Polyurethane shape-memory polymers. Huang, Yang Bin

374 Pages·2011·14.938 MB·English

by  W M Huang

Huang
Materials Science
Yang
Polyurethane Shape Fu
Polyurethane Shape
Memory Polymers
P
o
Memory Polymers
l
y
Shape memory polymers (SMPs) are some of the most important and valuable
u
engineering materials developed in the last 25 years. These fascinating
r
materials demonstrate remarkably versatile properties—including capacity e
for actuation and stimulus responsiveness—that are enabling technologists t
h
to develop applications to be used in the exploration of everything from the
outer reaches of space to the inside of the human body. a
n
Polyurethane Shape Memory Polymers details the fundamentals of SMP e
makeup, as well as their shape-recovery features and their seemingly endless
S
potential for use in applications ranging from macro- to submicron scales.
With an abundance of illustrations and vivid pictures to explain how SMPs h
and composites work and how they can be used, this book covers: a
p
• SMP history and most recent developments e
• Thermomechanical properties and behavior of the polymers and
their composites M
• Modification of SMPs and novel actuation mechanisms
e
• Large-scale surface pattern generation
m
• Multi-shape memory effect
• Fabrication techniques
o
• Characterization of composites
r
y
A must-have reference for anyone working in the materials science and

engineering fields, this book outlines the properties—such as light weight, P
low cost, and ability to handle high strain—that make the easily processed o
SMPs so useful in fields including aerospace, biomedicine, and textiles. It is l
y
intended to help readers understand and apply the knowledge and techniques
m
presented to develop new innovations that will further benefit society.
W.M. Huang
e
r
K11723 Bin Yang
s
ISBN: 978-1-4398-3800-6
90000 Yong Qing Fu
6000 Broken Sound Parkway, NW
Suite 300, Boca Raton, FL 33487
711 Third Avenue
New York, NY 10017
9 781439 838006
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Abingdon, Oxon OX14 4RN, UK www.crcpress.com
Polyurethane Shape
Memory Polymers
W. M. Huang
Bin Yang
Yong Qing Fu
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
CRC Press
Taylor & Francis Group
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© 2012 by Taylor & Francis Group, LLC
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Version Date: 20111003
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Contents
Forewords...................................................................................................................ix
Preface....................................................................................................................xiii
Authors......................................................................................................................xv
Chapter 1 Introduction...........................................................................................1
1.1. Shape.Memory.Materials.and.Shape.Memory.Polymers...........1
1.2. Mechanisms.of.Shape.Memory.Effects.in.Shape.
Memory Polymers......................................................................6
1.3. Typical.Applications.of.Shape.Memory.Polymers.....................9
1.4. Polyurethane.Shape.Memory.Polymers...................................13
1.5. Outline.of.Book........................................................................20
Acknowledgments...............................................................................21
References...........................................................................................21
Chapter 2 Thermomechanical.Behavior.of.Polyurethane.Shape.Memory.
Polymer...............................................................................................31
2.1. Introduction..............................................................................31
2.2. Glass.Transition.Temperature.and.Thermal.Stability..............33
2.3. Dynamic.Mechanical.Properties..............................................34
2.4. Uniaxial.Tension.in.Glass.State................................................36
2.5. Uniaxial.Tension.in.Rubber.State.............................................38
2.6. Recovery.Tests..........................................................................47
2.7. Summary..................................................................................48
Acknowledgment.................................................................................50
References...........................................................................................50
Chapter 3 Effects.of.Moisture.on.Glass.Transition.Temperature.
and.Applications..................................................................................51
3.1. Introduction..............................................................................51
3.2. Moisture.Absorption.in.Room-Temperature.Water..................51
3.3. Glass.Transition.Temperature.after.Immersion........................53
3.4. Evolution.of.Glass.Transition.Temperature.upon.
Thermal Cycling.......................................................................55
3.5. Interaction.of.Water.and.Polyurethane.SMP............................55
3.6. Correlation.of.Moisture,.Glass.Transition.Temperature,.
and.Hydrogen.Bonding.............................................................59
3.7. New.Features.Based.on.Effects.of.Moisture............................65
iii
iv Contents
3.8. Recovery.Tests..........................................................................66
3.9. Summary..................................................................................69
Acknowledgment.................................................................................69
References...........................................................................................69
