Design and analysis of smart diaphragm based on shape memory polymer

Currently, tank diaphragms are mostly applied in the field of aerospace but one of their limitations have to do with their inability to recycle. In the article, we discussed the modeling of a new kind of reversible diaphragm, so‐called shape memory polymer (SMP) diaphragm. A thermo‐mechanical modeling of SMP is implemented by the finite element method using a constitutive model. A single variable in this model is defined and used to simplify the model compared to other existing models. Evolution of the analysis is conducted by making use of the intermediate difference forms and Jacobian matrix, which is applied to all quantities within the model. The overturning and recovery behaviors of the SMP diaphragm are examined. And, the effect of several parameters, including thickness, height and radius of the diaphragm, as well as temperature on the overturning performance are investigated. This study led to the establishment of an optimized model with the objective function requiring minimum overturning pressure for completing deformation and design variables associated with thickness, height, radius, and temperature. An optimized SMP diaphragm is obtained under the critical pressure constraints. The results contribute to the design and application of novel SMP diaphragms. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46557.     

Stress-strain curves for polyurethane elastomers: A statistical assessment of constitutive models

Polyurethane elastomers (PUEs) are broadening applications attributed to their highly tunable mechanical properties, and the stress–strain curve is one of the most important characters. Theoretically, dozens of constitutive models have been developed to interpret the stress–strain curve for rubber-like materials but their applicability on PUEs is still suspicious, which results in the selection of models and the initialization of model parameters need expertise experience. We performed a statistical assessment of 25 constitutive models (10 physical and 15 phenomenological) based on a comprehensive dataset with 529 stress–strain curves for PUEs. The average coefficients of determination for the whole curve can be improved from 0.676 for the phantom model (1 parameter) to 0.990 for the Bechir model (6 parameters), and the percentage of well-fitted curves increases from 6% to 92%. Constitutive models with both the first- and the second-invariant, in logarithmic or exponential expression for strain perform better.     

Numerical study of smart honeycomb core using shape memory polymers

Shape memory polymers (SMPs) attract widespread attention because they are able to maintain a temporary deformation after unloading and recover the initial shape under high temperature conditions. Based on a three‐dimensionally constitutive equation of SMPs, a finite element program is followed by compiling user‐defined material subroutine, which describes the shape memory behavior of thermo‐mechanical experiment. A honeycomb core using SMP is designed, which has the ability to recover the initial shape after deformation and be used as a smart core for sandwich structures. To prove their advantages in the engineering application, a series of thermodynamic behaviors of the SMP honeycomb core are simulated, including loading at high temperature, cooling, unloading at the low temperature, and recovering original shape on heating. Shape memory behaviors of tensile, compressive, bending, and locally sunken deformations are demonstrated and the effect of time and temperature on the recovery process is discussed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45672.     

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     

Predicting embrittlement of polymer glasses using a hydrostatic stress criterion

In this study, the aging-induced embrittlement of three polymer glasses is investigated using a previously developed hybrid experimental–numerical method. The evolution of yield stress of unnotched tensile bars upon aging is coupled to the evolution of embrittlement of notched tensile bars using a numerical model combined with a critical hydrostatic stress criterion that determines the onset of failure. The time-to-embrittlement of notched tensile bars with a different notch geometry is predicted and in good agreement with the experimentally determined value. Next to that, the approach is extended to three polysulfone polymers, and it is shown that the value of the critical hydrostatic stress correlates well with the polymers entanglement density: : polymers with a denser entangled network display higher values, that is, a higher resistance against incipient cavitation. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47373.     

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.     

Wood‐based composites with thermoplastic polyurethane as matrix polymer

This research reports the influence of the mechanical properties of thermoplastic polyurethane (TPU) as a function of wood filler percentage. Wood flour was mixed with two different chemically based TPUs. Also, moisture content during compounding process as well as the origin of moisture (wood or TPU) were studied. All experimental designs and statistical analysis were done with the software Design Expert Version 10. Composite preparation took place in a multi‐stage process. The results showed that 70% wood filler can be incorporated in the composite manufacture. The properties of the composite were mainly influenced by the proportion of wood and TPU. Wood flour increased the density, hardness, water absorption, and tensile modulus with a decrease in impact resistance and abrasion resistance of the composite. Tensile strength exhibited a decrease up to ～35% wood content, but an increase with further addition of wood. Moisture content had only a minor influence on the mechanical and water absorption properties despite the noted severe moisture sensitivity of TPU, which usually leads to decline in mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46344.     

