TY - CONF A1 - Mirtschin, Nikolaus A1 - Pretsch, Thorsten T1 - Controlling Temperature-Memory Behavior in a Semicrystalline Poly(esterurethane) Elastomer T2 - Polydays 2014: Beyond Self-Assembly - Making Polymeric Materials More Versatile CY - Berlin, Germany DA - 2014-09-30 PY - 2014 AN - OPUS4-32079 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mirtschin, Nikolaus A1 - Pretsch, Thorsten T1 - Designing temperature-memory effects in semicrystalline polyurethane N2 - 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. KW - Poly(ester urethane) KW - Shape memory polymer KW - Temperature-memory effect KW - Thermo-responsiveness KW - Temperature-memory polymer KW - Programming KW - Thermomechanical properties PY - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-332856 SN - 2046-2069 VL - 5 IS - 57 SP - 46307 EP - 46315 PB - RSC Publishing CY - London AN - OPUS4-33285 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mirtschin, Nikolaus A1 - Pretsch, Thorsten T1 - Miniturization of QR code carriers based on shape memory polymer N2 - 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. T2 - SMASIS2012 - ASME 2012 Conference on smart materials, adaptive structures and intelligent systems CY - Stone Mountain, Georgia, USA DA - 2012-09-19 KW - Shape memory polymer KW - QR code KW - Poly(ester urethane) KW - Product and brand protection applications KW - Counterfeit-proof labels KW - Tags KW - Switchable information carriers KW - Functionalization KW - Miniaturization KW - Surface-specific dyeing KW - Victoria Blue B PY - 2012 N1 - Geburtsname von Mirtschin, Nikolaus: Fritzsche, N. - Birth name of Mirtschin, Nikolaus: Fritzsche, N. IS - SMASIS2012-8036 SP - 1 EP - 8 PB - ASME AN - OPUS4-27886 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mirtschin, Nikolaus A1 - Pretsch, T. T1 - Programming of one- and two-step stress recovery in a poly(ester urethane) N2 - This work demonstrates that phase-segregated poly(ester urethane) (PEU) with switching segments of crystallizable poly(1,4-butylene adipate) (PBA) can be programmed to generate two separate stress recovery events upon heating under constant strain conditions. For programming, two elongations are applied at different temperatures, followed by unloading and cooling. During the adjacent heating, two-step stress recovery is triggered. The results indicate that the magnitude of the stress recovery signals corresponds to the recovery of the two deformation stresses in reverse order. As demonstrated by further experiments, twofold stress recovery can be detected as long as the elongation at higher temperature exceeds the strain level of the deformation at lower temperature. Another finding includes that varying the lower deformation temperature enables a control over the stress recovery temperature and thus the implementation of so-called “temperature-memory effects”. Moreover, exerting only one elongation during programming enables a heating-initiated one-step stress recovery close to the deformation temperature. Based on these findings, such polymers may offer new technological opportunities in the fields of active assembly when used as fastening elements and in functional clothing when utilized for compression stockings. KW - DSC KW - Mechanical properties PY - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-393585 SN - 2073-4360 VL - 9 IS - 3 SP - Article 98, 1 EP - 12 PB - MDPI CY - Basel AN - OPUS4-39358 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mirtschin, Nikolaus A1 - Pretsch, Thorsten T1 - Programming of temperature-memory onsets in a semicrystalline polyurethane elastomer N2 - 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. KW - Poly(ester urethane) KW - Shape memory polymer KW - Temperature-memory effect KW - Thermo-responsiveness KW - Information carrier KW - QR code carrier KW - Temperature monitoring label KW - Supervising KW - technology KW - Programming KW - cold chain PY - 2014 U6 - https://doi.org/10.1021/ma501171p SN - 0024-9297 SN - 1520-5835 N1 - Geburtsname von Mirtschin, Nikolaus: Fritzsche, N. - Birth name of Mirtschin, Nikolaus: Fritzsche, N. VL - 47 IS - 17 SP - 5952 EP - 5959 PB - American Chemical Society CY - Washington, DC AN - OPUS4-31381 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - THES A1 - Mirtschin, Nikolaus T1 - Thermomechanisches Verhalten von semikristallinem Polyester-Urethan N2 - Formgedächtnispolymere werden durch thermomechanische Vorbehandlung, die Programmierung, in eine temporäre Form überführt. In die Ursprungsform kehren sie dann erst nach externer Stimulierung, durch Auslösen des Formgedächtniseffekts, wieder zurück. Um diesen Effekt zu optimieren, werden in dieser Arbeit thermomechanische Designoptionen analysiert und Stellschrauben der Programmierung diskutiert. Quantifiziert wird das Materialverhalten eines physikalisch vernetzten Polyurethans mit semikristalliner