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Nanostructured
Nonlinear Optical
Materials
Formation and Characterization
Rashid A. Ganeev
Optics and Spectroscopy Department,
Voronezh State University,
Voronezh, Russia
Elsevier
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Preface
The motivation in writing this book was related with the specific properties of small-
sized particles and structures and their nonlinear response in the field of strong laser
pulses, which became the area of interest from the very beginning of my career. The
topics presented in this book are mostly concerned with the nonlinear optical charac-
terization of various nanostructured media during my long-lasting collaboration with
numerous researchers and could not be realized without their generous efforts.
This book describes the analysis of the formation, characterization, and optical
nonlinearities of various nanostructures using different methods. The studies include
three groups of research fields. First group is related with the modification of the sur-
faces of materials for the formation of various nanostructures. Those studies include
the extended nanoripples formation using a few-cycle pulses, the analysis of the
nanoripples produced on the semiconductors possessing different bandgaps, and the
formation of nanopores, nanoholes, and nanowires using different conditions of laser-
matter interaction. Second group comprises the studies of ablated bulk and nanopar-
ticle targets, the low-order nonlinearities of metal and semiconductor nanoparticles,
and the nonlinear refraction and nonlinear absorption of c arbon-contained nanoparti-
cles. Finally, third group of studies is related with the high-order harmonic generation
in nanoparticle-contained plasmas.
These studies of the properties of nanostructured materials could not be realized with-
out the collaboration between various research groups involved in the studies of similar
topics. Among numerous colleagues I met and had the privilege to collaborate I would like
to thank H. Kuroda, M. Suzuki, T.Q. Jia, M. Baba (Saitama Medical U niversity, Japan),
T. Ozaki, L.B. Elouga Bom (Institut National de la Recherche Scientifique, Canada), P.D.
Gupta, P.A. Naik, H. Singhal, J.A. Chakera, U. Chakravarty, M. Raghuramaiah, R.A.
Joshi, R.K. Bhat (Raja Ramanna Centre for Advanced Technology, India), J.P. Marangos,
J.W.G. Tisch, C. Hutchison, T. Witting, D.Y. Lei (Imperial College, United Kingdom),
M. Castillejo, M. Oujja, M. Sanz, I. López-Quintás, M. Martín (Instituto de Química
Física Rocasolano, Spain), H. Zacharias, J. Zheng, M. Wöstmann, H. Witte (Westfäliche
Wilhelms-Universität, Germany), T. Usmanov, G.S. Boltaev, I.A. Kulagin, V.I. Redkore-
chev, V.V. Gorbushin, R.I. Tugushev, S.R. Kamalov (Institute of Ion, Plasma, and Laser
Technologies, Uzbekistan), O.V. Ovchinnikov (Voronezh State University, Russia), E.
Fiordilino, D. Cricchio, P.P. Corso (Università degli Studi Palermo, Italy), M.K. Kodirov,
P.V. Redkin (Samarkand State University, Uzbekistan), A.L. Stepanov (Physics Tech-
nical Institute, Kazan, Russia), N.V. Kamanina (Vavilov State Optical Institute, Saint
Petersburg, Russia), and A.A. Ishchenko (Institute of Organic Chemistry, Kiev, Ukraine)
for their activity in the development of this interesting field of nanoscience.
Finally, as husband, father, and grandfather, I feel the privilege to underline the
role of my family in most of my endeavors.
Rashid A. Ganeev
Voronezh State University, Optics and Spectroscopy
Department, 1 University Square, Voronezh, Russia
xiii

Introduction
B978-01243.6/ElsevirInc
The area of studies related with the small-sized objects is associated with the science
of nanotechnology, which commonly dubbed as nanoscience, and is an extremely de-
veloping field attracted the attention of enormous groups of researchers. It is hard to
imagine sizes of the book, which can describe all aspects of nanoscience. That is why
the researchers in their monographs dedicated to this area of studies try to restrict the
consideration of a few topics of the nanoscience. The frames of the reviews of previ-
ous studies overlap, from time to time, in these books, while providing a descriptive
character of the studies in the limited areas of interests of the authors. Present book
follows those principles and describes a few groups of studies, which for a long time
attracted the attention of this author. So we shortened the frames of consideration of
this extremely large field of nanoscience and tried to concentrate on some specific
topics, which did not previously find the attention from the point of view of nanopar-
ticles characterization.
As it was mentioned in preface, this book is dedicated to the analysis of the
formation, characterization, and, mainly, optical nonlinearities of various nanostruc-
tures using different methods. The discussed studies include three groups of research
fields. First group is related with the modification of the surfaces of materials for the
formation of various nanostructures including the extended nanoripples formation
using a few-cycle pulses, the analysis of the nanoripples produced on the semicon-
ductors possessing different bandgaps, and the formation of nanopores, nanoholes,
and nanowires using different conditions of laser-matter interaction. Second group
comprises the studies of ablated bulk and nanoparticle targets, the low-order non-
linearities of metal and semiconductor nanoparticles, and the nonlinear refraction
and nonlinear absorption of carbon-contained nanoparticles. Third group of stud-
ies is related with the high-order harmonic generation of ultrashort laser pulses in
nanoparticle-containing plasmas.
The formation of parallel fringes with characteristic spacing in the order of the
wavelength of the acting light (so-called “nanoripples”) is an interesting effect of
the interaction of ultrashort laser pulses with semiconductors and other materials. It
was primarily reported that the spacing between the fringes lay in the range of the
wavelength of the used femtosecond lasers, that is, it was about 800 nm or less for
most cases when Ti:sapphire lasers were employed. The interest in these periodic
surface structures was related to fundamental problems of interaction of ultrashort
pulses with different materials and to their possible practical applications. The ap-
pearance of these nanostructures was ascribed to the formation of diffraction gratings
with submicron spacing between the fringes; the interactions between laser light and
plasmon–polariton waves, which occur due to the initial heterogeneity of the surface,
the Bose condensation, and so on.
xv