Quantitative relation between the relaxation time and the strain rate for polymeric solids under quasi‐static conditions

Relaxation time is an essential physical quantity reflecting the hysteresis of the microstructure of materials. To associate the relaxation time with the strain rate, the stress–strain curves of six types of polymers at low strain rate were normalized, and a nondimensional generalized Maxwell model incorporating strain‐rate‐dependent relaxation times was obtained by the internal variable theory of irreversible thermodynamics. The results indicate that the constitutive equation may capture well the normalized stress–strain behaviors that are not related to the strain rate. The ratio of the initial modulus to the secant modulus at the maximum stress was also found to not rely on the strain rate anymore. Furthermore, strain‐rate independence occurred only when the relaxation time was proportional to the time interval for stress from zero to the maximum stress. The relaxation time varied in a power law with the strain rate. The explicit relation is helpful for providing a concise and promising solution for predicting the quasi‐static mechanical response of viscoelastic solids. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44114.     

Tensile mechanical properties and constitutive model for HTPB propellant at low temperature and high strain rate

To investigate the mechanical properties and fracture mechanisms of hydroxyl‐terminated polybutadiene (HTPB) propellant at low temperature and high strain rate, uniaxial tensile tests were conducted over the range of temperatures 233 to 298 K and strain rates 0.4 to 14.14 s^?1 using an INSTRON testing machine, and scanning electron microscope (SEM) was employed to observe the tensile fracture surfaces. The experimental results indicate that the deformation properties of HTPB propellant are remarkably influenced by temperature and strain rate. The characteristics of stress–strain curves at low temperatures are different from that at room temperature, and the effects of temperature and strain rate on the mechanical properties are closely related to the changes of properties and the fracture mechanisms of HTPB propellant. The dominating fracture mechanism depends much on the temperature and changes from the dewetting and matrix tearing at room temperature to the particle brittle fracture at low temperature, and the effect of strain rate only alters the mechanism in a quantitative manner. Finally, a nonlinear viscoelastic constitutive model incorporating the damage evolution and the effects of temperature and strain rate was developed to describe the stress responses of this propellant under the test conditions. During this process, the Schapery‐type constitutive theories were applied and one damage variable was considered to establish the damage evolution function. The overlap between experimental results and predicted results are generally good, which confirms that the developed constitutive model is valid, however, further researches should be done due to some drawbacks in describing the deformation behaviors at very large strain. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42104.     

Dependency of the shape memory properties of a polyurethane upon thermomechanical cyclic conditions

The relationship between the shape memory properties and thermomechanical cyclic conditions was investigated with a type of shape memory polyurethane (SMPU). The thermal and dynamic mechanical properties of the polyurethane were examined by using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). It was found that the SMPU exhibited good shape memory effects (SMEs) at deformation temperatures ranging from T_g to T_g + 25 °C. The strain recovery ratios increased with the increase of deformation speed and with the decrease in maximum strain. The recovery ratios also increased with increasing fixing speed. Therefore, in practical applications, in order to obtain better SMEs, the SMPU should be cooled to its frozen state as soon as possible after being deformed at a high temperature. The ‘fixity’ dramatically increased with the decrease in fixing temperature. To obtain optimal SMEs, the polymer has to be reheated up to the temperature at which the polymer deformed. In addition, the recovery ratios of the SMPU could increase slightly with the increase of recovery time. Copyright © 2004 Society of Chemical Industry     

Quantification of mechanical deformations induced by an electric field in a semicrystalline organic insulator

We studied mechanical deformations induced when an insulating material was subjected to a gradual increase in a direct‐current electric field. Poly(ethylene terephthalate) film was studied with an optical technique, which was nondestructive and involved no physical contact. The experimental results indicated that the level of the induced mechanical deformation depended on the strength of the applied electric stress, the linear dimensions of the area under study, and the thickness of the film. When the studied area was relatively small, the level of the mechanical deformation seemed to be more important. The relationship between the induced mechanical deformation and the electric conduction phenomenon was also examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2313–2321, 2004     

Shape‐memory behavior of high‐strength amorphous thermoplastic poly(para‐phenylene)

