共查询到20条相似文献,搜索用时 15 毫秒
1.
Tsuneo Okubo Junichi Okamoto Shinya Takahashi Akira Tsuchida 《Colloid and polymer science》2009,287(8):933-942
Drying dissipative structures of aqueous solution of poly(ethylene glycol) (PEG) of molecular weights ranging from 200 to
3,500,000 were studied on a cover glass, a watch glass, and a glass dish on macroscopic and microscopic scales. Any convectional
and sedimentation patterns did not appear during the course of drying the PEG solutions. Several important findings on the
drying patterns are reported. Firstly, the crystalline structures of the dried film changed from hedrites to spherulites as
the molecular weight and/or concentration of PEG increased. Secondly, lamellae were formed along the ring patterns especially
at high concentrations and high molecular weights. The coupled crystalline patterns of the spherulites and the lamellae were
observed in a watch glass along the ring structures, supporting the important role of the convection by the gravity during
the course of dryness. The coupled patterns were difficult to be formed on a cover glass and a glass dish, except at the outside
edge of the dried film. Thirdly, the size of the broad ring at the outside edge of the dried film especially on a cover glass
and a watch glass increased sharply as the molecular weight increased and also as the polymer concentration increased.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
2.
Tsuneo Okubo Akira Hagiwara Hiromi Kitano Junichi Okamoto Shinya Takahashi Akira Tsuchida 《Colloid and polymer science》2009,287(10):1155-1165
Drying dissipative structures of aqueous solution of sodium polymethacrylate (NaPMA) were studied on a cover glass, a watch
glass, and a glass dish. Any convectional and sedimentation patterns did not appear during the course of dryness. Several
important findings on the drying patterns are reported. Firstly, spherulite and hedrite dissipative crystals were observed
when the polymer solutions were dried. The crystalline structures changed from hedrites to spherulites as polymer concentration
increased. Secondary, the coupled structures of the spherulites and the broad rings were observed for NaPMA at the outside
edge of the broad ring. However, the coupled crystalline structures of the lamellaes from the broad ring and the spherulites,
which were observed for poly(ethylene glycol) (Okubo et al. 2009), were not observed clearly for NaPMA system. Thirdly, size of the broad ring at the outside edge of the dried film increased
sharply as polymer concentration increased. 相似文献
3.
Tsuneo Okubo Masashi Mizutani Shinya Takahashi Akira Tsuchida 《Colloid and polymer science》2010,288(14-15):1435-1444
Drying patterns of aqueous solutions of sodium salt of deoxyribonucleic acid (NaDNA) were studied on a cover glass, a watch glass, and a Petri glass dish at room temperature. Orientation of the rod-like single crystals of NaDNA molecules in the radial direction was observed especially at low polymer concentrations. The ratios of the size of the broad ring against initial size of the liquid on a cover glass and a watch glass were very small between 0.05 and 0.1 compared with those of the typical polyelectrolytes. Main cause is the compact conformation of NaDNA forming single or double stranded helix structures in the dried film. Microscopic drying patterns were long rods accompanied with the many short rods especially on a cover glass. Thick and short rods and dendritic crystals were fogrmed at the inward and outward areas of the dried films, respectively, on a watch glass and a Petri glass dish. Rod-like and dendritic crystals resembled the distorted hedrite and/or spherulite structures. Dissipative crystallization such as the orientation and accumulation of the single crystals of NaDNA were observed and the importance of the convectional and sedimentation processes was demonstrated during the course of crystallization. 相似文献
4.
Okubo T 《Colloids and surfaces. B, Biointerfaces》2011,87(2):439-446
Dissipative drying patterns of aqueous mixtures of potassium salts of poly(riboadenylic acid) (KPolyA) and poly(ribouridylic acid) (KPolyU) were studied on a cover glass, a watch glass and a glass dish at room temperature. Accumulation of the polymers forming the broad rings near the outside edge and the inner area of the dried film was observed. The fine multiple ring structures formed when the affinity of the polymer with the substrate is strong. Microscopic drying patterns changed drastically depending on the location in the dried film. Microscopic drying patterns were mainly dendritic long rods and sword (halberd)-like rods. They are assigned to the crystals of double-stranded and triple-stranded helices of the A:U and A:2U complexes, respectively. Cross-like drying patterns are also observed originated from the salt-polymer interaction. 相似文献
5.
