Évaluation de l'influence des changements de géométrie sur les déformations de séchage d'un milieu poreux fissuréInfluence of geometry changes on drying-induced strains in a cracked solid

The macroscopic response of a cracked solid subjected to drying is investigated within the framework of micromechanics. The originality of this contribution lies in the fact that the variations of the aspect ratios of cracks induced by the capillary pressure increase are accounted for. When the initial aspect ratio is small enough, it is shown that neglecting the geometrical changes yields an erroneous prediction of the sign of the macroscopic volume strain rate. To cite this article: X. Chateau et al., C. R. Mecanique 331 (2003).     

非饱和土的广义朗肯土压力

本文从 4条基本假设出发 ,建立了非饱和土的广义朗肯土压力公式 ,采用理想试验对该公式进行了验证 ,在北京地铁13号线的东直门车站基坑工程中理论分析结果和实测值非常接近 ,证明了该理论的有效性。土的广义朗肯土压力公式建立了土的试验指标与原位指标的关系 ,从理论上给出了用土的试验指标得到原位主动 (被动 )土压力的方法。对于非饱和土 ,采用简单易得的直剪试验指标应用广义朗肯土压力公式就可以得到相当精确的结果 ,弥补了扩展朗肯土压力理论的不足。而且广义朗肯土压力公式能够合理利用已有的工程经验和工程数据 ,为非饱和土力学的工程实用化提供了一条新的思路。     

A new myrsinol-type diterpene polyester from Euphorbia dracunculoides Lam

A new myrsinol-type diterpene polyester, 14-deoxo-3β-O-propinoyl-2α,5α,7β,15β-tetra-O-acetyl-14α-O-benzoyl-myrsinol (1), and its known analogue, 14-deoxo-3β-O-prorionyl-5α,15β-di-O-acetyl-7β-O-nicotinoyl-myrsinol-14β-acetate (2), together with a monoterpenoid, pubinernoid A (3), two indole alkaloids, neoechinulin A (4) and dihydroxyisoechinulin A (5), two benzene derivatives, siringin (6) and (3-methoxyphenyl) acetic acid (7), were isolated from the 70% acetone extract of the aerial parts of Euphorbia dracunculoides Lam. Their structures were elucidated on the basis of spectroscopic evidence and comparison with literature reports. The absolute configuration of 1 was deduced by comparing experimental and calculated ECD spectra. Among them, compounds 4 and 5 were first obtained from the plant source. In addition, the ¹³C NMR data of compound 2 was reported for the first time.     

Reactions of a,ß‐unsaturated N‐benzenesulfonyl Imine – N‐[(2E)‐3‐phenyl‐2‐propen‐1‐ylidene]benzenesulfonamide with Methyllithium

α,β‐Unsaturated N‐benzenesulfonyl imine 1 was treated with 1.1 eq methyllithium to afford 1,2‐addition adduct as a sole product. However, when compound 1 was treated with 2 eq MeLi, 1,2‐addition product, benzenesulfonamide derivative 3 and 2H‐1,2‐benzothiazine 1,1‐dioxide derivatives 4 and 5 were isolated.     

生物降解高分子——一类重要的生物材料 2.生物相容性及脂肪族聚酯的表面改性

脂肪族聚酯是一类越来越受到关注的生物可降解生物材料。由于所有的医疗和药物制品在临床应用时都将不同程度地同机体组织或血液接触,而其表面又将是首先与机体组织或血液接触的部分,因此脂肪族聚酯医用制品的表面生物相容性更是同制品生物安全性和有效性有直接关系的性质。本文在分析脂肪族聚酯自身特性及对其制品表面生物相容性影响因素的基础上,介绍了采用物理、化学和等离子体处理方法对脂肪族聚酯制品表面生物相容性的改进。在分析和讨论各表面改性方法优点的同时,也指出了该法所存在的缺点、不足和应用的局限性。从而可为提高具体的脂肪族聚酯医用制品的表面生物相容性提供可供选择的表面改性方法。     

No Strain,No Gain? Enzymatic Ring‐Opening Polymerization of Strainless Aliphatic Macrolactones

Starting from readily available oleic and erucic acid, macrocyclic nonadecalactone (C₁₉) and tricosalactone (C₂₃) can be synthesized in polymerization grade purity in a four‐step reaction sequence. Ring‐opening polymerization (ROP) of these strainless macrolactones can be performed utilizing an enzyme as a catalyst. Despite the missing ring‐strain as key driving force for smaller (strained) lactones, high molar masses (M _n ≈ 10⁵ g mol⁻¹) can be accessed in an entropically driven ROP. Polyester‐19 and polyester‐23 prepared feature melting temperatures well above 100 °C. Further analysis of the mechanical properties of these materials displays the resemblance to polyethylene. For example, Young's moduli on the order of 600 MPa are observed as a result of the high crystallinity of the polymer.

