TY - JOUR A1 - Ermeydan, Mahmut Ali A1 - Cabane, Etienne A1 - Masic, Admir A1 - Koetz, Joachim A1 - Burgert, Ingo T1 - Flavonoid insertion into cell walls improves wood properties JF - ACS applied materials & interfaces N2 - Wood has an excellent mechanical performance, but wider utilization of this renewable resource as an engineering material is limited by unfavorable properties such as low dimensional stability upon moisture changes and a low durability. However, some wood species are known to produce a wood of higher quality by inserting mainly phenolic substances in the already formed cell walls a process so-called heartwood formation. In the present study, we used the heartwood formation in black locust (Robinia pseudoacacia) as a source of bioinspiration and transferred principles of the modification in order to improve spruce wood properties (Picea abies) by a chemical treatment with commercially available flavonoids. We were able to effectively insert hydrophobic flavonoids in the cell wall after a tosylation treatment for activation. The chemical treatment reduced the water uptake of the wood cell walls and increased the dimensional stability of the bulk spruce wood. Further analysis of the chemical interaction of the flavonoid with the structural cell wall components revealed the basic principle of this bioinspired modification. Contrary to established modification treatments, which mainly address the hydroxyl groups of the carbohydrates with hydrophilic substances, the hydrophobic flavonoids are effective by a physical bulking in the cell wall most probably stabilized by pi-pi interactions. A biomimetic transfer of the underlying principle may lead to alternative cell wall modification procedures and improve the performance of wood as an engineering material. KW - wood cell wall KW - heartwood formation KW - chemical modification KW - Raman spectroscopy KW - dimensional stability KW - nanoindentation Y1 - 2012 U6 - https://doi.org/10.1021/am301266k SN - 1944-8244 VL - 4 IS - 11 SP - 5782 EP - 5789 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Hardy, John G. A1 - Bertin, Annabelle A1 - Torres-Rendon, Jose Guillermo A1 - Leal-Egana, Aldo A1 - Humenik, Martin A1 - Bauer, Felix A1 - Walther, Andreas A1 - Cölfen, Helmut A1 - Schlaad, Helmut A1 - Scheibel, Thomas R. T1 - Facile photochemical modification of silk protein-based biomaterials JF - Macromolecular bioscience N2 - Silk protein-based materials show promise for application as biomaterials for tissue engineering. The simple and rapid photochemical modification of silk protein-based materials composed of either Bombyx mori silkworm silk or engineered spider silk proteins (eADF4(C16)) is reported. Radicals formed on the silk-based materials initiate the polymerization of monomers (acrylic acid, methacrylic acid, or allylamine) which functionalize the surface of the silk materials with poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), or poly(allylamine) (PAAm). To demonstrate potential applications of this type of modification, the polymer-modified silks are mineralized. The PAA- and PMAA-functionalized silks are mineralized with calcium carbonate, whereas the PAAm-functionalized silks are mineralized with silica, both of which provide a coating on the materials that may be useful for bone tissue engineering, which will be the subject of future investigations. KW - biomaterials KW - chemical modification KW - photochemistry KW - silkworm silk KW - spider silk Y1 - 2018 U6 - https://doi.org/10.1002/mabi.201800216 SN - 1616-5187 SN - 1616-5195 VL - 18 IS - 11 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Rychkov, Dmitry A1 - Gerhard, Reimund A1 - Ivanov, Vadim A1 - Rychkov, Andrey T1 - Enhanced electret charge stability on Polyethylene Films treated with Titanium-Tetrachloride vapor JF - IEEE transactions on dielectrics and electrical insulation N2 - Low-density polyethylene (LDPE) films have been treated with titanium-tetrachloride vapor by means of the molecular-layer-deposition method. It is shown that such a treatment leads to a considerable improvement of the electret properties for both positively and negatively charged films. The temperature stability of the electret homo-charge has been increased by approximately 60 degrees C. At the same time, the temporal stability of charge is also considerably improved. Modified low-density polyethylene films show no "cross-over phenomenon" when charged to higher voltages. Thus, it is now possible to produce electrets from polyethylene films with high initial charge densities, but without a strongly reduced charge stability. The influence of a chemical treatment with titanium-tetrachloride vapor on charge injection from aluminum electrodes into polyethylene films was also investigated. It is found that the interface between an aluminum electrode and a modified LDPE surface layer has different injection properties for positive and negative charges. Electrons can be injected across the modified interface, whereas injection of holes is either very limited or non-existent. KW - Electrets KW - chemical modification KW - surface treatment KW - space-charge stability KW - charge-carrier transport KW - polyethylene KW - low-density polyethylene KW - injection Y1 - 2012 SN - 1070-9878 VL - 19 IS - 4 SP - 1305 EP - 1311 PB - Inst. of Electr. and Electronics Engineers CY - Piscataway ER - TY - JOUR A1 - Rychkov, Dmitry A1 - Gerhard, Reimund A1 - Kuznetsov, Alexey A1 - Rychkov, Andrey T1 - Influence of charge density on the trap energy spectrum in fluoroethylenepropylene copolymer films with chemically modified surfaces JF - IEEE transactions on dielectrics and electrical insulation N2 - Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) films were treated with titanium-tetrachloride vapor by means of molecular-layer deposition. The treatment leads to considerable improvements of the electret-charge stability on positively charged films. A slight improvement is also observed for negatively charged films. In line with our previous findings, we attribute the improvement in electret properties to the formation of deeper traps on the chemically modified polymer surfaces. Here, we investigate the influence of the charge density on electret stability of FEP films with modified surfaces. Trap-energy spectra obtained from thermally-stimulated-discharge measurements indicate that the charge stability on modified FEP films depends on how the surface traps are populated and on the availability of additional deeper traps. KW - Electrets KW - chemical modification KW - surface treatment KW - space-charge stability KW - charge-carrier transport KW - polytetrafluoroethylene (PTFE) KW - fluoroethylenepropylene (FEP) copolymer Y1 - 2018 U6 - https://doi.org/10.1109/TDEI.2018.007437 SN - 1070-9878 SN - 1558-4135 VL - 25 IS - 3 SP - 840 EP - 844 PB - Inst. of Electr. and Electronics Engineers CY - Piscataway ER - TY - GEN A1 - Wang, Jingwen A1 - Rychkov, Dmitry A1 - Gerhard, Reimund T1 - Influence of Charge Density on Charge Decay in Chemically Modified Polypropylene Films T2 - 2018 IEEE 2nd International Conference on Dielectrics (ICD) N2 - Previous work has shown that surface modification with orthophosphoric acid can significantly enhance the charge stability on polypropylene (PP) surface by generating deeper traps. In the present study, thermally stimulated potential-decay measurements revealed that the chemical treatment may also significantly increase the number of available trapping sites on the surface. Thus, as a consequence, the so-called "cross-over" phenomenon, which is observed on as-received and thermally treated PP electrets, may be overcome in a certain range of initial charge densities. Furthermore, the discharge behavior of chemically modified samples indicates that charges can be injected from the treated surface into the bulk, and/or charges of opposite polarity can be pulled from the rear electrode into the bulk at elevated temperatures and at the high electric fields that are caused by the deposited charges. In the bulk, a lack of deep traps causes rapid charge decay already in the temperature range around 95 degrees C. KW - polypropylene KW - surface charge stability KW - thermally stimulated discharge KW - cross-over effect KW - chemical modification Y1 - 2018 SN - 978-1-5386-6389-9 U6 - https://doi.org/10.1109/ICD.2018.8514718 PB - IEEE CY - New York ER -