Thermomechanical and shape memory properties of thermosetting shape memory polymer under compressive loadings

Shape memory polymers (SMPs) are an emerging class of active polymers that may be used for a range of reconfigurable structures. In this study, the thermomechanical and shape memory behavior of a thermosetting SMP was investigated using large‐scale compressive tests and small‐scale indentation tests. Results show that the SMP exhibits different deformation modes and mechanical properties in compression than in tension. In glassy state, the SMP displays significant plastic deformation and has a much higher modulus and yield strength in comparison to those obtained in tension. In rubbery state, the SMP behaves like a hyperelastic material and again has a much higher modulus than that obtained in tension. The SMPs were further conditioned separately in simulated service environments relevant to Air Force missions, namely, (1) exposure to UV radiation, (2) immersion in jet‐oil, and (3) immersion in water. The thermomechanical and shape recovery properties of the original and conditioned SMPs were examined under compression. Results show that all the conditioned SMPs exhibit a decrease in T_g as compared to the original SMP. Environmental conditionings generally result in higher moduli and yield strength of the SMPs in the glassy state but lower modulus in the rubbery state. In particular, the UV exposure and water immersion, also weaken the shape recovery abilities of the SMPs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

热固性环氧树脂形状记忆效应研究

将新型的高分子固化剂与环氧树脂(EP)进行共混,经适度交联固化后制备出一种具有较低玻璃化转变温度(Tg)的无定型EP体系,并对该EP固化体系的力学性能、形状记忆特性和动态力学性能等进行了研究。结果表明:适度交联固化的EP体系具有良好的形状记忆特性,固化剂用量是影响该形状记忆体系综合性能的主要因素;其最大形变恢复率均为100%,形变恢复速率基本上随固化剂用量增加而增大,最大形变恢复速率为0.023 s-1;形变固定率随固化剂用量增加而减小,当w(固化剂)=37.5%或54.5%时,形变固定率为100%或96%。     

Thermomechanical studies of aluminum nitride filled shape memory polymer composites

High thermal conductivity polyurethane shape memory polymer (SMP) composites filled with aluminum nitride (AlN) were fabricated, and their thermal and thermomechanical properties were studied. The purpose of this microstructure is to improve the thermal properties of the SMPs at low filler content. Morphology of AlN filler in polyurethane SMP matrix and the resulting thermal conductivity was also investigated. Thermal studies have shown that AlN is an effective filler for reinforcement of the polyurethane SMP and that it does not deteriorate the stable physical crosslink structure of the polyurethane, which is necessary to store the elastic energy in the service process of the shape memory material. The thermal conductivities of these SMP composites in relation to filler concentration and temperature were investigated, and it was found that the thermal conductivity can increase up to 50 times in comparison with that of the pure SMP. Furthermore, differential scanning calorimetry tests have shown a significant decrease in the glass transition temperature of the switching segment. Dynamic mechanical studies have shown that the storage modulus of the composites increase with higher AlN content in both glassy and rubbery state. Damping peak decreases and also the curve of damping becomes broader with increasing filler content. Strain fixity rate which expresses the ability of the specimens to fix their strain has been improved slightly in the presence of AlN filler but the final recovery rate of the shape memory measurement has decreased evidently. POLYM. COMPOS., 28:287–293, 2007. © 2007 Society of Plastics Engineers     

Influence of uniaxial compression on the shape memory behavior of vitrimer composite embedded with tension-programmed unidirectional shape memory polymer fibers

Tension programmed shape memory polymer (SMP) fibers have been used as sutures for closing wide-opened cracks per the close-then-heal strategy. However, the composite may be subjected to compression loading during service. These compression loads can reduce the amount of recoverable strain in these pre-tensioned fibers, limiting their ability to close cracks. The purpose of this study is to investigate the effect of in-service compression loading on the shape memory effect (SME) of composites consisting of SMP fiber and SMP matrix. To this end, pre-stretched shape memory Polyethylene Terephthalate (PET) fibers were embedded into a shape memory vitrimer to obtain composite samples with different fiber volume fractions. The SME of both the PET fiber and the vitrimer was investigated. The effect of compression load on the SME of the composite was studied. It is found that, uniaxial compression on the composite along the fiber direction significantly reduced the shrinking ability of the embedded pre-tensioned SMP fibers. Hence, this is a factor that needs to be considered when designing such types of self-healing composites.     

Harnessing irreversible thermal strain for shape memory in polymer additive manufacturing

Shape transformation upon annealing of fused filament fabrication additively manufacturing structures is investigated as a one-way shape memory strategy using commodity thermoplastics. Irreversible thermal strain, which is a measurement of shape transformation upon annealing, is shown to depend on both raster angle and layer thickness, both of which are parameters than can be easily adjusted on most FFF printers. We present an algorithm based on our understanding of the underlying micromechanics of the system that allows for input of desired final dimensions and output the necessary print parameters. We also demonstrate that this approach is extensible to other materials and report more complex shape memory geometries. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48239.     