xvi Introduction
At the same time, the information about nanostructures with periods notably
smaller than the wavelength of the light (∼200 nm [1,2]) have aroused additional
interest connected, in particular, with the uncertain mechanism of the formation of
these structures. Several theoretical models have been proposed to explain the ap-
pearance of these short-periodic structures based on the principles used for interpret-
ing of nanostructures with long periods [3,4]. Note that a common feature of the
latter structures was approximate correspondence between the laser light wavelength
and the interfringe spacing. At the same time, the observed short-period structures,
which occur on semiconductor surfaces show not only much shorter distances be-
tween the fringes but also demonstrate some other specific features, among which are
the effects of the laser light polarization, bandgap width of the semiconductor, and
angle of incidence on the structural properties of short-period nanostructures. The
elucidation of the mechanisms of formation of short-period nanostructures requires
additional study because none of the mechanisms proposed thus far can explain, in
full measure, all characteristic features of this process.
Direct femtosecond laser surface nano- and micro-structuring is a versatile
method to tailor material surface morphologies, which enhance diverse interesting
physical properties. These include the ability to permanently modify the surface ab-
sorption spectrum or change appearing colors of metals and semiconductors without
any addition of pigments, the possibility to fabricate super-hydrophobic and self-
cleaning surfaces, and so on. In this context, the formation of laser-induced periodic
surface structures in the form of subwavelength ripples is extensively studied. By
carefully adjusting laser parameters like wavelength, polarization, pulse duration,
pulse number or pulse fluence, the shape, size, and orientation of the structures created
can be controlled, as shown by numerous empirical studies. Because this method of
structuring is an easy-to-implement, low-cost, top-down method, which is able to
fabricate periodic structures on the nanoscale without the sophisticated multistep pro-
cesses and ultrashort wavelengths needed for nanolithography, high spatial frequency
periodic structures has gained increasing attraction for practical applications.
Previous experimental studies have shown that the periodic nanostructure forma-
tion develops through the bonding structure change, the near-field ablation, and the
excitation of surface plasmon polaritons in the thin layer on the target surface. It has
also been demonstrated that use of multiple shots of low-fluence femtosecond pulses
is important for suppressing undesirable thermal processes in the nanostructures for-
mation through the ablation. The purpose of those studies was to analyze specific
features of the formation of nanostructures and short period nanostructures on the
surfaces of different semiconductors under variable experimental conditions. The
studies in this field include the analysis of different aspects of nanoripples formation
([5–12] to mention few of them).
In this book, we analyze the effect of the aforementioned and some other ex-
perimental parameters (light polarization, duration of the acting femtosecond pulses,
bandgap width of the semiconductor, angle of incidence of the laser beam upon the
surface, characteristics of the surrounding medium, and so on) on the pattern of the
nanostructure, including the cases when the regimes of formation of the long- and
Introduction xvii
short-period structures could be distinguished. We also show, in some cases, the for-
mation of nanoholes and nanodots on the surface of different semiconductors.
The third-order nonlinear optical susceptibilities of various media change in a
broad range. Nonlinearities responsible for variations in the refractive and absorb-
ing properties are especially important because they strongly affect the propagation
of intense radiation in media. Numerous investigations have been performed in this
field due to increasing interest in applications of nonlinear optical effects in opto-
electronics, various nonlinear optical devices, optical switching, and so on. Inter-
est in nonlinearities of different nanostructure media is also caused by their strong
nonlinear optical response attributed to the quantum size effect. The application of
nanostructures in the aforementioned fields and optical computers, storage devices,
nonlinear spectroscopy, and so on can lead to considerable developments of new
methods of the studies of matter. The studies in this field [13–15] were dedicated
to different aspects of applications and developments of new devices based on the
advanced nonlinear optical properties of nanoparticles.
In this book, we present the studies of the low-order nonlinear optical parameters
of different nanoparticles. Some of these nanostructured media are analyzed from the
point of view of their application as optical limiters of the laser radiation intensity.
The results of measurements of the nonlinear refractive indices, nonlinear absorption
coefficients, and third-order nonlinear susceptibilities of these media are presented
and discussed.
Coherent short-wavelength radiation is of increasing importance for a broad spec-
trum of basic and applied research in various fields of physical, chemical, and life
sciences. Among them, femtosecond time-resolved coherent diffractive imaging and
photo-induced processes on surfaces and nanoparticles, as well as lithography, plasma
diagnostics, and materials processing and diagnostics are of foremost interest. High-
order harmonic generation from femtosecond visible laser pulses allows producing
coherent radiation in the extreme ultraviolet spectral range. Table-top lasers render
these processes possible with the prospect of widespread scientific applications.
So far, however, only low conversion efficiencies for high-order harmonic
generation have been obtained, despite the enormous efforts. Many interesting ex-
periments can be performed by harmonic generation based on laboratory scale fem-
tosecond lasers. These sources easily cover the spectral range between the 10- and
100-eV photon energy of the harmonics, and with few-cycle laser systems, even up
to several hundred eV. For practical applications of high-order harmonic sources,
higher conversion efficiency and, thus, an increase in the photon flux and the maxi-
mum photon energy of the harmonic radiation would be beneficial. High-order har-
monic generation itself can be used as a spectroscopic tool for analysis of the optical,
nonlinear optical, and structural properties of the harmonic generation emitters, pres-
ently comprising a few noble gases.
The generation of higher harmonics in laser-produced plasmas from various
solid-state targets, being for this purpose a relatively new and largely unexplored
medium, promises to yield these advances. Most interestingly, the studies have
shown that enhanced higher harmonics can also be generated from gas clusters
xviii Introduction
and ablated nanoparticles, which opens the door to applications of local field
enhancement [16–22]. Thus, the above approach may be useful for producing an
efficient source of short-wavelength ultrashort pulses for various applications and
studies of the properties of harmonic emitters. Laser ablation-induced high-order
harmonic generation spectroscopy is a new method for materials science and can
be considered as one of the most important applications of harmonic generation.
In this book, we also discuss the realization of new ideas that have emerged over
the last few years, which led to further improved high-order harmonic generation
conversion efficiency through harmonic generation in specially prepared nanopar-
ticle-containing plasmas and allowed the spectral and structural studies of matter
through plasma harmonic spectroscopy. Nanoparticle research has demonstrated the
feasibility of increasing the efficiency of harmonic generation with the use of cluster
media. We note that the majority of previous works on harmonic generation involv-
ing nanoparticles was limited to the analysis of rather exotic clusters (Ar,Xe) that
were formed during rapid cooling resulting from the adiabatic expansion of gases
issuing from jet sources under high pressure.
The interest for nonlinear optical characterization of materials is closely related
to the new field of nanostructures formation during laser-matter interaction. The
formation of nanoripples, nanogrooves, nanoparticles, nanowires, and other exotic
nanostructures during laser ablation of different materials, formation of plasma
plumes containing clusters, characterization of their structural, morphological, opti-
cal, and nonlinear optical properties, use of nanostructures for various applications,
such as, for example, optical limiting and high-order harmonic generation, and many
other features of newly developed and commercially available nanoparticles open the
doors for their use in photonics, electronic industry, medicine and other scientific and
industrial applications.
The content of book shows that the advantages of nanomaterials for different
applications (in present case, nonlinear optical research) may further push this field
of morphology and high-order nonlinearities studies toward both fundamental and
practical needs thanks to better understanding of the processes involving in the laser-
nanostructure interactions. The formation of various nanostructures using different
methods is a broad field of studies, which shows specific methods, as well as advan-
tages and disadvantages of each approach. As main method of nanostructures forma-
tion in this book is, to some extent, a laser ablation, one can expect consideration of
other methods as well. Obviously, this book cannot be considered as a completed
review of those methods, as some of them are too sophisticated and are out of the
scope of this book. Meanwhile, it can provide some bridge between the existing
methods of nanoparticles and nanostructures formation.
One can assume that single authorship can provide more homogeneity in the dif-
ferent topics and grant a better explanation from the basics. Being an author of this
book, I tried to combine different aspects of nanostructuring, nanoformation, charac-
terization, and application of small-sized species. These efforts obviously resulted in
broadening of the topics of this book. Combined by reasonable logic, various topics
can offer better overview and understanding of the main goals of this monograph.
Introduction xix
There are several books on nanomaterials. However, neither of them were dedi-
cated to their nonlinear properties and laser processing or laser characterization in
general. Often these publications are the multiauthor books that do not give enough
introductory information on the nonlinear optical properties of small sized species.
Indeed, there are not so much competitive books in this relatively new field. Most
of them combine different issues of nanomaterials studies. Meanwhile, the chapters
of those books are not closely related with each other. Obviously, different authors
are trying to underline some specific topics, which resulted in some incoherency in
presentation of a whole book. I, for myself, was an author of some chapters in such
books and can evaluate both drawbacks and advances in such sort of presentation.
The necessity in this book is related with the frequent requests of researchers
from different fields to the author to provide the information obtained during his nu-
merous studies of the nanomaterials. Currently, these studies are disseminated in dif-
ferent journals. The collection of these studies in a single book may help the reader to
learn about the interconnection of the morphological, optical, and nonlinear optical
features of these species.
The primary groups of the readers of this book comprise the researchers in the
fields of laser physics, nanomaterial studies, plasma physics, and nonlinear optics.
The book would be of interest for both academics and professionals in the applied
fields. Meantime, the book can be served as the source of information in different
fields of nanoscience for the high education students and postdocs, who are inter-
ested in further development of their career in the fields of laser-matter interaction,
coherent extreme ultraviolet sources, laser-produced plasmas, and nonlinear optics
of nanomaterials.
Obviously, it is an extreme task to combine in a single book the topics, which at-
tract different groups of readers. I tried to balance between pedagogical introductory
parts and more advanced topics so that the readership can include students as well as
more experienced researchers. The processing and characterization of nanomaterials
are certainly an important topic in the science of condensed matter. This book is not
only of interest to advanced students in physics, but also in chemistry and engineer-
ing. Thus the book can represent a reference textbook for advanced graduate courses.
The proposed field could be useful to Ph.D. students especially after one to two
years of experience. Based on my experience, as more advanced the paper (or book)
as more students will be interested in it. Obviously, it is not a text book. However,
the young people trying to advance in nanoscience have to make some efforts to
reach the level, which allows the reading of such sort of research studies. Conclud-
ing, though this book is mostly addressed to the experiences auditory, the PhD and
postdoc students can find many new and interesting information in this collection of
different topics of a specific field of nanoscience.
This book is organized as follows. To emphasize previous studies of periodic
structures, we discuss in Chapter 1 various methods of nanoripples formation on
the semiconductors possessing different bandgaps. In Chapter 2, the principles of
the formation of nanoparticles, nanopores, nanoholes, and nanowires using differ-
ent conditions of laser-matter interaction are analyzed. Chapter 3 is dedicated to
xx Introduction
the analysis of laser ablated bulk and nanoparticle targets and different modes of
nanostructured materials formation. The low-order nonlinear optical properties of
metal nanoparticles is discussed in Chapter 4. Chapter 5 considers nonlinear ab-
sorption and refraction in semiconductor and carbon-containing nanoparticles.
In Chapter 6, frequency conversion of ultrashort pulses in fullerenes is analyzed.
Chapter 7 is dedicated to the studies of the high-order harmonic generation in car-
bon-containing nanoparticles. Harmonic generation in metal and semiconductor
nanoparticles is discussed in Chapter 8. In Chapter 9 we analyze the peculiarities of
high-order harmonic generation in nanoparticles. Finally, we summarize the discus-
sion of the properties of nanostructured nonlinear optical materials.
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CHAPTER
Periodic nanoripples
formation on the
semiconductors possessing
different bandgaps
1
1.1 NANORIPPLE FORMATION ON DIFFERENT BANDGAP
SEMICONDUCTOR SURFACES USING FEMTOSECOND PULSES
Surface structuring with lasers is a highly competitive method due to its capabil-
ity to implement changes in the structure design. Compared to the picosecond and
the nanosecond laser pulses, the energy in a femtosecond pulse can be precisely
and rapidly deposited in a solid material with fewer thermal effects. Therefore the
femtosecond lasers are widely used for microfabrication in transparent materials,
metals, and semiconductors for applications such as modifying the optical prop-
erties of the surface [1], improvement of photovoltaic devices [2] by increasing
their effective surface area, and in turn increasing the response and conversion effi-
ciency. The other applications include modification inside refractive index of bulk
materials for fabricating photonic devices, optical data storage, and biophotonic
components [3–5]. Mid-infrared femtosecond laser radiation is generally used for
the generation of surface ripples, also known as laser-induced periodic surface
structures (LIPSS).
Various mechanisms have been proposed to explain the nanoripple formation.
Initially, it was thought to be the result of the interference between the incident laser
light and the scattered light from the surface roughness [6]. However, if this mecha-
nism was to be true, nanoripple width should always be of the order of the incident
laser light wavelength, whereas, in many experiments, very narrow ripple formation
has been observed. For example, Ozkan et al. [7] found that ripples resulting from
248 nm femtosecond laser irradiation of thin diamond films had a period varying
between 50 and 100 nm. Yasumaru et al. [8] reported formation of ripple patterns
with mean periods of 100–125 and 30–40 nm on TiN and diamond-like carbon after
irradiation with 800 and 267 nm femtosecond pulses, respectively. To explain the
nanoripple formation in the case of metals, the surface plasmon created during initial
random surface heterogeneities was considered [9]. In dielectrics, the coupling of
the electron plasma wave and incident laser explains the observed periodic structure
in glass [10]. Other proposed mechanisms for ripple formation are self-organization
[11], Coulomb explosion [12], influence of second harmonic generation [13], aniso-
tropic local field enhancement invoking nanoplasmonics [14], etc.
Nanostructured Nonlinear Optical Materials. http://dx.doi.org/10.1016/B978-0-12-814303-2.00001-5 1

