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Characterization Methods for Shape-Memory Polymers

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Shape-Memory Polymers

Part of the book series: Advances in Polymer Science ((POLYMER,volume 226))

Abstract

Shape-memory polymers (SMPs) are able to fix a temporary deformed shape and recover their original permanent shape upon application of an external stimulus such as heat or light. A shape-memory functionalization can be realized for polymer based materials with an appropriate morphology by application of a specific shape-memory creation procedure (SMCP). Specific characterization methods have been tailored to explore the structure-function relations of SMPs in respective applications. This paper reviews characterization methods on different length scales from the molecular to the macroscopic level.

On the molecular morphological level SMPs are comprised of netpoints determining the permanent shape and reversible crosslinks fixing the temporary shape. For polymers with covalent permanent netpoints the crosslinking density plays an important role, which can be quantified by means of swelling experiments or nuclear magnetic resonance (NMR) methods. In contrast, thermoplastic SMPs are typically phase-segregated polymers, where each domain is related to a different thermal transition, which can be explored by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). Further suitable techniques for investigations of the SMP morphology on different levels of hierarchy are polarized light microscopy (POM), scanning or transmission electron microscopy (SEM, TEM) and atomic force microscopy (AFM) as well as wide and small X-ray scattering (WAXS, SAXS).

On the macroscopic level the extent to which a temporary deformation can be fixed and the recovery of the permanent shape or the recovery stress are the most important characteristics of the shape-memory effect (SME), which can be quantified in cyclic, thermomechanical tensile tests or bending tests. Such cyclic tests consist of a SMCP module that can be performed either under stress or strain control followed by a recovery module under stress-free or constant strain conditions. The obtained shape-memory properties are strongly influenced by temperature dependent test parameters like deformation and fixation temperature or applied heating and cooling rate. In addition cyclic, photomechanical testing of light-induced dual-shape polymers, where the temporary shape is fixed by photoreversible chemical crosslinks and the testing of magnetically-induced shape-memory composites are described. In contrast multi-phase polymer networks, which exhibit a triple-shape effect, are explored in cyclic, thermomechanical experiments utilizing a specific two-step SMCP. Furthermore a selection of application-oriented tests for characterization of SME is presented.

Finally, as part of a comprehensive characterization, modeling approaches for simulating the thermomechanical behavior of SMPs are presented. At the beginning linear viscoelastic models were applied consisting of coupled spring, dashpot and frictional elements. More recent approaches consider in detail the specific molecular transition underlying the SME, e.g. glass or melting transition. Currently models that incorporate the strain rate dependence and time dependent behavior are under development.

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Abbreviations

βc :

Cooling rate

βh :

Heating rate

ε:

Nominal strain

εb :

Strain at break

εm :

Default strain in a cyclic, thermomechanical experiment

εp :

Recovered strain in a cyclic, thermomechanical experiment

εu :

Fixed strain after unloading in a cyclic, thermomechanical experiment

σ:

Stress

σm :

Stress after stretching a sample to εm in a cyclic, thermomechanical experiment

DMTA:

Dynamic mechanical thermal analysis

DSC:

Differential scanning calorimetry

E :

Young’s modulus

E ′ :

Storage modulus

E ′′ :

Loss modulus

G :

Shear modulus

HRMAS:

High resolution magic angle spinning in NMR-spectroscopy

Hz:

Hertz

IPN:

Interpenetrating polymer network

MA:

Methacrylate

m d :

Mass of the extracted and dried network

m iso :

Mass of the unextracted polymer network

M n :

Number average molecular weight

m q :

Mass of the swollen polymer network

N :

Consecutive number in a cyclic, thermomechanical experiment

NMR:

Nuclear magnetic resonance

Q :

Degree of swelling

R f :

Shape fixity ratio

R r :

Shape recovery ratio

SME:

Shape-memory effect

SMP:

Shape-memory polymer

tanδ:

Loss factor

T deform :

Deformation temperature

T g :

Glass transition temperature

T high :

Temperature at which recovery is performed

T low :

Temperature at which temporary shape is fixed

T m :

Melting temperature

T sw :

Switching temperature of the SME

T trans :

Thermal transition temperature (T m or T g)

T trans,A :

Thermal transition temperature of shape A for materials with two shapes in memory

T trans,B :

Thermal transition temperature of shape B for materials with two shapes in memory

w G :

Gel content

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Acknowledgments

The authors are grateful to Dr. K. Schmälzlin for valuable support with figures and format issues as well as to Prof. Dr. D. Hofmann for proof-reading the manuscript.

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Authors and Affiliations

  1. Center for Biomaterial Development, Institute of Polymer Research, GKSS Research Center Geesthacht GmbH, Kantstr. 55, 14513, Teltow, Germany

    Wolfgang Wagermaier, Karl Kratz, Matthias Heuchel & Andreas Lendlein

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  1. Wolfgang Wagermaier
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  2. Karl Kratz
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  3. Matthias Heuchel
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  4. Andreas Lendlein
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Correspondence to Andreas Lendlein .

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  1. Geesthacht GmbH, Institut für Chemie, GKSS Forschungszentrum, Kantstraße 5, Teltow, 14513, Germany

    Andreas Lendlein

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Wagermaier, W., Kratz, K., Heuchel, M., Lendlein, A. (2009). Characterization Methods for Shape-Memory Polymers. In: Lendlein, A. (eds) Shape-Memory Polymers. Advances in Polymer Science, vol 226. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2009_25

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