Thermo-responsive Shape Memory Polymer Research Articles

Thermodynamically-consistent constitutive modeling of moisture- and thermo-responsive shape memory polymers

Abstract Taking into account that shape memory polymer (SMP)-based devices are often subject to multiple environmental conditions during application, it is difficult to accurately predict their shape memory effect (SME). Thus, constitutive modeling for SMPs in multi-field environments is of great importance. However, most of the models available are limited to describing the temperature-driven SME and do not refer to multi-field conditions. In this paper, a constitutive model for SMPs in hygrothermal environments is developed under a consistent thermodynamic framework. The derivation is based on an additive decomposition of the Helmholtz free energy density and satisfying the first law and second law of thermodynamics. In this paper, the absorbed moisture is categorized into free and bound phases and it is considered that they have different effects on the material properties. Accordingly, it is the first time to study the variation of configurational entropy with different phases in the polymer–moisture system during the moisture diffusion process. For the first time, the validity of the constitutive model proposed in this paper can be confirmed by systematically comparing the modeling results and experimental data of various types of hygrothermal-induced shape memory cycles.

A novel polymer based on ethylene-methyl acrylate copolymer/chloroprene rubber thermoplastic vulcanizates with rapid thermo-responsive shape memory property

A simple and effective strategy for preparing thermo-responsive shape memory polymers (TSMPs) can be designed where the novel TSMPs based on ethylene-methyl acrylate copolymer (EMA) and chlorinated polyethylene rubber (CR) thermoplastic vulcanizates (TPVs) were prepared using dynamic vulcanization. The morphology of the EMA/CR TPVs exhibited a sea-island structure obviously; moreover, the EMA served as the continuous phase and mainly provided the shape fixation (SF) capability of the blend, while the highly elastic CR was acted as the dispersed phase and provided the primary driving force during the shape recovery (SR) process. The SF and SR behaviors of the EMA/CR TPVs can be effectively controlled by varying the weight ratio of EMA/CR blends. Increasing the weight ratio of EMA/CR, the SF% of the EMA/CR TPVs was enhanced while the SR% was decreased remarkably. The shape memory behaviors of EMA/CR TPVs were significantly influenced by temperature. Notably, when the fixation and recovery temperatures were all set at 95°C, both the SF% and SR% of the EMA/CR TPVs with a weight ratio of 80/20 exceeded 95%, and the SR time was 15∼20s, demonstrating the excellent shape memory property.

Nucleation, Development and Healing of Micro-Cracks in Shape Memory Polyurethane Subjected to Subsequent Tension Cycles.

Thermoresponsive shape memory polymers (SMPs) have garnered increasing interest for their exceptional ability to retain a temporary shape and recover the original configuration through temperature changes, making them promising in various applications. The SMP shape change and recovery that happen due to a combination of mechanical loading and appropriate temperatures are related to its particular microstructure. The deformation process leads to the formation and growth of micro-cracks in the SMP structure, whereas the subsequent heating over its glass transition temperature Tg leads to the recovery of its original shape and properties. These processes also affect the SMP microstructure. In addition to the observed macroscopic shape recovery, the healing of micro-crazes and micro-cracks that have nucleated and developed during the loading occurs. Therefore, our study delves into the microscopic aspect, specifically addressing the healing of micro-cracks in the cyclic loading process. The proposed research concerns a thermoplastic polyurethane shape memory polymer (PU-SMP) MM4520 with a Tg of 45 °C. The objective of the study is to investigate the effect of the number of tensile loading-unloading cycles and thermal shape recovery on the evolution of the PU-SMP microstructure. To this end, comprehensive research starting from structural characterization of the initial state and at various stages of the PU-SMP mechanical loading was conducted. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM) were used. Moreover, the shape memory behavior in the thermomechanical loading program was investigated. The obtained average shape fixity value was 99%, while the shape recovery was 92%, which confirmed good shape memory properties of the PU-SMP. Our findings reveal that even during a single loading-unloading tension cycle, crazes and cracks nucleate on the surface of the PU-SMP specimen, whereas the subsequent temperature-induced shape recovery process carried out at the temperature above Tg enables the healing of micro-cracks. Interestingly, the surface of the specimen after three and five loading-unloading cycles did not exhibit crazes and cracks, although some traces of cracks were visible. The traces disappeared after exposing the material to heating at Tg + 20 °C (65 °C) for 30 min. The crack closure phenomenon during deformation, even without heating over Tg, occurred within three and five subsequent cycles of loading-unloading. Notably, in the case of eight loading-unloading cycles, cracks appeared on the surface of the PU-SMP and were healed only after thermal recovery at the particular temperature over Tg. Upon reaching a critical number of cycles, the proper amount of energy required for crack propagation was attained, resulting in wide-open cracks on the material's surface. It is worth noting that WAXS analysis did not indicate strong signs of typical highly ordered structures in the PU-SMP specimens in their initial state and after the loading history; however, some orientation after the cyclic deformation was observed.

