（PSF—PDMS—PHS）n／PSF共混物的相容性及表面组成

利用ＤＳＣ、ＤＭＡ、ＴＥＭ和ＸＰＳ对［ＰＳＦ－ＰＤＭＳ－ＰＨＳ］ｎ／ＰＳＦ共混物的相容性及表面组成进行了研究．结果表明，ＰＤＭＳ在共混物表面的富集与ＰＳＦ均聚物和［ＰＳＦ－ＰＤＭＳ－ＰＨＳ］ｎ中硬段的相容性有关；ＰＤＭＳ在相容的共混物体系表面的富集与对应的多嵌段共聚物组成基本相近；不相容共混物体系表面ＰＤＭＳ的富集程度相对较高，当共混物本体中有机硅含量从１％增至５％，表面层ＰＤＭＳ的含量迅速增加，可达到嵌段共聚物中ＰＤＭＳ的含量．     

Thermal redistribution reactions in crosslinked polysiloxanes

The thermolysis under argon of various polysiloxane resins containing D, T, D^H, or T^H units was investigated using thermogravimetric analysis combined with mass spectroscopy (TG/MS analysis) and solid-state ²⁹Si-NMR. Redistribution reactions involving the exchange of Si? C/Si? O bonds or Si? H/Si? O bonds were evidenced in addition to the exchange of Si? O/Si? O bonds reported to date. These reactions significantly modify the initial siloxane units and lead to an escape of volatile silanes or siloxanes. The exchange of Si? H/Si? O bonds takes place at lower temperatures (300°C) than the exchange of Si? C/Si? O bonds (500°C).     

Poly(N-acylethylenimine) copolymers containing pendant pentamethyldisiloxanyl groups. III. Surface properties and abhesion

The surface properties and abhesion of both N/Si and U/Si series of random copolymers were studied by contact angle and peel strength measurements. When these copolymers are coated on clean glass slides, the contact angles of water on the polymer films are over 105° for copolymers with less than 50 mol % of Si , and 98-104° for those with more than 50 mol % of Si. All the polymers have similar critical surface energies, 21 dyn/cm (from hydrocarbon probes) and 20 dyn/cm (from EtOH/H₂O probes), within the experimental error. This demonstrates that the amide groups in the polymer backbones are buried and all the polymers have methyl surfaces. The copolymers with less than 50 mol % Si (for N/Si copolymers) or 20 mol % (for U/Si copolymers) are stable and show good abhesive properties toward Scotch magic tape at or below 50°C. The peel strengths of Scotch magic tape with the copolymer coated slides rise dramatically as the annealing temperatures approach to the melting points of the polymers.     

Thermal and thermo-oxidative stabilities of some poly(siloxane-azomethine)s

Thermal and thermo-oxidative stability of some poly(siloxane-azomethine)s obtaining starting from bis(formyl-p-phenoxymethyl)tetramethyldisiloxane and different organic diamines have been investigated by TG+DTG+DSC simultaneous analyses performed in argon flow and air static atmosphere, respectively. TG, DTG and DSC curves of each polymer showed three or four successive degradation steps at different temperatures according to the composition of the sample and the gaseous atmosphere in which the thermal analysis was performed. For each process, the following parameters were evaluated: total mass loss, temperature corresponding to the maximum reaction rate, maximum reaction rate, temperature corresponding to certain mass loss. In order to determine the thermal and thermo-oxidative stabilities of investigated polymers, the following values were determined: T _x% — temperature corresponding to x% mass loss, and %Δm _T — mass loss at a given temperature T. The obtained orders of stability were correlated with the structure of investigated polymers.     

Ultrafast dynamics in noble metal clusters: The role of internal vibrational redistribution

We present a theoretical study of the ultrafast dynamics in noble metal clusters interacting with molecular oxygen which is of fundamental importance for the understanding and design of cluster-based heterogenous nanocatalysts. We demonstrate that intrinsic dynamical properties can significantly promote the reactivity of small noble metal clusters towards O₂. This concept is illustrated by performing collision simulations between and clusters and O₂ in the framework of the ab initio molecular dynamics (MD) using density functional theory (DFT). We show that different nature and efficiency of the internal vibrational energy redistribution (IVR) during the collisions with O₂ are responsible for considerably different sticking probabilities of O₂ to silver and gold clusters, respectively. In the case of , resonant IVR between the cluster and the O₂ subunit activates the O–O bond and promotes the subsequent oxidation reaction. In contrast, in the case of fast dissipative IVR on the time scale of 1 ps leads to a higher sticking probability for O₂ but the O–O bond is very rapidly deactivated and cannot participate in further oxidation processes. These findings allow us to introduce the nature of IVR as a criterion for promoting the reactivity of noble metal clusters. Such different behaviour of silver and gold clusters colliding with O₂ originates from difference in relativistic effects which are considerably more pronounced in the case of gold clusters causing more directional rigid bonding in contrast to silver clusters with more s-metallic floppy character. Moreover, we demonstrate that breaking of O–O bond can be induced in by a selective excitation of the O–O bond with an ultrashort pulse in the infrared spectral range. This opens the perspective to control the action of nanocatalysts by employing shaped laser pulses and thus bridges the fields of femtochemistry and cluster nanocatalysis.     

