Drying dissipative structures of aqueous solution of poly (ethylene glycol) on a cover glass

Macroscopic and microscopic dissipative structural patterns formed in the course of drying a series of poly (ethylene glycol) (PEG) having molecular weights ranging from 1,000 to 2×10⁶ in aqueous solution have been studied on a cover glass. The broad ring patterns of the hill accumulated with the polymers are formed irrespective of the molecular weights of PEG molecules. The single round hills are formed also in the center in the macroscopic scale, when the molecular weight is large. The characteristic convection flow of the polymers and the interactions among the polymers and substrate are important for the macroscopic pattern formation. Cross-like fractal patterns are observed, especially for the diluted solutions in the microscopic scale. These patterns are determined mainly by the electrostatic and polar interactions between the polymers and/or between the polymer and the substrate in the course of solidification. Interestingly, these microscopic patterns are reflected based on the shape and size of the PEG polymers.     

Drying dissipative structures of the deionized aqueous suspensions of colloidal silica spheres ranging from 29 nm to 1 μm in diameter

Macroscopic and microscopic dissipative structural patterns formed in the course of drying a series of the colloidal silica spheres ranging from 29 nm to 1 m in diameter have been observed in the aqueous deionized suspension on a cover glass. The broad ring patterns of the hill accumulated with the silica spheres are formed around the outside edges in the macroscopic scale for all spheres examined. The spoke-like cracks are also observed in the macroscopic scale and their number decreases sharply as sphere size increases. The pattern area and the time for the dryness have been discussed as a function of sphere size and concentration. The convection flow of water accompanied with that of the silica spheres and interactions among the silica spheres and substrate are important for the macroscopic pattern formation. The microscopic fractal structures of the wave-like patterns and branched strings are formed. Their fractal dimensions are determined. Microscopic patterns form in the narrow range of sphere sizes and concentrations and are determined mainly by the electrostatic and polar interactions between the spheres and/or between the sphere and substrate in the course of solidification.     

Drying dissipative structures of Chinese black ink on a cover glass and in a dish

Macroscopic and microscopic dissipative structural patterns are formed in the course of drying a suspension of Chinese black ink on a cover glass and in a dish. The time for the drying and the pattern area increased as the particle concentration increased. The broad ring patterns of the hills accumulated with the particles formed around the outside edges on a macroscopic scale. The height and the width of the broad ring increased as the particle concentration increased. The spokelike patterns of the rims accumulated with particles were also formed on a macroscopic scale. Microscopic patterns of colloidal accumulation were observed over the whole region of the pattern area. Various types of convection cells were observed on a cover glass and in a dish at 25–80 °C. A time-resolved observation of the drying process was also made. The convections of water and the colloidal particles at different rates under gravity and the translational and rotational Brownian movement of the particles were important for the macroscopic pattern formation. Microscopic patterns were determined by the translational Brownian diffusion of the particles and the electrostatic and the hydrophobic interactions between the particles and/or between the particles and the cell wall in the course of the solidification of the particles.     

Drying dissipative patterns of biological polyelectrolyte solutions

Drying dissipative structural patterns of aqueous solutions of biological polyelectrolytes, sodium poly (α, L-glutamate; NaPGA) and poly (-L-lysine hydrobromide; PLL.HBr), were studied on a cover glass. Below the critical polymer concentration, m* (ca. 0.003 and ca. 0.01 monoM for NaPGA and PLL.HBr, respectively), the dried patterns shrank only around the center of the initial solution area wetted on a cover glass. Above the m* values, on the other hand, the drying pattern extended throughout the initial solution area. The m* values agreed excellently with the critical polymer concentrations, where the surface tensions started to decrease sharply as the polymer concentrations increased. The broad rings were always observed in the drying patterns of any solutions examined. The spoke-like cracks appeared at the polymer concentrations above the m* values and only in the area of the broad rings. Microscopic structures such as cross-like, rod-like, and block-like patterns formed irrespective of polymer concentrations. Especially, the city-road-like microscopic pattern was observed for PLL.HBr solutions, which strongly supports the formation of crystal structures of PLL.HBr that remain in the whole processes of dryness. These patterns were correlated deeply with the crystal-like orientation of the biological polyelectrolytes at the air–solution interfaces.     

