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HIERARCHICAL STRUCTURES
IN BIOLOGY AS A GUIDE FOR
NEW MATERIALS
TECHNOLOGY
COMMITTEE ON SYNTHETIC HIERARCHICAL STRUCTURES
NATIONAL MATERIALS ADVISORY BOARD
COMMISSION ON ENGINEERING AND TECHNICAL SYSTEMS
NATIONAL RESEARCH COUNCIL
NMAB-464
NATIONAL ACADEMY PRESS
Washington, D.C. 1994
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NOTICE: The project that is the subject of this report was approved
by the Governing Board of the National Research Council, whose
members are drawn from the councils of the National Academy of
Sciences, the National Academy of Engineering, and the Institute of
Medicine. The members of the committee responsible for the report
were chosen for their special competences and with regard for
appropriate balance.
This report has been reviewed by a group other than the authors
according to procedures approved by a Report Review Committee
consisting of members of the National Academy of Sciences, the
National Academy of Engineering, and the Institute of Medicine.
This study by the National Materials Advisory Board was conducted
under Contract No. MDA 972-92-C-0028 with the U.S. Department
of Defense and the National Aeronautics and Space Administration.
Library of Congress Catalog Card Number 94-69232
International Standard Book Number 0-309-04638-6
Available in limited supply from: Additional copies are available for
sale from:
National Materials Advisory Board National Academy Press
2101 Constitution Avenue, NW 2101 Constitution Avenue, NW
HA-262
Washington, D.C. 20418
202-334-3505
Box 285
Washington, D.C. 20055
800-624-6242 or 202-334-3313 (in
the Washington Metropolitan Area)
Copyright 1994 by the National Academy of Sciences. All rights
reserved.
Printed in the United States of America.
Cover photograph: Scanning electron micrograph of the fracture
surface of the wing cover of a Bessbeetle (Popilitls disjunctusJ.
Courtesy of Steve Gunderson, University of Dayton Research
Institute.
Cover diagram: Structural hierarchy of cellulose in wood. Courtesy
of D. Kaplan, U. S. Army.
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COMMITTEE ON
SYNTHETIC HIERARCHICAL STRUCTURES
DAVID A. TIRRELL, Chair, University of Massachusetts, Amherst
ILHAN AKSAY, Princeton University, Princeton, New Jersey
ERIC BAER, Case Western Reserve University, Cleveland, Ohio
PAUL D. CALVERT, University of Arizona, Tucson
JOSEPH CAPPELLO, Protein Polymer Technologies, San Diego,
California
EDMUND A. DIMARZIO, National Institute of Standards and
Technology, Gaithersburg, Maryland
EVAN A. EVANS, University of British Columbia, Vancouver
JOHN FESSLER, University of California, Los Angeles
JOHN D. HOFFMAN, The Johns Hopkins University, Baltimore,
Maryland
MICHAEL JAFFE, Hoechst Celanese Research Division, Summit,
New Jersey
GEORGE MAYER, University of Pittsburgh, Pittsburgh,
Pennsylvania
VAN C. MOW, Columbia-Presbyterian Medical Center, Columbia
University, New York, New York
STEPHEN A. WAINWRIGHT, Duke University, Durham, North
Carolina
Government Liaison Representatives
ED CHEN, U.S. Army Laboratory Command, Army Research Office,
Research Triangle Park, North Carolina
FREDERICK L. HEDBERG, Air Force Office of Scientific
Research, Washington, D.C.
· · .
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DAVID KAPLAN, Department of the Army, Natick Research
Development and Engineering Center, Natick, Massachusetts
MICHAEL MARRON, Office of Naval Research, Arlington, Virginia
IRA SKURNICK, Advance Research Projects Agency/Defense
Sciences Office, Arlington, Virginia
NORMAN TALLAN, Wright Patterson Air Force Base, Ohio
RONALD TAYLOR, National Academy of Sciences, Washington,
D.C.
