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 Spectroscopic Methods for
Nanomaterials Characterization

Volume 2

Edited by
Sabu Thomas
Raju Thomas
Ajesh K. Zachariah

Raghvendra Kumar Mishra

Elsevier
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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Copyright © 2017 Elsevier Inc. All rights reserved.

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Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional practices, or
medical treatment may become necessary.

Practitioners and researchers may always rely on their own experience and knowledge in
evaluating and using any information, methods, compounds, or experiments described herein. In
using such information or methods they should be mindful of their own safety and the safety of
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instructions, or ideas contained in the material herein.
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List of Contributors
Rameshwar Adhikari
Tribhuvan University, Kathmandu, Nepal; Nepal Polymer Institute (NPI), Kathmandu,
Nepal
Basheer Ahamed
B.S. Abdur Rahman University, Chennai, India
Gudimamilla Apparao
Acharya Nagarjuna University, Guntur, India
Anjali Bishnoi
Indian Institute of Technology HauzKhas, New Delhi, India
Jayesh Cherusseri
Indian Institute of Technology Kanpur, Kanpur, India
Kuppanna Chidambaram
VIT University, Vellore, India
Yogesh S. Choudhary
Indian Institute of Space Science and Technology, Thiruvananthapuram, India
Andrea Delfini
Sapienza University of Rome, Rome, Italy
Kalim Deshmukh
B.S. Abdur Rahman University, Chennai, India
Aastha Dutta
Maharashtra Institute of Technology, Aurangabad, India
Jianwu Fang
Chang’an University, Xi’an, People’s Republic of China
Gejo George
HLL Lifecare Limited, Trivandrum, India
Sony George
University of Kerala, Trivandrum, India
Gurram Giridhar
Acharya Nagarjuna University, Guntur, India
Sven Henning
Fraunhofer Institute for Microstructure of Materials and Systems (IMWS), Halle/Saale,
Germany
Saravanakumar Jagannathan
Universiti Teknologi Malaysia, Johor Bahru, Malaysia
Nebu John
University of Kerala, Trivandrum, India; Mar Thoma College, Tiruvalla, India

xiii
xiv List of Contributors

Lavanya Jothi
Indian Institute of Space Science and Technology, Thiruvananthapuram, India
Jithin Joy
Newman College, Thodupuzha, India
R.R.K.N. Manepalli
The Hindu College, Machilipatnam, India
Mario Marchetti
Sapienza University of Rome, Rome, Italy
Marta Marszalek
Institute of Nuclear Physics Polish Academy of Sciences, Krakow, Poland
Davide Micheli
Sapienza University of Rome, Rome, Italy
Goerg H. Michler
Martin Luther University Halle-Wittenberg, Halle/Saale, Germany
Raghvendra Kumar Mishra
Mahatma Gandhi University, Kottayam, India
Gomathi Nageswaran
Indian Institute of Space Science and Technology, Thiruvananthapuram, India
Khadheer S.K. Pasha
VIT University, Vellore, India
Roberto Pastore
Sapienza University of Rome, Rome, Italy
Deepalekshmi Ponnamma
Qatar University, Doha, Qatar
Shaohua Qu
Northwestern Polytechnical University, Xi’an, People’s Republic of China
P.S. Rama Sreekanth
National Institute of Science and Technology, Odisha, India
Kishor K. Sadasivuni
Qatar University, Doha, Qatar
Sowmya Sankaran
B.S. Abdur Rahman University, Chennai, India
Fabio Santoni
Sapienza University of Rome, Rome, Italy
Mengtao Sun
University of Science and Technology Beijing, Beijing, People’s Republic of China;
Chinese Academy of Sciences, Beijing, People’s Republic of China
Sabu Thomas
Mahatma Gandhi University, Kottayam, India
 List of Contributors xv

Antonio Vricella
Sapienza University of Rome, Rome, Italy
Liuding Wang
Northwestern Polytechnical University, Xi’an, People’s Republic of China
Runcy Wilson
HLL Lifecare Limited, Trivandrum, India
Guanglei Wu
Qingdao University, Qingdao, People’s Republic of China
Hongjing Wu
Northwestern Polytechnical University, Xi’an, People’s Republic of China
Hui Xing
Northwestern Polytechnical University, Xi’an, People’s Republic of China
Duyang Zang
Northwestern Polytechnical University, Xi’an, People’s Republic of China
Editor Biographies
Professor (Dr.) Sabu Thomas is the Director of International and
Interuniversity Center for Nanoscience and Nanotechnology, Mahatma
Gandhi University, Kottayam, Kerala, India. He is also a full professor of
Polymer Science and Engineering and School of Chemical Science of the
same University. He is a fellow of many professional bodies. Professor
Thomas has co-authored many papers in international peer-reviewed
journals in the area of polymer processing. He has organized several
international conferences. Professor Thomas’s research group is in
specialized areas of polymers, which includes polymer blends, fiber-filled
polymer composites, particulate-filled polymer composites and their
morphological characterization, aging, and degradation, pervaporation
phenomena, sorption, and diffusion, interpenetrating polymer systems,
recyclability and reuse of waste plastics and rubbers, elastomeric cross-
linking, and dual porous nanocomposite scaffolds for tissue engineering.
Professor Thomas’s research group has extensive exchange programs with
different industries, research, and academic institutions all over the world
and is performing world-class collaborative research in various fields. The
Professor’s Center is equipped with various sophisticated instruments and
has established state-of-the-art experimental facilities which cater to the
needs of researchers within the country and abroad. He has more than 700
publications, 50 books, H Index-78 and 3 patents to his credit. He is a
reviewer to many international journals. Professor Thomas has attained
5th Position in the list of Most Productive Researchers in India in 2008e16.

