Structure des savons alcalins

Summary This is a systematic X-ray diffraction study of the structure of the mesomorphic phases occurring with potassium soaps ranging from C₈ to C₂₂.Four types of structure have been identified. The first is lamellar with both polar groups and paraffin chains in the crystalline state. The second is also lamellar, but with both polar groups and paraffin chains in the liquid state. The third corresponds to the localization of indefinitely long ribbons on a two-dimensional oblique lattice; polar groups are crystalline and paraffin chains desorganized. The fourth corresponds to the localization of discs on a three-dimensionnalB-faces centered orthorhombic lattice; polar groups are crystalline and paraffin chains disorganized.The structural parameters and the polymorphism of the polar groups have been discussed.

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Zusammenfassung Wir beschreiben hier eine systematische Röntgenstrahlendiffraktionsforschung der Struktur der mesomorphen Phasen von Kalium Seifen von C₈ bis C₂₂.Vier Strukturtypen wurden gefunden. Die erste Struktur ist lamellar; beides, die polaren Gruppen und die Paraffinketten sind kristallisiert. Die zweite Struktur ist auch lamellar; aber in diesem Falle sind beides, die polaren Gruppen und Paraffinketten geschmolzen. Die dritte Struktur entspricht einer Lokalisation von Seifenbändern in einem zweidimensionalen monoklinen Gitter; die polaren Gruppen sind kristallisiert und die Paraffinketten geschmolzen. Die vierte Struktur entspricht einer Lokalisation von Seifenscheiben in einemB-flächenzentrierten orthorhombischen Raumgitter; die Polargruppen sind kristallisiert und die Paraffinketten geschmolzen.Wir haben aus den experimentellen Resultaten einige Schlußfolgerungen gezogen.

     

Structure des savons alcalins

Summary In the first part of this work we describe the results of a systematic X-ray diffraction study of the structure of cesium soaps at high temperatures. Three types of structure have been identified. The first is lamellar with both polar groups and paraffin chains in the crystalline state. The second is also lamellar, but with both polar groups and paraffin chains in the liquid state. The third corresponds to the localization of polar groups in the crystalline state within discs surrounded by paraffin chains in a partially disorganized configuration. In the second part of this work we discuss the mechanism of the stepwise melting of alkali-metal soaps, the polymorphism exhibited by polar groups when crystallized and the amphipathic character of soaps. We present some empirical rules which seem to govern the occurrence of different types of structure as a function of the nature of the cation and the length of the paraffin chains.

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Zusammenfassung Es werden Ergebnisse der Untersuchung der Strukturen von C?siumseifen bei hohen Temperaturen mit R?ntgenstrahldiffraktion beschrieben. Drei Strukturtypen wurden gefunden. Die erste, in welcher die polaren Gruppen und die Paraffinketten kristallisiert sind, ist lamellar. Die zweite ist ebenfalls lamellar; aber die polaren Gruppen und Paraffinketten sind geschmolzen. Die dritte Struktur entspricht diskusf?rmigen Strukturelementen; die polaren Gruppen befinden sich im kristallinen Zustand in Scheiben, die von zum Teil ungeordneten Paraffinketten umgeben sind. Im zweiten Teil dieser Arbeit diskutieren wir den Mechanismus des stufenweisen Schmelzens von Alkaliseifen, die Polymorphie der kristallisierten polaren Gruppen und den amphipathischen Charakter der Seifen. Wir schlagen einige empirische Regeln vor, welche die verschiedenen Strukturtypen in Hinsicht auf die Natur des Kations und auf die L?nge der Paraffinketten zu bestimmen scheinen.

     

高分子量级分含量对熔体挤出拉伸法制备聚丙烯微孔膜的影响

通过熔体挤出拉伸法以两种聚丙烯为原料制备微孔膜.通过考察原料分子量数据发现高分子量聚丙烯(PPH)在高分子量级分(重均分子量>106)含量上大于低分子量聚丙烯(F401).PPH的弛豫时间在相同条件下也远大于F401.红外二向光法结果表明,PPH在相同熔体牵伸比下片晶取向度较F401高.相同加工条件下PPH微孔膜片较F401成孔分布更均匀,孔径尺寸也更均匀.2种微孔膜孔隙率都随熔体牵伸比的增加而提高,微孔分布随着熔体牵伸比的提高和片晶取向度的增加而趋于均匀,孔尺寸也随之区域均匀.研究表明,聚合物树脂中高分子量级分含量是影响预制膜中片晶取向度、冷热拉伸成孔分布和尺寸均匀度的重要影响因素.     