Tsuneo Okubo 《Colloid and polymer science》2014,292(6):1419-1427
Drying patterns of aqueous solutions of potassium salts of poly(riboguanylic acid) (KPolyG), poly(ribocytidylic acid) (KPolyC), and their mixtures KPolyG + KPolyC were studied on a cover glass, a watch glass, and a glass dish at room temperature. Accumulation of the polymers forming the broad rings near the outside edge and also in the inner area of the dried film was observed. The fine multiple ring structures formed, which supports the fact that the affinity of the polymer with the substrate is strong. Typical microscopic drying patterns of KPolyG, KPolyC, and KPolyG + KPolyC were spherulites, dendritic long rods, and sword (harberd)-like rods, respectively. The patterns changed depending on the location in the dried film. The dendritic long rods and sword-like rods were assigned to the crystals of double-stranded and/or triple-stranded helices of the G:C and 2G:C complexes. Cross-like drying patterns that originated from the salt-polymer interaction are also observed. The relationship between the polymer complexation of KPolyG + KPolyC systems and the drying patterns is similar to that of KPolyA (potassium salt of poly(adenylic acid)) + KPolyU (potassium salt of poly(uridylic acid)). 相似文献
6.
Drying dissipative patterns were observed at room temperature on a cover glass, a watch glass, and a Petri glass dish during the course of dryness of aqueous solution of sodium salts of poly (d-glutamic acid), poly (l-glutamic acid), and their low molecular weight analogs, monosodium d-glutamate, monosodium l-glutamate, and monosodium dl-glutamate. The low molecular weight analogs were hygroscopic and their drying patterns were observed in a dry box coexisted with the bags of desiccant. The broad rings, which are the typical macroscopic drying patterns, were observed for all the samples. Optical isomeric effects on the drying patterns were not recognized. Spherulite (or hedrite) and rod-like crystals from the assemblies of helical main chains of the polymers are formed mainly at the inner area from the broad ring (except central area) and the broad ring area, respectively. Coexistence of sodium chloride enhanced the crystal structures by the cooperative interactions between the polymers and the salts. The typical dissipative crystallization such as accumulation, segregation, and orientation effects of crystals were observed in the drying patterns. 相似文献
7.
The drying dissipative patterns of aqueous solutions of simple electrolytes, KCl, NaCl, CaCl2, and LaCl3, were observed on a cover glass. The macroscopic broad rings were formed at the outside edge of the drying film area, which
shrunk from the initial solution area especially at low salt concentrations. The drying area and the broad ring size decreased
as the salt concentration decreased. The microscopic block-like and dendritic cross-like patterns were observed for all the
salts. Size of single crystals dried on a cover glass increased as salt concentration increased. The drying patterns of the
binary mixtures of the salts were also observed. Size of the broad ring increased sharply by mixing. The microscopic patterns
were, on the other hand, insensitive to the mixing. 相似文献
8.
The sedimentation and drying dissipative structural patterns were formed during the course of drying binary mixtures among
colloidal silica spheres of 183 nm, 305 nm, and 1.205 μm in diameter in aqueous suspension on a watch glass, a glass dish,
and a cover glass, respectively. The broad ring-like sedimentation patterns were formed within several hours in suspension
state for all the substrates used. Colorful macroscopic broad ring-like drying patterns were formed for the three substrates.
In a watch glass, macroscopic drying patterns were composed of the outer and inner layers of small and large spheres, respectively.
The two colored layers were ascribed to the Bragg diffractions of light by the dried colloidal crystals of the corresponding
spheres. The width ratio of the layers changed in proportion to the mixing ratio of each spheres. In a glass dish, wave-like
macroscopic drying patterns were observed in the intermediate areas between the outside edges of the broad ring and the inner
wall of the cell. On a cover glass, the sphere mixing ratios were analyzed from the widths of the drying broad rings of the
small spheres at the outside edge. High and distinct broad rings of small spheres and the low and vague broad one formed at
the outer edges and in the inner area, respectively. Drying dissipative pattern was clarified to be one of the novel analysis
techniques of colloidal size in binary colloidal mixtures. 相似文献
9.
