Optimizing the Thermomechanics of Shape-Memory Polymers for Biomedical Applications

2004 ◽  
Vol 855 ◽  
Author(s):  
Christopher M. Yakacki ◽  
Ken Gall ◽  
Robin Shandas ◽  
Alicia M. Ortega ◽  
Nick Willett ◽  
...  
Keyword(s):  
Shape Memory ◽  
Biomedical Applications ◽  
Shape Recovery ◽  
Polymer Networks ◽  
Shape Memory Polymers ◽  
Strain Recovery ◽  
Stress Recovery ◽  
High Deformation ◽  
Flexural Tests ◽  
Free Strain

ABSTRACTWe examine the shape-memory effect in polymer networks intended for biomedical applications. The polymers were photopolymerized from tert-butyl acrylate (tBA) with polyethyleneglycol dimethacrylate (PEGDMA) acting as a crosslinker. Three-point flexural tests were used to systematically investigate the thermomechanics of shape-storage deformation and shape recovery. The glass transition temperature (Tg) of the polymers varied over a range of 100°C and is dependent on the molecular weight and concentration of the crosslinker. The polymers show 100% strain recovery up to maximum strains of approximately 80% at low and high deformation temperatures (Td). Free strain recovery was determined to depend on the temperature during deformation; lower deformation temperatures (Td < Tg) decreased the temperature required for free strain recovery. Constrained stress recovery shows a complex evolution as a function of temperature and also depends on Td. The thermomechanical results are discussed in light of potential biomedical applications and a prototype stent that can be activated at body temperature is presented.

Effect of chemical crosslinking on the free-strain recovery characteristics of amorphous shape-memory polymers

2009 ◽  
Vol 1190 ◽  
Author(s):  
Alicia M. Ortega ◽  
Christopher Michael Yakacki ◽  
Sean A. Dixon ◽  
Alan R. Greenberg ◽  
Ken Gall
Keyword(s):  
Shape Memory ◽  
Polymer Networks ◽  
Crosslinking Agent ◽  
Shape Memory Polymers ◽  
Weight Percent ◽  
Strain Recovery ◽  
System Response ◽  
Wide Range ◽  
Memory Applications ◽  
Free Strain

AbstractThe goal of this study is to investigate the fundamental relationship between the extent of crosslinking and shape-memory behavior of amorphous, (meth)acrylate-based polymer networks. The polymer networks were produced by copolymerization of tert-butyl acrylate (tBA) and poly(ethylene glycol) dimethacrylates of differing molecular weights (PEGDMA). Polymer compositions were tailored via the amount (weight percent (wt%)) and molecular weight of the PEGDMA crosslinking agents added to produce four materials with varying levels of crosslinking (0, 2, 10, and 40 wt% crosslinking agent corresponding to 0, 0.6, 3.2, and 16.6 mole%) and nearly equal glass transition temperatures (Tg). The effect of crosslinking on deformation limits and free-strain recovery is evaluated. Near complete strain recovery was demonstrated by all materials; however, absolute recovery strain decreased with increasing crosslinking due to a corresponding decrease in strain-to-failure. The results provide insights regarding the link between polymer structure, deformation limits, and strain-recovery capabilities of this class of shape-memory polymers. An improved understanding of this relationship is pivotal for optimizing system response for a wide range of shape-memory applications.

Thermomechanics of the Shape Memory Effect in Polymers

2004 ◽  
Vol 855 ◽  
Author(s):  
Yiping Liu ◽  
Ken Gall ◽  
Martin L Dunn ◽  
Alan R Greenberg
Keyword(s):  
Shape Memory ◽  
Polymer Network ◽  
Entropy Change ◽  
Strain Recovery ◽  
Large Strains ◽  
Stress Recovery ◽  
Recovery Stress ◽  
Strain Stress ◽  
Strain Storage ◽  
Free Strain

ABSTRACTShape memory polymers (SMPs) have the capacity to store and recover relatively large strains when subjected to a unique thermomechanical cycle. In this study, the thermomechanics of strain storage and strain/stress recovery are investigated in a shape memory polymer deformed under uniaxial tension and compression. During heated recovery, three cases of constraint are examined: unconstrained (free) strain recovery, stress recovery under pre-strain constraint, and stress recovery under fixed-strain constraint. Based on the experimental results, a one-dimensional SMP constitutive model is developed, which is motivated by the shape memory mechanism of the polymer network. The foundation of the model is that the entropy change is gradually stored during cooling and released during reheating as free recovery strain or constrained recovery stress. When fit to free strain recovery data, the model can predict the trends of the stress evolution during shape fixation and constrained strain/stress recovery under various thermomechanical conditions.

A Thermoviscoelastic Approach for Modeling Shape Memory Polymers

2009 ◽  
Vol 1190 ◽  
Author(s):  
Thao D Nguyen
Keyword(s):  
Time Dependence ◽  
Shape Memory ◽  
Shape Memory Polymers ◽  
Stress Recovery ◽  
Strain Response ◽  
Memory Response ◽  
Rate Dependent ◽  
Dependent Strain ◽  
Recovery Response ◽  
Free Strain

AbstractThis paper presents a thermoviscoelastic model for shape memory polymers (SMPs). The model has been developed base on the hypothesis that structural and stress relaxation are the primary shape memory mechanisms of crosslinked, glassy SMP, and that consideration of these mechanisms is essential for predicting the time-dependence of the shape memory response. Comparisons with experiments show that the model can reproduce the rate-dependent strain-temperature and stress-strain response of a crossslinked, glassy SMP. The model also captures many important features of the temperature and time dependence of the free strain recovery and constrained stress recovery response.

