Shape-Memory Polymers (SMPs) can be stretched to large deformations and recover induced strains when exposed to an appropriate stimulus, such as heat. This emerging class of functional polymers has attracted much interest and found applications in medicine and engineering. Nevertheless, prior to any application, their physical and mechanical properties must be thoroughly studied and understood in order to make predictions or to design structures thereof. In this contribution, the viscoelastic behavior of a polyether-based polyurethane (Estane) and its rate- and temperature-dependent behavior have been studied experimentally and by the mean of simulations. The model-inherent material parameters are identified with the assumption of the thermo-rheological complexity. Here, the numerical results of uni-axial stress relaxations were compared with the associated experiments in conjucation with the Levenberg-Marquard optimization method to determine the parameters of the Prony equation. The ability of the model to simulate the thermo-mechanical properties of Estane was evaluated by data-rich experimental observations on tension and torsion in various temperature ranges. Heterogeneous tests are included into the experimental program to cover a broader spectrum of loading scenarios.

Magneto-rheological fluids (MRF) are known as a category of smart materials because they exhibit sudden viscosity changes upon application of magnetic field. In contrast to normal fluids, MRFs can sustain shear up to a yield stress. Stability and resistance against movement are important factors which determine the extent of application of a MRF. In this work, new MRFs are developed using engine oil as carrier liquid, carbonyl iron powder as magnetic particle, stearic acid and CHRYSO (R) Optima100 as additives. Stability of the samples is measured over time. The samples are exposed to magneto-rheological tests with combined liquid and Peltier temperature control. Samples A, B and C are prepared with low, medium and high particle fractions respectively and tested at different temperatures (-10 degrees C, 5 degrees C, 60 degrees C) but for samples D, E, F and G the rheology tests are conducted in room temperature (25 degrees C) but at variable magnetic field and shear rate. Inherent assumption of the existing constitutive models is that the flow curve of MRF is shifted by a field-dependent yield stress. In this paper the effect of magnetic field is formulated and based on the physical properties of MRFs, a new method is introduced for identification of material parameters. This method predicts the yield stress by comparing the storage and shear moduli. Obtained results are compared with those obtained from fitting the experimental flow curves and also with those obtained from Bingham model. It is shown that, results of the proposed model are in good agreement with the experimental data. Moreover, the calculated sedimentation ratio shows that simultaneous use of stearic acid and Optima100 significantly improves stability of MRFs.

Polymers that allow the adjustment of Shape-Memory properties by the variation of physical parameters during programming are advantageous compared with their counterparts requiring synthesis of new material. Here, we explored the influence of hydrolytic (physical) aging on the Shape-Memory properties of the polyetherurethane system Estane, programmed in repeated thermomechanical cycles under torsional load. We were able to demonstrate that physical aging occurred through water adsorption influencing the existing free volume of the samples as well as the functional properties of Estane. Dynamic Mechanical Thermal Analysis determined the glass transition temperatures of dry and hydrolytically aged samples. According to our results, Estane takes up to 3 wt % water for two weeks (at an ambient temperature of θ = 20 °C). The glass transition temperatures of dry samples decreased within this period from 55 to 48 °C as a consequence of a plasticization effect. Next, for both samples, six subsequent thermomechanical cycles under torsional loading conditions were performed. We were able to confirm that hydrolytically aged samples showed higher shape recovery ratios of Rr ≥ 97%, although dry samples revealed better shape fixity values of about 98%. Moreover, it was observed that the shape fixity ratio of both dry and hydrolytically (physically) aged samples remained almost unchanged even after six successive cycles. Besides this, the shape recovery ratio values of the aged samples were nearly unaltered, although the shape recovery values of the dry samples increased from Rr = 81% in the first cycle to 96% at the end of six repeated cycles. Further, the evolution of the free volume as a function of temperature was studied using Positron Annihilation Lifetime Spectroscopy. It was shown that the uptake of two other organic solvents (acetone and ethanol) resulted in much higher specific free volume inside the samples and, consequently, a softening effect was observed. We anticipate that the presented approach will assist in defining design criteria for self-sufficiently moving scaffolds within a knowledge-based development process.

In this contribution, diffusion of water, acetone, and ethanol into a polymer matrix has been studied experimentally and numerically by finite element approaches. Moreover, the present study reports an assessment of different thermomechanical conditions of the shape-memory (SM) performance, for example, stress- or strain-holding times in stress- or strain-controlled thermomechanical cycles and the effect of maximum strain. According to the results presented here, the uptake of acetone in Estane is much higher than ethanol and follows classical Fickian diffusion. Further, a series of thermomechanical measurements conducted on dry and physically (hydrolytically) aged polyether urethanes revealed that incorporation of water seems to have an appreciable impact on the shape recovery ratios which can be attributed to the additional physical crosslinks. However, no obvious difference in shape fixation of dry and physically (hydrolytically) aged samples could be recognized. Furthermore, by decreasing the strain-holding time, shape recovery improves significantly. Moreover, the shape fixity is found to be independent of holding time. The shape recovery ratio decreased dramatically with an increase in the stress-holding time.

Shape-Memory Polymers (SMPs) have the ability to be deformed and memorize this deformation until an external activation stimulus (e.g., heat) is applied. Therefore, they have attracted great interest in many areas, especially for applications where reconfigurable structures are required (e.g., Shape-Memory (SM) stents or micro air vehicles). Nevertheless, prior to technical application, the effective thermomechanical behavior of SMPs must be thoroughly understood. In the current contribution, an assessment of thermorheological properties of the commercially available polyurethane system ESTANE is presented. Thermorheological properties were investigated using Dynamic Mechanical Thermal Analysis (DMTA) and complementary uniaxial stress relaxation experiments. Upon material parameter optimization, a finite viscoelastic and incompressible material model was used to model experimentally observed viscoelastic properties.

An atomistic molecular dynamics simulation approach is applied to model the influence of urethane linker units as well as the addition of water molecules on the simulated shape-memory properties of poly[(rac-lactide)-co-glycolide] (PLGA) and PLGA-based copolyester urethanes comprising different urethane linkers. The shape-memory performance of these amorphous packing models is explored in a simulated heating-deformation-cooling-heating procedure. Depending on the type of incorporated urethane linker, the mechanical properties of the dry copolyester urethanes are found to be significantly improved compared with PLGA, which can be attributed to the number of intermolecular hydrogen bonds between the urethane units. Good shape-memory properties are observed for all the modeled systems. In the dry state, the shape fixation is found to be improved by implementation of urethane units. After swelling of the copolymer models with water, which results in a reduction of their glass transition temperatures, the relaxation kinetics during unloading and shape recovery are found to be substantially accelerated.

It is well known that the environmental conditions e.g. humidity can alter the shape-memory properties of polymers. In this work we applied an atomistic molecular dynamics simulation approach to model the influence of the addition of 1 wt% and 2 wt% water on the simulated shape-memory behavior of the amorphous switching domains of poly(L-lactide) (PLLA) with a molecular weight of M-n = 52,000 g mol(-1). For the dry as well as the water swollen PLLA-models, two subsequent uniaxial thermomechanical test cycles have been calculated, whereby the applied uniaxial deformation epsilon(m) was varied between 50% and 150%.All simulated PLLA models showed high shape fixity ratio of R-f >= 84%. The shape-memory properties obtained at epsilon(m) = 100% for the dry PLLA and the models containing 1 wt% water were almost identical with a shape recovery ratio in the first and second test cycle around R-r = 61%-64%. In contrast PLLA with 2 wt% water exhibited higher values of R-r = 76% during the first test cycle, but a lower R-r = 52% in the subsequent second cycle. Furthermore, increasing the applied epsilon(m) resulted in a decrease of R-r from 82% to 42% for the dry PLLA, whereas PLLA with 2 wt% water did not show a dependence of R-r on epsilon(m). We anticipate that these observations can be attributed to differences in the initial structure of the various simulated PLLA models e.g. the different distribution of the free volume elements. (C) 2013 Elsevier Ltd. All rights reserved.

The thermally induced shape-memory effect of polymers is typically characterized by cyclic uniaxial thermomechanical tests. Here, a molecular-dynamics (MD) simulation approach of such a cyclic uniaxial thermomechanical test is presented for amorphous switching domains of poly(L-lactide) (PLLA). Uniaxial deformation of the constructed PLLA models is simulated with a Parinello-Rahman scheme, as well as a pragmatic geometrical approach. We are able to describe two subsequent test cycles using the presented simulation approach. The obtained simulated shape-memory properties in both test cycles are similar and independent of the applied deformation protocols. The simulated PLLA shows high shape fixity ratios (Rf 94%), but only a moderate shape recovery ratio is obtained (Rr 30%). Finally, the structural changes during the simulated test are characterized by analysis of the changes in the dihedral angle distributions.

Aim The hydrolytic degradation behavior of degradable aliphatic polyester-based polymers is strongly influenced by the uptake or transport of water into the polymer matrix and also the hydrolysis rate of ester bonds. Methods We examined the volumetric swelling behavior of poly[(rac-lactide)-co-glycolide] (PLGA) and PLGA-based poly-urethanes (PLGA-PU) with water contents of 0 wt%, 2 wt% and 7 wt% water at 310 K using a molecular modeling approach. Polymer systems with a number average molecular weight of Mn = 10,126 g·mol−1 were constructed from PLGA with a lactide content of 67 mol%, whereby PLGA-PU systems were composed of five PLGA segments with Mn = 2052 g·mol−1, which were connected via urethane linkers originated from 2,2,4-trimethyl hexamethylene-1,6-diisocyanate (TMDI), hexamethyl-1,6-diisocyanate (HDI), or L-lysine-1,6-diisocyanate (LDI). Results The calculated densities of the dry PLGA-PU systems were found to be lower than for pure PLGA. The obtained volumetric swelling of the PLGA-PU was depending on the type of urethane linker, whereby all swollen PLGA-PUs contained larger free volume distribution compared to pure PLGA. The mean square displacement curves for dry PLGA and PLGA-PUs showed that urethane linker units reduce the mobility of the polymer chains, while an increase in backbone atoms mobility was found, when water was added to these systems. Consequently, an increased water uptake of PLGA-PU matrices combined with a higher mobility of the chain segments should result in an accelerated hydrolytic chain scission rate in comparison to PLGA. Conclusions It can be anticipated that the incorporation of urethane linkers might be a helpful tool to adjust the degradation behavior of polyesters.

