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SAUNDERS
An Imprint of Elsevier Science

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St. Louis, Missouri 63146

PHILLIPS’ SCIENCE OF DENTAL MATERIALS ISBN 0-7216-9387-3

Copyright „ 2003, Elsevier Science (USA). All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any means, electronic
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then ‘Obtaining Permissions’.

NOTICE

Dentistry is an ever-changing field. Standard safety precautions must be followed, but as new
research and clinical experience broaden our knowledge, changes in treatment and drug therapy may
become necessary or appropriate. Readers are advised to check the most current product information
provided by the manufacturer of each drug to be administered to verify the recommended dose, the
method and duration of administration, and contraindications. It is the responsibility of the licensed
prescriber, relying on experience and knowledge of the patient, to determine dosages and the best
treatment for each individual patient. Neither the publisher nor the editor assumes any liability for
any injury and/or damage to persons or property arising from this publication.

Previous editions copyrighted 1996, 1991, 1982, 1973, 1967, 1960, 1954, 1946, 1940, 1936 by
W.B. Saunders Company

Library of Congress Cataloging-in-Publication Data

Phillips’ science of dental materials / [edited by] Kenneth J. Anusavice; selected artwork by José dos
Santos Jr. — 11th ed.
p. ; cm.
Includes bibliographical references and index.
ISBN 0-7216-9387-3
1. Dental materials. I. Title: Science of dental materials. II. Anusavice, Kenneth J. III. Phillips,
Ralph W.
[DNLM: 1. Dental Materials. WU 190 P5625 2003]
RK652.5.P495 2003
617.6′95—dc21 2003045747

Publishing Director: Linda L. Duncan

Executive Editor: Penny Rudolph
Senior Developmental Editor: Kimberly Alvis
Publishing Services Manager: Patricia Tannian
Project Manager: Sharon Corell
Designer: Gail Morey Hudson
Cover Design: Julia Dummitt

Printed in the United States of America

Last digit is the print number: 9 8 7 6 5 4 3 2 1

 Contributors

Sibel A. Antonson, DDS, PhD Barry K. Norling, BSChE, MSChE, PhD

Assistant Professor and Director of Dental Associate Professor
Biomaterials Department of Restorative Dentistry
Department of Restorative Dentistry University of Texas Health Science Center at San
NOVA Southeastern University Antonio
College of Dental Medicine San Antonio, Texas
Fort Lauderdale, Florida
Rodney D. Phoenix, DDS, MS
William A. Brantley, PhD Associate Professor and Head, Removable Partial
Professor and Director, Graduate Program in Dental Denture Division
Materials Science Department of Prosthodontics
Section of Restorative Dentistry, and Prosthetic The University of Texas Health Science Center at
Dentistry San Antonio
College of Dentistry San Antonio, Texas
The Ohio State University
Columbus, Ohio H. Ralph Rawls, PhD
Professor and Head, Division of Biomaterials
Paul Cascone, PhD Department of Restorative Dentistry
Senior Vice President, Technology University of Texas Health Science Center at San
The Argen Corporation Antonio
San Diego, California San Antonio, Texas

Josephine F. Esquivel-Upshaw, DMD, MS Chiayi Shen, PhD

Assistant Professor Associate Professor
Department of General Dentistry Department of Dental Biomaterials
University of Texas Health Science Center at San University of Florida
Antonio Gainesville, Florida
San Antonio, Texas
John C. Wataha, DMD, PhD
Grayson W. Marshall, Jr., DDS, MPH, PhD Professor
Professor and Chair, Division of Biomaterials and Department of Oral Rehabilitation
Bioengineering Medical College of Georgia
Department of Preventive and Restorative Dental Augusta, Georgia
Sciences
University of California, San Francisco
San Francisco, California

Sally J. Marshall, PhD

Professor and Vice Chair for Research
Department of Preventive and Restorative Dental
Sciences
University of California, San Francisco
San Francisco, California

v
This page intentionally left blank
 The eleventh edition of
Phillips’ Science of Dental Materials
is dedicated to the memory of
Dr. Harold Stanley
who passed away in 2001.

Stan’s remarkable contributions to the field of

dental materials will benefit the dental profession and
our dental patient population well into the future.
He has served dentistry with the highest level of
moral and ethical standards, and he has set the standard for
excellence in scholarship for all future dental materials scientists.
This page intentionally left blank
 Preface

This book represents a comprehensive overview prepared tooth or a prosthesis indirectly in a

of the composition, biocompatibility, physical dental laboratory before placement in the oral
properties, mechanical properties, manipula- cavity, respectively.
tive variables, and performance of direct and The previous 30 chapters have been con-
indirect restorative materials and auxiliary densed into the 23 chapters of the eleventh edi-
materials used in dentistry. The book is tion by combining Chapters 3 and 16 into the
intended as a textbook for dental students, den- new Chapter 3, Physical Properties of Dental
tal hygiene students and practicing hygienists, Materials; Chapters 6, 7, and 8 into the new
laboratory technicians, and dental materials Chapter 9, Impression Materials; Chapters 22
scientists. It is also designed as an authoritative and 23 into the new Chapter 12, Casting
reference book for dentists, dental assistants, Investments and Procedures; Chapters 24 and 25
and corporate marketing staff. Although the sci- into the new Chapter 16, Dental Cements;
entific concepts presented in some chapters are Chapters 17 and 18 into the new Chapter 17,
somewhat advanced, the text information in Dental Amalgams; and Chapters 20 and 27 into
most chapters can be readily understood by the new Chapter 19, Dental Casting and
individuals with a general college education. Soldering Alloys. This condensed format places
The eleventh edition of Phillips’ Science of similar topics into one chapter, making it easier
Dental Materials is divided into four sections to to find information on any given topic.
reflect the focus of the chapters contained in Each of the chapters contains an introduc-
each part. Part I, General Classes and Properties of tory terminology section that is designed to
Dental Materials, consists of eight chapters familiarize the reader with key words and defi-
that cover the structure, physical properties, nitions and a number of critical thinking ques-
mechanical properties, and biocompatibility tions, which are intended to stimulate thinking
of restorative and auxiliary materials used in and to emphasize important concepts. The
dentistry. Part II: Auxiliary Dental Materials, answers to these questions are generally found
contains five chapters on impression materials, in the section or sections immediately after
gypsum products, dental waxes, casting invest- each question. Although the terminology is
ments and procedures, and finishing and pol- associated with generally accepted scientific
ishing abrasives and procedures. Part III: Direct and dental definitions, it is not intended to be
Restorative Materials, is focused on five areas, a comprehensive dictionary of all terms used in
bonding, restorative resins, dental cements, dental biomaterials science.
dental amalgams, and direct-filling gold. Part Several of the chapters represent totally new
IV: Indirect Restorative Materials, consists of five approaches to the specific subject. Chapter 1
chapters including dental casting and solder- has been revised to provide an introductory
ing alloys, wrought metals, dental ceramics, overview of the use of dental materials, the his-
denture base resins, and dental implants. torical evolution of biomaterials, and standards
Direct and indirect materials are used to for safety and quality assurance. Chapters 5, 6,
restore function and/or aesthetics in mouths 19, and 20 have been restructured to reflect an
containing damaged, decayed, or missing teeth updated review of casting and wrought metals.
by producing the restoration directly within the Chapter 7 reflects a new approach on the

ix
x Preface

science of dental polymers. Chapter 8 is a One of the differences between a profes-

totally new summary of the basic principles sional and a tradesman is that the former pos-
and clinical implications of biocompatibility sesses basic knowledge with which he or she
evaluation. Chapter 9 represents an integration can establish conditions for a situation such
of the three previous chapters on impression that a prediction of eventual success of a proj-
materials. Chapter 14 is a new overview of the ect is reasonably ensured. A riveter must be
systems and principles for use of dental adhe- responsible for the joined beams in a bridge,
sives. Chapter 15 reflects a more applied review but the engineer is responsible for the design of
of restorative resins. Chapter 16 on dental the bridge, especially where the rivets and every
cements is an expanded description of cement truss and beam are to be placed and joined,
composition, manipulative characteristics, and and for the selection of the materials with
clinical performance based on the integration which the structure is constructed. If the engi-
of the previous Chapters 24 and 25. Chapter 21 neer knew nothing about the physical and
represents an updated summary of ceramics chemical properties of the steels and other met-
used for metal-ceramic and all-ceramic prosthe- als with which the bridge is made, the structure
ses. Finally, Chapter 23 is a new overview of would be more likely to fail.
dental implants with an emphasis on implant The dentist and the engineer have much in
material and design considerations relative to common. Dentists must estimate the stresses
clinical performance. present in a dental prosthesis that they will
build and be guided by such analyses in the
design of the structure. They should possess a
Aims and Need for This Book sufficient knowledge of the physical properties
The aims of this textbook are: (1) to introduce of the different types of materials that they use
dental materials science to students with little so that they can exercise the best judgment pos-
or no dental background and facilitate their sible in their selection. For example, they must
study of physical and chemical properties that know whether the clinical situation requires the
are related to selection of these products by the use of an amalgam, a resin-based composite, a
dentist, (2) to describe the basic properties of cement, a casting alloy, a ceramic, or a metal-
dental materials that are related either to clini- ceramic. Only if they know the physical and
cal manipulation by dentists and/or dental chemical properties of each of these materials
laboratory technicians, (3) to characterize the are they in a position to make such a judgment.
durability and aesthetics of dental restorations In addition to the mechanical requirements of
and prostheses made from the restorative mate- the materials, there are also certain aesthetic
rials, and (4) to identify characteristics of and physiologic requirements that often com-
materials that affect their biological safety. It is plicate the situation beyond the difficulties usu-
assumed that the reader possesses an introduc- ally experienced by the engineer.
tory knowledge of physics as well as inorganic Once the dentist has selected the type of
and/or organic chemistry. material to be used, a commercial product
The information in this book is intended to must be chosen. It is the intention of major
bridge the gap between the knowledge dental manufacturers to cooperate with den-
obtained in basic courses in materials science, tists in supplying them with materials of the
chemistry, physics, and the dental clinic. As pre- highest quality. The competition is keen, how-
viously noted, a dental technique does not ever, and the dentist should be able to evaluate
need to be an empirical process, but rather it the claims of the respective manufacturers from
can be based on sound scientific principles as an informed, intelligent perspective. It is unfor-
more information is available from further tunate that there are a few unprincipled dental
research. In any basic science, principles should manufacturers who make preposterous claims
be emphasized. The chapters that follow focus and who exploit the dentist for their own
more on why the materials react as they do and profit. For the dentists’ protection and for the
how the manipulation variables affect their protection of their patients, they must be able
performance in a dental laboratory or dental to recognize spurious practices of this sort.
clinic. Courses or lectures in dental materials attempt
 Preface xi

to provide dentists with certain criteria of ciples of the physical sciences and engineering
selection so as to enable them to discriminate and microstructure govern the properties of all
between fact and unproven claims. materials, it is logical to study the microstruc-
Furthermore, it is hoped that students of tural characteristics before proceeding to the
dental materials are given an appreciation of macrostructural features.
the broad scientific scope of their chosen pro- Following the overview of dental materials
fession. Because a great deal of the daily prac- (Chapter 1), Part I focuses on the structure and
tice of dentistry involves the selection and use properties of materials. This importance of
of dental materials for patient treatment proce- relating properties of a material to its atomic or
dures, it is obvious that the science of dental crystalline structure is emphasized in Chapter
materials is critically important. 2, which deals with the structure of matter and
The advances being made in dental materials certain principles of materials science that are
science suggest that intriguing changes will not usually included in a college physics
continue to occur in the practice of dentistry. course. These principles are in turn related to
Based on your knowledge of materials science the properties of dental materials, as discussed
principles, you should be prepared to analyze in Chapters 3 and 4. The requirements placed
the benefits and limitations of these dental on dental structures and materials are demand-
materials to make rational decisions on their ing and unique. To design prostheses appro-
selection and use in a clinical practice. priately, the dentist must be aware of the
Not all the materials used in dentistry are limitations of restorative materials and the
included in this book. For example, anesthetics, demanding conditions that exist in the oral
medicaments, and therapeutic agents such as cavity. These factors are also discussed in
fluoride varnish, xylitol, and chlorhexidine are Chapters 3 and 4. One should be increasingly
not within the scope of this book. The science aware of the difficulties involved in selecting a
of dental materials generally encompasses material that is technique insensitive, biocom-
some of the properties of natural oral tissues patible, and durable. These characteristics are
(enamel, dentin, cementum, pulp tissue, peri- emphasized in the discussions that follow on
odontal ligament, and bone) and the synthetic specific materials.
materials that are used for prevention and Following the chapters on the structure of
arrest of dental caries, for periodontal therapy, matter and the physical and mechanical prop-
and for reconstruction of missing, damaged, or erties of dental materials are overview chapters
unaesthetic oral structures. These categories dealing with metals and alloys, polymers, and
include materials employed in dental disci- ceramics, and the biocompatibility of dental
plines such as preventive dentistry, public materials.
health dentistry, operative dentistry, oral and The basic science of physical metallurgy is
maxillofacial surgery, orthodontics, periodon- concerned with the properties of metals and
tology, pediatric dentistry, and prosthodontics. alloys, whereas the study of metallography
involves the microstructure of metals that result
from their solidification (Chapter 5). The con-
Organization
stitution of alloys represents the equilibrium
The engineering curriculum of most major uni- phases that result in an alloy system as a func-
versities includes the discipline of materials sci- tion of temperature and composition (Chapter
ence. This is concerned with the microstructural 6). Chapter 7 focuses on dental polymers.
features of materials and with the dependence It is obvious from the earlier discussion of
of properties on these internal structures. The the regulatory agencies in dentistry, such as the
sequence of instruction generally progresses ADA Council on Scientific Affairs, the FDA,
from atomic to macroscopic structures, from the ISO and the FDI that the precursor to the
the simple to the more complex. Knowledge in marketing or selection of a dental material is
this field is derived from various disciplines, its biocompatibility with oral tissues. These
such as physical chemistry, solid-state physics, biological considerations are covered in
polymer science, ceramics, engineering mechan- Chapter 8 and are noted thereafter throughout
ics, and metallurgy. Because fundamental prin- the book.
xii Preface

Chapters 9 through 13 in Part II describe alloys (Chapter 19), wrought metals (Chapter
auxiliary materials and techniques that are used 20), dental ceramics (Chapter 21), denture base
to fabricate and finish the surfaces of dental resins (Chapter 22), and dental implants
restorations and prostheses. These materials (Chapter 23).
include impression materials (Chapter 9), gyp- Many branches of science are incorporated
sum products (Chapter 10), dental waxes in the information presented and various spe-
(Chapter 11), casting investments and proce- cialized branches of chemistry are applied.
dures (Chapter 12), and finishing and polish- Practically all of the engineering applied sci-
ing materials (Chapter 13). ences have contributed to the subject. There is
The chapters in Part III for direct restorative also an increasing awareness by the dentist that
materials include bonding (Chapter 14), the biological properties of dental materials
restorative resins (Chapter 15), dental cements cannot be divorced from their mechanical and
(Chapter 16), dental amalgams (Chapter 17), physical properties. Thus, interwoven through-
and direct filling gold (Chapter 18). out the book are discussions of the pertinent
Chapters in Part IV on indirect restorative biological characteristics to be considered in
materials include dental casting and soldering the selection and use of dental materials.
Kenneth J. Anusavice, PhD, DMD

