Polyacrylamide is a popular material for many bio-related applications ranging from electrophoretic separation to cellular supports. A limitation of polyacrylamide-based hydrogels, however, is their mechanical compliance. The current study examines the effect of colloidal particles as a reinforcing filler phase to enhance the mechanical stiffness of polyacrylamide-polyacrylate hydrogels. Measurements with oscillatory rheology show that for a fixed polymer volume fraction, the presence of colloidal particles with various surface modifications generally results in an increase of the shear storage modulus of the hydrogel-particle composite. Interestingly, this study indicated that no discernable trends can be linked between the values of the shear storage modulus and the particle surface characteristics.

Tailoring of properties and functions of shape-memory polymer networks to the requirements of specific applications demands a knowledge-based approach. A comprehensive database enabling the analysis of structure-property relationships is obtained by the systematic variation of molecular parameters. In detail we investigated the influence of the nature of thermal transition on the shape-memory behavior of polymer networks. Furthermore, additional amorphous phases were introduced enabling tailoring of elastic properties especially in the temporary shape as a consequence of the formed polymer morphology. Enabling higher elasticity, adjustable hydrolytic degradability, and the possibility to tailor the transition temperature of shape-memory to a temperature between room temperature and body temperature are considered to be substantial steps to improve the applicability of these active polymers in medicine.

Phantomlike elastomer simulations do not always deform globally affinely in the way that classical theory predicts. Assuming that each crosslink will deform affinely with its topological neighbors gives much better results, and creates a way to isolate crosslinks with unpredictable deformation properties. The correlation of non-affinities and network properties depends on the constitutive model and boundary condition used. We always find a correlation between local density of crosslinks and degree of non-affinity.

Here we discuss a novel capacitive-type chemical sensor structure that uses recently discovered porous nanocrystalline silicon (pnc-Si) membranes [1] covered with metal as the capacitor plates while a polymer layer sandwiched between them serves as the sensing layer for solvent vapor detection. Pnc-Si is new ultrathin (15 nm) membrane material with pore sizes ranging from 5 to 50 nm and porosities from < 0.1 to 15 % that is fabricated using standard silicon semiconductor processing techniques. We present a study of pnc-Si membranes as a platform for such a sensor. The degree of swelling and the reversibility of the polymer/pnc-Si membrane system immersed in analyte-containing vapors are observed using optical and electrical techniques.

Our experience with shape memory polymers (SMP) began with a project to develop an embolic coil release actuator in 1996. This was the first known SMP device to enter human trials. Recent progress with the SMP devices include multiple device applications (stroke treatments, stents, other interventional devices), functional animal studies, synthesis and characterization of new SMP materials, in vivo and in vitro biocompatibility studies and device-tissue interactions for the laser, resistive, or magnetic-field activated actuators. We describe several of our applied SMP devices.

Poly(methylsilsesquioxane) (PMSSQ) based hybrid materials are promising candidates to produce substrate-independent stable and adherent surface coatings. Usually these materials are synthesized by controlled radical polymerization from inorganic precursors. The presented synthetic pathway in here demonstrates how to graft PMSSQ networks from an endgroup-functionalized organic polymer and thus enlarges the range of accessible inorganic/organic hybrid coating materials.

Biocompatible shape-memory polymers are of high significance for application in medical devices or instruments for minimally invasive surgery. To follow the medical device placement or changes in shape of the device in vivo by imaging methods like X-ray techniques, radiopacity of the polymer is required. In this work, we explored the shape-memory properties of radiopaque polymer composites prepared by incorporation of barium sulphate micro-particles in a biomedical grade polyether urethane (PEU) by co-extrusion technique. The filler content was varied from 5 wt% to 40 wt%, which was confirmed by thermal gravimetric analysis (TGA) measurements, while the particle distribution was visualized by scanning electron microscopy (SEM). The thermal and mechanical properties of the composites were investigated by means of dynamic mechanical analysis at varied temperature (DMTA) and tensile tests. The shape-memory properties of PEU composites were quantified in cyclic, thermomechanical experiments. A significant increase in Young’s modulus and a decrease in elongation at break were observed for PEU composites with increasing content of BaSO4, while the DMTA results were not affected by incorporation of the fillers. All samples exhibited excellent shape-memory properties with shape fixity rates (Rf) above 98% and values for shape recovery rate (Rr) in the range of 81% to 93%. The maximum stress (σmax) obtained under constant strain recovery conditions increased from 0.6 MPa to 1.4 MPa with raising amount of BaSO4, while the corresponding temperature (Tσ,max) as well as the switching temperature (Tsw) determined under stress-free conditions remained constant for all polymer composites.

