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Composite materials designed by nature, such as nacre, can display unique mechanical properties and have therefore been often mimicked by scientists. In this work, we prepared composite materials mimicking the nacre structure in two steps. First, we synthesized a silica gel skeleton with a layered structure using a bottom-up approach by modifying a sol-gel synthesis. Magnetic colloids were added to the sol solution, and a rotating magnetic field was applied during the sol-gel transition. When exposed to a rotating magnetic field, magnetic colloids organize in layers parallel to the plane of rotation of the field and template the growing silica phase, resulting in a layered anisotropic silica network mimicking the nacre's inorganic phase. Heat treatment has been applied to further harden the silica monoliths. The final nacre-inspired composite is created by filling the porous structure with a monomer, leading to a soft elastomer upon polymerization. Compression tests of the platelet-structured composite show that the mechanical properties of the nacre-like composite material far exceed those of nonstructured composite materials with an identical chemical composition. Increased toughness and a nearly 10-fold increase in Young's modulus were achieved. The natural brittleness and low elastic deformation of silica monoliths could be overcome by mimicking the natural architecture of nacre. Pattern recognition obtained with a classification of machine learning algorithms was applied to achieve a better understanding of the physical and chemical parameters that have the highest impact on the mechanical properties of the monoliths. Multivariate statistical analysis was performed to show that the structural control and the heat treatment have a very strong influence on the mechanical properties of the monoliths.

Soft photonic materials formed from nanoscale colloidal crystals are versatile platforms for sensing and signaling in biomedical, chemical, and mechanical application scenarios. A particularly leve...

Biopolymer aerogels are an emerging class of materials with potential applications in drug delivery, thermal insulation, separation, and filtration. Chitosan is of particular interest as a sustainable, biocompatible, and abundant raw material. Here, we present urea-modified chitosan aerogels with a high surface area and excellent thermal and mechanical properties. The irreversible gelation of an acidic chitosan solution is triggered by the thermal decomposition of urea at 80 °C through an increase in pH and, more importantly, the formation of abundant ureido terminal groups. The hydrogels are dried using either supercritical CO2 drying (SCD) or ambient pressure drying (APD) methods to elucidate the influence of the drying process on the final aerogel properties. The hydrogels are exchanged into ethanol prior to SCD, and into ethanol and then heptane prior to APD. The surface chemistry and microstructure are monitored by solid-state NMR and Fourier transform infrared spectroscopy, scanning electron microscopy, and nitrogen sorption. Surprisingly, large monolithic aerogel plates (70 × 70 mm2) can be produced by APD, albeit at a somewhat higher density (0.17-0.42 g/cm3). The as prepared aerogels have thermal conductivities of ∼24 and ∼31 mW/(m·K) and surface areas of 160-170 and 85-230 m2/g, for SCD and APD, respectively. For a primarily biopolymer-based material, these aerogels are exceptionally stable at elevated temperature (TGA) and char and self-extinguish after direct flame exposure. The urea-modified chitosan aerogels display superior mechanical properties compared to traditional silica aerogels, with no brittle rupture up to at least 80% strain, and depending on the chitosan concentration, relatively high E-moduli (1.0-11.6 MPa), and stress at 80% strain values (σ80 of 3.5-17.9 MPa). Remarkably, the aerogel monoliths can be shaped and machined with standard tools, for example, drilling and sawing. This first demonstration to produce monolithic and machinable, mesoporous aerogels from bio-sourced, renewable, and nontoxic precursors, combined with the potential for reduced production cost by means of simple APD, opens up new opportunities for biopolymer aerogel applications and marks an important step toward commercialization of biopolymer aerogels.