ACKNOWLEDGMENTS
I express my appreciation to those who con-
The eleventh edition of Phillips’ Science of tributed to the tenth edition of this textbook,
Dental Materials, previously named Skinner’s but who were not contributors to the eleventh
Science of Dental Materials in the ninth and ear- edition. Several of the revised chapters may
lier editions, has undergone significant changes contain portions of the sections they created
that are consistent with the rapidly changing in the last edition. They include Charles
trends in the field of dental materials science F. DeFreest, Jack Ferracane, J. Rodway Mackert,
and the practice of dentistry. Increased empha- Jr., Miroslav Marek, Victoria A. Marker, Robert
sis has been placed on biocompatibility, Neiman, Karl-Johan Söderholm, and Harold R.
adhesion, dentin bonding principles, fluoride- Stanley. These individuals provided significant
releasing materials, resin-based composites, input to the tenth edition in which several sig-
ceramic-based prostheses, dental polymers, and nificant changes had been introduced to
dental implants. enhance readability and the clinical perspec-
Many individuals should be recognized both tives of dental biomaterials. In their quest to
for their contributions to the fields of dental promote evidence-based dentistry, they
materials science and to the revision of this blended basic science and applied research
textbook. Foremost is Chiayi Shen of our findings with manipulative variables to provide
Department of Dental Biomaterials at the improved balance between science and clinical
University of Florida. Dr. Shen has made signif- practice.
icant recommendations for modifying the for- Proofreading assistance was provided by my
mat of the eleventh edition by consolidating wife, Sandi, who has supported my academic
the 23 chapters into four main sections. He is pursuits in many ways. Her patience and under-
also one of the main contributors to Chapters 9 standing during the preparation of the eleventh
and 16. William Brantley also made significant edition were critically important to its timely
contributions to the revision of Chapters 3, 5, completion.
6, 19, and 20. New chapters were written by I also express my gratitude to those who
Ralph Rawls, John C. Wataha, Barry Norling, helped to shape my professional career. These
and Josephine Esquivel-Upshaw. Much of the individuals include Robert T. DeHoff, Professor
new artwork was created by José dos Santos, Jr. of Materials Science and Engineering at the
Other individuals who provided significant University of Florida, who guided my PhD
input include Michael Bagby, Wulf Brämer, training and enhanced my technical writing
Paul Cascone, Ivar Mjör, and Sam Sarma. skills, Robert Kinzer, a former Chairman of
 Preface xiii

Restorative Dentistry at the Medical College of support during my dental career has been pro-
Georgia, who encouraged me to pursue dental vided by the National Institute of Dental and
school training and who supported the devel- Craniofacial Research of the National Institutes
opment of my didactic and clinical teaching of Health. This support is greatly appreciated.
skills, and Carl W. Fairhurst, former Professor Finally, I would like to thank the staff at
of Restorative Dentistry at the Medical College Elsevier Inc. for their assistance in organizing
of Georgia, who provided opportunities to and expediting the activities related to publish-
advance my research skills. My research career ing the eleventh edition. These individuals
has advanced more rapidly because of their include Penny Rudolph, Kimberly Alvis, and
guidance and support. In addition, financial Courtney Sprehe.
Kenneth J. Anusavice, PhD, DMD
 1
Overview of Materials for Dental Applications
Kenneth J. Anusavice

OUTLINE
What Are Dental Materials?
Historical Use of Restorative Materials
Standards for Dental Materials
ADA Acceptance Program
General Provisions for ADA Acceptance
U.S. Food and Drug Administration Regulations
International Standards
ISO Standards, Subcommittees, and Working Groups
Other Dental Standards Organizations
How Safe Are Dental Restorative Materials?

KEY TERMS
Auxiliary dental—Substance that is used in the construction of a dental prosthesis but that
does not become a part of the structure.
Direct restorative material—A cement, metal, or resin-based composite that is placed and
formed intraorally to restore teeth or enhance aesthetics.
Indirect restorative material—A ceramic, metal, metal-ceramic, or resin-based composite
used extraorally to produce prostheses, which replace missing teeth, enhance aesthetics,
and/or restore damaged teeth.
Preventive dental material—Cement, coating, or restorative material that either seals pits and
fissures or that releases a therapeutic agent such as fluoride or chlorhexidine to prevent or
arrest the demineralization of tooth structure.
Restorative dental—Metallic, ceramic, metal-ceramic, or resin-based substance used to
replace, repair, or rebuild teeth, and/or to enhance aesthetics.
Temporary restorative material—Cement or resin-based composite used for a period of a few
days to several months to restore or replace missing teeth or tooth structure until a more
long-lasting prosthesis or restoration can be placed.

CRITICAL QUESTION
What are the differences among preventive, restorative, preventive/restorative, and auxil-
? iary dental materials used for the construction of a fixed partial denture (bridge)?

3
4 PART I ■ General Classes and Properties of Dental Materials

WHAT ARE DENTAL MATERIALS?

The overriding goal of dentistry is to maintain or improve the quality of life of the
dental patient. This goal can be accomplished by preventing disease, relieving pain,
improving mastication efficiency, enhancing speech, and improving appearance.
Because many of these objectives require the replacement or alteration of tooth struc-
ture, the main challenges for centuries have been the development and selection of
biocompatible, long-lasting, direct-filling tooth restoratives and indirectly processed
prosthetic materials that can withstand the adverse conditions of the oral environ-
ment. Figure 1-1 is a schematic cross-section of a natural tooth and supporting bone
and soft tissue. Under healthy conditions, the part of the tooth that extends out of
adjacent gingiva tissue is called the clinical crown, and that below the gingiva is called
the tooth root. The crown of a tooth is covered by enamel. The root is covered by
cementum, and it consists of dentin and tissue within one or more root canals.
Historically, a wide variety of materials have been used as tooth crown and root
replacements, including animal teeth, bone, human teeth, ivory, seashells, ceramics,
and metals. Restorative materials for the replacement of missing portions of tooth
structure have evolved more slowly over the past several centuries.
The four groups of materials used in dentistry today are metals, ceramics, poly-
mers, and composites. Despite recent improvements in the physical properties of
these materials, none of these are permanent. Dentists and materials scientists will
continue the search in the 21st century for the ideal restorative material. An ideal
restorative material would (1) be biocompatible, (2) bond permanently to tooth
structure or bone, (3) match the natural appearance of tooth structure and other vis-
ible tissues, (4) exhibit properties similar to those of tooth enamel, dentin, and
other tissues, and (5) be capable of initiating tissue repair or regeneration of miss-
ing or damaged tissues.

Enamel

Pulp Gingiva
chamber

Dentin
Periodontal
membrane
Cementum

Alveolar
bone

Spongy
bone Cortical
bone

Fig. 1-1 Schematic illustration of a cross-sectional view of a natural anterior tooth and supporting
tissues.
 CHAPTER 1 ■ Overview of Materials for Dental Applications 5

Dental materials may be classified as preventive materials, restorative materials, or

auxiliary materials. Preventive dental materials include pit and fissure sealants; seal-
ing agents that prevent leakage; materials that are used primarily for their antibacter-
ial effects; and liners, bases, cements and restorative materials that are used primarily
because they release fluoride (compomer, hybrid ionomer, glass ionomer cement,
zinc silicophosphate cement), chlorhexidine, or other therapeutic agents used to pre-
vent or inhibit the progression of tooth decay (dental caries). Table 1-1 summarizes
the types of preventive and restorative materials, their applications, and their poten-
tial durability. In some cases a preventive material may also serve as a restorative
material that may be used for a short-term application (up to several months), for
moderately long time periods (1 to 4 years), or for longer periods (5 years or more).
Dental restoratives that have little or no therapeutic benefit may also be used for
short-term (temporary) use, or they may be indicated for applications requiring
moderate durability or long-term durability. For example, restorative materials that
do not contain fluoride can be used for patients who are at a low risk for caries.
Restorative dental materials consist of all synthetic components that can be used
to repair or replace tooth structure, including primers, bonding agents, liners, cement
bases, amalgams, resin-based composites, compomers, hybrid ionomers, cast metals,
metal-ceramics, ceramics, and denture polymers. These materials can also be

Table 1-1 Comparative Applications and Durability of Preventive

and Restorative Dental Materials
Material type Applications of products Potential preventive benefit Durability

Resin adhesive A F (certain products) M

Resin sealant S S M
Resin cement L F (certain products) M
Compomer B, L, R F M
Hybrid ionomer B, L, R F M
Glass ionomer (GI) A, B, L, R, S F, S L, M
Metal-modified GI R F L, M
Zinc oxide–eugenol B, L, T L, M
Zinc phosphate B, L M
Zinc polycarboxylate B, L M
Zinc silicophosphate B, L F M
Resin composite R F (certain products) H
Dental amalgam R H
Ceramic R H
Metal/ceramic R H
Metal/resin R M, H
Acrylic resin (temporary use) T L
Denture acrylic R H
Cast metal R H
Wrought metal R H
Applications: A, Adhesive; B, base; L, luting agent; S, pit/fissure sealant; R, restorative; T, temporary restorative.
Potential preventive benefit: F, Fluoride-releasing material; S, sealing agent.
Durability: L, Low; M, moderate; H, high.
6 PART I ■ General Classes and Properties of Dental Materials

designed as controlled-delivery devices for release of therapeutic or diagnostic agents.

Restorative materials may be used for temporary, short-term purposes (such as tem-
porary cements and temporary crown and bridge resins), or for longer-term applica-
tions (dentin bonding agents, inlays, onlays, crowns, removable dentures, fixed
dentures, and orthodontic appliances). Restorative materials may further be classified
as direct restorative materials or indirect restorative materials, depending on
whether they are used (1) intraorally to fabricate restorations or prosthetic devices
directly on the teeth or tissues or (2) extraorally, in which the materials are formed
indirectly on casts or other replicas of the teeth and other tissues. Auxiliary dental
materials are substances that are used in the process of fabricating dental prostheses
and appliances but that do not become part of these devices. These include acid-
etching solutions, impression materials, casting investments, gypsum cast and model
materials, dental waxes, acrylic resins for impression and bleaching trays, acrylic
resins for mouth guards and occlusion aids, and finishing and polishing abrasives.
Temporary restorative materials are a subcategory of restorative materials and
include products used for dental restorations and appliances that are not intended for
moderate-term or long-term applications. Examples include temporary cements used
for luting, temporary cements, or other restoratives used for fillings, orthodontic wires,
and acrylic resins used for temporary inlays, onlays, crowns, and fixed partial dentures.

CRITICAL QUESTION
What technological advances led to the development of a more precise fit of indirectly
? made prostheses?

HISTORICAL USE OF RESTORATIVE MATERIALS

Dentistry as a specialty is believed to have begun about 3000 B.C. Gold bands and
wires were used by the Phoenicians (after 2500 B.C.). Around 700 B.C. the Etruscans
carved ivory or bone for the construction of partial denture teeth that were fastened
to natural teeth by means of gold wires or bands. The gold bands were used to posi-
tion extracted teeth in place of missing teeth.
Although inscriptions on Egyptian tombstones indicate that tooth doctors were
considered to be medical specialists, they are not known to have performed restora-
tive dentistry. However, some teeth found in Egyptian mummies were either trans-
planted human teeth or tooth forms made of ivory. The earliest documented
evidence of tooth implant materials is attributed to the Etruscans as early as 700 B.C.
Around 600 A.D. the Mayans used implants consisting of seashell segments that were
placed in anterior tooth sockets. Hammered gold inlays and stone or mineral inlays
were placed for aesthetic purposes or traditional ornamentation by the Mayans and
later by the Aztecs. The Incas performed tooth mutilations using hammered gold,
but the material was not placed for decorative purposes.
Cavities in teeth have been replaced or restored since ancient times to the eigh-
teenth century with a variety of materials including stone chips, ivory, human teeth,
turpentine resin, cork, gums, and metal foils (lead and tin). More recently, gutta per-
cha, cements, metal-modified cements, unfilled synthetic resin, composites, other
metals (gold leaf, amalgam, and a variety of cast metals and alloys), ceramics, and
metal-ceramics have been used for tooth restoration. Paré (1509–1590), surgeon to
four kings, used lead or cork for tooth fillings. Queen Elizabeth I (1533–1603) used
cloth fragments to fill the cavities in her teeth. Fauchard (1678–1761), the father of
modern dentistry, used tin foil or lead cylinders for filling tooth cavities. Wealthy
 CHAPTER 1 ■ Overview of Materials for Dental Applications 7

patients preferred to have teeth that were made of agate, mother of pearl, silver, or
gold. Modern dentistry began in 1728, when Fauchard published a treatise describ-
ing many types of dental restorations, including a method for the construction of
artificial dentures made from ivory.
Gold foil has also been employed for dental restorative purposes. Pfaff
(1715–1767), the dentist of Frederick the Great of Prussia, used gold foil to cap
the pulp chamber. Bull began producing beaten gold in Connecticut for dental
applications in 1812. Arculanus recommended gold-leaf dental fillings in 1848.
Sponge gold was introduced in 1853 in the United States and England to replace
gold leaf. In 1855 Arthur promoted the use of cohesive gold in the United States.
In 1897 Philbrook described the use of metal fillings made from wax patterns of
the tooth cavity.
Using filings from silver coins mixed with mercury, Taveau (1816) developed
in France what is likely the first dental amalgam. The Crawcour brothers, who
emigrated from France to the United States, introduced Taveau’s amalgam fillings
in 1833; however, graduates of the Baltimore Dental College subsequently took
an oath not to use amalgams in their practices. Many dentists criticized the poor
quality of the early amalgam restorations. This controversy led to the “amalgam
war” from 1840 to 1850, during which time heated debates occurred over the
benefits and drawbacks of dental amalgam. Research on amalgam formulations
from the 1860s through the 1890s greatly improved the handling properties and
the clinical performance of amalgam filling materials. In 1895 Black proposed
standardized cavity preparations and manufacturing processes for dental amal-
gam products.
Gold shell crowns were described by Mouton in 1746, but they were not patented
until 1873 by Beers. In 1885 Logan patented a porcelain fused to a platinum post,
replacing the unsatisfactory wooden posts previously used to build up intraradicu-
lar (within the tooth root) areas of teeth. In 1907 the detached-post crown was
introduced, which was more easily adjustable.
In 1756 Pfaff described a method for making impressions of the mouth in wax,
from which he constructed a model with plaster of Paris. Pfaff’s use of plaster of
Paris allowed dentists to make impressions of the patient’s edentulous jaws in the
mouth. Duchateau, a French pharmacist, and de Chemant, a dentist, designed a
process in 1774 for producing hard, decay-proof porcelain dentures. In 1789 de
Chemant patented an improved version of these “mineral paste” porcelain teeth.
The porcelain inlay was introduced soon thereafter in the early 1800s. However,
porcelain bonding to metals was not fully refined for metal-ceramic crowns until
the mid 1900s.
The dentures of George Washington (1732–1799) fit poorly, and he suffered ter-
ribly throughout his presidency (1789–1797). Washington never wore wooden
teeth as has been erroneously reported; he wore dentures made of some of his own
teeth, cows’ teeth or hippopotamus’ teeth, ivory, or lead. Prior to his first term as
president, he had worn partial dentures that were fastened to his remaining teeth.
During the inauguration for his first term as president in 1789, Washington had
only one natural tooth remaining and he wore his first full set of dentures made by
John Greenwood. The base of these dentures was made of hippopotamus ivory
carved to fit the jaw ridges. The upper denture contained ivory teeth, and the lower
denture consisted of eight human teeth fastened by gold rivets that screwed into the
denture base. The two dentures were secured in his mouth by spiral springs.
In 1808 Fonzi, an Italian dentist, developed an individual porcelain tooth form
that was held in place with an embedded platinum pin. Planteau, a French dentist,
first introduced porcelain teeth in the United States in 1817. In 1822 Charles Peale,
8 PART I ■ General Classes and Properties of Dental Materials