Professor (Dr.) Raju Thomas is currently Vice Chancellor of Middle East

University FZE, Al Hamra, Ras Al Khaimah, United Arab Emirates.
Dr. Thomas started his Professorship from the Research and Postgraduate
Department of Chemistry, Mar Thoma College, Thiruvalla-3, Kerala,
India. Dr. Thomas procured his PhD under the supervision of Professor
(Dr.) Sabu Thomas, Director of International and Interuniversity Center
for Nanoscience and Nanotechnology, Mahatma Gandhi University,
Kottayam, Kerala, India. He has extensive research experience in
Nanoscience and Nanotechnology. He has 12 years of research experience
in the Organic Chemistry and Polymer Chemistry laboratories of the
School of Chemical Sciences, Mahatma Gandhi University, Kottayam,
Kerala, India. He has also worked in the laboratory of Applied Rheology
and Polymer processing of Katholieke University, Leuven, Belgium, and
in the laboratory at Leibniz Institute of Polymer Research, Dresden,

xvii
xviii Editor Biographies

Germany. He has widely studied the kinetics of curing, morphology

development, and structural characteristics of in situ-cured
nanocomposites based on epoxy resin and reactive rubbers. His research is
reflected in his six published research articles in international journals, and
additional articles which are currently under review. In addition, many
articles have been published in popular journals. He has co-authored many
chapters and is co-editor of a book entitled Micro and Nanostructured
Epoxy/Rubber Blends which was recently published by Wiley and Sons.
He has attended many national and international seminars/conferences and
presented many research papers. He is an approved research guide in
Chemistry at Mahatma Gandhi University, Kottayam, India and has
availed projects from University Grants Commission (UGC), Department
of Science and TechnologyeScience and Engineering Research Board
(DSTeSERB) and Kerala Science Council for Science, Technology, and
Environment (KSCSTE).

Dr. Ajesh K. Zachariah is working as Assistant Professor in the

Department of Chemistry, Mar Thoma College, Kerala, India. He has
many publications in the field of materials chemistry, and polymer
nanocomposites and has one national patent. He is an expert in
sophisticated techniques such as Atomic Force Microscopy (AFM), X-ray
diffraction Technique (XRD), Gas Permeability Tester, and Dynamic
Mechanical Analyzer (DMA). He has many years’ experience in the field
of nanoscience and nanotechnology.

Raghvendra Kumar Mishra is currently working as Senior Research

Fellow at the International and Interuniversity Center for Nanoscience and
Nanotechnology, Mahatma Gandhi University, India. He has received
India’s most prestigious Visvesvaraya Research Fellowship, and he is
currently serving as Visvesvaraya Fellow. He has widely studied the
processing of blends, in situ generation micro- and nanofibrillar
composites, electromagnetic shielding effect of nanocomposites,
decorating and alignment of carbon nanotubes, and thermal, dynamic
mechanical, and structural relationships in polymer blends and
nanocomposites. He has won several awards from different organizations
and technology events. He is serving as reviewer in many international
journals, for example, Environmental Chemistry Letters (Springer). He has
research experience in Mechanical Engineering, Materials Science and
Technology, and Nanoscience and Nanotechnology. His areas of research
are multidisciplinary, which include thermodynamics, heat transfer,
refrigeration and air-conditioning, fluid mechanics, machine design, solid
mechanics, machine theory, power plant engineering, metal and ceramic
 Editor Biographies xix

processing. In addition, he specializes in polymers, which include polymer

recycling, polymer blends, fiber-filled polymer composites, particulate-
filled polymer composites and their morphological characterization, aging
and degradation, nanomaterials e.g., metallic, metallic oxide, carbon
nanotubes, graphene, conducting polymer blends, composites and
nanocomposites, biodegradable polymer blends and composites. He has
expertise in sophisticated characterization techniques such as dynamic
mechanical analyzer, differential scanning calorimetry, thermogravimetric
analysis, spectroscopy, vector network analyzer, scanning electron
microcopy, and atomic force microscopy (AFM).
 Atomic Force Microscopy as a
Chapter
1
Nanoanalytical Tool
Rameshwar Adhikari1, 2, Sven Henning3 and Goerg H. Michler4
1
Tribhuvan University, Kathmandu, Nepal; Nepal Polymer Institute (NPI), Kathmandu, Nepal; 3Fraunhofer Institute for
2

Microstructure of Materials and Systems (IMWS), Halle/Saale, Germany; 4Martin Luther University Halle-Wittenberg,
Halle/Saale, Germany

CHAPTER OUTLINE
1.1 Introduction 1
1.2 Specimen Preparation 7
1.2.1 Thin Films 7
1.2.2 Physical and Chemical Etching, Ion Etching 7
1.2.3 Ultramicrotomy 8
1.3 Typical Examples of Nanomaterials Characterization by Atomic Force
Microscopy 8
1.3.1 Nanoparticles Imaging and Manipulation 8
1.3.2 Biobased Nanomaterials and Nanoencapsulation 10
1.3.3 Comparison With Electron Microscopy 12
1.4 Concluding Remarks 14
Acknowledgments 15
References 15

1.1 INTRODUCTION
As the development of new materials has played a considerable role in the
advancement of human civilization, microscopic techniques have offered
probably the most important contribution toward the development of the
new materials themselves. The microscope delivers the most direct informa-
tion on the structure and properties of materials on different length scales,
not only allowing the experimentalist to interpret the correlation between

Spectroscopic Methods for Nanomaterials Characterization. http://dx.doi.org/10.1016/B978-0-323-46140-5.00001-7

Copyright © 2017 Elsevier Inc. All rights reserved. 1
2 CHAPTER 1 Atomic Force Microscopy as a Nanoanalytical Tool

very internal structures of the materials and their properties but also permit-
ting the innovator to design new structures relevant for targeted specific ap-
plications. In this regard, the electron microscope, and more recently the
scanning probe microscope (SPM), have been developed as reliable tools
for the characterization of nanomaterials. It should be noted that different
scattering techniques, in particular the X-ray methods, have made signifi-
cant contributions to the understanding of the structureeproperty correla-
tions of the materials, although the information is averaged over a large
volume. An SPM not only can access the structure of materials in the
macroscopic to nanoscale range but also studies various phenomena such
as adhesion, friction, electrical, magnetic, mechanical, and thermal proper-
ties of the materials on a very local level.
Owing to their ability to offer nanoscale resolution and versatile applica-
bility, SPM techniques have emerged as an indispensable nanomaterials
characterization tool. The invention of the first atomic force microscope
by Binnig and its introduction by Binnig et al. [1,2] in 1986 opened up
the possibility of obtaining surface images with atomic resolution on con-
ductors and insulators by utilizing very small tipesample interaction forces.
Thus, among the SPM techniques, the AFM is a highly versatile and popular
nanoanalytical tool. Thus, it has been common practice in past decades to
supplement electron microscopy with the AFM.
A brief survey of the fundamentals and relevant applications of this tech-
nique in nanomaterials research is presented in this chapter. For a detailed
account of the fundamentals and application of AFM techniques applied to
different materials, the readers may consult more concise reviews [3e7].
In atomic force microscopy, the solid surfaces are scanned in a raster pattern
by an extremely sharp mechanical probe attached to a cantilever. Highly
localized tipesample interaction forces are measured as a function of the
specimen’s local position. In its basic function, AFM provides high-
resolution imaging of the surface relief of the specimen between lateral
scales of a few nanometers to about a hundred micrometers as demonstrated
by some examples presented in Fig. 1.1.
Fig. 1.1 presents tapping-mode AFM images of different magnifications of
thin isotactic polypropylene (iPP) film sandwiched between polystyrene
(PS) layers prepared by the microlayer coextrusion technique [8e10]. The
most popular AFM mode of operation is the so-called “tapping” mode or
“intermittent-contact” mode, in which the sample is scanned with an oscil-
lating probe. The contrast mechanism in the AFM operation is based on
the local mechanical properties of the specimen [11e14].
 1.1 Introduction 3