The sedimentation and drying dissipative structural patterns were formed during the course of drying ternary mixtures of colloidal silica spheres of 183 nm, 305 nm, and 1.205 μm in diameter in aqueous suspension on a watch glass, a glass dish, and a cover glass. The patterns were observed by closed-up pictures, metallurgical optical microscopy, 3D profile microscopy, reflection spectroscopy and AFM images. The concentrations of the three spheres ranged from 0.0023 to 0.0128 keeping the same concentrations for each spheres. Broad ring-like sedimentation patterns were formed within a short time in suspension state especially in a glass dish. In a watch glass, colorful three layered ring-like drying patterns were observed and composed of the outer, middle and inner layers of small, medium, and large spheres, respectively. The three colored segregated layers were formed by the balancing between the outward convectional flow and the inward sedimentation of spheres. In a glass dish, wave-like macroscopic drying patterns were observed in the intermediate areas between the outside edge of the broad ring at the central area and the inner wall of the cell especially at low sphere concentrations. The size of the broad ring at the central area increased as sphere concentration increased. On a cover glass, size segregation also took place, i.e., small, medium, and large spheres located at the outer, medium, and central areas, though these segregations were not so complete compared with those on a watch glass. 相似文献
10.
Tsuneo Okubo Daisuke Suzuki Tomoyo Yamagata Akihiro Katsuno Masashi Mizutani Hiroshi Kimura Akira Tsuchida 《Colloid and polymer science》2011,289(7):807-816
Drying dissipative patterns were observed at 25 °C, 33 °C, and 45 °C on a cover glass, a watch glass, and a Petri glass dish
during the course of dryness of colloidal crystals of the thermo-sensitive gels of poly(N-isopropylacrylamide) (PNIPA). Two kinds of broad rings, i.e., transparent ring at the outside edge and the ring in the inner
area from the edge, were observed. Sizes of the former were the same as those of the initial liquids irrespective of gel concentration,
whereas sizes of the latter decreased as gel concentration decreased. These broad rings were composed mainly of the monomeric
and the agglomerated gel particles, respectively. Formation of the monodispersed agglomerated particles and their ordered
arrays in the inner area of the dried film were observed especially on a Petri glass dish and a watch glass. The important
role of the electrical double layers formed around the agglomerated particles is supported for the ordering of the agglomerated
particles. The essential differences in the drying patterns between PNIPA gel spheres and the typical colloidal particles
did not appear. 相似文献
11.
Drying dissipative patterns of de-ionized suspensions (colloidal crystal-state at high concentrations) of the thermosensitive gels of poly (N-isopropylacrylamide) with various sizes (ca. 400–1,500?nm in diameter at 20?°C) were observed at 20 and 45?°C on a cover glass, a watch glass, and a Petri glass dish. The broad rings were observed and their size decreased as gel concentration decreased. Formation of the monodispersed agglomerated particles and their ordered arrays were observed irrespective of gel size. The macroscopic flickering spoke-like patterns were observed for the gel spheres from 70 to 600?nm in diameter at 20?°C, but almost disappeared for extremely large spheres, poly(N-isopropylacrylamide)(1500-5). This work clarified the formation of the drying microscopic structures of (a) ordered rings, (b) flickering ordered spoke lines, (c) net structure, and (d) lattice-like ordered structures of the agglomerated particles. The ordered rings became rather vague as gel size increased. The large net structures formed so often for large gels. Size effect on the lattice patterns was not recognized so clearly. The role of the electrical double layers around the agglomerated particles and the interaction of the particles with the substrate surfaces during dryness are important for the ordering. The microscopic drying patterns of gel spheres were quite different from those of linear type polymers and also from typical colloidal hard spheres, though the macroscopic patterns such as broad ring formation at the edges of the dried film were similar to each other. 相似文献
12.
Drying dissipative patterns of the linear-type thermosensitive homopolymer poly(N-isopropylacrylamide) lpNIPAm in deionized aqueous solution and suspension were observed on a cover glass, a watch glass, and a Petri glass dish at 22 and 50 °C, respectively. The size and ζ potential of the globule aggregates of lpNIPAm at 47.5 °C were 140 nm in diameter and ?22 mV from the electrophoretic light-scattering measurements. A single broad ring formed in the inner region (on a cover glass and a watch glass) and near the outside edge (in a glass dish) in the macroscopic drying pattern at 22 °C. On the other hand, two to three kinds of broad rings were observed at the outside edge and inner region at 50 °C. Microscopic drying structures of ordered rings, flickering ordered spoke-lines, and net structures of the agglomerated particles were observed. Formation of the similar-sized agglomerates and their ordered arrays were observed during the course of dryness. These results of lpNIPAm at 50 °C are quite similar to the agglomeration and the ordering of the thermosensitive gel spheres of poly(N-isopropylacrylamide), pNIPAm. The surface structures of the similar-sized agglomerates of lpNIPAm will be similar to those of pNIPAm gel spheres, since the chemical components of the homopolymers and the gels are almost the same. The role of the electrical double layers around the agglomerates and their interaction with the substrates are important for the ordering. Dendritic large aggregates (from 50 to 600 μm in size) formed in the presence of sodium chloride. 相似文献
13.
