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Eingeladener Vortrag
- nein (18)
Hydrolytic degradation and functional stability of a segmented shape memory poly(ester urethane)
(2009)
In order to understand the effects of water and hydrolytic ageing on semi-crystalline poly(ester urethane) and its shape memory functionality, water immersion experiments at elevated temperature have been performed on a model substance and various parameters were monitored: change of the melting/crystallisation temperatures, substantial increase in crystallinity, temperature dependence of the water diffusion coefficient and solubility, hydrogen-bonding index and phase mixing by peak deconvolution of the FT-IR carbonyl region and day-to-day tensile and thermo-mechanical cyclic tensile tests. A rising fraction of freezable water agglomerates in the polymer was found for specimens cooled from the immersion temperature. The degradation process could be divided into three phases: an induction phase, a phase of continuous degradation and a phase of accelerated degradation. Shape recovery remains fairly constant during phase one and decreases slowly during phase two. The increase in crystallinity in phase two is accompanied by an increase in shape fixing ability.
Thermo-mechanical Effects of hydrolytic Aging on an active Polymer with Triple-Shape Properties
(2010)
In two hydrolytic degradation studies the tensile (mechanical) and functional (thermo-mechanical) properties of a hydrolysis-stabilized shape memory poly(ester urethane) and its non-stabilized analog were investigated. Hydrolytic degradation was enforced by specimen immersion in de-ionized water at 80 °C. Significant differences in the fundamental shape memory parameters were monitored as function of aging time for the stabilized and non-stabilized polymer. This included the ability to recover strain (shape recoverability) and stress (stress recoverability) on heating after shape programming. Hydrolysis-related mechanical and functional changes were correlated with morphological ones, detected by differential scanning calorimetry (DSC). The shape memory poly(ester urethane), which was protected by a carbodiimide-based hydrolysis stabilizer, revealed significantly improved resistance towards hydrolysis with respect to various mechanical and shape memory parameters.
A series of cyclic thermo-mechanical measurements was conducted on segregated poly(ester urethane) to study substantial changes in triple-shape properties as a result of hydrolytic aging (80 °C). Prior to the analysis of aging effects, a concept of triple-shape testing was elaborated, starting with the implementation of two distinct programming units. The first one included a deformation at 60 °C to εm1 = 100% (temporary shape B) and its fixing through soft segment crystallization by cooling to -20 °C under constant strain. The second one consisted of a deformation at -20 °C to εm2 = 200% (temporary shape A) and its stabilization through soft segment vitrification as achieved by cooling to -60 °C under fixed strain constraint. Then, gradual heating of the polymer from below to above its thermal transition temperatures gave two independent shape recovery responses in the reverse order of shape fixing: A → B through passing the glass transition by heating from -60 to 23 °C and B → C (back to the permanent shape), when heating the material from 23 to 60 °C and thus above its soft segment melting temperature. In a progressive approach, the storage of loading history through the sequential fixing of two temporary shapes was proven by the development of shape recovery stresses under constrained environment. With the implementation of the two testing methods several aging-related effects could be detected. Good shape fixing abilities ≥90% for both shapes were found and contrasted by significant changes in shape recoverabilities and stress storage capacities. Further insights derived from differential scanning calorimetry (DSC) measurements, indicating an aging-related growth in soft segment crystallinity, and dynamic mechanical analysis (DMA), suggesting a plasticizer effect of water onto the polymer matrix and that aging favoured an increase in cross-linking density.
Temperature-memory polymers are able to generate a substantial mechanical response when heated above the temperature, at which a preceding deformation was carried out. Here we show how to design the temperature-memory effect (TME) by thermomechanical treatment. As a model polymer, phase segregated poly(ester urethane) (PEU) containing crystallizable segments of poly(1,4-butylene adipate) (PBA) was used. For programming, strain elongation was applied at temperatures within the PBA melting transition area, before temperature holding, unloading and cooling were carried out. Upon heating under stress-free or constant strain recovery conditions, precisely set temperature-memory onsets could be witnessed. Most importantly, strain fixities and recoverabilities the same as maximum recovery stresses turned out to be controllable by strain rate and temperature holding time after deformation, while transition temperatures remained largely unaffected. The tailoring of thermoresponsiveness was structurally enabled by different PBA crystallinities in the programmed state as verified by wide-angle X-ray scattering (WAXS). The reported studies intend to design TMEs in semicrystalline polyurethanes according to user-defined needs to make this technology broadly applicable.
