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- ItemStructure formation of ultrathin PEO films at solid interfaces-complex pattern formation by dewetting and crystallization(Basel : MDPI AG, 2013) Braun, H.-G.; Meyer, E.The direct contact of ultrathin polymer films with a solid substrate may result in thin film rupture caused by dewetting. With crystallisable polymers such as polyethyleneoxide (PEO), molecular self-assembly into partial ordered lamella structures is studied as an additional source of pattern formation. Morphological features in ultrathin PEO films (thickness < 10 nm) result from an interplay between dewetting patterns and diffusion limited growth pattern of ordered lamella growing within the dewetting areas. Besides structure formation of hydrophilic PEO molecules, n-alkylterminated (hydrophobic) PEO oligomers are investigated with respect to self-organization in ultrathin films. Morphological features characteristic for pure PEO are not changed by the presence of the n-alkylgroups.
- ItemEffect of Molar Mass on Critical Specific Work of Flow for Shear-Induced Crystal Nucleation in Poly (l-Lactic Acid)(Basel : MDPI, 2021) Du, Mengxue; Jariyavidyanont, Katalee; Kühnert, Ines; Boldt, Regine; Androsch, RenéThe concept of specific work of flow has been applied for the analysis of critical shearing conditions for the formation of crystal nuclei in poly (l-lactic acid) (PLLA). Systematic variation in both time and rate of shearing the melt in a parallel-plate rheometer revealed that these parameters are interconvertible regarding the shear-induced formation of crystal nuclei; that is, low shear rate can be compensated for by increasing the shear time and vice versa. This result supports the view that critical shearing conditions can be expressed by a single quantity, providing additional options for tailoring polymer processing routes when enhanced nuclei formation is desired/unwanted. Analysis of PLLA of different mass-average molar masses of 70, 90, 120, and 576 kDa confirmed improved shear-induced crystal nucleation for materials of higher molar mass, with critical specific works of flow, above which shear-induced nuclei formation occurs, of 550, 60, 25, and 5 kPa, respectively.
- ItemStructure Mediation and Properties of Poly(l-lactide)/Poly(d-lactide) Blend Fibers(Basel : MDPI, 2018) Yang, Bo; Wang, Rui; Ma, Hui-Ling; Li, Xiaolu; Brünig, Harald; Dong, Zhenfeng; Qi, Yue; Zhang, XiuqinPoly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) blend as-spun fibers (50/50, wt.%) were prepared by melt spinning. Structure mediation under temperature and stress and properties of poly(l-lactic acid)/poly(d-lactic acid)(PLLA/PDLA) as-spun fibers were investigated by wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). The results show that highly oriented stereocomplex (SC) crystals can be formed in PLLA/PDLA blend fibers drawn at 60 °C and annealed at 200 °C. However, at drawn temperature of 80 °C, only lower oriented SC crystals can be formed. For PLLA/PDLA blend fibers drawn twice at 60 °C (PLLA/PDLA-60-2), the crystallinity of SC crystals increases with annealing temperature in the range of 200 to 215 °C, while the degree of orientation decreases slightly. When the annealing temperature is 210 °C, the crystallinity and orientation of SC crystals in PLLA/PDLA-60-2 fibers reach 51% and −0.39, respectively. Moreover, PLLA/PDLA-60-2-210 fibers exhibit excellent heat-resistant property even at 200 °C. The results indicate that the oriented PLLA/PDLA blend fibers with high SC crystals content can be regulated in a short time.
- ItemA new strategy to improve viscoelasticity, crystallization and mechanical properties of polylactide(Amsterdam [u.a.] : Elsevier Science, 2021) Huang, Ying; Müller, Michael Thomas; Boldt, Regine; Zschech, Carsten; Gohs, Uwe; Wießner, SvenBiodegradable polylactide/masticated natural rubber (PLA/mNR) blends were prepared by electron induced reactive processing (EIReP) without using any chemical additives. The PLA/mNR blends showed droplet-matrix morphology with decreased mNR particle size after EIReP treatment. The absolute value of complex viscosity and storage modulus increased significantly for the EIReP modified blends, suggesting the improved melt strength and elasticity. The crystallization investigation showed that the cold crystallization peak of PLA phase gradually disappeared after EIReP modification. Instead, the crystallization peak arose during melt cooling process. Consequently, the crystallinity of PLA phase increased from 6.2% to 39.0% as the mNR content increased from 0 to 20 wt%. It was found that the softening temperature of PLA examined by dynamic mechanical analysis increased effectively with the characters of higher modulus compared to the non-modified blends. The EIReP modified blends exhibited excellent mechanical properties with 7-fold increase of impact toughness compared with neat PLA, implying a superior interfacial adhesion and chain interactions between the two polymer phases. Furthermore, the thermogravimetric analysis demonstrated that the thermal stability was slightly enhanced for the EIReP modified blends.