HOLLIS WICKMAN, National Science Foundation, Washington, D.C.
National Materials Advisory Board Staff
THOMAS E. MUNNS, Senior Program Officer
AIDA C. NEEL, Senior Project Assistant
1V
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ACKNOWLEDGMENTS
The Committee on Synthetic Hierarchical Structures is grateful to
many individuals for their presentations covering specific technical
areas relevant to hierarchical systems. Speakers included Dr. Richard
Farrell and Mr. Russell McCalley of Johns Hopkins University's
Applied Physics Laboratory, who discussed cornea structure and its
effects on corneal transparency; Dr. Donald Johnson of Weyerhaeuser,
who spoke of the production of bacterial cellulose; Dr. Clement
Furlong of the University of Washington, who talked on the
production of proteins for commercially useful self-assembly systems;
and Dr. Robert Newnham of Pennsylvania State University, who
discussed electroceramics, which included smart materials and
biomimetics.
The committee is also grateful to the government liaison
representatives for their participation in a number of committee
discussions in particular to Dr. David Kaplan of the U.S. Army's
Natick Laboratory, who described some of the laboratory's in-house
programs and interests in hierarchical systems and whose own research
is reflected in these pages, and to Michael Marron of the Office of
Naval Research, who identified needs in adhesive bonding.
The chair of the committee thanks the members for their dedication
and patience during the numerous iterations and revisions of the
report.
Finally, the committee gratefully acknowledges the support of Dr.
Stanley Barkin, the senior program officer who supported the study
until his retirement in April 1992; his successor, Mr. Thomas E.
Munns; and administrative assistants, Ms. Cathryn Summers and Ms.
Aida C. Neel.
v
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The National Academy of Sciences is a private, nonprofit, self-
perpetuating society of distinguished scholars engaged in scientific and
engineering research, dedicated to the furtherance of science and
technology and to their use for the general welfare. Upon the
authority of the charter granted to it by the Congress in 1863, the
Academy has a mandate that requires it to advise the federal
government on scientific and technical matters. Dr. Bruce M. Alberts
is president of the National Academy of Sciences.
The National Academy of Engineering was established in 1964,
under the charter of the National Academy of Sciences, as a parallel
organization of outstanding engineers. It is autonomous in its
administration and in the selection of its members, sharing with the
National Academy of Sciences the responsibility for advising the
federal government. The National Academy of Engineering also
sponsors engineering programs aimed at meeting national needs,
encourages education and research, and recognizes the superior
achievements of engineers. Dr. Robert M. White is president of the
National Academy of Engineering.
The Institute of Medicine was established in 1970 by the National
Academy of Sciences to secure the services of eminent members of
appropriate professions in the examination of policy matters
pertaining to the health of the public. The Institute acts under the
responsibility given to the National Academy of Sciences by its
congressional charter to be an adviser to the federal government and,
upon its own initiative, to identify issues of medical care, research,
and education. Dr. Kenneth I. Shine is president of the Institute of
Medicine.
The National Research Council was organized by the National
Academy of Sciences in 1916 to associate the broad community of
science and technology with the Academy's purposes of furthering
knowledge and advising the federal government. Functioning in
accordance with general policies determined by the Academy, the
Council has become the principal operating agency of both the
National Academy of Sciences and the National Academy of
Engineering in providing services to the government' the public, and
the scientific and engineering communities. The Council is
administered jointly by both Academies and the Institute of Medicine.
Dr. Bruce M. Alberts and Dr. Robert M. White are chairman and vice
chairman, respectively, of the National Research Council.
.
V1
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ABSTRACT
Hierarchical structures are assemblages of molecular units or their
aggregates that are embedded or intertwined with other phases, which
in turn are similarly organized at increasing size levels. The multilevel
architectures are capable of conferring unique properties to the
structure. Hierarchical structures are found in practically all complex
systems, particularly naturally occurring ones. Synthetic hierarchical
structures can be prepared from metals, ceramics, or polymers, or
from hybrids of various classes of these materials.
