Intrinsic Point Defects in Silica for Fiber Optics Applications

Due to its unique properties, amorphous silicon dioxide (a-SiO2) or silica is a key material in many technological fields, such as high-power laser systems, telecommunications, and fiber optics. In recent years, major efforts have been made in the development of highly transparent glasses, able to resist ionizing and non-ionizing radiation. However the widespread application of many silica-based technologies, particularly silica optical fibers, is still limited by the radiation-induced formation of point defects, which decrease their durability and transmission efficiency. Although this aspect has been widely investigated, the optical properties of certain defects and the correlation between their formation dynamics and the structure of the pristine glass remains an open issue. For this reason, it is of paramount importance to gain a deeper understanding of the structure–reactivity relationship in a-SiO2 for the prediction of the optical properties of a glass based on its manufacturing parameters, and the realization of more efficient devices. To this end, we here report on the state of the most important intrinsic point defects in pure silica, with a particular emphasis on their main spectroscopic features, their atomic structure, and the effects of their presence on the transmission properties of optical fibers.

Superior Properties through Feedstock Development for Vat Photopolymerization Additive Manufacturing of High-Performance Biobased Feedstocks

Vat photopolymerization additive manufacturing (Vat AM) technologies have found niche industrial use being able to produce personalized parts in moderate quantity. However, Vat AM lacks in its ability to produce parts of satisfactory thermal and mechanical properties for structural applications. The purpose of this investigation was to develop high-performance resins with glass transition temperatures (Tg) above 200 °C for Vat AM, evaluate the properties of the produced thermosets and establish a structure–property relationship of the thermosets produced. Herein, we have developed SLA-type resins that feature bio-derived monomer hesperetin trimethacrylate (HTM) synthesized from the flavonone hesperetin. Diluents 4-acryloyl morpholine, styrene, 4-methyl styrene and 4-tert butylstyrene (tbutylsty) were photocured with HTM as the monomer and all produced thermosets with Tg values above 200 °C. Investigations of suitable crosslinkers urethane dimethacrylate, the vinyl ester CN 151 and Ebecryl 4859 (Eb4859) showed that each crosslinker displayed different benefits when formulated with HTM as the monomer and tbutylSty as the diluent (HTM:crosslinker:tbutylSty with mass ratio 2:1:2). The crosslinker CN 151 produced the thermoset of greatest onset of thermal decomposition temperature (T0) of 352 °C. Eb4859 produced the thermoset of highest tensile strength, 19 ± 7 MPa, amongst the set of varied crosslinkers. The formulation featuring UDM (HTM:UDM:tbutysty) offered ease of processing and was seemingly the easiest to print. Investigations of reactive diluent showed that styrene produced the thermoset of the highest extent of cure and the overall highest tensile strength, 25 ± 5 MPa, while tbutylSty produced the thermoset with the greatest Tan-δ Tg, 231 °C. HTM was synthesized, formulated with diluents, crosslinkers and initiators. The HTM resins were then 3D printed to produce thermosets of Tg values greater than 200 °C. The polymer properties were evaluated and a structure–reactivity relationship was discussed.

Hammett Correlation in the Accelerated Formation of 2,3-Diphenylquinoxalines in Nebulizer Microdroplets

The accelerated formation of 2,3-diphenylquinoxalines in microdroplets generated in a nebulizer has been investigated by competition experiments in which equimolar quantities of 1,2-phenylenediamine, C6H4(NH2)2, and a 4-substituted homologue, XC6H3(NH2)2 [X = F, Cl, Br, CH3, CH3O, CO2CH3, CF3, CN or NO2], or a 4,5-disubstituted homologue, X2C6H2(NH2)2 [X = F, Cl, Br, or CH3], compete to condense with benzil, (C6H5CO)2. Electron-donating substituents (X = CH3 and CH3O) accelerate the reaction; in contrast, electron-attracting substituents (X = F, Cl, Br and particularly CO2CH3, CN, CF3 and NO2) retard it. A structure–reactivity relationship in the form of a Hammett correlation has been found by analyzing the ratio of 2,3-diphenylquinoxaline and the corresponding substituted-2,3-diphenylquinoxaline, giving a ρ value of −0.96, thus confirming that the electron density in the aromatic ring of the phenylenediamine component is reduced in the rate-limiting step in this accelerated condensation. This correlation shows that the phenylenediamine acts as a nucleophile in the reaction.

Ni–Cu High-Loaded Sol–Gel Catalysts for Dehydrogenation of Liquid Organic Hydrides: Insights into Structural Features and Relationship with Catalytic Activity

The heightened interest in liquid organic hydrogen carriers encourages the development of catalysts suitable for multicycle use. To ensure high catalytic activity and selectivity, the structure–reactivity relationship must be extensively investigated. In this study, high-loaded Ni–Cu catalysts were considered for the dehydrogenation of methylcyclohexane. The highest conversion of 85% and toluene selectivity of 70% were achieved at 325 °C in a fixed-bed reactor using a catalyst with a Cu/Ni atomic ratio of 0.23. To shed light on the relationship between the structural features and catalytic performance, the catalysts were thoroughly studied using a wide range of advanced physicochemical tools. The activity and selectivity of the proposed catalysts are related to the uniformity of Cu distribution and its interaction with Ni via the formation of metallic solid solutions. The method of introduction of copper in the catalyst plays a crucial role in the effectiveness of the interaction between the two metals.

Atmospheric Chlorine Reaction with N-Methyl-2-Pyrrolidinone (NMP)

Density functional theory (DFT) and Complete Basis Scale methods (CBS-QB3, G3B3) are used to investigate the reactivity, the mechanism, structure-reactivity relationship and the kinetics of N-methyl-2-pyrrolidinone (NMP) with Cl atom. To obtain rate constants of the reaction, the RRKM theory is employed at atmospheric pressure and temperature range 273–380 K. This study provides the rate coefficients and detailed H-abstraction mechanism for the reaction of Cl with NMP at high level of theoretical methods. The obtained rate constant ~ 0.92 x 10− 10 to 8.98 × 10− 10cm 3 molecule− 1s− 1 at 298 K agreed with those obtained previously for N,N-dimethyl formamide (DMF) and N,N-dimethyl acetamide (DMA). The study shows that the reaction mechanism of Cl with NMP goes favorably through an H-abstraction from N-methyl groups and adjacent CH2. The rates constants obtained for the three amides confirm our prediction regarding the structure-reactivity relationship where 1000/T.