Flexible shape memory structures with low activation temperatures through investigation of the plasticizing effect

Shape memory polymers (SMP) are a class of stimuli-responsive materials that are able to respond to external stimulus such as heat by altering their shape. Bio-compatible SMPs have a number of advantages over static materials and are being studied extensively for biomedical and clinical applications (such as tissue stents and scaffolds). A previous study has demonstrated that the bio-compatible polymer blend of polylactic acid (PLA)/ thermoplastic polyurethane (TPU) (50/50 and 70/30) exhibit good shape memory properties. In this study, the mechanical and thermo-mechanical (shape memory) properties of TPU/PLA SMP blends were characterized; the compositions studied were 80/20, 65/35, and 50/50 TPU/PLA. In addition, porous TPU/PLA SMP blends were fabricated with a gas-foaming technique; and the morphology of the porous structure of these SMPs foams were characterized with scanning electron microscopy (SEM). The TPU/PLA bio-compatible SMP blend was fabricated with melt-blending and compression molding. The glass transition temperature (Tg) of the SMP blends was determined with a differential scanning calorimeter (DSC). The mechanical properties studied were the stress-strain behavior, tensile strength, and elastic modulus; and the thermomechanical (or shape memory) properties studied were the shape fixity rate (Rf), shape recovery rate (Rr), response time, and the effect of recovery temperature on Rr. The porous 80/20 PLA/TPU SMP blend was found to have the highest tensile strength, toughness and percentage extension, as well as the lowest density and uniform pore structure in the micron and submicron scale. The porous 80/20 TPU/PLA SMP blend may be further developed for specific biomedical and clinical applications where a combination of tensile strength, toughness, and low density are required.

The work presented here describes a paradigm for the design of materials for additive manufacturing platforms based on taking advantage of unique physical properties imparted upon the material by the fabrication process. We sought to further investigate past work with binary shape memory polymer blends, which indicated that phase texturization caused by the fused filament fabrication (FFF) process enhanced shape memory properties. In this work, two multi-constituent shape memory polymer systems were developed where the miscibility parameter was the guide in material selection. A comparison with injection molded specimens was also carried out to further investigate the ability of the FFF process to enable enhanced shape memory characteristics as compared to other manufacturing methods. It was found that blend combinations with more closely matching miscibility parameters were more apt at yielding reliable shape memory polymer systems. However, when miscibility parameters differed, a pathway towards the creation of shape memory polymer systems capable of maintaining more than one temporary shape at a time was potentially realized. Additional aspects related to impact modifying of rigid thermoplastics as well as thermomechanical processing on induced crystallinity are also explored. Overall, this work serves as another example in the advancement of additive manufacturing via materials development.

In this paper, the effect of thermomechanical loading on the behavior of deflection-based harvested energies from a shape memory polymer system is experimentally investigated. Samples are created with honeycomb cells from poly-lactic acid using additive manufacturing techniques. The shape memory effect in shape recovery and force recovery paths are studied under thermomechanical tests in bending and tensile modes. The maximum recoverable strain energy is computed as well. According to the conducted thermomechanical tests, it is shown that the thermal expansion coefficient is much more dominant in the tensile mode. Some procedures are proposed to reduce the thermal expansion effect on the force recovery and arrive at higher energy harvested from a shape memory system.