Magnetic hyperthermia has the potential to play an important role in cancer therapy and its efficacy relies on the nanomaterials selected. Superparamagnetic iron oxide nanoparticles (SPIONs) are excellent candidates due to the ability of producing enough heat to kill tumor cells by thermal ablation. However, their heating properties depend strongly on crystalline structure and size, which may not be controlled and tuned during the synthetic process; therefore, a postprocessing is needed. We show how thermal annealing can be simultaneously coupled with ligand exchange to stabilize the SPIONs in polar solvents and to modify their crystal structure, which improves hyperthermia behavior. Using high-resolution transmission electron microscopy, X-ray diffraction, Mössbauer spectroscopy, vibrating sample magnetometry, and lock-in thermography, we systematically investigate the impact of size and ligand exchange procedure on crystallinity, their magnetism, and heating ability. We describe a valid and simple approach to optimize SPIONs for hyperthermia by carefully controlling the size, colloidal stability, and crystallinity.

Magnetic nanoparticles and their ability to convert electromagnetic energy into heat are of explicit interest for various applications. However, precise quantification of their heating efficiency is not always upfront, and several parameters render comparative studies challenging. This paper describes the theory behind lock-in thermography, a new technique for quantifying the heating properties of magnetic nanoparticles. This technique allows the investigation of some of the potential sources of variability: key factors such as magnetic field inhomogeneity and its effects on the heating power are explored in detail. The presented results, obtained from various nanoparticle batches of different origins, highlight the importance of pursuing a standardized and systematic approach when quantifying the heating efficiency of magnetic nanoparticles.

Because of their similarity with extracellular matrix, hydrogels are ideal substrates for cell growth. Hydrogels made of synthetic polymers are excellent alternatives to natural ones and offer the key advantage of precisely controllable degradation times. In this work, hydrogels have been prepared from modified poly(ethylene glycol) macromonomers, functionalized on both ends first with a few lactic acid units, and then with methacrylate groups. A library of hydrogels has been prepared using free- radical polymerization of the macromonomers, by changing both the macromonomer concentration and their type, i.e., the number of lactic acid repeating units. The degradation kinetics of these hydrogels, caused by the hydrolysis of the lactic acid units, have been carefully monitored in terms of swelling ratio, mass loss, and Young’s modulus. A complete mathematical model, accounting for hydrogel degradation, swelling, and reverse gelation, has been developed and used to predict all the measured quantities until complete disappearance of the gels. The model is capable of accurately predicting the time evolution of all the properties investigated experimentally. To the best of our knowledge, this is the first study where such a systematic comparison between model predictions and experimental data is presented.

We have studied the long-term dynamics of shear-induced breakage of individual colloidal clusters, covering a wide range of fractal dimensions, using Stokesian dynamics. We found that the time evolution of the normalized average size of the fragments generated by the breakup process could be scaled using a unique dimensionless time defined by multiplying the real time with the cluster breakage rate constant (τ = t·kB). Clusters with different masses but the same fractal dimension exhibited almost identical breakage dynamics when exposed to equal overall hydrodynamic forces (ηγRg,0²). The steady-state values of the average size, mass, and standard deviation of fragment mass distribution showed a universal scaling depending only on the overall hydrodynamic force, irrespective of the initial cluster properties. We also identified two asymptotic regimes for the evolution of the fractal dimension, ⟨df⟩, of fragments: open clusters (d f ≤ 2.1) produced dense fragments with a limiting ⟨df⟩ ≈ 2.4 ± 0.1; conversely, dense clusters (df ≥ 2.5) produced fragments with ⟨df⟩ ≈ 2.5 ± 0.1.

The ultrasound-induced cleavage of macromolecules has become a routine experiment in the emerging field of polymer mechanochemistry. To date, it has not been conclusively proven whether the molecular weight of a polymer or its contour length is the determining factor for chain scission upon ultrasonication. Here we report comparative experiments that confirm unequivocally that the contour length is the decisive parameter. We utilized postpolymerization modifications of specifically designed precursor polymers to create polymers with identical chain length but different molecular mass. To demonstrate the universality of the findings, two different polymer backbones were utilized—poly(styrene) and poly(norbornene imide alkyne)—whose molecular weights were altered by bromination and removal of pendant triisopropylsilyl protecting groups, respectively. Solutions of the respective polymer pairs were subjected to pulsed ultrasound at 20 kHz and 10.4 W/cm² in order to investigate the chain scission trends. The effects of cleavage and sonochemical treatments were monitored by size exclusion chromatography. In both series, experimental data and calculations show that the molecular weight reduction upon sonication is the same for polymers with the same contour length.

