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An Introduction to Metallic
Glasses and Amorphous
Metals
An Introduction to Metallic
Glasses and Amorphous
Metals
Zbigniew H. Stachurski
Gang Wang
Xiaohua Tan
Elsevier
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Contents
CHAPTER 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
CHAPTER 2 Making of metallic glasses and applications . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1 Applications of metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Aerospace and beyond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Protective shield . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Application as compliant mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Application as gears . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Application as mirrors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Application to corrosion resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Application to solar wind collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Application as magnetic sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Application as super-conducting sensor . . . . . . . . . . . . . . . . . . . . . . . . . 16
Biological applications of metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Recent developments of metallic glasses as biomaterials . . . . . . . . . . . . . 17
Mg60 Zn35 Ca5 alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Ti40 Cu36 Pd14 Zr10 alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Non-degradable metallic glasses (Ti-, Zr-, Fe-, Pt-based MGs) . . . . . . . . 19
Zr-based metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Fe-based metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Pt-based metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Mg-, Zn-, Ca-, Sr-based metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . 21
Metallic glass transformers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Sporting equipment and personal items . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Optical, magnetic, and electrical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Amorphous silicon solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Jewellery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Metallic plasticine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Rewritable DVDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Manufacturing process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
How the material functions in a system? . . . . . . . . . . . . . . . . . . . . . . . . . 29
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.2 Making metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Casting into a mold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Spinning wheel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
High-pressure torsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Ti–Ni alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Fe78 B8.5 Si9 P4.5 alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
v
vi Contents
ZrTiNiCu alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Ball milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Cold rolling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
CHAPTER 3 Solidification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.1 Solidification by crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Liquid → solid transformation by crystallization . . . . . . . . . . . . . . . . . . . . . . 45
Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Nucleation phenomenon and physical process . . . . . . . . . . . . . . . . . . . . 47
Nucleation kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Embryos, nuclei, and critical size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Temperature dependence of nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Structural dependence of nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Crystal growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Kinetics of crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Assumptions for isothermal crystallization . . . . . . . . . . . . . . . . . . . . . . . 59
Homogeneous nucleation and spherical growth . . . . . . . . . . . . . . . . . . . . 61
Instantaneous heterogeneous nucleation and spherical growth . . . . . . . . . 61
Random nucleation and surface growth . . . . . . . . . . . . . . . . . . . . . . . . . 62
Random nucleation and diffusion controlled spherical growth . . . . . . . . . 62
Microstructure of solidified metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Stereology of micro-structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Analysis of the KJMA equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Temperature dependence of the crystallization rate . . . . . . . . . . . . . . . . . 66
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.2 Solidification of glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
The process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
Use of the terms “amorphous” and “glass” . . . . . . . . . . . . . . . . . . . . . . . 71
Variety of glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Three characteristics common to all glasses . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Diffuse halo X-ray scattering pattern . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Step at Tg on DSC curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Gradient change at Tg in dilatometry . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Relationship between cooling rate and vitrification . . . . . . . . . . . . . . . . . . . . . 74
TTT diagram for aluminium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Continuous cooling transformation (CCT) diagrams . . . . . . . . . . . . . . . . 78
Brief history of metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
Glass-forming ability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Reduced glass transition temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Fragility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
The cage effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Contents vii
CHAPTER 4 Characterization of metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

4.1 Glass transition theories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Kinetic theory (WLF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Free volume theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
Entropy theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Stress fluctuations’ theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Viscoelastic theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Mode coupling theory (MCT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
Geometrical frustration theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Cluster jamming theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Space-time bubbles’ theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Local transition events . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.2 Mechanical testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
Tensile testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Measuring the sample . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Calculating elastic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Compression testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
Shear testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Hydrostatic testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
Surface hardness testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
The science and engineering of hardness testing . . . . . . . . . . . . . . . . . . . . . . . 131
Testing at high temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
Dynamic mechanical testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
CHAPTER 5 Models of structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Atomic arrangements in solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Atoms and their properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Models of atomic packing in crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Models of atomic packing in metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . 141
Ideal amorphous solid structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
Structure based on randomly oriented clusters . . . . . . . . . . . . . . . . . . . . 144
Models of micro-structure in metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
Poly-crystalline metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
Heterogeneity of structure in poly-crystalline metals . . . . . . . . . . . . . . . . 147
Heterogeneity of structure in metallic glasses . . . . . . . . . . . . . . . . . . . . . 148
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
CHAPTER 6 Magnetic properties of amorphous metallic alloys . . . . . . . . . . . . . . . . . . . . 157
Section 1. The history of magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
Ancient period (from the 1st to 18th century) . . . . . . . . . . . . . . . . . . . . . 157
Electromagnetic age (the 19th century) . . . . . . . . . . . . . . . . . . . . . . . . . . 158
viii Contents
Development of magnetism (the 20th century) . . . . . . . . . . . . . . . . . . . . 161

Age of applications (from the 20th to 21st century) . . . . . . . . . . . . . . . . . 162
Atomic-scale magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Magnetism of one electron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Orbital moment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Spin moment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
The total magnetic moment of one electron . . . . . . . . . . . . . . . . . . . . . . 166
Magnetism of one atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
Pauli exclusion principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
Magnetic moment of an atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
Hund’s rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Macroscopic-scale magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Magnetization (M) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Magnetic susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
Diamagnetism and paramagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
Ferromagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Molecular field theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Hysteresis loop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
The classification of ferromagnetic materials . . . . . . . . . . . . . . . . . . . . . 174
Hard magnetic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
Soft magnetic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
Section 2. Applications of amorphous alloys . . . . . . . . . . . . . . . . . . . . . . . . . 175
Soft magnetic behavior of Fe-based amorphous alloys . . . . . . . . . . . . . . 175
Fabrication techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Copper mold casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
J-quenching combined with fluxing technique . . . . . . . . . . . . . . . . . . . . 177
Powder metallurgy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
Additive manufacturing (or 3D printing) technique . . . . . . . . . . . . . . . . . 178
Enhancement of soft magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
Applications of commercialized Fe-based BMGs . . . . . . . . . . . . . . . . . . . . . . 179
Magnetic behavior of Nd-based amorphous hard magnets . . . . . . . . . . . . . . . 180
Models for the coercivity of Nd-based amorphous alloys . . . . . . . . . . . . 180
Microstructure and compositional characteristics of amorphous phase in
the Nd60 Fe30 Al10 bulk magnet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Enhancing the magnetic property by alloying elements . . . . . . . . . . . . . . . . . . 184
Magneto-caloric bulk amorphous alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
Magneto-caloric effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
A brief history of the magneto-caloric effect . . . . . . . . . . . . . . . . . . . . . . . . . 186
Characterization of magneto-caloric materials . . . . . . . . . . . . . . . . . . . . . . . . 186
Magneto-caloric bulk metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
Section 3. Outlook of magnetic amorphous alloys . . . . . . . . . . . . . . . . . . . . . 188
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
Contents ix
CHAPTER 7 Elasticity of metallic gasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193

