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Fire-Resistant Paper
Emerging Materials and Technologies
Series Editor
Boris I. Kharissov
Recycled Ceramics in Sustainable Concrete: Properties and Performance
Kwok Wei Shah and Ghasan Fahim Huseien
Photo-Electrochemical Ammonia Synthesis: Nanocatalyst Discovery, Reactor

Design, and Advanced Spectroscopy
Mohammadreza Nazemi and Mostafa A. El-Sayed
Fire-Resistant Paper: Materials, Technologies, and Applications

Ying-Jie Zhu
Sensors for Stretchable Electronics in Nanotechnology

Kaushik Pal
Polymer-Based Composites: Design, Manufacturing, and Applications

V. Arumugaprabu, R. Deepak Joel Johnson, M. Uthayakumar, and P. Sivaranjana
Nanomaterials in Bionanotechnology: Fundamentals and Applications

Ravindra Pratap Singh and Kshitij RB Singh
Biomaterials and Materials for Medicine: Innovations in Research, Devices,

and Applications
Jingan Li
Advanced Materials and Technologies for Wastewater Treatment

Sreedevi Upadhyayula and Amita Chaudhary
Green Tribology: Emerging Technologies and Applications

T V V L N Rao, Salmiah Binti Kasolang, Xie Guoxin, Jitendra Kumar Katiyar, and
Ahmad Majdi Abdul Rani
Biotribology: Emerging Technologies and Applications

T V V L N Rao, Salmiah Binti Kasolang, Xie Guoxin, Jitendra Kumar Katiyar, and
Ahmad Majdi Abdul Rani
Bioengineering and Biomaterials in Ventricular Assist Devices

Eduardo Guy Perpétuo Bock
Materials, Technologies, and Applications
Ying-Jie Zhu
First edition published 2022
by CRC Press
6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742
and by CRC Press

2 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN
© 2022 Ying-Jie Zhu

CRC Press is an imprint of Taylor & Francis Group, LLC
Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot
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Library of Congress Cataloging‑in‑Publication Data
Names: Zhu, Ying-Jie, author.

Title: Fire-resistant paper : materials, technologies, and applications /
Ying-Jie Zhu.
Description: First edition. | Boca Raton, FL : CRC Press, 2021. | Series:
Emerging materials and technologies | Includes bibliographical
references and index. | Summary: “While paper is a valued product, the
paper industry contributes to environmental pollution and consumption of
natural resources, and the organic substances out of which traditional
paper is made render it highly flammable and easy to burn. This book
introduces a new technology to develop environmentally friendly
fire-resistant paper using highly flexible ultralong hydroxyapatite
nanowires and discusses applications and potential for
commercialization. This work is aimed at materials scientists, chemical
engineers, industrial chemists, and other researchers from across the
scientific and engineering disciplines interested in development of this
exciting alternative to traditional paper”-- Provided by publisher.
Identifiers: LCCN 2021009053 (print) | LCCN 2021009054 (ebook) | ISBN
9780367700058 (hbk) | ISBN 9780367700065 (pbk) | ISBN 9781003144205
(ebk)
Subjects: LCSH: Fire-resistant paper.
Classification: LCC TS1127 .Z58 2021 (print) | LCC TS1127 (ebook) | DDC
676/.04--dc23
LC record available at https://lccn.loc.gov/2021009053
LC ebook record available at https://lccn.loc.gov/2021009054
ISBN: 978-0-367-70005-8 (hbk)

ISBN: 978-0-367-70006-5 (pbk)
ISBN: 978-1-003-14420-5 (ebk)
Typeset in Times
by Deanta Global Publishing Services, Chennai, India
Contents
Preface.......................................................................................................................ix
Author Biography.......................................................................................................xi
Chapter 1 Introduction........................................................................................... 1
1.1. History of Paper.......................................................................... 1
1.2. Role of Paper in the Development of Human Society................2
1.3. Technical Aspects of Papermaking............................................3
1.4. Problems Facing Traditional Flammable Paper......................... 3
Chapter 2 Highly Flexible Ultralong Hydroxyapatite Nanowires......................... 7

2.1. Introduction to Hydroxyapatite................................................... 7
2.2. How to Solve Problem of High Brittleness of
Hydroxyapatite Materials........................................................... 8
2.3. Synthetic Methods, Equipment, and Characterization
Techniques.................................................................................. 8
2.4. Properties.................................................................................. 15
2.5. Highly Ordered Self-Assembly and Derived Products............ 16
2.6. Comparison of Ultralong Hydroxyapatite Nanowires with
Cellulose Fibers........................................................................ 18
Chapter 3 Novel Fire-Resistant Paper Based on Ultralong Hydroxyapatite

Nanowires............................................................................................ 21
3.1. Background for the Invention of the Fire-Resistant Paper....... 21
3.2. Preparation of the Fire-Resistant Paper.................................... 22
3.2.1. Raw Materials and Structural Design of the Fire-
Resistant Paper............................................................ 22
3.2.2. Papermaking Processes and Equipment..................... 22
3.2.3. Characterization Techniques....................................... 23
3.3. Properties of the Fire-Resistant Paper......................................24
3.4. Advantages of the Fire-Resistant Paper................................... 27
Chapter 4 Functionalized Fire-Resistant Paper................................................... 29

4.1. Introduction to Functionalization of Fire-Resistant Paper....... 29
4.2. Waterproof Fire-Resistant Paper.............................................. 29
4.3. Antibacterial Fire-Resistant Paper........................................... 39
4.4. Waterproof Electrically Conductive Fire-Resistant Paper....... 49
4.5. Waterproof Magnetic Fire-Resistant Paper.............................. 58
4.6. Waterproof Photoluminescent Fire-Resistant Paper................60
v
vi Contents
4.7. Catalytic Fire-Resistant Paper.................................................. 63

4.8. Photothermal Fire-Resistant Paper........................................... 65
4.9. Light-Driven Self-Propelled Superhydrophobic
Photothermal Fire-Resistant Paper........................................... 69
Chapter 5 Applications of the Fire-Resistant Paper............................................. 77

5.1. Fire-Resistant Paper as a Specialty Paper................................ 77
5.1.1. Protection and Permanent Safe Preservation of
Important Documents, Archives, and Books.............. 77
5.1.2. Fire-Resistant “Xuan Paper” for Calligraphy and
Painting....................................................................... 77
5.1.3. High-Temperature-Resistant Label Paper................... 89
5.1.4. Highly Smooth and Highly Glossy Fire-
Retardant Paper...........................................................96
5.2. Applications of Fire Resistance and Heat Insulation............. 101
5.2.1. Fire-Resistant Paper Tape for Electric Cables and
Fiber-Optic Cables.................................................... 101
5.2.2. Automatic Fire Alarm Fire-Resistant Wallpaper...... 104
5.3. Multimode Anti-Counterfeiting............................................. 107
5.4. Encryption and Decryption for Secret Information............... 112
5.5. Environmental Protection....................................................... 116
5.5.1. Recyclable Adsorption Paper for Removal of
Organic Solvents and Rapid Separation of Water
and Oil....................................................................... 116
5.5.2. Water Purification and Wastewater Treatment.......... 120
5.5.3. Solar Energy–Driven Desalination of Seawater........ 146
5.5.4. Filter Paper for Polluted Air Purification and
Anti-Haze Face Mask................................................ 157
5.6. Energy-Related Applications.................................................. 165
5.6.1. High-Temperature-Resistant Separator for
Advanced Lithium-Ion Battery................................. 166
5.6.2. Fire-Resistant Electrode Material for Advanced
Lithium-Ion Battery.................................................. 176
5.6.3. High-Temperature-Resistant Separator and
Electrode Material for High-Energy-Density
Lithium-Ion Capacitor............................................... 185
5.7. Biomedical Applications........................................................ 192
5.7.1. Deformable Biomaterials Based on Ultralong
Hydroxyapatite Nanowires........................................ 192
5.7.2. High-Performance Biomedical Paper....................... 193
5.7.3. Bone Defect Repair and Bone Regeneration.............205
5.7.4. Rapid Test Paper........................................................ 212
5.8. Other Applications................................................................. 220
Contents vii
Chapter 6 Acid/Alkali-Proof Fire-Resistant Paper Based on Barium

Sulfate Fibers..................................................................................... 239
Chapter 7 Commercialization Potential and Future Prospects of the

Fire-Resistant Paper.......................................................................... 245
References.............................................................................................................. 249
Index....................................................................................................................... 257
Preface
Paper was one of the greatest inventions in the world, and it greatly promoted the
rapid development of human civilization. Even in today’s electronic information age,
paper is still a multi-purpose product that is indispensable to people’s daily work
and life. However, there are some problems for traditional paper based on cellulose
fibers from plants which need to be solved. For example, papermaking consumes a
large amount of precious natural resources, such as wood—about 20% of the world’s
wood is used for papermaking—and another problem is the environmental pollu-
tion caused by the papermaking industry. Cellulose is a polysaccharide composed
of glucose, which is usually combined with hemicellulose, pectin, and lignin. These
organic substances are highly flammable, so traditional paper is highly flammable
and easy to burn. In the long history of mankind, fire devoured countless precious
paper relics, documents, and books, and turned them into ashes in an instant. This is
undoubtedly an immeasurable and irrevocable loss for humankind.
The aim of this book is to comprehensively introduce a new kind of fire-resistant
paper based on ultralong hydroxyapatite nanowires from all aspects, including its
invention, synthesis, properties, and applications, and to bring this new material and
new knowledge to the readers, and to arouse the attention and interest of researchers
and readers from different disciplines for more intensive research on this new kind
of fire-resistant paper, especially on the research and development of its commercial-
ization and large-scale applications.
More than 20 different kinds of fire-resistant paper based on ultralong hydroxy-
apatite nanowires are presented in this book. In addition, the applications of these
different kinds of fire-resistant paper are also discussed, including fire-resistant spe-
cialty paper for protection and permanent safe preservation of important documents,
archives, and books; fire-resistant “Xuan Paper” for calligraphy and painting; high-
temperature-resistant label paper; highly smooth and glossy fire-retardant paper;
applications for fire resistance and heat insulation; fire-resistant paper tape for elec-
tric cables and fiber-optic cables; automatic fire alarm fire-resistant wallpaper; mul-
timode anti-counterfeiting, encryption and decryption for secret information; paper
for environmental protection, such as recyclable separation paper for the removal
of organic solvents and rapid separation of water and oil, water purification, and
wastewater treatment; solar energy–driven desalination of seawater; filter paper for
polluted air purification and anti-haze face mask; energy-related applications such
as high-temperature-resistant separator for advanced lithium ion battery; biomedical
applications such as deformable biomaterials, high-performance biomedical paper,
bone defect repair and bone regeneration, rapid test paper, and other applications.
This book is divided into seven chapters.
ix
Author Biography
Ying-Jie Zhu received his Ph.D. from the University of
Science and Technology of China in 1994. From 1994 to
1997, he worked as Assistant Professor and then Associate
Professor in University of Science and Technology of
China. From 1997 to 2002, he worked as Visiting Scholar
at University of Western Ontario (Canada), Alexander von
Humboldt Research Fellow at Fritz-Haber-Institut der Max-
Planck-Gesellschaft (Germany), and Postdoctoral Fellow at
University of Utah and University of Delaware (USA). In
2002, he was selected by the Chinese Academy of Sciences
under the Program for Recruiting Overseas Outstanding
Talents, and started to work as Full Professor at Shanghai Institute of Ceramics,
Chinese Academy of Sciences. In 2007, he was selected under the Program of
Outstanding Leader of Shanghai Subject Chief Scientist. His main research interests
include nanostructured biomaterials and a new type of fire-resistant paper based on
ultralong hydroxyapatite nanowires. He has published more than 370 peer-reviewed
journal papers and three book chapters. From 2014 to 2019, he was among the
Elsevier’s annual list of Most Cited Chinese Researchers for six consecutive years.
In addition, he has 65 granted patents.
xi
1 Introduction
1.1. HISTORY OF PAPER
Paper was first invented in ancient China and was one of the greatest inventions in
the world, which ended humanity’s history of writing with bamboo and wood chips
and greatly promoted the development of culture, knowledge, science, technology,
and civilization of mankind. Paper is a thin nonwoven material made from plant
fibers as the main raw material together with some additives, such as fillers, sizing
agents, retention aids, defoamers, and bleaching agents. It is primarily used for writ-
ing, printing, artworks, and packaging. It is commonly white because of bleaching.
The first papermaking process was documented in China during the Eastern Han
period. During the 8th century, Chinese papermaking spread to the Islamic world.
By the 11th century, papermaking was brought to Europe. Although precursors
such as papyrus (a thick, paper-like material produced from the pith of the Cyperus
papyrus plant) in ancient Egypt and other Mediterranean cultures and amate in pre-
Columbian Americas existed, these materials were actually the lamination of natural
plants and strictly should not be defined as true paper in the real sense. A sheet of
papyrus was made from the stem of the plant. The outer rind was first stripped off,
and the sticky fibrous inner pith was cut lengthwise into thin strips. The strips were
placed side by side on a hard surface with their edges slightly overlapping, and then
another layer of strips was laid on top at a right angle, and the layers were hammered
together into a single sheet and then dried.[1] Parchment made from animal skins and
used principally for writing also cannot be considered as paper.[2] These materials
are not considered as paper because they did not possess the main features of paper.
The characteristic features of papermaking are: (1) complete separation of the cel-
lulose fibers from each other; and (2) well dispersion of cellulose fibers in water to
form pulp.
The history of paper can be traced back to the ancient times more than 2,000
years ago. The literature commonly recognizes Lun Cai from China’s Eastern Han
dynasty (25–220) as the inventor of paper in the year A.D. 105[3, 4] Figure 1.1 shows the
portrait of Lun Cai. However, there are evidences suggesting that paper was invented
a few hundred years before Lun Cai.[5] One mainstream view is that the paper made
before Lun Cai was poor in quality and not widespread, and Lun Cai improved the
papermaking craft based on the experiences of his predecessors. He made the “Cai
Hou Paper” with much improved quality using the tree bark, hemp heads, old rags,
and fishing nets, and these materials were easily available and cheap. Because of the
improved quality and relatively low cost of the “Cai Hou Paper,” it gradually spread
to many areas and was used by more and more people afterward. Therefore, the “Cai
Hou Paper” is considered as the origin of the modern paper. However, with more
paper cultural relics being excavated from earlier times than China’s Eastern Han
1
2 Fire-Resistant Paper
FIGURE 1.1 A portrait of Lun Cai.
dynasty, for example, some from China’s Western Han dynasty (202 B.C.–A.D. 8) or
even earlier, there has been a debate on whether Lun Cai or someone else who lived
in earlier times should be recognized as the inventor of paper.
As a result of the invention of paper, Lun Cai was selected as the most influential
100 persons in history by Michael H. Hart in his book titled The 100: A Ranking of
the Most Influential Persons in History.[6] In 2007, Time magazine selected Lun Cai
as one of the best inventors: “The Chinese had written on expensive silk and heavy
bamboo slats, but this eunuch of the imperial court created paper out of bark, fishnet,
and bamboo, which he pressed thin.”[7]
1.2. ROLE OF PAPER IN THE DEVELOPMENT OF HUMAN SOCIETY

