Cationic ring-opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms

The ring-opening polymerization of hexamethylcyclodisilazane (D_2NMe), initiated by methyl triflate in 1,2-dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D_4NMe). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D_3NMe). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back-biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.     

Microfabrication by X‐ray‐induced polymerization above the lower critical solution temperature

A polymer synthesis method is presented in which chain growth driven by exothermic reaction stimulates a gradual chain collapse. The globular precipitates in such systems can be restrained from coalescing by polymerizing in a quiescent environment. Time‐resolved small‐angle scattering study of the methacrylic acid polymerization kinetics in a quiescent system above its lower critical solution temperature (LCST) in water reveals the following features of this method: (a) growing oligomers remain as rigid chains until a critical chain length is reached, at which they undergo chain collapse, (b) radius of gyration increases linearly with time until a critical conversion is reached, and (c) radius of gyration remains constant after the critical conversion, even while conversion is gradually increasing. Following this self‐stabilizing growth mechanism, we show that nanoparticles can be directly synthesized by polymerizing N‐isopropylacrylamide above its LCST in water. The average size of nanoparticles obtained from a polymer–solvent system is expected to be the maximum extent of reaction spread at that monomer concentration. This hypothesis was then verified by polymerizing N‐isopropylacrylamide above their LCST in water, but by initiating the reaction with X‐rays shielded by a mask. The microfabricated patterns conform well to the size and shape of the mask used confirming that the growing chains do not propagate beyond the exposed regions as long as the reaction temperature is maintained above the LCST. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 429–425, 2006     

纳米镓/聚甲基丙烯酸甲酯复合材料的原位超声合成与表征

超声作用于低熔点金属镓,使其超细化为纳米级的镓粒子,并采用无引发剂的乳液聚合方法制备出GA/聚甲基丙烯酸甲酯(PMMA)纳米复合粒子,并分析了其微观结构。结果表明纳米镓的形态和结构因有无表面改性剂而不同;乳液聚合得到的纳米镓复合粒子是核壳结构型,粒子大小为50~80 NM,内核金属镓粒径为30~50 NM,与聚合物存在一定的化学作用。     

Evidence of thermally induced borehole elongation: a case study at Soultz, France

When they occur, borehole breakouts are considered strong markers of principal stress directions at depth. An innovative processing method for automatically identifying breakouts from ultrasonic borehole wall images has been developed. It has been applied to data sets from two deep, sub-vertical wells (GPK1 and GPK2) at the Soultz geothermal site in eastern France. In well GPK1, below 3 km depth, compression breakouts, with a 95°±7° azimuth, increasingly occur with depth. They result from time dependent compression failure at sub-critical stress levels and are indicators of the minimum horizontal principal stress orientation. However, in the uppermost logged section of well GPK2 (1.6–2.9 km depth), continuous borehole elongations share roughly the same azimuth with so called drilling-induced fractures (164°±18° and 175°±17° azimuth, respectively). Both features concomitantly vanish with depth, together with the amplitude of the thermal perturbation induced by drilling. It is proposed that these latter borehole elongations result from a pervasive, cooling-induced, tensile micro-cracking process prior to macroscopic failure localization. They are termed thermal elongations and are indicators of the maximum horizontal principal stress orientation. Had a simple logging caliper tool been used for this work, these thermal elongations might have been confused with classical compression breakouts. A simple criterion for differentiating compression breakouts from thermal elongation is proposed.     

有机镍化合物催化烯烃聚合的研究进展

综述了有机镍化合物如烯丙基镍、乙酰丙酮镍、茂镍、二亚胺镍等催化烯烃聚合的研究进展。有机镍化合物可催化烯烃、α-烯烃(如乙烯、丙烯等)的齐聚及聚合、催化极性单体(如甲基丙烯酸甲酯、降冰片烯等)以及位阻较大的环烯烃、取代二烯烃、苯乙烯等的均聚和共聚。     