Continuum mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Affine and non-affine deformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Example of macroscopic elastic deformation . . . . . . . . . . . . . . . . . . . . . 194
Strain measured by the Voronoi method (atomic level) . . . . . . . . . . . . . . 195
Strain measured by the X-ray method: crystalline solids . . . . . . . . . . . . . 197
Strain measured by the X-ray method: amorphous solids . . . . . . . . . . . . 198
Deformation in bulk metallic glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Elastic modulus by the X-ray method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
Deformation in Zr55 Al10 Ni5 Cu30 metallic glass . . . . . . . . . . . . . . . . . . . . . . . 202
Contact probability and average spacing . . . . . . . . . . . . . . . . . . . . . . . . . 203
Deformation in Zr46.5 Cu45 Al7 Ti1.5 metallic glass . . . . . . . . . . . . . . . . . . . . . . 205
Deformation in Zr64 Cu16 Ni10 Al10 metallic glass under cooling . . . . . . . . . . . 207
Deformation in thin film metallic glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
Structural evolution in Zr50 Cu50 metallic glass during compression . . . . . . . . 211
Structural evolution in Zr64.13 Cu15.75 Ni10.12 Al10 during heating . . . . . . . . . . . 213
Changes in atomic structure revealed by radial distribution . . . . . . . . . . . . . . . 215
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
CHAPTER 8 Introduction to anelastic deformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
Creep . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Stress relaxation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
Mechanical relaxation and dynamic loss modulus . . . . . . . . . . . . . . . . . . . . . 224
Time and temperature dependent behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
Creep of aluminium-based metallic glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
Creep of Zr-based metallic glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
Dynamic relaxation in Fe63 Al27 metallic glass . . . . . . . . . . . . . . . . . . . . . . . . 228
Free-volume anelastic deformation of metallic glasses . . . . . . . . . . . . . . . . . . 228
The β relaxation in La–Ni–Al metallic glass . . . . . . . . . . . . . . . . . . . . . . . . . 231
Definitions of shear viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
1. Newton’s definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
2. Stokes’ definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
3. Hagen–Poiseuille’s definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
CHAPTER 9 Plastic deformation and yield strength of metals . . . . . . . . . . . . . . . . . . . . . . 235
Time–temperature deformation maps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
T–T deformation map for poly-crystalline metal (silver) . . . . . . . . . . . . . 237
T–T deformation map for metallic glass . . . . . . . . . . . . . . . . . . . . . . . . . 238
Mechanisms of plasticity at the atomic level . . . . . . . . . . . . . . . . . . . . . . 238
Plasticity in metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Plastic flow in MGs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Serrated flow at macroscopic level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
Environmental temperature effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
Dynamical behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
Micro-structure effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
x Contents
Serrated flow at microscopic level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281

Serrated flow during nano-indentation . . . . . . . . . . . . . . . . . . . . . . . . . . 281
Serrated flow during nano-scratching . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
CHAPTER 10 Fracture mechanics of metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Fracture strength of an uncracked material . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Shear fracture – Coulomb–Mohr theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
Tensile fracture – Griffith’s fracture criterion . . . . . . . . . . . . . . . . . . . . . . . . . 318
Calculation of elastic strain energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
Calculation of crack surface energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
Solution for fracture stress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
Fracture toughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Limits of applicability of Eq. (10.24) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Irwin fracture criterion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
Fatigue and fracture of metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Loads and variation during use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Time to crack initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Crack growth rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
Life prediction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
Dependence of strength on sample size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
Instability and morphology of fracture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
APPENDIX A Thermodynamics of a system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Molecular system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
Forces between atoms, molecules, and particles . . . . . . . . . . . . . . . . . . . . . . . 341
Types of physical forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Interatomic forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Lennard-Jones interatomic potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Buckingham potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Morse potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
Many-atom potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
Stillinger–Weber potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Embedded atom model potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Gibbs free energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Liquid-to-solid phase transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Computation of cluster potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
CHAPTER
Introduction
1
Aristotle stated at the beginning of his book on Metaphysics that “all men, by their nature, desire to
know.” Aristotle was an ancient Greek philosopher (384–322 BCE) and a scientist born in the city
of Stagira, Chalkidiki, in the north of Classical Greece. All people naturally are curious and acquire
knowledge for practical usage as well as for disseminating knowledge. An indication of this is our
esteem for the senses; for apart from their use we value them for their own sake, and most of all, the
sense of sight. Not only with a view to action, but even when no action is contemplated, we prefer
sight, generally speaking, to all the other senses. The reason of this is that of all the senses sight best
helps us to know things, and reveals many distinctions.
Another philosopher, Xiang Liu, in Western Han Dynasty of ancient China said: “Seeing is better
than hearing, and practice is better than seeing.”
It is from memory that people acquire experience because numerous memories of the same thing
eventually produce the effect of a single experience. Experience seems very similar to science and art,
but actually it is through experience that men acquire science and art.
FIGURE 1.1
(a) The Great Pyramid of Giza (ca. 3000 BCE); (b) a bronze vase of China (ca. 1300 BCE); and (c) iron axe from
Sweden (ca. 1500 ago).
Archaeologists investigate historic and prehistoric sites and physical artifacts found at the sites to
understand human activities in the past. In this process they reveal the advancements of various aspects
of human life and reconstruct history of human civilizations. As a result of their extensive studies, they
have defined the long span of human civilization into three eras distinguished by the use of materials
as listed below, and with examples illustrated in Fig. 1.1:
An Introduction to Metallic Glasses and Amorphous Metals. https://doi.org/10.1016/B978-0-12-819418-8.00005-X
1
2 Chapter 1 Introduction
• The Stone Age – prehistory to ca. 3000 BCE