The invention of paper brought about the revolution of writing materials for the
world. Once paper was widely available, knowledge, culture, science, technology,
and other information were quickly and widely disseminated, which promoted the
rapid development of human civilization. Even in today’s electronic information age
with rapid development of science and technology, paper is still a multi-purpose
product that is indispensable to people’s daily work and life. In the second half of
the 20th century, the global paper consumption increased approximately six times.
During the Shang (1600–1050 B.C.) and Zhou (1050–256 B.C.) dynasties of
ancient China, documents were ordinarily written on bones or bamboo strips, which
were very heavy, awkward, and hard to transport. The light material of silk was
sometimes used as a writing medium, but was very expensive. After its invention
and spread, paper played an important role in early Chinese written and reading
Introduction 3
culture.[8] The paper books were light in weight, small in size, and could be carried
by hand instead of being transported by cart, as was the case before the use of paper.
During the Song dynasty (960–1279), the government produced the world’s first-
known paper-printed money, or banknote. Paper money was bestowed as gift to gov-
ernment officials in special paper envelopes.[9] During the Tang dynasty (618–907),
China became the world leader in book production. In addition, the gradual spread of
woodblock printing from the late Tang and Song dynasties further boosted China’s
lead ahead of the rest of the world.[10] From the 4th century to about 1500, the big-
gest library collections in China were 3–4 times larger than the largest collections
in Europe. The imperial government book collections in the Tang dynasty numbered
about 5,000–6,000 titles (89,000 juan) in 721.[10] Paper became central to the three
types of art in China—poetry, painting, and calligraphy.
Another way that paper has transformed the human society is by supplement-
ing human memory. In many centuries, paper has been competing with the human
mind—and now with the computer—as a preferred means of storing knowledge.
Memory systems based on writing have proven advantageous, especially when it is
important to retain the information reliably for a long period of time.[11]
1.3. TECHNICAL ASPECTS OF PAPERMAKING

The traditional papermaking process is complex and involves many procedures,
including soaking, cooking, pounding, degumming, fiber cutting, pulping, paper-
making, drying, etc. Figure 1.2 shows a schematic illustration of the traditional
handmade papermaking procedures. About 2,000 years later, modern paper facto-
ries are able to complete the whole papermaking process automatically and quickly.
However, no matter how improved and optimized modern papermaking technology
has become, using cellulose fibers from plants such as trees as raw materials for
papermaking has not changed.
1.4. PROBLEMS FACING TRADITIONAL FLAMMABLE PAPER

What happens when paper comes in contact with fire? It only takes a few seconds
for paper to quickly burn to ashes. The main component of fibers from trees is cel-
lulose, which is a polysaccharide composed of glucose and is usually combined with
hemicellulose, pectin, and lignin. These organic substances are highly flammable,
so traditional paper is highly flammable and easy to burn. As the saying goes, “Fire
cannot be wrapped up in paper.” Fire is the natural enemy of paper. Encountering
fire will be a disaster for paper cultural relics, books, and documents. In the long
history of mankind, countless precious paper cultural relics and books have been
burned in fire. This is also one of the main reasons for the destruction and disappear-
ance of many paper cultural relics, documents, and books in many centuries. This is
undoubtedly an immeasurable and irrevocable loss for humankind.
For example, on January 30, 2015, a major fire broke out at the Institute for
Scientific Information on Social Sciences Library in Moscow, one of Russia’s largest
public libraries. Founded in 1918, the library is the biggest social science research
FIGURE 1.2 Schematic illustration of the traditional handmade papermaking procedures.
center in Russia, with about 14 million documents in ancient and modern Eastern
European languages, including works dating to the 16th century. Unfortunately, the
fire lasted for more than ten hours, and millions of precious ancient books, historic
documents, and other materials were destroyed in the fire.
Furthermore, paper produced by the mechanical pulping process contains a sig-
nificant amount of lignin, a component of wood, which can form a yellow material
in the presence of light and oxygen, which is why newspapers and many other types
of paper yellow with age. Traditional paper is also at risk of acid decay because cel-
lulose itself produces acidic materials. In addition, papermaking involves the felling
of a large number of precious trees and other natural resources and consumes a huge
amount of electricity, having a significantly negative impact on the environment. In
addition, papermaking also causes environmental pollution. To solve these problems
Introduction 5
of traditional paper, it is necessary to explore new materials as building material for

paper. As a result of considerable effort in recent years, the author’s research group
developed a novel synthetic method and successfully synthesized highly flexible
ultralong hydroxyapatite nanowires.[12] This new nanostructured material provides
a possibility for the development of a new kind of fire-resistant paper to tackle the
problems of traditional paper.
2 Highly Flexible Ultralong
Hydroxyapatite
Nanowires
2.1. INTRODUCTION TO HYDROXYAPATITE
Hydroxyapatite (Ca10(OH)2(PO4)6), also called “basic calcium phosphate” or hydroxyl
calcium phosphate, is a member of the calcium phosphate family, and is of great sig-
nificance especially for vertebrates, since it is the main inorganic constituent of bone
and tooth. The content of hydroxyapatite in human tooth enamel is more than 90 wt.%,
and is about 70 wt.% in bone. Because it is a kind of biomaterial in the human body,
hydroxyapatite has high biocompatibility, excellent environmental friendliness, and
wide biomedical applications.[13–15] Hydroxyapatite has high whiteness, high melting
point (~1,650oC), high-temperature resistance, and nonflammability. Unfortunately,
hydroxyapatite is usually as hard and brittle as tooth and bone, and is not suitable for
making the soft fire-resistant paper.
Hydroxyapatite is formed in vertebrates through the biomineralization process,
which is regulated by a complex physiological system. It is known that the biominer-
alized hard tissues have well-defined micro- and nano-structures.[13, 14] For example,
human dental enamel consists of highly ordered hydroxyapatite nanorods and forms
a complex hierarchical ordered structure. Unlike the hydroxyapatite formed in the
mild in vivo environment, the synthetic conditions of hydroxyapatite materials are
much harsher, such as high temperatures (sometimes high pressures), various pH
values, organic solvents, etc. This may significantly accelerate the nucleation and
crystal growth of hydroxyapatite materials, shorten the preparation time.
Synthetic hydroxyapatite materials have promising applications in various fields
such as bone defect repair, drug delivery, and bio-imaging. The rapidly increas-
ing demands for high-performance materials in biomedical and other fields inspire
researchers to explore new hydroxyapatite nanostructured materials. Intensive stud-
ies have focused on the synthesis, microstructure, morphology, properties, and appli-
cations of the as-prepared hydroxyapatite materials. In the last several decades, the
studies on hydroxyapatite-based materials have aroused much interest worldwide.
Readers may refer to some recent review articles on the synthesis and applications of
hydroxyapatite materials.[16–21]
Figure 2.1 shows the rapidly increasing number of papers published each year on
hydroxyapatite-based materials from 1995 to 2018, the number of yearly published papers
regarding hydroxyapatite-related materials exceeded 4,000 in 2017 and 2019, indicating
that hydroxyapatite-based materials have become a hot research topic worldwide.
7
FIGURE 2.1 Number of papers published on hydroxyapatite-based materials each year

from 1995 to 2018. The data were obtained from a search in Web of Science using the key
word “hydroxyapatite.”
2.2. HOW TO SOLVE PROBLEM OF HIGH BRITTLENESS

OF HYDROXYAPATITE MATERIALS
Since 2008, the author’s research team has done a lot of research work on hydroxyap-
atite nanostructured materials and their applications. In 2013, the author’s research
group developed the calcium oleate precursor solvothermal method for the synthesis
of ultralong hydroxyapatite nanowires. The ultralong hydroxyapatite nanowires are
defined as the hydroxyapatite nanowires with diameters of smaller than 100 nm,
lengths of larger than 100 μm, and aspect ratios of higher than 1,000. The lengths of
the as-prepared ultralong hydroxyapatite nanowires were several hundred of microm-
eters, and the diameters of nanowires were only about 10 nm, which is equivalent to
about 1/10,000 of the thickness of a human hair. The aspect ratios of the as-prepared
ultralong hydroxyapatite nanowires were ultrahigh, which could reach more than
10,000, leading to high flexibility of ultralong hydroxyapatite nanowires, which can
solve the problems of high brittleness and hardness of the hydroxyapatite materi-
als. The author put forward the innovative idea of using highly flexible ultralong
hydroxyapatite nanowires as the raw material for making a new type of fire-resistant
inorganic paper. After many experiments, for the first time the author’s team suc-
cessfully developed a new type of fire-resistant inorganic paper.
2.3. SYNTHETIC METHODS, EQUIPMENT, AND

CHARACTERIZATION TECHNIQUES
The synthesis of hydroxyapatite nanowires was reported in the literature. Several
synthetic methods were reported for the synthesis of hydroxyapatite nanowires,
Highly Flexible Ultralong Hydroxyapatite Nanowires 9
including the solvothermal/hydrothermal method,[22–25] microwave-assisted synthe-

sis,[26] hard template,[27, 28] sol-gel hydrothermal process,[29] and reverse micelles.[30]
However, the lengths of hydroxyapatite nanowires were usually short and less than
10 μm, and these hydroxyapatite nanowires with relatively small aspect ratios were
still brittle and not flexible. The synthesis of highly flexible ultralong hydroxyapatite
nanowires with lengths larger than 100 μm and aspect ratios higher than 1,000 is a
great challenge.[31, 32]
In 2013, the author’s research group developed the calcium oleate precursor solvo-
thermal method for the synthesis of ultralong hydroxyapatite nanowires.[12] Ultralong
hydroxyapatite nanowires were synthesized using CaCl2, oleic acid, NaH2PO4·2H2O,
and NaOH in mixed solvents of water, ethanol and oleic acid by the calcium ole-
ate precursor solvothermal method. The reaction suspension was transferred into
a Teflon-lined stainless steel autoclave, sealed, and thermally treated at 180oC for
different times (5–23 hours). Then, the reaction system was cooled down naturally to
room temperature. The product after solvothermal treatment was collected, washed
with ethanol, and deionized water several times, and dried at 60oC.
Caution: During the solvothermal/hydrothermal synthetic process, the tempera-
ture and pressure are high inside the autoclave, and there may be safety risks; the
temperature and pressure inside the autoclave should be controlled strictly below
the limits of the safe temperature and pressure.
Figure 2.2 shows the characterization results of ultralong hydroxyapatite nanow-
ires synthesized by the calcium oleate precursor solvothermal method. The scanning
electron microscopy (SEM) and transmission electron microscopy (TEM) images
in Figure 2.2a–c show that the product consisted of single-crystalline ultralong
hydroxyapatite nanowires. The as-prepared ultralong hydroxyapatite nanowires had
diameters of ~10 nm and lengths of up to several hundred micrometers and very high
aspect ratios (up to > 10,000). The as-prepared ultralong hydroxyapatite nanowires
were highly flexible and could bend naturally. The X-ray diffraction (XRD) patterns
in Figure 2.2e indicate that the precursor was a single phase of calcium oleate, and
the product obtained by the calcium oleate precursor solvothermal method was sin-
gle-phase hydroxyapatite. When ultralong hydroxyapatite nanowires were dispersed
in ethanol and stirred with a glass rod, a long fiber with a length of 28 mm and a
high flexibility was formed (Figure 2.2d). The high flexibility of ultralong hydroxy-
apatite nanowires was mainly attributed to their ultrahigh aspect ratios and ultralong
lengths.
It was found that the hydrophilicity/hydrophobicity of ultralong hydroxyapatite
nanowires could be adjusted by varying the experimental parameters, and both
hydrophilic and hydrophobic ultralong hydroxyapatite nanowires could be prepared.
The contact angles of the tablet samples prepared by pressing the as-prepared pow-
ders of ultralong hydroxyapatite nanowires were measured (Figure 2.2f–j). Ultralong
hydroxyapatite nanowires synthesized using 0.0926 g of NaH2PO4·2H2O for a sol-
vothermal time of 5 hours was highly hydrophobic with a contact angle of 137oC
(Figure 2.2f), but the contact angle decreased to 108oC for a solvothermal time of 23
hours (Figure 2.2g). When the amount of NaH2PO4·2H2O was increased to 0.120 g,
the contact angle of ultralong hydroxyapatite nanowires was 95oC and 20oC for a
FIGURE 2.2 Characterization of ultralong hydroxyapatite nanowires prepared by the cal-