     

Deformation and stress from in-pore drying-induced crystallization of salt

The deformation and the fracture of porous solids from internal crystallization of salt is explored in the framework of the thermodynamics of unsaturated brittle poroelasticity. In the first place the usual theory of crystal growth in confined conditions is further developed in order to include both the deformation and the drying of the porous solid. The thermodynamics reveals the existence of a dilation coefficient associated with the crystallization process, and provides a solute-crystal equilibrium condition which involves the relative humidity, the supersaturation, and the salt characteristics. This thermodynamic condition and the mechanical equilibrium of the solution-crystal interface combine to give the current crystallization pore radius. Upscaling this information at the macroscopic scale, and taking into account the salt mass supplied by the invading solution, the approach leads to a quantitative analysis of the role of the pore size distribution on the crystal growth under repeated imbibition-drying cycles. The deformation and the fracture of the porous solid from drying-induced crystallization are then considered in the context of brittle poroelasticity. The current unsaturated macroscopic poroelastic properties are upscaled from the microscopic elastic properties of the solid matrix and from the current liquid, crystal and gas saturations. The adoption of a fracture criterion based on the elastic energy that the solid matrix can ultimately store finally leads to the determination of how long a stone can resist repeated cycles of drying-induced crystallization of salt.     

The amphiphilic multiarm copolymers based on hyperbranched polyester and lysine: Synthesis and self-assembly

The amphiphilic multiarm copolymers were synthesized through the modification of commercially available hyperbranched polyesters(Boltorn H40) with N-ε-carbobenzoxy-L-Lysine N-carboxyanhydride(ZLys-NCA).After being condensed with N-Boc-phenylalanine(Boc-~NPhe) and deprotected the Boc-groups in trifluoroacetic acid(TFA),the original terminal hydroxyl groups were transformed into the amino groups and then initiated the ring-opening polymerization of ZLys-NCA.The hydrophilic poly(L-lysine) was grafted to the surface of Boltorn H40 successfully after the protecting benzyl groups were removed by the HBr solution in glacial acetic acid(33 wt%).The resulting multiarm copolymers were characterized by the ~1H-NMR,GPC and FTIR.The arm length calculated by NMR and GPC analysis was about 3 and 13 lysine-units for H40-Phe-PLysl and H40-Phe-PLys2 respectively.Due to the amphiphilic molecular structure,they displayed ability to self-assemble into spherical micelles in aqueous solution with the average diameter in the range from 70 nm to 250 nm.The CMC of H40-Phe-PLysl and H40-Phe-PLys2 was 0.013 mg/mL and 0.028 mg/mL,respectively, indicating that H40-Phe-PLysl with shorter arm length is easier to self-assemble than H40-Phe-PLys2 with longer arm length.     

紫外光固化超支化聚酯的合成及性能

以季戊四醇为核,2,2-羟甲基丙酸为臂,采用熔融缩聚法合成并表征了末端含大量羟基的超支化聚酯,其支化度高,黏度低,具有良好的热稳定性.以甲基丙烯酸酐改性超支化聚酯,得到链末端含有C=C的超支化甲基丙烯酸酯,在最佳反应条件下改性反应的转化率可达89%以上.改性后的超支化聚酯表现出更低的黏度,热失重曲线呈现为两段,玻璃态转...     

具有苯烷基侧链的芳香液晶聚酯的合成及性质

以熔融缩聚方法全盛了具有苯烷基侧链取代的全芳香液晶聚酯，用TG，DSC，热台偏光显微镜研究了聚酯的热性能，并讨论了取代基对聚酯热性能的影响，所有合成的聚酯均为热致型液晶，且具有较低的相转变温度。特别是当聚对苯二甲酸对苯二酚酯的两个苯环上分别取代了叔丁基和苯烷基，或取代了两个苯烷基侧链后，聚酯的熔融温度下降到225℃以下，并可在室温下溶于普通的有机溶剂中。