• The Bronze Age – approximately 3000–1000 BCE
• The Iron Age – approximately 1000 BCE – CE 1000
In modern times, the period from 1850 to 2000 is sometimes referred to by different names:
• the Age of Steel,
• or the Age of Plastics,
• or the Age of Nanomaterials.
Perhaps many decades from now, this period of time will be referred to as The Age of New Materials,
to which metallic glasses belong. High-tech companies, such as SpaceX, Orbital Sciences Corporation,
or XCOR Aerospace, are rapidly developing transportation systems for exploration of the neighboring
planets. It is more than likely that metallic glasses will play a significant role in these endeavors. Of
course, it may even be called the Age of Quantum Computing or something else.
An accumulated knowledge, which comprises skills, art, techniques, and skillful shaping and con-
struction, constitutes an accumulated know-how that involves experience (skills and familiarity) and
requires holding in memory an amount of information (i.e., a number of facts, or simply information).
Note that know-how is sufficient to repeat the activity as many times as required. For example, large
man-made stone structures begin to appear around 10,000 years ago. Suitably shaped rocks were se-
lected for the purpose, with timber trunks used as rollers, and ropes used as slings and for hoisting. In
today’s terms, the construction of the stone structure would be called civil engineering. However, from
this experience the more observant individuals would hold in memory not only the effort of labor and
the know-how of the construction, but also such facts as hardness and surface smoothness of the rock
for lower friction, the strength of rope for pulling and lifting and the hardness and resistance to splitting
of tree trunks for rolling applications. All of these are properties of the materials used in the engineering
activity that would be retained in memory and in due course become knowledge of materials.
The longest experience with materials was that with stone and wood, of which stone is the ever-
lasting as is evident in Fig. 1.2. Smelting and shaping of iron followed the experience and know-how
of making bronze from an earlier age, and went on for centuries without significant advances, until
the middle of the 19th century when the confluence of two major factors revolutionized iron smelting
into steel making, superseding the age old process. This new method of steel making, and its wide
application, had a pronounced effect on our civilization in the modern era.
The first major contributing factor was the expansion of manufacturing and construction, created by
demands of the industrial revolution in the developing world, and hence the need for large quantities of
strong materials for machinery, construction, and civil engineering connecting continents by railroads.
The second essential factor was the discovery by chemists (metallurgists) that “pig iron” contained
too much carbon dissolved in it, which had to be removed by lengthy and costly reprocessing to give
a more useful “wrought” iron. Prior to that time, the crude iron material was produced in the blast
furnace, using raw minerals such as iron ore, lime, coke for fuel, and other ingredients. The product of
this process, the pig iron, had a very high content of carbon, between 4% and 5%, together with silica
and other impurities which rendered it brittle and not of much use directly. (The traditional molds
were formed in sand, with a central channel branching into many individual ingots at right angles,
resembling a litter of suckling piglets, hence the name pig iron). Chemistry was developing into a
powerful science, equipped with analytical tools and theoretical understanding of the gas, liquid, and
Chapter 1 Introduction 3
FIGURE 1.2
Megalithic man-made structures from the Stone Age: (a) Single chamber tomb in Korea (ca. the 9th millennium
BCE); (b) Stone structures in the municipality of Borger-Odoorn, Netherlands (ca. the 4th millennium BCE).
solid state. Chemical elements were being discovered and identified at a rapid rate. Already in 1722,
René Antoine Ferchault de Réaumur demonstrated that iron was transformed into steel through the
absorption of some substance, later found to be carbon, for which A.L. Lavoisier proposed the name
“carbon” in 1789 from the Latin word for “charcoal.” In 1774, J. Priestley found that air is a mixture
of gases, one of which was the highly reactive gas he called “dephlogisticated air,” later identified as
oxygen, which had great affinity for carbon.
In 1856, the Englishman Henry Bessemer became aware of the significance of the seemingly un-
saturated demand for steel, and suddenly realized that carbon could be burned out of the molten iron
by air. He took out a patent on making steel directly by blowing air through the molten iron mixture.
By the turn of the century, large companies were set up in the USA and Europe to manufacture steel
by the Bessemer method. Later on, oxygen steelmaking eventually replaced the open hearth furnace.
Oxygen was liquefied in a stable form for the first time in 1883 by Polish scientists from Jagiellonian
University, Zygmunt Wróblewski and Karol Olszewski.
Today, steel (together with concrete) is the most widely used material in the world.
Similar circumstances occurred in the middle of 20th century with respect to the discovery and
development of metallic glasses – the new materials. The most important application of metallic glasses
is in the field of magnetic and ferromagnetic devices. The exceedingly low magnetization loss of these
materials is used to a good advantage in high efficiency transformers at low frequency power lines.
Also electronic surveillance devices (such as theft control passive ID tags) often use metallic glasses
because of these special magnetic properties.
It is important to bring to notice the fact that amorphous solids, other than metallic glasses, are
widely used: silica glass in windows, in optical devices, and in optical fibers for telecommunication.
Glassy (amorphous) solids have been positively identified in terms of their amorphous atomic struc-
ture at the beginning of the 20th century with the aid of X-ray diffraction studies. The first structure
of an amorphous solid, namely that of plain silica glass, was identified by an X-ray scattering study
by (Warren, 1934) and more recently corroborated by the so-called fluctuating electron microscopy.
Chemists had some prior ideas about random networks and chain molecules as is known from the
works of Zachariasen (1932) and Staudinger (1933). The technology of processing of glasses and their
manifold uses are very advanced and extensive, yet there is no adequate underlying theory of amor-
phous structure as for crystalline solids. What is generally known and accepted at this stage is that
amorphous solids do not possess as a rule any crystallinity, and that the atomic arrangements are con-
sidered to be random, having no long-range order as in crystals. In some circumstances they are called
“frozen liquids.”
The understanding of the atomic-scale structure of solids (from which modern technology and
society benefit so greatly) has come about to a large degree because of the development of the methods
of geometry and X-ray crystallography. From the first discovery of the diffraction of X-rays by a crystal
by (Friedrich et al., 1913) and (Bragg, 1913), to the present day when structures of large molecules are
determined routinely, crystallography has developed from small beginnings to become an enormously
successful and powerful tool for the study of atomic arrangements in solids.
The other contributing factor towards discovering metallic glasses was the advancement of Mate-
rials Science, especially in the field of plasticity of metals and metallic alloys. Theory of dislocations
within the ordered crystalline structure, and verification of their existence by electron microscopy, pro-
vided a sound basis for a clear understanding of the plasticity of metals, especially of pure metals, in
terms of dislocations’ motion in the polycrystalline structure. Soon after, the strengthening mechanisms
of strain hardening, precipitations, and alloying were identified. It was concluded that making metallic
alloys with smaller and smaller grain size leads to step-wise improvements in strength. Eventually, in
the limiting case of zero grain size, an amorphous structure was envisioned, possessing mechanical
strength approaching that of the theoretical strength of materials.
In the mid-20th century, the alloy system of gold–silicon (Au–Si) was well studied, and was known
to have a hexagonal close-packed crystalline structure in solidified alloys. Interestingly, the Au–Si
alloy system shows a deep eutectic at a composition of approximately 20% atomic weight of Si in
Au, with a low melting point of 636 K, compared to the melting point of Au of 1337 K, and 1687 K
for Si. This eutectic melt, when rapidly quenched on a spinning copper wheel, solidified into thin
ribbon-like objects, and appeared to have no crystallinity on the basis of X-ray diffraction pattern of
the “quenched” Au80 Si20 composition. This was the first case of a metallic amorphous alloy reported in
the scientific literature. Very high cooling rates had to be employed, of the order of 106 K/s, to produce
small amounts of long amorphous metal of approximately 0.1 × 10 mm in cross-section, hence the
description “ribbon-like” metallic glasses.
The first bulk metallic glass (BMG), with centimeter dimension, was the ternary Pd–Cu–Si alloy
prepared by Chen et al. in 1974. A simple suction-casting method was used to form rods of the metallic
glass at a cooling rate of 103 K/s. In 1982, Turnbull and coworkers successfully prepared the Pd–Ni–P
BMG using boron oxide fluxing method to purify the melt and to eliminate heterogeneous nucleation.
The experiments showed that a glass transition temperature, Tg ≈ 2/3 Tm , was achieved when hetero-
geneous nucleation was suppressed. The ingot was of centimeter size, solidified at cooling rates of the
order of 10 K/s. Although the formation of Pd-based BMG is an exciting achievement, however, due
to the high cost of palladium metal, the experiments were only followed in academic circles, and the
interest faded after some years.
In the late 1980s, Inoue and his coworkers in Tohoku University of Japan succeeded in finding
new multi-component alloy systems consisting mainly of common metallic elements with lower crit-
Chapter 1 Introduction 5
Table 1.1 Properties of metallic glasses (from Ashby and Greer, 2006).
Attributes Attractive properties
general the absence of microstructural features such as grain and phase
boundaries allows components with features of near-atomic scale
mechanical high hardness, giving good wear and abrasion resistance
high yield strength, very high fracture toughness
low mechanical damping (low dissipation losses)
thermal for some metallic glasses, Tg Tc , allowing processing as super-cooled
liquid (thermo-plastic forming: injection molding, hot pressing, etc.)
Tg – glass transition temperature, Tc – crystallization temperature
electrical resistivity is almost independent of temperature
magnetic high magnetic permeability
chemical high corrosion resistance
processing low solidification shrinkage and no grain structure give
high precision and finish in castings
aesthetics very high surface polish due to lack of microstructure
durability high hardness and corrosion resistance gives durability
ical cooling rates. Having systematically investigated ternary alloys of rare-earth materials with Al
and ferrous metals, they observed exceptional glass forming ability in the rare-earth-based alloys, for
example, La–Al–Ni and La–Al–Cu, by casting the alloys’ melt in water-cooled Cu molds.
By the early 2000s, many hundreds of BMGs have been produced around the world. The interest
in amorphous metallic materials is evidenced by a USA company, LiquidMetal, which introduced the
first commercial amorphous alloy, Zr-based Vitreloy, in 2003. The Vitreloy BMG has been used in
sporting, medical, and industrial products.
Metallic glasses seem unusual. They are hard and brittle like glass, but not transparent; they have
the softening point like glass well below their crystalline melting point, yet, unlike optical glasses, they
do not conduct light, but are good conductors of electricity. Indeed, metallic glasses are like metals
and glasses, exhibiting some properties common to both. They posses the characteristics of the two
types of materials because the arrangement of atoms in metallic glasses is similar to those in organic
and inorganic glasses, yet the chemistry and electronic structure is that of metals. The main aim of
this textbook is to describe metallic glasses in terms of their physical characteristics, their uses and
applications, the methods of their manufacture, and their inner atomic structure.
The challenges of studying and developing metallic glasses are numerous, carrying excitement of
new discoveries and new applications, based on their inherent advantages shown in Tables 1.1 and 1.2.
It can be said with a high degree of certainty that petrol and diesel motorcars have limited life as
they are reaching their peak in performance and efficiency, but continue to contribute significantly to the
environmental pollution. They will gradually disappear from our lives like steam engines and sailing
ships of earlier times. Electric motors are far superior to reciprocating piston engines, and therefore, are
the future of all our transportation and mechanical movement actions. The use of electric motors are
presently limited only by the supply of high capacity batteries. Metallic glasses are excellent candidates
for electric motor applications, and great advances in their use and design are anticipated. Imagine the
future without air polluting cars and trucks.
In fact, the very first motorcar had an electric motor (for a commercial example, see Fig. 1.3) – it
was the lack of adequate batteries that stalled its progress. France and the Great Britain were the first
Table 1.2 Current and potential applications of metallic glasses (Wang et al., 2004).
Property Primary applications Secondary applications
high strength machines and devices
high hardness cutting tools wear resistant medical devices
high fracture toughness die materials
high reflection ratio optical precision materials
high frequency permeability high magnetostrictive materials
high wear resistance medical devices
all of the above space applications
FIGURE 1.3
An 1901 advertisement for a commercial electric car.
nations to support the widespread development of electric vehicles in the 1890s. Ferdinand Porsche’s
design and construction of an all-wheel drive electric car in Germany was powered by an electric motor
in each hub, and has set several speed records at the time. Electric vehicles have a number of significant
advantages over their present day competitors. Most importantly, they do not have the vibration, smell,
and noise associated with gasoline and diesel cars. They also do not require gear changes. If their
batteries are charged from renewable energy sources, their effect on air pollution is close to zero by
comparison with today’s cars.
(For comparison, electric motors are typically 95% efficient in transforming input energy into ro-
tational energy, whereas internal combustion engines are only 35% efficient at best – the rest of the
fuel’s calorific value dissipates as air friction, and escapes as heat and exhaust gasses. The efficiency
of steam locomotives of the past was as low as 10%.)
Intelligent reflections on the relationship between the observed properties and performance of ma-
terials lead to enhanced personal knowledge, with social advantage to people carrying out engineering
References 7
activity. The level of knowledge depends on the ability to conceptualize the relationships between the
elements of the information, and an ability to manipulate the concepts and facts to derive the life ad-
vantage, which leads to understanding. (Knowledge may be thought of as the database collected by
Facebook, whereas understanding is analogous to the algorithm which characterizes each person on
the database by the information held.) Thus, science is a branch of knowledge dealing with a body of
truthful facts arranged to reveal general laws, gained through observation and experimentation.
Materials Science, a branch of the Physics of Solid State, is based on the knowledge and under-
standing of the following fundamental relationship:
atomic/molecular structure → material’s properties
that is, the chemistry and structure of solids governs the behavior of the solid materials.
The use of this relationship for applied practical ends is the field of Materials Engineering. An
important relationship exists between the methods and conditions of processing of materials and their
final microstructure.
processing of materials → material’s microstructures
The basis of the first relationship can be traced back in history to the ancient Greece, when Leccipus
of Miletus and Democritus of Abdera (in ancient Greece) proposed that matter is composed of atoms
(indivisible volume – derived from Greek). Furthermore, they hypothesized that atoms have shapes that
make them possess and exhibit properties, such as acidity, sweetness, stickiness, and smoothness, and
allow them to bond to make up other matter.
In the two relationships above, the term “atomic/molecular structure” refers to the arrangement of
atoms in the solid material, and “property” refers to the physical, chemical, electrical, mechanical,
and other properties of materials that we make use of in particular applications. The metallic glasses
connect the “amorphous” structure with “metallic” bonding; they are thus expected to possess unique
properties that do not exist in other materials.
Indeed, it is the aim of this book to provide deep insight into these relationships, as well as to
consolidate the existing knowledge on metallic glasses and related subjects. The hope of the authors is
that this textbook provides much of the information the student reader is searching for, and furthermore,
that it points the readers accurately and efficiently to other sources where more information can be
found so that deep personal knowledge can be acquired and enriched.
References
Bragg, W.L., 1913. The diffraction of short electromagnetic waves by a crystal. Proceedings of the Cambridge
Philosophical Society 17, 43–57.
Friedrich, W., Knipping, P., Laue, M., 1913. X-ray diffraction from single crystals. Annals of Physics 346 (10),
971–988.
Wang, W.H., Dong, C., Shek, C.H., 2004. Bulk metallic glasses. Materials Science & Engineering. R, Reports 44,
45–89.
Warren, B.E., 1934. X-ray determination of the structure of glass. Journal of the American Chemical Society 17,
249–254.
CHAPTER
Making of metallic glasses and

