity becomes dominant in the deformation of most grains, hence
enhancing the GB relaxation process (Zhang et al. 2018). As the GB relaxation
process is triggered by plastic deformation, it may not happen in the nanograined
1.1 Introduction 11

metals which possess high GB energy and hence poor thermal stability (Zhou et al.
2018; Wrobel 2012).
According to the results of kinetic modeling, carried out within the developed
dislocation model, considering the wholeness of all the possible deformation mech-
anisms and presenting the development of the well-known composite models, the
temperature alteration of the plastic deformation brings to the activation or suppres-
sion of some deformation processes in GBs of Cu with different microstructures. On
the one hand, the temperature increases as well as the hydrostatic pressure growth
activates the work of the Frank-Read sources. The efficiency of GBs as the sinks for
dislocations increases. Both the annihilation of the screw dislocations during their
double cross-slip and their annihilation during the nonconservative motion increase
(Alexandrov and Chembarisova 2012).
In the intermediate nanocrystalline grain size range above approximately 10 nm
and below 100 nm, it is likely that there exists competition between conventional
lattice dislocation slip and diffusional deformation, with the relative contributions of
these deformation modes being dependent upon the distribution of grain sizes
(Gapontsev and Kondrat’ev 2002).
If the deformation is governed by the dislocation sliding, the strength increases as
the grain size decreases. This continues up to a grain size limit, then the deformation
is governed by the grain boundary deformation, and the strength starts to decrease as
the grain size decreases; this is commonly known as the Hall-Petch inversion
(Fig. 1.11).
The Hall-Petch inversion has been observed for many nanocrystalline metals
produced via different routes (Bober et al. 2016). The shear deformation process of

Fig. 1.11 Qualitative crystal strength vs. grain size

12 1 Nanostructuring of Metals, Alloys, and Composites

nanocrystals based on assuming an athermal deformation has been modeled. In

accordance with them the shear propagation is composed of the grain boundary
sliding and the shear deformation of crystalline matrix occurring mostly near the
grain boundary plane. The latter deformation may be a twinning deformation, partial
dislocation glide, or a stress-induced amorphization leading to a grain boundary
thickening (Sitek and Degmová 2006). Because of the distribution of the angles
between the boundary planes and the shear plane its width varies from a boundary to
another. If the thickness of the boundary is t, the average width of the boundary
region in the shear plane is αt, where α is about 2. If the stress necessary to propagate
the shear front in the boundary region is σ b and that in the crystalline matrix is σ c,
then σ c > σ b, and hence as the grain boundary region increases the deformation
stress decreases, leading to an inverse H-P relation. Along the shear front, the
fraction of the boundary region is αt/d and that of the crystalline region is 1αt /d.
Thus, the stress necessary to propagate the shear front is written as
   
αt αt
σ ¼ 1 σc þ σ
d d b

The value of σ c is material dependent while the value σ b depends on the material,
its purity, the processing to produce the nanocrystal, and the history of the treatment,
because the structure of the boundary which affects σ b should be sensitive to the
purity and processing.
The quantitative variation of yield strength as a function of grain size for pure Ni,
Cu, Fe, and Ti is shown in Fig. 1.12.
In Zhao et al. (2003) it is shown how the melting temperature of the nanostruc-
tured crystals decreases with decreasing particle size; the Hall-Petch relationship
becomes limited and is no longer sufficient for grain sizes less than around
15–30 nm. They proposed a model where there is a numerical maximum whose
location depends on the bulk melting enthalpy of the crystals:
" #
h i
12 1 H m =3R
σ ðdÞ ¼ σ 0 þ k t þ k d D exp  D
T d 6h 1

where
 
T m0
k 0t
kt ¼ exp
2T d
 
00 T m0
kd ¼ kd exp
2T d
H m ¼ T m0 Sm

If the bulk melting enthalpy is applied to nanostructured Ni (Fig. 1.13), the

transition grain size can be calculated.
1.1 Introduction 13

Fig. 1.12 Yield strength vs. grain size for pure Ni, Cu, Fe, and Ti
14 1 Nanostructuring of Metals, Alloys, and Composites

Fig. 1.13 Flow stress vs. grain size based on the bulk melting enthalpy

Fig. 1.14 Young’s modulus variation with grain size

Another physical property to vary as the grain size is reduced is the Young’s
modulus. In Fig. 1.14 the E variation with grain size for different electrodeposited
pure metals is shown.
1.1 Introduction 15