The purpose of this study was to investigate the shape‐memory behavior of poly(para‐phenylene) (PPP) under varying programming temperatures, relaxation times, and recovery conditions. PPP is an inherently stiff and strong aromatic thermoplastic, not previously investigated for use as a shape‐memory material. Initial characterization of PPP focused on the storage and relaxation moduli for PPP at various frequencies and temperatures, which were used to develop continuous master curves for PPP using time–temperature superposition (TTS). Shape‐memory testing involved programming PPP samples to 50% tensile strain at temperatures ranging from 155°C to 205°C, with varying relaxation holds times before cooling and storage. Shape‐recovery behavior ranged from nearly complete deformation recovery to poor recovery, depending heavily on the thermal and temporal conditions during programming. Straining for extended relaxation times and elevated temperatures significantly decreased the recoverable deformation in PPP during shape‐memory recovery. However, PPP was shown to have nearly identical full recovery profiles when programmed with decreased and equivalent relaxation times, illustrating the application of TTS in programming of the shape‐memory effect in PPP. The decreased shape recovery at extended relaxation times was attributed to time‐dependent visco‐plastic effects in the polymer becoming significant at longer time‐scales associated with the melt/flow regime of the master curve. Under constrained‐recovery, recoverable deformation in PPP was observed to have an exponentially decreasing relationship to the bias stress. This study demonstrated the effective use of PPP as a shape‐memory polymer (SMP) both in mechanical behavior as well as in application. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42903.     

Modeling the viscoelasticity of polyetherimide

Viscoelasticity is a mechanical phenomenon where the material modulus varies with time and temperature. Modern experimental methods can determine material properties within certain time and temperature ranges, but modeling the viscoelastic behavior remains challenging, mainly because the data processing is complex and different materials have distinct properties. Using polyetherimide as an example and based on the change in the secondary bonds of polyetherimide in different viscoelastic stages, we proposed a new shift factor model in Arrhenius format with alterable activation energy. We also used two methods based on nonlinear least squares to obtain the Maxwell model of the polyetherimide, and we then used a novel method integrated with Laplace transforms and partial fraction decomposition to convert the Maxwell model into the Voigt model. The results of our model are reliable and self‐consistent, showing its potential for modeling the viscoelasticity of other materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46102.     

Molecular weight influence on shape memory effect of shape memory polymer blend (poly(caprolactone)/styrene-butadiene-styrene)

The shape memory effect (SME) does not only concern the macroscopic structure. It concerns also the polymer structure at morphological, macromolecular, and molecular scales. This effect may depend on different physicochemical properties like morphology heterogeneity, chain rigidity, steric hindrance, chain polarity, free volume, cross-linking or entanglement density, molecular shape and weight, and so on. Hence, finding the relationship between the SME and these properties is very important. This can help to obtain the knowledge about the phenomenon origin and mechanism. One of the basic polymer properties, which can have direct SME, may be the molecular weight (M_w ). The question here is: If the M_w of a shape memory polymer (SMP) changes, for different reasons like degradation, what will be the effect of this change on its SME. In order to answer to this question, the investigation is focused on an SMP blend of 40% poly(ɛ-caprolactone) (PCL) and 60% styrene-butadiene-styrene (SBS). Then, enzymatic hydrolysis is performed on this blend to change its M_w . It is shown that this change is only related to the variation in the M_w of PCL. After that, different samples with a distinct average M_w are prepared and characterized by various experimental methods. Shape memory tests are performed on these blends, and the recovery rate (R_r ) for each of them is determined. It is found that when M_w of PCL decreases, its degree of crystallinity, its glass transition, and its melting temperatures, corresponding to the PCL phase, increase. However, the elongation at break of the blend declines with the reduction in M_w . The tests show that the alteration in the blend's M_w influences its SME. Indeed, R_r of the (PCL/SBS) mixture drops with the decrease in M_w of PCL.     