cium oleate precursor solvothermal method. (a, b) Scanning electron microscopy (SEM)
images; (c) transmission electron microscopy (TEM) image, and the inset of (c) was a selected-
area electron diffraction pattern of a single hydroxyapatite nanowire; (d) the formation of a
long fiber with a length of 28 mm obtained by stirring a dispersion of ultralong hydroxyapa-
tite nanowires in ethanol; (e) X-ray diffraction (XRD) patterns of the calcium oleate precursor
and ultralong hydroxyapatite nanowires (sample H-0.120 g–5 h); (f–j) water contact angle
images of different samples: (f) H-0.0926 g–5 h, (g) H-0.0926 g–23 h, (h) H-0.120 g–5 h, (i)
H-0.120 g–9 h, and (j) H-0.120 g–23 h; the samples synthesized with different amounts of
NaH2PO4·2H2O (labeled as x gram, for example, 0.120 g) and different solvothermal reaction
times (labeled as y hours, for example, 5 hours), while the other experimental conditions were
kept the same, were labeled as “H-x g–y h” (e. g., H-0.120 g–5 h). (Reprinted with permission
from reference [12])
solvothermal time of 5 and 9 hours, respectively (Figure 2.2h and i), and ultralong
hydroxyapatite nanowires with excellent hydrophilicity was obtained for a solvo-
thermal time of 23 hours (Figure 2.2j). The difference in hydrophilicity/hydropho-
bicity was attributed to the adsorption of oleic acid molecules or oleate groups with
long hydrophobic hydrocarbon chains on the surface of ultralong hydroxyapatite
nanowires.
The calcium oleate precursor solvothermal method could be extended to the syn-
thesis of ultralong hydroxyapatite nanowires using various monohydroxy alcohols[31]
and a variety of phosphate salts.[32] For example, ultralong hydroxyapatite nanow-
ires with lengths of close to 1 mm could be synthesized by the calcium oleate pre-
cursor solvothermal method using methanol instead of ethanol.[31] Figure 2.3 shows
ultralong hydroxyapatite nanowires dispersed in deionized water after washing
with ethanol and deionized water. From Figure 2.3 one can see that the as-prepared
ultralong hydroxyapatite nanowires exhibited a high whiteness, good dispersibility,
and high stability. The aqueous dispersion of ultralong hydroxyapatite nanowires
was stable for a long period of time without obvious precipitation.
In addition, ultralong hydroxyapatite nanowires could also be rapidly synthe-
sized by the highly efficient, low-cost, environmentally friendly and energy-saving
microwave-assisted calcium oleate precursor solvothermal/hydrothermal method in
a short period of heating time.[33] This method was based on the green chemistry
FIGURE 2.3 Ultralong hydroxyapatite nanowires dispersed in deionized water; ultralong

hydroxyapatite nanowires were prepared by the calcium oleate precursor solvothermal
method using methanol in a Teflon-lined stainless-steel autoclave with a volume of 1 L.
strategy, using water as the only solvent in the absence of organic solvents. Ultralong
hydroxyapatite nanowires with diameters of tens of nanometers and lengths of hun-
dreds of micrometers could be synthesized in a short period of time (within 20 min-
utes), which could significantly shorten the synthetic time by about two orders of
magnitude compared with the conventional hydrothermal method, showing advan-
tages such as high efficiency and significant energy saving.
A more environment-friendly and low-cost calcium oleate precursor hydrother-
mal method was developed for the synthesis of ultralong hydroxyapatite nanowires
using water-soluble calcium salt such as CaCl2, sodium oleate, and water-soluble
phosphate such as NaH2PO4 in water as the only solvent without using any organic
solvent.[34] The calcium oleate precursor hydrothermal method is different from
the calcium oleate precursor solvothermal method for the synthesis of ultralong
hydroxyapatite nanowires using water-soluble calcium salt such as CaCl2, oleic acid,
NaH2PO4·2H2O (or other water-soluble phosphates), and NaOH in mixed solvents
of water, ethanol (or other alcohols), and oleic acid. In the calcium oleate precur-
sor hydrothermal method, monodisperse hydroxyapatite nanowires with lengths of
several hundred nanometers are formed in the reaction system from the molecular to
the nanoscale level, and then hydroxyapatite nanowires self-assemble into long fibers
with lengths up to several hundred micrometers and further into two-dimensional
nanowire networks from the nanoscale to the microscale. Monodisperse hydroxy-
apatite nanowires were prepared by simply washing the hydrothermal product with
a small amount of water to remove the impurities. Self-assembled hydroxyapatite
nanowire networks were obtained by introducing ethanol into the hydrothermal
product containing monodisperse hydroxyapatite nanowires.
Figure 2.4 shows the calcium oleate precursor hydrothermal synthesis and hier-
archical assembly from monodisperse hydroxyapatite nanowires (Level 1), to long
fibers (Level 2), and to nanowire networks (Level 3). As shown in Figure 2.4a,
sodium oleate reacted with calcium chloride at room temperature to form calcium
oleate as a precursor, which further reacted with NaH2PO4 to form monodisperse
hydroxyapatite nanowires under hydrothermal conditions. Because of its small solu-
bility product constant, calcium oleate could release Ca2+ ions slowly into the aque-
ous solution, leading to slow nucleation of hydroxyapatite and growth of nanowires.
The oleate groups could be adsorbed on the surface of hydroxyapatite nanowires to
form the oleate bilayer, leading to excellent monodispersity and self-assembly in par-
allel alignment of the as-prepared hydroxyapatite nanowires in the aqueous system
(Figure 2.4b–d) due to the electrostatic interaction. The as-prepared hydroxyapatite
nanowires had uniform diameters of 6.7 ± 1.0 nm and lengths of 436 ± 259 nm with
an aspect ratio of about 65. The as-synthesized monodisperse hydroxyapatite nanow-
ires could self-assemble into long fibers at the nanoscale by binding short nanowires
in parallel arrangement induced by ethanol (Figure 2.4e and f), and further into
densely connected two-dimensional nanowire networks by crosslinking long fibers
at the microscale induced by ethanol (Figure 2.4g and h).
The experiments indicated that the oleate groups played a key role in the self-
assembly of monodisperse hydroxyapatite nanowires into flexible two-dimensional
nanowire networks. The formation of the bilayer of oleate groups adsorbed on the
FIGURE 2.4 The calcium oleate precursor hydrothermal synthesis and hierarchical assem-
bly from monodisperse hydroxyapatite nanowires (Level 1), to long fibers (Level 2), and to
nanowire networks (Level 3). (a) Schematic illustration of the synthetic route to hydroxyapa-
tite nanowires in an aqueous reaction system; (b) schematic illustration of the hierarchical
assembly processes of hydroxyapatite nanowires to form hydroxyapatite nanowire networks;
(c, d) TEM images of monodisperse hydroxyapatite nanowires; (e, f) SEM images of long
fibers formed by self-assembly of hydroxyapatite nanowires; (g, h) TEM images of networked
hydroxyapatite nanowires. (Reprinted with permission from reference [34])
surface of hydroxyapatite nanowires led to monodispersity of hydroxyapatite nanow-

ires in aqueous solution. The paper sheet made from hydroxyapatite nanowires
washed with ethanol twice exhibited a superhydrophilic property. However, the sam-
ples made from hydroxyapatite nanowires washed with ethanol twice and water once
exhibited a high hydrophobicity (144o). This experimental result could be explained
by that the bilayer of oleate groups was broken during the water washing process
but not in the initial ethanol washing process. A possible formation mechanism was
proposed for the hierarchical assembly from monodisperse hydroxyapatite nanow-
ires to flexible two-dimensional nanowire networks. By the addition of ethanol, the
self-assembly process of monodisperse hydroxyapatite nanowires could be triggered
immediately. In the first assembly process (from hydroxyapatite nanowires to long
hydroxyapatite fibers), only part of the outer shell of the oleate bilayer was broken by
ethanol washing, and hydroxyapatite nanowires were spontaneously bound together
into long hydroxyapatite fibers along the longitudinal direction. These long hydroxy-
apatite fibers could also be bound together by oleate groups at the contact points in
all directions, thus forming dense two-dimensional hydroxyapatite nanowire net-
works (the second assembly process: from long hydroxyapatite fibers to dense two-
dimensional nanowire networks). Owing to the high density of nanowire junctions
bound by oleate groups and the sufficient interspace among the nanowires, these
dense two-dimensional nanowire networks were mechanically strong and highly
flexible. Figure 2.4g shows that the two-dimensional hydroxyapatite nanowire net-
works was even foldable or bendable naturally, exhibiting a high flexibility. Thus,
the two-dimensional hydroxyapatite nanowire networks are an excellent building
material for constructing highly flexible, high-strength and fire-resistant paper.[34]
Other compounds with similar structures and properties to sodium oleate, such
as sodium stearate and sodium laurate, could also be used to synthesize network-
structured hydroxyapatite nanowires by the calcium oleate precursor hydrothermal
method. In addition, a series of commonly used water-soluble inorganic phosphates
such as (NaPO3)6 and Na2HPO4·12H2O, K3PO4·3H2O, K2HPO4·3H2O, K4P2O7·3H2O,
(NH4)3PO4·3H2O, NH4H2PO4, and (NH4)2HPO4 could be used as the phosphorous
source for the synthesis of network-structured hydroxyapatite nanowires.
The calcium oleate precursor hydrothermal method could be scaled up for the
synthesis of hydroxyapatite nanowires and nanowire networks using a stainless steel
autoclave with a volume of 10 L.[34] Figure 2.5 shows the schematic illustration for the
scaled-up synthesis of hydroxyapatite nanowires and nanowire networks. The large-
scale production of nanostructured materials is a universal challenge in the fields of
nanotechnology and materials science, especially in dealing with highly ordered nano-
structured materials. However, the large-scale production of nanostructured materials
is a key factor for the realization of their practical applications. The laboratory synthesis
of nanostructured materials is usually in a small scale of less than 100 mL volume reac-
tion system. The author’s research group successfully realized large-scale (autoclaves
with a volume of 10 L and 100 L) synthesis of hydroxyapatite nanowires and nanowire
networks by the calcium oleate precursor hydrothermal method. This method is envi-
ronmentally friendly, cost-effective, and thus more suitable for industrial production.[34]
The synthetic equipment for ultralong hydroxyapatite nanowires was the hydrother-
mal/solvothermal autoclave, the reaction liquid containing the reactants, additives, and
solvents was added in the autoclave, sealed, and heated to a desired temperature and
maintained at that temperature for a fixed time. Caution: During the synthetic process,
the temperature and pressure are high inside the autoclave, and there may be safety
risks; the temperature and pressure inside the autoclave should be controlled strictly
below the limits of the safe temperature and pressure. In addition, the author’s research
FIGURE 2.5 Scaled-up synthesis of hydroxyapatite nanowires/nanowire networks by the

calcium oleate precursor hydrothermal method. (a) Schematic illustration of the scaled-up
synthesis procedure; (b) digital images of the hydroxyapatite nanowires dispersed in aqueous
solution (left beaker) and self-assembled nanowire networks in ethanol (right beaker); (c, d)
TEM images of the as-prepared hydroxyapatite nanowire networks. (Reprinted with permis-
sion from reference [34])
group extended the synthesis to a larger scale, a larger stainless steel autoclave with a
volume of 10 L and 100 L were used. Figure 2.6 shows various autoclaves used for the
synthesis of ultralong hydroxyapatite nanowires in our laboratory.
As discussed above, in addition to SEM, TEM, XRD, and water contact angle,
other commonly adopted characterization techniques for ultralong hydroxyapatite
nanowires include Fourier transform infrared (FTIR) spectroscopy, surface area
analysis, thermogravimetric and differential scanning calorimetry, zeta potential, etc.
2.4. PROPERTIES
As discussed above, ultralong hydroxyapatite nanowires synthesized by the calcium
oleate precursor solvothermal method had diameters of about 10 nm and lengths of
several hundred micrometers with ultrahigh aspect ratios of > 10,000. Ultralong
hydroxyapatite nanowires exhibited high flexibility owing to their small diameters
and ultrahigh aspect ratios. Highly flexible ultralong hydroxyapatite nanowires can
overcome the high brittleness of traditional hydroxyapatite materials, and they can
be used for making highly flexible functional materials.[35]
The hydrophilicity and hydrophobicity of the as-prepared ultralong hydroxyapa-
tite nanowires could be controlled by adjusting synthetic parameters or post-washing
process.[12] In addition to changing the experimental conditions, the post-washing
FIGURE 2.6 Teflon-lined stainless steel autoclaves with a volume of 50 mL and 1 L, respec-
tively, stainless steel autoclaves with a volume of 10 L and 100 L, respectively.
process could also be used to control the surface properties of the as-prepared
ultralong hydroxyapatite nanowires. Generally, thorough washing using ethanol and
water many times of the product could produce hydrophilic ultralong hydroxyapatite
nanowires; however, no washing or less washing would obtain hydrophobic ultralong
hydroxyapatite nanowires. Therefore, depending on the purpose and application,
ultralong hydroxyapatite nanowires with desirable surface properties could be pre-
pared. Furthermore, the zeta potential measurements indicated that the as-prepared
ultralong hydroxyapatite nanowires were negatively charged in aqueous solution.[34]
In addition, the as-prepared ultralong hydroxyapatite nanowires were stable in
the weak acidic, neutral, and highly alkaline solutions, but were soluble in the strong
acidic solution. This property could be used for some special applications such as the
pH-responsive drug delivery.[36]
2.5. HIGHLY ORDERED SELF-ASSEMBLY

AND DERIVED PRODUCTS
Currently, the preparation of large-sized highly ordered hydroxyapatite nanostruc-
tured materials remains a great challenge, especially for the fabrication of large-sized
highly ordered ultralong hydroxyapatite nanowires because ultralong hydroxyapatite
nanowires are easily tangled and aggregated. As discussed above, hydroxyapatite
nanowires synthesized by the calcium oleate precursor hydrothermal method could
self-assemble to form long fibers with an ordered alignment structure and further to
form network-structured hydroxyapatite nanowires.[34]
The author’s research group developed a novel strategy for the rapid automated
preparation of highly flexible, large-sized, fire-resistant nanorope consisting of self-
assembled highly ordered ultralong hydroxyapatite nanowires at room temperature,
and the various derived flexible fire-resistant highly ordered architectures, such as
highly flexible fire-resistant textiles, and three-dimensional printed well-defined
highly ordered fire-resistant patterns. The nanorope was prepared by simply inject-
ing the solvothermal product slurry containing ultralong hydroxyapatite nanowires
into absolute ethanol at room temperature using the homemade automated equipment
with round-end needles. The fire-resistant nanorope was successively formed from
the nanoscale to the microscale then to the macroscale, and the ordering direction
was controllable. The as-prepared fire-resistant nanorope was smooth on the surface
and highly flexible and easy to be picked up and rolled up, as shown in Figure 2.7a
and b. SEM images in Figure 2.7c–e show the highly ordered ultralong hydroxyapa-
tite nanowires in the fire-resistant nanorope. The length of the fire-resistant nanorope
could be controlled by injecting a certain amount of the solvothermal product slurry
containing ultralong hydroxyapatite nanowires, and the diameter of the nanorope
could be controlled by the inner diameter of the needle used for injection.[35]
A variety of biological materials in natural organisms provide excellent structural
design guidelines and inspirations for the construction of advanced structural materials
with excellent mechanical properties. Inspired by the natural nacre and human bone, the
authors research group prepared a flexible macroscopic ribbon fiber made from highly
ordered alignment of ultralong hydroxyapatite nanowires and sodium polyacrylate with
a “brick-and-mortar” layered structure by a scalable and convenient injection method.
FIGURE 2.7 Characterization of the highly flexible, large-sized, fire-resistant nanorope

consisting of self-assembled highly ordered ultralong hydroxyapatite nanowires prepared by
simply injecting the solvothermal product slurry containing ultralong hydroxyapatite nanow-
ires into absolute ethanol at room temperature. (A, B) Digital images showing the large-sized
fire-resistant nanorope; (C−E) SEM images of the as-prepared fire-resistant nanorope con-
sisting of highly ordered ultralong hydroxyapatite nanowires. (Reprinted with permission
from reference [35])
The quasi-long-range orderly liquid crystal of ultralong hydroxyapatite nanowires was

used and spun into the continuous flexible macroscopic ribbon fiber consisting of highly
ordered ultralong hydroxyapatite nanowires. The highly ordered ultralong hydroxy-
apatite nanowires acted as the hard “brick” and sodium polyacrylate acted as the soft
“mortar,” and the nacre-mimetic layer-structured architecture was obtained. The as-pre-
pared flexible macroscopic ribbon fiber with a highly ordered structure showed superior
mechanical properties, and the maximum tensile strength and Young’s modulus were as
high as 203.58 ± 45.38 MPa and 24.56 ± 5.35 GPa, respectively. In addition, benefiting
from the excellent flexibility and good knittability, the as-prepared macroscopic ribbon
fiber could be woven into various flexible macroscopic architectures. Additionally, the
as-prepared flexible macroscopic ribbon fiber could be further functionalized by incor-
poration of various functional components, such as magnetic and photoluminescent con-
stituents. The as-prepared flexible macroscopic ribbon fiber is promising for applications
in various fields such as smart wearable devices, optical devices, magnetic devices, and
biomedical engineering.[37]
2.6. COMPARISON OF ULTRALONG HYDROXYAPATITE

NANOWIRES WITH CELLULOSE FIBERS
The main differences between ultralong hydroxyapatite nanowires and cellulose
fibers are summarized as follows:
(1) Classification: hydroxyapatite is inorganic; however, cellulose is organic.
FIGURE 2.8 Size and morphology comparison of a human hair (a), cellulose fibers (b), and
ultralong hydroxyapatite nanowires (c, d).
(2) Chemical composition: cellulose (C6H10O5)n is a long-chain polymeric

polysaccharide carbohydrate consisting of glucose units and constitutes
the main part of the cell walls of plants, and is the raw material of paper.
Hydroxyapatite (Ca10(OH)2(PO4)6) is also called “basic calcium phosphate”
or hydroxyl calcium phosphate, and is a member of the calcium phosphate
family, which is the main inorganic constituent of bone and tooth.
(3) Size and morphology: cellulose fibers have a belt morphology with widths
in the microscale and lengths in the millimeter or centimeter scale, depend-
ing on the type of the plant. In contrast, ultralong hydroxyapatite nanowires
have diameters of about 10 nm and lengths of several hundred microm-
eters. Figure 2.8 shows the size and morphology comparison of ultralong
hydroxyapatite nanowires with cellulose fibers and a human hair.
(4) Flexibility: both cellulose fibers and ultralong hydroxyapatite nanowires
have good flexibility.
(5) Thermal stability: cellulose fibers are thermally stable below about 200oC.
Cellulose fibers will be carbonized, blackened, and even burned to ashes
at higher temperatures. However, ultralong hydroxyapatite nanowires have
very high thermal stability; they are still stable at temperatures above
1,000oC.
(6) Fire resistance: cellulose fibers are highly flammable; that is why the tradi-
tional paper can be burned to ashes in seconds in fire. In contrast, ultralong
hydroxyapatite nanowires are nonflammable and have excellent fire-resis-
tant performance.
3 Novel Fire-Resistant
Paper Based on
Ultralong Hydroxyapatite
Nanowires
3.1. BACKGROUND FOR THE INVENTION

OF THE FIRE-RESISTANT PAPER
As discussed earlier, although hydroxyapatite has excellent biocompatibility and
environmental friendliness, high whiteness, high melting point (~1650°C), high-tem-
perature resistance, and nonflammability, unfortunately, hydroxyapatite is usually as
hard and brittle as tooth and bone, and is not suitable for making soft fire-resistant
paper.
Since 2008, the author’s research team has done a lot of research work on hydroxy-
apatite nanostructured materials and their applications including drug delivery,[36,
38–51] bio-imaging,[40] and bone defect repair.[45, 52–54] In 2013, the author’s research
group developed the calcium oleate precursor solvothermal method, and success-
fully synthesized ultralong hydroxyapatite nanowires by this method. The lengths of
the as-prepared ultralong hydroxyapatite nanowires were several hundred microm-
eters, and the diameters of nanowires were only about 10 nm, which is equivalent to
about 1/10,000 of the thickness of human hair. The aspect ratios of the as-prepared
ultralong hydroxyapatite nanowires were ultrahigh, which could reach more than
10,000, leading to high flexibility of ultralong hydroxyapatite nanowires, which
can solve the problem of high brittleness and hardness of traditional hydroxyapa-
tite materials. The author put forward the innovative idea of using highly flexible
ultralong hydroxyapatite nanowires as the raw material to develop a new kind of
fire-resistant paper. After many experiments, the author’s team successfully devel-
oped a new type of fire-resistant paper based on ultralong hydroxyapatite nanow-
ires for the first time.[12] The fire-resistant paper based on ultralong hydroxyapatite
nanowires is in a real sense a new kind of inorganic fire-resistant paper with high
flexibility, high whiteness, high surface smoothness, good mechanical properties,
excellent resistance to both fire and high temperatures, and high similarity to tradi-
tional cellulose fiber paper in appearance. In addition, the fire-resistant paper based
on ultralong hydroxyapatite nanowires can be used for writing and printing, which is
the basic function of paper. Importantly, the fire-resistant paper based on ultralong
hydroxyapatite nanowires exhibits superior mechanical properties because of strong
interactions such as hydrogen bonding between ultralong hydroxyapatite nanowires.
21
Two-dimensional fire-resistant products, including fire-resistant cloths, felts,

and blankets, are important energy-saving materials in high-temperature industrial
fields. Inorganic fibers are common building materials to make fire-resistant paper-
like products. Common types of inorganic fibers include aluminum silicate, mag-
nesium silicate, basalt, aluminum oxide, silicon dioxide, etc. Inorganic fibers are
commonly produced by the wire-drawing process in the melting state. However,
inorganic fibers produced by common methods have usually large diameters (usually
more than 10 μm) and low aspect ratios, with poor flexibility. The paper sheets made
from these thick inorganic fibers usually have poor mechanical properties due to the
weak interactions between thick fibers (no hydrogen bonds can be formed between
many inorganic fibers because they contain no hydroxyl groups or other functional
groups which can form hydrogen bonds), and have very rough surface which cannot
be used for writing and printing and can only be used for industrial purposes. In
addition, since paper is frequently used in daily work and life, the biocompatibility
of paper is an important issue. Although some inorganic fibers, such as asbestos
fibers, are used to make special paper-like products, the asbestos fibers are toxic and
have a major concern to human health.[55]
3.2. PREPARATION OF THE FIRE-RESISTANT PAPER

3.2.1. Raw Materials and Structural Design of the Fire-Resistant Paper
The single-phase fire-resistant paper consisting of only ultralong hydroxyapatite
nanowires as the raw material without any additives exhibited poor mechanical
properties—for example, its tensile strength was usually lower than 1 MPa. In order
to enhance the mechanical properties of the fire-resistant paper, the author’s research
group designed and optimized the structure of the fire-resistant paper. The new type
of fire-resistant paper possessed a “steel-reinforced concrete structure,” similar to
that used in tall buildings; it consisted only of inorganic components, including
ultralong hydroxyapatite nanowires as the main building material (like a cement),
micrometer-sized inorganic fibers as the reinforcing skeleton material (like concrete
reinforcing steel bars), and an inorganic adhesive as the binder. In the fire-resis-
tant paper, ultralong hydroxyapatite nanowires were mutually interwoven to form a
porous network structure, coupled with the mechanical support and reinforcement of
the micrometer-sized inorganic fibers and the binding effect of the inorganic adhe-
sive; the three synergistic effects could significantly enhance the mechanical proper-
ties of the fire-resistant paper.
3.2.2. Papermaking Processes and Equipment

The new kind of fire-resistant paper is prepared using ultralong hydroxyapatite
nanowires as the main raw material, a certain amount of micrometer-sized inor-
ganic fibers such as glass fibers, and an inorganic adhesive prepared in the author’s
laboratory. The preparation process of the fire-resistant paper is similar to that of
traditional cellulose fiber paper, including the following main procedures: (1) the
Novel Fire-Resistant Paper 23
FIGURE 3.1 Papermaking equipment for the preparation of the fire-resistant paper. (a) A
paper sheet former with a diameter of 20 cm; (b) an A3-size (420 mm × 297 mm) paper sheet
former; (c) a presser with a heating function and temperature controller; (d) a paper dryer with
a flat surface.
preparation of aqueous suspension containing ultralong hydroxyapatite nanowires,

micrometer-sized inorganic fibers, and inorganic adhesive; (2) the vacuum-assisted
filtration of the aqueous suspension; (3) pressing; and (4) drying. It should be noted
that traditional papermaking needs bleaching and sizing procedures; however,
bleaching and sizing are not necessary for the preparation of the fire-resistant paper.
Therefore, the papermaking process for fire-resistant paper is more environmentally
friendly and cost-effective compared with traditional papermaking. In addition, tra-
ditional papermaking equipment was used for the preparation of the fire-resistant
paper in the author’s laboratory, as shown in Figure 3.1.
3.2.3. Characterization Techniques
The properties of the fire-resistant paper can be measured and analyzed using vari-
ous instruments used for traditional paper based on plant fibers. These instruments
include the thickness tester, whiteness tester, smoothness tester, folding resistance
tester, stiffness tester, tear strength tester, bursting strength tester, water absorption
tester, tensile tester, and water content analyzer, as shown in Figure 3.2.
FIGURE 3.2 The instruments used for measuring various properties of the fire-resistant
paper.
3.3. PROPERTIES OF THE FIRE-RESISTANT PAPER

The new type of fire-resistant paper has high flexibility and can be curled arbitrarily.
It shows high whiteness without adding any bleaching agent, which is environment
friendly, unlike traditional papermaking in which bleaching is necessary. It should
be noted that one unique feature of the fire-resistant paper is its layered structure in
the thickness direction,[56, 57] which is different from traditional paper based on plant
fibers. The fire-resistant paper can be used for writing and color printing, which
is the primary function of paper. Figure 3.3 shows digital images of an A4-sized
(29.7 cm × 21 cm) fire-resistant paper consisting of ultralong hydroxyapatite nanow-
ires as the main raw material. The as-prepared A4-sized highly flexible fire-resistant
paper exhibited a high whiteness, and it looked like traditional cellulose fiber paper
in appearance. The fire-resistant paper could be bent and rolled without any visible
damage, indicating the high flexibility of this new kind of fire-resistant inorganic
paper. The text could be clearly printed in color on the fire-resistant paper by directly
using a commercial ink-jet printer.
The most amazing thing is that the as-prepared ultralong hydroxyapatite nanow-
ires-based highly flexible inorganic paper is highly resistant to both high temperature
and fire. Figure 3.4a shows the excellent fire-resistant performance of the ultralong
hydroxyapatite nanowires-based inorganic paper. The temperature in the flame of
an alcohol lamp is close to 700°C; the fire-resistant paper could not be burned in
the flame even after a long period of time, exhibiting an excellent fire-resistant per-
formance. In contrast, traditional cellulose fiber paper was immediately burned to
FIGURE 3.3 Digital images of an A4-size fire-resistant paper consisting of ultralong

hydroxyapatite nanowires as the main raw material. The A4-size fire-resistant paper could be
directly used for color printing using a commercial ink-jet printer. (Reprinted with permis-
sion from reference [34])
ashes in just a few seconds in the flame of an alcohol lamp. It is expected that the
fire-resistant paper can be used for permanent, safe preservation of important docu-
ments, archives, and books, avoiding their destruction in fire. In addition, the butane
spray gun was also used to test the resistance performance to high temperature and
fire. Although the flame temperature of the butane spray gun was about 1300°C, the
fire-resistant paper could well resist such a high temperature, and was not flammable
at all, as shown in Figure 3.4b.
The fire-resistant paper based on ultralong hydroxyapatite nanowires exhibits an
excellent thermal insulation performance. Figure 3.5 shows the adiabatic and flexible
properties of the fire-resistant paper under high-temperature conditions. As shown
in Figure 3.5a and b, the common filter paper based on cellulose fibers and the fire-
resistant paper were placed on the flame of a spirit lamp with a piece of silk cocoon
placed on them. When being exposed to the flame, the common filter paper and the
silk cocoon immediately caught fire and were burned to ashes in only 5 seconds.
However, the fire-resistant paper with written characters and the silk cocoon on it
could be well preserved after being exposed to the flame for 5 minutes, indicating
the excellent fire resistance and heat insulation properties of the fire-resistant paper.
Figure 3.5c shows the temperature variation curves of a thermocouple wrapped with
a 150 μm-thick fire-resistant paper and a bare thermocouple which were placed on
FIGURE 3.4 (a) The excellent fire-resistant performance of the as-prepared fire-resistant
inorganic paper based on ultralong hydroxyapatite nanowires; when the fire-resistant paper
was heated in the flame of the alcohol lamp, it was totally nonflammable (Reprinted with per-
mission from reference [58]); (b) the excellent resistant performance of the fire-resistant paper
to high flame temperature (about 1300°C) of the butane spray gun.
FIGURE 3.5 Adiabatic and flexible properties of the fire-resistant paper based on ultralong
hydroxyapatite nanowires under high-temperature conditions. (a, b) Thermal insulation tests:
protecting silk cocoon from fire using the common filter paper (a) and fire-resistant paper
(b); (c) temperature variation curves of a bare thermocouple and 150 μm-thick fire-resistant
paper wrapped thermocouple placed on the flame; (d) flexibility tests of the fire-resistant
paper by performing bending-stretching cycles on the flame. (Reprinted with permission
from reference[34])
the flame of a spirit lamp. After being heated for more than 5 minutes, the tempera-
ture of the thermocouple gradually reached an equilibrium, and the temperature of
the thermocouple wrapped with the fire-resistant paper was more than 200°C lower
than that of the bare thermocouple, showing excellent adiabatic property and the
potential heat-shielding application of this new kind of fire-resistant paper. In addi-
tion, the fire-resistant paper could maintain a good flexibility under high-tempera-
ture conditions, as shown in Figure 3.5d. The fire-resistant paper could be bent and
stretched back and forth on the flame for more than 50 cycles without breaking, indi-
cating the good mechanical properties and flexibility even under high-temperature
conditions.[34]
Furthermore, ultralong hydroxyapatite nanowires have a pH-responsive property.
Ultralong hydroxyapatite nanowires are stable in weak acidic, neutral, and strong
alkaline solutions. However, ultralong hydroxyapatite nanowires will be rapidly dis-
solved in a strong acidic solution. This property can be used to destroy the ultralong
hydroxyapatite nanowires-based fire-resistant paper when necessary.
3.4. ADVANTAGES OF THE FIRE-RESISTANT PAPER

The fire-resistant paper based on ultralong hydroxyapatite nanowires has obvious
advantages, for example, (1) high flexibility; (2) high-quality white color; (3) high
biocompatibility and environmental friendliness; (4) no need for bleaching and
sizing, which are required for traditional cellulose fiber paper; (5) can be used for
writing and color printing using a commercial printer; (6) highly resistant to high
temperatures; (7) excellent fire resistance; (8) can be used for long-term safe pres-
ervation of important documents such as archives and books; (9) has many other
applications; and (10) good application prospects in many fields. In addition, the
ultralong hydroxyapatite nanowires, which are the raw material of the new type of
fire-resistant paper, can be synthesized artificially using common chemicals without
consuming valuable natural resources such as trees and without negatively impact-
ing the environment. The whole manufacturing process of the fire-resistant paper is
environmentally friendly and will not pollute the environment; thus, the new fire-
resistant paper has a tempting prospect for commercialization and large-scale appli-
cations. It is expected that in the near future the new fire-resistant paper may be able
to move from the laboratory to the market, into book stores and libraries, to protect
important documents, archives, and books, and for applications in various fields.
4 Functionalized
4.1. INTRODUCTION TO FUNCTIONALIZATION
OF FIRE-RESISTANT PAPER
The fire-resistant paper based on ultralong hydroxyapatite nanowires has the same
functions as traditional paper based on plant fibers, such as writing and printing.
In addition, the fire-resistant paper has abilities such as excellent resistance to both
high temperatures and fire, which traditional paper does not possess. Therefore, the
fire-resistant paper can be used in a variety of fields where traditional paper cannot
be applied. In order to expand the application areas, the functionalization of the fire-
resistant paper is a useful strategy.
Up until now, the author’s research group has successfully developed more than
20 new types of fire-resistant paper based on ultralong hydroxyapatite nanowires
with various functions, for example, the waterproof fire-resistant paper, fire-resistant
“Xuan paper,” high-temperature-resistant label paper, antibacterial fire-resistant
paper, waterproof photoluminescent fire-resistant paper, waterproof electrically
conductive fire-resistant paper, catalytic fire-resistant paper, waterproof magnetic
fire-resistant paper, automatic fire-alarm fire-resistant wallpaper, photothermal fire-
resistant paper, high-temperature-resistant battery separator, fire-resistant paper tape
for electric cables and fiber-optic cables, secret information encryption and decryp-
tion fire-resistant paper, light-driven self-propelled waterproof fire-resistant paper,
water purification filter paper, air purification filter paper, biomedical paper, antibac-
terial biomedical paper, rapid test paper, etc. In the following sections, some repre-
sentative examples of the functionalized fire-resistant papers will be discussed.
4.2. WATERPROOF FIRE-RESISTANT PAPER

As the saying goes, “water and fire are ruthless.” Both water and fire are natural ene-
mies of paper. Traditional paper made from plant fibers is neither fire-resistant nor
waterproof. These shortcomings limit the applications of traditional paper, and the
long-term preservation of valuable documents, archives, and books has a potential
danger. For many centuries, countless precious paper cultural relics, documents, and
books were destroyed in fires and floods. For example, in January 2014, the French
National Library suffered a flood, and more than 10,000 precious books were dam-
aged, and the same tragedy struck the library again in 2004. On January 30, 2015,
a major fire broke out at the Institute for Scientific Information on Social Sciences
Library in Moscow and lasted for more than ten hours, and millions of precious
ancient documents, books, and other materials were ruined in the fire. It is even
29
worse that more documents and books were damaged during the fire extinguishing
process, when a large amount of water was used. Is it possible to develop a super
paper that is both waterproof and fire-resistant? If you have this kind of super paper
that is not afraid of water and fire, the tragedy of a large number of precious paper
cultural relics and books being destroyed in fire and floods could be avoided. As
discussed above, the new type of fire-resistant paper we developed was not afraid
of fire, it was still afraid of water, so it was necessary to tackle the non-waterproof
problem of the fire-resistant paper.
To solve the non-waterproof problem of the new type of fire-resistant paper based
on ultralong hydroxyapatite nanowires, it is necessary to make the fire-resistant
paper have the superhydrophobic property (superhydrophobicity). What is super-
hydrophobicity? Superhydrophobicity means that the stable contact angle of water
droplets on the surface of the material is greater than 150° and the rolling contact
angle is less than 10°; materials with the superhydrophobic property have the advan-
tages of being waterproof, anti-fouling, anti-fog, self-cleaning, etc., and have good
application prospects in many fields.
The superhydrophobicity and self-cleaning functions of the lotus leaf, namely
the lotus leaf effect, have aroused great interest in researchers. The construction of
superhydrophobic materials usually imitates the surface structure of the lotus leaf.
Figure 4.1 shows a photograph of spherical water droplets on a lotus leaf. There are
two surface structural features in the lotus leaf, one is the unique micro-nano-sized
structures; the other is a waxy layer consisting of a low-surface-energy substance on
the surface. The surface of the lotus leaf has many micrometer-sized convex struc-
tures, and many nanostructures grow on the surface of each micrometer-sized con-
vexity, thus forming many micro-nano-sized small chambers filled with air. Water
droplets will form spherical water droplets on the surface of the lotus leaf due to the
effect of surface tension, because the surface tension of water is the smallest and
most stable in the spherical state. Spherical water droplets usually have sizes in the
millimeter scale, and cannot enter smaller chambers filled with air, and they can
FIGURE 4.1 A photograph showing spherical water droplets on a lotus leaf. (Courtesy:
http://www.ivsky.com/tupian/ heye_v23651/)
Functionalized Fire-Resistant Paper 31
only roll around on the top of smaller air chambers, that is, these small air chambers
act as physical supports for spherical water droplets. On the other hand, the surface
of the lotus leaf is also covered with a layer of a biological wax-like substance with
a low surface energy. The micro-nano-sized structures and the low-surface-energy
substance on the surface of the lotus leaf work together, resulting in the superhydro-
phobic property. The contact area between the surface of the lotus leaf and a water
droplet or dust is small, thus spherical water droplets on the surface of the lotus leaf
can take away the dust; that is, the lotus leaf exhibits the self-cleaning function.
In recent years, superhydrophobic materials have caught the attention of research-
ers owing to their high application value. Researchers used various methods to
prepare superhydrophobic materials with regard to two aspects: (1) constructing
micro-nano-sized structures on the surface of materials, and (2) reducing the surface
energy. However, some preparation methods need strict requirements for equipment,
leading to high cost; some methods use fluorine-containing reagents to chemically
modify the surface of the materials to reduce its surface energy. However, fluorine-
containing compounds are generally expensive and have certain toxicity, and have
safety concerns in terms of the human health and the environment.
In 2016, the author’s research group successfully developed a new kind of
waterproof fire-resistant paper made from ultralong hydroxyapatite nanowires
with adsorbed oleic acid molecules on the surface.[59] The ultralong hydroxyapa-
tite nanowires with oleic acid molecules adsorbed on the surface can be artificially
synthesized using common chemicals by the calcium oleate precursor solvothermal
method[12] or the calcium oleate precursor hydrothermal method.[34] For example,
ultralong hydroxyapatite nanowires could be synthesized in a reaction system con-
taining CaCl2, NaOH, oleic acid, NaH2PO4, ethanol, and deionized water by the cal-
cium oleate precursor solvothermal method at 180°C in 24 hours. The as-prepared
ultralong hydroxyapatite nanowires were stirred in ethanol and water, separately,
at 60°C overnight to remove the impurities, and stored in deionized water. A cer-
tain volume of the colloid suspension containing ultralong hydroxyapatite nanowires
was treated by vacuum filtration to form a wet paper sheet, which was immersed in
a sodium oleate aqueous solution with a concentration of 0.02 mol L−1 for 1 hour
under magnetic agitation, followed by vacuum-assisted filtration. The waterproof
fire-resistant paper was obtained after drying at 60°C.[59]
Ultralong hydroxyapatite nanowires had no obvious change after surface modi-
fication with sodium oleate, as shown by the XRD patterns in Figure 4.2. FTIR
spectra in Figure 4.3 of ultralong hydroxyapatite nanowires before and after surface
modification were consistent with the XRD analysis. The FTIR spectra of ultralong
hydroxyapatite nanowires before and after surface modification exhibited similar
characteristic peaks of the hydroxyl group (3,565 and 633 cm−1), PO43− (1,093, 1,028,
962, 604, and 561 cm−1), and adsorbed water (3,442 and 1,635 cm−1). The peaks at
2,921 and 2,852 cm−1 in the FTIR spectra of ultralong hydroxyapatite nanowires
after surface modification were attributed to the asymmetric and symmetric C−H
stretching vibration of the alkyl group of oleate.
In fact, a simpler method was developed by the author’s research group to pre-
pare the waterproof fire-resistant paper. Oleic acid molecules were adsorbed on the
FIGURE 4.2 XRD patterns of ultralong hydroxyapatite nanowires modified with