Fig. 1.15 Young’s modulus variation with grain size for nanocrystalline Fe

Given that the values of a material’s elastic constants reflect the bonding nature of
its constituent atoms, it seems logical to expect that nanocrystalline materials would
exhibit different moduli of elasticity compared to coarse-grained polycrystalline
solids because of the high volume fraction of atoms located at or near the grain
boundaries, triple junctions, and quadruple nodes (Ramesh 2009). In particular,
since the degree of atomic structural disorder is greater within a grain boundary as
compared to the crystal lattice, the average atomic distance within it is generally
known to be larger. It could then be concluded that the grain boundary as a whole
exhibits a lower bond strength and, therefore, has local elastic moduli values lower
than those of the lattice (Zhu and Zheng 2010).
Different calculations and experimental analyses of pure Fe revealed a remark-
able difference in Young’s modulus with grain size (Fig. 1.15).
It is known that ultrafine-grained materials follow the Hall-Petch grain size
strengthening behavior into the nanocrystalline regime. On the other hand, at some
grain size transition from the regular to inverse Hall-Petch has also been reported in
literature. The dependency of yield strength or hardness on grain size may become
weaker, and even reverse at extremely fine-grain sizes. This phenomenon is known
as the “inverse Hall-Petch effect” or “softening effect” (Carlton and Ferreira 2007).
The reasons for the transition are a changing balance between competing deforma-
tion mechanisms (Zhou and Qu 2019). When conventional grain size metals are
deformed at room temperature strain is carried exclusively by dislocations. Under
these circumstances, grain boundaries influence deformation but they are not carriers
of it. At the nanoscale, grain boundaries can mediate deformation more directly by
sliding and shear-coupled migration or serving as dislocation sources and sinks.
Another Random Scribd Document
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his eyes from the Squaw Spy.
“Artena is mad,” he said, at length, after looking her in the eye. “She
knows not what she says. Steamboat, take her.”
He looked at the young warrior who had stepped to her side, and his
red hands encircled her arms.
But she wrenched herself loose, displaying in the action a strength
that astonished the spectators, and before Steamboat Dick could
secure her, she stood beyond reach, and his Spencer rifle was
clutched in her hands.
“Artena’s head is not cracked!” she cried, directing her words at
Captain Jack. “She means just what she says. If Mouseh raises his
revolver to Cohoon’s head again, the Modocs shall be chiefless!”
Jack glanced from the girl to his tribe, then back again.
“Artena,” he said, “is a Modoc, Cohoon is a Warm Spring dog. His
forefathers fought ours long years ago. The tree of hatred has
thrived between the two nations, and the river of death has watered
its roots. She can not love the man who— Ha! what says Artena
now?”
The Squaw Spy was a prisoner, for a savage had suddenly leaped
through an opening in the ceiling, and encircled her with his long red
arms. She gritted her teeth and struggled, but all to no purpose; the
giant Modoc was too much for her, and she submitted, while the
Indians clapped their hands in approval of their brother’s deed.
Nor did the captor handle his prize decently. One hand suddenly flew
to her throat, and, strangled until her face assumed a darker color
than its own natural one, she became as limp as a cloth in his hands,
and appeared senseless.
Captain Jack, in the ebullition of his wrath, permitted this, and there
was but one in the whole assemblage who tried to resent the
indignity.
This person was Cohoon!
He sprung forward with a cry of horror when he saw Artena’s
condition; but was confronted by Captain Jack, whose right hand
hurled him back.
“There’s some infernal treachery between these two,” he cried,
glancing at his braves. “Artena would not strike for Cohoon if he was
nothing to her. Say—girl, what—”
He was flung aside by Cohoon’s clenched hand, and, before he
could recover, Steamboat Dick was hurled upon him, and Artena lay
upon the spy’s arm.
The severing of Cohoon’s bonds was ’Reesa South’s work!
Unable to control the spirit that suddenly swept over her, she had
snatched a knife from the belt of a young savage who stood near,
and liberated Cohoon before the astonished chiefs and braves could
interpose a hand.
And she gained the spy’s side unharmed, and, smiling over her
triumph, faced the array of rifles and knives.
“Back!” yelled Jack, rising and throwing himself before his maddened
braves, who were pressing forward. “Leave all this to me. This night
we will rid ourselves of every enemy that infest this cave!”
Then he wheeled upon Cohoon, whose Spencer was leveled at his
breast.
“What is Artena to Cohoon?” he cried.