Structure des savons alcalins

Summary This is a systematic x-ray diffraction study of the structure of alkali-metal di-soaps as a function of temperature. Two types of structure have been identified. The first is lamellar with both polar groups and paraffin chains in the crystalline state. The second is also lamellar, but with polar groups and paraffin chains in the liquid state. These structures have been discussed and compared to those of usual alkali-metal and alkaline-earth soaps.

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Zusammenfassung Aus r?ntgenographischen Daten wurde die Struktur der Lithium-, Natrium-, Kalium-, Rubidium- und C?siumsalze von Alkylendicarbons?uren („Doppelseifen“) abgeleitet. Es wurden zwei lamellare Strukturtypen gefunden. In einer davon entspricht die Anordnung der polaren Gruppen und der Paraffinketten dem kristallisierten Zustand, in der anderen dem geschmolzenen Zustand. Die beobachteten Strukturen wurden mit denen der einfachen Seifen (Monos?uren) mit einwertigen und zweiwertigen Metallen verglichen.

     

Etude par diffraction des rayons X des gels de polysavons derivant du copolymere alterne anhydride maleique-hexadecylvinylether

Low and wide angle X-ray diffraction was used to study the structural behaviour at low temperature of aqueous gels of an alternating copolymer of maleic anhydride with hexadecyl vinyl ether characterized at high temperatures by either a lamellar structure or a cylindrical structure. This study has shown the importance at low temperature of the crystallization of the paraffin chains. Only the lamellar structure can be observed. In this structure, both polymer skeletons and paraffin chains are assigned to be regularly arranged in space, the former at the interfaces, the latter inside the lamella.     

Synthesis of needle-like crystalline particles by chemical-oxidative dispersion polymerization of xylidine

 Chemical-oxidative dispersion polymerization of 3, 5-xylidine was carried out in an aqueous medium with ammonium persulfate as an oxidant and polyvinylalcohol as a stabilizer. The polymerization proceeded smoothly at room temperature, resulting in a stable polyxylidine (PXy) dispersion. The produced PXy particles had two types of shapes: needle-like and spherical. Results obtained by electron diffraction and X-ray diffraction measurements indicated that the PXy needle-like particles had a crystalline structure. Received: 14 January 1997 Accepted: 03 September 1997     

Crystallizing Self-Standing Covalent Organic Framework Membranes for Ultrafast Proton Transport in Flow Batteries

Covalent organic frameworks (COFs) display great potential to be assembled into proton conductive membranes for their uniform and controllable pore structure, yet constructing self-standing COF membrane with high crystallinity to fully exploit their ordered crystalline channels for efficient ionic conduction remains a great challenge. Here, a macromolecular-mediated crystallization strategy is designed to manipulate the crystallization of self-standing COF membrane, where the −SO₃H groups in introduced sulfonated macromolecule chains function as the sites to interact with the precursors of COF and thus offer long-range ordered template for membrane crystallization. The optimized self-standing COF membrane composed of highly-ordered nanopores exhibits high proton conductivity (75 mS cm⁻¹ at 100 % relative humidity and 20 °C) and excellent flow battery performance, outperforming Nafion 212 and reported membranes. Meanwhile, the long-term run of membrane is achieved with the help of the anchoring effect of flexible macromolecule chains. Our work provides inspiration to design self-standing COF membranes with ordered channels for permselective application.     