TPU/PLA nanocomposites with improved mechanical and shape memory properties fabricated via phase morphology control and incorporation of multi-walled carbon nanotubes nanofillers

Shape memory polymer nanocomposites based on thermoplastic polyurethane (TPU)/polylactic acid (PLA) blends filled with pristine multi-walled carbon nanotubes (MWCNTs) and modified MWCNTs─COOH were fabricated by direct melt blending technique and investigated for its morphology, mechanical, thermal, electrical, and shape memory properties. Morphological characterizations by using transmission electron microscope (TEM) and field emission scanning electron microscope (FESEM) revealed better dispersion of MWCNTs─COOH in the polymer blend, which is attributed to the improved interfacial interactions between the polymer blends and MWCNTs-COOH. Loading of the MWCNTs-COOH in the TPU/PLA blends resulted in the significant improvements in the mechanical properties such as tensile strength and elastic modulus and these effects are more pronounced on increasing the MWCNTs─COOH loading amount, when compared to the pristine MWCNTs filled system. Thermal analysis showed that the glass transition temperature of the blends increases slightly with increasing loading of both pristine and modified MWCNTs in the system. The resistance of nanocomposites decreased from 2 × 10¹² Ω to 3.2 × 10¹⁰ Ω after adding 3% MWCNTs─COOH. The shape memory performance tests showed that the enhancement of shape recovery by 252% could be achieved at 3% MWCNTs loading, when compared to that of TPU/PLA blends.     

A study of rheological limitations in rotary jet spinning of polymer nanofibers through modeling and experimentation

The recently popularized method of rotary jet spinning (RJS) or centrifugal spinning is investigated to evaluate the rheological limitations of polymer solutions and melts to optimal spinnability. The influence of Newtonian or non-Newtonian behavior of the polymer on spinnability is discussed. We observe that highly viscous polymers tend to block the die channels within a rotary jet spinneret and therefore suggest the use of relatively low Newtonian viscosities of between 1 and 10 Pa s for optimal fiber production. Computational fluid dynamics simulations are used in conjunction with experimental data to establish important processing parameters, such as typical shear rates in the device and optimal polymer melt or solution viscosities. A theoretical model for RJS is compared to measured fiber diameters. The comparison shows that although fiber diameters can be estimated very roughly in the case of polymer solutions, the prediction of fiber diameter in the case of polymer melts require further modeling work. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48963.     

Permeability properties of a pressure induced compacted polymer liner in gas cylinder

The permeability properties of composite gas cylinders for breathing gas with polymer inner-liner are investigated. The cylinder wall can be described as a composite membrane consisting of two layers. The permeability properties of the cylinder are presented as permeability coefficient and permselectivity. Deviation from the expected gas components might lead to incidents and potentially harmful situations when breathing gas from a compressed gas cylinder. Hence, gas permeability and potential changes in gas composition, must be considered when choosing cylinder materials. Cases of decompression sickness initiated this study. Experimental data show that pressure and oxygen fraction in the gas cylinder drops and that the permeability coefficient varies depending on the inner pressure. Permeability coefficients of 0.62–0.90 Barrer for oxygen and 0.44–0.56 Barrer for nitrogen are measured. Cracks in the inner-liner have caused an accentuated drop in of oxygen fraction and pressure.     

Polyurethane nanocomposites with click‐coupled nanodiamonds exhibiting enhanced mechanical and shape memory effects

Poly(?‐caprolactone)diol (PCL)–functionalized nanodiamonds (f‐NDs) were synthesized using a click chemistry reaction between the azide‐moiety PCL and alkyne‐moiety NDs and were incorporated into shape memory polyurethane (PU) at f‐ND concentrations of 0, 0.5, 1, and 2 wt % to produce high‐performance shape memory nanocomposites. The PU/f‐ND nanocomposites exhibited better shape recovery, shape recovery stress, and breaking stresses than pure PU. Shape recovery of greater than 95% was demonstrated for all the nanocomposites in the third cycle, and the shape recovery stresses increased significantly with the f‐ND content. These enhanced mechanical and shape recovery properties are ascribed to increased interactions between the f‐NDs and PU matrix due to incorporation of click‐coupled f‐NDs. The click‐coupled NDs can be used as nanofillers to enhance the mechanical and shape memory properties of polymers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45465.     

Application of a fractional model for simulation of the viscoelastic functions of polymers

In the present work the dynamic behavior of two representative polymeric materials, experimentally studied in previous works, has been analyzed by a fractional derivative model. It is shown that the well‐known fractional derivative Zener model, in its simplest form as a four‐parameter model is capable of capturing the main features of the dynamic moduli of the polymeric structures examined. Furthermore, the time dependent viscoelastic functions, namely the compliance and the relaxation modulus could be simulated with the same model parameter values, indicating this way that the fractional model can provide a method of interconversion between viscoelastic material functions. The model's inadequacy of describing the loss modulus peak asymmetry, exhibited by the materials, has been encountered by the five‐parameter version of the fractional Zener model. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43505.