The answer followed quickly upon the heels of the interrogative, and
startled every one.
“His wife!”
The sentence roused Artena, and, starting up, she knocked the rifle
from its level.
Cohoon tried to remedy the accident; but the whiz of an arrow
prevented him.
He groaned; the weapon dropped from his hands, and, with a barbed
shaft sticking in his side, he dropped upon his knees.
A wild yell greeted the result of the shot; but it was broken in twain
by the Squaw Spy, who snatched the rifle from the ground, and, with
a cry of defiance, threw herself before the man who had called her
wife!
 CHAPTER XI.
NEW YORK HARRY.
The gray light of morning was revealing the camp of the United
States troops when the sentry before General Alvin Gillem’s head-
quarters halted a stalwart Indian who, with aboriginal boldness, was
stalking toward the door.
“What blue-coat stop Indian for?” demanded the red-man.
“For the simple reason that you have no business with the General.”
“Indian much talk with gold-star chief. He lookin’ for Klamath.”
“But I shall not disturb him on your account,” said the sentry. “You
can loiter about the camp till sunrise.”
The Klamath did not move, but burst into a hearty cachinnation,
decidedly English.
“So you thought I was an Indian, Tom Baird,” he said. “Well now,
that’s a rich joke. Can’t you tell old Kit South from a Klamath?”
“Kit South it is, upon my honor!” exclaimed the sentry. “Here, give me
your hand; but don’t tell the boys how you sold me.”
The scout took the extended hand, and shook it heartily while he
laughed.
“I reckon, Tom, you’ll let me see Gillem now,” he said, and as the
sentry moved toward the tent, the curtains parted and a head was
thrust forth.
“Well, well, Kit,” said the voice of Gillem. “You do make an excellent
Klamath. What’s the news from Arrow-Head? But, come in, and we’ll
talk matters over while I dress.”
Tom Baird stepped aside, and the ranger entered the General’s tent.
Kit threw himself upon a blanket and burst into a fit of laughter.
“’Reesa’s in a bad fix, and Cohoon’s in a worser,” he said; “but I must
laugh when I think how readily Jack swallowed our story about
Arrow-Head. You see, General, he had been itching to b’lieve such a
thing for so long, that he took right to the tale we brought. But once
thar, we stood on the edge of perdition, and I had to do a deed that
went ag’in’ my grain.”
Gillem dropped his boot-straps, and looked up at the scout.
“While we war talkin’ to Jack, in pops an Indian boy, and he war goin’
to tell who we war; but I don’t know how he knew the truth unless he
see’d us fix up. But I sp’iled his story before he got started. I just
caught him up, and I guess I let a spoonful o’ blood out’n his breast. I
didn’t want to kill the little fellow; he looked as innocent as a lamb,
but I hed to do it to save my own skin.”
“I hope you may be forgiven for that blow,” said the soldier, with a
smile.
“I hup so, too, General; but what riles me, the red devils hev still got
’Reesa—Baltimore Bob, in particular.”
“That fellow again?” queried Gillem. “He must be a demon, Kit.”
“That’s just what he is. When a white man turns Injun, Satan
registers a new devil on his books.”
“A white man, Kit? You don’t mean that—”
“Yes, I do. Baltimore Bob is a white chap called Rafe Todd,” and then
the scout detailed a history of the renegade’s crime, and subsequent
desertion. “You see, I knowed nothing of this when he came about
our parts,” he continued, “and he began cutting around ’Reesa. But,
she wouldn’t have any thing to do with him, for she was rather soft
on a fellow named Harris,” and there was a merry twinkle in the
father’s eye while he spoke the last sentence. “Finally, he insulted
’Reesa and I wanted to cowhide him. By Jehu! I would have skinned
’im alive, I guess; ’Van took it up, and one night they fought a duel
with rifles along Lost River. ’Van hit the fellow somewhere, and he
tumbled over the bank into the water. We saw him floating down-
stream, dead, as we thought. But he isn’t dead. ’Van saw Jack
unmask him the other day, and after that the white devil shot ’Van in
the head.”
“Is Harris dead?”
“No; I brought him off from the last fight, and he’s in Cap. Jackson’s
tent now, nigh about as well as anybody. When Bob, or Rafe Todd,
found that he wasn’t dead, he put him into the clutches of their Curly-
headed Doctor, with eye-orders to get him out o’ the way. The
medicine fool tried it, but ’Van took care of an advantage, and
knocked the doctor down. Then he broke an’ run, got into the river,
was strangled, and Cohoon got him out when he was nigh about
gone. I guess we’ll never see Cohoon ag’in. They’ll make short shrift
of the brave red fellow. Where’s Artena and Donald?”
Gillem shook his head.
“Their absence perplexes me. I never liked the idea of sending that
girl among the Modocs. She walks into the jaws of death every time
she enters the lava-caves. If the Modoc chiefs ever get a good
