Time and Temperature Dependent Recovery of Epoxy-Based Shape Memory Polymers

Author(s):  
Francisco Castro ◽  
Kristofer K. Westbrook ◽  
Jason Hermiller ◽  
Dae Up Ahn ◽  
Yifu Ding ◽  
...  

Shape memory polymers (SMPs) are a group of adaptive polymers that can recover the permanent shape from a temporary shape by external stimuli on demand. Among a variety of external stimuli for polymer actuation, temperature is the most extensively used. In SMP applications, one of the major design considerations is the time necessary to recover the shape without external deformation constraints, or free recovery, and the amount of the recoverable strain. This paper investigates the amount of the recoverable strain and the recovery rate of an epoxy-based SMP (Veriflex® E, VFE1-62 (CRG, Dayton, OH)) under different thermal conditions. In particular, the free recovery behaviors of the SMPs under two experimental protocols, isothermal and shape memory (SM) cycle, are studied. It is found that free recovery in isothermal experiments is much faster than that in a SM cycle at the same recovering temperature and the material is fully recoverable at the temperature above differential scanning calorimetry Tg. Furthermore, for the recovery in SM cycle experiments, reshaping the sample at a low temperature and recovering from the deformation at a high temperature yield the fastest recovery rate, while reshaping at a high temperature and recovering at a low temperature cannot recover the original shape within this work’s experimental time frame. The possible mechanism for these observations is discussed.

Author(s):  
Tianjiao Wang ◽  
Jun Zhao ◽  
Chuanxin Weng ◽  
Tong Wang ◽  
Yayun Liu ◽  
...  

Shape memory polymers (SMPs) that change shapes as designed by external stimuli have become one of the most promising materials as actuators, sensors, and deployable devices. However, their practical applications...


1991 ◽  
Vol 246 ◽  
Author(s):  
J.A. Horton ◽  
E.P. George ◽  
C.J. Sparks ◽  
M.Y. Kao ◽  
O.B. Cavin ◽  
...  

AbstractA survey by differential scanning calorimetry (DSC) and recovery during heating of indentations on a series of nickel-aluminum alloys showed that the Ni-36 at.% Al composition has the best potential for a recoverable shape memory effect at temperatures above 100°C. The phase transformations were studied by high temperature transmission electron microscopy (TEM) and by high temperature x-ray diffraction (HTXRD). Quenching from 1200°C resulted in a single phase, fully martensitic structure. The initial quenched-in martensites were found by both TEM and X-ray diffraction to consist of primarily a body centered tetragonal (bct) phase with some body centered orthorhombic (bco) phase present. On the first heating cycle, DSC showed an endothermic peak at 121°C and an exothermic peak at 289°C, and upon cooling a martensite exothermic peak at 115° C. Upon subsequent cycles the 289°C peak disappeared. High temperature X-ray diffraction, with a heating rate of 2°C/min, showed the expected transformation of bct phase to B2 between 100 and 200°C, however the bco phase remained intact. At 400 to 450°C the B2 phase transformed to Ni2Al and Ni5Al3. During TEM heating experiments a dislocation-free martensite transformed reversibly to B2 at temperatures less than 150°C. At higher temperatures (nearly 600°C) 1/3, 1/3, 1/3 reflections from an ω-like phase formed. Upon cooling, the 1/3, 1/3, 1/3 reflections disappeared and a more complicated martensite resulted. Boron additions suppressed intergranular fracture and, as expected, resulted in no ductility improvements. Boron additions and/or hot extrusion encouraged the formation of a superordered bct structure with 1/2, 1/2, 0 reflections.


Polymers ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 542 ◽  
Author(s):  
David Santiago ◽  
Dailyn Guzmán ◽  
Francesc Ferrando ◽  
Àngels Serra ◽  
Silvia De la Flor

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.


2014 ◽  
Vol 70 (12) ◽  
pp. 1153-1160 ◽  
Author(s):  
Jan Fábry ◽  
Michal Dušek ◽  
Přemysl Vaněk ◽  
Iegor Rafalovskyi ◽  
Jiří Hlinka ◽  
...  

The structures of 4-chloro-3-nitroaniline, C6H5ClN2O2, (I), and 4-iodo-3-nitroaniline, C6H5IN2O2, (II), are isomorphs and both undergo continuous (second order) phase transitions at 237 and 200 K, respectively. The structures, as well as their phase transitions, have been studied by single-crystal X-ray diffraction, Raman spectroscopy and difference scanning calorimetry experiments. Both high-temperature phases (293 K) show disorder of the nitro substituents, which are inclined towards the benzene-ring planes at two different orientations. In the low-temperature phases (120 K), both inclination angles are well maintained, while the disorder is removed. Concomitantly, thebaxis doubles with respect to the room-temperature cell. Each of the low-temperature phases of (I) and (II) contains two pairs of independent molecules, where the molecules in each pair are related by noncrystallographic inversion centres. The molecules within each pair have the same absolute value of the inclination angle. The Flack parameter of the low-temperature phases is very close to 0.5, indicating inversion twinning. This can be envisaged as stacking faults in the low-temperature phases. It seems that competition between the primary amine–nitro N—H...O hydrogen bonds which form three-centred hydrogen bonds is the reason for the disorder of the nitro groups, as well as for the phase transition in both (I) and (II). The backbones of the structures are formed by N—H...N hydrogen bonding of moderate strength which results in the graph-set motifC(3). This graph-set motif forms a zigzag chain parallel to the monoclinicbaxis and is maintained in both the high- and the low-temperature structures. The primary amine groups are pyramidal, with similar geometric values in all four determinations. The high-temperature phase of (II) has been described previously [Gardenet al.(2004).Acta Cryst.C60, o328–o330].