an artist, fired mineral teeth in Philadelphia, and Samuel Stockton began the
commercial production of porcelain teeth soon thereafter in 1825. Ash further
developed an improved porcelain tooth in England around 1837.
Evans (1836) refined the method of making accurate measurements in the
mouth. However, it was not until 1839 that Charles Goodyear’s invention of a low-
cost vulcanized rubber allowed dentures to be molded accurately and to fit the
mouth. Vulcanized rubber denture bases that held denture teeth accelerated the
demand for accurately fitting dentures at a reasonably low cost. Since 1839 denture
bases have advanced in quality through the use of acrylic resins and cast metals. In
1935 polymerized acrylic resin was introduced as a denture base material to support
artificial teeth.
Up to this point, we have focused primarily on the historical evolution of direct
filling materials and some rather crude indirect materials. Prior to the 20th century,
because of inadequate technology and lack of electricity, fillings were of rather poor
quality and did not fit well within the teeth. However, in 1907 Taggert developed a
more refined method for producing cast inlays. Cast alloys were introduced later in
the 20th century, further developing this technology. Commercially pure titanium
(CP Ti), noble alloys, and base metal alloys of nickel-chromium, cobalt-chromium,
or cobalt-nickel-chromium are now available for use in the production of cast
inlays, onlays, crowns, and frameworks for fixed all-metal or metal-ceramic dentures
and for removable dentures. Few major improvements in the construction of fixed
partial dentures (bridges) occurred until the early 1900s. Mason developed a detach-
able facing to a crown to hold an artificial tooth in place for an adjacent missing
tooth. Thomas Steele (1904), a colleague of Mason, introduced interchangeable fac-
ings that solved the problem of fractured facings.
Even though the practice of dentistry antedates the Christian era, comparatively
little historical data exist on the science of dental materials. The use of fluoride to
prevent tooth demineralization originated from observations in 1915 of low decay
rates of people in areas of Colorado whose water supplies contained significant flu-
oride concentrations. Controlled water fluoridation (1 ppm) to reduce tooth decay
(demineralization) began in 1944, and the incidence of tooth decay in children
who have had access to fluoridated water has decreased by 50% since then. The use
of pit and fissure sealants and fluoride-releasing varnishes and restorative materials
has reduced the caries incidence even further.
Little scientific information about dental restorative materials has been available
until recently. Prior to this knowledge, the use of these materials was entirely an art,
and the only testing laboratory was the mouth of the patient. Today, despite the
availability of sophisticated technical equipment and the development of standard-
ized testing methods for evaluating the biocompatibility of preventive and restora-
tive materials, this testing sometimes still occurs in the mouths of our patients. The
reasons for this situation are diverse. In some instances, products are approved for
human use without being tested in animal or human subjects. In other instances,
dentists use materials for purposes that were not indicated by the manufacturer; for
example, a ceramic product may be used for posterior fixed partial dentures (FPDs)
when the product has been recommended only for inlays, onlays, crowns, and ante-
rior three-unit FPDs.
The first important awakening of scientific interest occurred during the middle of
the 19th century, when research studies on amalgam began. At about the same time,
some reports appeared in the literature of studies on porcelain and gold foil. These
sporadic advances in knowledge finally culminated in the investigations of
G.V. Black, who began his research studies in 1895. Hardly a phase of dentistry
exists that was not explored and advanced by this pioneer in restorative dentistry.
 CHAPTER 1 ■ Overview of Materials for Dental Applications 9

STANDARDS FOR DENTAL MATERIALS

The next great advance in the knowledge of dental materials and their manipulation
began in 1919. During that year the U.S. Army requested the National Bureau of
Standards (now known as the National Institute of Standards and Technology [NIST])
to set up specifications for the evaluation and selection of dental amalgams for use
in federal service. This research was done under the leadership of Wilmer Souder,
and an excellent report on this study was published in 1920.
The information contained in the Souder report was received enthusiastically by
the dental profession, and similar testing data were then requested for other dental
materials. At that time, the U.S. government could not allocate sufficient funds to
continue the work, so a fellowship was created and supported by the Weinstein
Research Laboratories. Under such an arrangement, the sponsor provided money for
the salaries of research associates and a certain amount of equipment and supplies.
The associates then worked in the National Bureau of Standards under the direction
of the staff members. For all practical purposes, these associates were members of
the staff supported by private interests. All findings were published and became
common property under this particular arrangement. Working under Dr. Souder’s
direction, several research associates investigated the properties of dental wrought
gold materials, casting gold alloys, and accessory casting materials. This phase of the
work resulted in the publication of an extensive and valuable research report.
In 1928, the Dental Research Fellowship at the National Bureau of Standards was
assumed by the American Dental Association (ADA). The research carried out by the
ADA research associates in conjunction with the staff members of NIST has been of
inestimable value to the dental profession, and it has earned for this group an inter-
national reputation. Researchers such as Wilmer Souder, George C. Paffenbarger,
and William T. Sweeney will undoubtedly be remembered historically as the pio-
neers whose work began a new era of intense research in the field of dental materi-
als. It was the enthusiasm of these men that prompted the organization of the first
academic courses in dental materials to be taught in U.S. dental schools and abroad.

CRITICAL QUESTION
What is the primary purpose of specifications and standards for dental materials?
?
ADA ACCEPTANCE PROGRAM
The work at the American Dental Association (ADA) is divided into a number of cat-
egories, including the measurement of the clinically significant physical and chem-
ical properties of dental materials and the development of new materials,
instruments, and test methods. Until 1965, one of the primary objectives of the
facility at NIST was to formulate standards or specifications for dental materials.
However, when the ADA Council on Dental Materials and Devices (now known as
the Council on Scientific Affairs) was established in 1966, it assumed responsibility
for standards development and initiated the certification of products that meet the
requirements of these specifications.
Such specifications are standards by which the quality and properties of particu-
lar dental materials can be gauged. These standards identify the requirements for the
physical and chemical properties of a material that ensure satisfactory performance
if the material is properly manipulated and used by the dental laboratory technician
10 PART I ■ General Classes and Properties of Dental Materials

and the dentist. The Acceptance Program of the Council on Scientific Affairs incor-
porates these specifications in the evaluation of dental products, and the products
are tested for compliance with specification requirements. When a product is classi-
fied as Accepted, the manufacturer is permitted to signify on the label of the product
the notation “ADA Accepted.”
The ADA, accredited by the American National Standards Institute (ANSI), is also
the administrative sponsor of two standards-formulating committees operating under
the direction of ANSI. The ADA Standards Committee for Dental Products (SCDP)
develops specifications for all dental materials, instruments, and equipment, with the
exception of drugs and x-ray films. The Council on Scientific Affairs (CSA) is also
responsible for the evaluation of drugs, tooth-cleaning and tooth-whitening agents,
therapeutic agents used in dentistry, dental equipment, and dental x-ray film.
Working groups of ADA SCDP formulate the specifications. When a specification
has been approved by the ADA SCDP and the ADA CSA, it is submitted to the
American National Standards Institute. On acceptance by that body, it becomes an
American National Standard. Thus the Council on Scientific Affairs also has the
opportunity of accepting it as an ADA specification.
New specifications are continually being developed to apply to new program
areas. Likewise, existing specifications are periodically revised to reflect changes in
product formulations and new knowledge about the behavior of materials in the
oral cavity, for example, the ANSI/ADA Specification No. 1 for dental amalgam,
which was revised in January 2003.

The ADA Seal of Acceptance

Dentists and consumers of dental products have long recognized the ADA Seal of
Acceptance as an important symbol of a dental product’s safety and effectiveness.
For more than 125 years, the ADA has sought to promote the safety and effective-
ness of dental products. The first Seal of Acceptance was awarded in 1931. Although
this program is strictly voluntary, over 400 companies participate in the Seal pro-
gram. Manufacturers commit significant resources to evaluate, test, and market
products in the Seal program. Approximately 1250 dental products carry the Seal of
Acceptance. Of these, about 60% are products prescribed or used by dentists, such
as antibiotics or dental restorative materials. The remaining 40% are dental prod-
ucts sold to consumers, such as toothpaste, dental floss, manual and electric tooth-
brushes, and mouth rinses.

Classification of Products Evaluated by the ADA Council on

Scientific Affairs
Products that meet the standards of acceptance with respect to safety, efficacy, com-
position and labeling, package inserts, advertising, and other promotional material
are accepted. Once accepted, the products are listed and may be described in suitable
reports and advertisements in The Journal of the American Dental Association. The man-
ufacturer may then use the Council’s Seal of Acceptance and may be required to use
an authorized statement if the ADA Seal is used in the advertisement. Products are
usually accepted for a period of up to 5 years. Acceptance is renewable and may
be reconsidered at any time. If there is a change in the manufacturer or distributor of
a product, the period of acceptance expires automatically. Provisionally accepted prod-
ucts consist of those that lack sufficient evidence to justify classification as accepted,
but for which there is reasonable evidence of safety and usefulness, including clinical
feasibility. These products meet the other qualifications established by the Council.
 CHAPTER 1 ■ Overview of Materials for Dental Applications 11

The Council may authorize the use of a suitable statement to define specifically the
area of usefulness of products classified as provisionally accepted. Classification in this
category is reviewed each year and is not ordinarily continued for more than 3 years.
Products that are obsolete, markedly inferior, ineffective, or dangerous to the health
of the user are declared unaccepted. When it is in the best interest of the public or the
profession, the Council may submit reports on unaccepted products to the editor for
publication in The Journal of the American Dental Association. Decisions of the Council
are based on available scientific evidence and are subject to reconsideration at any
time that a significant amount of new evidence becomes available.

CRITICAL QUESTION
Can a manufacturer alter the composition of an ADA-accepted product and maintain the
? ADA Seal of Acceptance?

GENERAL PROVISIONS FOR ADA ACCEPTANCE

Composition, Nature, and Function
A quantitative statement of composition and adequate information on the proper-
ties of all ingredients must be provided to the Council. For instruments and equip-
ment, a description of the materials used in the construction and the method of
operation must be provided. Any change in the composition, nature, or function of
an accepted product must be submitted to the Council for review and approval
before a modified product is marketed.
The company that seeks ADA acceptance should provide evidence that manufac-
turing and laboratory control facilities are under the supervision of qualified per-
sonnel, that these facilities are adequate to ensure purity and uniformity of
products, and that products are produced in compliance with the Good
Manufacturing Practice Code. The company must permit representatives of the
Council to visit laboratories and factories on request. For products whose guidelines
include an official American Dental Association Specification, the manufacturer
must conduct testing on a regular basis to determine continued compliance with the
specification; these test records must be made available to the Council on request.
In addition the manufacturer must make available to the Council on request test
records and data for any batch of an accepted product.

Required Information
The product must conform to appropriate standards or specifications. For products
that fall under the scope of official American Dental Association Specifications, the
following information should be submitted: (1) the serial or lot number; (2) the
composition; (3) the physical properties, as obtained by standard test methods; and
(4) data covering every provision of the official specification. Responsibility for
guaranteeing that the product complies with an official specification lies solely with
the manufacturer and not with the American Dental Association.
The Council, at any time and without notice to the manufacturer, may authorize
the testing of any or all such products. In the event that a sample fails the testing,
the product will be removed from the List of Accepted Products. Test samples are
procured at the expense of the manufacturer. If a product is removed from the List
of Accepted Products, it may subsequently be resubmitted provided that the prod-
uct that failed the testing has been removed from the market.
12 PART I ■ General Classes and Properties of Dental Materials

Names that are misleading or that suggest diseases or symptoms are not accept-
able. This provision may not apply to certain biological products such as serums
or vaccines. Because the uses of a product may change, the product name should
indicate the generic type of material or its composition rather than a proposed use
for the product. However, under certain circumstances the Council may accept a
name that denotes a long-established physiological action or use, particularly for
a mixture.
Evidence pertaining to mechanical and physical properties, operating character-
istics (when applicable), actions, dosage, safety, and efficacy must be submitted by
the company. Information on acceptable standard test methods for physical prop-
erties may be secured by request to the Council on Scientific Affairs. In general, the
data required on physical tests must include a brief description of the apparatus
used in performing the tests, a complete statement of the results obtained, the
names of the observers, and the date of the test.
The company must provide objective data from properly designed clinical and
laboratory studies. Extended clinical experience may be used, in part, as a basis for
evaluation of a product. Products that fall under the scope of an official American
Dental Association Specification will be tested for compliance with the specification
by the American Dental Association. Test samples, unless otherwise indicated in the
appropriate specification, may be procured on the open market at the expense of
the manufacturer.
The company must disclose any past, present, or anticipated financial arrange-
ments between the clinical investigator and the company, its affiliates, or sub-
sidiaries, including, but not limited to, consulting agreements, speakers’ fees,
grants or contracts to conduct research, or membership on the company’s advi-
sory committees. If the Council determines that the financial interests raise a
question about the integrity of the data, the Council may take any action it deems
necessary to ensure the reliability of the data, including, but not limited to the
following:
■ Requesting that the company submit further analyses of the data
■ Requesting that the company conduct additional independent studies
■ Rejecting the data

Information Required for Renewal of Acceptance

For renewal of acceptance the manufacturer may be required to submit evidence
demonstrating continued acceptable clinical performance of the product. This evi-
dence may be in the form of new clinical studies, reports of adverse reactions or fol-
low-up investigations of previously submitted clinical studies.
The Council may occasionally find it necessary to review the status of a product’s
acceptance. Decisions of the Council are based on available scientific evidence and
are subject to reconsideration at any time. If a significant amount of new scientific
evidence demonstrates that a product is no longer safe or effective, or if a product is
deemed obsolete, markedly inferior, or dangerous to the health of the user, Council
acceptance will be withdrawn.