The goal of this study is to investigate the fundamental relationship between the extent of crosslinking and shape-memory behavior of amorphous, (meth)acrylate-based polymer networks. The polymer networks were produced by copolymerization of tert-butyl acrylate (tBA) and poly(ethylene glycol) dimethacrylates of differing molecular weights (PEGDMA). Polymer compositions were tailored via the amount (weight percent (wt%)) and molecular weight of the PEGDMA crosslinking agents added to produce four materials with varying levels of crosslinking (0, 2, 10, and 40 wt% crosslinking agent corresponding to 0, 0.6, 3.2, and 16.6 mole%) and nearly equal glass transition temperatures (Tg). The effect of crosslinking on deformation limits and free-strain recovery is evaluated. Near complete strain recovery was demonstrated by all materials; however, absolute recovery strain decreased with increasing crosslinking due to a corresponding decrease in strain-to-failure. The results provide insights regarding the link between polymer structure, deformation limits, and strain-recovery capabilities of this class of shape-memory polymers. An improved understanding of this relationship is pivotal for optimizing system response for a wide range of shape-memory applications.

One of widely investigated materials for photodiode, light-emitting device, and solar cell applications is a soluble conjugated polymer poly(2-methoxy-5- (2,9-ethyl-hexyloxy)-1,4-phenylene vinylene) or MEH-PPV. In this paper we present experimental results on MEH-PPV polymer and ITO/PEDOT:PSS/MEH-PPV/Al photodetector, where ITO and PEDOT:PSS stand for indium tin oxide and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), respectively. Thin polymer films were fabricated by spin-coating technique. The characterization of the material and devices are done in air at room temperature. The experimental results include optical absorption of MEH-PPV and determination of the optical absorption coefficient, photocurrent dependence on optical power, light wavelength, bias voltage, and polymer thin film thickness. Theoretical modeling is based on drift-diffusion and continuity equations for hole polarons, as well as assumption that the charge carrier recombination process is bimolecular. The bimolecular recombination mechanism implies that the photocurrent depends on the square root of the optical power, which is confirmed with our experimental results.

The general design principle of shape-memory polymers (SMP) requires two key compo-nents: covalent or physical crosslinks (hard domains) determining the permanent shape and switching domains fixing the temporary shape as well as influencing the switching temperature Tsw. In conventional thermoplastic SMP hard and switching domains determining segments are combined in one macromolecule, e.g. block copolymers such as polyurethanes. Recently, binary polymer blends having shape-memory properties, from two different multiblock copolymers have been presented, whereby the first one is providing the segments forming hard domains and the second one the segments forming the switching domains. Besides the shape-memory proper-ties, the mechanical properties of such materials are application relevant. Here we investigate how the blend composition influences mechanical properties of this new class of shape-memory materials.

We study the thermodynamic properties of solutions of the physically gelling poly(N-isopropylacrylamide-2-hydroxyethyl methacrylate) [poly(NIPPAm-HEMA)]. We construct its phase diagram and characterize its kinetics of phase separation. This material belongs to a class of thermosensitive, “smart” polymers, that exhibit complex phase behavior. The copolymer studied is liquid at low temperatures and undergoes phase separation near 28°C, with negligible dependence on concentration. Above the transition temperature we observe coexistence between a polymer-dilute solution and a gel. We show that, upon quick heating, liquid solutions form a homogeneous gel that phase separates (shrinks) from a dilute polymer solution. We find that the evolution of the gel volume fraction is well described by a double exponential decay, indicating the presence of two shrinking regimes in a close parallel to the behavior of chemically cross-linked gels. The first stage is characterized by quick water ejection. In the second stage, slower shrinking is observed associated with internal reorganization of the polymers that allows the creation of gel-forming contacts.

Shape-memory polymer foams based on poly(ω-pentadecalactone) (PPDL) and poly(ε-caprolactone) (PCL) multiblock copolymer with 60 wt% PCL content were prepared by environmentally-friendly high pressure supercritical carbon dioxide scCO2 foaming technique. A foam with a density of approximately 0.11 ± 0.02 g/cm3 and an average pore size of 150-200 μm with excellent compressibility and shape-memory properties was created at 25 bar/s depressurization rate in the temperature range between 78 and 84 °C. The shape-memory behavior of this foam was investigated using different programming modules, such as, under stress-free condition and under constant strain condition. The thermally-induced shape-memory effect (SME) was found to be strongly dependent on the programming conditions. Excellent shape fixity has been observed for all foams indicating the high efficiency of the switching domains to fix the temporary shape by crystallization. The stress recovery of this foam could be controlled by changing compression percentage (εc%) at a constant compression temperature. The production of these foams with unprecedented properties by commercially available processing equipment raises much hope with the potential to provide new materials with a unique combination of shape-memory properties and porous structure as well as desired properties for many industrial and biomedical applications