chance at her—”
“Why, she’s gone. But it puzzles me about Mack,” said Kit. “If he got
out of the river, he would have been hyar afore this, I think.”
“Something startling may detain him. Recollect, he has friends to
save.”
“And I—I have a wife to avenge!” cried the scout, springing to his
feet, all the anger of his nature aroused. “General, I had a dream,
during the short sleep I snatched in Jackson’s tent, last night. It’s too
long to tell, but it amounted to this; I killed the man who sent the red
devils against my cabin—Rafe Todd. I don’t b’lieve in dreams very
much; but I dreamt this one over three times in an hour, and I know
thar’s something in it. If he don’t deserve—”
The sentence was suddenly shortened by the appearance of the
sentry, who announced that several soldiers were conducting a
Modoc prisoner to head-quarters.
Gillem glanced at Kit and smiled, as he rose to his feet.
“We’re decimating their ranks at the rate of one per week,” he said.
“This war is costing Uncle Sam a neat little figure.”
“Yes,” said Lava-Bed Kit. “It costs about two millions to kill a Modoc;
half that sum to give one a flesh-wound. Reg’lars can’t fight Indians
in California.”
“Please don’t reflect upon the regulars, Kit,” responded Gillem. “You
know I won’t argue with you on the question you have sprung; but let
us take a look at the solitary captive of the whole army.”
The two men left the tent, and greeted a sturdy sergeant and two
privates who had halted before it with the captive Modoc.
This fellow, they said, had entered the camp with a white rag
streaming from his gun-barrel, and declared himself disgusted with
the Modoc cause. He would fight no more against the Government,
and wished to be released on parole. His name, he said, was New
York Harry, and his rank a sub-chief under the Modoc rebel.
General Gillem relieved him of his arms, a fine Spencer rifle, a brace
of silver-mounted revolvers, and a bowie-knife, and released him on
his word of honor.
“I will tell my men of you,” he said, through Kit, who acted as
interpreter on the occasion, “and if you attempt to pass the lines, you
will be shot dead.”
The savage expressed himself fully satisfied with the restrictions,
and, after delivering some important information concerning Jack,
was allowed to depart.
Gillem and the scout watched the Indian a while, and then
separated, after a brief conversation.
New York Harry sauntered about the camp and conversed with
numerous scouts. He found his way to Colonel Mason’s head-
quarters, and was soon enrolled in the United States service as a
scout. A new Spencer rifle and revolver were furnished him, and he
was to lead a squad of soldiers to Jack’s retreat at nightfall. He
harbored a deadly hatred against the Modoc, and exhibited a fresh
scar, which extended across his right cheek, as a mark of Jack’s
affection for his followers.
“Well, ’Van, do you think you can go with me to the Beds, to-night?”
“I do, Kit. I am going with you,” replied the young man, who lay upon
a pallet in the tent of Captain Jackson of the—th regular infantry. “I
want to help snatch ’Reesa from the red cutthroats, to save Cohoon,
if I can, and to settle accounts with Rafe Todd.”
“You’ve got too many irons in the fire,” said South, with smile. “Take
a couple out, ’Van.”
The young ranger shook his head.
“Not for Joe, or, rather, not for ’Van Harris,” he said, returning the
scout’s smile. “If I burn any of those irons, it will be my own fault, Kit.
We are going alone, I suppose.”
“Yes; though there’s one fellow who’d like to go along, I’m thinking!”
“Who is he—Mack?”
“Lord bless you, no!” exclaimed the scout. “Here it’s sundown
almost, and Mack hasn’t showed his face. Gillem’s gettin’ flustered
about him, an’ I mus’ own that somethin’ of that nature’s troublin’ me.
We’ll look for Donald, too, when we get to the Beds. But the fellow
what would like to go with us is an Indian—a genuine Modoc.”
“The fellow who surrendered this morning?” asked the ranger.
“That’s the chap.”
“Jackson was telling me about him to-day, and I wouldn’t be
surprised to learn that the fellow is a spy. And to think that Mason
would commission him as a scout! I must say that our army officers
are forgetting the lessons they learned in the rebellion.”
“It looks that way,” said Kit. “I’ve been watching the Indian nigh all
day, but I’ve see’d nothing suspicious about him.”
“Well, he may be in earnest. I’d like to see him.”
“Then we’ll walk out a bit. I want you to see Davis and Gillem afore
we go back to the caves. Blast the luck! I wish our plot to kidnap
Jack had succeeded. I know something now. That young Oregonian
who come into camp the other day was Rafe Todd.”
“He was. I learned enough from the Indians to satisfy me on that
point,” said ’Van Harris. “He lay behind a rock while you and Artena
conversed with Gillem, and it was he who denounced the girl as a
traitress. He beat her to the cave.”
Kit South did not speak, but gritted his teeth with rage, and they left
the tent.
The young ranger had completely recovered from his wound, and
seemed much refreshed by his day’s rest. He belonged to McKay’s
Lava-Bed Rangers; and had been of signal value to the service since
the inauguration of the Modoc war. He had offered his services
simultaneously with Kit South, and at once enlisted under the
chieftainship of the Warm Spring hero.
Like the giant scout, he could speak the Modoc tongue without
difficulty, and was well versed in the cunning toils of Indian warfare.
The scouts held brief conversations with the two Generals in Gillem’s
head-quarters, and about seven o’clock took their departure.
“I’m not coming back this time without ’Reesa,” said Kit, while he
held Davis’ hand.
“Nor I without a canceled account with Rafe Todd,” chimed in the
young ranger.
“You can’t kill him!” said Kit, turning to the young speaker. “I told you
about my dream. I b’lieve it now as firmly as I b’lieve I live. I’m going
to kill that devil myself.”
“Bring him alive into camp, Kit, and we’ll hang him for killing the
sergeant, at Fort Crook.”
“Never mind, Gen’ral; I’ll settle the army’s bill against him when I
settle mine.”
A few minutes later the scouts left the officers, and, well disguised,
hurried toward the outskirts of the camp.
“Why the Indian intends staying about to-night after all,” suddenly
whispered Kit to his companion. “I thought Luke Davis, Dave Webb,
and Sam Thatcher, war goin’ to the beds with him.”
“The Indian—where is he?” asked young Harris. “I want to see him.”
“There he goes, now look, quick—he’s turning—coming this way—
going right toward the boys’ tent.”
The scout quickly drew his young comrade into a tent, near at hand,
and, parting the curtains just the least, they watched the savage.
He was walking directly toward the Sibley, and was distinctly visible
in the soft April gloaming.
His Spencer was slung on his back, and he walked rapidly, as
though something on the other side of the camp demanded his
attention.
Suddenly, when New York Harry had arrived opposite the tent, Evan
Harris caught Kit’s arm.
“Don’t you know him?” he cried, looking up into the scout’s face,
excitedly.
“Know him—yes; he’s a Modoc scoundrel.”
“He is not,” said the younger ranger. “His name is Rafe Todd.”
The old scout started at the mention of the deserter’s name, but
shook his head.
“That won’t do, boy. When did you see Rafe last?”
“Yesterday.”
“Had he a scar on his face?”
“No.”
“Well, this fellow has a scar on his cheek—a tremendous scar, too,
and it’s at least five days old. I think he is playing some little game,
but the boys are posted, and at the first sign of treachery, they’ll put
him out of the way forever. Come, we’ll go, now.”
They left the tent, but the young ranger could not take his eyes from
New York Harry.
“You may reason soundly, Kit,” he said, at length, “but I will bet my
life that Rafe Todd stands in that fellow’s moccasins.”
“He can’t,” said the scout, quickly and confidently. “That scar says he
is not Rafe Todd, and didn’t I look him squarely in the eye when you
lay about dead in Jack’s cave, and see that his face was as smooth
as your’n, barring his paint? And then that Indian is a better man—
physically—than the white villain.”
The youth did not reply to this argument; but his countenance told
that he still adhered to his opinion regarding the identity of New York
Harry.
 CHAPTER XII.
A TURNING OF TABLES.
To acquaint the reader with Artena’s sudden appearance before
Cohoon’s would-be-torturers, we must needs return to the bank that
overlooked the interior of the cave.
For many minutes after Donald McKay’s departure in search of the
boat, which was intended to convey her from Jack’s stronghold,
Artena kept her eye fixed upon the sleeping spies and their
surroundings. She felt suspicious of Baltimore Bob, indeed, she had
reached the conclusion that he had recognized the two men, despite
their paint and Klamath garments, and she looked for some coming
treachery on his part.
Therefore, so intent upon these thoughts was the Indian’s mind, that
the footsteps that loosened a pebble and caused it to roll into the
black water, did not disturb her in the least. True, the noise was
scarcely distinguishable above the swash of the waves; but it was
big with events.
A dark figure wearing a cavalry jacket and Indian leggings was
crawling upon the watcher with the movements of the panther, and
the look that shot from the dark eyes was indicative of the fiercest
triumph and revenge, strangely commingled.
Once or twice the Indian—for an Indian the girls’ foe undoubtedly
was—paused and listened, as if he knew that Donald McKay was
not far off; but he never took his eyes from his prey.
Suddenly crouching very near the ground, imitating the movements
of the panther in every particular, he sprung upon the watcher, who
was secured before she could comprehend her situation.