Copyright © 2018 Elsevier Inc. All rights reserved.
2 CHAPTER 1 Periodic nanoripples formation on the semiconductors
Below, we analyze surface nanoripple formation on different bandgap semicon-

ductors [15]. A study of the ripple formation with different laser parameters and
ambient media is presented with the objective of identifying conditions of forming
narrow period ripples. Nanoripples were formed using a Ti–sapphire laser with 8 mJ
energy, 45 fs pulse duration, and 800 nm wavelength (1.56 eV) at a fluence in the
range of 100 mJ cm−2–1 J cm−2. The effects of the number of laser shots, the angle
of incidence, polarization of the laser, fluence, incident laser wavelength (λ), band-
gap, and ambient medium were studied. Depending upon the experimental param-
eters, the nanoripple sizes varied in the range of λ/9–λ. Narrow nanoripples were
formed on the wide bandgap (WBG) semiconductors. The width of the nanoripples
decreased with the laser wavelength and the laser fluence. The observation of high
and low spatial frequency ripples in different conditions is explained considering the
transient metallic nature of the semiconductor surface on irradiation with intense
femtosecond pulses. The surface eventually supports the surface plasmon excita-
tion, which interferes with incident laser light for ripple formation. The very delicate
dependence of ripple period with incident laser parameters is attributed to the critical
role of electron density. The finding helps identifying suitable bandgap materials and
laser parameters for obtaining nanoripple period considerably small compared to the
incident laser wavelength.
1.1.1 EXPERIMENTAL ARRANGEMENTS AND RESULTS

For studying the nanoripple formation from ultrashort laser pulse irradiation of semi-
conductor materials of different bandgaps, the following semiconductor materials of
narrow (<1.5 eV, which is the energy of the incident 800 nm photon) bandgap mate-
rials such as InAs (0.36 eV), GaAs (1.42 eV), InP (1.35 eV), and wide (>1.5 eV)
bandgap materials such as GaP (2.3 eV), GaN (3.4 eV), SiC (3.37 eV), and ZnSe
(2.82 eV) were used. Multiple laser shots from a Ti–sapphire laser with 45 fs pulse
duration, and 800 nm wavelength were focused in air on the semiconductor wafers at
a fluence in the range of 100 mJ cm−2–1 J cm−2, that is, around the plasma formation
threshold. Using a beta barium borate (BBO) crystal, the second harmonic (400 nm)
of the 800 nm laser beam was also used to study the influence of the laser wavelength
on the ripple formation while keeping the other parameters the same.
Fig. 1.1 shows the surface morphologies resulting from the irradiation of a GaP
wafer by femtosecond pulses with two different polarizations and in two different
spatial regions. Fig. 1.1A shows the formation of spherical nanoparticles (∼100 nm)
with circularly polarized laser light also reported by several groups [16]. Fig. 1.1B
shows narrow nanoripples with ∼200 nm spacing at the peripheral regions of the laser
irradiated spot with linearly polarized laser pulses. Fig. 1.1C shows wider nanorip-
ples with about 600 nm spacing near the central hot region of the laser-irradiated
spot. As expected, for linearly polarized light, the nanoripple orientation was always
orthogonal to the laser polarization [17,18]. Nanoripple formation was observed with
10–100 shots fired on the semiconductors. It was also observed that number of shots
fired on the semiconductor did not have any effect on the ripple period.
1.1 Nanoripple formation 3
FIGURE 1.1 GaP Irradiated by 800 nm Ultrashort Laser Pulses,

(A) with circularly polarized beam, and (B) and (C) with linearly polarized beam in two
different regions; (B) is around the periphery of the irradiated spot (low fluence); and (C)
is in the central region (high fluence). [The length of the horizontal bar is 1 µm in (A), (B),
and 2 µm in (C).].
Reproduced with permission from U. Chakravarty, R.A. Ganeev, P.A. Naik, J.A. Chakera, M. Babu, P.D. Gupta,
Nanoripple formation on different band-gap semiconductor surfaces using femtosecond pulses, J. Appl. Phys.
109 (8) (2011) 084347, AIP Publishing.
Fig. 1.2 shows the nanoripple formation using linearly polarized laser pulses. In
the narrow bandgap semiconductors such as GaAs and InP, the scanning electron
microscope (SEM) pictures of the irradiated spot show the spacing to be of the order
of 500–600 nm. On the contrary, in WBG materials such as GaN and SiC, the spac-
ing is of the order of 170–270 nm. Thus it was observed that, in general, the narrow
nanoripples are formed from material with a WBG. This observation of narrow ripple
formation in WBG semiconductor is consistent with previous reported results by
Borowiec et al. [19], but no explanation of the physical processes involved was given
in those experiments.
Fig. 1.3 shows different microstructure formations using different fluences and
ambient conditions for narrow bandgap semiconductors such as GaAs. The SEM pic-
ture of the irradiated spot, as seen in Fig. 1.3A, shows that, at a high fluence in air, no
nanoripple formation takes place, and only random heterogeneities of a few microns
order appear. Fig. 1.3B shows formation of nanoripples of a typical size of 600 nm
at low fluence (in air). Interestingly, Fig. 1.3C shows formation of nanoholes at high
fluence in water. Fig. 1.3D shows narrow nanoripples of 150 nm size in GaAs at low
fluence in water. This shows the crucial role of the ambient medium in formation of
the nanoripples. Very narrow nanoripples were observed in narrow bandgap materi-
als such as GaAs in water, whereas in air, the corresponding nanoripple period was
of the order of the laser wavelength. Even for a WBG material such as GaP, which
FIGURE 1.2 Nanoripple Formation Using 800 nm Pulses in Narrow Bandgap Semiconductors:
(A) GaAs and (B) InP; and in wide bandgap semiconductors: (C) GaN and (D) SiC [The
length of the horizontal bar is 1 µm in (A), (B), (C), and (D).].
109 (8) (2011) 084347, AIP Publishing.
FIGURE 1.3 Nanoripple Formation Using 800 nm Pulses in GaAs:

(A) at high fluence in air, (B) at low fluence in air, (C) at high fluence in water, and (D) at
low fluence in water. [The lengths of the horizontal bars correspond to 5 µm in (A), (B),
and (C), and 1 µm in (D).].
109 (8) (2011) 084347, AIP Publishing.
shows narrow nanoripples of period ∼200 nm in air, a narrower period of 150 nm

was observed during irradiation in water.
Fig. 1.4 shows the angular dependence of nanostructure size obtained from nar-
row (GaAs) and wide (GaP) bandgap materials irradiated by 800 nm pulses in water.
It was observed that, for the narrow bandgap (GaAs) semiconductor, the ripple size
increased with increasing angle of incidence, as shown in Fig. 1.4A. In the case of
the WBG (GaP) material with increasing angle of incidence, the ripple period first
increases and becomes constant at higher angles, as shown in Fig. 1.4B. It was men-
tioned earlier in the context of Fig. 1.3C that, at high fluence, nanoholes are formed
in GaAs. Fig. 1.4C shows that the size of the holes increases with increasing the
angle of incidence of the incident p-polarized light. In many photonic applications,
for example, two-dimensional photonic crystals and micro-diffraction elements, the
nano/micro holes on the surface of bulk materials are required as the building blocks.
Although the mechanism of formation of such structures is still not clear, this process
was achieved during irradiation in water medium, thus emphasizing the role of dense
surrounding medium in formation of such novel hole structures.
It is commonly accepted that the nanoripple width is dependent on the wave-
length of the incident light. Therefore to obtain narrow nanoripples, second harmonic
of the fundamental laser radiation is a better choice. Fig. 1.5 shows the influence of
laser wavelength on nanoripple formation. Fig. 1.5A and B show that, in the case of
SiC, the use of 400 nm wavelength reduces the ripple period by more than a factor of
two as compared to the nanoripples produced by the 800 nm pulses (from 190 nm to
about 90 nm). Similarly, for a narrow bandgap material such as InP, there is a reduc-
tion of ripple period from 620 nm to about 280 nm, as shown in Fig. 1.5C and D. It
may be noted that, for GaP, the ripple period using 400 nm pulse becomes larger than
that formed using 800 nm pulses (from 180 nm to about 300 nm).
1.1.2 DISCUSSION OF EXPERIMENTAL RESULTS AND DESCRIPTION

OF THE MODEL
The consistent observations regarding the nanoripple formation are as follows: (1)
the ripple period is larger at higher fluence, (2) the ripple period is large for the mate-
rials having bandgap narrower than the incident photon energy compared to that for
materials having a wider bandgap, and (3) a denser ambient medium results in the
formation of narrower ripple period. The plausible explanation for such observations
is consistent with the theory that ripple formation is due to excitation of the surface
plasmon at the semiconductor surface by the incident laser light with the rough tar-
get surface. The surface plasmon is a well-known phenomenon in the context of the
metals, which have free electrons for excitation of this longitudinal charge density
oscillation. However, in the case of semiconductors, the origin of free electrons is
because of the excitation of free electrons due to multiphoton ionization by the laser.
The typical intensity of 2 × 1012 W cm−2 is just sufficient to start plasma formation
for an ultrashort (45 fs) laser pulse, wherein multiphoton ionization is the dominant
process. These laser-generated free electrons give a transient metallic character to
FIGURE 1.4 Angular Dependences of Formation of Various Nanostructures Using 800 nm

Pulses in Water.
(A) Nanoripple formation in GaAs, (B) Nanoripple formation in GaP, and (C) Nanohole
formation in GaAs.
109 (8) (2011) 084347, AIP Publishing.
FIGURE 1.5 Nanoripple Formation Using 800 nm Pulses and 400 nm Pulses Respectively in
Wide Bandgap Semiconductors:
SiC (A) and (B), GaP (E) and (F), and in narrow bandgap semiconductor InP (C) and (D).
[The length of the horizontal bar is 2 µ m in (A), 500 nm in (B), 5 µ m in (C), 1 µm in (D),
1 µm in (E), and 2 µm in (F).].
109 (8) (2011) 084347, AIP Publishing.
the molten surface, which can now support the surface plasmon. During the initial
few shots, the surface roughness is enhanced due to irradiation by the high-intensity
pulses and formation of random nanostructures. The subsequent shots fired on the
roughened surface lead to more efficient excitation of surface plasmon. The molten
material assumes the shape of a grating, which satisfies the relation between wave
vectors of the incident laser (which depends on its wavelength, the angle of inci-
dence, and the refractive index of the ambient medium) and the surface plasmon
(which depends on the electron density of the molten surface). This grating gets
frozen once the material cools down as soon as the laser pulse ends giving rise to the
observed nanoripples. The wave vector of this grating satisfies the following relation,
as per the momentum conservation [18]
G = k i − ks , (1.1)
where ki is the wave vector of incident laser and ks is the wave vector of surface
plasmon. By substituting the expression for k's in terms of corresponding wave-
lengths, and |G| as 2π/d (where d is the ripple period), one gets the expression for
d as [18]
λL
d= (1.2)
λL
± µ sin θ
λS
Here λL, λS, θ, and µ are the incident laser wavelength (in vacuum), the sur-
face plasmon wavelength, the incident angle, and the refractive index of the ambient
medium, respectively. It is clear from Eq. (1.2) that for normal incidence (i.e., θ = 0)
d = λS. Thus at normal incidence the ripple period d is equal to the surface plasmon
wavelength, which is obtained from its dispersion relation as
λL
λS = (1.3)
εε m
ε + εm
Here ε is dielectric constant of the surface plasma created by the intense femto-
second pulse, and εm is the dielectric constant of the ambient medium (i.e., εm = µ2;
1 for air and 1.76 for water).
Because the multiphoton ionized surface has free electrons, its dielectric constant
can be taken similar to a plasma, that is, (neglecting the collision term frequency)
ne
ε = 1− (1.4)
nc
where ne is the surface plasma free electron density, and nc is the critical density cor-
responding to the laser wavelength. Putting the expression of ε in Eq. (1.3) and then
using Eq. (1.2), one gets for the case of normal incidence
λL
d= (1.5)
(
ε m 1−
ne
nc )
ε m + 1− ( ne
nc )
From Eq. (1.5), it is clearly seen that the ripple period is related to the incident
laser wavelength, electron density of the surface plasma, and the dielectric constant
of the ambient medium. It is also evident from the expression that real values of d
will be obtained only if
ne < nc or ne > ( ε m + 1) nc (1.6)
When this condition given by Eq. (1.6) is not satisfied, the nanoripples are not
formed. Fig. 1.6A shows the variation of nanoripple period in air and water with
electron density plotted using Eq. (1.5) for 800 nm wavelength. Fig. 1.6B shows the
same curve for 400 nm wavelength.
FIGURE 1.6 Nanoripple Period as a Function of the Electron Density for Air (Dotted Line) and
Water (Continuous Line),
using (A) 800 nm pulses and (B) 400 nm pulses.
109 (8) (2011) 084347, AIP Publishing.
A few conclusions can be made from these figures. Two branches of solutions
exist for the nanoripples; one is the super-wavelength nanoripple, and the other is
the subwavelength nanoripple. The super wavelength can be formed if the elec-
tron density is below the critical density, but such structures are not observed pri-
marily due to two reasons; the first one is that being a low electron density process
the plasmon excitation is very weak, and the second one is that the long period
structure will have lower groove depth, so that any short period structure may
overshadow the long period one. The third possible reason could be that at such
low fluence, the material simply does not melt to reorganize, thereby precluding
any possibility of ripple formation. The subwavelength nanoripples are formed if
the electron density is greater than (εm + 1)nc. The nanoripple period is equal to
laser wavelength if the electron density is high, and a very sharp decrease in the
ripple period is observed when the electron density starts approaching (εm + 1)nc.
If water is the ambient medium, then the nanoripple period is smaller for the same
electron density.
Further, the graph also brings out the critical role of electron density in formation
of large and narrow ripple formation. Because the electron density generating surface
during femtosecond laser pulse irradiation depends on the laser parameters such as
fluence and wavelength, a drastic change in the nanoripple period is expected on a
small variation of these parameters.
Now let us explain the experimental observations in terms of the aforementioned
formulation. The observation from Fig. 1.1 regarding narrow ripple of 200 nm width
at the periphery of the focal spot and wider 600 nm ripple width in the central hot
spot region can be explained as follows. Because the electron density of the laser
irradiated surface is proportional to the incident laser fluence, higher intensity of irra-
diation in the central region of the focal spot will generate a higher electron density
leading to formation of wider nanoripples of 600 nm spacing, whereas, at the region
of the edges of focal spot, a lower fluence generates a lower electron density, which
leads to a narrower (∼200 nm) ripple formation. It is also seen from Fig. 1.6, that a
slight change in the electron density can cause a drastic change of the ripple period,
and this explains the observation of the large difference in the ripple period in two
spatial regions.
The abrupt change in the ripple period is because, as explained earlier, it is very
critically dependent on the electron density (see Fig. 1.6). At high intensity, ripples
slightly smaller than the laser wavelength are formed, and at mid-range intensity
or lower intensity, the ripple period can become very narrow depending on the free
electron density generated on the surface. At very low intensities, no rippling takes
place, as explained earlier. Of course, the semiconductor material chosen, its band-
gap and material breakdown property, and irradiation intensity decide the electron
density generated.
The main observation that narrow LIPSS are formed on WBG material can also
be explained in a similar way. When a femtosecond laser irradiates a narrow band-
gap material semiconductor surface, more free electrons are likely to be available
in comparison to the case if the WBG material is irradiated by the same laser. This
is because in addition to the multiphoton excitation of electrons, the single pho-
ton absorption process will also allow the excitation of free electrons, provided the
incident photon energy is larger than the bandgap. Therefore, the absorption of the
ultrashort pulses in narrow bandgap semiconductor material is through a combina-
tion of linear and nonlinear absorption processes leading to a larger availability of
free electrons in the conduction band. Therefore as observed from Fig. 1.2, the ripple
period is large (∼600 nm) in the case of narrow bandgap materials, as a higher elec-
tron density [ne >> (εm + 1)nc] leads to formation of larger width nanoripples. On
the other hand, as the generated electron density for WBG material is low as single
photon absorption is not possible, narrow ripples are formed in this case (provided
the incident laser intensity is low).
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NICKEL STEEL.
The addition of a few per cent of nickel to mild steel adds greatly
to its strength—so much so that nickel steel is now world-renowned
as used in armor-plate for navy vessels, and for great guns. Recent
reports from the ordnance bureaus indicate that it will also be of
great use in the barrels of small arms, by means of which they may
be made lighter, and still of sufficient strength. Nickel is so expensive
and it adds so much to the cost of steel that its use for ordinary
structural purposes, bridges, etc., has not been found to be
economical.
Some years ago careful experiments were made with nickel alloy
in a fine grade of high-carbon tool-steel to find out whether such
steel would be improved as much as are the mild steels.
In such case the expense would not count, for if the best steel
can be made better there are many users who would gladly pay a
higher price for a better service.
The results were not encouraging. The high-carbon nickel steel
was not as strong as the same quality of steel without nickel; the
mixture seemed to be imperfect, containing little dark specks,
supposed to be carbon thrown into the graphitic state. The steel did
not refine as well and was not as strong as the carbon steel.
All of this applies to high-carbon tool-steel, hardened and
tempered; no tests were made of the steel unhardened, for they
would have been of no practical use.
ALUMINUM STEEL.
When a heat of steel is boiling violently, is wild, and unfit to be
poured, the addition of a minute quantity of aluminum will have the
effect of quieting it quickly. Half an ounce to an ounce of aluminum to
a ton of steel will be enough usually, and for this purpose aluminum
has become useful to steel-makers. If a little too much aluminum be
added, the ingots will pipe from end to end; therefore the use of
aluminum is restricted to small quantities. Experiments have shown
that a considerable percentage of aluminum adds no good properties
to steel; therefore aluminum steel so called may be treated later
under a different heading.
IV.
CARBON.
Of all of the abundant elements of nature carbon is presented in

the greatest variety of forms, and admits of the greatest number of
useful applications.
In the form of the diamond it is the hardest of substances, and is
the base used in determining the comparative hardness of all others.
In the form of graphite it is soft and smooth, and is one of the
best and most durable of lubricants.
In the form of soot it is probably the softest of solids.
In the form of coal it is the one great and abundant fuel of the
world, while as graphite again it is one of the best of refractory
materials.
Hard, soft, highly combustible, almost infusible, refractory, it lends
itself to the greatest variety of useful applications. To the iron- and
steel-maker or worker it is simply indispensable; as charcoal or coke
it is the fuel of the smelter; as gas, either carbon monoxide or as a
hydrocarbon, it is the cheapest and most manageable fuel for
melting and for all operations requiring heat.
As graphite, plumbago, mixed with a little fire-clay as a binder, it
is the best material for crucibles in which to melt metals; as soot it
forms the best coating for moulds into which metals are to be cast.
Durable beyond almost any other substance, it would make the
very best paint for metal structures if there were any known way to
make it adhere.
CARBON IN IRON.
Carbon may be introduced into iron in any quantity from a few
hundredths of one per cent as usually found in wrought iron, and in
what is known as dead-soft steel, up to about four per cent as found
in cast iron. By the addition of manganese as high as six or seven
per cent of carbon has been introduced into iron. Carbon does not
form a true alloy with iron, neither does it form any stable chemical
compound. Its condition in iron seems to be as variable as it is in
nature, and sometimes it has been supposed to be as capricious as
it is variable. It is hoped that the reader of these pages will find that
there is no caprice about it, that its action is governed by as sure
laws as any in nature, and that certain results may be predicated
upon any treatment to which it is subjected.
The theories of its actions are as numerous and variable as are
the actions themselves, and they will be treated in a separate
chapter, this chapter being confined to a statement of known facts.
As stated in Chap. I, carbon may be introduced into iron by
heating carbon and iron in contact when air is excluded; and,
conversely, carbon is burned out of cast iron by the Bessemer and
open-hearth processes to reduce the cast iron to cast steel.
In the crucible any quantity of carbon may be obtained in steel by
melting a mixture of high blister-steel and wrought iron, or cast iron
and wrought iron, or by charging with wrought iron the necessary
quantity of coke or charcoal. When using plumbago crucibles, the
iron takes up some carbon from the crucible; also the spiegel-eisen
or ferro-manganese used adds some carbon; and for these two
sources of carbon the melter allows when he decides upon the
quantity of charcoal needed.
Results from crucible-melting are not strictly uniform; even if
every charge were weighed in a chemical balance accurately the
product would not be uniform, because one crucible gives off more
carbon than another; in one crucible a little more charcoal may be
burned and escape as gas than in another; and most variable of all,
unless the charcoal has been dried thoroughly, is the quantity of
moisture in the charcoal. One charge of charcoal may be dry, and
the next may contain as much as twenty-five per cent of moisture;
obviously equal weights in such a case would not give equal
quantities of carbon to the steel.
In crucible steel this is no disadvantage; a skilful mixer will get
from 75% to 90% of his ingots of the desired temper; the other ingots
will all be in demand for other uses, and as he can separate them all
with absolute certainty by ocular inspection, as described before, he
labors under no fear of bad results.
In the Bessemer process it is usual to burn out all of the carbon
and then to add the required amount in the spiegel; for structural
steels and for rails this method is satisfactory. For high steel—from
fifty to a hundred or more carbon—the spiegel method does not
answer so well, because it increases the quantity of manganese to
too great an amount; higher carbon is then sometimes put in by the
addition of a given quantity of pure pig iron previously melted, or by
putting coke in the ladle, but this is very uncertain on account of the
tendency of the coke to float, and be dissipated as a gas instead of
entering the steel.
The Darby method is to place in the way of the stream of steel as
it is poured from the vessel to the ladle a refractory-lined, funnel-
shaped vessel filled with finely divided, but not powdered, coke. As
the stream rushes through the coke it absorbs carbon with great
rapidity, and it is asserted that the currents and eddies formed in the
ladle by the rush of the stream cause an even distribution of carbon.
That carbon will be taken up in this way is certain; that a required
amount, evenly distributed, can be obtained is not so certain.
In the acid open-hearth as in the Bessemer process for milder
steels it is usual to burn the carbon out almost entirely, and then to
add the desired amount with the spiegel. Higher carbon may be
obtained by the addition of pure pig iron, or by using carbon bricks
pasted together with tar and weighted with iron turnings; these bricks
may be pushed under the surface in different parts of the bath, and
in this way the carbon can be distributed pretty evenly. In good
practice now the melt is stopped at the carbon desired with great
success, thus saving time and expense. In the basic open-hearth the
melter, by the use of a little care and good judgment, stops his melt
at the required carbon, and so avoids any additional operations,
unless his charge is excessively high in phosphorus and his steel is
to be very low in the same; in that case he may have to melt clear
down and re-carbonize.
Steel of 130 carbon with phosphorus <.05 may be made on the
basic hearth from a charge containing 10 to 12 phosphorus without
melting below 130 carbon.
If high-carbon Bessemer steel is not uniform, it is not to be
wondered at, but as a matter of fact it is usually found to be fairly
uniform, sufficiently so to work well.
If open-hearth steel of high carbon is not uniform, it is clearly
because the maker would not take a little trouble to have it so.
Assuming that for convenience cast steel is graded for carbon
content by even tens, and that the different tempers are separated
half-way between the tens, we have:
Carbon.
.10 including from .05 to .15
.20 “ “ .16 “ .25
.30 “ “ .26 “ .35
.40 “ “ .36 “ .45
.50 “ “ .46 “ .55
.60 “ “ .56 “ .65
.70 “ “ .66 “ .75
.80 “ “ .76 “ .85
.90 “ “ .86 “ .95
1.00 “ “ .96 “ 1.05
1.10 “ “ 1.06 “ 1.15
1.20 “ “ 1.16 “ 1.25
1.30 “ “ 1.26 “ 1.35
1.40 “ “ 1.36 “ 1.45
Carbon.
1.50 “ “ 1.46 “ 1.55
This covers the usual commercial range from what is known as
dead-soft steel up to a high, lathe-temper steel.
Higher steels are used sometimes, even up to 225 carbon, but
they are so exceptional that it is not worth while to continue the list
above 150.
This list allows a variation of .05 carbon above and below the
datum of each temper; some margin must be had of course, and this
is sufficient in the hands of a careful steel-maker; it is found in
practice to be satisfactory to the user. Even in the highest lathe-steel
where the strains from hardening are the greatest, because the
change in volume due to a degree of temperature is the greatest, a
variation of three or four points above and below the mean does not
make enough difference in the results to throw a skilful temperer off
from his desired conditions.
On the other hand, a difference of a full temper will throw the
most skilful worker off from the track, and so that much variation is
not allowable. For instance, if a man be working 130 carbon, and he
should receive a lot of steel of 120 carbon, he would get his work too
soft in following his regular methods; then if he doubted himself, as
he would be apt to do, and raised his heat to correct his supposed
aberration, he would get his work too hard, coarse-grained, and
brittle; if he tried to correct this by drawing to a lower temper color,
his tools would be too soft. Again, if he received a lot of steel of 140
carbon and proceeded in his regular way, he would get a lot of
cracked tools. So that in either case the result would be confusion. It
is probable that in almost any case either 120 or 140 carbon would
make a thoroughly good tool if the temperer knew what he was
working with and adapted his heats to the carbon. But he does not
know of the variation, and even if he did he would say, very rightly,
that he did not propose to make daily changes in his methods to suit
the convenience or the carelessness of the steel-maker.
It must not be understood, however, that this narrow range for
each temper limits the capacity of the steel; it merely gives the limit
for regular easy working.
To illustrate: A good lathe-tool may be made of 100-carbon steel,
and of 150 carbon; but no worker could use these tempers
indiscriminately, nor even alternately, although he knew which was
which, because he could not change all of his heats say every five
minutes and turn out satisfactory work. A spring of given size, and to
carry a given load, may be made equally good of 60-carbon steel or
of 140 carbon, and such work is done frequently in shops that are
attached to steel-works; but the spring-maker must be told
beforehand what he is to work with, and he must be given enough of
one kind of steel to make say a day’s work, so that he can go along
regularly. The springs will be good, but the one containing 140
carbon will have the highest elasticity and the most life, although
both will have the same modulus of elasticity. The spring-maker who
buys his steel will not submit to any such variations, and he ought
not to be asked to do it, because one temper of steel costs no more
than another, and the selecting out and separating the tempers is
only a matter of a little care.
Is it practicable to keep steel uniform in carbon within such
narrow limits?
In crucible-steel practice it is very easy to do so. All ingots of 60
carbon upwards up to four or four and one half inches square may
be broken completely off at the top, and then the clean fracture will
indicate the quantity of carbon invariably, and after the ingot has
been glanced at and marked properly it is as easy to put it on its
proper pile as to put it on any other. In a good light a competent
inspector will mark thirty or forty ingots per minute and do it correctly;
it is as easy to the trained eye as it is to read a printed page.
This inspection is so important that it should never be neglected.
It is not costly, much less than a dollar a ton.
With larger ingots only a piece can be broken off from the edge,
but if the topper does his work properly, enough can be taken off to
show the temper clearly. Large ingots containing the contents of a
number of crucibles are liable to unevenness of temper from having
uneven mixtures in the pots and from bad teeming into the moulds;
this can be detected usually in the ingot inspection, and if not it can
be found later during another inspection. Such variations are often
called segregations. This question of segregation will be discussed
in a future chapter.
In the Bessemer and the open-hearth practice ocular inspection
of ingots to determine carbon is not used.
Enough examinations have been made to show that the
fractures, although differing from those of crucible-steel, are quite as
characteristic, and ocular inspection could be used. The ingots are
large usually and to handle and top them would be expensive; but
the heats are also large,—from five tons up to thirty tons in one heat,
—and as they are supposed to be homogeneous, one chemical
carbon analysis is enough for each heat.
Below 50 carbon a quick color analysis is accurate enough;
above 50 carbon combustion should be used, for in high carbons the
color test in the best hands is only the wildest guess-work.
The ten-point range of carbon is far more difficult to attain in high-
carbon open-hearth practice than in the crucible. In one case where
the limit fixed in a specification was 90 to 110 carbon, two full
tempers, one of the most skilful and successful concerns in the world
failed to meet the specification in twenty-ton and thirty-ton furnaces.
It was supposed at first that the trouble came from using different
heats, and large lots of billets were sent out with the heat number
stamped on each billet. The same variations were found in every
heat, the carbon ranging from 80 to 120. The specification was met
without any trouble in five-ton furnace.
This illustration should not lead to the conclusion that practically
uniform steel cannot be obtained; there is little doubt that if the 30-
ton heats had been stirred thoroughly in the furnace the required
limits would have been obtained.
Neither is it to be understood that the same variation would occur
in mild steel under 30 carbon. A call for 20 carbon would not result in
steel ranging from below 10 to above 30,—such a result would show
gross carelessness on the part of the melter,—the variation would go
by percentage; thus the variation in the high steel is from 15% below
to 15% above the mean of 100, or even as much as 20%.
If 20-carbon steel be required, a variation of 20% would give a
range from 16 to 24 carbon, or well within the limits of one temper.
This matter will be considered farther under the head of
Segregation.
The appropriate applications of the different tempers of steel
have been stated in a general way, with the advice that for all tool
purposes it is better to leave the selection of the temper to the steel-
maker; also in structural work it may prove to be better to leave the
question of temper, or carbon content, to the steel-maker, who
should know how to meet any specification that is within the capacity
of steel. On the other hand, every engineer should know what is
attainable, and an effort to give this information in more definite form
will be made in later chapters. A general view will now be taken of
what may be called the carbon-line.
Let the horizontal line represent iron, the inclined line iron plus
carbon, and the verticals physical properties.
We do not know the physical properties of pure iron. Assuming
them to be uniform, let the vertical at .05 represent the tensile,
torsional, transverse, or compressional strength of steel of 5 carbon;
then for every increment of carbon up to 90 to 100 there will be an
increase of strength to resist any of these strains, increasing in such
regular amounts as to make the resulting carbon-line practically
straight, as shown in the sketch. Above 100 carbon these
resistances will all decrease, except resistance to compression.
So far as it is known, compressive strength increases slightly with
the carbon, until cast iron is fairly reached; then the presence of
silicon, and the fact that we are dealing with a casting instead of
forged or rolled metal, causes a rapid fall in all resistances until the
strength is below that of 5 carbon steel.
With increase of carbon there is a reduction of ductility, so that
the extension of length and reduction of area decrease as the
strength increases. In every case the engineer must decide how little
ductility he can do with safely in securing the ultimate strength or the
elastic limit he may require.
The highest strength and the greatest ductility cannot be had
together; they are inverse functions one of the other.
If the exact resistances due to carbon were known along the
whole line, it would be of great value to give them here but nearly all
of the thousands of tests published are influenced by the quantities
of silicon, phosphorus, sulphur, manganese, or oxides present, and
an effort to determine the effects of the carbon-line exactly would be
hazardous.
Kirkaldy’s tests of Fagerota steel, published in 1876, furnish a
valuable guide in this direction.
Webster’s experiments on the effects of the different elements,
phosphorus, manganese, etc., are interesting and valuable, but he
has not yet tested a complete carbon-line with no other variables.
It has been stated time and again by experienced steel-makers
that the best steel, the most reliable under all circumstances, is that
which comes nearest to pure iron and carbon.
Some intelligent steel-makers, and engineers cast doubts upon
this statement, and assert that because phosphorus up to a certain
limit, or manganese, or silicon, or in fact it may be said almost any
element, added to dead-soft steel will give an increase of strength,
therefore the presence of one or more of these elements is not only
not harmful, but beneficial.
As a matter of fact, however, every one of these elements is
harmful, either in producing cold-shortness, or red-shortness, or
brittleness, and not one of them will add any good quality to steel
that may not be obtained better by the use of carbon. Given a
uniform minimum content of these impurities, the carbon-line may be
depended upon to furnish any desirable quality that is obtainable in
steel; and it is certain, always sure, that that steel which is the
nearest to pure carbon and iron will endure the most punishment
with the least harm.
That is to say, that such a steel when overheated a little, or
overworked, or subjected to any of the irregularities that are
inevitable in shop practice, will suffer less permanent harm than a
steel of equal strength where there is less carbon and the additional
strength is given by any other known substance.
It is difficult to show this from testing-machine data, indeed it is
doubtful if any such data exist, but experience in the steel-works, in
the bridge- and machine-shops, and in the field proves it to be true.
For further discussion of this question see Chap. X.
The effects of a small difference in phosphorus or in silicon
contents are shown plainly and unmistakably in high-carbon steel,
and not so plainly in low-carbon steel; but as there is no known hard
and fast line that divides low steel, medium steel, and high steel, so
there is no marked difference in their properties. The same rules
hold all along the line, the same laws govern all of the way through.
There is no set of properties peculiar to low steel and another set
peculiar to high steel; the same laws govern all, and differences are
those of degree and not of law.
Given three samples of steel of the following compositions:
No. 1. No. 2. No. 3.
Silicon .02 .20 .02
Phosphorus .01 .01 .02
Sulphur .005 .005 .005
Manganese .100 .100 .100
No. 1. No. 2. No. 3.
Carbon 1.100 1.100 1.100
A skilful worker, not knowing the composition of any, will pick
them out invariably by tempering them and testing them with a hand-
hammer and by inspecting the fractures.
He will pronounce No. 1 to be the best and the strongest in every
way; No. 2 to be not quite as strong as No. 1, and more liable to
crack from a little variation in heat; No. 3 to be not so strong as No.
1, and that it will not come quite as fine as either of the others, and,
like No. 2, it will not stand as much variation in heat as No. 1.
Give a ton of each to a skilful axe-maker, from which he will make
one thousand axes of each, and he will be sure to report No. 1 all
right; No. 2 good steel, more loss from cracked axes than in No. 1.
No. 3 good steel, some inclination to crack; it will not refine as
well as No. 1 and is not as strong.
This is no guess-work, nor is it a fancy case; it is simple fact,
borne out by long experience.
Give a skilful die-maker one hundred blocks of each to be made
into dies. He will not break one of No. 1 in hardening them; he will
probably break five to ten of No. 2; and if he breaks none of No. 3—a
doubtful case—he will find in use that No. 1 will do from twice to
twenty times as much work as either of the others. If he is making