Two design approaches for multifunctional information carriers are introduced. In the first one, quick response (QR) code carriers, which were composed of poly(ester urethane) (PEU) and microencapsulated thermochromic pigments (T-PIGs), differing in color and color switching temperature (CST), were prepared. The obtained material systems exhibited machine-readable QR codes at 23 °C and a two-stage decolorization when heated, culminating in unreadable QR codes at temperatures above the highest CST of the employed T-PIGs. In the second scenario, information carriers were sealed with a dark, thermochromic PEU layer. As a result, the QR codes were hidden at 23 °C and became readable upon heating due to color fading. Beyond the characterization of the employed components, preparation methods, functionality analyses and durability investigations are reported. When heated after thermo-mechanical programming, pronounced shape memory properties could be verified. The thermo-responsiveness of such multifunctional material systems may qualify them for usage in anti-counterfeiting applications.
Auch Kunststoffe können sich erinnern. Das zeigt das Beispiel eines neuen thermoplastischen Polyurethans. Das Formgedächtnispolymer kann vorübergehend in einem deformierten Zustand fixiert und dann wieder nahezu in seine ursprüngliche Gestalt zurückverwandelt werden. Einsatzchancen hat es unter anderem im Markenschutz und Maschinenbau sowie in der Textil-, Sport-, Freizeit- und Spielzeugindustrie.
Plastics can also remember things. This is made clear by a new thermoplastic polyurethane. The shape memory polymer can be temporarily fixed in a deformed state and then converted back almost entirely into its original shape. Potential applications exist in trademark protection and mechanical engineering as well as in the textile, sports, leisure and toy industries.
Solvent-cast films from shape memory poly(ester urethane) (PEU) containing different weight contents of microencapsulated thermochromic pigments (T-PIGs) were prepared by drying in air. Spectrophotometric investigations unveiled that gradual loading with T-PIG black resulted in continuous darkening of the films up to filler contents of 20 wt%, accompanied by a steady enhancement of thermochromic properties. Taking this composition as standard, PEU films equipped with T-PIG black, blue and red were deposited atop PEU plaques to obtain laminate structures. Herein, the cover layer thickness (100 ± 5 µm) and the good dispersion of T-PIGs inside the polymer matrix were verified by scanning electron microscopy. Machine-readable information carriers were prepared by laser engraving quick response (QR) codes into the cover layer of the laminates and subsequently cutting cuboidal samples therefrom. Finally, thermo-mechanical programming of the QR code carriers was applied to randomly distort the code patterns, thus rendering them unreadable. Upon heating, surface decolorization and shape recovering occurred; during the ensuing cooling, the surface color and contrast reappeared whereupon the QR codes could be read out. Spectrophotometric, calorimetric and thermo-mechanical investigations gave evidence that the color switching temperature of the T-PIGs roughly coincided with the melting temperature of the ester-based switching segment and thus with the activation temperature of the shape memory effect. Apart from that unique functionality, manifold design concepts may render information carriers difficult-to-copy. Therefore, we anticipate tremendous potential as anti-counterfeiting technology.
Herein, we report on how to teach a thermoplastic polyurethane elastomer completely stress-free, bidirectional motion. Briefly spoken, we applied training, consisting of extensive tensile deformation in the specimen's viscoelastic state, initiating deformation-induced crystallization. Once unloaded, thermo-reversible specimen expansion and contraction could be detected. Following the microstructural evolution of such a trained specimen by in situ wide-angle X-ray scattering gave evidence for progressive growth of oriented crystallites during cooling. Upon heating, crystallite melting resulted in structural disorder. Beyond this, modification of the training method was used to introduce a geometrically more complex crystalline order. Here, actuation in the form of a decrease and an increase in sample thickness and specimen twisting and untwisting were witnessed. The novel semi-crystalline polymer actuator highlights an enormous potential for realizing versatile reversible shape changes in elastomers.
Ein neu entwickeltes thermoplastisches Polyurethan (TPU) ist alles andere als „vergesslich". Formteile aus dem Material lassen sich in einer temporären Form fixieren und wieder nahezu in ihre ursprüngliche Gestalt zurückverwandeln. Dieser Formgedächtniseffekt hat gute Anwendungschancen - vom Marken- und Produktschutz über den Maschinen- und Automobilbau, bis hin zur Freizeit- und Spielzeugindustrie.