0.02 mol L−1 sodium oleate aqueous solution for different times: (a) without surface modifica-
tion; (b) 1 hour; (c) 2 hours; (d) 3 hours. (Reprinted with permission from reference [59])
FIGURE 4.3 FTIR spectra: (a) sodium oleate; (b–e) ultralong hydroxyapatite nanowires
modified with 0.02 mol L−1 sodium oleate aqueous solution for different times: (b) without
surface modification; (c) 1 hour; (d) 2 hours; (e) 3 hours. (Reprinted with permission from
reference [59])
surface of ultralong hydroxyapatite nanowires synthesized by the calcium oleate pre-

cursor solvothermal method or the calcium oleate precursor hydrothermal method.
If the as-prepared ultralong hydroxyapatite nanowires were slightly washed using
ethanol once, and collected and dispersed in water, then the waterproof fire-resistant
paper could be obtained using the ultralong hydroxyapatite nanowires. If ultralong
hydroxyapatite nanowires were thoroughly washed using ethanol and water for many
times, the fire-resistant paper obtained was superhydrophilic instead of superhydro-
phobic. In addition, the entire manufacturing process of the new waterproof fire-
resistant paper is environmentally friendly without causing severe pollution to the
environment.
Why is oleic acid used in the preparation of the waterproof fire-resistant paper?
Oleic acid has many advantages, such as non-toxicity, environment friendliness, and
relatively low price. Oleic acid is widely present in nature, mainly in the form of
glyceride in animal and vegetable oils. Oleic acid plays an important role in the
metabolism of the human body, and is an indispensable nutrient in food. To cite a few
examples of vegetable oils, the content of oleic acid is as high as 80% or more in tea
oil, more than 50% in peanut oil, and 55–83% in olive oil. In addition, the sodium or
potassium salt of oleic acid is one of the ingredients of soap.
How is the superhydrophobicity of the waterproof fire-resistant paper realized?
In the process of making the waterproof fire-resistant paper, ultralong hydroxyapa-
tite nanowires with oleic acid molecules adsorbed on their surface form a porous
networked structure through overlapping, interweaving, and entanglement. This
provides the paper with unique micro-nano-sized structures; in addition, the oleic
acid molecules adsorbed on the surface of ultralong hydroxyapatite nanowires are a
low-surface-energy substance. The synergy of these two combined features results
in the superhydrophobic effect with the waterproof function, as shown in Figure
4.4. The waterproof fire-resistant paper has a variety of advantages, such as high
flexibility, environmental friendliness, excellent and stable superhydrophobic per-
formance, good self-cleaning function, excellent heat insulation, and fire resistance.
The experiments showed that the waterproof fire-resistant paper exhibited excellent
superhydrophobic property not only for water but also for various commercial bever-
ages, such as mineral water, orange juice, tea, milk, and coffee. In addition to excel-
lent superhydrophobic property, the waterproof fire-resistant paper also possessed
excellent resistance to fire.
FIGURE 4.4 (a, b) SEM images of the cross-section of the fire-resistant paper made from
ultralong hydroxyapatite nanowires synthesized by the calcium oleate precursor solvothermal
method and washed thoroughly with ethanol and deionized water, that is, clean ultralong
hydroxyapatite nanowires with almost no oleic acid molecules adsorbed on the surface
(unmodified), showing a layered structure; (c, d) SEM images of the surface morphology of
the unmodified fire-resistant paper; (e) a water droplet on the unmodified fire-resistant paper;
(f, g) SEM images of the cross-section of the waterproof fire-resistant paper with surface
modification using sodium oleate aqueous solution, showing a layered structure as well; (h, i)
SEM images of the surface morphology of the layer-structured waterproof fire-resistant paper
with surface modification; (j) a water droplet on the layer-structured waterproof fire-resistant
paper with surface modification. (Reprinted with permission from reference [59])
The well-dispersed ultralong hydroxyapatite nanowires after thorough washing

could be dispersed in water to form a stable wool-like suspension. After vacuum-
assisted filtration, the ultralong hydroxyapatite nanowires self-assembled into a free-
standing, layer-structured, highly flexible fire-resistant paper (Figure 4.4a and b).
The layered structure can be clearly observed in Figure 4.4b. SEM images (Figure
4.4c and d) show that the ultralong hydroxyapatite nanowires in the paper were inter-
twined with one another to form a porous network. The ultralong hydroxyapatite
nanowires self-assembled along the longitudinal direction into nanowire bundles to
form nanofibers and microfibers. Such a hierarchical structure could increase the
roughness of the paper surface and thus achieve an excellent superhydrophobic per-
formance. Without surface modification of the ultralong hydroxyapatite nanowires
after thorough washing, the paper exhibited an intrinsic superhydrophilicity, and a
water droplet could spread out immediately when it was dropped on the paper sur-
face (water contact angle was ~0o) (Figure 4.4e). In the process of vacuum-assisted
filtration, a layered structure was spontaneously formed (Figure 4.4a and b). During
the filtration, ultralong hydroxyapatite nanowires were inclined to adhere together by
the van der Waals force and hydrogen bonding between oxygen (hydrogen)-contain-
ing groups. In addition, the electrostatic repulsion forces induced by the negatively
charged ultralong hydroxyapatite nanowires could prevent them from complete
compacting. Furthermore, the interaction among water molecules adsorbed on the
oxygen-containing groups of the ultralong hydroxyapatite nanowires led to repul-
sive hydration forces. The balance between the attractive forces (van der Waals
and hydrogen bonding) and repulsive forces (electrostatic repulsive and hydration
forces) was responsible for the formation of the layer-structured fire-resistant paper.
Furthermore, the micrometer-sized corrugated layers assembled by the ultralong
hydroxyapatite nanowires also contributed to the formation of the layered struc-
ture.[57, 59]
Compared with expensive perfluorinated compounds, the sodium oleate used for
the surface modification of ultralong hydroxyapatite nanowires is low-cost with good
biocompatibility. Therefore, sodium oleate was selected as the surface-modifying
agent to lower the surface energy of the ultralong hydroxyapatite nanowires. The
waterproof fire-resistant paper exhibited a superhydrophobicity, and a water droplet
was nearly spherical on its surface with a water contact angle of >150o (Figure 4.4j).
Surface modification of the ultralong hydroxyapatite nanowires with sodium oleate
aqueous solution for 1 hour was enough to achieve the superhydrophobicity of the
fire-resistant paper (contact angle = 154.40 ± 1.05°). The SEM images in Figure 4.4f–
i show that the waterproof fire-resistant paper made from surface-modified ultralong
hydroxyapatite nanowires exhibited similar surface and cross-sectional morpholo-
gies to those of the superhydrophilic fire-resistant paper made from unmodified
ultralong hydroxyapatite nanowires. The rough hierarchical surface structure and
the adsorbed oleic acid molecules as the low-surface-energy compound allowed the
fire-resistant paper to have the superhydrophobic property. No color trace was left
on the waterproof fire-resistant paper after it was dipped in and then taken out from
water dyed with methylene blue, as shown in Figure 4.5a, exhibiting the excellent
superhydrophobic property of the waterproof fire-resistant paper.
FIGURE 4.5 Liquid repellency tests for the waterproof fire-resistant paper. (a) A piece of
the waterproof fire-resistant paper was immersed in deionized water (dyed with methylene
blue) and taken out from the water (inset); (b−f) five common commercial drinks, includ-
ing mineral water (b), red tea (c), orange juice (d), milk (e), and coffee (f), were poured on
the waterproof fire-resistant paper. The waterproof fire-resistant paper exhibited excellent
waterproof performance. After immersing into the dyed water and then taking it out, the
waterproof fire-resistant paper was still white as before, without any color or water pollution
on the paper. (Reprinted with permission from reference [59])
Liquid repellency performance of the waterproof fire-resistant paper was tested

using pure water and various commercial drinks. As shown in Figure 4.5b–f, five
common commercial drinks were poured onto the waterproof fire-resistant paper
surface. In all experiments, not only transparent liquids (mineral water and red tea)
but also suspensions and emulsions (orange juice, milk, and coffee) could easily roll
off the horizontal surface of the waterproof fire-resistant paper. There were abundant
nanopores on the waterproof fire-resistant paper surface (Figure 4.4h and i), and the
air trapped in nanopores would lower the fraction of solid–liquid interface, which
could increase the water contact angle. Thus, the waterproof fire-resistant paper
exhibited excellent liquid repellency performance to various commercial drinks.[59]
The self-cleaning effect, one of the most attractive properties of superhydropho-
bic surfaces, is an effective tool to prevent the surfaces from the contamination with
water, dust, and other pollutants. The contaminants on the superhydrophobic surface
can be picked up and removed by water, such as rain. As an example of the appli-
cation of the self-cleaning effect, the shading of the collector area of photovoltaic
modules by contaminants could decrease the power output in the long-term. The
self-cleaning ability of the superhydrophobic surface may provide an ideal strat-
egy to avoid the accumulation of contaminants on the photovoltaic modules, thus
improving their performance and extending their working lifetime. As shown in
Figure 4.6a, the waterproof fire-resistant paper was attached to a tilted glass slide
at an angle of about 15°. The small nanopores in the waterproof fire-resistant paper
were small enough to prevent the dirt from penetrating into the interior. The con-
tact area between the paper surface and water was reduced drastically owing to the
superhydrophobicity of the paper surface. The tiny contact area could minimize the
adhesion between dirt and the paper surface. Both effects resulted in enhanced adhe-
sion between water droplets and dirt; thus water droplets and water flow could carry
and wash away dirt completely on the paper surface, exhibiting the excellent self-
cleaning performance (Figure 4.6c–f).[59]
Another challenge for the practical application of superhydrophobic surfaces is
thermal stability. The superhydrophobicity of the waterproof fire-resistant paper
exhibited high thermal stability, its superhydrophobic performance could be well
maintained at a temperature of 100 °C for 24 hours (Figure 4.7a) or 200 °C for
1 hour (Figure 4.7b). The thermogravimetric analysis of the waterproof fire-resis-
tant paper indicated that the oleate molecules adsorbed on the surface of ultralong
hydroxyapatite nanowires started to decompose at approximately 200°C, and the
superhydrophobic performance of the waterproof fire-resistant paper could be main-
tained below this temperature. The waterproof fire-resistant paper became hydro-
philic after heating at 250°C for 1 hour, and the conversion of superhydrophobicity
to superhydrophilicity occurred after heating at 300°C for 1 hour. Considering the
actual working environment in daily life, the as-prepared waterproof fire-resistant
paper is promising for various applications under high-temperature environments.
In addition, the superhydrophobicity of the waterproof fire-resistant paper exhib-
ited excellent resistance to mechanical damage. Common physical damages in daily
life may damage the paper surface severely and compromise the superhydrophobic
performance of the paper. Various mechanical damage tests similar to the common
physical damages in daily life, including the finger wipe, tape peeling, knife cutting,
and sandpaper abrasion, were conducted to investigate the mechanical durability
of the waterproof fire-resistant paper. Despite severe damage of the paper surface
and exposure of underlying layers, the superhydrophobicity of the waterproof fire-
resistant paper could be well preserved, indicating its highly stable superhydropho-
bicity. This was attributed to the layered hierarchical structure of the waterproof
fire-resistant paper.
FIGURE 4.6 Self-cleaning tests for the waterproof fire-resistant paper. (a, b) Schematic
illustration of the self-cleaning tests in different media: (a) in air and (b) in oil; (c) the dirt
was placed on the waterproof fire-resistant paper surface before self-cleaning test; (d) the dirt
was removed by water droplets from a syringe; (e) the dirt was washed away by a water flow;
(f) the waterproof fire-resistant paper was clean again after the self-cleaning test. (Reprinted
with permission from reference [59])
The waterproof fire-resistant paper possessed excellent resistance to high tempera-

tures and excellent heat insulation performance, and could be used as a fire-shielding
protector to protect flammable objects. In a control experiment, commercial print-
ing paper consisting of flammable cellulose fibers was burned to ashes in 5 seconds
without the protection of the waterproof fire-resistant paper, as shown in Figure 4.8a.
Other documents randomly have
different content
The diseased areas should then be dressed with some fatty
substance, to soften the crusts and enable them to be removed
without injury.
Dressings are useless unless these crusts have been removed, for
the spores are always in the deepest recesses and in the follicles, so
that the drugs employed never come in contact with them.
Once the skin is cleansed, numerous chemical substances may be
utilised, the solutions being applied for several days in succession.
Amongst them may be mentioned tincture of iodine, oil of cade, 10
per cent. solution of sulphate of iron, and solution of perchloride of
iron. Such drugs, however, must not be used for a long time, as they
all attack the skin to some extent.
When the patches are small and well defined the following mixture
proves very efficacious:—
Crystallised carbolic acid } Equal parts.

Tincture of iodine }
Chloral hydrate }
Two or three applications generally prove successful.

Despite the natural activity of the spores, which are capable of
germination after three months’ desiccation, some medicines are
useful, although it is necessary, in order to judge of their effects, to
wait for the renewal of the skin, hair follicles, and hair.
Where the disease is generalised this form of treatment is scarcely
practicable, or at least it becomes more difficult.
Nevertheless, by dressing with soft soap the disease may be cured
in a few months. The soap should remain on the skin for some hours
and then be washed off, after which dressings of creolin, lysol, or
chloral solution, etc., should be employed.
RINGWORM IN THE SHEEP, GOAT, AND PIG.
Little information regarding the dermatomycoses of the sheep,

goat, and pig is available. Allowing for modifications due to the
nature of the coat, the symptoms of recorded cases seem to indicate
a close relationship with ringworm in the horse and ox.
In sheep suffering from ringworm, the wool is at first matted into
small irregular tufts, which grow larger and more numerous. The
coat appears felted together at various points. The neck, chest,
shoulders and back exhibit crustaceous patches covered with
branlike epidermal scales, and the animals suffer from marked
pruritus, which causes them to rub and injure the coat.
Ringworm is very obstinate in the goat.
Two pigs described by Siedamgrotsky showed irregular, rounded
patches, due to trichophyton, from 1 inch to 2 inches in diameter,
reddish in tint, without exudation, but covered with abundant scales.
In the pig ringworm attacks the croup, sides of the chest, flanks
and sides of the abdomen, but is commonest on the back and outside
of the quarters. It forms red isolated patches, from 1 to 2 inches in
diameter, covered with miliary vesicles, which in turn are replaced by
brown crusts. The bristles remain unchanged, and are not shed or
broken. There is no pruritus. Contagion from pig to pig occurs
readily. The disease may be conveyed from oxen to pigs through the
medium of litter removed from the cowsheds to the piggery.
Gerlach was unable to inoculate sheep or pigs with ringworm from
the ox. Perroncito mentions a case of contagion from the ox to a
lamb. Schindelka has seen sheep contract ringworm as a result of
confinement to sheds previously occupied by oxen suffering from the
disease.
Siedamgrotsky successfully inoculated two pigs and two sheep
with ringworm from the horse and a goat with the bovine form of the
disease. The two pigs inoculated two others by contact. Contagion
from the goat to the ox was noted in the canton of Zürich in 1852.
Fuller particulars on these heads will be found in a series of
articles by Neumann in the Revue Vétérinaire, January to June,
1905.
In 1876 Laillier communicated to a French medical society a letter
written by Lespiau describing an endemic of trichophyton disease in
the cantons of Céret and Arles-sur-Tech. Thirty-four persons,
including twenty-eight children, were affected. A dog was first
attacked and seems to have inoculated a pig, which in these districts
often lives with the human family. The pig inoculated the human
beings. A moist season appears to have favoured the development of
the disease. The parts principally attacked were the head, eyebrows,
cheeks, and neighbourhood of the genital organs. The subjects
showed considerable pruritus.
CHAPTER IV.
WARTS IN OXEN.
Warts are cutaneous tumours, real papillomata, which most

commonly attack young animals such as heifers. As a rule they are
pedunculated, smooth, wrinkled or deeply cracked on the surface,
but in some cases they are sessile.
Causation. The cause is difficult to ascertain. It has been referred
to the growth of bacteria (Bacterium porri) in the superficial layers
of the skin. It is at least certain that warts can be transmitted by
inoculation or through the medium of cutaneous injuries.
Symptoms. On their first appearance warts consist in
hypertrophy of the cutaneous papillæ, which become covered with
layers of actively growing epidermis and end by projecting above the
general surface. The lesions may remain isolated, or they may
become confluent or unite at their base. This form is fairly common,
the warts attaining the size of a man’s fist or more.
The disease attacks the most tender portions of the skin, such as
that covering the udder, internal surface of the thighs, lower
abdominal wall, region of the elbow, posterior surface of the ears,
etc. In rarer cases warts may be seen on the limbs.
When they extend over a considerable surface they become
infected, suppurate and give rise to various complications, the most
serious being pyæmia. The patients lose condition and value.
Diagnosis. The diagnosis is easy. It has been proved that warts
are contagious, not only as between animal and animal, but as
between animal and man.
Prognosis. Warts are not dangerous to life, but they diminish the
value of the animals, particularly that of milch cows when the teats
are affected.
Treatment. Leaving out of account internal medication with
calcined magnesia, many medicines that are still recommended are
of comparatively little value.
Peuch and Cruzel recommend friction with oil of cade. Repeated
cauterisation with nitric acid is declared to give good results by
destroying the new tissue.
These modes of treatment, however, are impracticable in dealing
with large multiple lesions, nor does the elastic ligature give much
better results.
Total removal with the scissors or bistoury, or simply tearing out
by hand, is preferable to any other course. Troublesome bleeding
may follow, but is rarely of great importance. It usually stops in a few
minutes, even where small arteries of the size of several millimètres
in diameter have been divided. As a measure of precaution, however,
the little wounds may be touched with the red-hot blade of the
thermo-cautery.
The écraseur is rarely required. The smaller warts are generally
sessile, and can be removed with a bistoury or a sharp curette. The
removal of those about the udder requires considerable precaution to
avoid injuring the teats.
Fig. 267.
All the growths are usually removed at one operation; Moussu has
thus taken away 30 lbs. weight without the slightest ill effect. After
the wounds have been washed with an antiseptic, the raw surfaces
are powdered with a mixture of equal parts of boric acid, tannin, and
calcined alum; cicatrisation occurs in a few days.
URTICARIA IN THE PIG.
This disease usually attacks pigs during the spring or summer,

producing characteristic cutaneous lesions, which, however, are of a
benign character. It seems to arise from some form of alimentary
intoxication.
Symptoms. At first the dominant symptoms point to disturbance
of digestion. The appetite is lost, and the bowels may be confined or
there may be diarrhœa. This is sometimes accompanied by vomiting,
and by fever.
The symptoms may develop fully in from six to twelve hours;
sometimes the skin is covered with slightly prominent reddish
patches, varying in size from ⅓ of an inch to 1¼ inches in diameter.
The patches may also become confluent and form large, irregular
red or violet flattened swellings, sensitive to the touch and spread
over the upper and lateral portions of the body. Only in exceptional
cases is there any oozing of blood.
In favourable cases recovery takes place in forty-eight hours, and
even in grave cases in from five to six days.
Diagnosis. It is sometimes very difficult to distinguish this
condition from swine erysipelas, particularly in the first few cases,
although the congested or hæmorrhagic patches occupy different
positions.
The prognosis is usually favourable.
Treatment. The disease being unquestionably of digestive origin,
the animals should be kept without food and receive repeated doses
of mild purgatives according to their age and condition, sulphate of
soda, 4 to 12 drachms, or calomel, 1½ to ·8 grains. Recovery is rapid.
SCLERODERMA.
This term is applied to a disease characterised by thickening and

hardening of the skin. Up to now it has been described only in the
pig, and principally in male animals or old animals of either sex.
The symptoms are difficult to detect, and in many cases are only
discovered after slaughter. Without any change in external
appearance, the skin becomes thick, hard and sclerosed over limited
or extensive areas, and is thus transformed into hard, rigid,
inextensible and inelastic plates, sometimes as much as 1 to 2 inches
in thickness. The change usually commences about the dorsal region,
and extends irregularly towards the chest and sometimes towards
the limbs.
The patient thus becomes imprisoned in a kind of cuirass, which
interferes with its movements and causes unaccountable stiffness.
Palpation of the skin gives the impression of a piece of wood, for it is
hard and resistant over the affected regions, whilst over the belly,
inner surface of the thighs, and region of the elbow, it retains its
usual pliability.
The patient exhibits no other symptoms, the principal functions of
the body appearing to be properly performed. There is no fever, but
in time the animals lose condition and waste away.
Causation. This disease is also well known in man, but no
general agreement exists regarding its nature. Some refer it to
disturbance of the thyroideal function, though scleroderma is quite
different to myxœdema. Others attribute it to changes in the
cutaneous blood-vessels, others, again, to peripheral neuritis
accompanied by atrophic disturbance. Nothing, however, is proved.
The apparent lesions are limited to hypertrophic sclerosis of the
dermis, with progressive atrophy of the layers of subcutaneous
adipose tissue.
The diagnosis is comparatively easy.
The prognosis is grave, because it is never known how rapidly
the disease may develop.
No method of treatment being known, the animals should at once
be slaughtered.
CHAPTER V.
SUBCUTANEOUS EMPHYSEMA.
By subcutaneous emphysema is meant the condition produced by

the entrance of air or gas into the subcutaneous and interstitial
connective tissue. Emphysema may remain localised or it may
become generalised, according to the nature and extent of the lesion
which causes it, and the points where emphysema is developed.
Subcutaneous emphysema is common in the sheep and ox.
Symptoms. Sometimes the symptoms of subcutaneous
emphysema are extremely well defined. They consist in the presence
of diffuse or limited crepitant swellings which may appear at various
points—in the flank or the entrance to the chest; more rarely in the
region of the elbow, etc.
The limits of crepitation may be ascertained by palpation, while
percussion produces a peculiar abnormal sound. The subcutaneous
tissue and very often the interstitial tissue appear as though blown
out.
Emphysema may be generalised. Such an accident is rare, but may
occur in the ox as well as in the sheep and goat.
Provided the emphysema remains confined to the subcutaneous
tissue, the animals are not necessarily in danger. Where, however, it
also extends to the interstitial tissue, and particularly if the cause to
which it is due continues, death may result in a very short time. This
occurs, for example, when the emphysema extends into the
mediastinum, and thus gains the pleura and lung.
The symptoms of emphysema are then complicated with
respiratory and circulatory disturbance and with signs of asphyxia.
Causation. Subcutaneous emphysema may be produced in many
different ways.
If, for example, in puncturing the rumen the canula be carelessly
withdrawn so that the skin is slightly separated from the subjacent
tissues, gas may pass from the rumen into the channel produced by
the instrument. It then becomes distributed throughout the
subcutaneous tissue, and if the cutaneous opening is displaced its
escape is confined to the connective and interstitial tissues in the
region of the flank. Diffuse suppuration may then be set up in these
parts, and may extend far beyond them.
In the ox emphysema rarely becomes generalised, but in the sheep
and goat extension is more common; the patients perish of
intoxication, caused by reabsorption of septic gases.
Under other circumstances emphysema may be due to an injury in
some region where the connective tissue is loose and pliable, as for
instance the region of the elbow, the internal surface of the shoulder,
or the fold of the flank. Every time the animals move the tissues are
displaced, and air being drawn in, it is imprisoned by the valve-like
action of the injured part and gradually finds its way into the
subcutaneous tissue.
Accidental injuries to the trachea, particularly injuries produced by
dogs biting sheep or goats, are always accompanied by local
emphysema, unless the wounds in the skin and trachea correspond,
which rarely happens. At every respiration a portion of the air
expelled passes into the peritracheal tissue, from which it gradually
invades neighbouring parts, and may attain the mediastinum, etc.
The injured animal thus inflates its own tissues and dies from
asphyxia.
The open lesions due to pulmonary echinococcosis, and the
accidents associated with pneumo-thorax, tuberculous caverns and
abscesses, or pulmonary emphysema may become points of
departure for local, general, interstitial or subcutaneous emphysema.
The diagnosis of accidental emphysema presents no difficulty,
for the local swellings can only be mistaken for those of black-
quarter. In the latter disease, however, fever is a constant
accompaniment, whilst in simple emphysema it is absent.
Nevertheless, it is well to remember the possibility of
complications due to compression, asphyxia, and even intoxication.
The prognosis may be very hopeful or very grave. Everything
depends on the primary lesion, and it is therefore important that the
practitioner should know how to interpret the course of affairs.
Treatment. In slight cases the best method is to immobilise the
parts and await developments, but in grave cases, for instance where
the trachea is much injured, the animal should at once be
slaughtered.
Scarification, cutaneous incisions, and massage were formerly
recommended as a means of aiding the escape of gas accumulated in
the tissues. Such methods, however, are useless, and have the
disadvantage of causing numerous suppurating wounds.
Provided the initial wounds are not seriously infected and the
animals are kept quiet, in a well-ventilated place, the gas gradually
becomes reabsorbed, and healing may take place in a fortnight or
three weeks.
SECTION IX.
DISEASES OF THE EYES.
In domesticated animals, apart from parasitic diseases, the

diseases of the eye which particularly deserve description and offer a
special clinical interest are very few. These are the diseases that
affect the globe of the eye or the organs annexed to it.
FOREIGN BODIES.
Foreign bodies become lodged on the internal surface of the
eyelids, in the folds of the conjunctiva, in the thickness of the cornea,
and sometimes, though rarely, in the anterior chamber, the lens, or
the vitreous humour. They include particles of grit or dust, the awns
and glumes of grain, etc.
The eyes are half closed and the conjunctiva is swollen, whilst the
eye weeps and the animals dread the light.
Diagnosis. This is somewhat difficult, for the parts rapidly
become very sensitive, and the animals violently resist examination.
When the foreign body penetrates the anterior chamber or the lens,
it produces suppuration or traumatic cataract.
Before anything can be done it is often necessary to render the
parts anæsthetic by instilling a few drops of cocaine solution into the
eye.
The foreign body may then be discovered by close observation. If
the pain is very intense, and great resistance is offered to opening the
eye, the practitioner may confine himself to passing a soft camel-hair
brush saturated with cocaine solution over the surface of the eye and
into the conjunctival sacs. The brush loosens, and often removes, the
offending body. In the absence of a camel-hair brush, the little finger,
covered with a piece of fine linen, may be used.
Where the parts cannot be touched owing to the resistance of the
animal, lukewarm solutions of antiseptics such as boric acid may be
occasionally injected into the eye by means of a syringe, but care
must be taken to prevent the animal injuring itself against the
syringe by sudden movements.
CONJUNCTIVITIS AND KERATITIS.
Inflammation of the conjunctiva and inflammation of the cornea
almost always occur together, and reciprocally induce one another
when of a certain degree of intensity. They may be simple, that is to
say, produced by simple causes, or they may be specific, and of a
contagious character.
Simple inflammation is caused by the action of cold, draughts,
dust, or mechanical injuries. Specific inflammations, the nature of
which is still little understood, occur in the ox and goat. They are
very contagious, and may successively attack all the animals of a
herd.
The symptoms of acute and specific inflammation differ very
little. They comprise congestion, lachrymation, chemosis, a certain
amount of suppuration, and sometimes superficial ulceration of the
cornea. The patients suffer very acute pain, avoid the light, present
all the symptoms of photophobia, and are affected with spasm of the
orbicularis muscle.
In simple cases these symptoms frequently disappear, provided
the byres are kept clean and astringent eye-washes are applied.
In contagious keratitis, however, the cornea may suppurate and
even become perforated after a few weeks.
Treatment. The chief object of treatment under any
circumstances must be to insure the most perfect cleanliness both of
the globe of the eye and the conjunctival sacs.
The eye must, therefore, be irrigated with lukewarm water, the
stream being injected beneath the lids. Each irrigation is followed by
the use of an anodyne and astringent eye-wash containing borate of
soda or sulphate of zinc, combined if necessary with cocaine.
Distilled water 100 parts.

Borate of soda 4 „
Hydrochlorate of cocaine 1 „
But saturated solution of boric acid is simple, and no less effective.

In contagious keratitis the eye lotion may contain 2 to 3 per cent.
of nitrate of silver, the excess of silver being neutralised by washing
out with a weak solution of common salt. After three or four
applications this should be changed for a saturated solution of boric
acid.
VERMINOUS CONJUNCTIVITIS.
This form of conjunctivitis, described by Rodes in 1819, is due to
the presence of the Filaria lachrymalis, which varies in length
between ⅜ of an inch and 1 inch.
Like ophthalmia, the disease attacks cattle reared in wet localities.
Symptoms. The symptoms are those of acute conjunctivitis, and
consist first of lachrymation, then of injection of the blood-vessels of
the conjunctiva, together with swelling of the eyelids and
photophobia. The animals keep the eye closed, and display extreme
sensitiveness. Here again cocaine proves of value.
Examination is rather difficult, the worms being sometimes
displaced towards the cornea or membrana nictitans, although more
commonly they remain hidden in the folds of the mucous membrane
towards the point where the membrana nictitans is inserted. It is,
therefore, necessary to thoroughly expose the folds of the mucous
membrane in order to discover them.
In time conjunctivitis becomes complicated with diffuse
ulceration, keratitis, and sometimes with ophthalmia and
suppuration of the eye.
Diagnosis. The diagnosis is rather troublesome, and cocaine is of
great assistance.
Prognosis. This is rather grave.
Treatment. The object of treatment is the complete removal of
the parasites. This can sometimes be attained by means of the finger,
a pair of forceps, or a very clean feather.
Treatment is completed by injecting an antiseptic and anti-
parasitic eye lotion for several days, lest some of the worms should
remain hidden in the folds of the mucous membrane. One per cent.
creolin or 1 in 2,000 sublimate solution may be used.
If in some exceptional case it is difficult to remove the parasites,
they may be got rid of by injections or free irrigation. The stream of
liquid, pointed in different directions, distends the mucous
membrane and washes away the foreign bodies on its surface.
VERMINOUS OPHTHALMIA OF THE OX.
This ophthalmia is due to the presence of a small worm, ⅔ of an
inch to 1¼ inches in length, which has been regarded as the larval
form of the Filaria cervina of the serous cavities.
It is very common in animals which are kept permanently in low-
lying meadows particularly in some parts of France, as for instance
in Normandy, in the departments of the Sarthe and the Mayenne.
Not infrequently it occurs as an epizootic, and is then regarded as a
contagious ophthalmia. Verminous ophthalmia occurs chiefly during
the spring and autumn.
Symptoms. The disease is accompanied by lachrymation, signs of
conjunctivitis, and fear of light. Very soon the media of the eye
become turbid, the sclerotic and cornea are injected, and finally
exhibit marked opalescence.
On examination the eye appears extremely sensitive; in fact, it can
scarcely be touched unless cocaine solution is previously applied.
The parasites, two or three as a rule, but in exceptional cases from
five to seven in number, are seen rolled up within the anterior
chamber of the eye. A week after the beginning of the attack,
however, they begin to move about, and are then found close behind
the cornea, upon the lens, or suspended in the aqueous humour.
The irritation produced sets up inflammation of Descemet’s
membrane and the cornea, together with iritis, and, secondly,
keratitis and changes in the lens.
Unless treatment is adopted verminous ophthalmia inevitably
ends in cataract.
Diagnosis. Diagnosis is always uncertain on account of the
difficulty of examination. When the cornea is very opaque
examination necessarily gives a negative result.
The prognosis is grave.
Treatment. Eye lotions containing tincture of aloes, creolin,
corrosive sublimate, etc., have been suggested, but are practically
useless, because they can have no action on a parasite enclosed
within the globe of the eye. The most logical treatment consists in
aseptic puncture of the anterior chamber of the eye towards its lower
border with a cataract needle.
The escaping liquid carries with it the parasites, and recovery is
then only a matter of time, provided the wound does not become
inflamed. The great danger consists in inflammation and
suppuration of the eye. This, however, can be avoided by antisepsis
and by applying a surgical wool dressing, which can be left in place
for a few days.
SECTION X.
INFECTIOUS DISEASES.
COW-POX—VACCINIA.
The name cow-pox, or vaccinia, is employed to describe a special
disease which in animals of the bovine species is characterised by the
development of pustules at points where the skin is fine, and more
particularly the mammary region.
It can be conveyed both to man and the domestic animals.
This disease has been known from time immemorial, and it would
appear that first of all in the East and later in England it was a
general belief that its attacks rendered human beings proof against
small-pox. Medical men, it must be admitted, long regarded this
belief as a popular delusion, as is proved by their continuing to
practise inoculation with true small-pox material.
Jenner in 1770 was the first to declare the truth of this popular
opinion, and by his wise foresight to confer on humanity one of the
most beneficent discoveries ever made, although the weight of
modern opinion is in favour of the identity of cow-pox and human
variola. Having observed that milkmaids who happened to have
small cuts or sores about the hands sometimes contracted the
disease in a mild form, and that they did not afterwards suffer from
small-pox, he was struck with the advantages consequent on such a
discovery, and having proved the possibility of inoculating human
beings artificially, he immediately formulated the principles of
vaccination. A child eight years of age was vaccinated with cow-pox,
and afterwards inoculated with pus from a small-pox patient. It
contracted vaccinia in consequence of the first inoculation, but
entirely resisted the attempt to inoculate it with small-pox.
Vaccination had been discovered.
Jenner furthermore proved that cow-pox was transmissible from
cow to cow and from man to man, but it seemed to him that the
original disease was to be sought elsewhere, and that the pustular
affection originated primarily with the horse. The horse is sometimes
the subject of a pustular disease called horse-pox; this disease when
inoculated in man confers immunity against small-pox, just as does
cow-pox, and Jenner believed that the disease did not attack cows

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© 2022 Ying-Jie Zhu

Library of Congress Cataloging‑in‑Publication Data

Names: Zhu, Ying-Jie, author.

ISBN: 978-0-367-70005-8 (hbk)

Chapter 2 Highly Flexible Ultralong Hydroxyapatite Nanowires......................... 7

Chapter 3 Novel Fire-Resistant Paper Based on Ultralong Hydroxyapatite

Chapter 4 Functionalized Fire-Resistant Paper................................................... 29

4.7. Catalytic Fire-Resistant Paper.................................................. 63

Chapter 5 Applications of the Fire-Resistant Paper............................................. 77

Chapter 6 Acid/Alkali-Proof Fire-Resistant Paper Based on Barium

Chapter 7 Commercialization Potential and Future Prospects of the

FIGURE 1.1 A portrait of Lun Cai.

1.2. ROLE OF PAPER IN THE DEVELOPMENT OF HUMAN SOCIETY

1.3. TECHNICAL ASPECTS OF PAPERMAKING

1.4. PROBLEMS FACING TRADITIONAL FLAMMABLE PAPER

FIGURE 1.2 Schematic illustration of the traditional handmade papermaking procedures.

of traditional paper, it is necessary to explore new materials as building material for

FIGURE 2.1 Number of papers published on hydroxyapatite-based materials each year

2.2. HOW TO SOLVE PROBLEM OF HIGH BRITTLENESS

2.3. SYNTHETIC METHODS, EQUIPMENT, AND

including the solvothermal/hydrothermal method,[22–25] microwave-assisted synthe-

FIGURE 2.2 Characterization of ultralong hydroxyapatite nanowires prepared by the cal-

FIGURE 2.3 Ultralong hydroxyapatite nanowires dispersed in deionized water; ultralong

surface of hydroxyapatite nanowires led to monodispersity of hydroxyapatite nanow-

FIGURE 2.5 Scaled-up synthesis of hydroxyapatite nanowires/nanowire networks by the

2.5. HIGHLY ORDERED SELF-ASSEMBLY

FIGURE 2.7 Characterization of the highly flexible, large-sized, fire-resistant nanorope

The quasi-long-range orderly liquid crystal of ultralong hydroxyapatite nanowires was

2.6. COMPARISON OF ULTRALONG HYDROXYAPATITE

(1) Classification: hydroxyapatite is inorganic; however, cellulose is organic.

(2) Chemical composition: cellulose (C6H10O5)n is a long-chain polymeric

3.1. BACKGROUND FOR THE INVENTION

Two-dimensional fire-resistant products, including fire-resistant cloths, felts,

3.2. PREPARATION OF THE FIRE-RESISTANT PAPER

3.2.2. Papermaking Processes and Equipment

preparation of aqueous suspension containing ultralong hydroxyapatite nanowires,

3.3. PROPERTIES OF THE FIRE-RESISTANT PAPER

FIGURE 3.3 Digital images of an A4-size fire-resistant paper consisting of ultralong

1.2. ROLE OF PAPER IN THE DEVELOPMENT OF HUMAN SOCIETY

1.3. TECHNICAL ASPECTS OF PAPERMAKING

1.4. PROBLEMS FACING TRADITIONAL FLAMMABLE PAPER

2.2. HOW TO SOLVE PROBLEM OF HIGH BRITTLENESS

2.3. SYNTHETIC METHODS, EQUIPMENT, AND

2.5. HIGHLY ORDERED SELF-ASSEMBLY

2.6. COMPARISON OF ULTRALONG HYDROXYAPATITE

3.1. BACKGROUND FOR THE INVENTION

3.2. PREPARATION OF THE FIRE-RESISTANT PAPER

3.2.2. Papermaking Processes and Equipment

3.3. PROPERTIES OF THE FIRE-RESISTANT PAPER

3.4. ADVANTAGES OF THE FIRE-RESISTANT PAPER

4.2. WATERPROOF FIRE-RESISTANT PAPER