applications
2
SUBCHAPTER
Applications of metallic glasses

2.1
Aerospace and beyond
Metallic glasses (MGs) are considered as a novel class of materials, different from crystalline metallic
alloys. Over the past decades, experimental and theoretical researchers have devoted time and effort to
understand and characterize the nature of amorphous solids. Metallic glasses possess excellent proper-
ties, and are regarded as potential materials in mechanical, chemical, magnetic, and optical engineering.
Various metallic glassy alloys based on Zr-, Fe-, Ce-, Ti-, and Mg- elements attract great interest
for applications in medicine, electrical engineering, aeronautics, and astronautics. The relevant research
work has been conducted in the field of space research and devices in aerospace vehicles, including
protective shields and various aerospace components such as compliant mechanisms, gears, magneto-
electric components, solar wind collector plates, etc.
Space environment is so different and complex compared that on the Earth’s surface that the
aerospace vehicles are subjected to extreme conditions: temperature as low as −200◦ C, extreme hu-
midity and desert environment before launch, ultraviolet exposure, ion irradiation, and debris striking,
which demand exceptional properties of the metallic glassy alloys applied in aerospace. The structural
evolution and performance of MGs at cryogenic temperatures have been studied, and a ductile–brittle
transition was observed going from lower to higher temperatures, and vice-versa. The ion irradia-
tion resistance of MGs has also been investigated under different ion sources. There was no significant
damage observed on Ta38 Ni62 MG surface irradiated by He2+ ions. However, thermally induced partial
crystallization occurred under prolonged exposure at 360◦ C for Cu60 Zr20 Hf10 Ti10 MG, which means
that this alloy is not suitable for irradiation environments for extended periods of time. Recently, a
novel high-temperature Ir35 Ni20 Ta40 B5 MG alloy has been developed by combinatorial methods, and
it is expected that it will be applied in aerospace under both high and cryogenic temperatures.
Cold welding occurs under high vacuum (i.e., in aerospace) between the atomically clean metal
surfaces, even without heat applied, and under static contact, caused by the mutual diffusion of atoms
An Introduction to Metallic Glasses and Amorphous Metals. https://doi.org/10.1016/B978-0-12-819418-8.00006-1
9
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and seventh about equal; first four abruptly cut out on the inner web;
secondaries broad and rounded. Tail rather long, broad, slightly
rounded.
Bill light blue at the base, with the margins yellowish, the tip black;
the cere yellow. Iris hazel. Feet yellow; claws black, at the base
bluish. The general colour of the upper parts is chocolate-brown. The
quills are of the general colour externally, but the primaries are black
toward the tip, a great part of the inner web, with the shaft, white,
and barred with brownish-black, the bars more extended on the
secondaries. The tail is marked with about ten dusky bars on a
reddish-brown ground, tinged with grey, the last dark bar broader,
the tips paler. The eyelids are whitish, as is the throat, which is
longitudinally streaked with dusky. The rest of the lower parts are
yellowish or brownish white, barred with brown. The lower wing-
coverts are white, barred or spotted with dusky; the white of the inner
webs of the primaries forms a conspicuous patch, contrasted with
the greyish-black of their terminal portion.
Length to end of tail 23 inches; wing from flexure 17; tail 10 1/2; bill
along the ridge 1 8/12, along the edge of lower mandible 1 7/12; tarsus
3 5/12; hind toe 1, its claw 1 1/12; middle toe 1 10/12, its claw 1 1/12.
Another specimen in my possession, procured by Dr Townsend on

the plains of Snake River, has the upper parts brown, streaked and
spotted with reddish-white; the upper tail-coverts white, barred with
dusky, the lower parts as above described. The colours however
vary, and in some the upper parts are deep brown, the lower reddish
or brownish white, barred with reddish-brown.
When compared with European specimens, mine have the bill
somewhat stronger; but in all other respects, including the scutella
and scales of the feet and toes, and the structure of the wings and
tail, the parts are similar.
Marsh Hare.
Lepus palustris, Bachman.