Mit Formgedächtnispolymeren auf Basis von TPU sind Bauteile spritzgieß- oder extrudierbar, die sich vorübergehend durch eine gezielte thermomechanische Behandlung in einer anderen temporären Form fixieren und stabilisieren lassen. Damit können Informationen gespeichert, vorübergehend sicher verschlüsselt und als Quick Response (QR)-Codes mit schaltbarer Lesbarkeit auf TPU-Etiketten eingraviert werden.
Following a guest diffusion approach, the surface of a shape memory poly(ester urethane) (PEU) was either black or blue colored. Bowtie-shaped quick response (QR) code carriers were then obtained from laser engraving and cutting, before thermo-mechanical functionalization (programming) was applied to stabilize the PEU in a thermo-responsive (switchable) state. The stability of the dye within the polymer surface and long-term functionality of the polymer were investigated against UVA and hydrolytic ageing. Spectrophotometric investigations verified UVA ageing-related color shifts from black to yellow-brownish and blue to petrol-greenish whereas hydrolytically aged samples changed from black to greenish and blue to light blue. In the case of UVA ageing, color changes were accompanied by dye decolorization, whereas hydrolytic ageing led to contrast declines due to dye diffusion. The Michelson contrast could be identified as an effective tool to follow ageing-related contrast changes between surface-dyed and laser-ablated (undyed) polymer regions. As soon as the Michelson contrast fell below a crucial value of 0.1 due to ageing, the QR code was no longer decipherable with a scanning device. Remarkably, the PEU information carrier base material could even then be adequately fixed and recovered. Hence, the surface contrast turned out to be the decisive parameter for QR code carrier applicability.
Poly(ester urethane) with varying polyester chain length: Polymorphism and shape-memory behavior
(2013)
The swelling, viscoelastic, and mechanical behavior of phase-segregated poly(ester urethane) (PEU) block copolymers, composed of 4,4'-methylenediphenyl diisocyanate, 1,4-butanediol as a chain extender, and crystallizable poly(1,4-butylene adipate) (PBA) with molecular weights between 1330 and 4120 g mol-1, are investigated. Wide-angle X-ray scattering (WAXS) is employed to study the overall PEU crystallinity, which increases from 8.6 to 13.6% at higher PBA contents. The existence of two crystalline, polymorphic PBA phases, a thermodynamically stable α phase and a metastable β phase, is confirmed by further WAXS measurements. Calorimetric and thermomechanical investigations give evidence for controllable PBA polymorphic behavior. The crystallization conditions, like the cooling rate, affect the emerging polymorphic mixture, whereas the storage conditions either promote or inhibit the polymorphic (β to α) transition. The introduced concepts represent a new approach for gaining control over programmable thermoresponsiveness, which may be transferable to other shape-memory polymers with polymorphic switching segments.
We demonstrate that phase-segregated poly(ester urethane) (PEU) with crystallizable switching segments of poly(1,4-butylene adipate) (PBA) excels as high-performance temperature-memory polymer. Temperature-memory effects (TMEs) with regard to strain and stress recovering could be programmed by polymer elongation at temperatures below or within the PBA melting transition, followed by cooling under constant stress below the PBA crystallization transition and unloading. Beyond that conventional approach, a novel TME programming route was designed, mostly consisting in specimen elongation and unloading at the same temperature. As a result, an enhanced control over the onsets of strain and stress recovering could be achieved. With these findings, the TME could be exploited to switch quick response (QR) codes in recently developed information carriers from unreadable to readable. We conjecture that such behavior can be programmed into virtually all semicrystalline elastomers and anticipate applicability as label technology to monitor temperature abuse of food and pharmaceuticals.
The selective compression of quick response (QR) and Data Matrix code carriers based on shape memory polymer (SMP) with a freely configurable steel ball type indenter and adjacent thermo-mechanical shape fixing gave notched, room temperature (23 °C) stable, temporary shapes with non-decipherable codes. The microscopic investigation of cryomicrotome sections unveiled indentation-related shape fixities of about 90 %. Independent of the selected two-dimensional code, the triggering of the SM effect resulted in sufficient shape recoveries to restore the code readability so that a maximum number of characters including 122 for a QR code (version 7) and 112 in case of a Data Matrix code (version 12) could be read with a scanning and decoding device. Due to the large number of difficult to copy shapes with on demand releasable information, SMPs may serve as viable information carriers for product and brand protection applications.
