Mechanical properties of liquid-filled shellac composite capsules

This paper describes the mechanical properties of thin-walled, liquid-filled composite capsules consisting of calcium pectinate and shellac. In a series of experiments we measured the deformation of these particles in a spinning drop apparatus. For different pH-values we studied the elastic properties of these particles and compared the obtained results with the mechanical response measured by squeezing capsule experiments. In analogy to these experiments, we also investigated liquid-filled unloaded calcium pectinate capsules without the addition of shellac. The deformation properties of these experiments and the surface Young moduli were in good agreement. Furthermore we investigated the liquid-filled calcium pectinate and the composite capsules by NMR microscopy. These experiments allowed investigations of the membrane thickness and the kinetics of membrane growing. Additional characterizations by stress controlled small amplitude surface shear experiments of similar composed gel layers provided coherent results for the surface Young modulus.     

Dissolution of iron oxide nanoparticles inside polymer nanocapsules

The structure of poly(organosiloxane) nanocapsules partially filled with iron oxide cores of different sizes was revealed by small angle X-ray scattering and X-ray diffraction. The nanocapsules are synthesized by the formation of a poly(organosiloxane) shell around iron oxide nanoparticles and the simultaneous partial dissolution of these cores. Due to the high scattering contrast of the iron oxide cores compared to the polymer shell, the particle size distribution of the cores inside the capsules can be measured by small angle X-ray scattering. Additional information can be revealed by X-ray diffraction, which gives insights into the formation of the polymer network and the structure of the iron oxide cores. The study shows how the crystallinity and size of the nanoparticles as well as the shape and width of the size distribution can be altered by the synthesis parameters.     

Large Scale Porous Structure in Gels and Relationship with Their Plastic Behavior

Silica gels (classical aerogels and composite aerogels) have been prepared by classical gelation and addition of silica soot in the gelifying solution before gelation. Due to the aggregation mechanisms, these structures are characterized by a fractal organization. The fractal network previously described in the literature (1–100 nm) which results from the aggregation mechanism of the organosiloxane is affected by the addition of the silica soots. Ultra Small Angle X-ray Scattering (USAXS) experiments (done at ESRF) shows that besides the fractal network built by the organosiloxane, the silica soots are forming another porous structure at a higher scale.The mechanical properties seem to be dependent on this large pore structure. Under isostatic pressure, aerogels display an irreversible shrinkage caused by plastic deformation. As a consequence of this plastic shrinkage it is possible to densify, by the pore collapse tending towards the silica glass. The densification mechanism is different from the one obtained by a sintering at high temperature. The pore collapse mechanism is favored by the large pores structure of the composite aerogels, in contrast to viscous sintering.     

Polyamide 6,6 fibers: Tensile deformation behavior and chain scission

The strain dependence of the elastic, anelastic and plastic components of deformation energy was determined by means of cyclic stress-strain experiments for a set of polyamide 6,6 fibers obtained by different processing techniques. Small angle X-ray scattering experiments revealed that the deformation of the supermolecular lattices of the fibers, consisting of crystalline lamellae and amorphous regions, was identical to the macroscopic deformation of the sample.ESR experiments showed that deformation gives rise to chain rupture events obviously occurring in the amorphous regions in all fibers above a critical strain level. The strain dependence of the free radical concentration was found to agree closely with the corresponding behavior of the plastic deformation energy. This indicates that chain rupture events influence stress-strain properties, particularly at large strains. The absolute values of the experimentally determined plastic deformation energy and of the theoretical value, however, calculated from the number and energy balance of ruptured chains, disagree strongly. Possible explanations are free radical recombinations and secondary dissipative processes resulting from chain rupture.     

The influence of anisotropic membrane inclusions on curvature elastic properties of lipid membranes

A membrane inclusion can be defined as a complex of protein or peptide and the surrounding significantly distorted lipids. We suggest a theoretical model that allows for the estimation of the influence of membrane inclusions on the curvature elastic properties of lipid membranes. Our treatment includes anisotropic inclusions whose energetics depends on their in-plane orientation within the membrane. On the basis of continuum elasticity theory, we calculate the inclusion-membrane interaction energy that reflects the protein or peptide-induced short-ranged elastic deformation of a bent lipid layer. A numerical estimate of the corresponding interaction constants indicates the ability of inclusions to sense membrane bending and to accumulate at regions of favorable curvature, matching the effective shape of the inclusions. Strongly anisotropic inclusions interact favorably with lipid layers that adopt saddlelike curvature; such structures may be stabilized energetically. We explore this possibility for the case of vesicle budding where we consider a shape sequence of closed, axisymmetric vesicles that form a (saddle-curvature adopting) membrane neck. It appears that not only isotropic but also strongly anisotropic inclusions can significantly contribute to the budding energetics, a finding that we discuss in terms of recent experiments.     