One of the scarlet hands prevented her from crying aloud, and down
the bank with his captive the savage hurried.
He knew his path in the gloom, and avoided the numerous crags that
projected riverward as dexterously as though he could see like the
owl. By and by he took his hand from Artena’s mouth, cautioning her
at the same time not to utter a word, and at length executed a halt, in
the midst of Stygian darkness.
He had bound the nether limbs of the Squaw Spy in the light of the
fire beside which the spies slept, and he placed her on the ground,
while he turned his attention to the kindling of a fire.
In this he succeeded, and the blaze told Artena that her captor was a
gigantic young savage, named Hunter Phil.
She had known him for years; in truth, from girlhood—known him as
a vindictive lover, who had persecuted her with his attentions without
a moment’s cessation, when she was in his presence. But she had
not, until that hour of capture, encountered him for some time, and
had begun to hope that some Union bullet had terminated his
existence.
“Artena with Phil once more,” said the Indian, turning from the fire
and throwing himself before the girl, who sat on the stony floor of the
little cavern. “Phil no let Jack catch her again, for he’d kill her for
spying in his stony lodges for blue-coats.”
“Then, what are you going to do with me?” asked the girl, anxiously,
but with great calmness.
“Phil going to leave Modocs,” was the reply. “Blue-coats whip ’em, by
’m by. Jack’s cause lost, and Phil want to save his neck, for big
General hang Jack and his braves. So, Phil leave cave when night
come again, and Artena go with him to Arrow-Head.”
“But blue-coat law take Phil there.”
“Then Phil go to Feather river. Won’t catch him there!”
“Ah! but they will,” said the girl, with a smile at the Indian’s fear of
justice.
“Then Phil get in big ship, an’ go out on ocean. If blue-coats follow
him there, then he go to—” he paused and looked up into Artena’s
eyes—“to the devil!”
The girl laughed at the expression of triumph that sat enthroned
upon the Indian’s face. He had solved the difficult problem of
ultimate escape, and was proud thereof.
“Does Phil think that Jack would kill Artena?” asked the girl, quickly
returning to seriousness.
The Indian nodded.
“Kill her in minute! Don’t he know that she Davis’ spy? Hasn’t Phil
lain beside the big General’s tent and heard Artena tell him about
Jack? And Baltimore Bob came right from the camp after hearing
Artena and Kit talking to Davis, and told Jack that she was a
traitress. Ah, Artena, Jack knows all at last. You go with Phil now,
eh?”
The girl nodded, and almost beside himself with joy, the savage drew
his knife and severed her bonds.
Then she continued to converse with her dusky lover, until,
completely hoodwinked by her cunning words, he was thrown off his
guard, and never dreamed of treachery.
Without resistance, she possessed herself of his tomahawk, talking
the while of their future life among the Klamaths, and all at once the
weapon shot up into space, and as quickly and irresistibly
descended upon the unprotected head of the red-skin!
It took a terrible blow to fell the giant; but Artena’s arm was equal to
the emergency, and with a groan, he sunk to the ground.
She did not wish to kill him, for to him, no doubt, she owed her life,
and with throbless heart, she bent over the stricken lover, and felt his
pulse. For a moment it beat to the ratio of one hundred beats per
minute, and then they lessened until they ceased altogether.
Hunter Phil was dead!
Quite assured of this, the Squaw Spy rose to her feet, and once
more possessed herself of her own weapons. Now she would return
to the bank, where Donald, no doubt, waited for her, and wondered
at her absence. She knew that Phil was not aware of the ranger’s
presence: his words had told her this; and she was too far remote
from the bank to hear the shots that broke the stillness there a while
after her departure. Thoroughly acquainted with the intricacies of the
Lava-Beds, Artena thought that she could return to the spot without
difficulty, and left the dead lover’s cave on her mission.
But she missed the proper corridor, and followed one which led her
to a contemplation of the scene which was transpiring in Jack’s cave
—the arraignment of Cohoon as a spy.
She watched it from the shadow of a lava-crag, with an interest
bordering on terror, and when the Modoc’s arm was lifted to take the
Warm Springer’s life, by a well-directed pistol-shot she disarmed the
executioner, and then fearlessly showed herself, as the reader has
already witnessed.
Immediately after shooting the pistol from Jack’s hand, she flung her
weapons into the deeper gloom, deeming it policy to deny the act,
which was ascribed to McKay by the Indians.
What followed her surrender is described in chapter ten, so far as it
goes, and now we resume the thrilling narrative.