2015 ◽  
Vol 1095 ◽  
pp. 140-144
Author(s):  
Ke Lu Wang ◽  
Shi Qiang Lu ◽  
Gui Fa Li ◽  
Jun Wei Liu ◽  
Er Min Wang

Using the method of expanding diameter in low temperature and water bath heating, this paper studied the effect of pre-deformation strain on shape memory recovery characteristics of Ni47Ti44Nb9 alloy Φ8 mm pipe joint. The results showed that the transformation hysteresis was relative stable along with the pre-deformation strain more than 12.1%, which was 130°C. And the radial recoverable strain got maximum value 8.4% when the pre-deformation strain was in 10.8%~12.5%. But the radial recovery rate of inside diameter declined smoothly with the pre-deformation strain. Systems considering the three parameters of transformation hysteresis, recoverable strain and strain recovery rate, it seemed the excellent predeformed strain for Ni47Ti44Nb9 alloy Φ8 mm pipe joint was just in 12%~17%.


1990 ◽  
Vol 68 (4) ◽  
pp. 604-611 ◽  
Author(s):  
Julian Haines ◽  
D. F. R. Gilson

The phase transition behaviour of cycloheptene has been investigated by differential scanning calorimetry, proton spin-lattice relaxation, and vibrational spectroscopy (infrared and Raman). Two solid–solid phase transitions were observed, at 154 and 210 K, with transition enthalpies and entropies of 5.28 and 0.71 kJ mol−1 and 34.3 and 3.4 JK−1, respectively. Cycloheptene melted at 217 K with an entropy of melting of 4.5 JK−1 mol−1. The bands in the vibrational spectra of the two high temperature phases were broad and featureless, characteristic of highly disordered phases. The presence of other conformers, in addition to the chair form, was indicated from bands in the spectra. The ring inversion mode was highly phase dependent and exhibited soft mode type behaviour prior to the transition from the low temperature phase. The low frequency Raman spectra (external modes) of these phases indicated that the molecules are undergoing isotropic reorientation. In the low temperature phase, the vibrational bands were narrow; the splitting of the fundamentals into two components and the presence of nine external modes are consistent with unit cell symmetry of either C2 or Cs with two molecules per primitive unit cell. A glassy state can be produced from the intermediate phase and the vibrational spectra were very similar to those of the high temperature phases, indicating that static disorder was present. The barriers to reorientation, as obtained from proton spin-lattice relaxation measurements, are 9.0 kJ mol−1 in both the high temperature phases, and 15.4 kJ mol−1 in the low temperature, ordered phase. Keywords: cycloheptene, phase transition, differential scanning calorimetry, NMR, vibrational spectroscopy.


Radiocarbon ◽  
2004 ◽  
Vol 46 (2) ◽  
pp. 893-900 ◽  
Author(s):  
J McGeehin ◽  
G S Burr ◽  
G Hodgins ◽  
S J Bennett ◽  
J A Robbins ◽  
...  

In this study, we applied a stepped-combustion approach to dating post-bomb lake sediment from north-central Mississippi. Samples were combusted at a low temperature (400 °) and then at 900 °. The CO2 was collected separately for both combustions and analyzed. The goal of this work was to develop a methodology to improve the accuracy of 14C dating of sediment by combusting at a lower temperature and reducing the amount of reworked carbon bound to clay minerals in the sample material. The 14C fraction modern results for the low and high temperature fractions of these sediments were compared with well-defined 137Cs determinations made on sediment taken from the same cores. Comparison of “bomb curves” for 14C and 137Cs indicate that low temperature combustion of sediment improved the accuracy of 14C dating of the sediment. However, fraction modern results for the low temperature fractions were depressed compared to atmospheric values for the same time frame, possibly the result of carbon mixing and the low sedimentation rate in the lake system.


2015 ◽  
Vol 5 (1) ◽  
Author(s):  
Xinli Xiao ◽  
Deyan Kong ◽  
Xueying Qiu ◽  
Wenbo Zhang ◽  
Yanju Liu ◽  
...  

2018 ◽  
Vol 2018 ◽  
pp. 1-13 ◽  
Author(s):  
Jing Li ◽  
Qiuhua Duan ◽  
Enhe Zhang ◽  
Julian Wang

Shape memory polymers (SMPs) have attracted significant attention from both industrial and academic researchers, due to their useful and fascinating functionality. One of the most common and studied external stimuli for SMPs is temperature; other stimuli include electric fields, light, magnetic fields, water, and irradiation. Solutions for SMPs have also been extensively studied in the past decade. In this research, we review, consolidate, and report the major efforts and findings documented in the SMP literature, according to different external stimuli. The corresponding mechanisms, constitutive models, and properties (i.e., mechanical, electrical, optical, shape, etc.) of the SMPs in response to different stimulus methods are then reviewed. Next, this research presents and categorizes up-to-date studies on the application of SMPs in dynamic building structures and components. Following this, we discuss the need for studying SMPs in terms of kinetic building applications, especially about building energy saving purposes, and review recent two-way SMPs and their potential for use in such applications. This review covers a number of current advances in SMPs, with a view towards applications in kinetic building engineering.


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