Spherulitic membranes of alkylated polyvinylalcohol: Water and salt transport in relation to their structure and to the state of swelling water

Membranes with well characterized structures were prepared for study of the relationship between the structure, the state of swelling water and the transport phenomena. These membranes consist of polyvinylalcohol (PVA) with various amounts of grafted octadecylic chains. The method of grafting leads to sequential grafting with unreacted hydroxylic groups between adjacent grafted paraffinic chains. A spherulitic texture, including an amorphous part made of ungrafted PVA, was observed. DSC and swelling measurements show that the water content of the lamellar spherulitic phase was constant regardless of the grafting ratio and that the water in this phase was unable to crystallize. In the amorphous zones, the crystallizable and non-crystallizable water co-existed in a ratio closely related to the grafting ratio. Transport properties have been studied using various methods. A porous type transport without selectivity occurs through the amorphous zones together with a selective diffusive type transport through the spherulites. Using a porous plug model, amorphous zones are characterized by an equivalent pore diameter of about 30 Å. The number of those pores increases when the grafting ratio decreases and their sizes vary under the effect of the applied pressure. The diffusive transport, unaffected by the applied pressure, takes place through the interlamellar spaces, which are characterized by a water thickness of about 15 Å in which the ordering of the water is probably responsible for the selectivity.     

Microporous membranes obtained from polypropylene blends with superior permeability properties

A blend of two polypropylene resins, different in molecular structure, one with linear chains and the other with long chain branches, was investigated to develop microporous membranes through melt extrusion (cast film process) followed by film stretching. The branched component significantly affected the row‐nucleated lamellar crystalline structure in the precursor films. The arrangement and orientation of the crystalline and amorphous phases were examined by wide angle X‐ray diffraction and Fourier transform infrared spectroscopy methods. It was found that blending of a small amount of a long chain branched polypropylene improved the orientation of the both crystalline and amorphous phases in the precursor films. Annealing, followed by cold and hot stretching were consequently employed to generate and enlarge pores in the films as a result of lamellae separation. SEM micrographs of the surface of the membranes obtained from the blend revealed elongated thin fibrils and a large number of lamellae. The lamellae thickness for the blend was much shorter in comparison to that of the linear PP precursor film. The permeability of the samples to water vapor and N₂ was significantly enhanced (more than twice) for the blend system. The porosity of the blend membrane showed a significant improvement with a value of 53% compared to 41% for the linear PP membrane. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 148–157, 2008     

Copolymerisation radiochimique des melanges cristallises styrene-methacrylate de lauryle

The crystallization of lauryl methacrylate is determined by the long paraffin chains which associate to form parallel bundles. Limited amounts of styrene can penetrate into the regions of the crystal where the methacrylic groups are concentrated. The irradiation of the solid mixture leads to a copolymer, the composition of which varies little with the composition of the monomer feed. The kinetics of the copolymerization are studied and compared with the polymerization of crystalline lauryl methacrylate in the presence of benzene, hexane and dodecane. The results are interpreted by considering the influence of these various additives on the crystal structure of lauryl methacrylate which can take two different forms depending on crystallization conditions.     

具有不同柱状结构的苯并菲盘状液晶化合物的合成及自组装

合成了3种含有不同长度烷基链的苯并菲盘状液晶化合物; 通过1H NMR 和 MALDI-TOF MS对其结构进行了表征; 利用差示扫描量热法(DSC)、热台偏光显微镜(POM)和小角X射线散射实验(SAXS)对3种液晶化合物的自组装行为进行了研究. 结果表明, 烷基链的长度对苯并菲盘状液晶化合物自组装结构的影响显著. 柔性链为辛基的苯并菲盘状液晶化合物自组装成六方柱状液晶相; 柔性链为十二烷基的化合物自组装成倾斜柱状液晶相; 而柔性链为十六烷基的化合物则未形成液晶相.     

Plasticization and cocrystallization in LLDPE/wax blends

The structure and thermal properties of linear low‐density polyethylene (LLDPE)/medium soft paraffin wax blends, prepared by melt mixing, were investigated by differential scanning calorimetry (DSC) and small‐ and wide‐angle X‐ray scattering (SAXS and WAXS). The blends form a single phase in the melt as determined by SAXS. Upon cooling from the melt, two crystalline phases develop for blends with more than 10 wt % wax characterized by widely different melting points. The wax acts as an effective plasticizer for LLDPE, decreasing both its crystallization and melting temperature. The higher melting point crystalline phase is formed by less branched LLDPE fractions. On the other hand, the lower melting point crystalline phase is a wax‐rich phase constituted by cocrystals of extended chain wax and short linear sequences of highly branched LLDPE chains. The presence of cocrystals was evidenced by standard DSC results, successive self‐nucleation and annealing (SSA) thermal fractionation and by the detection of a new SAXS signal attributed to the lamellar long period of the cocrystals. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1469–1482     