The Hare figured in the plate is thus described by my learned friend
Dr Bachman, in his excellent observations on the different species of
the genus Lepus inhabiting the United States and Canada, inserted
in the seventh volume of the Journal of the Academy of Natural
Sciences of Philadelphia:—
“Smaller than the American Hare. Ears much shorter than the head;
eyes rather small; tail very short; feet small, thinly clothed with hair.
Upper surface yellowish-brown; beneath, grey.
4 0—0 6—6
Incisors Canines Molars = 28
2, 0—0, 5—5,
“The upper incisors are longer and broader than those of the
American Hare, marked, like all the rest of the species, with a deep
longitudinal furrow. The small accessory incisors are smaller and
less flattened than those of the last mentioned species, and the
molars are narrower and a little shorter. The transverse diameter of
the cranium is much smaller, the vertical diameter about equal.
Orbits of the eyes one-third smaller. This is a striking peculiarity,
giving it a smaller and less prominent eye than that of any other
American species. The pterygoid processes of the temporal bone
project downwards nearly in a vertical line, whilst those of the
American Hare are almost horizontal.
“Head and ears shorter than those of the Lepus Americanus; legs
short, and rather small; body short and thick; feet small, thinly
clothed with hair beneath, so as not to cover the nails, which are
larger than those of the American Hare. Tail shorter than that of any
other species of true hare inhabiting the United States, except the
Lepus Nuttalli. Hair on the back long and somewhat rough. From the
short legs and ears of this species, and its general clumsy habit, it
has the appearance when running through the marshes, splashing
through mud and mire, and plunging into creeks and ponds of water,
of some large Norway Rat, hastening to escape from its pursuers.
“The teeth are yellowish-white; the eyes are dark brown, appearing
in certain lights quite black. Upper parts of the head brown and
greyish-ash. Around the orbits of the eyes slightly fawn-coloured.
Whiskers black. Ears dark greyish-brown. The back and whole upper
parts yellowish-brown, intermixed with many strong black hairs. The
hairs, when examined singly, are bluish-grey at the roots, then light
brown, and are tipped with black. The fur, beneath, is light
plumbeous; under the chin grey; throat yellowish-brown; belly light
grey, the fur beneath bluish. Under surface of the tail ash-colour,
edged with brown. During winter the upper surface becomes
considerably darker than in summer.
Dimensions, taken from a specimen in the flesh:

Length, from point of nose to insertion of tail, 13 inches
Height, from the top of the fore-shoulder to the 7
end of the middle claw
Length of the head, 3 1/2
..... ..... ears, 2 1/2
..... ..... hind foot, 3
..... ..... tail (vertebræ), 5/
6
..... ..... tail, including the fur, 1 1/2
Weight 2 1/2 lb.
“I have not heard of the existence of this small species of Hare to the
north of the State of South Carolina, nor is it found in the upper parts
of this State,—confining itself to the maritime districts, to low marshy
grounds partially inundated, to the borders of rivers subject to the
overflowing of their banks, and to the ponds, usually termed
reserves, where the waters intended to overflow the rice-fields are
preserved. In these situations, rendered almost inaccessible on
account of mud, entangled vines, and stagnant waters, sending up
poisonous miasmata, the fruitful source of disease, surrounded by
frogs, water-snakes, and alligators, this species resides through the
whole year, scarcely molested by man. In these forbidden retreats,
frequented by Herons (Ardea), Snake-birds (Plotus Anhinga), and
Ibises, this almost aquatic quadruped finds a home suited to its
habits; making up for its want of speed in eluding pursuit, by its
facility in winding through miry pools and marshes overgrown with
rank weeds and willows. In such situations, I have met with it fifty
miles north of Charleston; but, as soon as the traveller arrives at the
high grounds of the middle country, where the marshes disappear,
this Hare is no longer seen. It is common in all the lower parts of
Georgia, and I have observed it for sale in the market of Savannah.
It is abundant in East Florida, even at its farthest southern extremity.
I received a living animal of this species, taken on one of the islands
near Indian Key, called Rabbit Key, separated from the main-land by
several miles of sea; where it could have proceeded only by
swimming, but where it is now found in great numbers. In all the low
grounds of Florida, this species takes the place of the American
Hare, which has not been observed in those situations.
“The Marsh Hare is one of the most singular in its habits of all the
species. It runs low on the ground, and cannot be said to possess
the fine leaping gait of the American Hare. It is so slow of foot, that
nothing but the sheltered and miry situations in which it resides can
save it from being easily overtaken and captured. I have, indeed,
observed the domestics on a plantation, during a holiday, setting fire
to a piece of marsh ground, in a very dry season, and armed with
clubs, waiting till the flames drove these Hares from their retreats,
when they were run down and killed in considerable numbers, I
noticed that when the American Hare made its appearance it was
suffered to pass, on account of the speed they knew it to possess,
but no sooner did the Marsh Hare appear, than with a whoop, they
gave chase, and seldom failed to overtake it.
“The feet of the Marsh Hare are admirably adapted to its aquatic
habits. A thick covering of hair on its soles, like that on the other
species, would be inconvenient; they would not only be kept wet for
a considerable length of time, but would retard them in swimming. All
quadrupeds that frequent the water, such as the Beaver, Otter,
Muskrat, Mink, &c., and aquatic birds, have nearly naked palms; and
it is this peculiar structure, together with the facility of distending its
toes, that enables this quadruped to swim with such ease and
rapidity. The track, when observed in moist or muddy situations,
differs very much from that of the other species. Its toes are spread
out, each leaving a distinct impression, like those of the rat.
“The Marsh Hare deposits its young in a pretty large nest, composed
of a large species of rush (Juncus effusus) growing in a convenient
situation. These appeared to have been cut into pieces of about a
foot in length. I have seen these nests nearly surrounded by, and
almost floating on, the water. They were generally arched, by
carefully bending the rush-grass over them, admitting the mother by
a pretty large hole in the side. A considerable quantity of hair was
found lining the nest, but whether plucked out by the parent, or the
effect of the season, (it being late in spring when these animals shed
their coat) I was unable to ascertain. The young were from five to
seven. They evidently breed several times in the season, but I have
observed that the females usually produce their young two months
later, at least, than the American Hare. Twenty-one specimens were
obtained from the 9th to the 14th day of April; none of the females
had produced young that season, although some of them would
have done so in a very few days. On one occasion only, have I seen
the young in March. These bear a strong resemblance to the adults,
and may almost at a glance be distinguished from those of the last-
mentioned species.
“This species possesses a strong marshy smell at all times, even
when kept in confinement, and fed on the choicest food. Its flesh,
however, although dark, is fully equal, if not superior, to that of the
American Hare. The Marsh Hare never visits gardens or cultivated
fields, confining itself throughout the year to the marshes. It is
occasionally found in places overflown by salt or brackish water, but
seems to prefer fresh-water marshes, where its food can be most
conveniently obtained. It feeds on various grasses, gnaws off the
twigs of the young sassafras, and of the pond spice (Laurus
geniculata). I have seen many places in the low grounds dug up, the
foot-prints indicating that it was the work of this species in search of
roots. It frequently is found digging for the bulbs of the wild potato
(Apios tuberosa), as also for those of a small species of Amaryllis
(Amaryllis Atamasco).
“I possess a living animal of this species, which was sent me a few
weeks ago, having been captured when full grown. It became so
gentle in a few days that it freely took its food from the hand. It is fed
on turnip and cabbage leaves, but prefers bread to any other food
that has been offered to it. It is fond of lying for hours in a trough of
water, and seems restless and uneasy when the trough is removed,
scratching the sides of its tin cage until it has been replaced, when it
immediately plunges in, burying the greater part of its body in the
water.
“It has already shed a great portion of its summer, and resumed its
winter, dress. The hairs on the upper surface, instead of becoming
white at the point, as in the American Hare, have grown long and
black, through which the brownish parts beneath are still distinctly
visible.
“This species, like others of the genus existing in this country, as well
as in the deer and squirrels, is infested with a troublesome larva of
an œstrus in the summer and autumn, which, penetrating into the
flesh, and continually enlarging, causes pain to the animal, and
renders it lean. One of these larvæ dropped from an orifice in the
throat of the hare which I have in confinement. It was of the usual
cylindrical shape, but appears to differ in some particulars from the
Œstrus cuniculi.”
EVENING GROSBEAK.
Fringilla vespertina, Cooper.