In the present work, the aggregation behavior of polymeric particles possessing different glass transition temperatures (i.e., different "softnesses") has been studied to shed light on the interplay between aggregation and coalescence. In particular, the time evolution of the clusters hydrodynamic and gyration radii as well as of their structure factor has been monitored. With the help of an ad hoc developed deterministic model, based on population balance equations, it was possible to establish a link between the experimentally obtained light scattering data and the predicted particle size distribution. The simplicity of the model, involving one single adjustable parameter based on the coalescence characteristic time, allowed us to obtain a good accordance between simulations and experimental results with little computational effort.

In this work we build on our previous paper (Harshe, Y. M.; Lattuada, M. Langmuir 2012, 28, 283-292) and compute the breakage rate of colloidal aggregates under the effect of shear forces by means of Stokesian dynamics simulations. A library of clusters made of identical spherical particles covering a broad range of masses and fractal dimension values (from 1.8 to 3.0) was generated by means of a combination of several Monte Carlo methods. DLVO theory has been used to describe the interparticle interactions, and contact forces have been introduced by means of the discrete element method. The aggregate breakage process was investigated by exposing them to well-defined shear forces, generated under both simple shear and uniaxial extensional flow conditions, and by recording the time required to reach the first breakage event. It has been found that the breakage rate of clusters was controlled by the potential well between particles as described by DLVO theory. A semiempirical Arrhenius-type exponential equation that relates the potential well to the breakage rate has been used to fit the simulation results. The dependence of the breakage process on the radius of gyration, on the external shear strength, and on the fractal dimension has been obtained, providing a very general relationship for the breakage rate of clusters. It was also found that the fragment mass distribution is insensitive to the presence of electrostatic repulsive interactions. We also clarify the physical reason for the large difference in the breakage rate of clusters between simple shear and the uniaxial extensional flow using a criterion based on the energy dissipation rate. Finally, in order to answer the question of the minimum cluster size that can break under simple shear conditions, a critical rotation number has been introduced, expressing the maximum number of rotations that a cluster exposed to simple shear could sustain before breakage.

The preparation of anisotropic nanoparticles has drawn much attention in the literature, with most of the efforts being dedicated to convex particles. In this work, instead, we present a reliable method to synthesis silica nanobowls with one well-defined opening, covering a broad range of sizes. The nanobowls have been obtained from asymmetrically functionalized silica-polymer Janus nanodumbbells, used as templates, by removing of the polymer. Polystyrene seeds having different sizes as well as surface chemistry have been used as starting material in a two-step seeded emulsion polymerization, which leads to polymer nanodumbbells. These dumbbells are also asymmetrically functionalized due to the presence of silane groups on only one of their two hemispheres. This allows us to selectively coat the silane-bearing hemisphere of the dumbbells with a silica layer by means of a Stoeber process. The silica nanobowls are eventually obtained after either calcination or dissolution of the polymeric template. Depending on the route followed to remove the polymer, nanobowls made of pure silica (from calcination) or hybrid Janus nanobowls with a silica outer shell and a covalently bound hydrophobic polymer layer inside the cavity (from dissolution) could be prepared. The difference between the two types of nanobowls has been proved by electrostatically binding oppositely charged silica nanoparticles, which adhere selectively only on the outer silica part of the nanobowls prepared by polymer dissolution, while they attach both inside and outside of nanobowls prepared by calcination. We also show that selective functionalization of the outer surface of the Janus nanobowls from dissolution is possible. This work is one of the first examples of concave objects bearing different functionalities in the inner and outer parts of their surface.