Dissipative structures formed in the course of drying the colloidal crystals of silica spheres on a cover glass

Macroscopic and microscopic dissipative structural patterns formed in the course of drying the deionized aqueous colloidal crystal suspensions of silica spheres (diameter: 103 nm) on a cover glass have been observed. Spoke-like and ring-like patterns are formed in the macroscopic scale; the former is the crack in the sphere film and the latter is the hill accumulated with spheres formed around the outside edge. The neighbored inter-spoke angle, thickness of the film, and other morphological parameters have been discussed as a function of sphere concentration, concentration of sodium chloride, and the inclined angle of the cover glass. Fractal patterns of the mud cracks are observed in the microscopic scale. Capillary forces between spheres at the air-liquid surface and the relative rates between the water flow at the drying front and the convection flow of spheres are important for the pattern formation. Electronic Publication     

Dissipative structures formed in the course of drying the aqueous solution of<Emphasis Type="Italic"> n</Emphasis>-dodecyltrimethylammonium chloride on a cover glass

Macroscopic and microscopic dissipative structural patterns are formed in the course of drying an aqueous solution of n-dodecyltrimethylammonium chloride on a cover glass. Broad ring patterns of the hill accumulate with detergent molecules to form around the outside edges of the film solution in the macroscopic scale. The drying time (T) and the pattern area (S) decrease and increase respectively, as the detergent concentration increases. T decreases significantly as the ethanol fraction increases in the aqueous ethanol mixtures, whereas S increases as the fraction increases. Both T and S decrease as the concentrations of KCl, CaCl₂ or LaCl₃ increase. Cross-, branch-, and arc-like microscopic patterns are observed in the separated block regions. The convection of water and detergents at different rates under gravity and the translational and rotational Brownian movement of the latter are important for macroscopic pattern formation. Microscopic patterns are determined by the translational Brownian diffusion of the detergent molecules and the electrostatic and the hydrophobic interactions between the detergents and/or between the detergent and cell wall in the course of the solidification.     

Drying dissipative structures of the aqueous suspensions of monodisperse bentonite particles

Macroscopic and microscopic dissipative structural patterns formed in the course of drying the fractionated and monodisperse bentonite particles (plate-like in their shape) in aqueous deionized suspension and in the presence of NaCl have been studied on a cover glass. The patterns coexisted with the broad ring of the hill accumulated with the particles and with the round hills are formed around the outside edges of the film and in the center, respectively, in the macroscopic scale. By the addition of NaCl the pattern shifts from the broad ring to the round hill in the center. The spoke-like cracks, which have been observed for the suspensions of the spherical particles so often hitherto, are not observed at all for the bentonite suspensions. The characteristic convection flow of the particles and the interactions among the particles and substrate are important for the macroscopic pattern formation. Wrinkled, branch-like and/or star-like fractal patterns are observed in the microscopic scale. These patterns are determined mainly by the electrostatic and polar interactions between the particles and/or between the particle and the substrate in the course of drying.     

Drying dissipative structures of the aqueous solution of sodium <Emphasis Type="Italic">n</Emphasis>-alkyl sulfates on a cover glass

Macroscopic and microscopic dissipative structural patterns formed in the course of drying a series of the anionic detergents, sodium n-alkyl sulfate (n-alkyl = n-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl, and n-octadecyl), on a cover glass have been observed. The broad ring patterns of the hill accumulated with the detergent molecules are formed around the outside edges in the macroscopic scale. The microscopic patterns of the small blocks, star-like patterns, and branched strings are formed. The pattern area and the time for the dryness have been discussed as a function of detergent concentration and the number of carbons of the detergents. The convection flow of water accompanied by the detergent molecules, change in the contact angles at the drying frontier between the solution and substrate in the course of dryness, and interactions among the detergents and substrate are important for macroscopic pattern formation. Microscopic patterns are determined mainly by the shape and size of molecules, translational Brownian movement of detergent molecules, and the electrostatic and hydrophobic interactions between detergents and/or between the detergent and substrate in the course of solidification.     

Drying dissipative structure of sodium dextran sulfate in aqueous solution

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.     

Drying dissipative patterns of aqueous solutions of simple electrolytes and their binary mixtures on a cover glass

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.     

Drying dissipative structures of nonionic surfactants in aqueous solution

Macroscopic and microscopic dissipative structural patterns form in the course of drying a series of aqueous solutions of polyoxyethylenealkyl ethers. The shift from the single round hill with accumulated surfactant molecules to the broad ring patterns of the hill in a macroscopic scale occurs as the HLB (hydrophile-liophile balance) of the surfactant molecules increases. The patterns correlate intimately with the HLB values of the surfactants. Microscopic patterns of small blocks, starlike patterns, and branched strings are formed. The size and shape of the surfactant molecules themselves influence the drying patterns in part. The pattern area and the time to dryness have been discussed as a function of surfactant concentration and HLB of the surfactants. The convection flow of water accompanying the surfactant molecules, the change in the contact angles at the drying frontier between solution and substrate in the course of dryness, and interactions among the surfactants and substrate are important for the macroscopic pattern formation. Microscopic patterns are determined in part by the shape and size of the molecules, translational Brownian movement of the surfactant molecules, and the electrostatic and hydrophobic interactions between surfactants and/or between the surfactant and substrate in the course of solidification.     