Influence of temperature on molecular regroupings and chain rupture under stretching deformation of high‐oriented linear polyethylene

Conformational regrouping and rupture of macromolecular chains at different stretching deformation temperatures of highly oriented linear polyethylene samples (monofilaments) were studied. Measurements of the relative concentration of rotational isomers and chain rupture were determined by IR spectroscopy. Regroupings occur in the highly oriented polymer when elastic stretching of the sample exceeds a threshold value, irrespective of deformation temperature; this is assumed to be due to steric conditions that influence the cooperative transition of coiled‐chain isomers in the extended isomeric conformational state. Polymer stretching at elevated temperatures, in comparison with room temperature, occurred at considerably lower loads and showed increases in elastic deformation, extent of conformational regroupings of molecular segments and reduction in the number of macromolecular ruptures. Deformation at identical values was accompanied by a smaller decrease in concentration of coiled‐chain rotational isomers. The number of molecular chain ruptures, which is proportional to stress load, appeared to be unaffected by temperature. It is proposed that the small decreases observed in the content of coiled‐chain isomers and of chain rupture with deformation are facilitated by macromolecular slippage processes that occur through polymer crystallites.     

The dynamics of self-trapped beams of incoherent white light in a free-radical photopolymerizable medium

Detailed experimental studies of the dynamics of self-trapped beams of white light (400-800 nm) in a photosensitive organosiloxane medium are presented. Self-trapped white light beams with similar spatial profiles formed in the organosiloxane at intensities ranging across an order of magnitude (2.7-22.0 W.cm-2). Beam-profiling measurements showed that these spatially and temporally incoherent wave packets propagate without diffracting (broadening) by initiating free-radical polymerization of methacrylate groups and corresponding refractive index changes in the organosiloxane medium. Analyses of their temporal evolution showed that the intensity-dependent behavior of self-trapped white light is similar to that of self-trapped laser light despite the extreme differences in their phase structure and chromaticity; the self-trapped incoherent beams even show the complementary oscillations of width and intensity that is characteristic of self-trapped coherent light. Furthermore, the dynamics of the self-trapped white light beams was found to be strongly correlated to the kinetics of free-radical polymerization and corresponding rates of refractive index changes in the organosiloxane. These studies provide accessible photochemical routes to self-trapped incoherent wave packets, which are extremely difficult to generate in conventional nonlinear optical media that owe their responses to higher-order dielectric susceptibility tensors. This could enable the experimental verification of theoretical models developed for the nonlinear propagation of white light and stimulate research into more complex self-trapping phenomena such as the interactions of self-trapped incoherent beams and spontaneous pattern formation due to modulation instability in a uniform incoherent optical field. These findings also carry potential for the development of self-induced waveguide, optical solder and interconnect technology for incoherent light emitted by incandescent sources or LEDs.     

Release behavior of capsules loaded by volatile liquid in multicores

The vapor release behavior of capsules containing volatile liquids in multicores was derived theoretically and compared with experimental data. The time course of the release amount was expressed by the same polynomial functional form as that for capsules having a single core, neglecting the interaction between the releases from different cores. Alginate capsules containing tea tree oil in multicores prepared by the insolubilization reaction were used for vapor release experiment. The time course of the release amount was well expressed by the polynomial equation suggested by the theory. From the parameters determined by fitting of the data to the theoretical equations, the activation energy for permeation of vapor through the wall membrane was estimated.     

亲水性聚硅氧烷改性天然乳胶的性能

以亲水性聚硅氧烷KGF-903共混改性天然乳胶,通过拉力试验、老化试验、接触角测量和扫描电子显微镜等研究了聚硅氧烷的添加量对天然乳胶力学性能、抗老化性能、亲水性能和表面形貌的影响。结果表明,KGF-903含量在1.5%时拉伸强度有最佳的改性效果;KGF-903添加量约为3%时断裂伸长率达到最大,老化前后的断裂伸长率比改性前分别提高57%和50%。随着KGF-903含量的增加,改性天然乳胶片的水接触角逐渐减小;扫描电子显微镜观察的结果表明,添加聚硅氧烷能改变乳胶的分散状态。利用小试的最佳配方(即KGF-903的添加量为1.5%)生产了2批次医用导尿管,其表面光洁度、导尿管球囊的成品率、管身硬度、连接器与导尿管排泄锥形接口所承受的拉力和充气漏斗与引流漏斗连接处所承受的拉力等均有显著的提高,有效改善了产品的质量。     

Grundzüge der Deformationsprozesse in Metallen

The physical principles of our present understanding of the elastic, the anelastic, and the plastic deformation of metals are discussed. The following specific cases are considered in details.