We combine the analytical theory of nonaffine deformations of noncrystalline solids with numerical Stokesian dynamical simulations to obtain analytical closed-form expressions for the shear modulus of fractal aggregates in shear flows. The proposed framework also provides analytical predictions for the evolution of the fractal dimension df of the aggregate during the aggregation process. This leads to a lower bound on df below which aggregates are mechanically unstable (they possess floppy modes) and cannot survive without restructuring into more compact, higher-df configurations. In the limit of large aggregates, the predicted lower bound is df = 2.407. This result provides the long-sought explanation as to why all experimental and simulation studies in the past consistently reported df ≳ 2.4 for shear-induced colloidal aggregation. The analytical expressions derived here can be used within population balance calculations of colloidal aggregation in shear flows whereby until now the fractal dimension evo...

Sol-gel accompanied by phase separation is an established method for the preparation of porous silica monoliths with well-defined macroporosity, which find numerous applications. In this work, we demonstrate how the addition of (superpara)magnetic nanocolloids as templates to a system undergoing a sol-gel transition with phase separation leads to the creation of monoliths with a strongly anisotropic structure. It is known that magnetic nanocolloids respond to the application of an external magnetic field by self-assembling into columnar structures. The application of a magnetic field during the chemically driven spinodal decomposition induced by the sol-gel transition allows one to break the symmetry of the system and promote the growth of elongated needle-like silica domains incorporating the magnetic nanocolloids, aligned in the direction of the field. It is found that this microstructure imparts a strong mechanical anisotropy to the materials, with a ratio between the Young's modulus values measured in a direction parallel and perpendicular to the one of the field as high as 150, and an overall smaller average macropores size as compared to isotropic monoliths. The microstructure and properties of the porous monoliths can be controlled by changing both the system composition and the strength of the applied magnetic field. Our monoliths represent the first example of materials prepared by magnetically controlling a phase transition occurring via spinodal decomposition.

The aggregates morphology and the aggregation kinetics of a model monoclonal antibody under acidic conditions have been investigated. Growth occurs via irreversible cluster-cluster coagulation forming compact, fractal aggregates with fractal dimension of 2.6. We measured the time evolution of the average radius of gyration,R(g), and the average hydrodynamic radius,R(h), by in situ light scattering, and simulated the aggregation kinetics by a modified Smoluchowski's population balance equations. The analysis indicates that aggregation does not occur under diffusive control, and allows quantification of effective intermolecular interactions, expressed in terms of the Fuchs stability ratio (W). In particular, by introducing a dimensionless time weighed on W, the time evolutions ofR(h)measured under various operating conditions (temperature, pH, type and concentration of salt) collapse on a single master curve. The analysis applies also to data reported in the literature when growth by cluster-cluster coagulation dominates, showing a certain level of generality in the antibodies aggregation behavior. The quantification of the stability ratio gives important physical insights into the process, including the Arrhenius dependence of the aggregation rate constant and the relationship between monomer-monomer and cluster-cluster interactions. Particularly, it is found that the reactivity of non-native monomers is larger than that of non-native aggregates, likely due to the reduction of the number of available hydrophobic patches during aggregation.

We study the first breakage event of colloidal aggregates exposed to shear flow by detailed numerical analysis of the process. We have formulated a model, which uses stokesian dynamics to estimate the hydrodynamic interactions among the particles in a cluster, van der Waals interactions and Born repulsion to describe the normal interparticle interactions, and the tangential interactions through discrete element method to account for contact forces. Fractal clusters composed of monodisperse spherical particles were generated using different Monte Carlo methods, covering a wide range of cluster masses (N(sphere) = 30-215) and fractal dimensions (d(f) = 1.8-3.0). The breakup process of these clusters was quantified for various flow magnitudes (γ), under both simple shear and extensional flow conditions, in terms of breakage rate constant (K(B)), mass distribution of the produced fragments (FMD, f(m,k)), and critical stable aggregate mass (N(c)), defined as the largest cluster mass that does not break under defined flow conditions. The breakage rate K(B) showed a power law dependence on the product of the aggregate size and the applied stress, with values of the corresponding exponents depending only on the aggregate fractal dimension and the type of flow field, whereas the prefactor of the power law relation also depends on the size of the primary particles comprising a cluster. The FMD was fitted by Schultz-Zimm distribution, and the parameter values showed an analogous dependence on the product of the aggregate size and the applied stress similar to the rate constant. Finally, a power law relation between the applied stress and corresponding largest stable aggregate mass was found, with an exponent value depending on the aggregate fractal dimension. This unique and detailed analysis of the breakage process can be directly utilized to formulate a breakage kernel used in solving population balance equations.