In this work, dome structures in PVDF films were prepared as ultrasonic transducer. The domes are realized by a deep-drawing process. The dome-forming process leads to a phase transformation from the non-polar α into the polar β phase within dome wall and roof of the PVDF films. A ferroelectric polarization is obtained in these dome areas after suitable electrical poling which yields a piezoelectric activity. Because of the piezoelectric activity within the film plane, a dome-roof up-and-down actuation is observed with resonance frequencies in the range between 65 and 93 kHz.

The need of intelligent implant materials for applications in the area of minimally invasive surgery leads to tremendous attention for polymers which combine degradability and shape-memory capability. Application of heat, and thereby exceeding a certain switching temperature Tsw, causes the device to changes its shape. The precise control of Tsw is particularly challenging. It was investigated in how far Tg, that can be used as Tsw, of amorphous polymer networks from star-shaped polyester macrotetrols crosslinked with a low-weight linker can be controlled systematically by incorporation of different comonomers into poly(rac-lactide) prepolymers. The molecular mass of the prepolymers as well as type and content of the comonomers was varied. The Tg could be adjusted by selection of comonomer type and ratio without affecting the advantageous elastic properties of the polymer networks.

The present study represents a first step towards an understanding of what we refer to as the functional fatigue behaviour of shape-memory polymers. These materials have a processing shape B and a programmed shape A [1]. And when the material is exposed to an appropriate stimulus (in our case: heating above a critical temperature), a one way effect is observed: A → B (one way effect: 1WE). The objectives of the present study were to find out whether and how often programming can be repeated, whether repeated programming affects the 1WE and how much irreversible strain the material accumulates. We study the effect in dependence of different stress levels, and consider the effect of recovery temperature and recovery time. As a model material we examine the commercial amorphous shape-memory polymer Tecoflex® and subject it to 50 programming/1WE cycles. It turns out that programming, cooling, unloading and heating to trigger the 1WE causes an increase of irreversible strain and is associated with a corresponding decrease of the intensity of the 1WE in particular during the first thermomechanical cycles. 1. M. Behl and A. Lendlein, materials today 10, 20 (2007).

We have developed a set of new electrochromic devices (ECDs) for special application goggles, whose color can be switched between transparent and a specific color mode, i.e. blue (B). This paper will discuss the design, film deposition, device assembly and characterizations of the color switchable lens. The ECD is composed of a layer of thin film conducting polymer poly (3,4-(2,2-dimethylpropylenedioxy)thiophene) (PProDOT-Me2), a layer of thin film inorganic oxide V2O5-TiO2, and a layer of ionic conductive electrolyte. The thin films are electrochemically deposited on ITO coated flexible plastic substrate. The whole device is packaged with an UV cured flexible film sealant. The goggle lens exhibit tuneable shade in visible light wave length (380-800nm), with a maximum contrast ratio at 580nm. Meanwhile, other unique properties include fast switching speed, low driving voltage, memory function (no power needed after switching, bistable), great durability, high flexibility, light weight, and inexpensiveness.

We built up the way of fabricating IPMC actuator with palladium electrodes and we found that it showed large bending response than Au-plated IPMC actuator. An ionic polymer-metal composite (IPMC) consisting of a thin perfuorinated ionomer membrane, electrodes plated on both faces, undergoes large bending motion when a small electric field is applied across its thickness in a hydrated state. The characteristics of IPMC are ease of miniaturization, low density, and mechanical flexibility. Therefore, it is considered to have a wide range of applications from MEMS sensor to artificial muscle. However, there are problems on IPMC. First, its mechanical and electric characteristics have not been clarified because of the complex mechanism of the deformation. Second, it is high-priced because most of IPMC actuators use gold or platinum as electrodes. In order for IPMC actuator to be widely put to practical use, we should solve these problems. Hence, this research focuses on fabrication of IPMC actuator with palladium electrode, which is cheaper than gold or platinum, and evaluation of its mechanical properties such as its tip displacement. We fabricated IPMC consisting of a thin Nafion® membrane, which is the film with fluorocarbon back-bones and mobile cations, sandwiched between two thin palladium plates. The surface resistivity was 2.88±0.18Ω/sq., so it could be said to be enough small. Then, we observed its cross section by using FE-SEM. As a result, palladium plates were evenly coated and its thickness was about 30μm. Also, we carried out an actuation test for two kinds of IPMCs: one was fabricated by using Nafion®117 (thickness 183μm), the other was by Nafion®115 (thickness 127μm). In this test, the relationship between voltage (0˜4V) across its thickness and tip displacement for the cantilevered strip of the IPMC was measured. Then we found that IPMCs showed large bending motion under a low electric field. When Nafion®117 sample was subjected to voltage of 1.5V, the ratio of the tip displacement to the sample length was 0.35, which was lager bending than Au-plated IPMC actuator, whose ratio of the tip displacement to the sample length was 0.12 [1]. When Nafion®115 sample was applied to 1.5V, the ratio of the tip displacement to the sample length was 0.22. Then, we found that Nafion®117 bended in a larger way than Nafion®115. Reference [1]Sia Nemat-Nesser and Yongxian Wu,”Comparative experimental study of ionic polymer-metal composites with different backbone ionomers and in various cation forms”, Journal of Applied Physics,93,5255 (2003)

Embedded piezoresistive microcantilever (EPM) sensors provide a small, simple and robust platform for the detection of many different types of analytes. These inexpensive sensors may be deployed in battery-powered handheld units, or interfaced to small, battery-powered radio transmitter-receivers (motes), for deployment in mesh networks of many sensors. Previously, we have demonstrated the use of EPM sensors in the detection of hydrogen fluoride gas, organophosphate nerve agents, volatile organic compounds (VOC’s), chlorinated hydrocarbons in water, and others. Here, we report on the design of EPM sensors functionalized for the detection of chlorine gas, or Cl2. We have constructed EPM sensors using composite materials consisting of a polymer or hydrogel matrix loaded with agents specific for the detection of Cl2 such as NaI. These materials were tested in both controlled laboratory conditions and in outdoor releases. Stability of the sensing materials under conditions of high temperature were also studied. Results are presented for gas exposures ranging from 1000 ppm to 20 ppm.

Shape-memory polymers are of high scientific and technological interest in the biomedical field, e.g., as matrix for self-anchoring implantable devices. In this study, two different star-shaped copolyester tetroles, semi-crystalline oligo[(-caprolactone)-co-glycolide]tetrol (oCG) and amorphous oligo[(rac-lactide)-co-glycolide]tetrol (oLG), were synthesized and subsequently crosslinked by a low molecular weight diisocyanate resulting in copolyester urethane networks (N-CG, N-LG). Both networks could be loaded with model drugs and a diffusion controlled release of the drugs was observed without any effect on the mass loss as measure of hydrolytic degradation. However, the N-CG network’s capability of shape programming was disturbed as the crystallinity of the precursors got lost in the complex three dimensional architecture after crosslinking. By contrast, amorphous N-LG network showed an excellent shape-memory capability with a switching temperature around 36 °C corresponding to their glass transition temperature. This led to triple-functional materials combining biodegradability, shape-memory, and controlled drug release.

The super-molecular structure and morphology of shape-memory polymers (SMP) have an evident influence on the shape-memory effect (SME). More detailed information on these structure-function relations during the dynamic processes of programming and shape recovery are required to better understand the SME. Here we explore whether wide and small angle x-ray scattering (WAXS, SAXS) in combination with deformation experiments can help to characterize and better understand the respective materials super-molecular structure (spatial organization of chain segments in crystalline and non-crystalline regions, characterized by parameters such as crystallinity, crystallite-sizes, domain-sizes and -arrangements) and its changes upon varying mechanical loads and temperature increase as stimulus. Multiphase polymer networks based on poly(ε-caprolactone) and poly(cyclohexyl methacrylate), whose molecular structures allow formation of at least two separated domains, were investigated using WAXS and SAXS, to describe the respective super-molecular structures and morphologies and their development during cyclic, thermomechanical tensile tests reproducing key features of shape-memory programming and recovery. The creation of the triple-shape capability for this AB polymer network system is performed by a one-step process, which is similar to a conventional dual-shape programming process. It could be shown via SAXS that a long period between crystalline domains exists for these polymer networks. The value of this long period changes by some nanometers as a consequence of programming and the resulting elongation of the respective sample. Further insights could be obtained by investigating WAXS diffraction peaks, detected at different steps during the thermomechanical treatment. It could be shown that crystal sizes in this polymer system remain unaffected by the programming process, while the crystallization of the stretched samples during the cooling process leads to a spatial rearrangement (preferential orientation) of crystalline domains.