Tsuneo Okubo 《Colloid and polymer science》2011,289(11):1205-1213
Drying dissipative patterns were observed at room temperature on a cover glass, a watch glass, and a Petri glass dish during
the course of dryness of aqueous solution of sodium salts of carboxymethyl cellulose (NaCMC) having different molecular weights
in the presence of sodium chloride and in their absence. Without salt, the polymers were slightly hygroscopic and did not
dry up completely on the substrates. Single crystals of the NaCMC without salt were short rodlike and quite similar to those
of the other polysaccharides studied hitherto, i.e., hydroxypropyl cellulose and sodium dextran sulfate. Morphology of the
polymer crystals were short rods, long dendritic rods, and/or hedrite assemblies depending on location in the dried film and
in the presence of sodium chloride. Spoke-like orientation of the long dendritic rods appeared on a cover glass and a watch
glass especially for NaCMC of low molecular weights. 相似文献
14.
Drying dissipative patterns of de-ionized suspensions (colloidal crystal state above the critical concentrations of crystallization) of the thermo-sensitive gels of poly(N-isopropylacrylamide) with degrees of cross-linking of 10% and 2% (pNIPAm(200–10) and pNIPAm(200–2)) were observed at 20?°C and 45?°C on a cover glass, a watch glass, and a Petri glass dish. The broad rings were observed, and their size decreased as micro-gel concentration decreased. Formation of the monodispersed agglomerated particles and their ordered arrays were observed. Microscopic drying structures of (a) flickering ordered spoke-lines, (b) ordered rings, (c) net structure, and (d) lattice-like ordered structures of the agglomerated particles are observed. The net and lattice structures formed more favorably at high degrees of cross-linking, at high concentrations of the gels, and/or high temperatures. By the addition of sodium chloride, very large dendrite-like and net structures of the large agglomerated particles formed at 20?°C and 45?°C, respectively. Importance of the cooperated convectional flow of the agglomerated particles during the drying processes is supported for the ordered array formation. The role of the electrical double layers around the agglomerated particles and the interaction of the particles with the substrate surfaces during dryness are also important for the ordering. The microscopic drying patterns of gel spheres were different from those of linear type polymers and also from typical colloidal spheres, though the macroscopic patterns of gel system such as broad ring formation at the edges of the dried film were similar to other two systems. 相似文献
15.
Drying dissipative patterns of deionized suspensions (colloidal crystal state at high concentrations) of the thermo-sensitive
gels of poly(N-isopropylacrylamide) with low degree of cross-linking of 0.5% (318 nm and 116 nm in the hydrodynamic diameter at 25 °C and
45 °C) were observed at 20 °C and 45 °C on a cover glass, a watch glass and a Petri glass dish. The broad rings were observed
and their size decreased as micro-gel concentration decreased. Formation of the monodispersed agglomerated particles and their
ordered arrays were observed. This work clarified the formation of the drying microscopic structures of (a) flickering ordered spoke-lines, (b) ordered rings, (c) net structure, and finally (d) lattice-like ordered structures of the agglomerated particles. The net and lattice structures formed more favorably at higher temperatures
and/or higher degree of cross-linking of the gels. Importance of the convectional flow of the agglomerated particles during
the drying processes is supported for the ordered array formation. The role of the electrical double layers around the agglomerated
particles and the interaction of the particles with the substrate surfaces during dryness are also important for the ordering.
The microscopic drying patterns of gel spheres were quite different from those of linear-type polymers and also from typical
colloidal spheres, though the macroscopic patterns such as broad ring formation at the edges of the dried film were similar
to each other. 相似文献
16.
Drying dissipative structures of aqueous solutions of poly-d-lysine hydrobromide, poly-l-lysine hydrobromide, and their low-molecular-weight analogs were studied on a cover glass, a watch glass, and a Petri glass
dish. Size of the broad rings, one of the typical macroscopic patterns, decreased as the solute concentration decreased. Microscopic
drying crystal patterns of polylysine hydrobromides and their low-molecular-weight analogs, i.e., d-, l-, and dl-lysine hydrochloride changed as a function of the distance from the film center, which is one of the typical features of
dissipative crystallization. Macroscopic and microscopic drying patterns were quite similar to each other irrespective of their stereospecificity. The
crystal patterns of the mixtures of poly-d-lysine hydrobromide and poly-l-lysine hydrobromide were also similar to those of the corresponding single-component polymers. The stereospecific effects
were not observed in this work. 相似文献
17.
