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.     

Generic crack patterns in rubber‐modified polymers under biaxial stress states

The damage mechanisms in three different systems, namely, acrylonitrile‐butadiene‐styrene, methacrylate‐butadiene‐styrene modified poly(vinyl chloride), and styrene‐butadiene‐styrene have been investigated. The damage was analyzed over a range of biaxial stress states with confocal microscopy and scanning electron microscopy. The macroscopic yield followed a linear behavior for all the systems in an octahedral shear stress versus mean stress plot, whereas popular models for this class of materials predicted a nonlinear response. Over a certain range of biaxial stress states, a damage pattern generic to all the systems was observed. The damage pattern consisted of an array of cracks propagating perpendicular to the direction of the maximum tensile principal stress and arranged itself in a more or less periodic fashion. There was also self‐similarity in the patterns at various length scales. Similar patterns have also occurred in several other polymeric systems. The interaction in the ensemble of cracks created seems to lead to stress reduction at the crack tips, thereby limiting the crack sizes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2248–2256, 2003     

Correlation of crack patterns and ring bands in spherulites of low molecular weight poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactic acid)

Only a single type of circular circumferential crack is conventionally reported for poly(l-lactic acid) (PLLA). In this study, PLLA samples were found to exhibit as many as four crack types of different directions and patterns, which cannot be feasibly explained simply by the directional difference in coefficients of thermal expansion. Depending on crystallization temperature (T _c), PLLA crystallizes into ringless or ring-banded spherulites, whereas the crack patterns are dramatically different in these two types of spherulites. In ring-banded spherulites of PLLA crystallized at intermediate T _c, two uniquely different crack types are present: (1) twin circumferential cracks coinciding with the dark–bright and bright–dark boundary and (2) radial short-segmental voids coinciding on the bright bands in spherulites. The radial short-segmental cracks on the bright band of ring-banded spherulites may be caused by PLLA crystals of radial direction with various twisting that contract laterally upon cooling. Only circumferential cracks are present in PLLA crystallized into ringless spherulites, where concentric continuous circumferential cracks are present in the ringless spherulites at low T _c with finer lamellae, but discontinuous and irregular circumferential cracks are present in the ringless spherulites at high T _c with coarse lamellae. Although all cracks are triggered by cooling from T _c, all evidences indicate that the crack patterns and types are highly associated with the lamellar orientation, patterns, and coarseness in spherulites.     

Microflow and crack formation patterns in drying sessile droplets of liposomes suspended in trehalose solutions

Anhydrobiotic preservation potentially provides a means of long-term storage of mammalian cells in carbohydrate glasses under ambient conditions. During desiccation, sessile droplets of glass-forming carbohydrate solutions exhibit complex phenomena, including fluid flow, droplet deformation, and crack formation, all of which may alter the cell preservation efficacy. Cell-sized liposomes were employed as a model system to explore these phenomena in diffusively dried sessile droplets of trehalose solutions. Two factors were identified that strongly influenced the features of the desiccated droplets: the underlying surface and the liposomes themselves. In particular, the surface altered the droplet shape as well as the microflow pattern and, in turn, the moisture conditions encountered by the liposomes during desiccation. A ring deposit formed when the droplets were dried on polystyrene, as would be expected owing to the capillary flow that generally occurs in pinned droplets. In contrast, when dried on the more hydrophilic glass slide, the resulting droplets were thinner, and the liposomes accumulated near their centers, which was an unexpected result likely owing to the glass-forming nature of trehalose solutions. As might be anticipated given the variations in liposome distribution, the choice of surface also influenced crack formation upon continued drying. In addition to providing a preferential path for drying, such cracks are relevant because they could inflict mechanical damage on cells. The liposomes themselves had an even more profound effect on crack formation; indeed, whereas cracks were found in all droplets containing liposomes, in their absence few of the droplets cracked at all, regardless of the surface type. These complex drying dynamics merit further investigation in the development of anhydrobiotic preservation protocols, particularly with regard to the role therein of surface hydrophobicity and the cells themselves.     

Tailoring wettability change on aligned and patterned carbon nanotube films for selective assembly

The effects of oxygen reactive ion etching (RIE) on the surface wettability of aligned carbon nanotube (CNT) films have been systematically investigated. It was found that 3 s of RIE treatment could change the surface of CNT films from hydrophobic to more hydrophilic. The degree of modification in the surface wettability of the film could be controlled by the flow rate of O2 gas during the RIE process. It is proposed that such a surface hydrophobicity change is related to the opened structure and functionalized tip of as-treated CNTs by oxygen reactive ions. More importantly, after the RIE treatment, focused laser pruning was utilized to trim the surface layer of treated CNTs and revert them back to a hydrophobic surface. Combined with the laser pruning technique and O2 RIE treatment, CNT templates with interlaced wettability surfaces in a stripe pattern have been fabricated. It has been demonstrated that this interlaced and structured wettability pattern can be used to selectively assemble microspheres or quantum dots on the aligned CNT films with desired patterns.     

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     

Do directional primary and secondary crack patterns in thin films of maghemite nanocrystals follow a universal scaling law?

Cracks due to a shrinking film restricted by adhesion to a surface are observed in nature at various length scales ranging from tiny crack segments in nanoparticle films to enormous domains observed in the earth's crust. Here, we study the formation of cracks in magnetic films made of maghemite (gamma-Fe2O3) nanocrystals. The cracks are oriented by an external magnetic field applied during the drying process which presents a new method to produce directional crack patterns. It is shown that directional and isotropic crack patterns follow the same universal scaling law with the film height varying from micrometer to centimeter scales. Former experimental studies of scaling laws were limited to small variations in height (1 order of magnitude). The large variation in height in our experiments becomes possible due to the combined use of nanocrystals and electron microscopy. A simple two-dimensional computer model for elastic fracture leads to structural and scaling behaviors, which match those observed in the experiments.     

On the effect of the different notching techniques on the fracture toughness of PETG

The fracture toughness of poly (ethylene terephthalate) modified glycol (PETG) has been evaluated using notch sharpening techniques which could be grouped into contact and non-contact procedures. Razor blade tapping, razor blade sliding, razor pressing and broaching are part of the first group, while the femtolaser technique belongs to the second one. Not all the contact procedures generated valid sharp cracks for fracture parameter assessment; indeed none of the samples sharpened via razor sliding generated acceptable sharp cracks. The results revealed that the non-contact femtolaser technique produced the sharpest cracks in this polymer, with crack tip radii of only 0.5 μm, leading to the lowest fracture toughness values. On the contrary, the traditional notch sharpening technique based on razor tapping, recommended in ISO, ESIS and ASTM protocols and standards, generated larger crack tip radii than those introduced via femtolaser and, consequently, resulted in higher fracture toughness values. Both broaching and pressing methods created specimens with smaller crack tip radii compared to those obtained by razor tapping, and hence resulting in intermediate fracture toughness values.     

Fabrication of Gold Nano‐Structures with Azopolymer Templates

Fabrication of gold nano‐patterns has been demonstrated employing surface relief structures created on films of an azobenzene‐functionalized polymer as templates. The surface relief templates were photoinscribed on the azopolymer films in one‐step with two laser beams. Thin layers of gold were over‐coated on the polymer templates by thermal evaporation. Gold lines of a few hundred nanometer width were successfully fabricated by pyrolyzing the azobenzene polymer. Sub‐micron gold dots were also created. The resulting gold structures exhibited the same periodicity as the polymer templates.     

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.     

Moiré pattern nanopore and nanorod arrays by focused ion beam guided anodization and nanoimprint molding

Nanoporous anodic aluminum oxide has been intensively studied as templates in the fabrication of various nanomaterials. Most of the research focuses on highly ordered hexagonal nanopore arrangement with homogeneous area-specific pore density. Anodic aluminum oxide with alternating area-specific nanopore densities has seldom been addressed. In this study, focused ion beam patterned concave arrays created by overlapping two periodic patterns show the exceptional ability of guiding the subsequent anodization and fabricating porous anodic aluminum oxide with Moire? patterns, which have a wide range of interpore distances and area-specific pore densities. The periodicity of the Moire? patterns can be predicted by the interpore distance of the initial patterns and the rotation angle. The depth of the nanopores of these Moire? patterns is around 1 μm. Vertically aligned and high aspect ratio h-PDMS nanorod arrays with Moire? pattern arrangements have been successfully synthesized using the patterned porous anodic aluminum oxide as templates.     

Colloidal chemical approaches to inorganic micro- and nanostructures with controlled morphologies and patterns

The controlled synthesis of inorganic micro- and nanostructures with tailored morphologies and patterns has attracted intensive interest because the properties and performances of micro- and nanostructured materials are largely dependent on the shape and structure of the primary building blocks and the way in which the building blocks are assembled or integrated. This review summarizes the recent advances on the solution-phase synthesis of inorganic micro- and nanostructures with controlled morphologies and patterns via three typical colloidal chemical routes, i.e., synthesis based on catanionic micelles, reactive templates, and colloidal crystal templates, with focus on the approaches developed in our lab. Firstly, catanionic micelles formed by mixed cationic/anionic surfactants are used as effective reaction media for the shape-controlled synthesis of inorganic nanocrystals and the solution growth of hierarchical superstructures assembled by one-dimensional (1D) nanostructures. Secondly, reactive template-directed chemical transformation strategy provides a simple and versatile route to fabricate both hollow structures and 1D nanostructures. Thirdly, colloidal crystals are employed as very effective templates for the facile solution-phase synthesis of novel inorganic structures with controlled patterns, such as three-dimensionally (3D) ordered macroporous materials and two-dimensionally (2D) patterned nanoarrays and nanonets. Finally, a brief outlook on the future development in this area is presented.     

Planarizing surface topography by polymer adhesion to water-soluble templates with replicated null pattern

Water-soluble polymer templates are replicated from flat master surface patterns by spin-casting a poly(vinyl alcohol) film-forming solution that solidifies at standard ambient conditions in less than 1 min. The fabricated water-soluble templates are coupled to substrates with surface topography by polymer adhesion with an intervening reactive or photocurable liquid layer. After curing, the resulting two-layer solid structure is subjected to water thereby dissolving the soluble template to expose the underlying polymer adhesive layer with flat surface topography. The results demonstrate a reduction of surface topography from several micrometers to less than 100 nm. The chemical interactions involved in bonding the soluble template to the polymer adhesive and then dissolving are measured by Raman spectroscopy to demonstrate that the constituents comprising the water-soluble template are absent from the surface of the planarization material.     

Experimental studies on dynamic fracture behavior of thin plates with parallel single edge cracks

Dynamic fracture behavior of polymer PMMA thin plates with three- and four-parallel edge cracks was studied by means of the method of caustics in combination with a high-speed Schardin camera. A series of dynamic caustic patterns surrounding the crack tip and fracture path of the specimen were recorded simultaneously by two types of focused images. Some dynamic fracture parameters such as the dynamic stress intensity factor, crack velocity and acceleration were determined. The evolution of dynamic stress intensity factors on the parallel edge cracks, due to the dynamic unloading effect, was analyzed from the viewpoint of the release of elastic strain energy.     