Thermo-responsive shape memory polymer blends based on polylactic acid and polyethylene glycol

Thermo-responsive shape memory polymer blends based on polylactic acid and polyethylene glycol

Shape-Persistent Conductive Nerve Guidance Conduits for Peripheral Nerve Regeneration.

To solve the problems of slow regeneration and mismatch of axon regeneration after peripheral nerve injury, nerve guidance conduits (NGCs) have been widely used to promote nerve regeneration. Multichannel NGCs have been widely studied to mimic the structure of natural nerve bundles. However, multichannel conduits are prone to structural instability. Thermo-responsive shape memory polymers (SMPs) can maintain a persistent initial structure over the body temperature range. Electrical stimulation (ES), utilized within nerve NGCs, serves as a biological signal to expedite damaged nerve regeneration. Here, an electrospun shape-persistent conductive NGC is designed to maintain the persistent tubular structure in the physiological temperature range and improve the conductivity. The physicochemical and biocompatibility of these P, P/G, P/G-GO, and P/G-RGO NGCs are conducted in vitro. Meanwhile, to evaluate biocompatibility and peripheral nerve regeneration, NGCs are implanted in subcutaneous parts of the back of rats and sciatic nerves assessed by histology and immunofluorescence analyses. The conductive NGC displays a stable structure, good biocompatibility, and promoted nerve regeneration. Collectively, the shape-persistent conductive NGC (P/G-RGO) is expected to promote peripheral nerve recovery, especially for long-gap and large-diameter nerves.

Is grafting crystals the new art of making conventional elastomers smart?

AbstractConventional elastomers, such as polyisoprene, polybutadiene, and styrene–butadiene rubber, lack inherent shape memory properties due to their low glass transition temperature. Recently, researchers have discovered a method to incorporate external crystal moieties, thereby transforming these elastomers into thermoresponsive shape memory polymers. However, the question remains: what possibilities might this revolution unfold in the near future? This brief opinion piece celebrates the development of semi‐crystalline shape memory elastomers developed via grafting crystals onto conventional elastomers and offers personal insights into the potential directions this discovery could take us.

Investigation of Shape Memory Polyurethane Properties in Cold Programming Process Towards Its Applications.