Shape memory polymers (SMPs) are evolving intensively in smart materials research. SMPs can undergo large deformations, hold a temporary shape and then recover their original shape upon exposure to a particular external stimulus. The emerging development of fibre reinforced shape memory polymer composites (SMPCs) has improved SMPs’ mechanical properties to be comparable to modern fibre reinforced composites. Moreover, the inclusion of nanoparticles has enhanced the diversity in activation mechanisms and improved structural properties and durability.
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\nToday, the SMPCs are generally viewed as promising substances for engineered applications that have raised intensive interest among the scientists and engineers. Interestingly, stimulation by light enables unique and advanced shape memory effects (SMEs) in SMPCs that can fulfill the sophisticated demands of engineering. The ability to vary the light wavelength, intensity, periodicity, polarization and the irradiated position on the SMP component enables wavelength selective, reversible, sequential and multiple SMEs. Furthermore, light travel long distances in a vacuum, can be focussed onto a certain area, is safe to humans and, can be a control signal carrier and most notably, can be sent through optical fibres to extremely inaccessible areas.
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\nIncorporation of metallic, carbon and organic based photothermal fillers into a SMP matrix is a convenient proven method to prepare light activated shape memory polymer composites (LASMPCs). These photothermal fillers convert electromagnetic radiation into thermal energy that triggers the SMP matrix. The current study comprehensively reviewed the performances, mechanisms, challenges and limitations of the existing LASMPC systems and associated optical technologies. Predominantly this research was intended to develop reinforced LASMPC systems and allied optical technologies applicable for large scale structural engineering applications.
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\nIn this study, styrene and bisphenol A epoxy based thermosets and polylactic acid (PLA) based thermoplastic SMPs were used as polymer matrix materials. Carbon fibre, glass fibre, multiwalled carbon nanotube (MWCNT) and rare earth organic complexes of Nd(TTA)3Phen and Yb(TTA)3Phen were used as reinforcement and photothermal fillers. The samples were produced by means of vacuum bagging, mould casting and 4D printing. Morphological investigations were conducted to identify the microstructure and manufacturability of the LASMPCs. The samples’ mechanical and physical properties were tested by standard test methods for polymer matrix composites. Dynamic mechanical analysis was carried out to determine the thermomechanical characteristics. The photothermal effect was investigated through thermal imaging and associated shape memory behaviours were studied through shape fixing and recovery experiments. A finite element analysis was performed with ABAQUS to simulate the photothermal heating behaviour.
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\nThe current study established a material development framework for LASMPC materials and presented apt manufacturing methods for structural and large scale engineering applications. Different modes of light diffusion such as scattered low intensity light, focussed laser beams and light delivery through fibre optics were proved for structural LASMPCs. Sequential and selective wavelength activation of structural LASMPCs are presented. The FEA simulation provided additional understanding on light exposed LASMPCs’ 3-dimensional heating behaviour. Embedding a D-shaped optical fibre in an LASMPC created a single unit smart actuator, which was remotely activated by light. It was proven that flexible radiation shields can reduce the unanticipated shape recovery of LASMPCs components and protect the LASMPCs from polymer degradation due to radiation.
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\nThe improvements to their structural properties and innovative remote activation methodologies have justified LASMPCs’ aptness for space engineering applications. This study has proven its successful completion by three selected case studies of space applications. An LASMPC solar panel array model was sequentially deployed in four recovery steps. In a vacuum, a space habitat structure model was compressed to a third of its volume and then recovered its original shape. A 4D printed boom structure model was tested, proving customized LASMPC structures for sophisticated space equipment fabrication. The deployable LASMPC structures can reduce the occupied room in spacecraft. The improvements to the structural properties of LASMPCs while keeping the SME, understanding on thermomechanical and photothermal behaviours, remote actuation through optical fibres, radiation shields and the insight to space applications are the most significant novel outcomes of this study. This thesis opens up windows of opportunity for the scientific and engineering communities to provide innovative solutions to realize the sophisticated large scale engineering demands in aerospace and space applications and beyond.

4D printing of shape memory polylactic acid (PLA) components: Investigating the role of the operational parameters in fused deposition modelling (FDM)

Alcoholysis is a promising approach for upcycling postconsumer polylactide (PLA) products into valuable constituents. In addition, an alcohol-acidolysis of PLA by multifunctional 2,2-bis(hydroxymethyl)propionic acid (DMPA) produces lactate oligomers with hydroxyl and carboxylic acid terminals. In this work, a process for sizing down commercial PLA resin to optimum medium-sized lactate oligomers is developed at a lower cost than a bottom-up synthesis from its monomer. The microwave-assisted reaction is conveniently conducted at 220–240 °C and pressure lower than 100 psi. The PLA resin was completely converted via alcohol-acidolysis reaction, with a product purification yield as high as 93%. The resulting products are characterized by FTIR, 2D-NMR, 1H-NMR, GPC, DSC, and XRD spectroscopy. The effects of PLA: DMPA feed ratios and the incorporation of 1,4-butanediol (BDO) on the structures, properties, and particle formability of the alcohol-acidolyzed products are examined. The products from a ratio of 12:1, which possessed optimum size and structures, are used to synthesize PLA-based polyurethane (PUD) by reacting with 1,6-diisocyanatohexane (HDI). The resulting PUD is employed in encapsulating lavender essential oil (LO). Without using any surfactant, stable LO-loaded nanoparticles are prepared due to the copolymer’s self-stabilizability from its carboxylate groups. The effect of the polymer: LO feed ratio (1.25–3.75: 1) on the physicochemical properties of the resulting nanoparticles, e.g., colloidal stability (zeta potential > -60 mV), hydrodynamic size (300–500 nm), encapsulation efficiency (80–88%), and in vitro release, are investigated. The LO-loaded nanoparticles show non-toxicity to fibroblast cells, with an IC50 value higher than 2000 µg/mL. The products from this process have high potential as drug encapsulation templates in biomedical applications.