The Committee on Synthetic Hierarchical Structures made an
assessment of the opportunities to prepare hierarchical structures that
possess useful and unusual physical properties for civilian and military
applications. It conducted case-studies by selecting natural material
systems to be used as models for synthetic efforts. It reviewed the
state of the art of synthetic techniques and processes for assembling
synthetic hierarchical structures. The committee also characterized
properties, unusual characteristics, and potential end-use applications
for these synthetic systems. Finally, the committee recommended
research directions to expedite the understanding of the complex
phenomena involved, lead to increased coordination among disciplines,
and provide direction for future activities in the field.
· -
V11
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PREFACE
Many materials systems found in nature exhibit a combination of
properties that is not found in synthetic systems. The unique
performance of natural materials arises from precise hierarchical
organization over a large range of length scales. These materials
display unique properties that are affected by structure and generative
processes at all levels of the biological structural hierarchy.
At the request of the Department of Defense and the National
Aeronautics and Space Administration, the National Materials
Advisory Board convened a committee' the Committee on Synthetic
Hierarchical Structures, to review techniques related to the preparation
of hierarchical structures that possess useful and unusual physical
properties and assess the opportunities for these structures in civilian
and military applications. Although a broad range of functions are
represented in biological systems, the committee concentrated on
structural material systems.
The approach taken by the committee was to conduct case-studies
that selected natural material systems to be used as models for
synthetic efforts; characterize properties, unusual characteristics, and
potential end-use applications for these synthetic systems; review
state-of-the-art synthetic techniques and processes for assembling
synthetic hierarchical structures; and recommend research that will
expedite the understanding of the complex phenomena involved, lead
to increased coordination among disciplines, and provide direction for
future activities in the field.
In Chapter 1, the concept of hierarchical materials systems is
introduced. Chapter 2 examines hierarchical architecture and
illustrates its significance through a discussion of the structures and
properties of a variety of biological materials systems. Several
examples of synthetic hierarchical materials systems are described in
.
IX
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Chapter ]. Chapter 4 assesses the current capacl1y 10 produce such
materials. And Chapter ~ presents the conclusions and
recommendations of the committee, identifies grew of science sad
technology where hierarchical materials systems could play important
roles, and suggests the research objectives that must be met to realize
the potential of this new approach to malerlab technology.
David A. Tirrell
Chair
x
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CONTENTS
EXECUTIVE SUMMARY
1 INTRODUCTION
2 NATURAL HIERARCHICAL MATERIALS
Recurrent Use of Molecular Constituents, 18
Controlled Orientation, 23
Durable Interfaces Between Hard and Soft Materials, 26
The Role of Water, 27
Property Variation in Response to Changing Performance
Requirements, 32
Fatigue Resistance and Self-Repair, 34
Shape Control, 36
3 SYNTHETIC HIERARCHICAL SYSTEMS
Introduction, 39
One-Dimensional Hierarchy, 43
Two-Dimensional Hierarchy, 49
Three-Dimensional Hierarchy, 52
Adjustable Variables and Their Influence on Mechanical
Behavior of Synthetic Materials, 59
4 FABRICATION OF HIERARCHICAL SYSTEMS
Synthetic Processing, 75
Biologically Inspired Processing, 84
Xl
1
13
17
39
73
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CONCLUSIONS AND RECOH~ENDAlIONS:
SCIENlIfIC AND TECHNOLOGICAL OPPORTUNITIES 93
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frore~f",, ad
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"fNe~, Pa
a// Oppor'""f4~, 704
REFERENCES
APPENDIX ~ GLOSSARY OF leaks
APPENDIX ~ BIOGRAPHICAL SKETCHES OF
CO~HIllEE HEHHERS
. .
X11
111
123
127
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HIERARCHICAL STRUCTURES
IN BIOLOGY AS A GUIDE FOR
NEW MATERIALS
TECHNOLOGY
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