Drying dissipative patterns of cationic gel crystals of lightly cross-linked poly(2-vinyl pyridine) spheres (AIBA-P2VP, 170?~?180 nm in diameter) were observed on a cover glass, a watch glass, and a Petri glass dish. Convectional patterns were recognized with the naked eyes. Two kinds of the broad rings were observed at the outside edge and inner region in the macroscopic drying pattern, and their size at the inner regions first decreased and then turned to increase as gel concentration decreased. Formation of the similar-sized aggregates, i.e., hierarchical aggregation and their ordered arrays were observed. This work supported strongly the formation of the microscopic drying structures of (a) ordered rings, (b) flickering ordered spoke-lines, (c) net structure, and (d) lattice-like ordered structures of the aggregated particles. The ordering of the similar-sized aggregates of the cationic gel spheres (AIBA-P2VP) in this work is similar to that of the large cationic gel spheres of poly(2-vinyl pyridine) (385?~?400 nm in diameter) and further to that of the anionic thermosensitive gel spheres of poly(N-isopropyl acrylamide). Role of the electrical double layers around the aggregates and their interaction with the substrates during dryness are important for the ordering. The microscopic drying patterns of gel spheres were different from those of linear-type polymers and also from typical colloidal hard spheres, though the macroscopic patterns such as broad ring formation were similar to each other. 相似文献
18.
Tsuneo Okubo 《Colloid and polymer science》2011,289(2):159-167
Drying dissipative patterns were observed at room temperature on a cover glass, a watch glass, and a Petri glass dish during
the course of dryness of aqueous solution of sodium salts of dextran sulfate (NaDSS) having molecular weights of 5000, 36,000 ~ 50,000
and 500,000. These biopolyelectrolytes are one of the typical polysaccharides. The influences of the hexose units upon the
macroscopic and microscopic drying patterns are studied. Formation of some ordered structure is observed for NaDSS in high
polymer concentrations especially on a cover glass. Broad ring size decreased as polymer concentration decreased and/or its
molecular weight increased. Drying patterns are clarified to be formed by the successive and cooperative pattern formation
of convection, sedimentation, and solidification. 相似文献
19.
Dissipative patterns during the course of dryness of aqueous solution of potassium salt of poly(riboadenylic acid) (KPolyA) in the presence of potassium chloride were studied on a cover glass, a watch glass and a glass dish. Accumulation of KPolyA polymers forming the broad ring area and the drastic change in size and shape of the polymer single crystals depending on the location of the dried film, which are the typical effects of the dissipative crystallization, took place. Polymer crystals formed were spherulites, dendritic and rod-like assemblies, which are composed of the single or double helical chains depending on the pH-value of the initial solution. 相似文献
20.
Tsuneo Okubo Syuji Fujii Kodai Aono Yoshinobu Nakamura 《Colloid and polymer science》2013,291(4):1019-1030
Drying dissipative patterns of deionized and colloidal crystal-state suspensions of the cationic gel spheres of lightly cross-linked poly(2-vinyl pyridine) stabilized with poly(ethylene glycol) were observed on a cover glass, a watch glass, and a Petri glass dish. Convectional patterns were recognized with the naked eyes. The broad rings were observed in the drying pattern and their size and width decreased as gel concentration decreased. Formation of the monodispersed agglomerated particles and their ordered arrays were observed. This work clarified the formation of the drying microscopic structures of (a) ordered rings, (b) flickering ordered spoke-lines, (c) net structure, and (d) lattice-like ordered structures of the agglomerated particles. The ordering of the agglomerated particles of the cationic gel spheres is similar to that of the anionic thermo-sensitive gel spheres of poly(N-isopropyl acrylamide). The role of the electrical double layers around the agglomerated particles and the interaction of the particles with the substrates during dryness are important for the ordering. The microscopic drying patterns of gel spheres were different from those of linear-type polymers and also from typical colloidal hard spheres, though the macroscopic patterns such as broad ring formation at the edges were similar to each other. The addition of sodium chloride shifted the microscopic patterns from lattice to net structures. 相似文献