Chemically induced morphing in polyurethane shape memory polymer micro fibers/springs

Chemically induced morphing in polyurethane shape memory polymer (SMP) micro fibers/springs was investigated experimentally and theoretically. It was revealed that at the presence of water/ethanol, the release of the residual strain/stress (captured during the fabrication process of micro fibers/springs from melted polyurethane SMP) is the driving force for morphing (by means of self-winding and self-twisting/untwisting). A theoretical model was developed to explain the underlying mechanisms behind all types of observed morphing phenomena.     

Dielectric properties of polymer/ceramic composites based on thermosetting polymers

Summary A series of thermosetting polymer/ceramic composites were prepared. Three kinds of thermosetting polymers, i.e. cyanate resin, bismaleimide resin, and epoxy resin, were used as matrixes, and BaTiO₃ particles were as fillers. The dielectric properties of these composites were investigated. Experimental data of the dielectric constants were fitted to several theoretical equations in order to obtain the best-fitting equations of the dielectric constants of these composites. The result indicates that the dielectric constants of composites all increase with the increase of BaTiO₃ content. Using bismaleimide resin and epoxy resin as matrixes, the dielectric losses both increase obviously as the amount of BaTiO₃ particles is increased, but the dielectric loss of cyanate/BaTiO₃ composite decreases. With the increase of the frequency, the variation ranges of the dielectric constant and dielectric loss of cyanate/BaTiO₃ composite are both the smallest. The predications of the effective dielectric constants by Lichterecker mixing rule are in good agreement with experiment data.     

形状记忆功能高分子材料的研究现状

讨论了形状记忆功能高分子材料的类型和特点,概述了反式聚戊二烯、交联聚乙烯、聚降冰片烯及聚氨酯等形状记忆功能高分子材料的实验和理论研究进展。重点介绍了反式聚异 一烯的结构、特性、形状记忆功能的原理、配方、性能及其应用领域与前景。     

Stress memory of a thermoset shape memory polymer

The performance of stress recovery and shape recovery are equally important for high performance shape memory polymers (SMPs) in emerging applications. However, unlike shape recovery, stress recovery does not always follow a monotonic behavior, i.e., “stress plateau,” “stress overshoot,” and “stress undershoot” can be observed. In order to reveal the complicated stress memorization and recovery behavior, this study employs a phenomenological model which considers the recovery stress as the sum of residual programming stress, memorized stress, thermal stress, and relaxed stress for amorphous crosslinked SMPs. This model is demonstrated by a stress recovery experiment in which a polystyrene based SMP was programmed at two prestrain levels above the glass transition temperature, i.e., 20% (neo‐Hookean hyperelastic region) and 50% (strain‐hardening region), and two fixation temperatures, i.e., 20°C (below T_g) and 45°C (within the T_g region), respectively. In addition, a clear distinction between the memorized stress and recovery stress is presented. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42112.     

Nanoindentation of shape memory polymer networks

This work examines the small-scale deformation and thermally induced recovery behavior of shape memory polymer networks as a function of crosslinking structure. Copolymer shape memory materials based on diethylene glycol dimethacrylate and polyethylene glycol dimethacrylate with a molecular weight of 550 crosslinkers and a tert-butyl acrylate linear chain monomer were synthesized with varying weight percentages of crosslinker from 0 to 100%. Dynamic mechanical analysis is used to acquire the bulk thermomechanical properties of the polymers, including the glass transition temperature and the elastic modulus over a wide temperature range. Instrumented nanoindentation is used to examine ambient temperature deformation of the polymer networks below their glass transition temperature. The glassy modulus of the networks measured using nanoindentation is relatively constant as a function of crosslinking density, and consistent with values extracted from monotonic tensile tests. The ambient temperature hardness of the networks increases with increasing crosslinking density, while the dissipated energy during indentation decreases with increasing crosslinking density. The changes in hardness correlated with the changes in glass transition but not changes in the rubbery modulus, both of which can scale with a change in crosslink density. Temperature induced shape recovery of the indentations is studied using atomic force microscopy. For impressions placed at ambient temperature, the indent shape recovery profile shifts to higher temperatures as crosslink density and glass transition temperature increase.     