Cohoon lay on the ground, like one dead; but he was still imbued
with life.
The arrow had produced a senseless state, so nearly akin to death
as to deceive the Indians, and they glared fiercely upon the youth
whose empty bow told that he had sped the fatal arrow.
“Here, boy,” and the speaker, Captain Jack, turned upon the youth.
“Here, I want you, I say.”
Several chiefs pushed the youth forward, and he soon found himself
lifted from the ground by Mouseh’s strong arms.
“Curse your little heart!” cried the chief. “You’ve punished the man
whom I alone had the right to punish. Now to the spirit-land I send
you. Yon lava-wall will be reddened by your blood, and may your fate
be a warning to future self-installed executioners.”
He raised the youth above his head, as he uttered the last sentence,
and darted a quick look at Artena, who, with ready rifle, stood over
her lover, her eyes fixed upon the youth, so speedily devoted to
death.
A moment of breathless suspense followed, and then the Indian boy
left the chief’s grasp.
But his body did not strike the stony wall.
No! it struck a wall of flesh and blood, and Artena and ’Reesa South
were hurled ten feet backward by the strange weapon!
“Secure them!” cried Jack, pointing to the stricken girls with an air of
triumph, and several braves snatched thongs from their girdles and
sprung to the task.
The Indian’s invention had baffled his foes, and the hurling of the
youth against them was an action unlooked-for by every occupant of
the cave.
The force of the body was absolutely irresistible; it flew from Jack’s
hands like a thunderbolt, and after prostrating the girls, it struck the
foot of the wall beyond, and quivered there like a piece of raw liver.
Jack’s victory was greeted with wild shouts of approbation, and he
stepped forward quietly and secured the Spencer which had fallen
from Artena’s hands.
Then he stooped over Cohoon, and smiled faintly when he looked up
at his braves again.
A moment later, the Warm Spring chief opened his eyes, and, with
the assistance of his stern captor, rose to his feet.
His hands had been lashed to his side, but his nether limbs were
free, and he looked around upon the scene.
Neither Artena nor ’Reesa had recovered from the attack. Side by
side they lay, like corpses, in the light of the fire, and when the spy’s
gaze fell upon them, he shot a look of vengeance at Jack.
“Dead?”
The question was quite natural, for the young red ranger could not
see the girls’ bonds, which the position of their bodies hid.
“Dead are Artena and the white girl,” answered the Modoc, to see
what effect such words would have upon the ranger, and also to
torture his inmost soul.
A tinge of pain quivered Cohoon’s lips, and the lurid light of a storm
flashed in his dark eyes. That light warned more than one Indian,
and the clicking of rifle-locks again broke the silence.
“Who else, then?” demanded the ranger, and he moved forward an
inch.
The lying answer accorded well with the torture which the chief’s first
words had inflicted.
“This hand,” cried Jack, stretching forth his right hand. “It sent
Cohoon’s traitress—”
The snapping of cords interrupted the sentence, and the next
moment the spy was among his enemies! Jack saw the veins on his
forehead swell to enormous size; but the storm burst before he could
prepare to receive it.
The strength of a Sampson slept in the ranger’s muscles, and he
leaped among the Modocs with a short, sharp cry, closely allied to
the vengeful sound that often emerges from the panther’s throat.
Captain Jack received a blow from the Spencer, which the madman
wrenched from his grip, and then the weapon was stained with other
blood.
His sudden onslaught nonplused the Indians. They dared not shoot,
