Surface tension-induced gel fracture. Part 1. Fracture of agar gels

This work involves an experimental investigation of the spreading of liquids on gel layers in the presence of surfactants. Of primary interest is the instability that accompanies the cracking of gels through the deposition and subsequent spreading of a drop of surfactant solution on their surfaces. This instability manifests itself via the shaping of crack-like spreading "arms", in formations that resemble starbursts. The main aim of this study is to elucidate the complex interactions between spreading surfactants and underlying gels and to achieve a fundamental understanding of the mechanism behind the observed phenomenon of the cracking pattern formation. By spreading SDS and Silwet L-77 surfactant solutions on the surfaces of agar gels, the different ways that system parameters such as the surfactant chemistry and concentration and the gel strength can affect the morphology and dynamics of the starburst patterns are explored. The crack propagation dynamics is fitted to a power law by measuring the temporal evolution of the length of the spreading arms that form each one of the observed patterns. The values of the exponent of the power law are within the predicted limits for Marangoni-driven spreading on thick layers. Therefore, Marangoni stresses, induced by surface tension gradients between the spreading surfactant and the underlying gel layer, are identified to be the main driving force behind these phenomena, whereas gravitational forces were also found to play an important role. A mechanism that involves the "unzipping" of the gel in a manner perpendicular to the direction of the largest surface tension gradient is proposed. This mechanism highlights the important role of the width of the arms in the process; it is demonstrated that a cracking pattern is formed only within the experimental conditions that allow S/Δw to be greater than G', where S is the spreading coefficient, Δw is the change in the width of the crack, and G' is the storage modulus of the substrate.     

Condition of lead iodide in the medium of lyophilic sols

The condition of lead chromate in gelatin and agar agar medium has been studied. In presence of agar agar medium the colloid formed is stabilised by lead ions and coagulated by the excess of chromate ions. Lead chromate forms a very stable colloid in the presence of gelatin sol which could not be precipitated by excess of lead ions or chromate ions. Due to the formation of a very stable colloid in gelatin medium, well defined rings of lead chromate are not obtained in gelatin gel.     

Anomalous spreading with Marangoni flow on agar gel surfaces

We have experimentally observed anomalous spreading of aqueous alcohol solutions on flat and rough fractal agar gel surfaces. On flat agar gel surfaces, extremely fast spreading [θ(D)(t) ∝ t(-0.92)] that differs from Tanner's law [θ(D)(t) ∝ t(-0.3)] was observed when the liquid contained over 9 wt % of 1-propanol in which strong Marangoni flow was observed as a fluctuation on the liquid surface. However, on fractal gel surfaces, different spreading dynamics [θ(D)(t) ∝ t(-0.58)] were observed, although Marangoni flow still occurred. We found the surface-dependent spreading can be discussed in terms of competition between Marangoni flow and the pinning effect due to surface roughness.     

On the Spreading of Partially Miscible Liquids

As time proceeds, partially miscible liquids spread as a cap surrounded by a primary film according to power laws, t(n), for both the leading edge (front) and the central cap. The corresponding exponents depend on the thickness, H, of the liquid aqueous substrate and the deviation of concentration from its saturation value, DeltaC=C-C(sat). As long as H is thick enough, here H>/=5 mm, the exponents are n=1/2 and n=1/3 for the front and the central cap, respectively. For thinner layers, H approximately 2 mm, and moderate DeltaC, the spreading is drastically hindered and the measured values can go down to n=0.1, due to the additional friction imposed by the confinement of the convective cells generated by dissolution below the primary film which anchor on the solid surface beneath the liquid substrate. Copyright 2001 Academic Press.     

Formation of Liesegang rings of mercuric chromate and the effect of gel medium on the condition of mercuric chromate

Summary For the formation of well defined Liesegang rings in different gel media, it is essential to study the effect of gel medium on the condition of the insoluble salt. In case of mercuric chromate, the well defined rings were developed in agar agar and starch gel as the sol formed is coagulable by one of the reactants. In gelatin medium, a very stable sol of mercuric chromate is formed, which is coagulated by hydrochloric acid. Beautiful bands of mercuric chromate were formed in gelatin gel only in presence of hydrochloric acid.

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Zusammenfassung Zur Bildung von gut definierten Liesegang-Ringen in verschiedenen Gel-Medien ist es wesentlich, die Wirkung des Gel-Mediums auf die Bedingung des unl?slichen Salzes zu untersuchen. Im Fall von Quecksilber werden die gut definierten Ringe in Agar-Agar und St?rkegel entwickelt, wenn das gebildete Sol durch einen der beiden Reaktanten koaguliert werden kann. In Gelatine wird ein sehr stabiles Sol von Quecksilber-Chromat gebildet, welches durch Salzs?ure koaguliert wird. Sehr sch?ne Ringe von Quecksilbersulfat bilden sich in Gelatinegel nur in Anwesenheit von Salzs?ure.

     

Adsorption-entanglement layers in flowing high molecular weight polymer solutions II. The effect of the nature of the surface

Adsorption-entanglement layers are thick, i.e. multimolecular, layers formed at solid surfaces from solutions of high molecular weight polymers in a state of flow. This publication, the second part of a series of four, is concerned with the effect that the chemical nature of the surface has on formation of these layers. It is shown that for the solutions of polyethylene (PE) and polymethylmethacrylate (PMMA) the layers form most readily on carbon surfaces. Further it is shown that in the case of PE, addition of aluminium stearate can prevent formation of the layers along steel surfaces.These and other effects reported in the paper all bear on actual situations encountered in rheological practice and in particular on the measurement of viscosities. It is concluded that the marked dependence of layer formation on the chemical nature and treatment of the surface is responsible for the differences in viscosity measurements featuring in earlier works by different authors.     

An experimental study of the surface rheology of adsorbed protein layers

Adsorbed gelatin layers have been characterized by measuring the surface equilibrium tension and surface rheological parameters of shear, found by surface creep experiments. After the determination of these parameters the solution below the adsorption layer (gelatin + phosphate buffer) was substituted by a gelatin-free phosphate-buffer-solution. The differences of the parameters calculated before and after the substitution of the bulk phase allowed us to prove some model assumptions of the protein adsorption and to characterize the physical contents of some of the surface rheological parameters determined. The parameters calculated and measured permit the distinction of three different concentration ranges of gelatin:

1. the range of reversible adsorption layer.
2. the ranges of saturated, irreversible adsorption layer, and
3. the range of multilayer formation.

     

Fundamental studies on the intermediate layer of a bipolar membrane V. Effect of silver halide and its dope in gelatin on water dissociation at the interface of a bipolar membrane

The effect of silver ions on the water dissociation of bipolar membranes was first investigated in this paper. To do this, the bipolar membranes were prepared by immersing the anion exchange layers in an AgNO3 solution and then coating a solution of sulfonated polyphenylene oxide (SPPO) on the anion exchange layers. XPS and AES observations indicated that silver at the intermediate layer was in the form of AgCl. The experimental results proved that AgCl has an excellent catalytic function for water dissociation in terms of I-V curves, and the quantity of AgCl played an important role in the behavior of a bipolar membrane. The bipolar membranes with gelatin and the gelatin doped with silver as a catalytic layer were also prepared in the same way, and their I-V behavior and the water dissociation pilot tests were also investigated. The experimental results showed that in the case of gelatin alone, the voltage drop increased slightly at high gelatin concentrations, due mainly to the steric effect and electrostatic interaction, but decreased at low gelatin concentrations due to the hydrophilicity. However, when gelatin was doped with AgCl, the bipolar membranes have an appreciable improvement in both stability and catalytic function, in comparison with those prepared from silver or gelatin.     

Band propagation, scaling laws and phase transition in a precipitate system. I: Experimental study

In the first part of this work, we present an experimental study of the precipitation/redissolution reaction-diffusion system of initially separated components in two distinct organic gels: agar and gelatin. The system is prepared by diffusing a concentrated ammonia solution into a gel matrix that contains nickel sulfate. In agar, the system exhibits a pulse propagation due to the concomitant precipitation reaction between Ni(II) and hydroxide ions and redissolution due to ammonia. At a later stage of propagation, a transition to Liesegang banding is shown to take place. The dynamics of the distance traveled by the precipitation pulse, its width, and mass are shown to exhibit power laws. Moreover, the mass of the bands is shown to oscillate in time, indicating the emergence of a complex mass enrichment mechanism of the formed Liesegang bands. At the microscopic level, we show evidence that the system undergoes a continuous polymorphic transition concomitant with a morphological change whereby the solid in the pulse, which consists of nanospheres of α-nickel hydroxide transforms to form the bands, which consists of larger platelets of β-nickel hydroxide. This clearly indicates the existence of a dynamic Ostwald ripening mechanism that underlies the dynamics on both scales. On the other hand, in gelatin, although we can still obtain similar power laws as in the case of agar, no transition to bands was observed. It is shown that in this case, the propagating pulse is made of nanoparticles of α-nickel hydroxide with an average diameter ~50 nm.     