Here, we present an investigation of the triple-shape properties of star-shaped polyhedral oligomeric silsesquioxane-poly(ε-caprolactone) polyurethanes (SPOSS-PUs), which have three-dimensional network structures. In a typical 'triple-shape functionalization process', mostly consisting of two tensile deformations at different temperatures, chain immobilization of the polymer network component poly(ε-caprolactone) (PCL) was successfully realized first through crystallization and then through vitrification. Subsequently, large parts of the respective strains were released under stress-free recovery conditions. The two-fold fixed ('programmed') specimens responded to heating with two independent length contractions (switching steps); the first shape change was associated with PCL devitrification and the second one with the melting of hitherto crystalline PCL. It was revealed that the triple-shape properties of SPOSS-PU networks considerably depend on PCL network chain length. When applying exactly the same 'triple-shape creation procedure', larger strain releases were detected in the first transition for polymers with a higher PCL network chain length, whereas the second transition was more accentuated for SPOSS-PU networks with a shorter PCL chain length. In the course of thermo-mechanical cycling, the formation of a neck during the second tensile deformation was repeatedly detected for SPOSS-PUs with higher PCL network chain length; in the subsequent recovery process the specimens even exhibited the highest total strain recoverability. Finally, gradual strain release could be achieved at temperatures below the PCL melting transition through the selection of up to four temperature holding steps, at which every time stable shapes were formed.
Smart Tags carrying QR Codes
(2012)
Herein we demonstrate the realization of a new technological concept, which enables the use of shape memory polymers (SMPs) as switchable information carriers. At first, we applied a surface-specific dyeing process based on 'guest-diffusion' on two sophisticated polymeric host materials, including a thermoplastic poly(ester urethane) SMP and a thermoset epoxy-based SMP. Upon drying, self-assembly of the dye molecules inside the polymer surfaces occurred, resulting in homogeneous color penetration depths of about 100 µm. Subsequently, the colored surfaces were patterned with quick response (QR) codes. For this purpose, laser ablation was used. The resulting cavity depth was exceeding the color penetration depth. This assured sufficient surface contrast and rendered the QR codes machine-readable. In a progressive approach, two thermo-mechanical functionalization protocols were designed in accordance with the thermal properties of the polymers. As a result of programming, the tag prototypes were converted into stable, temporary shapes with non-decodable QR code information. When thermally triggering the shape memory effect on the functionalized tags, we verified the mostly complete recovery of the polymer surface and the associated restoration into the almost original shape. As such, the QR code could again precisely be read out. We anticipate that tagging products with these information carriers is helpful for the purpose of secure one-time identification.
Polymere mit Formgedächtnis
(2013)
Phase-segregated PEU exhibits two-way shape changes under various constant stresses. Most distinct actuation (expansion on cooling and contraction on heating) can be detected between +60 and -20 °C when the maximum stress applied during a thermo-mechanical pretreatment approached the point where deformation-induced crystallization of the PBA soft segment sets in. The driving forces for the strain-related two-way shape changes consist of PBA crystallization and PBA melting-induced entropy elasticity. At low constant stresses (<1.5 MPa), entropy elasticity also contributes to specimen expansion on cooling. The results of multiple- cycling experiments imply that PEU is an appropriate candidate for the fabrication of thermoresponsive actuators working under constant stress conditions.
The surface of a shape memory poly(ester urethane)
(PEU) was either black- or blue-colored to obtain switchable
quick response (QR) codes after laser engraving and thermomechanical
functionalization (programming). The investigation
of dye and functional stability against UVA and hydrolytic
aging (at 23 and 60 °C) gave that contrast decline due to dye
decolorization (in case of UVA aging) or distinct dye diffusion
(in case of hydrolytic aging) finally inhibited the QR code
readability. By contrast, PEU as marked base material could be
adequately fixed and recovered even when the Michelson
contrast in the QR code region was falling in course of aging
below a crucial value of 0.1, whereupon the QR code was no
longer readable. Hence, we concluded that under the given
experimental conditions the decisive parameter for tag
applicability was the surface contrast.
Here we present a suitable tag prototype with phasesegregated
poly(ester urethane) (PEU) as base material for
effectively switching a quick response (QR) code in its surface
from non-readable to readable. In comparison with recently
introduced tags (different geometry) we minimized the
thickness from plaque (2 mm) to foil size (0.5 mm) and reduced
the lateral QR code length from 15 to 5 mm. Subsequent to
surface-dyeing by means of guest diffusion, the QR code was
laser-engraved. The implementation of thermo-mechanical
functionalization via tensile deformation and cooling resulted in
the formation of stable shapes, which exceeded the barrier of
QR code readability at an elongation of 20%. Once
functionalized, tags were switched on demand by heating. As
such the recovery of the PEU was accomplished and the QR
code could again be read out. QR code carriers based on shape
memory polymer can be used in product and brand protection
applications.