n FIGURE 1.1 Tapping-mode atomic force microscopy images of different magnifications of isotactic polypropylene illustrating the surface topography (A and C)
and phase morphology (B and D), showing the ability of the technique to image structural details at different length scales.

The images on the top in Fig. 1.1 show the so-called “spherulitic” texture of
the iPP with a sphere diameter of a few micrometers, which is not fully
grown due to quenching of the samples during processing. The height im-
ages are particularly helpful to illustrate the spherulitic texture and surface
topography of the sample. A portion of Fig. 1.1A and B is magnified in
Fig. 1.1C and D, respectively. The height image (Fig. 1.1C) still preserves
information on the surface topography of the specimen, whereas the nano-
structured surface morphology of the specimen with cross-hatched crystal-
line lamellae is visible in the phase image (Fig. 1.1D). By using image
processing software, which is usually made available by the atomic force mi-
croscope manufacturer, or by using common image processing tools, the
4 CHAPTER 1 Atomic Force Microscopy as a Nanoanalytical Tool

morphological details of the specimens can be easily evaluated. In the given

case, the thickness of bright-appearing crystalline lamellae in the iPP sample
can be measured as being about 10 nm, whereas the interlamellar distance is
about 15 nm.
Thus, by using the single probe, the morphological details including micro-
scopic structure as well as nanoscale phase information and materials het-
erogeneity can be accessed and quantified using the AFM.
Simultaneously, information about the sample topography can be quite pre-
cisely evaluated. AFM is the only nondestructive microscopic technique
that simultaneously provides thus the nanoscale structural information of
the material based on different physicomechanical properties as well as
topography and roughness.
By applying special investigation modes AFM can additionally be used to
measure normal and lateral forces, adhesion, friction, elastic/plastic me-
chanical properties (such as indentation hardness and modulus of elasticity),
and electrical and magnetic properties in dependence on the local position
on the sample surface. AFM not only allows the direct and straightforward
analysis of morphology but also enables the easy assessment of morphology
development under annealing conditions and upon loading [15e25]. The
most important advantage of the AFM is that the materials can be imaged
without any chemical modifications, thus allowing direct and straightfor-
ward evaluation of the nanostructure.
There are various kinds of atomic force microscopes available on the mar-
ket, one of the first manufacturers being Digital Instruments, Inc. (Santa
Barbara, CA, USA), which commercialized the trade names Multimode
and Dimension 3000 for the atomic force microscopes. These are quite
widely used and we illustrate the functioning of the atomic force micro-
scope on the basis of Dimension 3000 (D3000) instrumentation.
Fig. 1.2A depicts the main part of the D3000 atomic force microscope, a mi-
croscope particularly designed for large specimens, while the sketch in
Fig. 1.2B illustrates the AFM operation principle.
The sample is generally mounted on a motorized xy stage and the force
sensor (a sharp tip) is mounted on the cantilever holder and fixed at the
piezo-driven xyz scanner. The sample is held in fixed position while the
tube-shaped piezo-scanner attached with a sharp probe scans the surface
below along the x,y directions in a raster pattern. The scanner is designed
in such a way that its motion along the z direction controls the tipesample
surface distance precisely. A feedback loop linked to the sensed interaction
force drives the vertical scanner motion along the z direction.
 1.1 Introduction 5

n FIGURE 1.2 (A) A portion of the D3000 atomic force microscope (AFM) showing the scanner head;
and (B) a sketch showing the operational principle of the AFM. PZT, piezoelectric tube. Adapted from
H. Schönherr, G.J. Vancso, Scanning Force Microscopy of Polymers, Springer Laboratory, Springer-Verlag
Berlin Heidelberg, Germany, 1986.

The small-sample atomic force microscopes, such as multimode atomic

force microscopes, which are meant for more precise high-resolution imag-
ing of specimens, have slightly different construction of the specimen and
6 CHAPTER 1 Atomic Force Microscopy as a Nanoanalytical Tool

sensor holders. The specimen is placed on the top of the piezoelectric tube
xyz scanner and the force sensor is attached to the fixed cantilever. The tip
remains stationary while the xyz piezo-tube moves so than the sample surface
is scanned by the stationary probe. The distance-dependent tipesample
interaction forces provide the physical basis for AFM, whose nature is in
fact very complicated. A detailed account of these forces can be found in
Refs. [26e28].
Briefly, there is an interplay of superimposed short- and long-range forces
that lies in the range of several tens of piconewtons [9]. With decreasing
tipesurface distance, the net force becomes first attractive and then repul-
sive. Consequently, when the tip is brought in close proximity to the surface,
at first it senses an increasing attractive force, which reaches a maximum
value and then decreases. This attraction finally changes to a repulsion
that again rapidly increases with decreasing tipesurface distance. Thus,
atomic resolution with an AFM is possible only with a sharp tip positioned
on a flexible cantilever at a net repulsive force of 100 pN or lower.
When the tip attached to the piezoelectric scanner scans the surface, the
forces are measured through deflections of the cantilever, this being moni-
tored by the change in photodiode differential signal using a focused laser
beam. To achieve more controlled imaging conditions a feedback loop is
used, which monitors the tipesample force and adjusts the scanner z posi-
tion. In the so-called “constant force” mode, the feedback circuit is used to
modulate the voltage applied to the scanner and adjusts the height of the
piezo-element holding the cantilever vertical deflection (in other words,
the force between the tip and the sample) constant. Thus, the AFM records
the piezo-displacement along the z direction, which is a direct measure of the
sample roughness (sample topography). The data are presented in the form
of a height image. However, if the feedback gains are low, the piezo-tube
remains practically at a fixed position (i.e., at constant height), and the
atomic force microscope collects the cantilever vertical deflection data.
This operation mode is referred to as “constant-height” mode and the data
are presented in the form of a deflection image.
Depending on whether the probe is subjected to an additional oscillation or
not, the AFM techniques can be discriminated between the dynamic and the
static operation modes. The so-called contact mode, and lateral force micro-
scopy (or friction mode), belong to the static AFM operations, whereas
noncontact AFM, force-modulation, and tapping-mode techniques are cate-
gorized under the dynamic operation modes.
The commercially available tips usually consist of silicon (Si) or silicon
nitride (Si3N4) cantilevers microfabricated via photolithographic techniques.
 1.2 Specimen Preparation 7