Chitosan-based solid electrolyte composite membranes: I. Preparation and characterization

Some chitosan-based solid electrolyte composite membranes were prepared by incorporating potassium hydroxide as the functional ionic source, using glutaraldehyde as cross-linking agent. A three-layer structure with a porous intermediate layer for each composite membrane was observed using SEM. It was found that the concentration of potassium hydroxide solution used to prepare the composite membranes largely influenced the pore volume, porosity, pore size of the intermediate layer, as well as determined the content of potassium hydroxide inside the composite membranes, whereas the degree of cross-linking of composite membrane did not show notable effects. All composite membranes showed significant decreases in both their T_g and onset thermal degradation temperatures with respect to the solid cross-linked chitosan membranes without containing potassium hydroxide. Potassium hydroxide was found to be located inside the intermediate layer of composite membranes with shapes of bulky or fabric crystals. The crystalline properties of matrices of the composite membranes themselves were remarkably modified after being incorporated with potassium hydroxide and main crystalline peaks of matrices almost disappeared for all composite membranes.     

Recovery as a measure of oriented crystalline structure in poly(ether ester)s based on poly(ethylene oxide) and poly(ethylene terephthalate) used as shape memory polymers

Poly(ether ester)s consisting of poly(ethylene oxide) and poly(ethylene terephthalate) segments, EOET copolymers, could be used as shape memory polymers (SMP). Crystalline structural characters of the copolymers during the memory process were investigated by dynamic mechanical analysis, differential scanning calorimeter, wide-angle X-ray diffraction, polarizing microscopy, and recovery measurements. PEO crystals in stretched EOET copolymer preferentially oriented along fiber axis or stretch direction. During stretching, the structure of the copolymer undertake a transformation from spherulite to fiber, resulting in a crystalline morphology similar to shish-kebab, and recovery properties of stretched EOET samples were dependent on as-described crystalline structural characters that can be influenced by draw ratio. Driving forces for contraction come from the oriented chains, and only oriented or extended chains can be contributive to the recovery of deformation; these extended chains involve both crystalline and amorphous segments. The recovery process in shape memory behavior was noticed to be deorientation of oriented chains due to thermodynamic entropy effect, and was divided into three stages. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 101–112, 1999     

Effects of Paraffin Emulsion on the Structure and Properties of Soy Protein Films

In this work, the water-repellent capacity of the paraffin emulsion?covered soy flour (SF) substrate has been studied. Effect of paraffin emulsion content on the structure and properties of the resulting films were studied using laser particle size distribution analyzer, water absorption test, x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and tensile testing. Study on the emulsion particle size and stability revealed that the particle size distribution and stability were strongly dependent on the pH of the system. And the optimum pH was 9.9. The incorporation of paraffin emulsion produced at pH 9.9 could markedly enhance the water resistance of films. However, the improvement was realized at the expense of decreased thermal stability and tensile strength of SF?paraffin emulsion films. The addition of paraffin emulsion could destroy the crystalline domains of soy protein and change the protein secondary structure.     

Infrared intensity of 1-monolaurin-water systems in the gel phase

The infrared spectra of 1-monolaurin-water systems, where KSCN is added as the intensity standard, were observed and the infrared intensity of the bands due to acyl groups measured relatively to that of the CN stretching. The infrared intensities of the bands parallel and perpendicular to the paraffin chains decrease and increase, respectively, on going from the crystalline 1 phase to the gel phase, confirming that these intensity changes result from the long-range interaction among oscillating dipoles. The infrared spectra with no CH2 rocking and the splitting of the CH2 rocking are also discussed with the same interaction model.     