CRITICAL QUESTIONS
What are the differences among FDA Class I, Class II, and Class III devices? Which class of
? regulations does a dental implant need to satisfy?
 CHAPTER 1 ■ Overview of Materials for Dental Applications 13

U.S. FOOD AND DRUG ADMINISTRATION REGULATIONS

On May 28, 1976, legislation was signed into law that gave the U.S. Food and Drug
Administration (FDA) the regulatory authority to protect the public from hazardous
or ineffective medical (and dental) devices. This legislation was the culmination of
a series of attempts to provide safe and effective products, beginning with the
passage of the Food and Drug Act of 1906, which did not include any provision to
regulate medical device safety or the claims made for devices.
The newer legislation, named the Medical Device Amendments of 1976, requires
the classification and regulation of all noncustomized medical devices that are
intended for human use. According to the Federal Register, the term device includes any
instrument, apparatus, implement, machine, contrivance, implant, or in vitro reagent
that is used in the diagnosis, cure, mitigation, treatment, or prevention of disease in
man and that does not achieve any of its principal intended purposes through chemi-
cal action within or on the body of humans or animals and that is not dependent on
being metabolized for the achievement of any of its principal intended purposes.
Some dental products, such as those containing fluoride, are considered drugs,
but most products used in the dental clinic are considered to be devices, and thus
they are subject to control by the FDA Center for Devices and Radiological Health.
Also subject to this control are over-the-counter products sold to the public, such as
toothbrushes, dental floss, and denture adhesives.
The classification of all medical and dental items is developed by panels com-
posed of nongovernmental dental experts, as well as representatives from industry
and consumer groups. The Dental Products Panel identifies any known hazards or
problems associated with a device and then categorizes the item into one of three
classification groups based on relative risk factors. Class I devices are considered to
be of low risk, and they are subject to general controls, including the registration of
the manufacturer’s products, adherence to good manufacturing practices, and certain
record-keeping requirements. If it is deemed that such general controls are not in
themselves adequate to ensure safety and effectiveness as claimed by the manufac-
turer, the item is placed into the category of Class II devices. Products in this class are
required to meet performance standards established by the FDA or appropriate stan-
dards from other authoritative bodies, such as those of the ADA. These performance
standards may relate to components, construction, and properties of a device, and
they may also indicate specific testing requirements to ensure that lots or individual
products conform to the regulatory requirement.
Class III, the most stringent category, requires that devices be approved for safety
and effectiveness before they are marketed. All implanted or life-supporting devices
are placed in this premarket clearance category. Specific data must be provided to
demonstrate safety and efficacy before marketing. In certain instances, the product
or device may be substantially equivalent to other approved products, and under
these circumstances, only the demonstration of equivalence is necessary. Any item
that does not have adequate clinical or scientific information available to permit the
formulation of a performance standard is placed in the premarket approval category.
For example, one of these devices, the endosseous implant for prosthetic attach-
ment, is considered a high priority relative to the need for adequate data to demon-
strate safety and effectiveness. Manufacturers of this device need to submit
premarket approval applications for their implants. These are then evaluated by the
Dental Products Panel to determine whether new implants can be marketed.
Guidelines that have been developed by the FDA are available to all interested par-
ties to provide the preclinical and clinical requirements for the preparation of a pre-
market approval application.
14 PART I ■ General Classes and Properties of Dental Materials

Several hundred dental items have been classified into one of these three cate-
gories. The FDA program, in conjunction with the ADA Acceptance Program for
dental products, provides a crucial framework for standards development and pro-
vides initial evidence that the product will be safe and effective as claimed. Other
countries have national government agencies comparable to the FDA that also
include dental materials and devices within the jurisdiction of their regulatory
authority.

INTERNATIONAL STANDARDS
Two organizations, the Fédération Dentaire Internationale (FDI) and the
International Organization for Standardization (ISO), are working toward the estab-
lishment of specifications for dental materials on an international level. Originally,
the FDI initiated and actively supported a program for the formulation of interna-
tional specifications for dental materials. As a result of that activity, several specifi-
cations for dental materials and devices have been adopted.
The ISO is an international, nongovernmental organization whose objective is
the development of international standards. This body is composed of national
standards organizations from more than 80 countries. The American National
Standards Institute is the U.S. member. A request by the FDI to the ISO that they
consider FDI specifications for dental materials as ISO standards led to the for-
mation of an ISO technical committee (TC), TC 106–Dentistry. The responsibility
of this committee is to standardize terminology and test methods and to develop
standards (specifications) for dental materials, instruments, appliances, and
equipment. Additional information on ISO standards is provided in the following
section.
Several FDI specifications have now been adopted as ISO standards. Since 1963,
more than 100 new standards have been developed or are currently under develop-
ment in ISO TC 106 through cooperative programs with the FDI. Thus considerable
progress has already been realized in achieving the ultimate goal of a broad range
of international specifications for dental materials and devices.
The benefit of such specifications to the dental profession has been invaluable,
considering the worldwide supply and demand for dental materials, instruments,
and devices. Dentists are provided with criteria for selection that are impartial and
reliable. In other words, if dentists use primarily those materials that meet the
appropriate specifications, they can be confident that the materials will be satisfac-
tory. Probably no other single factor has contributed as much to the high level of
dental practice as has this specification program. Awareness by dental laboratory
technicians and dentists of the requirements of these specifications is essential in
recognizing the limitations of the dental materials with which they are working. As
is discussed frequently in the chapters to follow, no dental material is perfect in its
restorative role, just as no artificial arm or leg can serve as well as the original body
member that it replaces.
Research on dental materials supervised by the ADA Council on Scientific Affairs
or other national standard organizations is of vital concern in this textbook on den-
tal materials. The ADA specifications for dental materials are referred to throughout
the following chapters, although specific details regarding the test methods
employed are omitted. For those products sold in other countries, the counterpart
ISO standards, if applicable, should be used as a reference source. It is assumed for
the discussions in this textbook that the student has access to a collection of speci-
fications and Acceptance Program guidelines of the ADA or other national or inter-
national standards.
 CHAPTER 1 ■ Overview of Materials for Dental Applications 15

CRITICAL QUESTION
Of the seven ISO TC 106 subcommittees and 52 working groups, which ones are responsi-
? ble for direct and indirect restorative materials?

ISO STANDARDS, SUBCOMMITTEES, AND WORKING GROUPS

ISO Technical Committee 106
In 2002 the Internal Organization for Standardization had 224 TCs to develop
standards for testing the safety and efficacy of dental products. Of these TCs, TC
106 is the committee responsible for dental standards, terminology used in stan-
dards, methods of testing, and specifications applicable to materials, instruments,
appliances and equipment used in all branches of dentistry. A total number of 134
ISO dental standards have been published related to the TC and its subcommit-
tees (SCs) and working groups (WGs). In 2002 representatives from 25 member
countries and 20 observer countries were involved. There are seven subcommittees
for ISO standards involving dental products. The following subcommittees cover
all the dental products included in the ISO standards program under the direction
of TC 106.

TC 106/SC1: Filling and Restorative Materials. The following 10 working groups

are included: WG1—Zinc oxide–eugenol cements and noneugenol cements; WG2—
Endodontic materials; WG5—Pit and fissure sealants; WG7—Amalgam/mercury;
WG9—Resin-based filling materials; WG10—Dental luting cements, bases, and lin-
ers; WG11—Adhesion test methods; WG12—Resin-based cements; WG13—
Orthodontic products; and WG14—Orthodontic elastics.

TC 106/SC2: Prosthodontic Materials. The following 17 working groups develop

standards for prosthodontic materials: WG1—Dental ceramics; WG2—Dental base
metal alloys; WG6—Color stability test methods; WG7—Impression materials;
WG8—Noble metal casting alloys; WG9—Synthetic polymer teeth; WG10—
Resilient lining materials; WG11—Denture base polymers; WG12—Corrosion test
methods; WG13—Investments; WG14—Dental brazing materials; WG16—Polymer
veneering and die materials; WG17—Ceramic denture teeth; WG18—Dental waxes
and baseplate waxes; WG19—Wear test methods; WG20—Artificial teeth; and
WG21—Metallic materials.

TC 106/SC3: Terminology. There are four working groups in SC3: WG1—

Harmonization of dental codes and abbreviations; WG2—Dental vocabulary (Revision
of ISO 1942 and thematic coding of its terms); WG3—Communication and commu-
nications; and WG4—Definition of new terms related to the needs of dental standards.

TC 106/SC4: Dental Instruments. The following six working groups are included
in SC4: WG1—Dimensions of rotary instruments; WG5—Numbering system;
WG7—Dental handpieces; WG8—Dental hand instruments; WG9—Root-canal
instruments; and WG10—Dental injection systems.

TC 106/SC6: Dental Equipment. There are six working groups in SC6: WG1—
Dental operating light; WG2—Dental patient chair and dental unit; WG3—Dental
operator’s stool; WG5—Amalgamators, dispensers and capsules; WG7—Powered
polymerization activators; and WG8—Suction equipment.
16 PART I ■ General Classes and Properties of Dental Materials

TC 106/SC7: Oral Hygiene Products. The following four working groups are
included in SC7: WG1—Manual toothbrushes; WG2—Powered oral hygiene
devices; WG3—Auxiliary oral hygiene products; and WG4—Toothpastes.

TC 106/SC8: Dental Implants. The five working groups in SC8 are as follows:
WG1—Implantable materials; WG2—Preclinical biological evaluation and testing;
WG3—Content of technical files; WG4—Mechanical testing; and WG5—Dental
implants—Terminology.

How Are ISO Standards Developed?

Manufacturers, dental vendors, users, consumer groups, testing laboratories, gov-
ernments, the dental profession, and research organizations provide input informa-
tion and requirements for the development of standards. International
standardization is market-driven and is based on voluntary involvement of all inter-
ests in the marketplace.
The need for a standard is usually expressed by an industry sector, which com-
municates this need to a national member body. The latter proposes the new work
item to the ISO as a whole. Once the need for an International Standard has been
established, the first phase involves definition of the technical scope of the future
standard. This phase is usually carried out by working groups, which comprise tech-
nical experts from countries interested in the subject. Once agreement has been
reached on which technical aspects are to be covered in the standard, a second phase
is entered, during which countries determine the detailed specifications within the
standard. The final phase constitutes the formal approval of the resulting draft
International Standard, by 75% of all voting members, following which the agreed
text is published as an ISO International Standard.
Most standards require periodic revision because of technological evolution, new
methods and materials, new quality tests, and new safety requirements. To account
for these factors, all ISO standards should be reviewed at intervals of not more than
5 years. On occasion, it is necessary to revise a standard earlier.

OTHER DENTAL STANDARDS ORGANIZATIONS

The work at the National Institute of Standards and Technology in Gaithersburg,
Maryland, has stimulated comparable programs in other countries. The Australian
Dental Standards Laboratory was established in 1936 (until 1973 this facility was
known as the Commonwealth Bureau of Dental Standards). H.K. Worner and
A.R. Docking, the first two directors, are recognized for their leadership in the devel-
opment of the Australian specifications for dental materials. Other countries that
have comparable organizations for developing standards and certifying products are
Canada, Japan, France, Czech Republic, Germany, Hungary, Israel, India, Poland,
and South Africa. Also, by agreement among the governments of Denmark, Finland,
Iceland, Norway, and Sweden, the Scandinavian Institute of Dental Materials, better
known as NIOM (Nordisk Institutt for Odontologisk Materialprøvning), was estab-
lished in 1969 for testing, certification, and research regarding dental materials and
equipment to be used in the five countries. NIOM became operational in 1973.
Also in Europe, the Comité Européen de Normalisation (CEN) established Task
Group 55 to develop European standards. After the establishment of the European
Economic Community, the CEN was given the charge to outline recommendations
of standards for medical devices, including dental materials. In fact, the proper term
to describe dental materials, dental implants, dental instruments, and dental equipment
 CHAPTER 1 ■ Overview of Materials for Dental Applications 17

in Europe is medical devices used in dentistry. The CE marking on product labels

denotes the European mark of conformity with the Essential Requirements in the
Medical Device Directive that became effective on January 1, 1995. All medical
devices marketed in the European Union countries must have the CE mark of con-
formity. For certain products, some countries may enforce their own standards when
other countries or the international community have not developed mutually
acceptable requirements. For example, Sweden restricts the use of nickel in cast den-
tal alloys because of biocompatibility concerns, whereas no such restriction applies
to those alloys in the United States. Iceland, Liechtenstein, and Norway are also sig-
natories of the European Economic Area Agreement and require the CE marking
and NIOM’s Notified Body registration number on medical device packaging.
An increasing number of universities in the United States and abroad have estab-
lished laboratories for research in dental materials. In the past few years, this source
of basic information on the subject has exceeded that of all other sources combined.
Until recently, dental research activities in universities were centered solely in den-
tal schools, with most of the investigations being conducted by the dental faculty.
Now, however, research in dental materials is also being conducted in some univer-
sities that do not have dental schools. This dental-oriented research in areas such as
metallurgy, polymer science, materials science, engineering, and ceramics is being
conducted in basic science departments. These expanding fields of research in den-
tal materials illustrate the interdisciplinary aspects of the science. Since the final cri-
terion for the success of any material or technique is its service in the mouth of the
patient, countless contributions to this field have been made by dental clinicians.
The observant clinician contributes invaluable information by his or her keen obser-
vations and analyses of failures and successes. Accurate record keeping and well-
controlled practice procedures form an excellent basis for valuable clinical research.
The importance of clinical documentation for claims made relative to the in vivo
performance of dental materials is now readily apparent. For example, the
Acceptance Program of the Council on Scientific Affairs requires clinical data, when-
ever appropriate, to support the laboratory tests for physical properties. During the
past two decades there has been an escalation in the number of clinical investigations
designed to correlate specific properties with clinical performance criteria. These
studies are designed to establish the precise behavior of a given material or system.
In the chapters that follow, frequent reference is made to such investigations.
Another source of information is derived from manufacturers’ research laborato-
ries. The far-sighted manufacturer recognizes the value of a research laboratory rel-
ative to the development and production control of products, and unbiased
information from such groups is particularly valuable. During the writing of this
textbook, as with the previous edition, the counsel of scientists from dental and
nondental industries was called upon. In this way the product formulations
described in the succeeding chapters reflect with greater accuracy the commercial
materials used by the dentist.
This diversity of research activity is resulting in an accelerating growth in the body
of knowledge related to dental materials. For example, in 1978 approximately 10%
of all U.S. support for dental research was focused on restorative dental materials.
The percentage would no doubt be considerably higher if the money spent by indus-
try for the development of new materials, instruments, and appliances were
included. This growing investigative effort is resulting in a marked increase in the
number of new materials, instruments, and techniques being introduced to the pro-
fession. For these and other reasons, an intimate knowledge of the properties and
behavior of dental materials is imperative if the modern dental practice is to remain
abreast of changing developments.
18 PART I ■ General Classes and Properties of Dental Materials

CRITICAL QUESTION
How is it possible for dental materials that have not been accepted by the American
? Dental Association to be sold to dentists and consumers?

HOW SAFE ARE DENTAL RESTORATIVE MATERIALS?