Shape memory polymers (SMPs) have thermomechanical property drastically altering around the glass-transition temperature (Tg), temporary shape fixity and shape recovery property, and so on. To understand the mechanisms of such unique properties and design products including SMPs optimally, a mathematical model which is simple yet can represent these properties reasonably and accurately is necessary. Especially, it is important for the model to be able to consider the effect of temperature and strain history on the properties because the properties are considered to depend on not only the temperature and the strain themselves but also their history. Therefore, in this paper first the effect of the temperature and strain history on the shape fixity and shape recovery properties was examined. Then, a micromechanical model of SMP was developed to describe this effect. This model consisted of a lot of unit elements having four springs, two dash pots, one latch, and one thermal expansion element. Different Tg was assigned to each element because Tg depends on local condition inside of SMP and distributed in general. It was found from the experiment that the temperature and strain history applied to SMP when the shape is gradually frozen has an influence on the shape recovery process. With respect to the model, it was shown that the proposed micromechanical model can capture the thermomechanical behaviors of SMP and, especially, the temperature and strain histories dependence on the shape recovery process quite well.

In this study, we developed a variable-stiffness and deformable link using shape-memory material and the jamming transition phenomenon. Above its glass transition temperature (Tg), a shape-memory polymer (SMP) can be deformed by applying a small load. SMPs maintain the deformed shape after they have been cooled below Tg, and they return to their original shape when heated above Tg. The reversible change in the elastic modulus between the glassy and rubbery states of SMPs can be on the order of 100–1000 times. We exploited the characteristics of SMPs to develop robot components with variable stiffness and sensitivity. The jamming transition phenomenon for granular material has been widely used as a method to change the stiffness of robots. This phenomenon is the change from fluid-like to solid-like conditions by removing air from a space containing particles. In this study, we developed a variable-stiffness link by combining the SMP and the jamming transition phenomenon. Moreover, by replacing the SMP with shape-memory alloys (SMAs), whose recovery force and elastic modulus are larger than those of SMPs, we prepared a second prototype with variable stiffness. We evaluated the performance of both prototypes, using the SMP or the SMA, with experiments and confirmed the motion principle of the proposed link (e.g., shape recovery and shape fixity). Moreover, it was confirmed that the stiffness of these links can be changed among four states.

The glass transition temperatures of epoxy-based shape memory polymers (SMPs), which contain a flexibilizer at various contents of 0%, 5%, 10% and 15% respectively, are determined through DMA tests. The shape memory effect of such materials is investigated through shape recovery experiments. Experimental results show that the content of flexibilizer has much influence on the shape memory effect of epoxy-based SMP. A shape recovery equation is developed based on the results of shape recovery experiment. Numerical calculations show that the developed shape recovery equation well predicts the shape recovery behaviors of epoxy-based SMP.

Poly(lactic acid)/polycaprolactone-based self-programmed photothermal responsive shape memory polymers

This article, written by JPT Technology Editor Chris Carpenter, contains highlights of paper SPE 181361, “Advancement in Openhole Sand-Control Applications With Shape-Memory Polymer,” by Xiuli Wang and Gbenga Osunjaye, Baker Hughes, a GE company, prepared for the 2016 SPE Annual Technical Conference and Exhibition, Dubai, 26–28 September. The paper has not been peer reviewed. Conventional openhole sand-control techniques include standalone screens, expandable screens, and openhole gravel packing (OHGP). In some cases, the uniformity, size, and level of compressive strength of the formation dictate the use of an OHGP completion. However, OHGP is not always feasible or practical for some reservoirs and geographic locations. Shape-memory-polymer (SMP) technology can fill the gaps that exist with current OHGP techniques. This paper summarizes a technology using SMP to provide downhole sand control in openhole environments. Introduction The SMP conformable sand-control system consists of an engineered polymer material compacted onto a retainer cartridge (outer shroud, plain Dutch-weave mesh, and inner shroud). The assembly is then installed onto a perforated base pipe by mechanical means to provide a simple modular system for openhole sand-control applications. SMP Principle and Engineered Behaviors. The SMP typically has two different states: the glass state at low temperatures and the rubber state at higher temperatures. The point of change of state (the transition from the glass state to the rubber state), and the associated temperature, is referred to as the glass transit temperature (Tg). The engineered SMP has a defined Tg—the point where shape recovery starts. The initial SMP is first heated to the Tg of the polymer. Then, a mechanical force is applied to compact it to a smaller diameter and onto a retainer cartridge. The condensed SMP is then cooled below its Tg, and the force is removed. The SMP retains its compacted size until the surrounding temperature of the SMP reaches the Tg, at which point shape recovery begins. The bottomhole temperature (BHT) of the candidate reservoirs needs to be lower than the Tg to ensure that the SMP is rigid under the downhole conditions during the production phase. After the SMP sand-control system is installed in a wellbore, to expand the SMP under a BHT that is lower than the Tg, an activation fluid must be introduced. This activation fluid serves as a catalyst and temporarily reduces the Tg below the BHT so the SMP will be recovered to its initial shape. After the SMP is deployed, the activation fluid is flushed out. The SMP retains its recovered shape that conforms to the wellbore, and it is ready for production.

