scholarly journals Changes in Crystal Structure and Accelerated Hydrolytic Degradation of Polylactic Acid in High Humidity

Polymers ◽  
2021 ◽  
Vol 13 (24) ◽  
pp. 4324
Author(s):  
Yutaka Kobayashi ◽  
Tsubasa Ueda ◽  
Akira Ishigami ◽  
Hiroshi Ito

Highly crystallized polylactic acid (PLA) is suitable for industrial applications due to its stiffness, heat resistance, and dimensional stability. However, crystal lamellae in PLA products might delay PLA decomposition in the environment. This study clarifies how the initial crystal structure influences the hydrolytic degradation of PLA under accelerated conditions. Crystallized PLA was prepared by annealing amorphous PLA at a specific temperature under reduced pressure. Specimens with varied crystal structure were kept at 70 °C and in a relative humidity (RH) of 95% for a specific time. Changes in crystal structure were analyzed using differential calorimetry and wide-angle X-lay diffraction. The molecular weight (MW) was measured with gel permeation chromatography. The crystallinity of the amorphous PLA became the same as that of the initially annealed PLA within one hour at 70 °C and 95% RH. The MW of the amorphous PLA decreased faster even though the crystallinity was similar during the accelerated degradation. The low MW chains of the amorphous PLA tended to decrease faster, although changes in the MW distribution suggested random scission of the molecular chains for initially crystallized PLA. The concentrations of chain ends and impurities, which catalyze hydrolysis, in the amorphous region were considered to be different in the initial crystallization. The crystallinity alone does not determine the speed of hydrolysis.

Author(s):  
A Miranda ◽  
M Leite ◽  
L Reis ◽  
E Copin ◽  
MF Vaz ◽  
...  

The aerospace, automotive, and marine industries are heavily reliant on sandwich panels with cellular material cores. Although honeycombs with hexagonal cells are the most commonly used geometries as cores, recently there have been new alternatives in the design of lightweight structures. The present work aims to evaluate the mechanical properties of metallic and polymeric honeycomb structures, with configurations recently proposed and different in-plane orientations, produced by additive and subtractive manufacturing processes. Structures with configurations such as regular hexagonal honeycomb (Hr), lotus (Lt), and hexagonal honeycomb with Plateau borders (Pt), with 0°, 45°, and 90° orientations were analyzed. To evaluate its properties, three-point bending tests were performed, both experimentally and by numerical modeling, by means of the finite element method. Honeycombs of two aluminum alloys and polylactic acid were fabricated. The structures produced in aluminum were obtained either by selective laser melting technology or by machining, while polylactic acid structures were obtained by material extrusion using fused filament fabrication. From the stress distribution analysis and the load–displacement curves, it was possible to evaluate the strength, stiffness, and absorbed energy of the structures. Failure modes were also analyzed for polylactic acid honeycombs. In general, a strong correlation was observed between numerical and experimental results. The results show that the stiffness and absorbed energy increase in the order, Hr, Pt, Lt, and with the orientation through the sequence, 45°, 90°, 0°. Thus, Lt structures with 0° orientation seem to be good alternatives to the traditional honeycombs used in sandwich composite panels for those industrial applications where low weight, high stiffness, and large energy-absorbing capacity are required.


2016 ◽  
Vol 6 (1) ◽  
Author(s):  
Ryosuke Sinmyo ◽  
Elena Bykova ◽  
Sergey V. Ovsyannikov ◽  
Catherine McCammon ◽  
Ilya Kupenko ◽  
...  

Abstract Iron oxides are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary iron oxide with the hitherto unknown stoichiometry of Fe7O9. This new oxide was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions. By means of single crystal X-ray diffraction we determined that Fe7O9 adopts a monoclinic C2/m lattice with the most distorted crystal structure among the binary iron oxides known to date. The synthesis of Fe7O9 opens a new portal to exotic iron-rich (M,Fe)7O9 oxides with unusual stoichiometry and distorted crystal structures. Moreover, the crystal structure and phase relations of such new iron oxide groups may provide new insight into the cycling of volatiles in the Earth’s interior.


Author(s):  
Kohei Sasamoto ◽  
Tomoki Himiyama ◽  
Kunihiko Moriyoshi ◽  
Takashi Ohmoto ◽  
Koichi Uegaki ◽  
...  

The acetylxylan esterases (AXEs) classified into carbohydrate esterase family 4 (CE4) are metalloenzymes that catalyze the deacetylation of acetylated carbohydrates. AXE from Caldanaerobacter subterraneus subsp. tengcongensis (TTE0866), which belongs to CE4, is composed of three parts: a signal sequence (residues 1–22), an N-terminal region (NTR; residues 23–135) and a catalytic domain (residues 136–324). TTE0866 catalyzes the deacetylation of highly substituted cellulose acetate and is expected to be useful for industrial applications in the reuse of resources. In this study, the crystal structure of TTE0866 (residues 23–324) was successfully determined. The crystal diffracted to 1.9 Å resolution and belonged to space group I212121. The catalytic domain (residues 136–321) exhibited a (β/α)7-barrel topology. However, electron density was not observed for the NTR (residues 23–135). The crystal packing revealed the presence of an intermolecular space without observable electron density, indicating that the NTR occupies this space without a defined conformation or was truncated during the crystallization process. Although the active-site conformation of TTE0866 was found to be highly similar to those of other CE4 enzymes, the orientation of its Trp264 side chain near the active site was clearly distinct. The unique orientation of the Trp264 side chain formed a different-shaped cavity within TTE0866, which may contribute to its reactivity towards highly substituted cellulose acetate.