In this work we present experimental and simulation analysis of the breakage and restructuring of colloidal aggregates in dilute conditions under shear. In order to cover a broad range of hydrodynamic and interparticle forces, aggregates composed of primary particles with two sizes, d(p) = 90 and 810 nm, were generated. Moreover, to understand the dependence of breakage and restructuring on the cluster structure, aggregates grown under stagnant and turbulent conditions, having substantially different initial internal structures with fractal dimension d(f) equal to 1.7 and 2.7, respectively, were used. The aggregates were broken by exposing them to a well-defined elongational flow produced in a nozzle positioned between two syringes. To investigate the evolution of aggregate size and morphology, respectively, the mean radius of gyration,R(g), and d(f) were monitored during the breakup process using light scattering and confocal laser scanning microscopy. It was found that the evolution of aggregates' fractal dimension during breakage is solely controlled by their initial structure and is independent of the primary particles size. Similarly, the scaling of the steady-stateR(g)vs the applied hydrodynamic stress is independent of primary particle size, however, depends on the history of aggregate structure. To quantitatively explain these observations, the breakage process was modeled using stokesian dynamics simulations incorporating DLVO and contact interactions among particles. The required flow-field for these simulations was obtained from computational fluid dynamics. The complex flow pattern was simplified by considering a characteristic stream line passing through the zone with the highest hydrodynamic stress inside the nozzle, this being the most critical flow condition experienced by the clusters. As the flow-field along this streamline was found to be neither pure simple shear nor pure extensional flow, the real flow was approximated as an elongational flow followed by a simple shear flow, with a stepwise transition between them. Using this approach, very good agreement between the measured and simulated aggregate size values and structure evolution was obtained. The results of this study show that the process of cluster breakup is very complex and strongly depends on the initial aggregate structure and flow-field conditions.

Structures of colloidal gels prepared in the reaction-limited aggregation regime from fluorinated colloidal particles with two different sizes and different salt concentrations have been characterized by combining small-angle and wide-angle light scattering and small-angle neutron scattering techniques. In all cases, the scattering structure factors indicate the coexistence of two types of fractal structures at different scale lengths: a mass fractal scaling at the scale length of the clusters that constitute the gel and a surface fractal scaling for larger scale lengths. It has been found that, at the same particle volume fraction, the mass fractal dimension of the clusters in the gel increases as the primary particle size decreases. On the other hand, we show that both the mass and the surface fractal gel structures are independent of the salt concentration.

The characterization of complex colloidal dispersions is a relevant and challenging problem in colloidal science. In this work, we show how asymmetric flow-field flow fractionation (AF4) coupled to static light scattering can be used for this purpose. As an example of complex colloidal dispersions, we have chosen two systems undergoing aggregation. The first one is a conventional polystyrene latex undergoing reaction-limited aggregation, which leads to the formation of fractal clusters with well-known structure. The second one is a dispersion of elastomeric colloidal particles made of a polymer with a low glass transition temperature, which undergoes coalescence upon aggregation. Samples are withdrawn during aggregation at fixed times, fractionated with AF4 using a two-angle static light scattering unit as a detector. We have shown that from the analysis of the ratio between the intensities of the scattered light at the two angles the cluster size distribution can be recovered, without any need for calibration based on standard elution times, provided that the geometry and scattering properties of particles and clusters are known. The nonfractionated samples have been characterized also by conventional static and dynamic light scattering to determine their average radius of gyration and hydrodynamic radius. The size distribution of coalescing particles has been investigated also through image analysis of cryo-scanning electron microscopy (SEM) pictures. The average radius of gyration and the average hydrodynamic radius of the nonfractionated samples have been calculated and successfully compared to the values obtained from the size distributions measured by AF4. In addition, the data obtained are also in good agreement with calculations made with population balance equations.