Improved shape memory effects in multiwalled‐carbon‐nano‐tube reinforced thermosetting polyurethane composites

Shape memory thermosetting polyurethane (SMPU) composites containing different amount of multiwalled carbon nanotube (MWCNT) ranging from 0 to 0.250 phr were prepared. The shape memory behavior, tensile stress, and recovery stress were determined by using conventional thermomechanical cycle; however, the modified thermomechanical cycle designated as progressive stretch–relax–stretch (PSRS) cycle was also employed to create shape memory effects in studied composites. The test was carried out in water bath which was equipped with an electric heater, temperature controller, and tensile stress and strain measuring setup. The recovery and tensile stresses both were showing higher values for PSRS samples as compared with conventional samples. Loading of MWCNT improved the recovery stress of SMPU, thereby confirming reinforcing effect. The maximum recovery stress of 2.17 MPa for 0.188 phr MWCNT loading was observed as compared with 1.09 MPa of unreinforced SMPU specimen. The recovery time was also improved on reinforcement as demonstrated in this article. The morphology of fractured surface and degree of dispersion of MWCNT was studied using Field Emission Scanning Electron Microscope. The impact on glass transition temperature was also observed for MWCNT reinforcement on SMPU, which depends on the degree of dispersion and loading of MWCNT in the specimen. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44389.     

纳米SiO2/形状记忆聚氨酯复合材料的研究

在合成形状记忆聚氨酯(SMPU)的过程中加入经钛酸酯偶联剂表面处理的纳米SiO2粒子，制备了纳米SiO2／形状记忆聚氨酯复合材料。用FT-IR、DSC、SEM对其进行了分析，考察了它的形状记忆性能和力学性能。结果表明，偶联剂的用量对纳米粒子有很大影响，当钛酸酯用量为纳米粒子质量的80％时才能有效包敷好纳米粒子，而SMPU中只有包敷效果良好的纳米粒子，才能提高SMPU的形状回复温度及其力学性能，否则会使性能下降，而且偶联剂的引入对形状固定和形状稳定都有负面作用。     

Recent advances in polymer shape memory

Traditional shape memory polymers (SMPs) are those capable of memorizing a temporary shape and recovering to the permanent shape upon heating. Although such a basic concept has been known for half a century, recent progresses have challenged the conventional understanding of the polymer shape memory effect and significantly expanded the practical potential of SMPs. In this article, notable recent advances in the field of SMPs are highlighted. Particular emphasis is placed on how the new developments have changed the conventional view of SMPs, what they mean for practical applications, and where the future opportunities are.     

Biomimetic strain hardening in interpenetrating polymer network hydrogels

In this paper, we present the systematic development of mechanically enhanced interpenetrating polymer network (IPN) hydrogels with Young's moduli rivaling those of natural load-bearing tissues. The IPNs were formed by synthesis of a crosslinked poly(acrylic acid) (PAA) network within an end-linked poly(ethylene glycol) (PEG) macromonomer network. The strain-hardening behavior of these PEG/PAA IPNs was studied through uniaxial tensile testing and swelling measurements. The interaction between the independently crosslinked networks within the IPN was varied by (1) changing the molecular weight of the PEG macromonomer, (2) controlling the degree of PAA ionization by changing pH, and (3) increasing the polymer content in the PAA network. Young's moduli and the maximum stress-at-break of the swollen hydrogels were normalized on the basis of their polymer content. Strain hardening in the IPNs exhibited a strong dependence on the molecular weight of the first network macromonomer, the pH of the swelling buffer, as well as the polymer content of the second network. The results indicate that the mechanical enhancement of these IPNs is mediated by the strain-induced intensity of physical entanglements between the two networks. The strain can be applied either by mechanical deformation or by changing the pH to modulate the swelling of the PAA network. At pHs below the pK_a of PAA (4.7), entanglements between PEG and PAA are reinforced by interpolymer hydrogen bonds, yielding IPNs with high fracture strength. At pHs above 4.7, a “pre-stressed” IPN with dramatically enhanced modulus is formed due to ionization-induced swelling of the PAA network within a static PEG network. The modulus enhancement ranged from two-fold to over 10-fold depending on the synthesis conditions used. Variation of the network parameters and swelling conditions enabled “tuning” of the hydrogels' physical properties, yielding materials with water content between 58% and 90% water, tensile strength between 2.0 MPa and 12.0 MPa, and initial Young's modulus between 1.0 MPa and 19.0 MPa. Under physiologic pH and salt concentration, these materials attain “biomimetic” values for initial Young's modulus in addition to high tensile strength and water content. As such, they are promising new candidates for artificial replacement of natural tissues such as the cornea, cartilage, and other load-bearing structures.     