- ItemPoly(acrylonitrile-co-butadiene) as polymeric crosslinking accelerator for sulphur network formation(London [u.a.] : Elsevier, 2020) Hait, Sakrit; Valentín, Juan López; Jiménez, Antonio González; Ortega, Pilar Bernal; Ghosh, Anik Kumar; Stöckelhuber, Klaus Werner; Wießner, Sven; Heinrich, Gert; Das, AmitThe major controlling factors that determine the various mechanical properties of an elastomer system are type of chemical crosslinking and crosslink density of the polymer network. In this study, a catalytic amount of acrylonitrile butadiene copolymer (NBR) was used as a co-accelerator for the curing of polybutadiene (BR) elastomer. After the addition of this copolymer along with other conventional sulphur ingredients in polybutadiene compounds, a clear and distinct effect on the curing and other physical characteristics was noticed. The crosslinking density of BR was increased, as evidenced by rheometric properties, solid-state NMR and swelling studies. The vulcanization kinetics study revealed a substantial lowering of the activation energy of the sulphur crosslinking process when acrylonitrile butadiene copolymer was used in the formulation. The compounds were also prepared in the presence of carbon black and silica, and it was found that in the carbon black filled system the catalytic effect of the NBR was eminent. The effect was not only reflected in the mechanical performance but also the low-temperature crystallization behavior of BR systems was altered. © 2020 The AuthorsMaterials science; Materials chemistry; Crosslinking accelerator; Sulphur network; Solid state NMR; Curing kinetics; Activation energy; Acrylonitrile butadiene; Polybutadiene; Low-temperature; Crystallization. © 2020 The Authors
- ItemShear-induced crystallization of polyamide 11(Berlin ; Heidelberg ; New York : Springer, 2021) Jariyavidyanont, Katalee; Mallardo, Salvatore; Cerruti, Pierfrancesco; Di Lorenzo, Maria Laura; Boldt, Regine; Rhoades, Alicyn M.; Androsch, RenéShear-induced formation of crystal nuclei in polyamide 11 (PA 11) was studied using a conventional parallel-plate rheometer. Crystallization of PA 11 after shearing the melt at different rates for 60 s was followed by the evolution of the complex viscosity. The sheared samples showed in an optical microscope a gradient structure along the radius, due to the increasing shear rate from the center to the edge. The critical shear rate for shear-induced formation of nuclei was identified at the position where a distinct change of the semicrystalline superstructure is observed, being at around 1 to 2 s−1. Below this threshold, a space-filled spherulitic superstructure developed as in quiescent-melt crystallization. Above this value, after shearing at rates between 1 and 5 s−1, an increased number of point-like nuclei was detected, connected with formation of randomly oriented crystals. Shearing the melt at even higher rates led to a further increase of the nuclei number and growth of crystals oriented such that the chain axis is in parallel to the direction of flow. In addition, optical microscopy confirmed formation of long fibrillar structures after shearing at such condition. The critical specific work of flow of PA 11 was calculated to allow a comparison with that of polyamide 66 (PA 66). This comparison showed that in the case of PA 11 more work for shear-induced formation of nuclei is needed than in the case of PA 66, discussed in terms of the chemical structure of the repeat unit in the chains.
- ItemProcess induced skin-core morphology in injection molded polyamide 66(Basel : MDPI, 2020) Spoerer, Yvonne; Androsch, René; Jehnichen, Dieter; Kuehnert, InesPolyamide 66 (PA 66) was injection-molded to obtain samples with a structure gradient between skin and core, as it was revealed by analysis of the semi-crystalline morphology using polarized-light optical microscopy (POM). Wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS) were employed to characterize thin sections with a thickness in the order of magnitude of 50 µm, allowing detection of crystals of different perfection, as a function of the distance from the surface. It was found that the transparent and non-spherulitic skin layer contains rather imperfect α-crystals while the perfection of α-crystals continuously increases with extending distance from the surface. Since variation of the molding conditions allows tailoring the skin-core morphology, the present study was performed to suggest a reliable route to map the presence of specific semi-crystalline morphologies in such samples
- ItemEnthalpy relaxation, crystal nucleation and crystal growth of biobased poly(butylene isophthalate)(Basel : MDPI, 2020) Quattrosoldi, Silvia; Androsch, René; Janke, Andreas; Soccio, Michelina; Lotti, NadiaThe crystallization behavior of fully biobased poly(butylene isophthalate) (PBI) has been investigated using calorimetric and microscopic techniques. PBI is an extremely slow crystallizing polymer that leads, after melt-crystallization, to the formation of lamellar crystals and rather large spherulites, due to the low nuclei density. Based upon quantitative analysis of the crystal-nucleation behavior at low temperatures near the glass transition, using Tammann’s two-stage nuclei development method, a nucleation pathway for an acceleration of the crystallization process and for tailoring the semicrystalline morphology is provided. Low-temperature annealing close to the glass transition temperature (Tg) leads to the formation of crystal nuclei, which grow to crystals at higher temperatures, and yield a much finer spherulitic superstructure, as obtained after direct melt-crystallization. Similarly to other slowly crystallizing polymers like poly(ethylene terephthalate) or poly(l-lactic acid), low-temperature crystal-nuclei formation at a timescale of hours/days is still too slow to allow non-spherulitic crystallization. The interplay between glass relaxation and crystal nucleation at temperatures slightly below Tg is discussed.
- ItemAn NMR Study of Biomimetic Fluorapatite - Gelatine Mesocrystals([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, RüdigerThe mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers and with experimental observations of an amorphous cover layer in biominerals.