We demonstrated previously (Wu, H.; Zaccone, A.; Tsoutsoura, A.; Lattuada, M.; Morbidelli, M. Langmuir 2009, 25, 4715) that, for a colloid stabilized by charges from both polymer chain-end groups and adsorbed sulfonate surfactants, when the surfactant surface density reaches a certain critical value, the shear-induced gelation becomes unachievable at room temperature, even at an extremely large Peclet number, Pe = 4.6 x 10(4). This is due to the presence of the short-range, repulsive hydration force generated by the adsorbed surfactant. In this work, we investigate how such hydration force affects the shear-induced gelation at higher temperatures, in the range between 303 and 338 K. It is found that a colloidal system, which does not gel at room temperature in a microchannel at a fixed Pe = 3.7 x 10(4), does gel when temperature increases to a certain value. The critical initial particle volume fraction for the gelation to occur decreases as temperature increases. These results indicate that the effect of the hydration force on the gelation decreases as temperature increases. Moreover, we have observed that at the criticality only part of the primary particles is converted to the gel network and the effective particle volume fraction forming the gel network does not change significantly with temperature. The effective particle volume fraction is also independent of the surfactant surface coverage. Since the effective particle volume fraction corresponds to space filling requirement of a standing gel network, which is mainly related to the clusters structure, this result indicates that at a given shear rate the cluster structure does not change significantly with the surfactant surface coverage. On the other hand, since the cluster morphology is a strong function of the shear rate, we have observed that when the Peclet number is lowered from Pe = 3.7 x 10(4) to 1.7 x 10(4), the effective particle volume fraction reduces from 0.19 to 0.12 at 313 K.

In this work we studied the effect of intracluster multiple-light scattering on the scattering properties of a population of fractal aggregates. To do so, experimental data of diffusion-limited aggregation for three polystyrene latexes with similar surface properties but different primary particle diameters (equal to 118, 420, and 810 nm) were obtained by static light scattering and by means of a spectrophotometer. In parallel, a population balance equation (PBE) model, which takes into account the effect of intracluster multiple-light scattering by solving the T-matrix and the mean-field version of T-matrix, was formulated and validated against time evolution of the root mean radius of gyration,R(g), of the zero angle intensity of scattered light, I(0), and of the turbidity, tau. It was found that the mean-field version of the T-matrix theory is able to correctly predict the time evolution of all measured light scattering quantities for all sizes of primary particles without any adjustable parameter. The structure of the aggregates, characterized by fractal dimension, d(f), was independent of the primary particle size and equal to 1.7, which is in agreement with values found in literature. Since the mean-field version of the T-matrix theory used is rather complicated and requires advanced knowledge of cluster structure (i.e., the particle-particle correlation function), a simplified version of the light scattering model was proposed and tested. It was found that within the range of operating conditions investigated, the simplified version of the light scattering model was able to describe with reasonable accuracy the time evolution of all measured light scattering quantities of the cluster mass distribution (CMD) for all three sizes of primary particles and two values of the laser wavelength.