for their own brethren were likely to receive the balls, and only those
nearest Cohoon could get a sight of him.
He cleared a path for his daring feet.
Like Simon Kenton, among the savages of early Ohio, he fought his
way to the river bank, and then disappeared!
But not uninjured!
His escape from death seemed miraculous. It was his sudden
onslaught that saved him. It confused the savages, and almost in the
twinkling of an eye he was gone.
They could swear that his trail was marked with his own blood, and
when they returned to their chief, who was recovering from the spy’s
attack, it was to tell him that his foe would never cross his path
again.
This brave had sunk his knife into the scout’s side; that one had shot
him in the back as he fell into the stream, and a third had crushed
one shoulder with a clubbed carbine.
Not a savage could be found who had not inflicted some wound
upon the brave ranger, and amid the bestowal of self-praise, Jack
rose to his feet and pointed to the two captives still remaining in his
hands.
“Scar-face,” he said, “take them to the little spring cave, and let the
eyes of three of my best braves regard them until I command
further.”
Scar-faced Charley sprung to his task, and with the assistance of
four braves whom he selected from the band, the two helpless
captives were borne from the cave.
The chieftain was not in the humor to carry out his plans of
punishment at present. He pressed his hand to his head, but quickly
removed it, and saw it covered with blood.
“Look!” he cried, putting forth the gory member. “Mouseh’s blood is
flowing. Come, Modocs, swear that for every drop that falls from his
head, a blue-coat shall die!”
Then the cave resounded with shouts of vengeance; and stepping
toward the wall, with his own blood the murderer of Canby traced the
outlines of a gallows on the gray stone.
Then he turned to his braves, but spoke not.
They read the significance of the horrid design, and swore, for the
hundredth time, to die with rifles in their hands.
Some kept their oaths; but how Jack and others kept theirs, the
reader of the Modoc war has seen.
 CHAPTER XIII.
THE TRAITOR’S FLIGHT.
“Pale-faces stay here till Harry see if path clear. Jack’s spies may be
near.”
The speaker was the individual known as New York Harry, who had
surrendered to the troops on the morning of Kit South’s return to
camp, and he addressed the three men whom he had led to the
lava-beds, for the purpose, as he averred, to surprise a small
detachment of Modocs.
“Now look here,” said Sam Thatcher, one of the trio, who had been
warned by keen Kit South. “You’re not going alone. I’m going to
crawl for’ard with you, and by hokey! if I see a suspicious move on
your part, I’ll send a ray of starlight through your head.”
The Indian did not reply, and submitted to the border-man’s
company, with ill-humor plainly visible in his dark eyes.
“Now, stay hyar, boys, an’ keep eyes an’ ears open,” said Thatcher,
and as the guide, impatient to be off, moved slowly on, he added.
“This chap’s up to something—something devilish; I feel it away
down in my boots.”
Then the twain pushed forward together, and soon disappeared.
Ever and anon Harry would pause and listen intently, but not a sound
reached his ears. The stillness of the tomb brooded over the
fortresses of the renowned Modocs, and the stars shed a strange
light upon the death-traps of lava.
Sam Thatcher kept his eyes fastened upon his guide. He knew that
Kit South never suspicioned any one without cause, and when he
told him to watch Harry, he knew that treachery was in the air.
Suddenly the Modoc paused and turned his head.
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