PLATE CCCLXXIII. Male.
This fine species of Grosbeak was first introduced to the notice of

ornithologists by Mr William Cooper, who published an account of
it in the Annals of the Lyceum of New York. Mr Schoolcraft
observed a few individuals, in the beginning of April 1823, near the
Sault Sainte Marie in Michigan, from which the species was traced to
the Rocky Mountains. Dr Richardson mentions it as a common
inhabitant of the maple groves on the Saskatchewan plains, whence
“its native appellation of Sugar-bird.” The female remained utterly
unknown until it was obtained by Dr Townsend, who found this
Grosbeak abundant about the Columbia River, and procured a great
number of specimens, several of which are in my possession. The
following note from him contains all the information respecting its
habits that I can lay before you.
“Columbia River, May 27, 1836.—The Evening Grosbeak, Fringilla
vespertina, is very numerous in the pine-woods at this time. You can
scarcely enter a grove of pines at any hour in the day without seeing
numbers of them. They are very unsuspicious and tame, and I have,
in consequence, been enabled to procure a fine suite of specimens.
The accounts that have been published respecting them by the only
two authors to whom I have access, Mr Nuttall and Prince
Bonaparte, are, I think, in many respects incorrect. In the first place,
it is stated that they are retiring and silent during the day, and sing
only on the approach of evening. Here they are remarkably noisy
during the whole of the day, from sunrise to sunset. They then retire
quietly to their roosts in the summits of the tall pines, and are not
aroused until daylight streaks the east, when they come forth to feed
as before. Thus I have observed them here, but will not say but that
at other seasons, and in other situations, their habits may be
different. They are now, however, very near the season of breeding,
as the organs of the specimens I have examined sufficiently indicate.
They appear fond of going in large bodies, and it is rare to see one
alone in a tree. They feed upon the seeds of the pine and other
trees, alighting upon large limbs, and proceeding by a succession of
hops to the very extremities of the branches. They eat, as well as
seeds, a considerable quantity of the larvæ of the large black ant,
and it is probable that it is to procure this food that they are not
uncommonly seen in the tops of the low oaks which here skirt the
forests. Their ordinary voice, when they are engaged in procuring
food, consists of a single rather screaming note, which from its tone I
at first supposed to be one of alarm, but soon discovered my error.
At other times, particularly about mid-day, the male sometimes
selects a lofty pine branch, and there attempts a song; but it is a
miserable failure, and he seems conscious of it, for he frequently
pauses and looks discontented, then remains silent sometimes for
some minutes, and tries it again, but with no better success. The
note is a single warbling call, exceedingly like the early part of the
Robin’s song, but not so sweet, and checked as though the
performer were out of breath. The song, if it may be so called, is to
me a most wearisome one: I am constantly listening to hear the
stave continued, and am as constantly disappointed. Another error of
the books is this,—they both state that the female is similar to the
male in plumage. Now, this is entirely a mistake: she is so very
different in colour and markings, that were it not for the size and
colour of the bill, and its peculiar physiognomy, one might be induced
to suppose it another species. The specimens in possession of Mr
Leadbeater of London, and from which Prince Bonaparte drew up
his descriptions, must have been all males.”
In the present plate you will find the figure of a male only; but in Plate
CCCCXXIV. are representations of the young male and adult female,
which are however here described.
Fringilla vespertina, Cooper, Ann. Lyc. New York, vol. i. p. 220.—Ch.

Bonaparte, Synopsis of Birds of United States, p. 113.
Evening Grosbeak, Fringilla vespertina, Ch. Bonaparte, Amer. Orn. vol.
ii. pl. 14. fig. 1.
Coccothraustes vespertina, Evening Grosbeak, Richards. and Swains.
Fauna Bor.-Amer. vol. ii. p. 269.
Evening Grosbeak, Nuttall, Manual, vol. ii. Appendix, p. 594.
Adult Male. Plate CCCLXXIII.

Bill of moderate length, extremely thick, conical, pointed; upper
mandible with the dorsal line very slightly convex, the sides rounded;
the edges sharp, overlapping, with a slight sinus close to the acute
tip; lower mandible with the angle very short and broad, the dorsal
line straight, or very slightly concave, the back very broad, the sides
rounded, the edges inflected, the tip acute. Nasal sinus extremely
short and broad: nostrils round, basal, concealed by short reflected
bristly feathers.
Head large, roundish-ovate; neck short; body moderately full. Feet
short, of moderate strength; tarsus short, compressed, with seven
anterior scutella, and two plates behind forming a sharp edge; hind
toe large, outer toe somewhat longer than inner; claws rather large,
moderately arched, much compressed, acute.
Plumage full, soft, blended, the feathers oblong. Wings rather long,
broad, abruptly pointed; the outer three primaries almost equal, the
first longest; outer secondaries emarginate. Tail of moderate length,
rather narrow, emarginate, of twelve rather narrow feathers.
Bill yellow; iris hazel; feet flesh-colour, claws brown. The upper part
of the head and the occiput are brownish-black, bounded anteriorly
by a broadish band of bright yellow across the forehead, and laterally
by a streak of the same, passing over the eye; the stiff feathers over
the nostrils black, as is the loral space. The cheeks, hind neck, and
throat are dark yellowish-olive, and that colour gradually brightens
until, on the outer edges of the scapulars, the rump, the axillars and
inner lower wing-coverts, the abdomen and lower tail-coverts, it
becomes pure yellow. The smaller wing-coverts, alula, primary
coverts, three outer secondaries, outer web of the next, and the
bases of the inner secondaries, black; as is the tail; six of the inner
secondaries, inner web of the next, and inner margin of the rest, as
well as their coverts, white, the basal part excepted.
Length to end of tail 8 inches; wing from flexure 4 3/4; tail 3; bill along
1/2
the ridge 10/12, along the edge of lower mandible 11/12; tarsus 9 /12;
hind toe 5/12, its claw, 4 1/2/12; middle toe, 8/12, its claw 3 3/4/12.
Adult Female. Plate CCCCXXIV. Fig. 5.
The adult female, which is here figured and described for the first
time, from a specimen obtained from Dr Townsend, and marked
“Black Hills, Female, June 3, 1834,” wants the yellow band on the
forehead, the streak of the same colour over the eye, the black line
along the basal margin of the upper mandible, and the large patch of
white on the wings. The bill and feet are as in the male, but paler.
The upper part of the head is dark brownish-olive; the cheeks lighter;
the hind neck, back, and scapulars light brownish-grey, with a slight
olivaceous tint, shaded into brownish-yellow on the rump. The wings
are black; a portion of the edge of the wing, the tips and part of the
margins of the secondary coverts, a concealed band on the basal
part of the primaries, the outer three excepted, and the edges of all
the quills toward the end, white, which is broader on the
secondaries, and forms a band on them. Tail-coverts black, tipped
with a triangular spot of white; tail-feathers also black, with a white
spot on the inner web at the tip, eight-twelfths long on the outermost
feather, gradually diminishing towards the central feathers, which are
slightly tipped. Throat greyish-white, margined on either side by a
longitudinal band of black, from the base of the lower mandible, and
ten-twelfths in length; the lower parts yellowish-grey; abdomen and
lower tail-coverts white, axillars and some of the lower wing-coverts
yellow.
Length to end of tail 7 1/2 inches; wing from flexure 4 1/4; tail 2 10/12;
bill along the ridge 9 1/2/12.
Young Male. Plate CCCXXIV. Fig. 6.