Influence of bulk elasticity and interfacial tension on the deformation of gelled water-in-oil emulsion droplets: an AFM study

We used atomic force microscopy (AFM) to study the deformation and wetting behavior of large (50-250 microm) emulsion droplets upon mechanical loading with a colloidal glass probe. Our droplets were obtained from water-in-oil emulsions. By adding gelatin to the water prior to emulsification, also droplets with a bulk elasticity were prepared. Systematic variations of surfactant and gelatin concentrations were made, to investigate their effect on the deformation and wetting behavior of the droplets and to identify the contributions of interfacial tension, bulk elasticity, and expelled water. The AFM experiments were performed in force--distance mode and showed on approach a repulsive regime which in many cases was terminated by a jump-in of the probe. In the case of pure water (i.e. gelatin-free) droplets, the repulsive part of the curve showed a good linearity, thus allowing the extraction of an effective droplet spring constant. This quantity was found to decrease on raising the surfactant concentration from below the critical micelle concentration (cmc) to well above the cmc, and its numerical values were found to correspond remarkably well to literature values for the interfacial tension. Our findings indicate that, on gelatin increase inside the droplets, the bulk elasticity gradually becomes dominant and the droplets' stiffness does not depend anymore on surfactant concentration. Also the stability of the droplet interface against wetting, as measured by the force at which the jump-in instability occurs, was enhanced by gelatin. For gelatin concentrations of > or =15 wt %, the droplets were found to behave like purely elastic bodies. Both gelatin and surfactant contribute positively to the stability against interface breakup.     

Effect of the rate of diffusion of ions on the periodic precipitation of silver chromate

The effect of the rate of diffusion on the formation ofLiesegang rings of silver chromate in gelatin and agar agar medium has been studied. The rate of diffusion of silver ions in the agar agar gel is much slower than that in gelatin gel during the formation of rings of silver chromate. If the rate of diffusion of silver ions in agar agar gel is increased, even then rings do not form. The only change brought about by the rate of diffusion is for the distance between the successive rings.

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Zusammenfassung Der Einflu\ der Diffusionsgeschwindigkeit auf die Bildung vonLiesegang-Ringen aus Silberchromat in Gelatine und Agar-Agar wurde untersucht. Die Diffusionsgeschwindigkeit der Silberionen in den Agar-Agar-Gelen ist viel niedriger als in den Gelatinegelen während der Bildung der Ringe von Silberchromat. Wenn die Diffusionsgeschwindigkeit der Silberionen in Agar-Agar-Gelen gesteigert wird, bilden sich schlie\lich überhaupt keine Ringe. Der einzige Einflu\, den die Diffusionsgeschwindigkeit hervorruft, ist also änderung des Abstandes aufeinanderfolgender Ringe.

     

Protein ultrafiltration concentration polarization layer flux resistance I. Importance of protein layer morphology on flux decline with gelatin

The effect of added ethanol and (NH₄)₂SO₄ on the morphology of the gelatin concentration polarization (CP) layer during ultrafiltration (UF) was analyzed using protein ternary phase diagrams, as well as turbidity and intrinsic viscosity measurements. CP layer resistance was characterized by measuring the flux decline index (FDI) of a 0.10 wt% gelatin solution in a dead-end UF system at 40°C. Ethanol concentrations up to 30 wt% produced an aggregated CP layer morphology with a moderate FDI. However, above 30 wt%, a swollen macromolecular gel formed on the membrane surface, resulting in a lower FDI. Low salt levels led to the formation of compact protein particles in the CP layer that had a moderate FDI. In contrast, a concentration of 8 wt% produced a high FDI coacervate structure. The highest FDI was observed at salt concentrations above 12 wt%, where the surface morphology consisted of a dense particulate gel. Overall, the FDI could be altered by a factor of ∼3 by manipulating the concentration of solute in the solution.     

Study of structure and dynamics of gelatin gels by temperature ramped holographic relaxation spectroscopy

A technique combined temperature ramp with holographic relaxation spectroscopy (HRS) is used to investigate on the structure and dynamics of gelatin gels. Two kinds of photochromic probes are used. The first is the gelatin molecule covalently labeled with fluorescein-isothiocyanate. After gelation, some of the labeled gelatin molecules will form the gel and the rest will still be in the sol. Therefore, the mobility of labeled gelatin molecules in the sol and the gel are probed. The translational diffusion coefficient of gelatin molecules in the sol, the gel content and the gel melting temperature at different gelatin concentrations ranging from 1 to 15 weight-% are measured. The second probe is the small fluorescein molecule in the gelatin gel as a tracer. The mobilities of the tracer in the “gel” are probed. An HRS curve with double peaks is observed. It is experimentally proven that this “anomalous” HRS curve is related to the structure of the gelatin gels. During a normal cooling process (2 C/min), two kinds of networks are found. A “coarse” one is formed through the aggregation of collagen-like triple-stranded helices and a “fine” one is formed simply by entanglements between gelatin molecules.     

Characterization of the interaction between gelatin and a spread monolayer of octadecanoic acid

Surface rheological measurements of octandecanoic acid monolayers spread on gelatin solutions were performed. The interaction of the spread monolayer with the gelatin involves a strong rise of the solidity of the surface structure with distinct viscoelastic properties and is comparable with the experimental findings looking into the interaction between gelatin and an ionic surfactant. The results found by the addition of sodium-dodecylsulfate to the gelatin solution are discussed, assuming the formation of a multilayer consisting of octadecanoic acid molecules interacting to a negligible degree with the gelatin-surfactant complexes displaced from the surface. The surface rheological parameters are influenced by both layers in opposition to the dynamic behaviour at compression and dilation described in the first part of this paper. An analogous effect is found if the cationic hexadecyltrimethylammoniurn-bromide is added to the gelatin solution. The influence of CTAB is interpreted as the consequence of a steric hindrance, caused by the concentration of groups with opposite charges on the small polar ranges of the gelatin molecules. As a particular interaction of octadecanoic acid with the complexes is possible, a mixed adsorption layer is formed and the high solidity of the surface layer is prevented by the presence of molecules not interacting with the complexes.     

Drying of DNA droplets

The evaporation kinetics of droplets containing DNA was studied, as a function of DNA concentration. Drops containing very low DNA concentrations dried by maintaining a constant base, whereas those with high concentration dried with a constant contact angle. To understand this phenomenon, the distribution of the DNA inside the droplet was measured using confocal microscopy. The results indicated that the DNA was condensed mostly on the surface of the droplets. In the case of high concentration droplets, it formed a shell, whereas isolated islands were found for droplets of low DNA concentrations. Rheologic results indicate the formation of a hydro gel in the low concentration drops, whereas phase separation between the self-assembled DNA structures and the water phase occurred at higher concentration.     

Microtextured surfaces with gradient wetting properties

Patterned surfaces with microwrinkled surface structures were prepared by thermally evaporating thin aluminum (10-300 nm thick) (Al) layers onto thick prestrained layers of a silicone elastomer and subsequently releasing the strain. This resulted in the formation of sinusoidal periodic surface wrinkles with characteristic wavelengths in the 3-42 μm range and amplitudes as large as 3.6 ± 0.4 μm. The Al thickness dependence of the wrinkle wavelengths and amplitudes was determined for different values of the applied prestrain and compared to a recent large-amplitude deflection theory of wrinkle formation. The results were found to be in good agreement with theory. Samples with spatial gradients in wrinkle wavelength and amplitude were also produced by applying mechanical strain gradients to the silicone elastomer layers prior to deposition of the Al capping layers. Sessile water droplets that were placed on these surfaces were found to have contact angles that were dependent upon their position. Moreover, these samples were shown to direct the motion of small water droplets when the substrates were vibrated.     

Three dimension Liesegang rings of calcium hydrophosphate in gelatin

Three dimensional Liesegang spherical layers of CaHPO₄ in gelatin ball were performed by employing CaCl₂ and Na₂HPO₄ as the inner and outer electrolyte, respectively. Effects of concentrations of inner and outer electrolyte as well as pH on the morphologies of Liesegang rings (LRs) were investigated. As a result, it was observed that the time law, spacing law and width law found in 1D/2D gel systems were obeyed in this 3D gelatin system. The interaction of Ca²⁺ and HPO₄ ^2? with gelatin matrix played a key role to the formation of LRs due to the existence of carboxylic groups on the gelatin chains. Using Ca²⁺ as the inner electrolyte, LRs were prepared. However, employing HPO₄ ^2? as inner electrolyte, LRs were not obtained. Moreover, pH of gelatin solution greatly impacted on the formation of LRs. The number of LRs increased with the decrease of pH, whereas the width inversely decreased. pH 4.40 was a turn point, from which the spacing coefficient abruptly increased as pH increased. All these results indicated that the network was created by the interaction of Ca²⁺ and –COO^? of gelatin chains, which dominated the formation of CaHPO₄ LRs in gelatin.     

Synthetic thermally reversible gel systems. VI

Forming and conditioning thermally reversible aqueous gels of polyacrylyglycinamide (PAG) at various temperatures has little effect on either the melting point (T_m) of the gels or the heat of crosslinking (ΔH_c) except at temperatures where partial hydrolysis can occur. This is added evidence that unlike with gelatin, crystallite formation does not play a role in gel formation. For unfractioned PAG, the linear relationship between the logarithm of molecular weight and 1/T_m predicted and observed for gelatin gels, does not hold. With mixed gelatin-PAG gels, a gelatin/PAG ratio of ≥4 completely inhibits the formation of a PAG gel network. At lower gelatin/PAG ratios, the PAG network forms, and if gelatin is considered as an inert diluent, normal values for the melting points and ΔH_c for PAG gels are observed. At a gelatin/PAG ratio of 4, the presence of PAG reduces the ΔH_c for the gelatin gel by inhibiting the formation of as large or as ordered crystallite crosslinks. To reconcile the problem of aggregation preceding gelation one can assume that M?_w of an aggregate is a linear function of C². If this is done, the same relationship which normally relates C with T_m is obtained. The equilibrium swelling of PAG films in water at 25°C is markedly molecular weight-de-pendent and can vary from below 5 to about 40 wt-% polymer at equilibrium. It has been found that long-term dark storage of dry samples of PAG under ambient temperature conditions results in pronounced decreases in the intrinsic viscosities of their aqueous solutions. It is speculated that this results from weak links, perhaps peroxy, in the polymer backbone. The possible relationship of this phenomenon to the slow stage of the viscosity deterioration of aqueous polyacrylamide solutions is pointed out. The higher viscosity of low DP PAG in 2M NaCNS compared to H₂O and the larger percentage increse of [η] with increasing temperature in the latter, verify the greater solvent power of 2M aqueous thiocyanate for PAG. At a concentration level of 3%, aqueous PAG solutions are almost Newtonian whereas at higher concentrations (5%), the viscosity decreases appreciably with increasing rates of shear. The copolymerization of AG with isopropylacrylamide has been studied and the somewhat unusual results discussed. Copolymers containing an AG mole fraction greater than 0.40 do not exhibit a cloud point up to 100°C. If the isopropylacrylamide mole fraction approaches 0.60, the solutions do not gel down to 0°C. This ability to prepare copolymers over a narrow composition range that neither gel or undergo phase separation in the temperature range 0–100°C is probably related to the random distribution of monomer units in the copolymer backbone.     

The effects of solvent type on the concentration dependence of the compression modulus of thermoreversible isotactic polystyrene gels

Solutions of isotactic polystyrene in either trans-decalin or 1-chlorodecane were transformed into gels by quenching from a high temperature (ca. 180°C) to ?20°C. The relaxation modulus in compression of these gels was measured over a range of concentrations of from 0.04 g/g to 0.40 g/g. At 22°C, the gels show a double logarithmic stress relaxation rate, m, which is higher than for PVC and gelatin gel systems. 120 s isochronal modulus concentration diagrams exhibit non-power law behavior, i.e., not only is the general trend such that the double logarithmic slope decreases with increasing concentration, but there are also regions in which abrupt changes in modulus occur over narrow ranges in concentrations. These features in the concentration dependence of the modulus are less pronounced than those found previously¹ in isotactic polystyrene/cis-decalin gels. The behavior is interpreted to be inconsistent with a fringed micelle picture of the gel structure. Preliminary results are reported indicating that polymer fraction and temperature of gel formation can significantly affect the modulus of the gels.     

Consistency of surface mechanical properties of spread protein layers at the liquid–air interface at different spreading conditions

Π/A isotherms of spread β-lactoglobulin and β-casein at the air–water interface are measured under different spreading conditions. While the isotherms do not show drastic effects of the spreading concentration and the compression rate the interfacial shear rheological behaviour is significantly influenced. In particular, the shear viscosity of β-lactoglobulin layers depend directly on the spreading concentration. Significant viscosity increase is obtained at larger surface pressures when the spreading concentration is increased. In contrast the shear rheology of the spread β-casein layers can be normalised by plotting the viscosities as a function of the surface pressure Π. The different behaviour is discussed in terms of denaturation of the β-lactoglobulin during the monolayer formation process by adsorption from the spread thin protein solution layer.