Geotechnical Investigation Strategies for Lunar Base

Geotechnical characterization of potential lunar sites will be a critical part of the planning and design process. The strategies used to conduct a geotechnical investigation will be dictated by the specific needs of the lunar base, the unique environment of the lunar surface, and general character of the lunar soils and rocks. This paper outlines some of the types of geotechnical information that will be important and identifies some of the more promising strategies which might be used to obtain such information in the lunar environment. Some of the most important geotechnical information for planning and site development will be related to construction in the lunar soil. In addition to construction concerns, geotechnical data for foundation design (or verification of predesigned foundations) will be needed. The geotechnical site‐characterization work should include geophysical techniques, supplemented by conventional mechanical boring and testing only to the degree necessary to correlate geophysical measurements with conventional soil properties and to investigate anomalies. Equipment used for geotechnical site characterization will also serve for mineralogical exploration. Several techniques for geotechnical investigation that may provide very useful information in an expedient manner are described. Geophysical methods include seismic and electromagnetic methods, including seismic surveys that utilize surface waves. Electromagnetic methods such as ground‐penetrating radar are fast, efficient methods for mapping the subsurface, although these techniques do not measure soil characteristics that can readily be correlated with engineering properties. Seismic methods provide information that may correlate with soil strength, compressibility, and excavatability. In‐situ physical testing will likely include penetration testing for direct physical measurement of lunar soil behavior.     

用两亲聚合物制备大颗粒苯丙乳液

分别以两亲聚合物P(C9-AA)和P(DCPD-St-α-St-AA)作乳化荆，研究了制备大颗粒(约1μm)及具有一定稳定性的苯丙乳液的方法，讨论了乳化剂，温度及引发剂用量对乳液性能的影响。结果表明，以P(C9-AA)作乳化剂时，引发剂用量为单体质量的1．2％，90℃时可以合成性能良好的苯丙乳液；以P(DCPD-St-α-St-AA)作乳化荆时，引发剂用量为单体质量的1．2％，80℃时可以合成性能良好的苯丙乳液。     

Subsurface Characterization at Ground Failure Sites in Adapazari, Turkey

Ground failure in Adapazari, Turkey during the 1999 Kocaeli earthquake was severe. Hundreds of structures settled, slid, tilted, and collapsed due in part to liquefaction and ground softening. Ground failure was more severe adjacent to and under buildings. The soils that led to severe building damage were generally low plasticity silts. In this paper, the results of a comprehensive investigation of the soils of Adapazari, which included cone penetration test (CPT) profiles followed by borings with standard penetration tests (SPTs) and soil index tests, are presented. The effects of subsurface conditions on the occurrence of ground failure and its resulting effect on building performance are explored through representative case histories. CPT- and SPT-based liquefaction triggering procedures adequately identified soils that liquefied if the clay-size criterion of the Chinese criteria was disregarded. The CPT was able to identify thin seams of loose liquefiable silt, and the SPT (with retrieved samples) allowed for reliable evaluation of the liquefaction susceptibility of fine-grained soils. A well-documented database of in situ and index testing is now available for incorporating in future CPT- and SPT-based liquefaction triggering correlations.     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Restraining the associations of anthracene fluorophore by chemically linking to poly(methyl methacrylate)

Associations (dimer or aggregate) of anthracene (An) fluorophores tend to interrupt the monomer emission and reduce the quantum yield (Φ_PL); therefore, poly(methyl methacrylate) (PMMA) chain was used in this study to chemically link to anthracene and to block the mutual associations among the anthracene fluorophores. With this aim, the target polymers were prepared by anionic polymerizations with 9,10‐dibromoanthracene/s‐butyllithium as initiating system to proceed polymerizations of methyl methacrylate (MMA) directly or in the presence of 1,1‐diphenylethylene (DPE). Use of DPE before addition of MMA produces stable initiating anionic species and avoids potential side reactions during polymerization; however, it also introduces four β‐phenylene rings around the central anthracene ring, which interfere with the corresponding emission pattern and reduce the Φ_PL (32%) value due to potential interactions between phenylene rings and anthracene. On the contrast, polymerization without participation of DPE results in polymer with central anthracene ring directly connected to two PMMA chains, which gives clean vibronic emission pattern with limited association emissions and enhanced Φ_PL (52%) value. Physical blending of anthracene by PMMA is less efficient to restrain the associations and results in a film of lower Φ_PL (20%). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008