Thermoresponsive shape memory polymers (SMPs) with the remarkable ability to remember a temporary shape and recover their original one using temperature have been gaining more and more attention in a wide range of applications. Traditionally, SMPs are investigated using a method named often "hot-programming", since they are heated above their glass transition temperature (Tg) and after that, reshaped and cooled below Tg to achieve and fix the desired configuration. Upon reheating, these materials return to their original shape. However, the heating of SMPs above their Tg during a thermomechanical cycle to trigger a change in their shape creates a temperature gradient within the material structure and causes significant thermal expansion of the polymer sample resulting in a reduction in its shape recovery property. These phenomena, in turn, limit the application fields of SMPs, in which fast actuation, dimensional stability and low thermal expansion coefficient are crucial. This paper aims at a comprehensive experimental investigation of thermoplastic polyurethane shape memory polymer (PU-SMP) using the cold programming approach, in which the deformation of the SMP into the programmed shape is conducted at temperatures below Tg. The PU-SMP glass transition temperature equals approximately 65 °C. Structural, mechanical and thermomechanical characterization was performed, and the results on the identification of functional properties of PU-SMPs in quite a large strain range beyond yield limit were obtained. The average shape fixity ratio of the PU-SMP at room temperature programming was found to be approximately 90%, while the average shape fixity ratio at 45 °C (Tg - 20 °C) was approximately 97%. Whereas, the average shape recovery ratio was 93% at room temperature programming and it was equal to approximately 90% at 45 °C. However, the results obtained using the traditional method, the so-called hot programming at 65 °C, indicate a higher shape fixity value of 98%, but a lower shape recovery of 90%. Thus, the obtained results confirmed good shape memory properties of the PU-SMPs at a large strain range at various temperatures. Furthermore, the experiments conducted at both temperatures below Tg demonstrated that cold programming can be successfully applied to PU-SMPs with a relatively high Tg. Knowledge of the PU-SMP shape memory and shape fixity properties, estimated without risk of material degradation, caused by heating above Tg, makes them attractive for various applications, e.g., in electronic components, aircraft or aerospace structures.

Star-PCL shape memory polymer (SMP) scaffolds with tunable transition temperatures for enhanced utility.

Thermoresponsive shape memory polymers (SMPs) prepared from UV-curable poly(ε-caprolactone) (PCL) macromers have the potential to create self-fitting bone scaffolds, self-expanding vaginal stents, and other shape-shifting devices. To ensure tissue safety during deployment, the shape actuation temperature (i.e., the melt transition temperature or Tm of PCL) must be reduced from ∼55 °C that is observed for scaffolds prepared from linear-PCL-DA (Mn ∼ 10 kg mol-1). Moreover, increasing the rate of biodegradation would be advantageous, facilitating bone tissue healing and potentially eliminating the need for stent retrieval. Herein, a series of six UV-curable PCL macromers were prepared with linear or 4-arm star architectures and with Mns of 10, 7.5, and 5 kg mol-1, and subsequently fabricated into six porous scaffold compositions (10k, 7.5k, 5k, 10k★, 7.5k★, and 5k★) via solvent casting particulate leaching (SCPL). Scaffolds produced from star-PCL-tetraacrylate (star-PCL-TA) macromers produced pronounced reductions in Tm with decreased Mnversus those formed with the corresponding linear-PCL-diacrylate (linear-PCL-DA) macromers. Scaffolds were produced with the desired reduced Tm profiles: 37 °C < Tm < 55 °C (self-fitting bone scaffold), and Tm ≤ 37 °C (self-expanding stent). As macromer Mn decreased, crosslink density increased while % crystallinity decreased, particularly for scaffolds prepared from star-PCL-TA macromers. While shape memory behavior was retained and radial expansion pressure increased, this imparted a reduction in modulus but with an increase in the rate of degradation.

Dry and wet wrinkling of a silk fibroin biopolymer by a shape-memory material with insight into mechanical effects on secondary structures in the silk network.

