Drying dissipative patterns of colloidal crystals of silica spheres in organic solvents

Drying dissipative structural patterns formed in the course of drying colloidal crystals of silica spheres (110 nm in diameter) in water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, diethyl ether, and in the mixtures of ethyl alcohol with the other solvents above have been studied on a cover glass. The macroscopic broad rings were formed in the outside edges of the dried film for all the solvents examined. Furthermore, much distinct broad rings appeared in the inner area when the solvents were ethyl alcohol, methyl alcohol, and their mixtures. Profiles of the thickness of the dried films were sensitive to the organic solvents and explained well with changes in the surface tensions, boiling points, and viscosities of the solvents. The macroscopic and microscopic spoke-like crack patterns formed. The drying area (or the drying time) increased (or decreased) as the surface tension of the solvent decreased. However, the absolute values of these drying parameters are determined also by the boiling points of the solvents. Importance of the fundamental properties of the solvents is supported in addition to the characteristics of colloidal particles in the drying dissipative pattern formation.     

Drying dissipative patterns of the colloidal crystals of silica spheres in an dc-electric field

Drying dissipative structural patterns of the colloidal crystals of silica spheres were studied under an dc-electric field. Platinum plate electrodes of anode and cathode were set on a cover glass. The broad hills accumulated with the spheres were observed at the outer edges of the dried film without and also with the electric fields. The column-like structures were formed by the electric flux, and movement of the spheres took place toward anode. The dried film kept colloidal crystal structure, where the nearest-neighbored spheres contact each other more compactly in the areas closer to the anode. Drying times needed for the complete dryness of the suspensions decreased as the strength of the electric field increased. Addition of sodium chloride to the suspensions retarded the movement of spheres toward the anode substantially.     

Convectional,sedimentation, and drying dissipative patterns of colloidal crystals of poly (methyl methacrylate) spheres on a cover glass

Direct observation of the convectional dissipative patterns was successful during the course of dryness of colloidal crystals of poly (methyl methacrylate) spheres on a cover glass. Formation processes of the convectional patterns of spoke-like lines were observed as a function of sphere size and also sphere concentration. During dryness of the suspensions, the brilliant iridescent colors changed beautifully. Macro- and microscopic drying patterns and thickness profiles of the dried film were observed. Sharp broad rings were observed especially at low sphere concentrations. The water evaporation accompanied with the convectional flow of water and the colloidal spheres played an important role for these dissipative structure formation.     

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     

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.     

Sedimentation and drying dissipative patterns of colloidal crystals of poly(methyl methacrylate) spheres in a glass dish

In a series of our studies on the dissipative structure formation, this work focused on the sedimentation and drying patterns of colloidal crystals of poly(methyl methacrylate) colloidal spheres with different sizes (100, 200, 300, and 1,000 nm in diameter) in a glass dish. During the course of dryness, the brilliant iridescent colors changed. Drying frontier grew from the central area of the cell toward the outside edge. Macroscopic and microscopic drying patterns of the resulting film from dried colloidal suspensions showed outer and inner broad rings. Size of the outer rings increased with increasing sphere concentration but did not altered sphere size, while these factors affected the inner ring size. These observations do not support the pinning effect proposed by Deegan et al.     

Drying dissipative structures of colloidal crystals of silica spheres coated with polymer brushes of poly(carboxymethyl betaine)

Drying patterns of colloidal crystals of colloidal silica spheres coated with the brushes of zwitterionic poly(carboxymethyl betaine) (SiP-PCMB) and their parent silica spheres (SiP) were studied on a cover glass, a watch glass, and a Petri glass dish. Crystal structures kept the whole process of dryness of the suspensions of SiP-PCMB and SiP. Crystal structures of the dried films of SiP-PCMB were kept stable even when the initial suspensions contained 5 mM of sodium chloride, which is the important role of the excluded volume effects of the shells of the polymer brushes. On the other hand, crystal structures of SiP spheres in the dried films were much unstable and melted in the presence of 5 mM sodium chloride. In the suspension state, colloidal crystallization of SiP-PCMB took place stably by the contribution of the excluded volume effects besides the extended electrical double layers compared with that of SiP spheres, where only the double layer effect contributes to the crystallization. The fractal patterns of the complexation of SiP-PCMB or SiP spheres with sodium chloride were observed microscopically in the dried films. Several kinds of dissipative crystallization such as array and/or accumulation of the crystallites were observed, and the importance of the convectional and sedimentation processes during the course of dryness was demonstrated.     

Convectional,sedimentation and drying dissipative patterns of colloidal crystals of poly(methyl methacrylate) spheres on a watch glass

Direct observation of the convectional dissipative patterns at room temperature was successful on a cover glass during the course of dryness of colloidal crystals of poly(methyl methacrylate) colloidal spheres. Formation processes of the convectional patterns of spoke-like lines were observed as a function of sphere size and also sphere concentration. During dryness of the suspensions, the brilliant iridescent colors changed beautifully. Macroscopic and microscopic drying patterns of the dried film were observed. Multiple broad ring-like patterns were observed especially at low sphere concentrations. The water evaporation accompanied with the convectional flow of water and the colloidal spheres played an important role for the dissipative structure formation.     

Sedimentation and drying dissipative patterns of ternary mixtures of colloidal silica spheres having different sizes

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.     

Sedimentation and drying dissipative patterns of binary suspensions of colloidal silica spheres having different sizes

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.     

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.     