Novel photosensitive resin simultaneously with outstanding cryogenic strength and toughness for digital light processing three-dimensional Printing

With the increased demand for three-dimensional (3D) printing technology in various fields, it is important to develop high-performance resin that could withstand temperature changes to expand their application potential. A new photosensitive oligomer (BDM–DDM–ETPS–GMA) based on epoxy-terminated polyether siloxane (ETPS) and bismaleimide diphenylmethane/4, 4′-diaminodiphenylmethane (BDM–DDM) resin was synthesized and then mixed with other oligomers, reactive diluents, and photoinitiators to prepare a novel 3D printing resin. The results show that the resulting resins exhibit good fluidity and rapid photopolymerization ability, which satisfies the rheological prerequisites of 3D printing resin. Moreover, the incorporation of BDM–DDM–ETPS–GMA can simultaneously improve the cryogenic stiffness and toughness of commercial resin. Specifically, the tensile strength, elongation at break, flexural strength, impact strength, and storage modulus at ?30 °C of modified resin with 15% BDM–DDM–ETPS–GMA are 151.2 MPa, 10.9%, 146.2 MPa, 9.8 kJ/m², and 4,131 MPa, respectively, which are about 2.81, 1.70, 1.37, 1.81, and 1.54 times of that of commercial resin. A synergistic enhancement mechanism is believed to be attributed to these results, which includes the introduced flexible siloxane chain and the rigid bismaleimide structure as well as decreased cross-linking density. These attractive features of modified resins suggest that the method proposed herein is a new approach to develop high-performance 3D printing photosensitive resin simultaneously with outstanding cryogenic strength and toughness and thus has wide application potential in the aerospace, military industry, and other cutting-edge fields.     

Effect of normal processes on thermal conductivity of germanium,silicon and diamond

The effect of normal scattering processes is considered to redistribute the phonon momentum in (a) the same phonon branch — KK-S model and (b) between different phonon branches — KK-H model. Simplified thermal conductivity relations are used to estimate the thermal conductivity of germanium, silicon and diamond with natural isotopes and highly enriched isotopes. It is observed that the consideration of the normal scattering processes involving different phonon branches gives better results for the temperature dependence of the thermal conductivity of germanium, silicon and diamond with natural and highly enriched isotopes. Also, the estimation of the lattice thermal conductivity of germanium and silicon for these models with the consideration of quadratic form of frequency dependences of phonon wave vector leads to the conclusion that the splitting of longitudinal and transverse phonon modes, as suggested by Holland, is not an essential requirement to explain the entire temperature dependence of lattice thermal conductivity whereas KK-H model gives a better estimation of the thermal conductivity without the splitting of the acoustic phonon modes due to the dispersive nature of the phonon dispersion curves.      

Characterization of GaN nanostructures by electron field and photo-field emission

The electron field and photo-field emission from GaN nanostructures has been analyzed in this review. In order to explain the obtained experimental results, a model was proposed taking into account the change in carrier concentration distribution in the main and the satellite valley during the emission process. The lowering of work function (due to the increased number of carriers in the satellite valley) can explain the decrease in the Fowler-Nordheim plot slope. It was shown that the energy difference between the main and satellite valley in GaN was decreased in the case of quantum confinement, thus increasing the probability of electron transition from Γ to X valley at same electric fields.Investigations of electron photo-field emission demonstrated that the Fowler–Nordheim plots of the emission current have different slopes for nonilluminated and illuminated devices. A model based on the electron emission from valleys having different specific electron affinities is proposed to explain the experimental results. In the absence of illumination the emission takes place only from the lower valley. Upon UV illumination and presence of a high electric field at the emitter tip, the upper valley of the conduction band appears to be occupied by electrons generated at the valence band.     

Diacetylene–siloxane–carborane thermosets and ceramic precursors

Thermosets and ceramic chars were prepared and characterized from a diacetylene–siloxane–carborane polymer, DSCS, and a diacetylene–siloxane polymer, DS. The goal was to incorporate the known thermo‐oxidative stability found in the siloxane–carborane elastomers into high‐performance thermosets and ceramic chars. The DSCS thermoset had excellent thermo‐oxidative stability as determined by a low weight loss and tough residue after annealing for 100 h in air at 300 °C, but it had a low glass transition temperature (94 °C). The DS thermoset did not undergo a glass transition below 350 °C and had a low weight loss on thermo‐oxidative aging, but the residue was quite brittle. Two random copolymers were made to optimize the thermo‐oxidative stability and toughness of the DSCS thermoset and the higher glass transition of the DS thermoset. Significantly, the 50:50 DSCS/DS random copolymer when cured to a thermoset did not undergo a glass transition below 350 °C, yet retained much of the strength, toughness and thermo‐oxidative stability of the DSCS thermoset. Heat treatment of the poly‐DSCS to elevated temperatures resulted in a ceramic material with improved properties relative to the ceramic derived from poly‐DS. Both polymers had similar char yields to 800 °C, but the poly‐DSCS solidified to a 15% denser ceramic. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Gelatin-Siloxane Hybrids Derived through Sol-Gel Procedure

A new type of inorganic-organic hybrid materials incorporating gelatin and 3-(glycidoxypropyl) trimethoxysilane (GPSM) was prepared through sol-gel processing. A solid-state ²⁹Si NMR analysis indicated that all the methoxy silane groups of GPSM were polymerized to yield —Si—O—Si— bridging bonds. An amino acid analysis confirmed grafting reactions of GPSM against gelatin chains. The increasing GPSM/gelatin ratio stimulated gel formation, phase separation, and the density of GPSM-crosslinking of the gelatin chains as well as it changed the micro- and macro- structures and the viscoelastic properties of the final products.