Specifications and standards have been developed to aid producers, users, and con-
sumers in the evaluation of the safety and effectiveness of dental products. However,
the decision of producers to test their materials according to national and interna-
tional standards is purely voluntary. The existence of materials evaluation standards
does not preclude anyone from manufacturing, marketing, buying, or using dental
or medical devices that do not meet these standards. However, producers or mar-
keters of products and devices are expected to meet the safety standards established
for those products in the countries in which they are sold. Thus it is possible for a
producer to be given premarket approval by the FDA to sell a dental device such as
a dental restorative material without the device being approved by the ADA in accor-
dance with the specification or Acceptance Program requirements. Nevertheless,
these agencies are becoming increasingly dependent on one another to ensure that
all products marketed world-wide are safe and effective.
No dental device (including restorative materials) is absolutely safe. Safety is rela-
tive, and the selection and use of dental devices or materials are based on the assump-
tion that the benefits of such use far outweigh the known biological risks. However,
there is always uncertainty over the probability that a patient will experience adverse
effects from dental treatment. The two main biological effects are allergic and toxic
reactions. Paracelsus (1493–1541), a Swiss physician and alchemist, formulated revo-
lutionary principles that have remained an integral part of the current field of toxicol-
ogy. He stated that “all substances are poisons; there is none which is not a poison. The
right dose differentiates a poison from a remedy.” (Gallo and Doull, 1991.)
The major routes by which toxic agents enter the body are through the gastroin-
testinal tract (ingestion), lungs (inhalation), skin (topical, percutaneous, or dermal)
and parenteral routes (Klaassen and Eaton, 1991). Exposure to toxic agents can be sub-
divided into acute (less than 24 hr), subacute (repeated, 1 month or less), subchronic
(1 to 3 months), and chronic (longer than 3 months). For many toxic agents, the effects
of a single exposure are different from those associated with repeated exposures.
Like toxicity, chemical allergy may also be dose-dependent, but it often results from
low doses of chemical agents once sensitization has occurred. For a dental restorative
material to produce an allergic reaction, most chemical agents or their metabolic prod-
ucts function immunologically as haptens and combine with endogenous proteins to
form an antigen. The synthesis of sufficient numbers of antibodies takes 1 to 2 weeks.
A later exposure to the chemical agent can induce an antigen-antibody reaction and
clinical signs and symptoms of an allergy. Munksgaard (1992) concluded that occupa-
tional risks in dentistry are low and that patient risk for side effects of dental treatment
is extremely low. Adverse reactions to dental materials have been reported to occur in
only 0.14% of a general patient population (Kallus and Mjör, 1991) and in 0.33% of
a prosthetic patient population (Hensten-Pettersen and Jacobsen, 1991).

Acknowledgment
The author expresses appreciation to Dr. Wayne Wozniak and Dr. Sharon Stanford
of the American Dental Association for their helpful suggestions.
 CHAPTER 1 ■ Overview of Materials for Dental Applications 19

SELECTED READINGS
American Dental Association Seal Program, ADA website: Hensten-Pettersen A, and Jacobsen N: Perceived side effects
http://www.ada.org/public/topics/seal.html of biomaterials in prosthetic dentistry. J Prosthet Dent
Coleman RL: Physical Properties of Dental Materials. 65:138, 1991.
National Bureau of Standards Research Paper No. 32. International Organization for Standardization (ISO) web-
Washington, DC, US Government Printing Office, 1928. site: http://www.iso.org
This publication is the first major effort to relate physical prop- International Organization for Standardization (ISO)
erties of dental materials to the clinical situation. The American TC 106–Dentistry website: http://www.iso.org/iso/en/
Dental Association specification program was established based stdsdevelopment/techprog/workprog/TechnicalProgrammeTC
on this historical review of the philosophy and the content of the DetailPage.TechnicalProgrammeTCDetail?COMMID=2916
facility created at the National Bureau of Standards. Kallus T, and Mjör IA: Incidence of adverse effects of dental
Federal Register: Medical Devices; Dental Device materials. Scand J Dent Res 99:236, 1991.
Classification; Final Rule and Withdrawal of Proposed Klaassen CD, and Eaton DL: Principles of toxicology. In:
Rules. August 12, 1987, p 30082. Casarett and Doull’s Toxicology. New York, Pergamon
A listing of the dental materials and devices classified in Press, 1991, pp 12–49.
Category III by the Food and Drug Administration as of that Munksgaard EC: Toxicology versus allergy in restorative
date. dentistry. In: Advances in Dental Research. Bethesda,
Food and Drug Administration (FDA) website: http://www. International Association for Dental Research, Sept
fda.gov 1992, pp 17–21.
FDA Center for Devices and Radiological Health, website: Phillips RW: Changing trends of dental restorative materi-
http://www.fda.gov/cdrh/consumer/c-products.shtml als. Dent Clin North Am 33(2):285, 1989.
Gallo MA, and Doull J: History and scope of toxicology. In: A review of the trends in biomaterials that are influencing
Casarett and Doull’s Toxicology. New York, Pergamon dental restorative procedures, particularly in aesthetic dentistry.
Press, 1991, pp 3–11. Emphasis is on bonding technology and its application.

ADDITIONAL READINGS ON DENTAL HISTORY

American Dental Association: 125th anniversary commem- Guerini V: A History of Dentistry, from the Most Ancient
oration. J Am Dent Assoc 108(4):473-586, 1984. Times Until the End of the Eighteenth Century. Pound
Asbell MB: Dentistry, a Historical Perspective. Bryn Mawr, Ridge, NY, Milford House, 1909.
PA, Torrence & Co, 1988. Hoffmann-Axthelm W: History of Dentistry. Chicago,
An historical account of the history of dentistry from ancient Quintessence Publishing, 1981.
times, with emphasis on the United States from the colonial to Koch, CRE: History of Dental Surgery. Chicago, National
the present period. Art Publishing, 1909.
Bennion E: Antique Dental Instruments. New York, Lufkin AW: A History of Dentistry. Philadelphia, Lea &
Sotheby’s Publishing, 1986. Febiger, 1948.
Black CE, and Black BM: From Pioneer to Scientist. St. Paul, McCluggage RW: A History of the American Dental
MN, Bruce Publishing, 1940. Association, A Century of Health Service. Chicago,
The life story of Greene Vardiman Black, “Father of Modern American Dental Association, 1959.
Dentistry,” and his son Arthur Davenport Black, late Dean of Ring ME: Dentistry: An Illustrated History. New York, Harry
Northwestern University Dental School. N Abrams Inc, 1985.
Carter WJ, and Graham-Carter J. Dental Collectibles and Weinberger BW: An Introduction to the History of
Antiques. 2nd ed. Bethany, OK, Dental Folklore Books, Dentistry. St Louis, Mosby, 1948.
1992. Includes medical and dental chronology and bibliographic
Gardner PH: Foley’s Footnotes: A Treasury of Dentistry. data (2 volumes).
Wallingford, PA, Washington Square East Publishing, Weinberger BW: Pierre Fauchard, Surgeon-Dentist.
1972. Minneapolis, MN, Pierre Fauchard Academy, 1941.
Glenner RA, Davis AB, and Burns SB: The American A brief account of the beginning of modern dentistry, the first
Dentist. Missoula, MT, Pictorial Histories Publishing, dental textbook, and professional life 200 years ago.
1990. Wynbrandt J: The Excruciating History of Dentistry:
A pictorial history with a presentation of early dental photog- Toothsome Tales and Oral Oddities from Babylon to
raphy in America. Braces. New York, St Martin’s Press, 1998.
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 2
Structure of Matter and Principles of Adhesion
Kenneth J. Anusavice

OUTLINE
Change of State
Interatomic Primary Bonds
Interatomic Secondary Bonds
Interatomic Bond Distance and Bonding Energy
Thermal Energy
Crystalline Structure
Noncrystalline Solids and Their Structures
Diffusion
Adhesion and Bonding
Adhesion to Tooth Structure

KEY TERMS
Acid-etching technique—Process of roughening a solid surface by exposing it to an acid and
thoroughly rinsing the residue to promote micromechanical bonding of an adhesive to the
surface.
Adherend—A material substrate that is bonded to another material by means of an adhesive.
Adhesion—A molecular or atomic attraction between two contacting surfaces promoted by
the interfacial force of attraction between the molecules or atoms of two different species;
adhesion may occur as chemical adhesion, mechanical adhesion (structural interlocking),
or a combination of both types.
Adhesive—Substance that promotes adhesion of one substance or material to another.
Adhesive bonding—Process of joining two materials by means of an adhesive agent that solid-
ifies during the bonding process.
Cohesion—Force of molecular attraction between molecules or atoms of the same species.
Contact angle—Angle of intersection between a liquid and a surface of a solid that is meas-
ured from the solid surface through the liquid to the liquid/vapor tangent line originating at
the terminus of the liquid/solid interface; used as a measure of wettability, whereby no wet-
ting occurs at a contact angle of 180˚ and complete wetting occurs at an angle of 0˚.
Diffusion coefficient—Proportionality constant representing the amount of a substance dif-
fusing through a unit area and a unit thickness under the influence of a unit concentration
gradient at a given temperature.
Glass transition temperature—Temperature at which a sharp increase in the thermal expan-
sion coefficient occurs, indicating increased molecular mobility.
Heat of vaporization—Thermal energy required to convert a solid to a vapor.
Latent heat of fusion—Thermal energy required to convert a solid to a liquid.
Linear coefficient of expansion—Relative linear change in length per unit of initial length dur-
ing heating of a solid per ˚K within a specified temperature range.

21
22 PART I ■ General Classes and Properties of Dental Materials

KEY TERMS—cont’d
Melting temperature (melting point)—Equilibrium temperature at which heating of a pure
metal, compound, or eutectic alloy produces a change from a solid to liquid.
Metallic bond—Primary bond between metal atoms.
Micromechanical bonding—Mechanical adhesion associated with bonding of an adhesive to
a roughened adherend surface.
Self-diffusion—Thermally driven transfer of an atom to an adjacent lattice site in a crystal
composed of the same atomic species.
Smear layer—Tenacious deposit of microscopic debris that covers enamel and dentin surfaces
that have been prepared for a restoration.
Stress concentration—State of elevated stress in a solid caused by surface or internal defects
or by marked changes in contour.
Supercooled liquid—A liquid that has been cooled at a sufficiently rapid rate to a point below
the temperature at which an equilibrium phase change can occur.
Surface tension—Interfacial tension, usually between a liquid and a solid surface, which
occurs because of unbalanced intermolecular forces.
Wettability—Relative affinity of a liquid for the surface of a solid.
Wetting—Relative interfacial tension between a liquid and a solid substrate that results in a
contact angle of less than 90˚.
Wetting agent—A surface-active substance that reduces the surface tension of a liquid to
promote wetting or adhesion.
Vacancy—Unoccupied atom lattice site in a crystalline solid.
van der Waals forces—Short-range force of physical attraction that promotes adhesion
between molecules of liquids or molecular crystals.

CHANGE OF STATE
To gain an understanding of dental materials, we must begin with a basic knowledge
of their atomic or molecular structure and their behavior during handling and use
in the oral environment. Our scientific understanding of this behavior is limited.
Because environmental factors are critically important for clinical success, extrapo-
lation of in vitro information to the clinical (in vivo) situation should be
approached with extreme caution.
The performance of all dental materials, whether ceramic, polymeric, or metallic,
is based on their atomic structure. The collective physical and chemical reactions of
the atoms determine the properties of the material. Therefore a short review of mat-
ter is justified to lay a foundation for a basic understanding of dental materials.
Atoms and molecules are held together by atomic interactions. When water boils,
energy is needed to transform the liquid to vapor; this quantity of energy is known as
the heat of vaporization. During condensation of water vapor, the same amount of
heat is released to the environment, thus satisfying the conservation of energy. The
heat of vaporization is defined as the amount of heat needed to evaporate 1 g of liq-
uid to the vapor state at a given temperature and pressure. For example, 540 cal of heat
is required to vaporize 1 g of water at 100˚ C at a pressure of 1 atm. Thus we can con-
clude that the gaseous state possesses more kinetic energy than does the liquid state.
Although molecules in the gaseous state exert a certain amount of mutual attrac-
tion, they can move readily because of their high kinetic energy. This also explains
why gaseous molecules need to be confined to avoid dispersion. Atoms present in a
liquid can also diffuse, but because their mutual attractions are greater in the liquid
state than in the gaseous state, kinetic energy of the liquid must be increased to
achieve separation. If the kinetic energy of a liquid decreases sufficiently when its
temperature is decreased, a second transformation in state may occur and the liquid
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 23

may change to a solid. Kinetic energy is released in the form of heat when the liq-
uid freezes. In this instance, the energy released is known as the latent heat of
fusion. For example, when 1 g of water freezes, 80 cal of heat are released. If 1 g of
a solid is changed to a liquid, the reverse is true and an input of energy is required.
For pure metals and some other solids, the temperature at which this change occurs
is known as the melting temperature.
Because energy is required for the transformation from a solid to a liquid state,
the attraction between atoms (or molecules) in the solid state must be greater than
that in either the liquid or the gaseous state. If this were not true, atoms would sep-
arate easily. In addition, metals would deform readily, and they could exist in the
vapor phase at low temperatures.
The temperature at which a liquid boils or solidifies depends partly on environ-
mental pressure. A liquid can vaporize (or evaporate) at any temperature between
its freezing and boiling points, provided that the space above the liquid is not
already saturated or supersaturated with the vapor. Within a closed container, as the
vapor density above the liquid increases, the vapor pressure produced by the mole-
cules in the gaseous state also increases. This vapor density, as well as the resulting
vapor pressure, attains a constant value in equilibrium, because the molecules enter
and leave the liquid phase at an equal rate. It is possible for some solids to trans-
form directly to a gas phase through the process of sublimation. However, this phe-
nomenon is of little practical importance with respect to dental materials.

CRITICAL QUESTION
Which types of primary bonds control the properties of dental resins and cast alloys?
?
INTERATOMIC PRIMARY BONDS
The forces that hold atoms together are called cohesive forces. These interatomic
bonds may be classified as primary or secondary. The strength of these bonds and
their ability to reform after breakage determine the physical properties of a material.
Primary atomic bonds (Fig. 2-1) may be of three different types: (1) ionic, (2) cova-
lent, and (3) metallic.

Ionic Bonds
Ionic bonds (Fig. 2-1, A) result from the mutual attraction of positive and negative
charges. The classic example is sodium chloride (Na+Cl-). Because the sodium atom
contains one valence electron in its outer shell and the chlorine atom has seven elec-
trons in its outer shell, the transfer of the sodium valence electron to the chlorine
atom results in the stable compound NaCl. Ionic bonds result in crystals whose
atomic configuration is based on a charge and size balance. In dentistry, ionic bond-
ing exists in certain crystalline phases of some dental materials, such as gypsum and
phosphate-based cements.

Covalent Bonds
In many chemical compounds, two valence electrons are shared by adjacent atoms
(Fig. 2-1, B). The hydrogen molecule, H2, is an example of covalent bonding. The
single valence electron in each hydrogen atom is shared with that of the other
24 PART I ■ General Classes and Properties of Dental Materials

ⴙ ⴚ ⴙ
A ⴚ ⴙ ⴚ
ⴙ ⴚ ⴙ

Electron
orbit
B

Fig. 2-1 A, Ionic bond formation—characterized by

electron transfer from one element (positive) to another
(negative). B, Covalent bond formation—characterized by
ⴙ ⴙ ⴙ
electron sharing and very precise bond orientations.
C, Metallic bond formation—characterized by electron “Gas” of
C ⴙ ⴙ ⴙ free
sharing and formation of a “gas” or “cloud” of electrons
electrons
that bonds the atoms (which become positively charged
because of the electron gas formation) together in a ⴙ ⴙ ⴙ
lattice. (Courtesy of K-J. Söderholm.)

Fig. 2-2 Carbon atom with an sp3 orbit formation. This type of hybrid
configuration is also common for silicon. (Courtesy of K-J. Söderholm.)

combining atom, and the valence shells become stable. Covalent bonding occurs in
many organic compounds, such as dental resins, in which the compounds link to
form the backbone structure of hydrocarbon chains. The carbon atom has four
valence electrons forming an sp3 hybrid configuration (Fig. 2-2) and can be stabi-
lized by combining with hydrogen. A typical characteristic of covalent bonds is their
directional orientation.