The commercially available cantilevers have different shapes (triangular or

rectangular) and have variable lengths (100e500 mm) and thicknesses
(1e4 mm). The spring constant of the cantilevers varies from 0.01 to
50 N/m. The cantilevers should be flexible enough to be deflected by small
forces, but also stiff enough to be withdrawn from the sample surface espe-
cially in the tapping-mode operations. The radius of curvature of the tip lies
typically in the range of a few nanometers. An extensive laboratory manual
of AFM operation, in particular with reference to the quantitative and qual-
itative analysis of nanomaterials, can be found in the literature [26e29].

1.2 SPECIMEN PREPARATION

In most of the literature related to AFM of nanomaterials it is claimed that
there is no necessity of sample preparation for AFM. It is true that chemical
modification of the specimen is not required for AFM investigations; i.e.,
the specimen can be imaged in its native state. Additionally, unlike during
electron microscopy, there is no risk of sample damage (and imaging of thus
obtained artifacts) due to exposure to the electron beam. However, there are
other sources of artifacts that may arise in the AFM imaging. A careful sur-
vey of AFM images published in the literature reveals, unfortunately, that
many of them recorded in a wide variety of samples under different condi-
tions look similar in many respects, which are clearly imaging artifacts [29].
A successful AFM imaging requires that the samples are properly prepared
with flat, clean, and artifact-free surfaces. Equally important are the choice of
imaging modes, selection of the probes, and other experimental parameters.
Some common methods of sample preparation for AFM studies of nanoma-
terials are briefly discussed next.

1.2.1 Thin Films

The ideal samples for AFM operations are thin films prepared by casting
and spraying or sputtering procedures [30e33]. Freshly prepared thin films
(ranging from a few tens of nanometers to a few micrometers in thickness)
cast from their solutions or suspensions can be most conveniently imaged by
the AFM. If the film surface is not sufficiently flat, one can study the sub-
strate side of the film. The experimentalist should be, however, aware that
the structures of the thin film in the presence of free air can be completely
different from those of the bulk material.

1.2.2 Physical and Chemical Etching, Ion Etching

This method is particularly interesting for polymer samples and their nano-
composites. The specimens can be prepared by means of chemical and
8 CHAPTER 1 Atomic Force Microscopy as a Nanoanalytical Tool

physical etching procedures or by ion etching [34e36]. The chemical

etching method is especially suitable for removing the matrix from the sur-
face so that the NPs can be exposed and measured [26].

1.2.3 Ultramicrotomy
Ultramicrotomy (and more frequently cryo-ultramicrotomy in the case of
soft materials) is the method of choice if the experimentalist is concerned
with the bulk morphology of and its correlation with the properties of the
sample [37]. The bulk surface left after the cryo-ultramicrotomy for trans-
mission electron microscopy (TEM) can be directly imaged by the AFM.
However, proper care should be taken to minimize the sectioning-induced
mechanical deformation of the sample, which might be a reason for erro-
neous interpretation of AFM data.

1.3 TYPICAL EXAMPLES OF NANOMATERIALS

CHARACTERIZATION BY ATOMIC FORCE
MICROSCOPY
Nanoparticulate materials having various dimensionalities can be prepared
in different ways including the solvent-assisted methods such as spraying
and dip and spin coating, even using different kinds of media and reducing
agents [23,38e47]. Different AFM imaging modes can be employed to
investigate the shape and size of nanoparticles (NPs) [27]. For soft materials,
the tapping mode or intermittent-contact mode is the method of choice,
whereas magnetic force microscopy is of particular interest for investigation
of the materials comprising magnetic NPs [38e41]. In this section, we will
introduce the typical applications of AFM in the characterization of the
structure and properties of nanomaterials.

1.3.1 Nanoparticles Imaging and Manipulation

One of the popular methods of dispersing the NPs is the ultracentrifugation
method, in which the size of the NP agglomerates can be adjusted via con-
centration of the colloidal solution as well as the agitation speed during
processing. Fig. 1.3 shows the National Institute of Standards and Technol-
ogy (NIST) standard of citrate-stabilized gold NPs (AuNPs) dispersed by
the ultracentrifugation method [48]. It can be seen that the NPs collected
on the freshly cleaved mica surface can be imaged successfully by the
AFM. The NPs have diameters of approximately 10 nm (Fig. 1.3A) and
30 nm (Fig. 1.3B), the same range as reported by the NIST standard.
 1.3 Typical Examples of Nanomaterials Characterization by Atomic Force Microscopy 9

n FIGURE 1.3 Typical atomic force microscopy micrographs of citrate-stabilized Au nanoparticles of different diameters prepared by the ultracentrifugation
method and deposited on a mica surface [48].

Imaging is a way to illustrate the structure of nanomaterials and correlate

that structural information with the material properties targeted to different
applications. The AFM offers, in addition, the possibility of manipulation of
the NPs, the process being extremely important for designing devices.
With an objective of investigation of the size-dependent mechanical prop-
erties of the NPs including substrate adhesion, interactions, and frictional
forces involved, several research works were conducted (for example,
Refs. [11e14,38,49,50]). One of the phenomena thus observed was a vari-
ation in frictional forces involved in the manipulation in the NPs [38]. An
example of NP imaging with manipulation of PS NPs deposited on a silicon
surface is presented in Fig. 1.4. The NPs can be pushed or dragged aside by
the AFM tip in a controlled way using a very small force. The AFM height

n FIGURE 1.4 Atomic force microscopy images of nanoparticles on the mica substrate (A) before and (B) after the manipulation [38].
10 CHAPTER 1 Atomic Force Microscopy as a Nanoanalytical Tool

image of the NPs is shown in Fig. 1.4A, showing a particle at the center to be
manipulated by the AFM tip. Fig. 1.4B shows the same specimen position
after the displacement of the NP toward the right of the image plane [38].
The ability of the AFM in the imaging of the NPs is not limited to spherical
particles but can be extended to any kind of NP. One basic requirement of
AFM imaging is, however, that the substrate should be absolutely flat and
free of any impurities on the surface. The AFM technique offers the most
straightforward way to image NPs but is limited to structural information
extraction from the surface of the NPs, the access to internal morphological
details being impossible. TEM provides the very useful complement to this
technique [38].