Dependence on strain rate of the nucleation of cracks in polystyrene at 293°K

The processes associated with the deformation and fracture of polystyrene tested in uniaxial tension have been studied over a range of strain rates from 1.4 × 10^?2 to 4.3 × 10^?7 sec^?1 and at constant stresses between 4.1 and 2.9 kg/mm². The effect of strain rate on the surface craze distribution prior to fracture, the fracture stress, the mechanism of nucleation of cracks, and the nature of fracture surfaces associated with slow and fast crack propagation have been determined. The changes in fracture surface appearance have been studied using optical and stereoscan microscopy. The observations are consistent with the model presented in a previous paper. Fracture is preceded by craze formation, cavitation in the craze, coalescence of cavities to form large planar cavities which propagate slowly until a critical stage is reached at which fast crack propagation occurs. The effect of changes of strain rate and material variables on these processes is discussed.     

无电沉积高密度钯金属纳米线阵列

利用介孔氧化硅薄膜作为模板,通过无电沉积路线在介孔薄膜孔道内合成了高密度钯金属纳米线阵列.利用介孔薄膜导向剂的疏水区作为载体,引进钯金属疏水化合物并经热解和还原,得到钯微粒,以此为催化中心引发无电沉积,避免了传统无电沉积复杂的工艺过程.结果表明,纳米线尺寸均一,长径比大于60,完全填充了介孔薄膜的孔道,并可通过介孔模板孔径的选择对纳米线直径加以调控.     

Two-dimensional colloid crystals templated by polyelectrolyte multilayer patterns

In this paper, we demonstrate that two-dimensional (2D) periodic patterns of polyelectrolyte multilayers (PEMs) can be used as surface templates for assembling highly ordered 2D colloidal microarrays. We report detailed structural features of the 2D colloid crystals produced by depositing silica microspheres onto periodic micrometer-scale PEM patterns arrayed in a square or hexagonal lattice with a pattern pitch (approximately) twice the pattern diameter. Analysis of the images of these 2D colloid monolayers reveals that the distributions of the distances by which the adsorbed particles deviate from the corresponding PEM pattern centers are typically bell-shaped, with the majority of the deposited particles located within a relatively short distance from the respective pattern centers. We show that this behavior reflects the effect of the electrostatic focusing force that (occurs because of the finite size of the PEM pattern and) becomes effective when the depositing particle approaches the pattern site to a small distance. Also, in these 2D colloid crystals, the orientations of the off-center displacements of the deposited particles are strongly correlated spatially over the entire sample size. We present experimental evidence that this unusually long-ranged orientational correlation is due to the close spacing of the patterns, which causes an overlap of the excluded volumes between the neighboring deposited particles.     

Characterization and modeling of slow crack growth behaviors of defective high-density polyethylene pipes using stiff-constant K specimen

In this study, slow crack growth (SCG) resistances of defective and normal high density polyethylene (HDPE) pipes were measured using the stiff-constant K (SCK) specimen, where the stress intensity factor (SIF) was maintained at a constant value within a certain crack length range. A significantly reduced SCG resistance was observed in the defective pipe; a detailed procedure for evaluating SCG kinetics using the SCK specimen has been provided herein. The results of a fracture surface analysis indicate that the white window patterns, resulting from poor carbon black dispersion, are the main reason for poor SCG performance. In addition, a crack layer (CL) model was derived for the SCK specimen geometry and was compared with experimental results. It was observed that the crack and process zone growth resistance parameters were significantly lower in the case of the defected pipe than those in the case of the normal pipe.     

Enhancement of char formation of polymer nanocomposites using a catalyst

Clay-based SAN nanocomposites with zinc chloride as a catalyst were prepared by the solvent casting method to explore possible synergistic flame retardant effects involving enhanced char formation using a catalyst and the formation of a surface-protective layer having a clay network structure. Although the heat release rate and total heat release were significantly reduced by the use of this combination, each additive contributed independently without the desired synergism. This is due to the early formation of many small cracks in the surface layer for SAN-clay nanocomposites (vigorous bubbling associated with evolving thermal degradation byproducts were observed in the cracks) while the rapid char formation by zinc chloride occurred only at the late stage of the fire test. Char formation at long times does not prevent the crack formation or crack growth, so that an effective protective surface layer without openings was not obtained.