Sedimentation and drying dissipative structures of colloidal silica (1.2 μm in diameter) suspensions in a watch glass

Sedimentation and drying dissipative structural patterns formed in the course of drying aqueous suspensions of colloidal silica spheres (1.2 μm in diameter) were observed in the various sizes of watch glasses. The macroscopic broad ring patterns were formed on the inner inclined watch glass in suspension state within a short time after suspension was set. The important role of the convectional flow of water and colloidal spheres for the pattern formation is supported. The influence of sodium chloride was also studied. It was clarified that the sedimentary spheres move toward upper and outer edges along the inclined cell wall by the cell convection and hence the patterns are formed by the balancing between the outside movement and the downward sedimentation of the spheres. Beautiful microscopic drying patterns were also observed from the optical microscopy.     

Drying dissipative structures of thermo-sensitive gel spheres of poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) with low degree of cross-linking

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.     

Drying dissipative patterns of dyes in ethyl alcohol on a cover glass

Drying dissipative structural patterns formed in the course of drying ethyl alcohol solutions of rhodamine 6G, uranine, 7-hydroxy coumarin, and 7-amino-4-(trifluoro methyl)-coumarin are studied on a cover glass. The macroscopic broad ring patterns form for all the solutions examined, which supported importance of the convectional flow of ethyl alcohol and dye solutes. Dried area increases as dye concentration increases above the critical dye concentration. Microscopic fine patterns including street-like, needle-like, and flower-like crystal structures are formed in the solidification processes. Change in the functional side group moieties of the dyes gives the strong effect on the microscopic drying patterns; even the main chemical structures are same. Kinetic aspect of the drying patterns is studied.     

Drying dissipative patterns of aqueous solutions of poly (4-vinyl-N-alkyl-pyridinium halide)

Drying dissipative structural patterns of aqueous solutions of poly (4-vinyl-N-alkyl-pyridinium halide) were studied on a cover glass. The broad rings were observed at the outside edge of the dried film. The broad ring size (or the area of the dried film, S) increased as polymer concentration increased. The broad ring size decreased and then turned to increase when the hydrophobicity of the polymers increased. The drying time from the initial liquid (T) was insensitive to the polymer concentration. But, T was sensitive to the kind of polymers, i.e., hydrophobicity of polycations, and roughly in the opposite order to that of S. Spoke-like macroscopic patterns appeared clearly for poly (4-vinyl-N-n-butylpyridinium bromide) (C4PVP), but were not observed clearly for the other polymers. Cross-like microscopic patterns appeared from which the polymers with the extended conformation are deduced to be crystallized during the course of dryness. The cooperative crystallization took place between the polymer and the salt in the C4PVP + KCl mixtures. When two different polymers were mixed, segregation and then independent crystallization of each single component polymers were observed. The dissipative effect is important for determining of the polymer crystal structure during the course of crystallization.     

Drying dissipative structures of thermosensitive gel spheres of poly (N-isopropylacrylamide). Influence of gel size

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.     

Regular patterns generated by self-organization of ammonium-modified polymer nanospheres

Macroscopic regular stripe-crack patterns have been observed in the course of drying the aqueous suspensions of ammonium-modified polymer nanospheres. These forms emerged because the evaporation of dispersed water and self-assembly of nanospheres originates shrinkage during drying the aqueous suspensions. The drying condition plays an important role as well as the nature of the ammonium-modified polymer nanospheres for the stripe-crack pattern formation. By means of the vertical deposition method, directional stripe-crack patterns have been achieved in the macroscopic scale. Surprisingly, we have still noted an interesting secondary stripe pattern occurred spontaneously on the stripes.     

Drying dissipative structures of lightly cross-linked poly(2-vinyl pyridine) cationic gel spheres stabilized with poly(ethylene glycol) in the deionized aqueous suspension

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.     

Drying dissipative structures of cationic gel spheres of lightly cross-linked poly(2-vinyl pyridine) (170 ∼ 180 nm in diameter) in the deionized aqueous suspension

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.     

Sedimentation and drying dissipative patterns of colloidal silica (560 nm in diameter) suspensions in a glass dish and a watch glass

The sedimentation and drying dissipative structural patterns formed during the course of drying colloidal silica spheres (CS550, 560 nm in diameter) in an aqueous suspension have been studied in a glass dish and a watch glass. Broad ring patterns were formed within 20 min in the suspension state by the convectional flow of the colloidal spheres and water. The sedimentary spheres always moved by the convectional flow of water, and the broad ring patterns became sharp with time. The sharpness of the broad rings was sensitive to the change in the room temperature and/or humidity. Colorful macroscopic structures were composed of the broad ring and wave-like patterns, and further colorful and beautiful microscopic fine patterns formed during the solidification processes based on the convectional and sedimentation structures. The drying patterns of the colloidal suspensions containing sodium chloride were different from the structures of CS550 or sodium chloride individuals, which support the synchronous cooperative interactions between the colloidal spheres and the salts.