1. Elastic deformation due to one of the following processes. Energy elasticity, vibrational entropy elasticity, anomalies in the elastic behaviour resulting from lattice instability or ferromagnetism. This behaviour is compared with the entropy and energy elasticity of polymers.
2. Anelastic deformation due to one of the following mechanisms. Difussion of solute atoms and/or point defects, dislocation relaxation, dislocation resonance interaction between dislocations and other lattice defects, migration of grain boundaries, phase boundaries or domain walls.
3. Plastic deformation of pure metals by cooperative shear, dislocation motion, mechanical twinning, martensitic transformations and by diffusion. The effect of alloying on these processes is discussed in the case of solid solutions, ordered alloys and precipitation hardened materials. The dominant deformation modes of polymers are different from those of metals because metals are formed by atoms with relatively isotropic interatomic forces, whereas polymers generally consist of long chains characterized by a strong anisotropy in chemical bonding. This difference makes the deformation stress of polymers and metals depend differently on temperature, pressure, and deformation rate. An other characteristic difference between the deformation of polymers and metals is that metals deform plastically, whereas a large fraction of the so-called plastic deformation of polymers is really anelastic.

     

Characterization of the mechanical properties of cross-linked serum albumin microcapsules: effect of size and protein concentration

A microfluidic technique is used to characterize the mechanical behavior of capsules that are produced in a two-step process: first, an emulsification step to form droplets, followed by a cross-linking step to encapsulate the droplets within a thin membrane composed of cross-linked proteins. The objective is to study the influence of the capsule size and protein concentration on the membrane mechanical properties. The microcapsules are fabricated by cross-linking of human serum albumin (HSA) with concentrations from 15 to 35 % (w/v). A wide range of capsule radii (～40–450 μm) is obtained by varying the stirring speed in the emulsification step. For each stirring speed, a low threshold value in protein concentration is found, below which no coherent capsules could be produced. The smaller the stirring speed, the lower the concentration can be. Increasing the concentration from the threshold value and considering capsules of a given size, we show that the surface shear modulus of the membrane increases with the concentration following a sigmoidal curve. The increase in mechanical resistance reveals a higher degree of cross-linking in the membrane. Varying the stirring speed, we find that the surface shear modulus strongly increases with the capsule radius: its increase is two orders of magnitude larger than the increase in size for the capsules under consideration. It demonstrates that the cross-linking reaction is a function of the emulsion size distribution and that capsules produced in batch through emulsification processes inherently have a distribution in mechanical resistance.     

Protrusion and deformation of an elastic particle at an advancing front interface

The response of an elastic particle to an extensional field close to an advancing liquid–gas interface in a capillary was examined both from an experimental and theoretical viewpoint. Experimental evidence is given on both the protrusion and deformation of an elastic particle at an advancing front interface. To interpret our experimental results, we followed and extended Hoffman's approach to the case of deformable particles. A hybrid approach was followed where the height of the bump was calculated theoretically as an equilibrium between capillary and drag forces for a given deformation of the particle, whereas the latter was supplied by an independent experimental measurement. For an elastic particle, the height of the bump goes through a maximum and further on decay almost linearly when plotted against the dimensionless parameter introduced by Hoffman. The difference between the theoretical prediction and the experimental data is discussed in relation to the asymmetry of the bump profiles observed in the experiment that could be responsible for a larger contribution of capillary forces from those calculated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1362–1374, 2003     

The cooperative role of membrane skeleton and bilayer in the mechanical behaviour of red blood cells

Red blood cell (RBC) shape, behaviour and deformability can be consistently accounted for by a model for the elastic properties of the RBC membrane that includes the elasticity of the membrane skeleton in dilation and shear, and the local and nonlocal resistance of the bilayer to bending. The role of the corresponding energy terms in different RBC shape and deformation situations is analyzed. RBC shape transformations are compared to the shape transformations of phospholipid vesicles that are driven by the difference between the equilibrium areas of the bilayer leaflets (DeltaA0). It is deduced that the skeleton energy contributions play a crucial role in the formation of an echinocyte. The effect of a transformation of the natural biconcave RBC shape into an echinocyte on its resistance to entry into capillary-sized cylindrical tubes is analyzed. It is shown that, during the aspiration of an echinocyte into a pipette, there are two competing skeleton deformation effects, which arise due to skeleton density changes, one due to spicule formation and the other due to deformation induced by micropipette aspiration. Furthermore, the shift of the observed dependence of the projection length on the aspiration pressure of more crenated cells towards higher aspiration pressures can be accounted for by an increase of the equilibrium area difference DeltaA0 and consequent modification of the nonlocal contribution to the cell elastic energy.     