Surface wrinkling provides an approach to modify the surfaces of biomedical devices to better mimic features of the extracellular matrix and guide cell attachment, proliferation, and differentiation. Biopolymer wrinkling on active materials holds promise but is poorly explored. Here we report a mechanically actuated assembly process to generate uniaxial micro-and nanosized silk fibroin (SF) wrinkles on a thermo-responsive shape-memory polymer (SMP) substrate, with wrinkling demonstrated under both dry and hydrated (cell compatible) conditions. By systematically investigating the influence of SMP programmed strain magnitude, film thickness, and aqueous media on wrinkle stability and morphology, we reveal how to control the wrinkle sizes on the micron and sub-micron length scale. Furthermore, as a parameter fundamental to SMPs, we demonstrate that the temperature during the recovery process can also affect the wrinkle characteristics and the secondary structures in the silk network. We find that with increasing SMP programmed strain magnitude, silk wrinkled topographies with increasing wavelengths and amplitudes are achieved. Furthermore, silk wrinkling is found to increase β-sheet content, with spectroscopic analysis suggesting that the effect may be due primarily to tensile (e.g., Poisson effect and high-curvature wrinkle) loading modes in the SF, despite the compressive bulk deformation (uniaxial contraction) used to produce wrinkles. Silk wrinkles fabricated from sufficiently thick films (roughly 250 nm) persist after 24 h in cell culture medium. Using a fibroblast cell line, analysis of cellular response to the wrinkled topographies reveals high viability and attachment. These findings demonstrate use of wrinkled SF films under physiologically relevant conditions and suggest the potential for biopolymer wrinkles on biomaterials surfaces to find application in cell mechanobiology, wound healing, and tissue engineering.

Thermo-Responsive Shape-Memory Dual-Cured Polymers Based on Vegetable Oils.

The development of thermo-responsive shape-memory polymers has attracted attention due to their ability to undergo reversible deformations based on temperature changes. Vegetable oils are confirmed to be an excellent biorenewable source of starting materials for the synthesis of polymers. Therefore, the objective of this research was to synthesize thermo-responsive shape-memory polymers based on vegetable oils by using the dual-curing technique and obtaining polymers with tailorable properties. Acrylated epoxidized soybean oil and two epoxidized vegetable oils, linseed oil and camelina oil, were chosen for dual curing with m-xylylenediamine. Rheological tests were used to analyze the curing kinetics of systems undergoing radical photopolymerization, thermal cationic polymerization, and dual-curing processes. The rheological, mechanical, and thermal characteristics of the polymers were enhanced by the second curing stage. Dual-cured vegetable oil-based polymers had shape-memory properties with a recovery ratio of 100%, making them suitable for a variety of applications, including electronics, biomedical devices, and robotics.

Swift 4D printing of thermoresponsive shape-memory polymers using vat photopolymerization

Shape-memory polymers (SMPs) are smart materials that have gained significant attention in recent years owing to their widespread application in smart structures and devices. Digital light processing (DLP), a vat-photopolymerization-based technique, is a significantly faster technology for printing a complete layer in a single step. The current study reports a facile and fast method for the 3D printing of SMP-based smart structures using a DLP 3D printer and a customized resin. A liquid crystal (LC, RM257) was combined with the resin to introduce shape-memory properties. The combination of LCs in photocurable resin provides the opportunity to directly 3D-print thermoresponsive structures, avoiding the complexity of SMP resin preparation. The structures were printed with different geometries, and the shape-memory response was measured. Lattice structures were fabricated and programmed to obtain tunable mechanical properties. Furthermore, the strain-sensing response was measured to demonstrate the utility of these lattice structures as smart patches for joint-movement sensing. The SMPs can be prepared conveniently and can potentially be used for various applications, such as smart tools, toys, and meta-material sensors.

Influence of thermoplastic polyurethane and elastomer polymers on self-folding behaviour of 4D-printed polymer-textile composites