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 Water Triggered Shape Memory Materials

2013 ◽  
Vol 3 (1) ◽  
pp. 49-50 ◽  
Author(s):  
Guoguang Niu
Keyword(s):  
Shape Memory ◽  
Shape Recovery ◽  
Shape Memory Polymers ◽  
Electrical Current ◽  
Light Illumination ◽  
Poly Ethylene Glycol ◽  
Thermally Induced ◽  
Permanent Shape ◽  
Poly Ethylene ◽  
Novel Strategy

The term "shape memory effect" refers to the ability of a material to be deformed and fixed into a temporary shape, and to recover its original, permanent shape upon an external stimulus (1). Shape memory polymers have attracted much interest because of their unique properties, and applied tremendously in medical area, such as biodegradable sutures, actuators, catheters and smart stents (2, 3). Shape memory usually is a thermally induced process, although it can be activated by light illumination, electrical current, magnetic, or electromagnetic field (4-6). During the process, the materials are heated directly or indirectly above their glass transition temperature (Tg) or the melting temperature (Tm) in order to recover the original shape. Non-thermally induced shape memory polymers eliminate the temperature constrains and enable the manipulation of the shape recovered under ambient temperature (7, 8). Herein, we report a novel strategy of water induced shape memory, in which the formation and dissolution of poly(ethylene glycol) (PEG) crystal is utilized for the fixation and recovery of temporary deformation of hydrophilic polymer. This water-induced shape recovery is less sensitive to temperature, of which 95% deformation is fixed in circumstance and over 75% recovery is reached even at 0 oC.

scholarly journals A Large-Deformation Theory for Thermally-Actuated Shape-Memory Polymers and its Application

2010 ◽  
Author(s):  
Shawn A. Chester ◽  
Vikas Srivastava ◽  
Claudio V. Di Leo ◽  
Lallit Anand
Keyword(s):  
Glass Transition ◽  
Shape Memory ◽  
Deformation Theory ◽  
Shape Recovery ◽  
Large Deformations ◽  
Shape Memory Polymers ◽  
The Body ◽  
Thermally Induced ◽  
Thermally Actuated ◽  
Common Shape

The most common shape-memory polymers are those in which the shape-recovery is thermally-induced. A body made from such a material may be subjected to large deformations at an elevated temperature above its glass transition temperature &Vthgr;g. Cooling the deformed body to a temperature below &Vthgr;g under active kinematical constraints fixes the deformed shape of the body. The original shape of the body may be recovered if the material is heated back to a temperature above &Vthgr;g without the kinematical constraints. This phenomenon is known as the shape-memory effect. If the shape recovery is partially constrained, the material exerts a recovery force and the phenomenon is known as constrained-recovery.

scholarly journals Bio-Based Epoxy Shape-Memory Thermosets from Triglycidyl Phloroglucinol

Polymers ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 542 ◽  
Author(s):  
David Santiago ◽  
Dailyn Guzmán ◽  
Francesc Ferrando ◽  
Àngels Serra ◽  
Silvia De la Flor
Keyword(s):  
Shape Memory ◽  
Shape Recovery ◽  
Memory Performance ◽  
Crosslinking Agent ◽  
Shape Memory Polymers ◽  
Crosslinking Density ◽  
Mechanical Analysis ◽  
Diglycidyl Ether ◽  
Partial Substitution ◽  
Scanning Calorimetry

A series of bio-based epoxy shape-memory thermosetting polymers were synthesized starting from a triglycidyl phloroglucinol (3EPOPh) and trimethylolpropane triglycidyl ether (TPTE) as epoxy monomers and a polyetheramine (JEF) as crosslinking agent. The evolution of the curing process was studied by differential scanning calorimetry (DSC) and the materials obtained were characterized by means of DSC, thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), stress-strain tests, and microindentation. Shape-memory properties were evaluated under free and totally constrained conditions. All results were compared with an industrial epoxy thermoset prepared from standard diglycidyl ether of Bisphenol A (DGEBA). Results revealed that materials prepared from 3EPOPh were more reactive and showed a tighter network with higher crosslinking density and glass transition temperatures than the prepared from DGEBA. The partial substitution of 3EPOPh by TPTE as epoxy comonomer caused an increase in the molecular mobility of the materials but without worsening the thermal stability. The shape-memory polymers (SMPs) prepared from 3EPOPh showed good mechanical properties as well as an excellent shape-memory performance. They showed almost complete shape-recovery and shape-fixation, fast shape-recovery rates, and recovery stress up to 7 MPa. The results obtained in this study allow us to conclude that the triglycidyl phloroglucinol derivative of eugenol is a safe and environmentally friendly alternative to DGEBA for preparing thermosetting shape-memory polymers.

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