Metallic Bonds
The third type of primary atomic interaction is the metallic bond (Fig. 2-1, C),
which results from the increased spatial extension of valence-electron wave func-
tions when an aggregate of metal atoms is brought close together. This type of bond-
ing can be understood best by studying a metallic crystal such as pure gold. Such a
crystal consists only of gold atoms. Like all other metals, gold atoms can easily
donate electrons from their outer shell and form a “cloud” of free electrons. The
contribution of free electrons to this cloud results in the formation of positive ions
that can be neutralized by acquiring new valence electrons from adjacent atoms.
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 25

Because of their ability to donate and recover electrons, atoms in a metal crystal
exist as clusters of positive metal ions surrounded by a cloud of electrons. This struc-
ture is responsible for the excellent electrical and thermal conductivity of metals and
also for their ability to deform plastically. The electrical and thermal conductivities
of metals are controlled by the ease with which the free electrons can move through
the crystal, whereas their deformability is associated with the slip of atoms along
crystal planes. During slip deformation, electrons easily regroup to retain the cohe-
sive nature of the metal.

INTERATOMIC SECONDARY BONDS

In contrast with primary bonds, secondary bonds (Fig. 2-3) do not share electrons.
Instead, charge variations among molecules or atomic groups induce polar forces
that attract the molecules. Since there are no primary bonds between water and
glass, it is initially difficult to understand how water drops can bond to an automo-
bile windshield when they freeze to ice crystals. However, the concepts of hydrogen
bonding and secondary bonding—two types of bonds that exist between water and
glass—allow us to explain this adhesion phenomenon.

Hydrogen Bonding
Hydrogen bonding can be understood by studying a water molecule (Fig 2-4).
Attached to the oxygen atom are two hydrogen atoms. These bonds are covalent
because the oxygen and hydrogen atoms share electrons. As a consequence, the pro-
tons of the hydrogen atoms pointing away from the oxygen atom are not shielded

ⴙ ⴙ ⴙ

ⴚ ⴚ

Fig. 2-3 Secondary bond formation. Charge

variations along molecules induce polar Differences in electron densities
forces that attract other molecules. (Courtesy result in charge variations
of K-J. Söderholm.) along the molecule

ⴚⴚ
ⴙ
ⴙ
ⴙ
ⴚⴚ
ⴙ

ⴚⴚ ⴙ

Fig. 2-4 Hydrogen bond formation between water

molecules. The polar water molecule ties up adjacent
water molecules via an H●●●O interaction between ⴙ
molecules. (Courtesy of K-J. Söderholm.)
26 PART I ■ General Classes and Properties of Dental Materials

efficiently by the electrons, and the proton side of the water molecule is positively
charged. On the opposite side of the water molecule, the electrons that fill the outer
orbit of the oxygen atom provide a negative charge. Thus a permanent dipole exists
that represents an asymmetric molecule. The hydrogen bond, which is associated
with the positive charge of hydrogen caused by polarization, is an important exam-
ple of this type of secondary bonding.
When a water molecule intermingles with other water molecules, the hydrogen
(positive) portion of one molecule is attracted to the oxygen (negative) portion of
its neighboring molecule and hydrogen bridges are formed. Polarity of this nature
is important in accounting for the intermolecular reactions in many organic com-
pounds, such as the sorption of water by synthetic dental resins.

Van der Waals Forces

Van der Waals forces form the basis of a dipole attraction (Fig. 2-5). For example,
in a symmetric molecule, such as an inert gas, the electron field constantly fluctu-
ates. Normally, the electrons of the atoms are distributed equally around the
nucleus and produce an electrostatic field around the atom. However, this field may
fluctuate so that its charge becomes momentarily positive and negative, as shown in
Figure 2-5. A fluctuating dipole is thus created that will attract other similar dipoles.
Such interatomic forces are quite weak.

INTERATOMIC BOND DISTANCE AND BONDING ENERGY

Bond Distance
Regardless of the type of matter, there is a limiting factor that prevents the atoms or
molecules from approaching each other too closely. This factor is the distance
between the center of an atom and that of its neighbor, which is limited by the
diameter of the atoms involved. Although the atom is treated as a discrete particle
with boundaries and volume, its boundaries are established by the electrostatic
fields of the electrons. If the atoms approach too closely, they are repelled from each
other by their electron charges. On the other hand, forces of attraction tend to draw
the atoms together. The position at which these forces of repulsion and attraction
become equal in magnitude (but opposite in direction) is the equilibrium position
of the atoms shown in Figure 2-6. In this position, the repelling forces are equal in
magnitude to the attracting forces. Atom B can be displaced to position B’ by a dis-
turbing mechanical, thermal, or electrical force. A force may also cause the atoms to
move more closely together (position B” in Fig. 2-6). As the forces of attraction

ⴙ ⴚ

ⴚ ⴙ

Fig. 2-5 Fluctuating dipole that binds inert ⴙ ⴚ

gas molecules together. The arrows show how
the fields may fluctuate so that the charges
become momentarily positive and negative.
(Courtesy of K-J. Söderholm.)
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 27

Attractive force

Intermolecular forces
Force balance

Interatomic
distance

Repulsive force

Equilibrium position

Attractive force

Fig. 2-6 Attractive and repulsive forces

balance each other, and atom B attains its
equilibrium position. (Courtesy of K-J.
Söderholm.) Repulsive force

increase, the interatomic space decreases. On the other hand, the forces of repulsion
remain relatively inactive until the atoms are sufficiently close to each other. The
sum or resultant of the two forces is indicated by the broken line in Figures 2-6 and
2-7. The resultant force in Figure 2-6 becomes zero; that is, the magnitudes of the
two forces are equal at the intersection of the broken line with the horizontal axis.
At equilibrium, the interatomic distance represents the distance between the centers
of the atoms involved (distance a in Fig. 2-7).

Resultant force
Force

Interatomic distance

Resultant force  0,
Fig. 2-7 When the equilibrium position is which results in an
reached, the interatomic distance is a. If the interatomic distance
equal to a
atom is moved from this position, either a
negative (repulsive) or a positive (attractive)
force is required to move the atom back to its
equilibrium position as shown in Fig. 2-6.
(Courtesy of K-J. Söderholm.)
28 PART I ■ General Classes and Properties of Dental Materials

Bonding Energy
Because conditions of equilibrium are usually described in terms of energy rather
than interatomic forces, the relationships in Figure 2-7 can be more logically
explained in terms of interatomic energy. According to the laws of physics, energy
can be defined as a force integrated over a distance. If the resultant force (F), repre-
sented by the dashed line in Figure 2-7, is integrated over the interatomic spacing
(a), the graph shown in Figure 2-8 will result. The horizontal axis in Figure 2-8 rep-
resents the interatomic distance, and the interatomic or bonding energy is plotted
on the vertical axis. In contrast with the resultant force plotted in Figure 2-6, the
energy does not change a great deal initially as two atoms come closer together. As
the resultant force approaches zero (see Fig. 2-7), the energy decreases (see Fig. 2-8).
The energy finally reaches a minimum when the resultant force becomes zero.
Thereafter the energy increases rapidly (see Fig. 2-8), because the resultant repulsive
force (see Fig. 2-7) increases rapidly with little change in interatomic distance. The
minimal energy corresponds to the condition of equilibrium and defines the equi-
librium interatomic distance.

THERMAL ENERGY
Thermal energy is accounted for by the kinetic energy of the atoms or molecules at
a given temperature. The atoms in a crystal at temperatures above absolute zero are
in a constant state of vibration, and the average amplitude is dependent on the tem-
perature. The higher the temperature, the greater the amplitude and, consequently,
the greater the kinetic or internal energy. Further consideration of Figures 2-7 and 2-
8 can provide additional interpretations of these phenomena.
For a certain temperature, the minimal energy occurs at equilibrium and is
denoted by the lowest point of the curve in Figure 2-8. As the temperature increases,
the amplitude of the atomic (or molecular) vibration increases. It follows also that
the mean interatomic spacing increases (see Figs. 2-8 and 2-9), as well as the inter-
nal energy. The overall effect represents the phenomenon known as thermal expan-
sion (Fig. 2-9).
If the temperature continues to increase, the interatomic spacing will increase
and eventually a change of state will occur. A solid changes to a liquid, and the liq-
uid subsequently changes to a vapor. It follows from Figure 2-9, A and B, that the
deeper the lowest point of the curve, the greater the amount of energy required to

Interatomic spacing
at a certain energy
level
Interaction energy

Fig. 2-8 By multiplying the force shown in Fig. Interatomic

2-7 by the atomic displacement from its distance at
equilibrium position, the energy change can be zero energy
plotted as a function of displacement in either
direction. (Courtesy of K-J. Söderholm.)
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 29

Interaction energy
Center of vibration
with increased energy
A

Interatomic
distance

Interaction energy
B
Fig. 2-9 The depth of the energy curve is
determined by the magnitude of the attractive-
Interatomic
repulsive forces. Thus for a shallower curve B, less
distance
energy is needed to separate the atoms than for
deeper curve A. (Courtesy of K-J. Söderholm.)

achieve melting and boiling and, consequently, the higher the melting and boiling
temperatures. By the same reasoning, it can be argued that the lower the minimum
value of the energy curve is, the lower the thermal expansion per degree of temper-
ature increase, because the interatomic spacing does not necessarily increase as the
depth of the trough increases. In other words, the linear coefficient of thermal
expansion (α) of materials with similar atomic or molecular structures tends to be
inversely proportional to the melting temperature.
Figures 2-7 and 2-8 illustrate another interesting relationship between melting
temperature and the force required to move atoms away from their equilibrium spac-
ing. As shown in Figure 2-7, the net force on the atoms at the equilibrium spacing is
zero, but small displacements result in rapidly increasing forces that maintain the
equilibrium spacing. The stiffness of the material is proportional to the rate of change
of the force, with a change in displacement measured by the slope of the net force
curve near at interatomic distance equal to a. A greater slope of the force curve versus
distance implies a narrower, deeper trough in the energy versus distance curve (see Fig.
2-8). Hence a high melting point is usually accompanied by a greater stiffness.
Thermal conductivity is related to interatomic spacing only to the extent that the
heat is conducted from one atom or molecule to the next as adjacent basic structural
units are affected by the kinetic energy of their neighbors. However, the number of
“free” electrons in the material influences its thermal conductivity. As discussed pre-
viously, metallic structures such as dental casting alloys and dental amalgams con-
tain many free electrons, and most metals are effective conductors of heat as well as
electricity. On the other hand, nonmetallic materials, such as resin-based compos-
ites and denture acrylics, do not contain many free electrons, and consequently, they
are generally poor thermal and electrical conductors.
The preceding principles represent generalities, and exceptions do occur.
Nevertheless, they allow us to estimate the influence of temperature on the proper-
ties of most of the dental materials to be discussed in subsequent chapters.
30 PART I ■ General Classes and Properties of Dental Materials

CRITICAL QUESTIONS
Which dental substances are examples of crystalline materials? Which are noncrystalline
? materials? Which are combinations of crystalline and noncrystalline materials?

CRYSTALLINE STRUCTURE
Thus far, for the purpose of explaining specific concepts, we have generally assumed
the presence of only two atoms or molecules. Dental materials consist of many mil-
lions of such units. But how are the structural units arranged in a solid, and how
they are held together? In 1665, Robert Hooke (1635–1703) simulated the charac-
teristic shapes of crystals by stacking musket balls in piles. It was 250 years later
before anyone knew that he had created an exact model of the crystal structure of
many familiar metals, with each ball representing an atom.
Atoms are bonded to each other by either primary or secondary forces. In the
solid state, they combine in a manner that ensures minimal internal energy. For
example, sodium and chlorine share one electron, as previously described. In the
solid state, however, the atoms do not simply form only pairs; in fact, all of the pos-
itively charged sodium ions attract all of the negatively charged chlorine ions. The
result is that they form a regularly spaced configuration known as a space lattice or
crystal. A space lattice can be defined as any arrangement of atoms in space in which
every atom is situated similarly to every other atom. Space lattices may be the result
of primary or secondary bonds.
There are 14 possible lattice types or forms, but many of the metals used in den-
tistry belong to the cubic system; that is, the atoms crystallize in cubic arrangements.
The simplest cubic space lattice is shown in Figure 2-10, with the spheres represent-
ing the positions of the atoms. Their positions are located at the points of intersec-
tion of three sets of parallel planes, each set being perpendicular to the other two
sets of planes. These planes are often referred to as crystal planes. All dental amal-
gams, cast alloys, wrought metals, gold foil, and dental amalgam are crystalline.
Some pure ceramics, such as alumina and zirconia core ceramics, are entirely crys-
talline. Other ceramics, such as dental porcelains, consist of noncrystalline glass
matrix and crystalline inclusions that provide desired properties, including color,
opacity, and increases in thermal expansion coefficients, radiopacity, strength, and
fracture toughness.

Fig. 2-10 Simple cubic space lattice. (Courtesy

of K-J. Söderholm.)
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 31

Shown in Figure 2-11, A, is one unit cell of the simple cubic space lattice. The cells
are repeated in three-dimensional space, as indicated in Figure 2-10. The simple
cubic arrangements are shown in Figures 2-10 and 2-11, A. The arrangements shown
in Figure 2-11, B and C, represent the cubic space lattices of practical importance.
Also, Figures 2-10 and 2-11 are diagrammatic only. The atoms are actually closely
packed so that the interatomic spacing is equal to the sum of their radii. The closer
packing arrangement for a model of a body-centered cubic structure is shown in
Figure 2-12, and a similar model for a face-centered cubic lattice is pictured
in Figure 2-13.
The type of space lattice is defined by the length of each of three unit cell edges
(called the axes) and the angles between the edges. For example, the cubic space

C
Fig. 2-11 Single cells of cubic space lattices. A, Simple cubic.
B, Body-centered cubic. C, Face-centered cubic. (Courtesy of
K-J. Söderholm.)

Fig. 2-12 Model of a body-centered cubic crystal. (Courtesy of K-J.

Söderholm.)

Fig. 2-13 Model of a face-centered cubic crystal. (Courtesy of K-J.

Söderholm.)
32 PART I ■ General Classes and Properties of Dental Materials

B
A

C D

E F

G H

Fig. 2-14 Other simple lattice types of dental interest. A, Rhombohedral. B, Orthorhombic.
C, Monoclinic. D, Triclinic. E, Tetragonal. F, Simple hexagonal. G, Close-packed hexagonal.
H, Rhombic. (Courtesy of K-J. Söderholm.)

lattice (see Fig. 2-11, A) is characterized by axes that are all of equal length and meet
at 90-degree angles. Other types of space lattices are diagrammed in Figure 2-14.