2020 ◽  
Vol 36 (3) ◽  
pp. 285-311
Author(s):  
Ali Tajdari ◽  
Amir Babaei ◽  
Alireza Goudarzi ◽  
Razie Partovi

In this research, first, ZnO nanorods were synthesized by hydrothermal method and characterized in terms of morphological and structural properties by means of field emission scanning electron microscopy, Fourier transform infrared, and X-ray diffraction techniques. Subsequently, polylactic acid/ZnO, polylactic acid/TiO2, and polylactic acid/ZnO/TiO2 nanocomposites with different percentages of nanoparticles and two different types of ZnO morphologies were prepared and their microstructural, optical, mechanical, hydrolytic degradation, and antibacterial properties were investigated. Field emission scanning electron microscopy results of polylactic acid/ZnO and polylactic acid/TiO2 samples showed a proper dispersion and nanoparticle distribution for low percentages (up to 5 wt%) and increased aggregation for the higher percentages. Besides, a large increase in the aggregation tendency was observed for combined nanoparticles (polylactic acid/ZnO/TiO2 nanocomposites). Results of the tensile test, the UV–Vis absorption tests, and the hydrolytic degradation tests of the samples showed an enhanced mechanical (approximately 55% increase in the presence of 3–5 wt% of nanoparticles) and light absorption and degradation (approximately 85% increase in the presence of 3–10 wt% of nanoparticles) for the polylactic acid by incorporating nanoparticles. It was also observed that, in addition to the quality of dispersion and distribution of nanoparticles in the polymeric matrix, the type of morphology of nanoparticles can contribute to the improvement of these properties. The cylindrical morphology of ZnO played a greater role on improving the polylactic acid mechanical properties compared to the spherical ZnO morphology (approximately 20%). On the contrary, the increased polylactic acid optical properties and degradation with ZnO spherical morphology were more pronounced (approximately 60%). Interestingly, when both ZnO and TiO2 were added, a synergistic effect in the case of UV-shielding and degradation rate and alternatively, a detrimental effect on the mechanical properties were detected. (The polylactic acid optical properties increased by about 17% and its degradation more than doubled.) Furthermore, the antibacterial activity of polylactic acid was investigated against the two Gram-positive Listeria monocytogenes and Gram-negative bacteria Escherichia coli by incorporating nanoparticles. The results indicated that as the nanoparticle percentage increases, the antibacterial activity steadily increases.


2019 ◽  
Vol 54 (15) ◽  
pp. 1947-1960 ◽  
Author(s):  
Lucas Ciccarelli ◽  
Frederik Cloppenburg ◽  
Sangeetha Ramaswamy ◽  
Stepan V Lomov ◽  
Aart Van Vuure ◽  
...  

Coir fibres, a byproduct of the coconut industry, have high performance qualities but are difficult to process by conventional textile methods. The purpose of the research is to combine the processibility of hemp and flax with the high-performance properties of coir to create a composite product worthy of industrial applications. The evaluation of coir fibre-reinforced composites focuses on the processibility of the coir fibre into a nonwoven, how well it interfaces with polylactic acid and an analysis of how the mechanical properties of the final product change when mixing coir with hemp and flax. The results show that the hybrid samples outperformed most of the researched values for coir composites, despite the reduced properties of control samples as in comparable research. Adding just 10% of either flax or hemp dramatically increased the mechanical properties compared to the pure coir–polylactic acid composite.


1984 ◽  
Vol 37 (6) ◽  
pp. 1369
Author(s):  
MP Hartshorn ◽  
KH Sutton ◽  
J Vaughan

The X-ray crystal structure determination of 4-t-butyl-r-2-(4'-t-butyl-2',6'-dimethylphenoxy)-t-6- hydroxy-2,6-dimethyl-t-5-nitrocyclohex-3-enone (3) is reported. This compound is formed by reaction of 4-t-butyl-2,6-dimethylphenol(1) with nitrogen dioxide (1 mol) in benzene, followed by removal of the benzene under reduced pressure.


2016 ◽  
Vol 848 ◽  
pp. 709-714 ◽  
Author(s):  
Gang Fu ◽  
Jiang Wang ◽  
Mao Hua Rong ◽  
Guang Hui Rao ◽  
Huai Ying Zhou

The rare-earth (RE) permanent magnets based on Nd2Fe14B with excellent magnetic properties have been widely used in industrial applications. In this work, the crystal structure, microstructure and magnetic properties of Nd2.28Fe13.58B1.14, Ce2.28Fe13.58B1.14 and Pr2.28Fe13.58B1.14 alloys prepared by arc-melting were investigated. The results show that all alloys are single phase with tetragonal Nd2Fe14B-type (space group P42/mnm). The Curie temperatures (Tc) of RE2.28Fe13.58B1.14 (RE=Nd, Ce, Pr) alloys are 583 K, 423 K and 557 K, respectively. On the other hand, the coercivities of Nd2.28Fe13.58B1.14 and Pr2.28Fe13.58B1.14 alloys are about 1.05 T and 1.23 T, respectively, while that of Ce2.28Fe13.58B1.14 alloy is only about 0.25 T due to the poor squareness of hysteresis loop. Meanwhile, the saturation magnetizations of Nd2.28Fe13.58B1.14 and Pr2.28Fe13.58B1.14 alloys are about 135 emu/g and 113 emu/g, respectively, while that of Ce2.28Fe13.58B1.14 alloy is about 97 emu/g. It was indicated that the Curie temperatures and magnetic properties of RE2.28Fe13.58B1.14 alloys with the same crystal structure are dependent on light rare earth elements.


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