Thermally-Induced Actuation of Magnetic Nanocomposites Based on Oligo(ω-Pentadecalactone) and Covalently Integrated Magnetic Nanoparticles

MRS Advances ◽  
2018 ◽  
Vol 3 (63) ◽  
pp. 3783-3791 ◽  
Author(s):  
M. Yasar Razzaq ◽  
M. Behl ◽  
A. Lendlein
Keyword(s):  
Magnetic Nanoparticles ◽  
Mechanical Performance ◽  
Shape Memory Polymer ◽  
Polymer Network ◽  
Polymer Networks ◽  
Melting Range ◽  
Magnetite Nanoparticle ◽  
Thermally Induced ◽  
Inorganic Particles ◽  
Chain Mobility

AbstractThe incorporation of inorganic particles in a polymer matrix has been established as a method to adjust the mechanical performance of composite materials. We report on the influence of covalent integration of magnetic nanoparticles (MNP) on the actuation behavior and mechanical performance of hybrid nanocomposite (H-NC) based shape-memory polymer actuators (SMPA). The H-NC were synthesized by reacting two types of oligo(ω-pentadecalactone) (OPDL) based precursors with terminal hydroxy groups, a three arm OPDL (3AOPDL, Mn = 6000 g mol·1-1) and an OPDL (Mn =3300 g · mol-1) coated magnetite nanoparticle (Ø = 10 ± 2 nm), with a diisocyanate. These H-NC were compared to the homopolymer network regarding the actuation performance, contractual stress (σcontr) as well as thermal and mechanical properties. The melting range of the OPDL crystals (ΔTm,OPDL) was shifted in homo polymer networks from 36 °C – 76 °C to 41°C – 81 °C for H-NC with 9 wt% of MNP content. The actuators were explored by variation of separating temperature (Tsep), which splits the OPDL crystalline domain into actuating and geometry determining segments. Tsep was varied in the melting range of the nanocomposites and the actuation capability and contractual stress (σcontr) of the nanocomposite actuators could be adjusted. The reversible strain (εrev) was decreased from 11 ± 0.3% for homo polymer network to 3.2±0.3% for H-NC9 with 9 wt% of MNP indicating a restraining effect of the MNP on chain mobility. The results show that the performance of H-NCs in terms of thermal and elastic properties can be tailored by MNP content, however for higher reversible actuation, lower MNP contents are preferable.

Thermo-mechanical Behavior of (Meth)Acrylate Shape-Memory Polymer Networks

2011 ◽  
Vol 1312 ◽  
Author(s):  
Carl P. Frick ◽  
Nishant Lakhera ◽  
Christopher M. Yakacki
Keyword(s):  
Shape Memory ◽  
Shape Memory Polymer ◽  
Polymer Network ◽  
Polymer Networks ◽  
Weight Fraction ◽  
Crosslinking Density ◽  
Mechanical Stiffness ◽  
Actuation Force ◽  
Order Of Magnitude ◽  
Cross Linker

ABSTRACTOur overall approach is based on developing a photocrosslinkable polymer network with a favorable shape-memory response, using polymer chemistry and crosslinking density to control thermo-mechanical properties. Three polymer networks were created and thermo-mechanically tested, each from tert-Butyl acrylate linear builder co-polymerized with a poly(ethylene glycol) dimethacrylate cross-linker. By systematically altering the molecular weight and the weight fraction of the cross-linker, it was possible to create three polymers that exhibited the same glass transition temperature, but varied by almost an order of magnitude in rubbery modulus. Therefore, the mechanical stiffness could be tailored to suit a given application. Recovery behavior of the polymers was characterized over a range of deformation temperatures. It has been implicitly assumed a linear relationship between Free-Strain (i.e. no actuation force) and Fixed-Stress (i.e. maximum actuation force), however, this has never been confirmed experimentally. The energy per unit volume performed by the shape-memory polymer was quantified, and observed to be a function of strain recovered. The maximum recoverable work was shown to increase with cross-linking density, although the overall efficiency is similar for all materials tested.