1.3.2 Biobased Nanomaterials and

Nanoencapsulation
Biobased polymeric materials, such as transparent nanocrystalline cellulose,
are becoming increasingly popular in applications such as optoelectronic
devices. Nanocellulose paper was successfully incorporated with conduc-
tive fillers such as carbon nanotubes (CNTs), silver (Ag) nanowires, tin-
doped indium oxide, etc. [51]. It has been demonstrated that such papers
may be useful in optoelectronics such as displays, touch screens, and inter-
active paper.
A suspension of nanocellulose was prepared by solution casting of the thin
film onto a mica substrate. Fig. 1.5A shows the tapping-mode AFM height

n FIGURE 1.5 (A) Atomic force microscopy height image of a nanocellulose film prepared by solution casting on a mica sheet. (B) Transparent and conductive
nanopaper based on tin-doped indium oxide with a performance of 12 U 12 U/sq. and 65% total transmittance at 550 nm [52].
 1.3 Typical Examples of Nanomaterials Characterization by Atomic Force Microscopy 11

image of a nanocellulose suspension dried on a freshly cleaved mica sheet.

The crystalline texture of the nanocellulose can be easily identified in the
height profile imaged by the tapping-mode AFM. Fig. 1.5B shows a photo-
graph of the transparent nanocellulose film after incorporation of tin-doped
indium oxide. The film was found to be highly conductive and had a total
transmittance of 65% at 550 nm. The nanocrystals of the cellulose were
further demonstrated as being made up of beaded structures [52].
Similarly highly transparent materials obtained by incorporation of amor-
phous calcium carbonate NPs were prepared with nanocellulose and studied
by AFM complemented by electron microscopic techniques [53]. Later
nanocomposites were prepared by surface functionalization of the single-
walled CNTs (SWCNTs) [48]. Controlled defibrillation of cellulose leading
to the formation of a nanostructured material was achieved and the
morphology of the material was studied using AFM.
It is needless to state that nanotechnological advancements have contributed
significantly to solving several problems in health sciences through the
development of many effective drug delivery systems and carriers including
nanobubbles and vesicles [46,54e56].
These developments have been triggered in many instances by the recent
progress in functional polymers and surfactants that can be used as coating
and stabilizers as well as additives in combination with nanomaterials.
Highly magnetic NPs with controlled shapes and size have wide application
in magnetic resonance imaging techniques, drug delivery, and various ther-
apeutic substances. Fig. 1.6 presents an example of tapping-mode AFM
height and phase imaging of polymethyl methacrylateegrafted magnetite
NPs that were prepared by a reversible addition/fragmentation chain transfer

n FIGURE 1.6 Tapping-mode atomic force microscopy height (A) and phase (B) image of polymethyl methacrylateegrafted Fe3O4/SiO2 magnetic nanoparticles [55].
12 CHAPTER 1 Atomic Force Microscopy as a Nanoanalytical Tool

polymerizationeassisted coating of polymer. The polymer-coated Fe3O4/

SiO2 hybrid NPs were well dispersed also in aqueous solution and coated
onto a flat surface. Fig. 1.6 shows that the size of the individual NPs was
around 40e50 nm, which was also confirmed by the TEM analysis [55].
A closer look at the micrographs reveals that the particles in the height im-
age (Fig. 1.6A) appear quite different from in the phase image (Fig. 1.6B).
The fact that the surface of the particles is smooth in the phase image implies
the compositional homogeneity of the sphere coating. The roughness of the
particles in the height image can be attributed to the shrinkage of the particles
during the processing onto the substrate, which might be partly contributed
by the interaction of the NPs with the substrate than with the polymer. Such
information, which is otherwise not straightforward to obtain by electron
microscopic methods, can be easily derived by the use of the AFM
technique.

1.3.3 Comparison With Electron Microscopy

In the previous section, some typical examples of AFM imaging of NPs
were presented. We have noted that different microscopic techniques may
be complementary for the comprehensive characterization of nanomaterials.
In this section, we shed more light on the comparative analysis of morpho-
logical features of heterogeneous material emphasizing the need for selec-
tion of a suitable technique depending on the solution of the problem at
hand.
In an attempt at preparing “soluble” SWCNTs, the nanotubes were chemi-
cally functionalized and further treated with surfactant [56] and coated onto
a mica surface followed by AFM imaging in tapping mode. The result is
shown in Fig. 1.7A. The nanotubes could be well dispersed in the given sol-
vent and were successfully imaged. The hollow tube-like structure of the
nanocarbons could not, however, be ascertained by the AFM. We prepared
a composite of multiwalled CNTs (MWCNTs) with a rubbery styrenee
butadiene copolymer [57] and imaged the cryo-fractured surface with a scan-
ning electron microscope (SEM) equipped with a field emission gun. The
well-dispersed MWCNTs could be wonderfully imaged in the composite
by the SEM. The same is true also for the sample prepared by a casting pro-
cedure. The structures imaged by the SEM are indeed more distinct than
those imaged by the AFM (compare also with Fig. 1.7C).
The same sample was ultramicrotomed under liquid nitrogen to harden the
material so as to avoid mechanical deformation during sectioning. The ul-
trathin sections (c. 70 nm thick) were studied by TEM, whereas the remain-
ing block face was investigated by tapping-mode AFM using phase imaging.
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requirements. Among such locks are included, besides high-grade, three-
tumbler locks, those that embody the cylinder principle and those that are
equipped as master-key locks.