Biostable shape memory polymers that remain stable in physiological conditions are beneficial for user-defined shape recovery in response to a specific stimulus. For potential commercialization and biocompatibility considerations, biomaterial synthesis must be simple and scalable. Hence, a library of biostable and cytocompatible shape memory polymers with tunable thermomechanical properties based on hard segment content was synthesized using a solvent-free method. Polymer surface chemistry, thermomechanical and shape memory properties, and biostability were assessed. We also investigated the effects of processing methods on thermomechanical and shape memory properties. All polymers showed high glass transition temperatures (>50 °C), which indicates that their temporary shape could be preserved after implantation. Polymers also demonstrate high shape fixity (73-80%) and shape recovery (93-95%). Minimal mass loss (<5%) was observed in accelerated oxidative (20% H2O2) and hydrolytic (0.1 M NaOH) media. Additionally, minimal shape recovery (∼0%) occurred in programmed samples with higher hard segment content that were stored in degradation media. After 40 days of storage in media, programmed samples recovered their primary shapes upon heating to temperatures above their transition temperature. Annealing to above the polymer melting point and solvent casting of polymers improved shape memory and thermal properties. To enable their potential use as biomaterial scaffolds, fiber formation of synthesized polyurethanes was compared with those of samples synthesized using a previously reported solvent-based method. The new method provided polymers that can form fibrous scaffolds with improved mechanical and shape memory properties, which is attributed to the higher molecular weight and crystalline content of polymers synthesized using the new, solvent-free approach. These biostable segmented polyurethanes could be coupled with a range of components that respond to specific stimuli, such as enzymes, magnetic field, pH, or light, to enable a specific shape change response, which could be coupled with drug and/or bioactive material delivery in future work.

A review on biomedical and dental applications of cerium oxide nanoparticles ― Unearthing the potential of this rare earth metal

Thermochemically responsive shape memory polymers (SMPs) can recover from a customized temporary shape to their permanent form in response to both thermal activation and solvent diffusion. This dual-driving characteristic effectively mitigates the potential risks associated with high driving temperatures in biomedical applications and enables SMPs to achieve the multi-shape memory effect (multi-SME). Heating induces complex solvent-polymer interactions that create structural disorder, posing significant challenges for controlling shape memory performance. In this study, we develop a nonequilibrium thermodynamic model that incorporates the concept of phase transition into the Avramov-Milchev framework to address this issue. Furthermore, we validate the efficacy of our proposed model by predicting the thermomechanical behavior and shape memory performance of tert-butyl acrylate (tBA) SMP and Nafion SMP, respectively. This study aims to develop a modeling framework for thermochemically driven SMPs to elucidate the mechanism of disorder-assisted glass transition and enable precise control of the multi-SME, thereby advancing their potential in biomedical applications.

Nanocomposite-based drug delivery systems with intrinsic controlled release properties are of great interest in biomedical applications. We report a novel polylactic acid (PLA)/halloysite nanotube (HNT) nanocomposite-based drug delivery system. PLA/HNT nanocomposites have shown immense potential for use in biomedical applications due to their favorable cyto- and hemo-compatibility. The objective of this study was to evaluate the release of active pharmaceutical ingredients (API) from PLA/HNT composites matrix and the effect of preloading the API into the lumen of the HNT on its release profile. Aspirin was used in this study as a model drug as it is a common nonsteroidal anti-inflammatory and antiplatelet agent widely used for various medical conditions. These two types of drug-loaded PLA/HNT nanocomposites were characterised by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), surface wettability and mechanical testing. Statistical analysis was conducted on numerical data. Drug entrapment and in vitro drug release studies were conducted using UV spectrophotometry. Results indicate that aspirin was successfully loaded into the lumen of HNT, which resulted in the sustained release of aspirin from the nanocomposites. Furthermore, the addition of HNT into the polymer matrix increased the mechanical properties, indicating its suitability as a drug-eluting reinforcing agent.