Body temperature-responsive two-way and moisture-responsive one-way shape memory behaviors of poly(ethylene glycol)-based networks

2017 ◽  
Vol 8 (25) ◽  
pp. 3833-3840 ◽  
Author(s):  
Guang Yang ◽  
Xueyang Liu ◽  
Alfred Iing Yoong Tok ◽  
Vitali Lipik
Keyword(s):  
Free Radical ◽  
Ethylene Glycol ◽  
Shape Memory ◽  
Shape Memory Polymer ◽  
Polymer Networks ◽  
Poly Ethylene Glycol ◽  
Thermally Induced ◽  
Temperature Responsive ◽  
Shape Memory Effects ◽  
Poly Ethylene

In this work, crosslinked shape-memory polymer networks were prepared by thermally induced free-radical polymerizations of methacrylate-terminated poly(ethylene glycol) (PEG) and n-butyl acrylate (BA), which integrate thermal-responsive two-way and moisture-responsive one-way shape memory effects (SME).

Triple-Shape Capability of Thermo-sensitive Nanocomposites from Multiphase Polymer Networks and Magnetic Nanoparticles

2009 ◽  
Vol 1190 ◽  
Author(s):  
Narendra Kumar Uttamchand ◽  
Karl Kratz ◽  
Marc Behl ◽  
Andreas Lendlein
Keyword(s):  
Polymer Network ◽  
Polymer Networks ◽  
Recovery Process ◽  
Tensile Tests ◽  
Monomethyl Ether ◽  
Shape Effect ◽  
Contact Activation ◽  
Thermal Transitions ◽  
Two Phase ◽  
Thermally Induced

AbstractThermo-sensitive multiphase polymer networks with triple-shape capability have been recently introduced as a new class of active polymers that can change on demand from a first shape A to a second shape B and from there to a permanent shape C. Such multiphase polymer networks consist of covalent cross-links that determine shape C and at least two phase-segregated domains with distinct thermal transitions Ttrans,A and Ttrans,B , that are associated to shape A and B. In general the application of a two step programming or a one step programming procedure is required for creation of triple-shape functionality. In this study we report about a series of CLEGC nanocomposites consisting of silica coated nanoparticles (SNP) incorporated in a multiphase graft polymer network matrix from crystallisable poly(ε-caprolactone) diisocyanatoethyl methacrylate (PCLDIMA) and poly(ethylene glycol) monomethyl ether monomethacrylate (PEGMA) forming crystallisable side chains. These CLEGC nanocomposites were designed to enabling non contact activation of triple-shape effect in alternating magnetic field. Composites with variable PCLDIMA content ranging from 30 wt-% and 70 wt-% and different SNP amounts (0 wt-%, 2.5 wt-%, 5 wt-% and 10 wt-%) were realized by thermally induced polymerization. The thermal and mechanical properties of the CLEG nanocomposites were explored by means of DSC, DMTA and tensile tests. The triple-shape properties were quantified in cyclic, thermomechanical experiments, which consisted of a two step programming procedure and a recovery module under stress-free conditions for recovery of shapes B and C. While the thermal properties and the Young’s modulus of the investigated polymer networks were found to be independent from the incorporated amount of SNP, the elongation at break (εB) decreases with increasing nanoparticle content. All investigated composites exhibit excellent triple-shape properties showing a well separated two step shape recovery process.

scholarly journals Thermally-Induced Shape-Memory Behavior of Degradable Gelatin-Based Networks

2021 ◽  
Vol 22 (11) ◽  
pp. 5892
Author(s):  
Axel T. Neffe ◽  
Candy Löwenberg ◽  
Konstanze K. Julich-Gruner ◽  
Marc Behl ◽  
Andreas Lendlein
Keyword(s):  
Shape Memory ◽  
Shape Memory Effect ◽  
Memory Effect ◽  
Shape Recovery ◽  
Polymer Networks ◽  
Water Soluble ◽  
Compression Tests ◽  
Thermally Induced ◽  
Thermomechanical Process ◽  
Triple Helices