Four-dimensional (4D) printing has led to the development of novel pre-configurable shape-memory textiles that transform with time. By 4D printing onto textile substrates, polymer-textile composites (PTCs) with unique mechanical properties have been developed for various applications. However, previous related research has only experimented with single driven/non-reversible polymers due to the difficulties of adhering smart polymers onto textiles which require further scientific inquiry. This study highlights the printing of thermoplastic polyurethane/elastomers (TPU/TPE) with 70 A/82 A/40D Shore hardness to enhance the interfacial bond between thermo-responsive shape-memory polymers (SMPs) and a nylon substrate. The aim is to investigate the influence of TPU/TPE on the peel resistance, mechanical properties, and shape recovery of 4DP PTCs. The results revealed that a 70 A Shore TPU can provide significantly higher peel strength (up to 1600%) compared to 82 A/40D. In addition, Shore hardness also affected 4DP PTC’s mechanical behaviours with 82 A 4DP PTCs recording a tensile strength of 652.30 N (warp) and 665.70 N (weft) with a modulus of 0.14Gpa (warp) and 0.18Gpa (weft). Its mechanical properties played a role in making it a more resistant material to give to deformation resulting in better shape recovery (94.72%, SD = 4.78) but lower shape fixity (88.90%, SD = 4.99) in comparison with other 70 A/40D specimens which are prone to better shape fixity but poorer shape recovery. The findings demonstrate the capacity of TPU/TPEs to achieve a consistent shape recovery and use as an alternative material to fabricate 4D printed textiles.

Innovative multiphysics approach for designing high-performance thermo-responsive shape memory polymer microvalve

Shape memory polymers (SMPs), classified as smart materials, have emerged as promising candidates for microfluidic devices due to their significant potential. In this study, we present the design and analysis of an SMP microvalve. The thermomechanical response of the SMP microvalve is studied using a recently introduced nonlinear constitutive model that incorporates nonlinear hyperelasticity and viscoelasticity for SMPs. This model is coupled with the fluid field and accounts for heat transfer in both fluid and solid physics. The governing equations for the multiphysics behavior are discussed. Then an overview of the finite element model is provided. The most important characteristics of the SMP valve, such as SMP thickness, flow rate, contact pressure, and pressure distribution, are examined numerically. The results expound upon the significance of employing fluid-solid interaction conjugated heat transfer analysis as a crucial factor in the proficient development of microvalves for diverse applications, with the primary objective being the prevention of overheating and the mitigation of potential failures.

Heat-Induced Actuator Fibers: Starch-Containing Biopolyamide Composites for Functional Textiles.

This study introduces the development of a thermally responsive shape-morphing fabric using low-melting-point polyamide shape memory actuators. To facilitate the blending of biomaterials, we report the synthesis and characterization of a biopolyamide with a relatively low melting point. Additionally, we present a straightforward and solvent-free method for the compatibilization of starch particles with the synthesized biopolyamide, aiming to enhance the sustainability of polyamide and customize the actuation temperature. Subsequently, homogeneous dispersion of up to 70 wt % compatibilized starch particles into the matrix is achieved. The resulting composites exhibit excellent mechanical properties comparable to those reported for soft and tough materials, making them well suited for textile integration. Furthermore, cyclic thermomechanical tests were conducted to evaluate the shape memory and shape recovery of both plain polyamide and composites. The results confirmed their remarkable shape recovery properties. To demonstrate the potential application of biocomposites in textiles, a heat-responsive fabric was created using thermoresponsive shape memory polymer actuators composed of a biocomposite containing 50 wt % compatibilized starch. This fabric demonstrates the ability to repeatedly undergo significant heat-induced deformations by opening and closing pores, thereby exposing hidden functionalities through heat stimulation. This innovative approach provides a convenient pathway for designing heat-responsive textiles, adding value to state-of-the-art smart textiles.

4D printable maleated poly(styrene-b-ethylene/butylene-b-styrene) / Poly(ethylene-co-vinyl acetate) thermoplastic elastomer blends; effects of blend composition on shape memory and mechanical properties

Shape memory polymers are attracting attention in materials science with their responsive properties and their application areas are gradually developing. By adapting these materials to the additive manufacturing process, four-dimensional (4D) printing technology has been developed. In this study, novel thermo-responsive shape memory polymer blends were prepared for high temperature applications from commercially available polymers using maleated poly(styrene-b-ethylene/butylene-b-styrene) (SEBS-g-MA) and poly(ethylene-co-vinyl acetate) (EVA) and their applicability in three-dimensional (3D) printing was explored. The presence of SEBS-g-MA led to an increase in the degree of crystallization and glass transition temperature of EVA, accompanied by a decrease in crystallization temperature. As the EVA content increased, the blend morphology transitioned from droplet to co-continuous structure. Higher EVA content resulted in an increase in Young's modulus, but a decrease in tensile strength. Nevertheless, these blends exhibited exceptional elongation at break, surpassing 1200%. The blend comprising 70 wt% SEBS-g-MA and 30 wt% EVA demonstrated a synergistic effect, yielding the highest values for elastic modulus, creep resistance, and storage modulus. Furthermore, the blend with 60 wt% SEBS-g-MA and 40 wt% EVA exhibited optimal shape memory performance, achieving a shape fixing ratio of 93.1% and a shape recovery ratio of 98.7%. The conducted analyses demonstrated that the shape recovery of the produced blends could be adjusted according to temperature, and the blends were able to consistently replicate the shape memory effect across multiple cycles. A filament was manufactured for a 3D printer from the blend of 60 wt% SEBS-g-MA and 40 wt% EVA. Using this filament, 4D models having complex geometries were successfully printed. The produced models were able to maintain their temporary shapes to a significant degree. When triggered by heat, these models rapidly returned to their original shapes within a very short period.

Investigating a shape memory epoxy resin and its application to engineering shape-morphing devices empowered through kinematic chains and compliant joints

4D printing is the additive manufacturing (3D printing) of objects that can transform their shape in a controlled and predictable way when subjected to external stimuli. A thermo-responsive shape memory polymer (SMP) is a highly suitable material to 4D print smart devices, due to its actuation function and the capability of recovering its original shape from the deformed one upon heating. This study presents the results of employing an epoxy resin in the additive manufacturing of complex-shaped smart devices with shape-morphing properties using laser stereolithography (SLA). To quantify the shape memory behaviour of the shape memory epoxy (SMEp), we first investigate the thermomechanical properties of the 3D-printed specimens in a tensile testing machine coupled with an environmental thermal chamber. This approach allows us to determine the shape fixity and recovery of SMEp. Next, we propose effective designs of complex-shaped devices, with the aim of promoting shape morphing through micro-actuators and compliant joints acting as active regions in combination with multiplying mechanisms or kinematic chains in each of the devices. We manufacture the complex-shaped prototypes by using SLA directly from the computer-aided designs. The shape memory trials of the 3D-printed prototypes reveal quite precise shape recovery of the devices, illustrating their shape-memory. In fact, the inclusion of micro-actuators and compliant joints within the complex-geometry devices allows for local triggering, deformation and recovery, resulting in a prompt response of the devices to heat. Therefore, innovative designs, along with the suitable smart material and high-quality manufacturing process, lead to 4D printed devices with fast actuation and shape-morphing properties. Overall, this research may contribute to the development of smart materials and 4D printing technology for applications in fields such as biomedical engineering, robotics, transport and aerospace engineering.

Direct Fused Deposition Modeling 4D Printing and Programming of Thermoresponsive Shape Memory Polymers with Autonomous 2D‐to‐3D Shape Transformations

Herein, direct 4D printing of thermoresponsive shape memory polymers (SMPs) by the fused deposition modeling (FDM) method that enables programing of 2D objects during printing for autonomous 2D‐to‐3D shape transformations via simply heating is focused on. The programming process during printing is investigated through designs and experiments. The capability of programming SMPs during printing is illustrated by prestrain and bending capabilities, which are highly related to printing settings, such as nozzle temperature, print speed, layer height, infill patterns, and ratio of active parts in a bilayer structure. A nearly linear relationship for prestrain and bending parameters is experimentally revealed for different printing factors. Quantitative results are presented to be used as a guidance for designing complex 3D structures via 4D printing of 2D structures. Helix structure, twisting structure, DNA‐like structures, and functional gripper are designed to demonstrate the potential of direct FDM 4D printing for creating complex 3D structures from simple 2D structures with advantages over traditional manufacturing methods. It is shown that, by removing the need for a layer‐by‐layer stacking process to achieve a complex 3D shape, FDM can promote sustainability via 4D printing of autonomous 2D‐to‐3D shape transformer structures with lower materials, time, energy, and longer service life.