Aim Multifunctional polymer-based biomaterials, which combine degradability with a shape-memory capability and in this way enable the design of actively moving implants such as self-anchoring implants or controlled release systems, have been recently introduced. Of particular interest are approved degradable polymers such as poly(L-lactide) (PLLA), which can be easily functionalized with a shape-memory effect. In the case of semicrystalline PLLA, the glass transition can be utilized as shape-memory switching domain. Methods In this work we applied a fully atomistic molecular dynamics simulation to study the shape-memory behavior of PLLA. A heating-deformation-cooling programming procedure was applied to atomistic PLLA packing models followed by a recovery module under stress-free conditions allowing the shape recovery. The recovery was simulated by heating the samples from Tlow = 250 K to Thigh = 500 K with different heating rates β of 125, 40 and 4 K·ns−1. Results We could demonstrate that the obtained strain recovery rate (Rr) was strongly influenced by the applied simulation time and heating rate, whereby Rr values in the range from 46% to 63% were achieved. On its own the application of a heating rate of 4 K·ns−1 enabled us to determine a characteristic switching temperature of Tsw = 473 K for the modeled samples. Conclusions We anticipate that the atomistic modeling approach presented should be capable of enabling further study of Tsw with respect to the molecular structure of the investigated SMP and therefore could be applied in the context of design and development of new shape-memory (bio)materials.

Nanocomposite Si3N4/TiO2 coatings were prepared by micro arc oxidation with Si3N4 nanoparticles in solution and the effects of time and current density on the coatings formation and growth were studied. X-ray diffraction analysis was utilized to detect the nanocrystalline and amorphous characteristics of the composite coatings. Surface morphology and nanostructure of coatings were observed by scanning electron microscopy and atomic force microscopy. The results showed that current density had great effects on phase transformation of Si3N4 nanoparticles in composite coatings. The moderate current density conduced to homogeneous distribution of silicon nitride nanoparticles in the coatings. Moreover, fine nanoparticles that entered and homogeneously distributed in the composite coating led to an increase in the barriers for nucleation of oxide-based grains and inhibition of grain growth. Therefore, the introduction of nanoparticles resulted in the formation of smaller oxide-based grains.

Nanocrystalline coatings were performed on the surface of 316L stainless steel plates mechanically with a mixture of Ti and WC powders under vacuum conditions. The targets were replaced in the end of the high energy milling rig, while Ti-WC mixture was milled as usual. It is shown that the coatings are nanocrystalline in nature with narrow distribution of average size of nanocrystallites. X-ray diffraction and scanning electron microscopy (with energy-dispersive spectrometer) revealed that the top layer of the coatings is uniform. Microhardness, roughness and primary corrosion tests (tafel tests) proved enhancement of coated samples with respect to raw materials. Transmission electron microscope image of deformed surface confirmed surrounding of nanoparticles by dislocation loops after plastic deformation.

In this paper, the effects of the average size of nanometric particles (ASNP) from submicron scale (less than 1 µm) to nanometric scale (less than 10 nm) have been studied on the properties of nanocomposite layers which usually have not been studied or rarely studied. These properties consist of corrosion current density after long time immersion, roughness of obtained layer and distribution of nanometric particles. All of the other effective factors for fabrication of nanocomposite coatings have been fixed for better studying the effect of the ASNP. It has been seen that decreasing the ASNP will lead to lower corrosion current densities however in some cases pitting phenomena has been observed. The roughness illustrated a minimum level while the distribution of nanometric particles will be more uniform by decreasing the ASNP.

A new method in plasma surface engineering called pulsed plasma electrolytic deposition (PPED) was applied to copper substrates. Corrosion properties of the produced layers were evaluated via potentiodynamic polarization. Results indicated relations among treatment time as well as peak applied voltage, frequency, and duty cycle on average density of TiO 2 nanorods significantly. Investigation of the corrosion characteristics showed that the magnitude of corrosion resistance strongly followed from the experimental parameters of applied treatment as well as the average density of TiO 2 nanorods. The average density of TiO 2 nanorods measurements was done via figure analysis with minimum possible errors.

Nanocrystalline carbonitrides were performed by pulsed plasma electrolytic carbonitriding on hard chromium coating deposited on AISI 1035 substrate by electroplating. The electroplated samples were connected cathodically to a high-current pulsed power supply and biased to a negative voltage. The treatment times were 30, 60 and 60 min. A thick compound layer was formed on the surface of Cr coating with microhardness of about 1200 HV0.15. The nanostructure of the treated layers depends strongly on the applied voltage. The wear resistance of the treated layers depended on process parameters. Overall mechanical properties of treated samples show strong relation to morphology and distribution of complex carbonitride nanocrystallites.