Chapter 4 Electrically.Conductive.Polyurethane.Shape.Memory.Polymers.......71
4.1. Introduction..............................................................................71
4.2. Preparation.of.Electrically.Conductive.Polyurethane.
SMP..........................................................................................72
4.3. Shape.Recovery.by.Passing.Electrical.Current........................73
4.4. Distribution.of.Carbon.Powder.in.Polyurethane.SMP.............73
4.5. Electrical.Resistivity.................................................................76
4.5.1. Dependence.on.Loading.of.Carbon.Powder...............76
4.5.2. Effects.of.Temperature.and.Uniaxial.
Mechanical Strain.......................................................77
4.6. Thermal.Stability......................................................................81
4.7. Uniaxial.Tensile.Testing.at.Room.Temperature.......................82
4.8. Shape.Memory.Properties.upon.Heating.................................84
4.8.1. Fixable.Strain..............................................................85
4.8.2. Recoverable.Strain......................................................85
4.8.3. Recovery.Stress...........................................................88
4.9. Summary..................................................................................90
Acknowledgment.................................................................................90
References...........................................................................................90
Chapter 5 Effects.of.Moisture.on.Electrically.Conductive.Polyurethane.
Shape.Memory.Polymers....................................................................93
5.1. Introduction..............................................................................93
5.2. Absorption.of.Moisture.in.Room-Temperature.Water..............93
5.3. Electrical.Resistivity.after.Immersion......................................95
5.4. Glass.Transition.Temperature.after.Immersion........................96
5.5. Evolution.of.Glass.Transition.Temperature.
upon.Thermal.Cycling..............................................................97
5.6. Correlation.of.Moisture.Absorption,.Loading.of.Carbon.
Powder,.and.Glass.Transition.Temperature..............................98
5.7. Effects.of.Moisture.on.Thermomechanical.Properties..........102
5.7.1. Damping.Capability..................................................102
5.7.2. Young’s.Modulus.......................................................105
5.7.3. Uniaxial.Tension.Behavior........................................108
5.7.4. Moisture-Responsive.Shape.Recovery......................111
5.8. Summary................................................................................114
Acknowledgment...............................................................................114
References.........................................................................................114
Contents v
Chapter 6 Magnetic.and.Conductive.Polyurethane.Shape.
Memory Polymers.............................................................................117
6.1. Introduction............................................................................117
6.2. Iron.Oxide.Micro.Particles.....................................................117
6.2.1. Influence.of.Moisture.on.T.......................................118
g
6.2.2. Alignment.of.Iron.Oxide.Micro.Particles.................120
6.2.3. Altering.Surface.Roughness.and.Morphology..........124
6.3. Nickel.Micro.and.Nano.Powders............................................127
6.3.1. Alignment.of.Ni.Powder...........................................127
6.3.2. Vertical.Chains..........................................................130
6.4. Electrically.Conductive.SMPs................................................130
6.4.1. Ni.Powder..................................................................133
6.4.2. Polyurethane–Carbon.Black.with.Additional.
Nickel.Powder...........................................................139
6.5. Summary................................................................................143
Acknowledgments.............................................................................143
References.........................................................................................144
Chapter 7 Shape.Memory.Polymer.Nanocomposites........................................147
7.1. Introduction............................................................................147
7.2. Synthesis.Techniques.of.SMP.Nanocomposites.....................150
7.2.1. Solution.Mixing.........................................................150
7.2.2. Melting.Mixing.........................................................151
7.2.3. In Situ.or.Interactive.Polymerization........................152
7.2.4. Electrospinning.........................................................153
7.2.5. Techniques.to.Enhance.Dispersion.of.CNTs.............153
7.3. Shape.Memory.Polymer.Nanocomposites.............................154
7.3.1. Nanocomposites.for.Mechanical.Enhancement........154
7.3.1.1. Nanoparticle-Based.
SMP Nanocomposites................................154
7.3.1.2. Clay-Based.SMP.Nanocomposites............156
7.3.1.3 CNT-Based.Nanocomposites.....................163
7.3.1.4. Carbon.Nanofibers.....................................165
7.3.2 SMP.Nanocomposites.for.Electrical.Actuation........167
7.3.2.1. Carbon.Nanoparticle-Based.
Nanocomposites.........................................168
7.3.2.2. CNF-.and.CNT-Based.
Nanocomposites.........................................169
7.3.2.3. Graphene-Based.Nanocomposites.............170
7.3.3. SMP.Nanocomposites.for.Magnetic.
Field Actuation..........................................................172
7.3.4. SMP.Nanocomposites.for.Optical.
and.Photovoltaic.Actuation.......................................172
7.3.5. Thermal.Properties.of.SMP.Nanocomposites...........173
vi Contents
7.4. Summary................................................................................174
Acknowledgment...............................................................................174
References.........................................................................................174
Chapter 8 Porous.Polyurethane.Shape.Memory.Polymers................................185
8.1. Introduction............................................................................185
8.2. Water.as.Foaming.Agent.for.Porous.SMPs............................188
8.2.1. Materials.and.Sample.Preparation............................189
8.2.2. Results.and.Discussion..............................................189
8.3. Formation.of.Bubbles.by.Heat.Treatment..............................190
8.3.1. Sample.Preparation.and.Bubble.Formation..............197
8.3.2. Tuning.Bubble.Sizes..................................................200
8.3.2.1. Bubble.Size.Adjustment.............................200
8.3.2.2. Reversible.Bubbles.....................................208
8.4. Thermomechanical.Behaviors.of.SMP.Foams.......................208
8.4.1. Sample.Preparation.and.Experimental.Setup...........208
8.4.2. Experiments.and.Results...........................................210
8.4.2.1. Compression.Test.......................................210
8.4.2.2. Free.Recovery.Test....................................214
8.4.2.3. Constrained.Cooling.Test..........................214
8.4.2.4. Gripping.and.Shape.Recovery.Test...........218
8.5. Yield.Surface.of.Foam............................................................222
8.5.1. Framework.................................................................224
8.5.2. Applications.in.Foams...............................................229
8.6. Influence.of.Storage.on.Polyurethane.SMP.Foams................231
8.6.1. Pre-Compression.and.Hibernation............................233
8.6.2. Recovery.Tests...........................................................233
8.6.2.1. Constrained.Recovery...............................233
8.6.2.2. Recovery.against.Constant.Load...............235
8.7. Summary................................................................................237
Acknowledgments.............................................................................238
References.........................................................................................238
Chapter 9 Shape.Memory.Effects.at.Micro.and.Nano.Scales...........................241
9.1. Introduction............................................................................241
9.2. SMP.Thin.Wires.....................................................................242
9.3. SMP.Micro.Beads..................................................................245
9.4. SMP.Thin.and.Ultrathin.Films..............................................250
9.4.1. Water.Float.Casting...................................................250
9.4.2. Spin.Coating..............................................................251
9.5. Surface.Patterning.atop.Shape.Memory.Polymers.................255
9.5.1. Butterfly-Like.Feature...............................................257
9.5.2. Patterning.by.Indentation,.Polishing,.
and.Heating.(IPH).....................................................261
9.5.3. Laser-Assisted.Patterning..........................................267
Contents vii
9.6. Summary................................................................................272
Acknowledgments.............................................................................272
References.........................................................................................272
Chapter 10 Wrinkling.atop.Shape.Memory.Polymers.........................................275
10.1. Introduction............................................................................275
10.2. Theory.of.Wrinkling..............................................................278
10.2.1. Semi-Analytical.Method...........................................279
10.2.2. Numerical.Simulation...............................................283
10.3. Wrinkling.atop.SMPs.............................................................284
10.3.1. Thermomechanical.Properties.of.SMP.Samples........284
10.3.2. Wrinkling.of.Gold.Thin.Film.atop.Flat.
SMP Substrate...........................................................285
10.3.3. Wrinkling.of.Gold.Thin.Film.atop.Curved.SMP......290
10.3.4. Wrinkling.atop.Patterned.Samples...........................301
10.4. Summary................................................................................303
Acknowledgment...............................................................................303
References.........................................................................................304
Chapter 11 Medical.Applications.of.Polyurethane.Shape.Memory.Polymers....307
11.1. Introduction............................................................................307
11.2 Thermo-Responsive.Feature-Based.Devices..........................309
11.3. Thermo-.and.Moisture-Responsive.Feature-
Based Devices........................................................................311
11.4. Toward.Micro.Machines.........................................................318
11.5. Summary................................................................................321
Acknowledgments.............................................................................321
References.........................................................................................322