Melting temperature of colloidal crystals of monodisperse silica spheres in ethanol-water and ethylene glycol-water mixtures

The melting temperature (T _m) of colloidal crystals of monodisperse silica spheres in ethanol-water and ethylene glycol-water suspensions has been measured by reflection spectroscopy. A sphere of 110 nm in diameter and 0.041 in monodispersity index is used after purification and deionization processes. Transformation from the body-centered cubic lattice to the face-centered cubic lattice subphases is observed as the suspension temperature rises, which is similar to the purely aqueous suspension of the same sphere. A phase diagram including liquid-like and crystal-like structures is obtained in the presence of ion-exchange resins coexisted. The data ofT _m are analyzed successfully with the theory of Williams, Crandall, and Wojtowicz. The heat of melting decreases by the addition of ethanol or ethylene glycol in the mixtures.     

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.     

Kinetic aspects in the drying dissipative crack patterns of colloidal crystals

Kinetics of the dissipative structure formation in the course of drying the colloidal crystals of silica spheres (103 nm in diameter) in aqueous deionized suspension on a rinsed cover glass has been studied by the close-up video observation. The patterns of the broad ring of the hill accumulated with the spheres coexisted with the many spoke-like cracks. The characteristic convection flow of the spheres and the interactions between the spheres and substrate were important for the pattern formation. Cracks formed suddenly in the course of drying along the outside edge first, then toward the center, and stopped around the middle point between the outside edges and the frontier of suspension area. The further growth of the cracks took place at the adjacent place of the previous crack side by side and cooperatively. After the fast formation of these cooperative spoke-like cracks was completed, then all the crack lines further developed very slowly and simultaneously toward the center with the similar rate as that of the movement of the drying frontier of the suspension area toward center. Rates of the fast and slow modes of crack formation were 6.2 mm/s and 0.0098 mm/s, respectively, at the sphere concentration of 0.033 in volume fraction.     

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.     

Sedimentation and drying dissipative patterns of colloidal silica (305 nm in diameter) suspensions in a glass dish and a watch glass

Sedimentation and drying dissipative structural patterns formed in the course of drying colloidal silica spheres (305 nm in diameter) in aqueous suspension have been studied in a glass dish and a watch glass. The broad ring sedimentation patterns formed within several tenth minutes in suspension state by the convectional flow of water and colloidal spheres. The sedimentary spheres always moved by the convectional flow of water, and the broad ring patterns became sharp with time. The width of the broad rings was sensitive to the change in the room temperature and/or humidity. In other words, the patterns became sharp or vague when the room parameters decreased or increased. Colorful macroscopic drying structures were composed of a broad ring and the wave-formed patterns. Iridescent colored fine patterns formed in the solidification processes on the bases of the sedimentation patterns. Beautiful drying patterns were observed for the suspension mixtures of CS300 and NaCl, and were different from the structures of CS300 or NaCl individuals, which support the synchronous cooperative interactions between the colloidal spheres and the salt.     

Drying dissipative structures of the thermosensitive gels of poly(N-isopropyl acrylamide) on a cover glass

Drying dissipative structural patterns of the thermosensitive gels of poly(N-isopropyl acrylamide) were studied on a cover glass. As the temperature of suspension and room rose from 25 to 50 °C, the small size of drying pattern area extended to the beautiful flickering spoke-like ones transitionally at the critical temperature ca. 35 °C. The principal patterns at 25 °C were the single or multiple broad rings of the hill accumulated with the gels. At 50 °C, on the other hand, the flickering spoke-like patterns were observed at the inner area of the broad ring especially at the gel concentrations higher than 1 × 10⁻³ g/ml. These observations support that the extended gels at low temperatures apt to associate weakly to each other, whereas the gels at high temperatures shrink and move rather freely with the convectional flow of water, though the very weak intergel attractions still remain. In the presence of sodium chloride at high temperatures, the cooperative patterns formed between the gel spheres and the salt. The gravitational and Marangoni convectional flow of the gels and the very weak interactions between the gels and substrate (cover glass) are important for the flickering spoke-like pattern formation.     

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.     

Electro-optic effects of colloidal crystals of polymer-modified silica spheres immobilized with gelator

Electro-optic responses of colloidal crystals consist of poly(maleic anhydride-co-styrene)-modified silica spheres (P(MA-ST)/SiO₂) in acetonitrile and the crystals immobilized with a gelator, N-benzyloxycarbonyl-L-isoleucilaminooctadecane (Z-L-Ile-C-18), are studied by reflected-light intensity measurements and time-resolved reflection spectroscopy. Application of an alternating electric field deforms P(MA-ST)/SiO₂ crystal lattices reversibly. The response waveforms from the crystals are dependent on the frequency and strength of the applied electric field; similar dependencies have been qualitatively observed for the colloidal crystals consisting of polystyrene or silica spheres in aqueous media in our previous studies. Both gelated and ungelated P(MA-ST)/SiO₂ crystals change the reflection intensity, however, the amplitude is larger for the latter. The small response for the gelated P(MA-ST)/SiO₂ crystals is attributed to the higher elastic modulus (G). The G value of the gelated P(MA-ST)/SiO₂ crystals in acetonitrile is estimated from the change in the inter-sphere distance to be 8.0 Pa, which is about 2.3 and 2.4 times larger than that for ungelated P(MA-ST)/SiO₂ crystals in acetonitrile and colloidal silica crystals in aqueous media, respectively.