The young male bears a considerable resemblance to the female,
differing chiefly in wanting the black bands on the throat, and in
having the upper parts much lighter, and the lower more yellow. Bill
yellow; iris hazel; feet flesh-colour, claws dusky. Head and cheeks
light greyish-brown, the rest of the upper parts of a paler tint, slightly
tinged with yellow on the margins. The wings and tail are black, as in
the female, and similarly spotted with white, but tinged with yellow.
The lower parts are yellowish-grey, the sides of the neck and the
axillars pale yellow, the abdomen and lower tail-coverts white.
The young male has been described as the adult female by Mr
Swainson in the Fauna Boreali-Americana, and has been made a
distinct species by M. Lesson, under the name of Coccothraustes
Bonapartii. The Prince of Musignano, it is observed, has erred in
stating that “no difference of any consequence is observable
between the sexes; though it might be said that the female is a little
less in size, and rather duller in plumage.”
BLACK-HEADED GROSBEAK.
Fringilla melanocephala.
PLATE CCCLXXIII. Male and Female.
The following account of this Grosbeak affords another proof of the

ardent zeal of my excellent friend Thomas Nuttall, who, though
more especially engaged with botany on his recent journey to the
Columbia, has not neglected opportunities of noting many interesting
facts relative to birds.
“On the central table-land of the Rocky Mountains, and on the upper
branches of the Colorado of the west, we first heard the powerful
song of this most delightful Finch. From thence, in the thick groves of
all the streams on our western course to the borders of the
Columbia, and throughout the dense forests of that river nearly to the
sea, we were frequently cheered amidst the wildest desolation by the
inimitable voice of this melodious bird. Jealous of all intrusion on his
lonely and wild haunts, it was seldom that we had the opportunity of
witnessing this almost fairy musician, which gave a charm to the
saddest gloom, and made the very woods as it were re-echo to his
untiring song. With the modesty of superior merit, and almost with
the solicitude of the Nightingale, our favourite Finch seeks the
darkest thicket of the deepest forest. The moment his eye rests on
the intruding observer he flits off in haste, calls to his mate, and
plunging into the thicket sits in silence till he is satisfied of the
restoration of solitude, when he again cautiously mounts the twig
and pours out afresh the oft-told but never-tiring tale of his affection
and devotion to the joys of nature. His song, which greatly resembles
that of the Red-breasted Grosbeak, is heard at early dawn, and at
intervals nearly to the close of night. It is a loud, varied, high-toned
and melodious fife, which rises and falls in the sweetest cadence;
but always, like the song of the nightingale, leaves a sensation of
pleasing sadness on the ear, which fascinates more powerfully than
the most cheering hilarity. In fact, the closing note of our bird is often
so querulous as to appear like the shrill cry of appealing distress: it
sinks at last so faintly, yet still so charmingly on the sense. When
seen, which is only by accident, he sits conspicuously on some lofty
bough, below the summit of the tree, and raising his head, and
swelling his throat with a rising motion, almost amounting to a flutter,
he appears truly rapt in ecstacy, and seems to enjoy his own powers
of melody as much as the listener. Even the cruel naturalist, ever
eager to add another trophy to his favourite science, feels arrested
by his appeal, and connives at his escape from the clutch of the
collector.
“About the month of July, in the Rocky Mountains, I observed the
female feeding her fledged young, and they also spent the summer
in the thickest branches, but with the nest and eggs I am
unacquainted. The song, as I have heard it, in the forests of
Columbia, seems to be like the syllables ’tait, weet, teet, weowit, teet
weowit, teet weeowit, verr, and sometimes terminating weet, weet,
weet, every note a loud tender trill of the utmost sweetness,
delivered in his own “wood-notes wild,” mocking nothing, but still
exulting in his powers, which, while exerted, seem to silence every
songster around. The Robin seems almost his pupil in song and
similarity of expression, but falls short, and after our Orpheus, seems
at best but a faultering scholar.”
Guiraca melanocephala, Swainson.

Adult Male. Plate CCCLXXIII. Figs. 2, 3.
Bill rather short, very robust, bulging at the base, conical, acute;
upper mandible with its dorsal outline a little convex, the sides
rounded, the edges sharp, ascending from the base to beyond the
nostrils, then deflected with a slight median festoon, and an obscure
notch close to the tip; lower mandible with the angle short and very
broad, the dorsal line straight, the back very broad at the base, the
sides high and convex, the edges inflected, the tip acute. Nostrils
basal, roundish, partly concealed by the feathers.
Head large, roundish-ovate; neck short; body rather full. Legs of
moderate length, rather strong; tarsus anteriorly covered with seven
scutella, posteriorly with two plates forming a sharp edge; toes rather
large, the first stout, the lateral nearly equal, the middle toe much
longer. Claws rather long, arched, much compressed, acute.
Plumage soft and blended. Wings of moderate length, broad. The
first quill two-twelfths shorter than the second, which is longest, but
scarcely exceeds the third, the fourth longer than the first;
secondaries slightly emarginate. Tail rather long, nearly even.
Bill with the upper mandible dusky, the lower white. Iris hazel. Feet
and claws wood-brown. Head, cheeks, and a small portion of the
throat black; the upper parts brownish-black; the feathers on the
lower part of the hind neck all round, a streak over each eye, another
along the middle of the hind head, the greater part of the rump, and
the lower parts generally, yellowish-red or brownish-orange; the
edges of some of the feathers on the back, a broad band formed by
the first row of small coverts, a narrow band formed by the tips of the
secondary coverts, a band on the base of the primaries, the outer
web of the first excepted, the margins of three of the primaries
toward the end, and a spot on the outer web of most of the
secondaries at the end; a large patch on the inner web of all the tail-
feathers, excepting the two middle, and largest on the outer, pure
white; the middle of the breast and abdomen, with the axillaries and
lower wing-coverts, yellow.
Length to end of tail 8 1/2 inches; wing from flexure 4 1/4; tail 3 8/12;
bill along the ridge 9/12, along the edge of lower mandible 10/12;
tarsus 11/12; hind toe 4 1/2/12, its claw 5/12; middle toe 8/12, its claw
3 1/2/ .
12
Adult Female. Plate CCCLXXIII. Fig. 4.

The female is much less beautiful. The bill is of a lighter brown
above, brownish-white beneath, with the edges and tip of the lower
mandible light brown; the feet and claws wood-brown. The upper
parts are wood-brown, the head darker, with three longitudinal bands
of brownish-white; a band of reddish-white across the hind neck, the
feathers of the back margined with whitish; the wings marked as in
the male, but with brownish-white; the tail without white spots. The
lower parts are of a much paler tint than those of the male; the
axillars and lower wing-coverts yellow.
Length to end of tail 8 1/4 inches; bill along the ridge 9/12; tarsus 11/12;
middle toe and claw 1 3/12.
SHARP-SHINNED OR SLATE-COLOURED HAWK.
Falco fuscus, Gmel.