expensive dies,—many dies cost hundreds of dollars each for the
engraving,—he will think No. 1 cheap at 25 cents a pound, and
either of the others dear at 15 cents a pound.
In such steel, then, the absence of a few points of silicon, or of a
point or two of phosphorus, is worth easily 10 cents a pound.
Now let the carbon in these three steels be reduced to 10,
making them the mildest structural steel. The differences to be found
in the testing-machine in tensile strength, elastic limit, extension, and
reduction of area will be almost or altogether nothing; in forging,
flanging, punching, etc., under ordinary conditions differences would
not be observable; therefore there would be no practical difference in
value. But let the silicon be raised to 30 or the phosphorus to 10,—
the Bessemer limit,—or let both be raised together, and both the
testing-machine and shop practice would show a marked difference.
This shows that in the absence of carbon the action of these
elements is sluggish as compared to their effects in the presence of
high carbon, or in the low-carbon steels their effects are not so
observable. That their influence is there, there can be no doubt, but if
it be not enough to endanger the material it is not worth while to take
it into account.
Is it safe and wise, then, for steel-users to ignore composition?
Users of tool-steel may do so safely, because the smallest
variations will manifest themselves so unmistakably that they give
immediate warning, and the steel-maker must keep his product up to
a rigid standard of excellence or lose his character and his trade.
Many of the ablest users of structural steel take a similar ground,
and say, We have nothing to do with method or composition if the
material meets our tests.
It is believed that if these men knew how easy it is for a skilful
worker to doctor temporarily an off heat by a little manipulation, and
how dangerous the same may become by a little off practice in the
field, they would be convinced that some limits should be put upon
composition, especially if they could realize that a reasonable
specification would add nothing to cost, as competition would take
care of that.
The reader is referred again to Chap. X on impurities.
V.
GENERAL PROPERTIES OF STEEL.
Steel is very sensitive to heat. In general it may be stated that, starting with
cold steel, every degree of heat added causes a change in size and in structure,
until the limit is reached where disintegration begins. The changes are not
continuous; there are one or two breaks in the line, notably at the point where we
have what is called recalescence; this is a marked phenomenon and it will be
considered later.
The effects of heat are permanent, so that it is a fact that every variation of
temperature which is marked enough to be visible to the naked eye will leave a
structure, due to that variation, when the steel is cold, which will be observable by
the naked eye, and such structure, when not influenced by external force, such
as by hammering or rolling, is as invariable and certain as is the structure of an
ingot due to the quantity of carbon present.
This property furnishes what may be called the steel-maker’s and the steel-
user’s thermometer. By its means the steel-maker can discover every irregularity
in heating that may have been perpetrated by the operatives; so also the steel-
user can decide whether the steel furnished him has been heated and worked
uniformly and properly, and later he can tell whether those who have shaped this
steel to its final forms have done their work properly. A thorough knowledge of
this property is essential to a steel-maker; until he possesses it he is not fit to
conduct his business. It is of great importance to the steel-user, and every
engineer should try to acquire a knowledge of it in order that he may not be
fooled by the carelessness or rascality of those who have preceded him. The
steel-maker acquires this knowledge by daily contact with the facts; the engineer
does not have it forced upon him in this way, but he should seek opportunities of
observation, which will be abundant in his earlier practice when he is sent upon
inspection duty. Like the structure of ingots, this heat-structure cannot be
illustrated on paper, and an attempt to do so would be misleading; attempts at
description will be made in the hope that by their means the engineer will have a
pretty good idea what to look for, and to know when his suspicions should be
aroused.
In addition to the ocular observations mentioned it has been shown by
specific-gravity determinations, and by delicate electrical tests through small
ranges of temperature, that steel is as truly thermometrical as mercury.
Steel passes through or into four general conditions due to heat. First, in the
cold state, it is a crystalline solid of no uniform structure, for its structure is
influenced by every element that enters into it, and by every irregularity of heat to
which it has been subjected.
Good steel may be described as having a bluish-gray color, uniform grain as
seen by the naked eye, and little lustre. But it should have some lustre and a silky
appearance. When it is right, a steel-worker will say it is “sappy,” and that name,
absurd as it may sound when applied to a metal, really expresses an
appearance, and implies an excellence that it would be hard to find a better word
for. If the structure be dull and sandy-looking, the steel-worker will say it is “dry,”
and that term is as suggestive and appropriate as the word “sappy.”
If the fracture be granular with bright, flashing lustre, the steel-worker will say
it is “fiery,” and again his term is expressive and proper.
It is perfectly safe to say that steel of a “sappy” appearance is good steel; but
in order to know what it is it must be learned by observation, it cannot be
described in exact terms.
It is equally certain that a “dry” fracture indicates a mean steel, a steel
inherently mean,—too much phosphorus, or silicon, or oxides, or all combined,—
and such a steel is incurable.
A “fiery” fracture indicates too much heat. It may be found in the best steel and
in the poorest; it may be corrected by simply heating to a proper temperature. It
shows that some one needs to be reprimanded for careless work.
If now an inquirer will take a piece of good steel of “sappy” fracture, and of
“dry” steel of dull, sandy fracture of the same carbon, and will heat them say first
to dark orange, then to bright orange, dark lemon, and so on, and examine the
fractures after each heating, he will find a “fiery” fracture in the “dry” steel at a
heat much below that which is necessary to make the “sappy” steel “fiery.” This is
one proof that good steel will endure more punishment than poor steel.
Cold steel is not plastic in the common acceptance of the word; strictly
speaking it has some plasticity, as shown in the extension noted in pulling it; this
is its measure of ductility.
Also it may be drawn cold to fine wire of only a few thousandths of an inch in
diameter, and it has been rolled cold to one five thousandth of an inch thick. But
this work must be done with great care; the steel soon becomes brittle, and a little
overdrawing or overrolling will crush the grain and ruin the steel; therefore the
work must be done a little at a time, and be followed by a careful annealing.
To reduce a No. 5 wire rod to .005 inch diameter will require with high steel
suitable for hair-springs about fourteen annealings.
A skilful hammerman will take a piece of mild cold steel, and by means of
light, rapid blows he will heat it up to a bright lemon heat without fracturing it; then
he will have it thoroughly plastic and malleable.
This has no practical commercial value; it is a beautiful scientific experiment
exhibiting high manual skill, and showing that there is no hard and fast line
between non-plasticity and plasticity.
The first condition, then, is cold steel, not plastic, not malleable.
When steel is heated, it begins to show color at about 700° to 800° F.; the first
color is known as dark cherry red, or, better, orange red: above this color it turns
to a distinct, rather dark, or medium orange color; this is the heat of recalescence,
a good forging-heat, and the best annealing- and quenching-heat. At this heat
and above it good steel is truly plastic and malleable; a roller or hammerman will
say, “It works like wax,” and so it does.
This is the second or plastic condition.
Heated above this plastic condition to a bright lemon in high steel, or to a
creamy, almost scintillating, heat in mild steel, steel will go to pieces under the
hammer or in the rolls; the workman will probably say it is burned, but it is not
burned necessarily; it is simply heated up to the third or granular condition; it is
the beginning of disintegration and the end of plasticity.
This granular condition is important in several ways. It is made use of in
Sweden, and has been demonstrated in the United States, to determine the
quantity of carbon in steel. An intelligent blacksmith is given a set of rods of
predetermined carbon, ranging from 100 carbon to zero, or through any range
that may be necessary; each rod is marked to indicate its carbon. He takes the
rods one by one and heats them until they scintillate, well up into the granular
condition, then lays them on his anvil and hammers them, observing carefully the
color at which each one becomes plastic as it cools slowly. After a little practice
he is given rods that are not marked, and by treating them in the same way he will
give them their proper numbers, rarely missing the carbon by as much as 10
points, or one temper.
It is a beautiful and useful illustration of the effect of carbon. The rule is, the
higher the carbon the lower the granulating-point; or, as is well known, high steel
will melt at a lower temperature than low steel.
This shows that every temper of steel has its disintegration temperature where
it passes from plastic to granular, as fixed as its fusion-point or its point of
recalescence.