Surface tension in bilayer membranes with fixed projected area

We study the elastic response of bilayer membranes with fixed projected area to both the stretching and shape deformations. A surface tension is associated to each of these deformations. By using model amphiphilic membranes and computer simulations, we are able to observe both the types of deformation, and thus, both the surface tensions, related to each type of deformation, are measured for the same system. These surface tensions are found to assume different values in the same bilayer membrane, in particular, they vanish for different values of the projected area. We introduce a simple theory which relates the two quantities and successfully apply it to the data obtained with computer simulations.     

Shape deformation and recovery of multilayer microcapsules after being squeezed through a microchannel

The deformation and recovery behaviors of multilayer microcapsules were investigated after being forced to flow through a microchannel. The microchannel device with a constriction (5.7 μm in depth) in the middle was designed, and the multilayer microcapsules with different size and layer thickness (and thereby different mechanical strength) were used. Deformation in the microchannel was observed for all the capsules with a size larger than the constriction height, and its extent was mainly governed by the difference between capsule size and constriction height. The squeezed microcapsules could recover their original spherical shape when the deformation extent was smaller than 16%, whereas permanent physical deformation took place when the deformation extent was larger than 34%. The capsules filled with polyelectrolytes could greatly enhance their shape recovery ability due to the higher osmotic pressure in the capsule interior and could well maintain the preloaded low-molecular-weight dyes regardless of the squeezing.     

Adsorption of polymethacrylic acid from aqueous solutions on disperse titanium dioxide

The state of macromolecules of polymethacrylic acid adsorbed on the surface of disperse titanium dioxide was assessed using a combination of the differential concentration approach to the determination of adsorption and methods for determining the size of disperse adsorbents by dynamic light scattering and sedimentation analysis in the field of centrifugal forces. Three sections were found on the isotherm of adsorption: in the first, isolated islands of adsorbed macromolecules formed; in the second, layers of macromolecules with a different degree of deformation were observed; in the third, determining the adsorption of macromolecules is complicated by other accompanying processes, and assessing the state of macromolecules in the adsorption layer becomes difficult.     

Mechanical properties of polyelectrolyte-filled multilayer microcapsules studied by atomic force and confocal microscopy

By using a combination of atomic force and confocal microscopy, we explore the deformation properties of multilayer microcapsules filled with a solution of strong polyelectrolyte. Encapsulation of polyelectrolyte was performed by regulation of the multilayer shell permeability in water-acetone solutions. The "filled"capsules prepared by this method were found to be stiffer than "hollow" ones, which reflects the contribution of the excess osmotic pressure to the capsule stiffness. The force-deformation curves contain three distinct regimes of reversible, partially reversible, and irreversible deformations depending on the degree of compression. The analysis of the shape of compressed capsules and of the inner polyelectrolyte spacial distribution allowed one to relate the deformation regimes to the permeability of the multilayer shells for water and inner polyelectrolyte at different stage of compression.     

Mechanistic model for deformation of polymer nanocomposite melts under large amplitude shear

We report the mechanical response of a model nanocomposite system of poly(styrene) (PS)-silica to large-amplitude oscillatory shear deformations. Nonlinear behavior of PS nanocomposites is discussed with the changes in particle dispersion upon deformation to provide a complete physical picture of their mechanical properties. The elastic stresses for the particle and polymer are resolved by decomposing the total stress into its purely elastic and viscous components for composites at different strain levels within a cycle of deformation. We propose a mechanistic model which captures the deformation of particles and polymer networks at small and large strains, respectively. We show, for the first time, that chain stretching in a polymer nanocomposite obtained in large amplitude oscillatory deformation is in good agreement with the nonlinear chain deformation theory of polymeric networks. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Effect of matrix elasticity on affinity binding and release of bioparticles. Elution of bound cells by temperature-induced shrinkage of the smart macroporous hydrogel

The first step of bacterial or viral invasion is affinity and presumably multisite binding of bioparticles to an elastic matrix like a living tissue. We have demonstrated that model bioparticles such as inclusion bodies (spheres of about 1 microm in size) Escherichia coli cells (rods 1 x 3 microm), yeast cells (8 microm spheres), and synthetic microgel particles (0.4 microm spheres) are binding via different affinity interactions (IgG antibody-protein A, sugar-lectin, and metal ion-chelate) to a macroporous hydrogel (MH) matrix bearing appropriate ligands. The elastic deformation of the MH results in the detachment of affinity bound bioparticles. The particle detachment on elastic deformation is believed to be due to multipoint attachment of the particles to affinity matrix and the disturbance of the distance between affinity ligands when the matrix is deformed. No release of affinity bound protein occurred on elastic deformation. The efficiency of the particle release by the elastic deformation depends on the density of the ligands at the particle surface as well as on the elasticity of the matrix for relatively large particles. The release of the particles occurred irrespectively of whether the deformation was caused by external forces (mechanical deformation) or internal forces (the shrinkage of thermosensitive macroporous poly-N-isopropylacrylamide hydrogel on increase in temperature).