Fig. 41
The unit-cylinder lock, illustrated in Fig. 41, is made by P. & F. Corbin.
This hardware specialty is a new departure in lock making. The
mechanism of the lock is contracted into the smallest possible space,
occupying only about 1½ in. × 3¼ in. Instead of being mortised into the
stile of the door, as is usual with the mortise lock, a piece is cut entirely
from the stile, as illustrated in Fig. 42. In order to prevent this operation
from weakening the stile of the door, the unit-cylinder lock is provided with
heavy escutcheon plates that are strongly ribbed on the back, so that
when these plates are secured to the stile at the top and bottom, they
supply the rigidity necessary to make up for the notching. As the name
implies, these locks are made in a unit, and the keyhole to the cylinder
lock is located in the knob. The unit-cylinder lock is made in two styles—
with dead-locking latch bolt and with additional dead bolt.

Fig. 42
38. High-Grade Interior Door Locks.—In Fig. 43 is shown a type of
high-grade, mortise-locking latch for interior doors. These locks are of
the heaviest construction, and are fitted with either brass or bronze fronts.
The bolts are operated with two or more tumblers constructed on an
improved pattern, and are of fine workmanship. The trim for a lock of this
character should be of the very best grade, with knobs of the screwless-
spindle type, which will be explained later.
The escutcheons should be of the high-collar or the bracket-bearing
type, and should conform to the character of the locks in quality and finish.
On the most important work, it is always expedient and usually feasible to
obtain expert advice from manufacturers or from dealers representing the
manufacturer, whose intimate knowledge of the product will be of great
assistance to the architect or owner in making suitable selections. The use
of high-grade hardware requires a considerable expenditure, and the
necessity for expert advice consequently becomes more imperative if the
best results are to be obtained.

Fig. 43
39. Master-Key Locks.—The type of lock known as the master-key
lock is generally used for public or office buildings, hotels, and
occasionally in the better class of residence work. These locks can be
grouped into two classes; namely, the Yale, or cylinder, and the lever-
tumbler types, the class first mentioned being the most desirable.
In the lever-tumbler type, illustrated in Fig. 39, the tumblers, or wards,
are so arranged that each lock can be operated only by its particular key,
the keys for all rooms being different and non-changeable; all of the locks,
however, can be operated by a key made for the purpose, termed a
master key. Each lock of this type has two sets of tumblers; one set is
operated by its individual key, and the other, being uniform in all locks of
the series, is acted on by the master key. Such locks may be obtained
either in the cheaper kind, with one tumbler and twelve changes, or in the
most intricate styles of hotel locks, with five tumblers and 48,000 changes
in one set, and all operated by one master key. The cylinder lock of this
type is illustrated in Fig. 44, which shows a Yale & Towne, mortise, front-
door lock.

Fig. 44
 40. Details of the Yale Type of Master-Key Locks. The Yale type of
cylinder lock, which is illustrated in Fig. 45 (a) and (b), is much preferred,
on account of the great security it gives and the small key required by it.
This lock is made in three systems; namely, the regular, the concentric,
and the paracentric, or duplex.
In the regular system, one regular cylinder is controlled by the change
and master keys, the pin tumblers being cut in two places, so that the
change key brings one set of the abutting planes of the tumbler in
alinement with the surface of the cylindrical plug. This plug is arranged so
that a separate key is required to operate each lock, the other line of
cleavage through the blocks being the same with all locks throughout the
series, so that they may be opened with the same key.
 Fig. 45

Fig. 46
The concentric cylindrical arrangement of this type of lock is shown
in Fig. 46 (a) and (b). Here, there is a larger cylinder encircling the key
plug. This is known as the master-ring, or larger, plug, and is indicated at
a. When the change key is inserted in the key plug b, the lower series of
breaks in the pins comes into alinement with the outer edge of the plug, as
shown at (a), and allows it to revolve in the master ring, the cam on the
inner side at c actuating the lock. When the master key is inserted, the
upper series of breaks comes into alinement with the outer edge of the
master ring, as shown at (b), allowing the plug and the ring to rotate
together with the turning of the key, and thus to produce the same result
as that caused by the operation of the change key.

Fig. 47
 The paracentric system, sometimes called the duplex system,
consists in having two separate cylinders to each lock, as illustrated in Fig.
47. One of these cylinders, generally the upper one, is operated by the
change key, and the lower one, by the master key. The interior
construction of the lock is so devised that each key performs the
necessary function of operating the same bolt, so that the individual lock
may always be opened by the change key, and all locks of the series by
the master key. This latter system of lock construction is more expensive
than the one-cylinder type, but it possesses an advantage in that it
provides greater security when a limited number of locks are grouped in
one series.
41. Owners or officials of large office buildings and industrial works
now avail themselves of the master-key system just explained. They are
able to obtain mortise locks, rim locks, and padlocks, all arranged to
operate with a master key, in one series. In fine residence work, this
system is also adopted. Such a system of locking is easily recognized as
convenient, especially where subordinates are held responsible for certain
rooms or departments to which they, individually, have access, as all of the
rooms or departments may be entered by the manager or superintendent
by the aid of the master key.
A series of master-key locks may also be “submaster-keyed” by
dividing it into subordinate groups. In such a case, each group is operated
by a master key of its own, and all the subordinate groups are controlled
by a grand master key. For example, a six-story office building could be
furnished throughout with locks having non-changeable keys; the doors of
each floor could be operated separately by a master key; and the doors of
the entire building could be operated by a grand master key. The
convenience of such a system is readily apparent in large buildings where
each janitor is responsible for a certain floor, and where the head janitor,
manager, or owner, has control of all the locks through the grand master
key.
In some instances, for additional security and for special work, the
corrugations in the keyway are changed in shape so that the
manufacturers’ regular type of key will not enter the keyway, or plug, thus
allowing no chance for the regular type of key to operate the lock.
42. Locks for Residence Use.—The front-door lock is distinctly a
lock having two bolts; namely, a dead bolt and a latch bolt. The latter is
operated by the knob, and is so arranged that, by means of stop-work in
the lock front, the outer knob may, at will, be set so as not to operate the
latch, the latch bolt being operated only from the outside by a key.