Small‐angle neutron scattering investigation of structural changes in nafion membranes induced by swelling with various solvents

The structure of Nafion‐117 perfluorosulfonate ionomer membranes was investigated with small‐angle neutron scattering techniques. Structural changes induced by the swelling of the membranes with water, alcohols, and dipolar, aprotic solvents were monitored at solvent‐swelling levels ranging from approximately 2 vol % to greater than 50 vol %. Membranes swollen up to approximately 50 vol % solvent exhibited two scattering maxima, one known to be associated with ionic regions of the membrane structure and one known to be associated with correlation distances between crystalline regions in the membrane structure. The positions of both maxima shifted toward lower scattering vector values as the solvent content in the membrane increased. The shift in the position of both maxima was linearly related to the solvent volume fraction in the membrane. The Bragg spacings corresponding to both the ionic‐feature scattering maximum and the crystalline‐feature scattering maximum were plotted versus the solvent volume fraction in the membranes, and the data fit with linear regression. The slopes associated with the curves of the spacing versus the solvent volume fraction were greater for the crystalline‐feature spacing than for the ionic‐feature spacing for all solvents other than water; this was indicative of preferential segregation of nonaqueous solvents into regions of the structure not directly associated with the ionic scattering maximum. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 387–400, 2002; DOI 10.1002/polb.10092     

Proton transfer in imidazole-based molecular crystals

Heterocycles' aggregates show rather good proton conductivity. In particular, condensed structures formed by imidazole rings that are held together by polymeric chains have attracted some interest as possible candidate materials for fuel cell membranes. However, the details of the proton diffusion process could not be resolved by means of experimental measurements because of the fast rearrangement of the structure after each proton exchange. In this work, we report in detail the results of ab initio molecular dynamics calculations, which were briefly presented in a previous Letter [M. Iannuzzi and M. Parrinello, Phys. Rev. Lett. 93, 025901 (2004)]. The conformational changes associated with the diffusion of protons in model crystalline structures containing chains of imidazole rings are described in the framework of an atomistic approach. In particular, the bonding pattern characterizing the structure of imidazole-2-ethylene-oxide doped by an excess proton is also studied through the calculation of the 1H NMR chemical shifts. The unresolved resonances appearing in the experimental spectra could be associated with specific structural features, in connection with the fluctuating hydrogen bonding. The analysis of the distortions that induce or are induced by the mobility of the protons offers some new hints for the engineering of new proton conducting materials.     

Micro-Raman investigations of myelins in aerosol-OT/water system

Surfactant outgrowth during dissolution as myelin figures, which happens on contact with water, is of prime importance in emulsification and detergency. Micro-Raman investigation of different lyotropic phases formed during dissolution of aerosol-OT (bis 2-ethylhexyl sulfosuccinate) in water during myelin formation reveals the flexible arrangement of the surfactant bilayers in myelin. The conformation around CC-CS bond and the hydrocarbon chains of aerosol-OT in the different liquid crystalline phases were identified from the fingerprints of CC-CS stretching, C-C stretching, C-H bending, and stretching frequencies. Existence of mixture of trans and gauche conformations around CC-CS bond and that of the hydrocarbon chains in myelin supports the fluid nature of bilayers by which it is made. Similar conformations of hydrocarbon chains in lamellar phase and in myelin support the concept of myelins being rolled up lamella. The observations are in line with the disorderness of the hydrocarbon chains in the bilayers of phospholipids that has been reported earlier. From the C-C stretching frequencies at the root of myelins, the kinked structure of the hydrocarbon chain is identified, and loose packing of molecules which would facilitate water transport across membranes is evident.     

Crystalline lipid domains: characterization by X-ray diffraction and their relation to biology

Biological membranes comprise thousands of different lipids, differing in their alkyl chains, headgroups, and degree of saturation. It is estimated that 5% of the genes in the human genome are responsible for regulating the lipid composition of cell membranes. Conceivably, the functional explanation for this diversity is found, at least in part, in the propensity of lipids to segregate into distinct domains, which are important for cell function. X-ray diffraction has been used increasingly to characterize the packing and phase behavior of lipids in membranes. Crystalline domains have been studied in synthetic membranes using wide- and small-angle X-ray scattering, and grazing incidence X-ray diffraction. Herein we summarize recent results obtained using the various X-ray methods, discuss the correlation between crystalline domains and liquid ordered domains studied with other techniques, and the relevance of crystalline domains to functional lipid domains in biological membranes.