The generation and geometrical analysis of clusters composed of rigid monodisperse primary particles with variable fractal dimension, df, in the range from 2.2 to 3 are presented. For all generated aggregate populations, it was found that the dimensionless aggregate mass, i, and the aggregate size, characterized by the radius of gyration, Rg, normalized by the primary particle radius, Rp, follow a fractal scaling, i = kf(Rg/Rp)df. Furthermore, the obtained prefactor of the fractal scaling, kf, is related to df according to kf = 4.46df-2.08, which is in agreement with literature data. For cases when df cannot be directly determined from light scattering or confocal laser scanning microscopy, it can be estimated from its relation with a perimeter fractal dimension, dpf, or a chord fractal dimension, dcf, both obtained from 2D projection of aggregates. A relation between df and dpf of the form df = or-1.5dpf + 4.4 was developed by fitting data obtained in this work for 2.2df3 together with data of Lee and Kramer [Adv. Colloid Interface Sci. 2004, 112(1-3), 49-57] for 1.8df2.4. It was found that the method of determining df via dpf is very robust with respect to an artificially introduced blur. In contrary, a relation between df and dcf could only be established for the case of ideal optical analysis, while the introduction of blur results in a significant effect on the chord length distribution (and its moments), up to the point of impeding the evaluation of dcf. Hence, for compact aggregates, it is recommended to determine df from dpf by applying the proposed relation, which is valid in a broad range of df relevant for industrial praxis, with little effect of blur on it. Apart from scaling relations with respect to aggregate mass and size, it was found that the 3D quantities, i and Rg, can be directly related to the area squared over perimeter, A2/P, and the 2D radius of gyration, Rg,2D, respectively, which are obtained from 2D projections. In particular, the following two relations are provided: i = 4.5(A2/P)0.9 and Rg/Rp = 1.47 (Rg,2D/Rp)0.99.

Janus nanoparticles have been synthesized consisting of approximately 5 nm magnetite nanoparticles coated on one side with a pH-dependent and temperature-independent polymer (poly(acrylic acid), PAA), and functionalized on the other side by a second (tail) polymer that is either a pH-independent polymer (polystyrene sodium sulfonate, PSSNa) or a temperature-dependent polymer (poly(N-isopropyl acrylamide), PNIPAM). These Janus nanoparticles are dispersed stably as individual particles at high pH values and low temperatures, but can self-assemble at low pH values (PSSNa) or at high temperatures (>31 degrees C) (PNIPAM) to form stable dispersions of clusters of approximately 80-100 nm in hydrodynamic diameter. The Janus nanoparticle compositions were verified using FTIR and XPS, and their structures observed directly by TEM. Their clustering behavior is analyzed by dynamic light scattering and zeta potential measurements.

The interfacial film of physically adsorbed ionic amphiphilic molecules on submicron particles dispersed in water was studied by a combination of surface tension measurements, laser light scattering (LLS) and high-shear experiments in a microchannel. General features in the structure and morphology of the molecular film are identified and understood in the framework of the two-step Langmuir adsorption model deduced from the adsorption isotherm. On the basis of this approach, the phase transitions and structural ordering of the film at the solid-liquid interface are analyzed in detail. A novel methodology based on high-shear aggregation experiments subsequently analyzed by means of LLS is proposed and turns out to be able to provide significant information on the phase transitions and structural arrangements of the adsorbed molecules (in substantial agreement with the adsorption isotherm model) as well as on the resulting interactions. Particularly important for applications is the result that, with no added salt, the films on two particles can adhere/fuse, leading to aggregation as long as an uncovered (hydrophobic) patch is present (unsaturated molecular layers). In the opposite case of fully developed layers, by analyzing the mechanism of shear aggregation of charged particles in the low-salt limit, we show that, when the hydrophobic attraction is absent, short-range hydration repulsive forces dominate over Derjaguin-Landau-Verwey-Overbeek (DLVO) forces and adhesion can never be achieved even upon application of very high collision energies. Consistently, a lower limiting boundary for the hydration interaction is calculated and found to be in agreement with data in the literature.