Chapter 12 Mechanisms.of.Multi-Shape.and.Temperature.Memory.Effects......325
12.1. Multi-Shape.Memory.Effect.and.Temperature.
Memory Effect.......................................................................325
12.2. Demonstration.of.Multi-SME.and.TME.in.
Polyurethane SMP..................................................................330
12.2.1. Multi-SME................................................................330
12.2.2. TME..........................................................................332
12.3. Mechanisms............................................................................333
12.3.1. Multi-SME................................................................333
12.3.2. TME..........................................................................337
12.3.3. Influence.of.Hysteresis..............................................339
12.4. Summary................................................................................340
Acknowledgments.............................................................................340
References.........................................................................................341
viii Contents
Chapter 13 Future.of.Polyurethane.Shape.Memory.Polymers............................343
13.1. Characterization.and.Modeling.of.SMPs...............................343
13.2. Stability.of.SME.....................................................................344
13.3. Cyclic.Actuation.....................................................................345
13.4. Alternative.Actuation.Techniques..........................................350
13.5. Multiple.Functions..................................................................351
Acknowledgments.............................................................................354
References.........................................................................................354
Forewords
This.book,.Polyurethane Shape Memory Polymers,.authored.by.Dr..Wei.Min.Huang,.
Dr..Bin.Yang,.and.Dr..Yong.Qing.Fu,.is.the first book dedicated.to.polyurethane.
shape.memory.polymers—some.of.the.most.important.types.of.shape.memory.poly-
mers.in.existence..As.a.senior.researcher.with.more.than.two.decades.of.experience.
in.this.field,.I.am.very.happy.to.see.the.publication.of.this.book.by.CRC.Press/Taylor.
&.Francis.Group.
This.book.is.suitable.not.only.for.macromolecule.engineers.and.researchers.work-
ing.on.developing.new.shape.memory.polymers.and.improving.the.performances.of.
existing.ones,.but.also.for.students.studying.polymer.chemistry.to.acquire.a.good.
understanding.of.the.fundamentals.of.shape.memory.polymers..On.one.hand,.this.
book.is.a.useful.reference.for.research.and.development;.on.the.other,.it.serves.as.a.
perfect.introduction.for.anyone.who.is.interested.in.learning.more.about.this.fantas-
tic.material.
The.content.of.this.book.is.carefully.structured.with.plenty.of.application.exam-
ples..I.am.sure.that.readers.will.be.fascinated.by.the.wonderful.world.of.shape.mem-
ory.polymers.
Dr. Shunichi Hayashi
SMP Technologies, Inc.
Japan
In.recent.years,.intelligent.or.smart.materials.have.attracted.worldwide.attention..
One.of.the.main.types.that.stimulated.research.into.intelligent.materials.is.the.shape.
memory.alloy..The.polyurethane.shape.memory.polymer,.in.particular,.also.has.been.
applied.practically.in.a.wide.variety.of.fields..Dependence.of.the.elastic.modulus.and.
yield.stress.on.temperature.in.a.shape.memory.polymer.is.quite.the.opposite.of.the.
principle.of.a.shape.memory.alloy..The.very.large.volume.change.of.a.shape.memory.
polymer.foam.makes.this.material.valuable.for.inflatable.structures.in.the.aerospace.
field..The.gas.permeability.of.the.shape.memory.polymer.thin.film.varies.signif-
icantly.above.and.below.the.glass.transition.temperature—a.property.with.many.
applications.in.the.medical.and.textile.fields..If.both.of.these.outstanding.qualities.of.
the.shape.memory.alloy.and.the.shape.memory.polymer.are.combined,.it.becomes.
possible.to.develop.a.shape.memory.composite.that.exhibits.completely.new.high-
performance.functions.
In.order.to.develop.shape.memory.polymer.elements,.it.is.also.important.to.under-
stand.the.thermomechanical.properties.of.these.materials..The.thermomechanics.of.
shape.memory.polymers.are.very.complex.because.they.depend.on.hysteresis..The.
most.basic.and.important.properties.of.the.polyurethane.shape.memory.polymer.are.
ix