The selective compression of quick response (QR) and Data Matrix code carriers based on shape memory polymer (SMP) with a freely configurable steel ball type indenter and adjacent thermo-mechanical shape fixing gave notched, room temperature (23 °C) stable, temporary shapes with non-decipherable codes. The microscopic investigation of cryomicrotome sections unveiled indentation-related shape fixities of about 90%. Independent of the selected two-dimensional code, the triggering of the SM effect resulted in sufficient shape recoveries to restore the code readability so that a maximum number of characters including 122 for a QR code (version 7) and 112 in case of a Data Matrix code (version 12) could be read with a scanning and decoding device. Due to the large number of difficult to copy shapes with on demand releasable information, SMPs may serve as viable information carriers for product and brand protection applications.
Shape memory polymers (SMP) belong to the class of stimuli-responsive materials and have generated significant research interest. Their capability to retain an imposed, temporary shape and to recover the initial, permanent shape upon exposure to an external stimulus depends on the "functional determinants", which in simplistic terms, can be divided into structural/morphological and processing/environmental factors. The primary aim of the first part of this review is to reflect the knowledge about these fundamental relationships. In a next step, recent advances in shape memory polymer composites are summarized. In contrast to earlier reviews, studies on the impairment of shape memory properties through various factors, such as aging, compression and hibernation, lubricants, UV light and thermo-mechanical cycling, are extensively reviewed. Apart from summarizing the state-of-the-art in SMP research, recent progress is commented.
The shape memory functionality of a segmented poly(ester urethane) and its hydrolytically aged specimens has been studied by cyclic thermo-mechanical measurements with an imposed strain of 100%. The shape memory effect was triggered by a melting transition in the soft segment phase. Aging was enforced by immersion in hot de-ionized water. In the course of the immersion the tensile properties (secant moduli, stress and strain at yield and break) were impaired by hydrolysis. Advanced specimen embrittlement finally led to rupture during the first thermo-mechanical cycle. This happened after 68 days of aging at 55 °C and correspondingly after 8 days at 80 °C. The residual strain after the first cycle, which was about 25%, increased significantly with aging time. Therefore, the total strain recoverability became ever smaller: aged specimens needed conditioning by at least two cycles for a full development of shape recoverability. Likewise the recovery force decreased continuously. Despite these degradation effects, it was observed that the shape fixity and the cycle-related shape recovery of appropriately conditioned specimens (number of cycles N > 2) remained on a constant high level (at round 100% and between 90% and 100%, respectively) throughout the whole aging period. These observations are discussed within the framework of a simplified model of the behavior of crystallizable shape memory polymers. The amorphous state of the polymer is described by the equation of the linear visco-elastic solid. As for the semi-crystalline state the material is assumed to react elastically with respect to deviations from the configuration, which was frozen up under constraint conditions. The curves of the dependence of the material behavior on aging time at 55 °C match perfectly those at 80 °C when the time axis is adjusted by a factor of 8.5, from which the apparent activation energy for hydrolytic aging in the amorphous state of 82 kJ mol-1 could be deduced.
Star-shaped polyhedral oligomeric silsesquioxane (SPOSS)-based multi-arm poly(ε-caprolactones) (PCLs) with various arm lengths were synthesized by ring opening polymerization of ε-caprolactone. Increasing the PCL arm lengths was observed to increase the melting temperature and also the melt crystallization temperature in SPOSS-PCLs. Star-shaped POSS-PCL polyurethanes (SPOSS-PUs) were then prepared by cross-linking SPOSS-PCLs with hexamethylene diisocyanate (HMDI) and their shape memory (SM) behaviour was determined. For this purpose two cyclic thermo-mechanical testing concepts with similar programming (deformation and shape fixing) but different recovery strategies (free strain versus fixed-strain constrained stress recovery) were used and the synthesized polymers were systematically investigated around the crystallization and melting temperatures of PCL. SPOSS-PU with the highest POSS content exhibited remarkable cycles-averaged (N = 2–5) shape fixities and strain recoverabilities of 98% and stress recoverabilities close to 100%. The main structural factors that were expected to reduce the SM performances with increasing PCL arm lengths were a lowering of cross-link density (content of octasubstituted POSS) and an increase in chain flexibility/molecular mobility.