Thermoresponsive Shape-Memory Biobased Photopolymers of Tetrahydrofurfuryl Acrylate and Tridecyl Methacrylate.

A series of thermoresponsive shape-memory photopolymers have been synthesized from the mixtures of two biobased monomers, tetrahydrofurfuryl acrylate and tridecyl methacrylate, with the addition of a small amount of 1,3-benzendithiol (molar ratio of monomers 0-10:0.5:0.03, respectively). Ethyl (2,4,6 trimethylbenzoyl) phenylphosphinate was used as photoinitiator. The calculated biorenewable carbon content of these photopolymers was in the range of (63.7-74.9)%. The increase in tetrahydrofurfuryl acrylate content in the photocurable resins resulted in a higher rate of photocuring, increased rigidity, as well as mechanical and thermal characteristics of the obtained polymers. All photopolymer samples showed thermoresponsive shape-memory behavior when reaching their glass transition temperature. The developed biobased photopolymers can replace petroleum-derived thermoresponsive shape-memory polymer analogues in a wide range of applications.

Two-Level 3D Column-like Nanofilms with Hexagonally-Packed Tantalum Fabricated via Anodizing of Al/Nb and Al/Ta Layers-A Potential Nano-Optical Biosensor.

Reanodizing metal underlayers through porous anodic alumina has already been used extensively to fabricate ordered columns of different metal oxides. Here, we present similar 3D multilayered nanostructures with unprecedented complexity. Two-level 3D column-like nanofilms have been synthesized by anodizing an Al/Nb metal layer in aqueous oxalic acid for forming the first level, and an Al/Ta layer in aqueous tartaric acid for forming the second level of the structure. Both levels were then reanodized in aqueous boric acid. The Ta layer deposited on partially dissolved porous anodic alumina of the first level, with protruding tops of niobia columns, acquired a unique hexagonally-packed structure. The morphology of the first and second levels was determined using scanning electron microscopy. Prolonged etching for 24 h in a 50%wt aqueous phosphoric acid was used to remove the porous anodic alumina. The formation mechanism of aluminum phosphates on the second-level columns in the process of long-time cold etching is considered. The model for the growth of columns on a Ta hexagonally-packed structure of the second level is proposed and described. The described approach can be applied to create 3D two- or three-level column-like systems from various valve metals (Ta, Nb, W, Hf, V, Ti), their combinations and alloys, with adjustable column sizes and scaling. The results of optical simulation show a high sensitivity of two-level column-like 3D nanofilms to biomedical objects and liquids. Among potential applications of these two-level column-like 3D nanofilms are photonic crystals for full-color displays, chemical sensors and biosensor, solar cells and thermoresponsive shape memory polymers.

Shape Memory Polymer Foam for Autonomous Climate-Adaptive Building Envelopes

Reducing the continuously growing cooling energy demand of buildings is an important part of achieving global emission targets. Here, we present an innovative scenario of how the integration of a programmable material into a climate-adaptive building envelope (CABE) can create an energy-efficient thermal management system inherent to the material. This novel concept is based on a thermoresponsive shape memory polymer foam (SMP) and is designed to regulate the flow of ambient air through the building envelope in order to enable natural cooling of the structure. Hygrothermal simulation data obtained by the software WUFI® Plus indicate that significant cooling energy saving potential may be accessible with this type of concept. As a possible material basis for a corresponding adaptive element, a reactive foamed polyurethane-based SMP foam is proposed, which is capable of executing a thermoreversible shape change of more than 20% while having a suitable switching temperature range. Finally, the ecological impact of such a functional foam element is evaluated in detail as well as its influence on the overall balance of a façade construction by means of a life cycle assessment (LCA).