PLATE CCCLXXIV. Male and Female.
There is a pleasure which that ornithologist only can feel who spends
his days in searching for the materials best adapted for his purpose,
and which arises from the contemplation of the objects he is anxious
to portray and describe, as they roam in freedom over Nature’s wild
domains. Another pleasure is derived from finding in different
countries birds so much alike in form, colour, and habits, that they
seem as if formed for the purpose of exercising our faculties of
observation and comparison. But this pleasure passes into pain, or
at least perplexity, when, as in the present instance, two species
differ so slightly that you cannot clearly define their characters,
although they yet seem to be distinct. In fact, I long felt uncertain
whether the American bird described by Wilson under the names of
Sharp-shinned Hawk, and Slate-coloured Hawk, was distinct from
the Sparrow Hawk, F. Nisus, of Europe.
It is mentioned in the Fauna Boreali-Americana, that a specimen of
this bird was killed in the vicinity of Moose Factory, and that it has
been deposited by the Hudson’s Bay Company in the Zoological
Museum of London. This specimen I have not seen, but confiding
entirely in the accuracy of every fact mentioned by the authors of
that work, I here adduce it as a proof of the extraordinary range of
this species in America, which from the extreme north extends to our
most southern limits, perhaps far beyond them, during its autumnal
and winter migrations. I have met with it in every State or Territory of
the Union that I have visited. In the spring of 1837, it was abundant
in Texas, where it appeared to be travelling eastward. I have a
specimen procured by Dr Townsend in the neighbourhood of the
Columbia River; and, when on my way towards Labrador, I met with
it plentifully as far as the southern shores of the Gulf of St Lawrence,
beyond which, however, none were observed by me or any of my
party.
I never saw this daring little marauder on wing without saying or
thinking “There goes the miniature of the Goshawk!” Indeed, reader,
the shortness of the wings of the Sharp-shinned Hawk, its long tail,
though almost perfectly even, instead of being rounded as in the
Goshawk, added to its irregular, swift, vigorous, varied, and yet often
undecided manner of flight, greatly protracted however on occasion,
have generally impressed upon me the idea alluded to. While in
search of prey, the Sharp-shinned Hawk passes over the country,
now at a moderate height, now close over the land, in so swift a
manner that, although your eye has marked it, you feel surprised that
the very next moment it has dashed off and is far away. In fact it is
usually seen when least expected, and almost always but for a few
moments, unless when it has procured some prey, and is engaged in
feeding upon it. The kind of vacillation or wavering with which it
moves through the air appears perfectly adapted to its wants, for it
undoubtedly enables this little warrior to watch and to see at a single
quick glance of its keen eyes every object, whether to the right or to
the left, as it pursues its course. It advances by sudden dashes, as if
impetuosity of movement was essential to its nature, and pounces
upon or strikes such objects as best suit its appetite; but so very
suddenly that it appears quite hopeless for any of them to try to
escape. Many have been the times, reader, when watching this
vigilant, active, and industrious bird, I have seen it plunge headlong
among the briary patches of one of our old fields, in defiance of all
thorny obstacles, and, passing through, emerge on the other side,
bearing off with exultation in its sharp claws a Sparrow or Finch,
which it had surprised when at rest. At other times I have seen two or
three of these Hawks, acting in concert, fly at a Golden-winged
Woodpecker while alighted against the bark of a tree, where it
thought itself secure, but was suddenly clutched by one of the
Hawks throwing as it were its long legs forward with the quickness of
thought, protruding its sharp talons, and thrusting them into the back
of the devoted bird, while it was endeavouring to elude the harassing
attacks of another, by hopping and twisting round the tree. Then
down to the ground assailants and assailed would fall, the
Woodpecker still offering great resistance, until a second Hawk
would also seize upon it, and with claws deeply thrust into its vitals,
put an end to its life; when both the marauders would at once
commence their repast.
On several such occasions, I have felt much pleasure in rescuing
different species of birds from the grasp of the little tyrant, as
whenever it seizes one too heavy to be carried off, it drops to the
ground with it, and being close by, I have forced it to desist from
committing further mischief, as it fears man quite as much as its poor
quarry dreads itself. One of these occurrences, which happened in
the neighbourhood of Charleston, in South Carolina, is thus related
in my journal.
Whilst walking one delightful evening in autumn, along a fine hedge-
row formed by the luxuriant Rocky Mountain rose-bushes, I observed
a male of this species alighted in an upright position on the top-bar of
a fence opposite to me. I marked it with particular attention, to see
what might follow. The Hawk saw me as plainly as I did him, and
kept peeping now at me, and now at some part of the hedge
opposite, when suddenly, and with the swiftness of an arrow, it shot
past me, entered the briars, and the next instant was moving off with
a Brown Thrush, Turdus rufus in its talons. The Thrush, though
seized by the sharp claws of the marauder, seemed too heavy for
him to carry far, and I saw both falling to the ground. On running up, I
observed the anxiety of the Hawk as I approached, and twice saw it
attempt to rise on wing to carry off its prize; but it was unable to do
so, and before it could disengage itself I was able to secure both.
The Thrush must have been killed almost instantaneously, for, on
examining it, I found it quite dead.
My friend Thomas Nuttall, Esq., tells us that in the “thinly settled
parts of the States of Georgia and Alabama, this Hawk seems to
abound, and proves extremely destructive to young chickens, a
single one having been known regularly to come every day until he
had carried away between twenty and thirty. At noon-day, while I was
conversing with a planter, one of these Hawks came down, and
without ceremony, or heeding the loud cries of the housewife, who
most reluctantly witnessed the robbery, snatched away a chicken
before us.” Again, while speaking of the wild and violent manner of
this bird, he adds “descending furiously and blindly upon its quarry, a
young Hawk of this species broke through the glass of the green-
house, at the Cambridge Botanic Garden; and fearlessly passing
through a second glass partition, he was only brought up by the
third, and caught, though little stunned by the effort. His wing-
feathers were much torn by the glass, and his flight in this way so
impeded as to allow of his being approached.”
Whilst travelling to some distance, the Sharp-shinned Hawk flies
high, though in a desultory manner, with irregular quick flappings of
the wings, and at times, as if to pause for a while and examine the
objects below, moves in short and unequal circles, after which it is
seen to descend rapidly, and then follow its course at the height of
only a few feet from the ground, visiting as it were every clump of low
bushes or briar patches likely to be supplied with the smaller birds,
on which it principally feeds. Again, after having satisfied its hunger,

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CHAPTER 4 Characterization of metallic glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

Development of magnetism (the 20th century) . . . . . . . . . . . . . . . . . . . . 161

CHAPTER 7 Elasticity of metallic gasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193

Serrated flow at microscopic level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281

• The Stone Age – prehistory to ca. 3000 BCE

atomic/molecular structure → material’s properties

processing of materials → material’s microstructures

Making of metallic glasses and

Applications of metallic glasses

Another specimen in my possession, procured by Dr Townsend on

Lepus palustris, Bachman.

Dimensions, taken from a specimen in the flesh:

Fringilla vespertina, Cooper.

This fine species of Grosbeak was first introduced to the notice of

Fringilla vespertina, Cooper, Ann. Lyc. New York, vol. i. p. 220.—Ch.

Adult Male. Plate CCCLXXIII.

Young Male. Plate CCCXXIV. Fig. 6.

The following account of this Grosbeak affords another proof of the

Guiraca melanocephala, Swainson.

Adult Female. Plate CCCLXXIII. Fig. 4.

Falco fuscus, Gmel.

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