Shape-memory hydrogels (SMH) are multifunctional, actively-moving polymers of interest in biomedicine. In loosely crosslinked polymer networks, gelatin chains may form triple helices, which can act as temporary net points in SMH, depending on the presence of salts. Here, we show programming and initiation of the shape-memory effect of such networks based on a thermomechanical process compatible with the physiological environment. The SMH were synthesized by reaction of glycidylmethacrylated gelatin with oligo(ethylene glycol) (OEG) α,ω-dithiols of varying crosslinker length and amount. Triple helicalization of gelatin chains is shown directly by wide-angle X-ray scattering and indirectly via the mechanical behavior at different temperatures. The ability to form triple helices increased with the molar mass of the crosslinker. Hydrogels had storage moduli of 0.27–23 kPa and Young’s moduli of 215–360 kPa at 4 °C. The hydrogels were hydrolytically degradable, with full degradation to water-soluble products within one week at 37 °C and pH = 7.4. A thermally-induced shape-memory effect is demonstrated in bending as well as in compression tests, in which shape recovery with excellent shape-recovery rates Rr close to 100% were observed. In the future, the material presented here could be applied, e.g., as self-anchoring devices mechanically resembling the extracellular matrix.

scholarly journals Shape memory polymer network with thermally distinct elasticity and plasticity

2016 ◽  
Vol 2 (1) ◽  
pp. e1501297 ◽  
Author(s):  
Qian Zhao ◽  
Weike Zou ◽  
Yingwu Luo ◽  
Tao Xie
Keyword(s):  
Shape Memory ◽  
Molecular Design ◽  
Shape Change ◽  
Shape Memory Polymer ◽  
Polymer Network ◽  
Stimuli Responsive ◽  
Responsive Materials ◽  
Device Applications ◽  
Temperature Ranges ◽  
Rational Molecular Design

Stimuli-responsive materials with sophisticated yet controllable shape-changing behaviors are highly desirable for real-world device applications. Among various shape-changing materials, the elastic nature of shape memory polymers allows fixation of temporary shapes that can recover on demand, whereas polymers with exchangeable bonds can undergo permanent shape change via plasticity. We integrate the elasticity and plasticity into a single polymer network. Rational molecular design allows these two opposite behaviors to be realized at different temperature ranges without any overlap. By exploring the cumulative nature of the plasticity, we demonstrate easy manipulation of highly complex shapes that is otherwise extremely challenging. The dynamic shape-changing behavior paves a new way for fabricating geometrically complex multifunctional devices.

Characterization of bi-layered magnetic nanoparticles synthesized via two-step surface-initiated ring-opening polymerization

2015 ◽  
Vol 87 (11-12) ◽  
pp. 1085-1097 ◽  
Author(s):  
Li Wang ◽  
Stefan Baudis ◽  
Karl Kratz ◽  
Andreas Lendlein
Keyword(s):  
Magnetic Nanoparticles ◽  
Ring Opening ◽  
Average Molecular Weight ◽  
Polymer Networks ◽  
Gel Permeation Chromatography ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
H Nmr ◽  
Transmission Electron

AbstractA versatile strategy to integrate multiple functions in a polymer based material is the formation of polymer networks with defined nanostructures. Here, we present synthesis and comprehensive characterization of covalently surface functionalized magnetic nanoparticles (MNPs) comprising a bi-layer oligomeric shell, using Sn(Oct)2 as catalyst for a two-step functionalization. These hydroxy-terminated precursors for degradable magneto- and thermo-sensitive polymer networks were prepared via two subsequent surface-initiated ring-opening polymerizations (ROPs) with ω-pentadecalactone and ε-caprolactone. A two-step mass loss obtained in thermogravimetric analysis and two distinct melting transitions around 50 and 85°C observed in differential scanning calorimetry experiments, which are attributed to the melting of OPDL and OCL crystallites, confirmed a successful preparation of the modified MNPs. The oligomeric coating of the nanoparticles could be visualized by transmission electron microscopy. The investigation of degrafted oligomeric coatings by gel permeation chromatography and 1H-NMR spectroscopy showed an increase in number average molecular weight as well as the presence of signals related to both of oligo(ω-pentadecalactone) (OPDL) and oligo(ε-caprolactone) (OCL) after the second ROP. A more detailed analysis of the NMR results revealed that only a few ω-pentadecalactone repeating units are present in the degrafted oligomeric bi-layers, whereby a considerable degree of transesterification could be observed when OPDL was polymerized in the 2nd ROP step. These findings are supported by a low degree of crystallinity for OPDL in the degrafted oligomeric bi-layers obtained in wide angle X-ray scattering experiments. Based on these findings it can be concluded that Sn(Oct)2 was suitable as catalyst for the preparation of nanosized bi-layered coated MNP precursors by a two-step ROP.

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