Steel passes from the granular condition to the liquid or fourth form.
There is little of interest in the liquid condition of steel to any but the steel-
maker; what there is to be said will be mentioned later.
Steel in cooling from the liquid passes through the granular and the plastic
conditions to the cold state.
The granular form is of special interest to the steel-maker for the reason that
in this condition the steel has more of adhesion than cohesion; it will stick to
anything it touches, and so cannot be made to flow. This is the cause of “bears,”
“stickers,” and many of the troubles of the melter. Therefore steel must be put into
the moulds while it is still molten, and moulds should be well smoked or lime-
washed to prevent stickers. This condition is of great interest to engineers,
because the failure to roll or shape molten steel by pouring it directly between the
rolls is doubtless due to this adhesive, non-cohesive condition.
To produce sheets, bars, and all sorts of shapes from molten steel direct,
without the expense of making, handling, and re-heating ingots, is an enticing
idea which has occupied the minds and efforts of many able mechanics and
engineers.
If steel passed directly from the liquid to the plastic condition as glass does,
hammers and rolls would soon be replaced by dies at a great saving of cost and
labor. It is no wonder that such a desirable end has led to many persistent and
costly efforts, but until some way can be devised to eliminate this granular form in
cooling it would seem that all such efforts must end in failure.
As steel cools down through the plastic condition the cooling is not
continuous; there are two or three points where it is arrested for a time, and at
one notable point the cooling is not only arrested, but after a few moments of stop
the operation is reversed, the steel becomes visibly hotter, and then the cooling
goes on regularly; there may be other slight pauses, but they are of little
importance compared to this one, which is known as the point of recalescence.
There are many theories of the cause of this recalescence; the ablest scientists
are still working at it; and until some definite conclusion is reached it is not worth
while to write pages of discussion which may be found fully stated and illustrated
over and over again in the various technical journals, and transactions of different
engineering societies.
There are some properties of steel of great interest which seem to cluster
around this recalescence-point; they will be noted as they are reached.
We have seen that there is a marked, definite structure of the grain of ingots
due to every quantity of carbon, and also that there is a fixed limit of malleability
for every quantity of carbon. It is known also that the recalescence-point shifts
slightly with a change of carbon, and that it is much more marked and brighter in
high-carbon steel than in low.
There are no other sure indications of the quantity of carbon present. As soon
as an ingot is heated up to orange color, or the recalescent-point, it loses its
distinctive structure and its fracture no longer furnishes a sure guide.
If three ingots of say, 20, 80, and 120 carbon respectively be heated to orange
and then cooled slowly, their fractures will be so different as to enable an expert
to place them properly in their order of carbon, and to classify them as mild, hard,
and harder; beyond that he could not go; if he attempted to give them their
temper numbers, he would be likely to miss by four or five numbers either way,
and a correct mark would be only a lucky guess.
Hammering and rolling heated steel affect the grain or structure profoundly; a
high steel may be worked so that the grain will look mild, and a mild steel may be
so worked that the grain will look hard. It is common to see a bar of steel with a
fine grain at one end and a coarse grain at the other, and this state of things often
frightens a consumer, who imagines that he has received a very irregular, uneven
article, and he is as often astonished when it is shown to him that at the same
proper heat the two ends will refine and harden equally well, and be exactly alike.
In such a bar one end has been finished a little hotter than the other, and the
grain is due to the heat in each case. This uneven heating may have been
incidental or careless; with skilful workers it is rare.
One end might have been finished so cold as to crush the grain, and the other
end so hot as to cause incipient disintegration, but a competent inspector would
discover either condition at once and reject the bar.
There is, then, a specific structure due to temperature; it is modified by carbon
and by treatment under the hammer or in the rolls. If a bar of steel be heated up
to the highest plastic limit, just so that it will not fall to pieces, and then cooled
slowly without disturbance, and a fracture be taken, it will be found to be coarse
and with an exceedingly brilliant lustre. Now let it be heated again to a bright
lemon color, but still plastic, and cooled as before; it will be found to be coarse,
with bright lustre, but neither so coarse nor so bright as the first piece. Then let it
be treated in this way to lemon color, light orange, medium orange, dark orange,
and orange red; as the heats go down the grain will be finer and the lustre will be
less, until at about medium orange the lustre will be absent.
If any number of bars of even composition be heated in this way, the fractures
will all be alike for each temperature.
If a series of bars of the different full tempers, about seven in all, be treated in
this way, the structures due to a given temperature will all be similar, but there will
be no two exactly alike, because high steel is much more profoundly affected by
heat than low steel.
Seven tempers are mentioned here, because that is the number of full
tempers in common use. Steel is graded out into fifteen tempers ordinarily by the
interpolation of half numbers; this is easy and sure in the ingot inspection. In the
above experiment the differences due to carbon are not quite so delicate, and the
work is hampered in the heating by the personal equation, so that the use of
seven full tempers is refinement enough. There is a difference due to every
separable quantity of carbon, which could be shown if all of the operations of the
experiment were exact.
If when a bar is broken cold the fracture is uneven, with coarse grain in one
part and fine grain in another, it shows that there has been uneven heating. If one
side has large grain and the other side is fine, the bar has been a great deal
hotter on the side having coarse grain than on the other: the heater has let the
bar lie in the furnace with one side exposed to a hot flame and the other
protected from the flame in some way; he has neglected to turn the bar over and
heat it evenly.
If the outside of the bar is fine and the centre is coarse, the bar has been very
hot all through and has been finished by light blows of the hammer or by light
passes in the rolls; it has been worked superficially and not thoroughly.
If the outside of the bar is coarse and the centre is fine, the steel has been
heated on the surface too hot and too quickly; it has not had time to get hot
through, and it has had too little work in the finishing.
If the grain is dark, with the appearance of a rather heavy india-ink tint, the
steel has been finished too cold, and it will be found to be brittle.
If the grain is very dark, especially about the middle, looking almost black,
then it has been finished altogether too cold: the grain is disintegrated, and the
bar is fit only for the scrap heap.
A bar of this kind containing enough carbon to harden will harden thoroughly,
and often appear to be sound and fine, but it is not sound and will not do good
work; if it be brought up to a proper heat and forged to a point, it will almost
certainly burst, showing that the integrity of the steel has been destroyed.
If a bar, or plate, or beam shows cracks on the surface or at the corners, with
rough, torn surfaces, the steel has either been superficially burned or it is red-
short. In either case it should be rejected, for the cracks, although small, will
provide starting-points for ultimate fractures, whether it be tool-steel that is to be
hardened, or structural steel that is to be strained without hardening. If the steel is
to be machined, so that all of the cracks can be cut out, then in machinery-steel
the removal of these surface defects might leave the finished piece sufficiently
sound and good. If, however the steel is to be hardened, and the defects should
be due to red-shortness, the piece would almost certainly break in the hardening;
and if it were not red-short, then unless the cracks were cut away entirely, if the
least trace of the crack is there, although it may not be visible, that trace will be
sufficient to start a crack when the piece is hardened.
EFFECTS OF COOLING.
Increase of heat causes increase of softness up to the liquid condition.
Decrease of heat—cooling—increases hardness up to the hardness of glass.

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Nanostructured Nonlinear Optical

Materials: Formation and

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[12] O. Varlamova, C. Martens, M. Ratzke, J. Reif, Genesis of femtosecond-induced nano-

Nanostructured Nonlinear Optical Materials. http://dx.doi.org/10.1016/B978-0-12-814303-2.00001-5 1

Below, we analyze surface nanoripple formation on different bandgap semicon-

1.1.1 EXPERIMENTAL ARRANGEMENTS AND RESULTS

FIGURE 1.1 GaP Irradiated by 800 nm Ultrashort Laser Pulses,

FIGURE 1.3 Nanoripple Formation Using 800 nm Pulses in GaAs:

shows narrow nanoripples of period ∼200 nm in air, a narrower period of 150 nm

1.1.2 DISCUSSION OF EXPERIMENTAL RESULTS AND DESCRIPTION

FIGURE 1.4 Angular Dependences of Formation of Various Nanostructures Using 800 nm

Of all of the abundant elements of nature carbon is presented in

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