Effects of stretch induced softening to the free recovery behavior of shape memory polymer composites

During a cyclic tension test, many elastomeric materials exhibit an appreciable softening in their mechanical properties resulting from the previous stretch, known as the Mullins effect. This paper explores the influence of the stretch induced softening effect to the free recovery behavior of an acrylate shape memory polymer (SMP) composite by incorporating carbon black (CB) as filler materials. The observed softening effect in this SMP composite is considered to be a consequence of stretch induced alternation of filler–polymer interactions inside the composite. Further experiments find that a larger prior stretch gives a larger increase in material softening, which in turn decreases the shape recovery speed. To capture the experimental observations, a multi-branch one dimensional (1D) model is applied, where the modulus in the equilibrium branch is modeled to decrease with stretching deformation following a damage-like softening function. It is found that the loss in modulus due to softening consequently reduces the driving force for recovery and thus results in a slow recovery. Parametric studies further demonstrate that the discounted shape recovery speed will finally reach a saturated level when gradually increasing the programmed strain level in a shape memory cycle.     

A novel type of shape memory polymer blend and the shape memory mechanism

A novel styrene-butadiene-styrene tri-block copolymer (SBS) and poly(?-caprolactone) (PCL) blend were introduced for its shape memory properties. Compared to the reported shape memory polymers (SMPs), this novel elastomer and switch polymer blend not only simplified the fabrication process but also offer a controllable approach for the study of mechanisms and the optimization of shape memory performances. Microstructures of this blend were characterized by differential scanning calorimetry (DSC), AFM microscope observation and tensile test. DSC results demonstrated the immiscibility between SBS and PCL. AFM images and stress-strain plot further confirmed the two-phase morphology within the blend. It was found that the SBS and PCL continuous phases contributed to the shape recovery and shape fixing performances, respectively. A detailed shape memory mechanism for this type of SMP system was then concluded and an optimized SMP system with both good recovery and fixing performances was designed from this mechanism.     

Valorization of bio-calcium carbonate based Chamelea gallina shell waste fillers in shape memory polymer composites

In recent years, the focus has been on the use of calcium carbonate-based seashell wastes in the production of new thermoplastic and thermoset polymer materials, paving the way for their use as biofillers in polymeric composites. In this study, it is aimed to obtain a new polymeric composite material by doping Chamelea gallina shells, on polylactic acid (PLA)/polyethylene glycol (PEG) blend. Structural characterization of the obtained PLA/PEG blend/C. gallina composite films was performed with attenuated total reflection infrared spectroscopy (ATR-IR). When the thermal properties of composite materials were examined by thermogravimetric analysis (TGA), it was determined that the thermal stability of polymeric composites increased with the addition of C. gallina. SEM images showed that the polymer blend films, which appeared to have a porous structure, filled the pores with increasing C. gallina ratio. It was observed that the biodegradability of PLA/PEG blend composite films decreased with increasing C. gallina shells addition. However, C. gallina had a positive effect on the swelling and water absorption capacities of polymeric composites. The increase in tensile strength and elongation at break values of PLA/PEG blend/C. gallina composite films with increasing C. gallina means that the mechanical properties of the polymer are improved.     

Modeling thermomechanical behaviors of shape memory polymer

The thermomechanical constitutive equations are critical for shape memory polymers (SMPs) in analyzing their shape, memory, and recovery responses under different constraints. In this study, a new physical‐based, temperature and time‐dependent constitutive model was proposed. The deformation mechanisms of this class of functional materials were explained, and the theoretical predicting values by different models were compared with available experimental results. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The electrical behavior of thermosetting polymer composites containing metal plated ceramic filler

This paper describes the electrical behavior of a thermosetting system, based on epoxy resin, containing metal plated fillers. Ceramic fillers such as chopped glass fibers and mica flakes were coated with copper by electroless plating and incorporated into an epoxy resin based on di‐glycidyl ether of bisphenol A (DGEBA) with tri‐ethylenetetramine (TETA) curing agent. The percolation threshold in these systems is obtained at very low copper contents of 0.11–0.44 vol%. The epoxy/copper coated mica system is characterized by an extremely large positive temperature coefficient (PTC) effect, which is not followed by a negative temperature coefficient (NTC) effect. Increasing the copper coated mica concentration raises the PTC temperature of the first temperature cycle, and exposing the material to continuous heating‐cooling cycles results in a decrease in the PTC temperature and an increase of its room temperature resistivity. Inverse relations were found between the coefficient of thermal expansion and the PTC temperature. Accordingly, the mechanism governing the PTC effect in the epoxy/copper coated mica composite is based on a larger thermal expansion coefficient of the matrix compared with the ceramic filler. POLYM. COMPOS., 26:12–19, 2005. © 2004 Society of Plastics Engineers.     

热致感应型形状记忆高分子材料与纤维

介绍了热致感应型形状记忆高分子材料的机理、制备方法及其应用,重点介绍了热致感应型形状 记忆纤维的混纺和后整理生产技术及国内外研究发展状况。指出今后应大力开发热致感应形状记忆纤维的 直接纺丝生产技术,提高纤维的形变回复力及尺寸稳定性,纤维的应用前景看好。