NONCRYSTALLINE SOLIDS AND THEIR STRUCTURES

Structures other than crystalline forms can occur in the solid state. For example,
some of the waxes used by a dentist or laboratory technician may solidify as amor-
phous materials so that the molecules are distributed at random. Even in this case,
there is a tendency for the arrangement to be regular.
Glass is also considered to be a noncrystalline solid, because its atoms tend to
develop a short-range order instead of the long-range order characteristic of crys-
talline solids. The ordered arrangement of the glass is more or less locally inter-
spersed with a considerable number of disordered units. Because this arrangement
is also typical of liquids, such solids are sometimes called supercooled liquids.
A resin-based composite consists of a resin matrix, filler particles, and an organic
coupling agent that bonds the filler particles to the resin matrix. In some cases, the
filler particles are made from radiopaque glasses that are noncrystalline. Composites
have a noncrystalline matrix and may or may not contain crystalline filler particles.
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 33

The structural arrangements of the noncrystalline solids do not represent such

low internal energies as do crystalline arrangements of the same atoms and mole-
cules. Noncrystalline solids do not have a definite melting temperature, but rather
they gradually soften as the temperature is raised. The temperature at which there is
an abrupt increase in the thermal expansion coefficient, indicating increased molec-
ular mobility, is called the glass transition temperature (Tg) and it is characteristic
of the particular glassy structure. Occasionally, the term is shortened to glass tem-
perature. Below Tg, the glassy structure loses its fluid characteristics and has signifi-
cant resistance to shear deformation. Synthetic dental resins are examples of
materials that often have glassy structures.

CRITICAL QUESTION
Why are mercury and gallium of interest as components of direct restorative materials?
?
DIFFUSION
Diffusion of molecules in gases and liquids is well known. However, molecules or
atoms diffuse in the solid state as well. As previously described, the atoms in a space
lattice are constantly in vibration about their centers. The average kinetic energy of
vibration over the entire crystal is related to the temperature. At absolute zero the
vibration ceases, the energy becomes zero, and the atom occupies the center of
vibration (see Fig. 2-9). At any temperature above the absolute zero temperature
(-273˚ C), atoms (or molecules) of a solid possess some kinetic energy. An under-
standing of diffusion in a solid requires two new concepts.
The first concept pertaining to diffusion in a solid is that all the atoms do not
possess the same amount of energy. Rather, there is a distribution of atoms with a
particular energy that varies from very low to high, with the average energy related
to the absolute zero temperature. Even at very low temperatures, some atoms have
high energies.
If the energy of a particular atom exceeds the bonding energy, it can move to
another position in the lattice. In a noncrystalline solid with only short-range order,
there is a strong probability that a high-energy atom will be located adjacent to a
vacant position.
The second concept required to describe solid-state diffusion in crystalline solids
is the fact that at any temperature above the absolute zero temperature, there are a
finite number of missing atoms (called vacancies), representing open areas through
which diffusion can occur. Atoms change position in pure, single-element solids
even under equilibrium conditions; this process is known as self-diffusion.
However, self-diffusion is generally not of practical importance, because no visible
or measurable dimensional changes occur. As with any diffusion process, the atoms
or molecules diffuse in the solid and liquid states in an attempt to reach an equi-
librium state. For example, sugar molecules in solution tend to diffuse to achieve a
uniform concentration. As discussed later, a concentration of atoms in a metal can
also be redistributed through the diffusion process.
Diffusion may also occur in the other direction to produce a concentration of
atoms in a solution. For example, if the sugar in the water becomes supersatu-
rated, the molecules of sugar diffuse toward each other, and the sugar crystallizes
out of solution. In the same manner, too many copper atoms in a solid alloy of
copper and silver may cause supersaturation and diffusion of the copper atoms
34 PART I ■ General Classes and Properties of Dental Materials

to increase the concentration of copper locally, causing them to precipitate out of

solution.
Diffusion rates for a given substance depend mainly on temperature and the
chemical potential gradient or concentration gradient. The higher the temperature
or the higher the chemical potential gradient, the greater the rate of diffusion. The
diffusion rate varies with the concentration gradients, atom size, interatomic or
intermolecular bonding, and lattice imperfections. Thus different dental materials
exhibit a range of characteristic diffusion rates. The diffusion constant that is
uniquely characteristic of a given element in a compound, crystal, or alloy is known
as the diffusion coefficient, usually designated as D. The diffusion coefficient is
defined as the amount of a substance that diffuses across a given unit area (e.g., 1
cm2), through a unit thickness of the substance (e.g., 1 cm), in one unit of time (e.g.,
1 sec). In general, the diffusion coefficient of a pure metal is related to its melting
temperature; that is, the lower its melting point, the greater its diffusion coefficient.
The diffusion coefficients of elements in most crystalline solids at room temper-
ature are very low. Diffusion in dental alloys is so slow at room temperature that it
cannot be detected in a practical sense; however, at temperatures only a few hundred
degrees higher, the properties of the metal change markedly by atomic diffusion.
Diffusion in a noncrystalline material may occur at a more rapid rate, and often may
be evident at room or body temperature. The disordered structure enables the mol-
ecules to diffuse more rapidly with less activation energy. Some metals melt at tem-
peratures below mouth temperature. For example, the melting points of mercury
and gallium are -38.36˚ C (-37.05˚ F) and 29.78˚ C (85.60˚ F) respectively. Thus,
because the diffusion rate of these atoms into solid alloy particles may be fairly
rapid at intraoral temperature, new metal compounds can be formed that may be
useful as direct restorative materials.

ADHESION AND BONDING

The phenomenon of adhesion applies to many situations in dentistry. For example,
leakage adjacent to dental restorative materials results from an insufficient or incom-
plete adhesion. The retention of artificial dentures is probably dependent, to some
extent, on adhesion between the denture and saliva and between the saliva and soft
tissue. Certainly, the attachment of plaque or calculus to tooth structure can be par-
tially explained by an adhesion mechanism. Therefore, an understanding of the fun-
damental principles associated with the phenomenon is essential to the dentist.
When two substances are brought into intimate contact with each other, the mol-
ecules of one substance adhere, or are attracted to, molecules of the other substance.
This force is called adhesion when unlike molecules are attracted and cohesion when
molecules of the same kind are attracted. The material or film used to cause adhesion
is known as the adhesive; the material to which it is applied is called the adherend.
In a broad sense, adhesion is simply a surface attachment process. The term adhe-
sion is usually qualified by specification of the type of intermolecular attraction that
may exist between the adhesive and the adherend.

Mechanical Bonding
Strong attachment of one substance to another can also be accomplished by
mechanical bonding or retention rather than by molecular attraction. Such struc-
tural retention may be gross in nature, as seen by applications involving the use of
screws, bolts, or undercuts. Mechanical bonding may also involve more subtle mech-
anisms such as the penetration of the adhesive into microscopic or submicroscopic
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 35

irregularities (e.g., crevices and pores) in the surface of the substrate. A fluid or
slightly viscous liquid adhesive is best suited for such a procedure, because it readily
penetrates into these surface defects. On hardening, the numerous adhesive projec-
tions embedded in the adherend surface provide the anchorage for mechanical
attachment (retention).
This micromechanical bonding mechanism has been commonly used in den-
tistry because of the absence of truly adhesive cements or restorative materials. For
example, retention of cast restorations, such as a cast gold alloy crown or a base
metal endodontic post and core, is enhanced by mechanical attachment of the
cementing agent into irregularities that exist on the internal surface of the casting
and those that are present in the adjoining tooth structure.
A more recent example of mechanical bonding is that of resin (plastic) restorative
materials. Because these resins do not have the capability of truly adhering to tooth
structure, leakage adjacent to the restoration may occur. Such leakage patterns con-
tribute to marginal stain, secondary caries, and irritation of the pulp. A specific tech-
nique must be used to minimize the risks associated with deleterious agents that may
migrate toward the pulp. Before insertion of the resin, the enamel of the adjoining
tooth structure is exposed to phosphoric acid for a short period. This is referred to as
the acid-etching technique. The acid produces minute pores and other irregularities in
the enamel surface into which the resin subsequently flows when it is placed into the
preparation. On hardening, these resin projections provide improved mechanical
retention of the restoration, thereby reducing the possibility of interfacial leakage.
The acid-etching technique is an example of how bonding between a dental
material and tooth structure can be achieved through mechanical mechanisms,
rather than through molecular adhesion. This process is sometimes referred to as
“micromechanical bonding.” The principles of adhesion and the factors associated
with this phenomenon are discussed further in the following sections.

Surface Energy
For adhesion to exist, the surfaces must be attracted to one another at their interface.
Such a condition may exist regardless of the phases (solid, liquid, or gas) compris-
ing the two surfaces, with the exception that adhesion between two gases is not
expected, because they lack an interface.
The energy at the surface of a solid is greater than that of its interior. For example,
consider the space lattice shown in Figure 2-15. Inside the lattice, all the atoms are
equally attracted to one another. The interatomic distances are equal, and the energy

Surface atom (B)

Interior atom (A)

Fig. 2-15 Comparing an atom under the

surface (A) with one on the surface (B) reveals
that a bond balance exists around interior
atom A, while surface atom B is free to
develop bonds to atoms or molecules
approaching the surface. (Courtesy of K-J.
Söderholm.)
36 PART I ■ General Classes and Properties of Dental Materials

is minimal. At the surface of the lattice, the energy is greater because the outermost
atoms are not equally attracted in all directions, as diagrammed in Figure 2-15. The
interior atom A has a balanced array of nearest neighbors surrounding it, whereas
surface atom B has an unbalanced number of adjacent atoms.
The increase in energy per unit area of surface is referred to as the surface energy
or surface tension. A soap film contracts, and drops of a liquid form spherical
shapes by minimizing surface area because this surface tension condition represents
the state of lowest energy.
The surface atoms of a solid tend to form bonds to other atoms in close proxim-
ity to the surface and reduce the surface energy of the solid. This attraction across
the interface between unlike molecules is called adhesion. For example, molecules
in the air may be attracted to the surface and become adsorbed on the material sur-
face. Silver, platinum, and gold adsorb oxygen readily. For gold, the bonding forces
are of the secondary type; but in the case of silver, the attraction may be controlled
by chemical or primary bonding, and silver oxide may form.
When primary bonding is involved, the adhesion is termed chemisorption, as com-
pared with physical bonding by van der Waals forces. In chemisorption, a chemical
bond is formed between the adhesive and the adherend. An example of this type of
adhesion is an oxide film formed on the surface of a metal or a layer of solder
bonded to a metallic substrate. Thus, van der Waals forces are weaker than primary
bonding because they are intermolecular rather than intramolecular.
The development of van der Waals forces invariably precedes chemisorption. As
the distance between the adhesive and the adherend diminishes, primary bonding
may become effective. However, chemisorption is limited to the monolayer of adhe-
sive present on the adherend. The surface energy and the adhesive qualities of a
given solid can be reduced by any surface impurity, such as adsorbed gas, an oxide,
or human secretions. The functional chemical groups available or the type of crys-
tal plane of a space lattice present at the surface may affect the surface energy. In
summary, the greater the surface energy, the greater the capacity for adhesion.

CRITICAL QUESTION
What conditions are necessary to achieve the strongest level of bonding?
?
Wetting
It is difficult to force two solid surfaces to adhere. Regardless of how smooth these
surfaces may appear, they are likely to be extremely rough when viewed on an
atomic or molecular scale. Consequently, when they are placed in apposition, only
the “peaks” or asperities are in contact. Because these areas usually constitute only
a small percentage of the total surface area, no perceptible adhesion takes place. The
attraction is generally negligible when the surface molecules of the attracting sub-
stances are separated by distances greater than 0.7 nm (0.0007 μm).
One method of overcoming this difficulty is to use a fluid that flows into these
irregularities to provide contact over a greater part of the surface of the solid. For
example, when two polished glass plates are placed one on top of the other and are
pressed together, they exhibit little tendency to adhere for reasons previously
described. However, if a film of water is introduced between them, considerable dif-
ficulty is encountered in separating the two plates. The surface energy of the glass is
sufficiently great to attract the molecules of water.
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 37

To produce adhesion in this manner, the liquid must flow easily over the entire
surface and adhere to the solid. This characteristic is known as wetting. If the liquid
does not wet the surface of the adherend, adhesion between the liquid and the
adherend will be negligible or nonexistent. If there is a true wetting of the surface,
adhesion failures should not occur. Failure in such instances actually occurs cohe-
sively in the solid or in the adhesive itself, not along the interface where the solid
and adhesive are in contact.
The ability of an adhesive to wet the surface of the adherend is influenced by a
number of factors. The cleanliness of the surface is of particular importance. A film
of water only one molecule thick on the surface of the solid may lower the surface
energy of the adherend and prevent any wetting by the adhesive. Likewise, an oily
film on a metallic surface may also inhibit the contact of an adhesive.
The surface energy of some substances is so low that few, if any, liquids wet their
surfaces. Some organic substances, such as dental waxes, are of this type. Close pack-
ing of the structural organic groups and the presence of halogens may prevent wet-
ting. Teflon (polytetrafluoroethylene), a commercial synthetic resin, is often used
when it is desirable to prevent the adhesion of films to a surface. Metals, on the
other hand, interact strongly with liquid adhesives because of their high surface
energy.
In general, the comparatively low surface energies of organic and most inorganic
liquids permit them to spread freely on solids of high surface energy. Formation of
a strong adhesive joint requires good wetting.

CRITICAL QUESTION
You observe a lack of soft or hard tissue details in a gypsum model you have made from a
? hydrophobic impression material. What step(s) can be taken to eliminate this problem
when using this impression material in the future?

Contact Angle of Wetting

The extent to which an adhesive wets the surface of an adherend may be deter-
mined by measuring the contact angle between the adhesive and the adherend.
The contact angle is the angle formed at the interface of the adhesive and the
adherend. If the molecules of the adhesive are attracted to the molecules of the
adherend as much as, or more than, they are attracted to themselves, the liquid
adhesive will spread completely over the surface of the solid, and no contact
angle (θ = 0 degrees) will be formed (Fig. 2-16, A). Thus the forces of adhesion
are stronger than the cohesive forces holding the molecules of the adhesive
together. A dental material such as an elastomeric impression may not be ideal
for replicating hard or soft oral tissues if an aqueous medium with a contact
angle of greater than 90˚ is poured into this rubber-type mold. Under this condi-
tion the impression material is considered to be hydrophobic. To improve the
wetting of the impression by an aqueous solution of a gypsum-forming model
material, the manufacturer could change the formulation to render the material
more hydrophilic or a wetting agent could be added to the aqueous gypsum-
forming mixture.
However, if the energy of the adherend surface is reduced slightly by contamina-
tion or other means, the surface tension of the solid (γSV) decreases and a slight
increase in the contact angle (θ) can be measured (Fig. 2-16, B). This increase in θ
retains the force balance shown in Figure 2-16, D. Note that as θ increases from 0 to
90 degrees, the value of cos θ decreases from 1 to 0. If a monolayer film of a
38 PART I ■ General Classes and Properties of Dental Materials

0
A


B


C

Fig. 2-16 Adhesion depends on wetting the

surface. A, When the contact angle (θ) is 0
degrees, the liquid contacts the surface LV
completely and spreads freely. B, Small
contact angle on slightly contaminated
surface. C, Large angle formed by poor θ
wetting. D, The relationships among the D
surface tension of the solid (γSV), the liquid SV LS
(γLV), and the contact angle (θ) can be used to
LV cos θ
determine the surface tension between the
liquid and the solid (γLS) according to the
equation, γSV = γLS+ γLV cosθ. (Courtesy of K-J. SV  LS  LV cos θ
Söderholm.)

contaminant is present over the entire surface, a medium angle might be obtained,
whereas a very high angle would result on a solid of low surface energy (γSV), such
as polytetrafluoroethylene (Fig. 2-16, C). Because the tendency for the liquid to
spread increases as the contact angle decreases, the contact angle is a useful indica-
tor of spreadability or wettability (Fig. 2-16, D). Complete wetting occurs at a con-
tact angle of 0˚, and no wetting occurs at an angle of 180˚.
Thus the smaller the contact angle between an adhesive and an adherend, the bet-
ter the ability of the adhesive to flow into and fill in irregularities within the surface
of the adherend. The fluidity of the adhesive influences the extent to which these
voids or irregularities are filled.
Solid “flat” surfaces are not actually planar. Surface imperfections represent a
potential impediment to the achievement of an adhesive bond. Air pockets may be
created during the spreading of the adhesive that prevent complete wetting of the
entire surface (Fig. 2-17). When the adhesive interfacial region is subjected to ther-
mal changes and mechanical stresses, stress concentrations develop around these
voids. The stress may become so great that it initiates a separation in the adhesive
bond adjacent to the void. This crack may propagate from one void to the next, and
the joint may separate under stress.
 CHAPTER 2 ■ Structure of Matter and Principles of Adhesion 39

Fig. 2-17 Air voids created in surface

irregularities. Such regions contribute to
propagation of adhesive failure by concentration of Air bubbles acting
stress at these sites. (Courtesy of K-J. Söderholm.) as stress concentrators

CRITICAL QUESTION
Micromechanical bonding of resin sealant to tooth enamel is usually quite effective in pre-
? venting pit and fissure areas from tooth decay. However, many factors can reduce the
bonding effectiveness, resulting in partial or total loss of the sealant. Which of these factors
are possible causes of debonding?