A model has been developed for describing the aggregation process of two fractal clusters under quiescent conditions. The model uses the approach originally proposed by Smoluchowski for the diffusion-limited aggregation of two spherical particles but accounts for the possibility of interpenetration between the fractal clusters. It is assumed that when a cluster diffuses toward a reference cluster their center-to-center distance can be smaller than the sum of their radii, and their aggregation process is modeled using a diffusion-reaction equation. The reactivity of the clusters is assumed to depend on the reactivity and number of their particles involved in the aggregation event. The model can be applied to evaluate the aggregation rate constant as a function of the prevailing operating conditions by simply changing the value of the particle stability ratio, without any a priori specification of a diffusion-limited cluster aggregation, reaction-limited cluster aggregation, or transition regime. Furthermore, the model allows one to estimate the structure properties of the formed cluster after the aggregation, based on the computed distance between the aggregating clusters in the final cluster.

We investigate experimentally the structural properties of colloidal gels, formed under both diffusion-limited and reaction-limited aggregation conditions, using light scattering measurements and compare the results with the literature Monte Carlo (MC) simulations. The scattering structure factors have been measured for the two classes of gels in the range of the particle volume fractions between 0.02 and 0.07. From these, the corresponding fractal dimension values have been estimated. These have been found to be in good agreement with those estimated from the structure factors computed from MC simulated gels. On the basis of our previous research (Lattuada et al. Langmuir 2003, 19, 6312), this confirms that the scattering structure factor of a gel provides erroneously a small fractal dimension value, which decreases as the particle volume fraction increases. Furthermore, it is observed that the average size of the fractal clusters is larger in real gels than in simulated gels.

The effect of the small difference in densities between dispersion medium and polymer particles on the kinetics of fast or diffusion-limited cluster aggregation (DLCA) has been investigated experimentally using small-angle light scattering (SALS). The density of the dispersion medium was tuned by varying the volume fraction of D2O from 0 to 80% so as to investigate the effect of both aggregates sedimentation and buoyancy. It is found that the time evolution of the average radius of gyration, 〈Rg〉 determined by SALS, initially follows the usual DLCA kinetics, i.e., a power law. However, when 〈Rg〉 reaches a certain value, the growth of 〈Rg〉 starts to accelerate. The onset of such acceleration shifts to larger 〈Rg〉 values for smaller density differences between the dispersion medium and the colloidal particles, thus indicating that the acceleration results from the sedimentation or buoyancy of the aggregates that reach a certain size. This is confirmed by the measured dependence of the scattering intensity a...

Gels are complex structures that can be described in terms of the fractal dimension, df, of the clusters that constitute them. Classical techniques, based on the structure factor obtained through scattering measurements, provide erroneous values of df, which differ from the values estimated from the corresponding particle-density correlation function. The source of this error is identified in this work, and a procedure to get the correct value of df from experimental scattering data is indicated.

The stability of a colloidal system composed of styrene-acrylate copolymer particles and potassium stearate (KS) anionic surfactant molecules has been determined in terms of the Fuchs stability ratio, W, as a function of the surfactant concentration, by measuring the initial aggregation kinetics using the small-angle light scattering (SALS) technique. The structure of the particle surface is peculiar, being irregularly patterned, and thus represents a model system to investigate colloidal stability of nonsmooth colloidal particles. From the SALS kinetic experiments, it is found that the stability increases dramatically with KS concentration until the saturation of the available surface occurs. At concentrations higher than the saturation concentration, the W value decreases markedly with KS, as a consequence of attractive depletion forces induced by formation of micelles in the water phase. The adsorption isotherm, determined through the surface tension technique, agrees with the W vs KS behavior, with respect to the onset of saturation and the surface-per-molecule value, and it can be described by the two-step Langmuir isotherm. Static light scattering spectra of the particles at different adsorbed amounts of KS have been fitted by means of the Lorenz-Mie theory and accounting for the experimentally determined particle size distribution. The increase in the particle diameter imputable to KS adsorption is sizable. Stability data measured under high fluid shear in a turbulent capillary (in the absence of any screening salt) fit well into this scenario. However, depletion forces are shown to be noncooperative with turbulent shear in the absence of screening electrolytes.