Fig. 48
The cylinder type of front-door lock illustrated in Fig. 44 is the best lock
for this purpose, as it provides the greatest security. This lock is operated
by a convenient key of the Yale type, which throws both latch and dead
bolt with one insertion into the cylinder.
Three-tumbler, front-door locks and latches are to be had at a low cost,
and are used in the cheaper class of dwellings. When the residence has
an inner, or vestibule, door, a similar lock is used without the dead bolt;
this lock is termed a vestibule latch. In all cases the vestibule lock should
“key-lock” with the front-door lock, so that one key will operate both. The
other exterior doors of a residence should have either Yale locks master-
keyed to the front door, for the better class of work, or locks of the 5-inch,
three-bolt variety, that are furnished with an extra bolt in addition to the
dead bolt, the third bolt being operated by a thumb knob on the inside.
When a cheaper trim is wanted, a 4-inch, two-bolt lock, supplemented by a
separate mortise or rim bolt, may be used.
 For the first- or parlor-floor folding doors, 4- or 4½-inch, two-bolt,
mortise locks are ordinarily employed. Where the doors are sliding, a 5½-
inch, sliding-door lock with dead bolt and pull, or handle, is provided. The
pull, or handle, is operated, or thrown out, when needed by pushing a
button, or stop, in the lock. This special type of sliding-door lock is
illustrated in Fig. 48.
For bedroom doors, a lock similar to that used on the minor exterior
doors is usually employed. The lock for these doors may be either a 5-
inch, three-bolt lock, or a 4-inch, two-bolt lock supplemented with a mortise
bolt. For communicating doors, it is best to use a three-bolt, knob lock, the
latch bolt of which is operated by the knob from either side. Arranged
above or below this latch bolt are two dead bolts, each being operated by
its respective thumb piece on opposite sides of the door. Locks of this
character are made for both swinging and sliding-doors.
43. Locks for Twin-Closet and Other Interior Doors.—Twin, or
double, doors are sometimes used between rooms in residences to
deaden sound or to increase privacy. Such doors should be fitted with the
same type of lock as other communicating doors, except that the lock
should be provided with two bolts, the same as the lock used for bathroom
doors. These locks are arranged with special trim on the abutting face of
each door, this trim having only a slight projection, and knobs or lever
handles projecting as little as possible, in order to avoid interference on
account of the limited space between the doors. Bathroom doors are best
fitted with a thumb bolt, either combined with a lock or separate.
In fitting closet doors, it is best to use a two-bolt lock about 4 inches in
size, with trim on both sides, so that the door may be operated from inside
in case it is accidentally closed on a person in the closet. The possibility of
this happening is slight, and usually a saving is effected by using a knob
latch without a dead bolt and a pair of knobs with roses.
For basement or attic doors, a cheap type of mortise lock is
appropriate, or a rim lock may be used, if cost is a consideration. Where
care is exercised in the selection of locks in any one building, great
convenience will result from having all the different class of locks about the
building of the same grade, so that they may be master-keyed in one set
and thus give the owner control, with one key, of all the locks. Each lock,
however, will have its own individual, or change, key, and should be
selected and ordered with this object in view. Another convenience may be
had by ordering each room and closet door keyed alike throughout the
house, or alike throughout each floor, so that the loss of a key will cause
little or no inconvenience.
44. Hotel and Office Locks.—The purpose and use of master-keyed
locks has already been explained, but the employment of such locks in
large groups, as in the equipment of hotels and office buildings, requires
further discussion. The term corridor door designates the entrance from a
corridor or a hallway to a bedroom or an office, while communicating doors
are those between adjoining rooms. Frequently, these doors are double,
and are then known as twin doors, while the term closet doors is self-
explanatory. Each of these doors requires a knob lock; that is, a lock
having the latch bolt operated by the knob and the dead bolt operated by a
key. Sometimes, in the case of locks on closet doors, the dead bolt on
communicating-door locks is omitted, and a thumb bolt substituted. While
all of the locks thus far enumerated are used in hotels, and most of them in
office buildings, technically speaking, a hotel lock is a master-keyed knob
lock for doors from the corridor to bedrooms, while an office lock is an
inverted lock; that is, a lock with the keyhole above the knob. These latter
locks are usually master-keyed, especially for the doors from the corridor
to the office. Such locks as these may be master-keyed on any of the
systems, as previously explained. For office work, a small key is desirable,
so that cylinder locks are ordinarily employed, as the key for the operation
of such locks may be conveniently carried. For hotels, however, a high-
grade lever-tumbler lock with round, substantial keys is desirable, because
the keys are liable to hard usage, and should not be convenient to carry in
the pocket.
Hotel keys vary widely in arrangement, as well as in size, quality, and
price. The kind of action, or mechanism, to be adopted in a hotel lock is
frequently determined by the preference and experience of the hotel
manager, and it is desirable that he should be consulted in advance; but
the location and use of each door should be considered in the selection of
the locks for this character of building. It will thus be seen that the subject
of hardware for a hotel is one that requires the most careful consideration
of the architect.
The grouping of locks in a hotel should be studied, and, usually, the
best plan in large hotels is to group all of the locks on each floor under one
master key and to provide a different master key for each floor, care being
taken to limit the issue of master keys to the smallest possible number of
responsible persons. In some cases, a grand master key is also provided
that will open all the locks on every floor. This arrangement of the locks
entails an additional expense, and also has the disadvantage that, in case
the grand master key is lost, all of the locks controlled by it should at once
be set to a new combination, in order to prevent access by the person into
whose hands the key has fallen. This procedure is both troublesome and
expensive.

Fig. 49
The foregoing remarks relating to hotel locks apply equally to office
locks, especially as to the arrangement for the operation with the master
key. In other respects, however, the locks for an office building differ
considerably from those used in hotels, for a hotel lock must secure the
door both when the room is occupied and when it is not, whereas an office
lock is used chiefly to secure it when not occupied. In consequence of this,
certain differences in action are employed. All office locks have a latch bolt
that is operated by the knob from both sides and yet permits free ingress
and egress. Various methods, however, are employed to lock the door
against ingress except by means of a key. Sometimes this is accomplished
by means of a separate dead bolt operated by a master key from either
side; in other cases it is accomplished by a latch bolt only, by providing the
latter with a stop-work like a front-door lock. By this arrangement, the outer
knob may be stopped so that the latch bolt cannot be operated from the
exterior except by the key; and, again, the latch bolt may be dead-locked
from the outside by the key. The choice of these arrangements is a matter
of personal preference.
45. Store-Door Trim.—The technical term store-door lock originally
designated a heavy rim or mortise dead lock, but is now applied to a
combined lock and latch, the former being operated by a key from either
side, and the latter by a thumb piece located above the pull handle. Such
locks are made in a large variety of sizes and styles, the best being of the
cylinder type, as shown in Fig. 49. In this lock, the latch is operated by the
thumb piece during the day, while the dead latch secures the door at night.
Plates and handles for the combined store-door lock and latch are also
made in many sizes and styles, from the plain rectangular type to the most
ornamental forms. Such trim offers good opportunity for effective
decoration, and no embellishment is so effective for a store’s entrance
door as a pair of handsome plates and handles of appropriate design. For
such trim, it is not uncommon to provide an outlay of from $25 to $30 per
door. Some of the more elaborate store-door handles are illustrated in
Figs. 50 and 51. The trim illustrated in these plates is very carefully
selected by the architect to match the style of architecture in which the
building is designed, and the finish is selected with as much care.
46. Padlocks.—While padlocks are not ordinarily included in builders’
hardware, they are extensively used for factories, stables, and other
buildings of this character; thus some care should be taken in their
selection. Padlocks are made in a great variety of sizes, styles, and
qualities, and retail at prices ranging from 10 cents, or less, to $5. Where
these locks are exposed to moisture or to the weather, they should be of
bronze or of brass, with all of the interior construction of the same material.
If required for great security, that is, for places where they are likely to be
subjected to violence, they should be very heavy, and preferably provided
with steel shackles. Padlocks constructed on the cylinder-lock principle
may be obtained, and should always be used where a series of locks that
are operated by separate keys and controlled by a master key is
employed. Ordinarily, a selection of padlocks should be made only after an
inspection of the actual samples, and not according to catalog
representations.

Fig. 50
 Fig. 51
47. Cabinet Locks.—The locks used in cabinetwork are distinct from
builders’ locks, though they are occasionally used in the construction of
the finer classes of interior finish, and, consequently, are of interest to the
architect. Cabinet locks are made chiefly of wrought metal, and in a vast
variety of kinds, sizes, and grades, so that care should be exercised in
their selection. The leading kind of cabinet locks are drawer, or till, locks;
wardrobe, or cupboard, locks; and chest, box, and desk locks. Special
locks are also manufactured for many other purposes. For the best work,
the Yale, or pin-tumbler, type is desirable where great security is required,
but for ordinary uses, other types, with either flat or round keys are
available. Many of the cabinet locks admit of being master-keyed, and
such locks are employed on lockers in club rooms, armories, etc.
 Fig. 52
48. Asylum and Prison Locks.—For the doors of cells in insane
asylums, hospitals, and prisons, locks of special construction are required.
For this reason, a distinct class of hardware is manufactured to meet the
peculiar conditions that prevail. These locks, which are designed primarily
to prevent escape from the rooms, or cells, are exceptionally exposed to
attempts at tampering, and are especially constructed to meet these
conditions. There is an extensive line of locks for these uses on the
market. This line includes both the Yale type and the lever-tumbler type of
lock, and these locks are constructed with both solid and barrel keys, thus
affording a wide range of selection. All such locks must be made so as to
be controlled by master keys.
In Fig. 52 are illustrated types of prison or asylum locks. The lock
shown at (a) is embedded, or built, in the jamb, while that at (b) is secured
to the door and the keeper is fastened in the jamb.
 Fig. 53
There are numerous other patterns of asylum and prison locks, such as
those illustrated in Fig. 53. The lock shown at (a) is arranged to operate
with a double-bitted key, while the one at (b) is operated by means of a
Yale key.
Nearly all modern locks for this purpose are operated with either
double-bitted or Yale keys, and those in common use are cylinder locks.
Information regarding these types of locks should be obtained in advance,
so that in preparing the plans and specifications, the type selected may be
clearly indicated and the arrangements made for any special construction
necessary to receive them. As the approved forms of asylum or prison
locks are built in the masonry during construction, they must be delivered
during the early stages of the erection of the building.
49. Bank and Safe Locks.—Locks for the doors of burglar-proof and
fireproof safes and vaults constitute a group distinct from all others. These
locks embody the most complicated mechanism, and represent the
highest art of modern lock making. The architect in preparing plans of
buildings for banks and trust companies is frequently called on to approve
or to specify the fastenings for vault and safe doors. While the owners of
such buildings will probably predetermine the kind of lock to be employed,
nevertheless they will be guided by the advice of the architect in the
selection of some particular make. The locks used on such vaults and
safes comprise time, or chronometer, locks; dial, or combination, locks;
and safe-deposit and subtreasury locks. There is also a device known as a
bolt-motor, or automatic lock, which is an allied product. In the
manufacture of these special locks, the skill of numerous experts and
specialists is required, and as their knowledge is at the disposal of the
architect or the engineer, they should be consulted in the selection of such
important pieces of mechanism.
 Fig. 54
The time lock is illustrated in Fig. 54, and is a locking device actuated
by clockwork. This type of lock is used in connection with the heavy
boltwork of a safe door, to prevent it from unlocking except during certain
hours determined beforehand. This lock is now recognized as an essential
part of the equipment of all first-class, burglar-proof vaults and safes. In its
standard form, the time lock has three chronometer movements of the
finest construction, each of which is competent to actuate the lock, so that,
in this way, almost absolute reliability is insured.
 Fig. 55
A dial, or combination, lock is shown in Fig. 55. The combination
commonly called the dial lock has completely superseded the key lock for
use on safe and vault doors. Essentially, the dial lock consists of a bolting
mechanism guarded by a set of changeable tumblers, or wheels. These
tumblers are actuated by a spindle passing through the door, this spindle
being provided on the outer end with a graduated dial. By rotating the dial
in a certain manner, the dial can be set and the lock operated. Dial, or
combination, locks are made in two grades, or varieties, designed
respectively for burglar-proof and for fireproof safes. The lock intended for
burglar-proof purposes is heavy and made to resist violence, while the
other locks are smaller, simpler, and cheaper, intended only to secure the
door against ordinary intrusion. Both of these locks should be absolutely
“non-pickable.”
In connection with the time lock, an automatic bolt-operating device is
now used on burglar-proof safes. The bolt-motor is a mechanism
containing heavy springs and is attached to the inside of a safe door.
These springs are set, or braced, while the door is closed, and when
released by the action of the time lock are capable of automatically
retracting the heavy boltwork of the door. This construction obviates the
necessity of any spindle through the door, and leaves the surface
absolutely unbroken, without any communication between the interior and
exterior.

Fig. 56
A form of safe-deposit lock is illustrated in Fig. 56. This lock is of a
new type, and is intended expressly for individual safes, or boxes, rented
by the safe-deposit companies. Such locks are nearly always provided