ADHESION TO TOOTH STRUCTURE

The fundamental principles of adhesion can be readily related to dental situations.
For example, when contact angle measurements are used to study the wettability of
enamel and dentin, it is found that the wettability of these surfaces is markedly
reduced after the topical application of an aqueous fluoride solution. Transferring
this information to the clinical setting, we find that the fluoride-treated enamel sur-
face retains less plaque over a given period, presumably because of a decrease in
surface energy. Thus, in addition to the recognized mechanism of reduced enamel
solubility in an acidic environment, it is conceivable that fluoride products may be
effective in reducing dental caries by providing a tooth surface that stays cleaner over
a longer period.
Similarly, because of the higher surface energy of many restorative materials
compared with that of the tooth surface, there is a greater tendency for the surface
and margins of the restoration to accumulate debris. This may in part account for
the relatively high incidence of secondary (recurrent) carious lesions seen in enamel
at the margins of certain types of dental fillings.
The following chapters include discussions of the leakage that occurs between
tooth structure and dental restorations. Under certain instances, secondary caries,
pulpal sensitivity after placement of the filling or restoration, and deterioration at
the margins of the restoration can be associated with a lack of adhesion between the
restorative material and the tooth. Extensive research is in progress to develop adhe-
sives that adhere to tooth structure. In subsequent chapters, we shall consider how
traditional dental restorative procedures are affected by such adhesive systems.
By applying the principles that influence adhesion to dental structures, we can
see that the problems associated with dental adhesives are indeed complex. The
composition of tooth structures is not homogeneous. The amounts of both organic
and inorganic components present in dentin differ from the amounts of these com-
ponents present in enamel. A material that can adhere to the organic components
may not adhere to the inorganic components, and an adhesive that bonds to
enamel may not adhere to dentin to the same extent.
After the dentist has completed a tooth preparation for a filling, tenacious micro-
scopic debris covers the enamel and dentin surfaces. This surface contamination,
called the smear layer, reduces wetting. In addition, the instruments used to cut the
cavity leave a rough surface that may increase air entrapment at the interface.
The greatest problems associated with bonding to tooth surfaces are the inade-
quate removal of etching debris and the contamination by water or saliva. The
40 PART I ■ General Classes and Properties of Dental Materials

inorganic components of tooth structure have a strong affinity for water. The com-
plete removal of water would require the heating of enamel and dentin to an unac-
ceptable temperature. This means that a tooth cannot be safely dried at mouth
temperature with the devices and agents currently available to the dentist. The pres-
ence of at least a monolayer of water on the surface of the prepared cavity must be
accepted. This water layer reduces the surface energy, and it may reduce the wetting
of the etched tooth surface by the adhesive restorative material.
In addition, fluid is exchanged through certain components of the tooth. The
dental adhesive must displace the water, react with it, or wet the surface more effec-
tively than the water already present on the surface and within the tooth structure.
Furthermore, the adhesive must sustain long-term adhesion to tooth structure in an
aqueous environment.
Although the obstacles are formidable, the progress of research in the field of
adhesive materials is promising. To enhance adhesive bonding, manufacturers and
dentists are developing and using more hydrophilic resins that are not as sensitive
to the presence of moisture as materials previously in use. Certainly, these goals are
worthy of the challenges presented. A truly adhesive filling material could replace
many of those used in restorative dentistry. Likewise, the technique for placement of
the material would be simplified, and the mechanical retention of the material in
the cavity preparation would be unnecessary.
Even more intriguing is the possibility of developing a material capable of forming
a thin, durable film on the tooth surface that could be topically applied to the intact
enamel surface. Such a film with low surface energy could serve as a barrier to the for-
mation of plaque, the development of caries, and even the deposition of calculus.

SELECTED READINGS
Buonocore MG: The Use of Adhesives in Dentistry. Phillips RW, and Ryge G (eds): Proceedings on Adhesive
Springfield, IL, Charles C Thomas, 1975. Restorative Dental Materials. Spencer, IN, Owen Litho
The problems associated with dental adhesives are well illus- Service, 1961.
trated. Many of the procedures using bonding technology dis- These historical transactions resulted from the first workshop
cussed in this text have since become commonplace. on the problems of, and potential solutions to, the development
Glantz P: On wettability and adhesiveness. Odont Rev of adhesive dental materials. The recommendations for critically
20:1(Suppl 17):1, 1969. important areas of research have provided an impetus for inves-
The first in a series of publications by this author suggesting tigations in this area.
that the use of topical fluorides provides an additional mecha- Van Vlack LH: Elements of Materials Science and
nism involved in reduction of dental caries, that is, lowering of Engineering, 5th ed. Reading, MA, Addison-Wesley, 1985.
the surface energy of tooth structure and thereby reducing plaque An excellent text on materials science. Recommended for a
accumulation over a given interval. more in-depth coverage of materials structure and properties.
Gordon JE: The New Science of Strong Materials, or Why Zisman WA: Influence of constitution on adhesion. Ind
You Don’t Fall Through the Floor? 2nd ed. Princeton, NJ, Eng Chem 55:19, 1963.
Princeton University Press, 1984. One of the pioneers in surface phenomena discusses parame-
A general discussion of the strength of materials from a fun- ters that influence wetting. Zisman was a leader in the use of
damental base. Structural materials such as timber, cellulose, contact angle measurements to screen the potential wetting of
teeth, and bone are particularly interesting. adhesives to selected adherends.
 3
Physical Properties of Dental Materials
Kenneth J. Anusavice and William A. Brantley

OUTLINE
What Are Physical Properties?
Abrasion and Abrasion Resistance
Viscosity
Structural and Stress Relaxation
Creep and Flow
Color and Color Perception
Thermophysical Properties
Introduction to Tarnish and Corrosion
Causes of Tarnish and Corrosion
Classification of Corrosion
Electrochemical Corrosion
Protection Against Corrosion
Corrosion of Dental Restorations
Evaluation of Tarnish and Corrosion Resistance
Clinical Significance of Galvanic Currents

KEY TERMS
Chroma—Degree of saturation of a particular hue.
Coefficient of thermal expansion (linear coefficient of expansion)—Change in length per unit
of original length of a material when its temperature is raised 1˚ K.
Color—Sensation induced from light of varying wavelengths reaching the eye.
Concentration cell—An electrochemical corrosion cell in which the potential difference is
associated with the difference in concentration of a dissolved species, such as oxygen, in
solution along different areas of a metal surface.
Corrosion—Chemical or electrochemical process in which a solid, usually a metal, is
attacked by an environmental agent, resulting in partial or complete dissolution. Although
glasses and other nonmetals are susceptible to environmental degradation, metals are gen-
erally more susceptible to such attack because of electrochemical reactions.
Creep—Time-dependent plastic strain of a material under a static load or constant stress.
Crevice corrosion—Accelerated corrosion in narrow spaces caused by localized electro-
chemical processes and chemistry changes, such as acidification and depletion in oxy-
gen content. Crevice corrosion commonly occurs when microleakage takes place
between a restoration and the tooth, under a pellicle layer, or under other surface
deposits.

41
Other documents randomly have
different content
back; and Rome herself, unmoved by the violence of the
flood, lay in dark imperial purples against the western sky.
They all looked silently and hurried on.

When they reached the road, other people had collected

who stared in amazement at the strange figures, at the
rescued baby. More than one had seen the cradle carried
down under the bridge, but had never thought of possible
deliverance. Now there were willing feet enough to start off
after the cradle, to run in the opposite direction in order to
get tidings of what little farm had been swept away. And
fortunately one or two carriages had driven out from Rome,
the owners of which almost contested the honour of taking
the little party back. It was a strange drive. Joy and sorrow
at times are almost inextricably interwoven. Phillis, with the
baby’s dark and curly head pressed tightly against her, sat
and looked at Jack, who was, indeed, given back to her
from the dead, and all over the broken clouds golden lights
were radiating, and flashing down upon a watery world. The
little pools in the road reflected some of the brightness, the
roofs were shining, the rain drops gleamed on the trees, it
was like enchantment, so suddenly had all this opal light
grown out of the gloom. And yet, not so far away, a mother
was running wildly by the river, crying out for her lost baby;
and, far down, men, with long poles trying to snatch some
of his spoil from Tiber, touched a black and floating object,
and let it go with a push—“only a dog,” was what they said,
“and dead.”

Two nights afterwards some of those who had been dining

at the table-d’hôte went out into the Piazza di Spagna.
There was an eclipse, or something which gave them the
excuse for coming into the solemn and wonderful darkness,
lit by tremulous stars, and musical with the constant cool
splash of the fountain. Carriages were flying backwards and
forwards, people lounging about, but they did not interfere
much with the beauty or the quiet. The group of friends
broke into little knots, two stood a little way up the Spanish
steps, and leaned against the parapet One of them, a man,
was saying:—

“Do not be afraid. These disappointments may sadden, but

they do not wreck our lives. You have given me memories
to cherish for ever, although this is a good-bye we are
saying; yes, good-bye, and God bless you, my dear. Susan
and I are going off to-morrow; there is south Italy to see, it
would never do for us, you know, to go home and to have
nothing to report of Vesuvius and Pompeii.”

She was crying softly, she felt the kind pressure of his hand,
she did not know that he had moved away because another
figure was running up the steps. “Phillis!” said Jack in a low
voice.

And then she turned and laid her head upon his shoulder.

“Oh, it is hard, hard!” she said. “Jack, must there always be

pain with one’s deepest happiness!”

He did not quite understand, but perhaps he guessed

enough, and he was very gentle with her. For indeed it
seemed as if the joy of their life had come to them through
death and sorrow of heart. Is it not so often? Will it not be
so to the very end?

Presently he began to talk about the baby; the mother had

been found the very day of the flood, and had walked and
run all the way into Rome, almost mad with the bliss of the
tidings. And Jack had been out to the spot where the little
farm had stood, and had seen all the desolation and ruin,
and was going to make his thank-offering and Phillis’s, take
the form of a new building. Over the door there would be
carved the figure of a dog, with a date.
Before this was done there were two weddings in Rome.
Bice and young Count Moroni were married first, and two or
three days after, Phillis Grey and John Ibbetson. It was one
of those bright Easter days when Rome breaks into delicious
harmonies of spring; when the banksia roses fling
themselves over the walls like foam, and delicate plants
spring out of the mighty brickwork, and the sky is one
unbroken depth of blue, and the sun shines on the fountain
of Trevi, on the falling waters which came rushing out, on
the pigeons which fly backwards and forwards, and perch
themselves on Neptune’s head. The wedding was very
quiet. Scarcely half a dozen people were in the Church, and
in an hour or two Jack and Phillis were to start for Florence
on their way to Venice. But before this Phillis had a wish
which naturally was to be gratified. They must drive to the
Ponte Molle and see the spot where Cartouche had died for
his master.

On their way Jack put into her hands a letter from his uncle,
written with some triumph, but little cordiality.

“Oliver Trent!” repeated Phillis, as she came to a sentence

with his name.

“Oliver Thornton, perhaps, one of these days,” said Jack,

folding the letter and putting it back in his pocket. “Who
knows? I’m sure I don’t. But if so, I hope Hetherton will
disagree with him.”

Phillis, who rather disliked the name of Hetherton, said

quickly:—

“We will not begrudge it to him.”

“Yes, I shall,” persisted Jack, “because I object to successful

villainy, and to being disappointed of my moral.” But seeing
that Phillis looked at him wistfully, he drew her closer to
him. “My darling, do you suppose Hetherton seems
anything to me now?”

They had not much time to spare, and walked quickly from
the bridge along the river side. So changed was it from that
other day, that it might, so Phillis thought, have been
another stream. Instead of wild anger there was only a
stately sweep in the slowly moving water, and though some
marks of past turbulence might be here and there visible on
the banks, they were not many, and under the warm sun all
the green bordering was springing into glad life once more.

But, though where it had been was now dry land, the little
bank was gone. Phillis grew pale and clung to Jack when
she saw this, she could not speak except by that mute
gesture, and he answered it mutely, too. For there where
Cartouche had died and he had been given back to life and
her, he kissed his wife, and held her in his arms.

Do people forget as quickly as we commonly believe?

Outward marks and signs of remembrance die away, it is
true, others fill the vacant places, and we look into smiling
faces and say “he or she is forgotten—it is the way of the
world.” But, after all, what do we know? Do not our own
memories often startle us? At all sorts of strange times,
with a silent foot-fall inaudible to any but ourselves, they
come warm, and strong, and living. We do not forget so
easily, nor perhaps shall we be forgotten so soon as we all
think. God gave good gifts to this husband and wife, and
the crown of happy love, but both of them remembered and
kept their memories sacred in their hearts. And a peasant
woman in a southern country has taught her children to
love animals and be good to them, for one of them, she
says, was once saved by a dog. The children listen, thrilled
by the familiar story. “Eccolo!” cries a girl, pointing, and
they all turn and look up where, over the door, is the carved
figure of a dog, with a date.

The End.

| Chapter 1 | | Chapter 2 | | Chapter 3 | | Chapter 4 | | Chapter 5 |

| Chapter 6 | | Chapter 7 | | Chapter 8 | | Chapter 9 | | Chapter 10
| | Chapter 11 | | Chapter 12 | | Chapter 13 | | Chapter 14 | |
Chapter 15 | | Chapter 16 | | Chapter 17 | | Chapter 18 | | Chapter
19 | | Chapter 20 | | Chapter 21 | | Chapter 22 | | Chapter 23 | |
Chapter 24 | | Chapter 25 | | Chapter 26 |
 *** END OF THE PROJECT GUTENBERG EBOOK CARTOUCHE ***

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