Polyester-Weichsegmentphase (PEU) in thermomechanischen Messungen, in denen das Polymer Dehnungen bis über 1000% fixiert. Deformationen im breiten Schmelzübergangsbereich der Weichsegmentphase ermöglichen die präzise Kontrolle über die Temperaturen der Dehnungs- und Spannungsrückstellung, den bekannten Temperaturgedächtniseffekt (TGE). Erst durch eine neuartige Programmierung wird jedoch der Beginn der Rückstellung einstellbar. Für diesen Onset-TGE wird das PEU direkt nach dem Recken entlastet und danach unter die Kristallisationstemperatur abgekühlt. In situ Röntgenstreuung zeigt, dass durch den frühen Entlastungszeitpunkt nur der Teil der kristallinen Weichsegmentphase zur Fixierung beiträgt, der auch beim Recken kristallin ist. Die Kristallinität bietet daher eine Stellschraube, um das thermomechanische Verhalten zu veredeln. Über die Optimierungsparameter Reckrate, Temperaturhaltezeit und maximale Dehnung erzielt das PEU hohe Fixierbarkeiten und Rückstellspannungen, ohne die Rückstellung und den Onset-TGE zu beeinträchtigen. Durch die Erweiterung der Programmierung des Onset-TGEs hin zu einer zweiten Deformation und Entlastung innerhalb des Schmelzübergangs zeigt das PEU einen bisher nicht berichteten zweistufigen Spannungsanstieg während der Rückstellung. Ein Temperaturlimit für den Onset-TGE stellt die Peak-Schmelztemperatur aus der dynamischen Differenzkalorimetrie dar. Durch die verbleibende Kristallinität oberhalb dieser Temperatur führt die Deformation und Entlastung direkt zur thermoreversiblen Aktuation mit Dehnungsänderungen bis zu 28%. Die Ergebnisse werden auf einen Miniaturisierungsansatz für schaltbare Informationsträger übertragen, mit denen eine maschinenlesbare Information von nichtlesbar nach lesbar geschaltet werden kann. In einer Machbarkeitsstudie wird der für Sensoranwendungen vielversprechende Onset-TGE genutzt, um die Lesbarkeit der Informationsträger bei einer vordefinierten Temperatur zu schalten. Das erweitert das potentielle Anwendungsfeld der Technologie vom Produkt- und Markenschutz zur Überwachung von Kühlketten. N2 - Shape memory polymers are able to change their shape upon application of an external stimulus. This behavior requires a thermomechanical treatment, so-called programming, to establish a temporary shape. To optimize the shape memory performance, thermomechanical design options will be analyzed and programming parameters discussed in the present thesis. The material behavior of a physically crosslinked polyurethane with semicrystalline polyester soft segments (PEU) is quantified by thermomechanical measurements, where the polymer fixes strains of above 1000%. The deformation within the broad melting transition of the soft segment phase enables the precise control over the temperatures of strain and stress recovery, also known as temperature-memory effect (TME). But only the herein introduced programming route, consisting in elongation and unloading prior to cooling below the crystallization transition, allows for fine-tuning the beginning of recovery. For the resulting onset-TME in situ X-ray scattering indicates that only soft segment crystals contribute to fixation, which are crystalline during deformation. Therefore, the crystallinity opens the door for gaining precisely control over the thermomechanical behavior. Optimization parameters for reaching high strain fixities and recovery stresses without compromising recovery nor the onset-TME are found in the strain rate, temperature holding time and maximum strain. When extending the programming route for onset-TMEs towards a second deformation and unloading step of PEU within the melting transition, an unreported two-step stress recovery is rendered possible. However, the peak melting temperature determined from differential scanning calorimetry represents a temperature limit for the onset control. Through the residual crystallinity above that temperature, deformation and unloading yield thermoreversible actuation with strain changes up to 28%. The findings are transferred to a miniaturization approach for switchable information carriers for switching encoded information from machine-unreadable to readable. In a proof-of-concept study the onset-TME – promising for sensor applications – can be exploited in order to predefine a temperature threshold value for readability of information carriers. This behavior widen their potential applicability from product and brand protection to cold chain supervision. T3 - BAM Dissertationsreihe - 156 KW - Formgedächtnispolymere KW - Temperaturgedächtnispolymere KW - Polyester-Urethan KW - Thermomechanische Eigenschaften KW - Programmierung PY - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-399648 SN - 978-3-9818270-5-7 SN - 1613-4249 VL - 156 SP - iii EP - 150 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-39964 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -