Cephalopod-Inspired High Dynamic Range Mechano-Imaging in Polymeric Materials
Clough, Jess M. ; Gucht, Jasper van der; Kodger, Thomas E. ; Sprakel, Joris - \ 2020
Advanced Functional Materials (2020). - ISSN 1616-301X
colloids - mechanochemistry - mechanochromism - photonics - polymers
Cephalopods, such as squid, cuttlefish, and octopuses, use an array of responsive absorptive and photonic dermal structures to achieve rapid and reversible color changes for spectacular camouflage and signaling displays. Challenges remain in designing synthetic soft materials with similar multiple and dynamic responsivity for the development of optical sensors for the sensitive detection of mechanical stresses and strains. Here, a high dynamic range mechano-imaging (HDR-MI) polymeric material integrating physical and chemical mechanochromism is designed providing a continuous optical read-out of strain upon mechanical deformation. By combining a colloidal photonic array with a mechanically responsive dye, the material architecture significantly improves the mechanochromic sensitivity, which is moreover readily tuned, and expands the range of detectable strains and stresses at both microscopic and nanoscopic length scales. This multi-functional material is highlighted by creating detailed HDR mechanographs of membrane deformation and around defects using a low-cost hyperspectral camera, which is found to be in excellent agreement with the results of finite element simulations. This multi-scale approach to mechano-sensing and -imaging provides a platform to develop mechanochromic composites with high sensitivity and high dynamic mechanical range.
Fragility and Strength in Nanoparticle Glasses
Scheer, Pieter van der; Laar, Ties van de; Gucht, Jasper van der; Vlassopoulos, Dimitris ; Sprakel, Joris - \ 2017
ACS Nano 11 (2017)7. - ISSN 1936-0851 - p. 6755 - 6763.
colloids - fragility - glasses - microgels - nanoparticles
Glasses formed from nano- and microparticles form a fascinating testing ground to explore and understand the origins of vitrification. For atomic and molecular glasses, a wide range of fragilities have been observed; in colloidal systems, these effects can be emulated by adjusting the particle softness. The colloidal glass transition can range from a superexponential, fragile increase in viscosity with increasing density for hard spheres to a strong, Arrhenius-like transition for compressible particles. However, the microscopic origin of fragility and strength remains elusive, both in the colloidal and in the atomic domains. Here, we propose a simple model that explains fragility changes in colloidal glasses by describing the volume regulation of compressible colloids in order to maintain osmotic equilibrium. Our simple model provides a microscopic explanation for fragility, and we show that it can describe experimental data for a variety of soft colloidal systems, ranging from microgels to star polymers and proteins. Our results highlight that the elastic energy per particle acts as an effective fragility order parameter, leading to a universal description of the colloidal glass transition.
Crystals, glasses and gels : synthesis and phase behavior of soft colloids
Appel, Jeroen - \ 2017
Wageningen University. Promotor(en): Frans Leermakers, co-promotor(en): Joris Sprakel. - Wageningen : Wageningen University - ISBN 9789463430104 - 139
colloids - crystals - gels - phases - physics - colloidal properties - physical chemistry - colloïden - kristallen - gels - fasen (chemie) - fysica - colloïdale eigenschappen - fysische chemie
Colloidal suspensions are an experimental model system for studying structural and mechanical properties of soft materials. These properties are manifested differently in colloidal solid-like phases such as crystals, glasses and gels. To further understand relations between structural and mechanical properties, it is necessary to develop well-defined colloids and employ techniques such as microscopy and rheology to study the structure and mechanics of their suspensions. This thesis presents five experimental chapters dealing with the synthesis and characterization of colloids and their suspensions. The first part of the thesis describes facile synthesis methods for latex, conjugated polymer and microgel colloids. In the second part, measurements of crystal-to-glass and glass-to-gel phase transformations in dense suspensions of microgel particles are presented.
Preparation of polylactide microcapsules at a high throughput with a packed-bed premix emulsification system
Sawalha, Hassan ; Sahin, Sami ; Schroën, Karin - \ 2016
Journal of Applied Polymer Science 133 (2016)24. - ISSN 0021-8995
biomedical applications - colloids - drug-delivery systems - membranes
Core-shell polymer microcapsules are well known for their biomedical applications as drug carriers when they are filled with drugs and gas-filled microcapsules that can be used as ultrasound contrast agents. The properties of microcapsules are strongly dependent on their size (distribution); therefore, equipment that allows the preparation of small and well-defined microcapsules is of great practical relevance. In this study, we made polylactide microcapsules with a packed-bed premix emulsification system that previously gave good results for regular emulsions. Here, we tested it for applicability to a system in which droplets shrank and solidified to obtain capsules. The packed-bed column was loaded with glass beads of different sizes (30-90 μm) at various bed heights (2-20 mm), and coarse emulsions consisting of the polymer, a solvent, and a nonsolvent were pushed repeatedly through this system at selected applied pressures (1-4 bar). The obtained transmembrane fluxes (100-1000 m3 m-2 h-1) were much higher than those recorded for other membrane emulsification techniques. The average size of the obtained microcapsules ranged between 2 and 8 μm, with an average span of about 1; interestingly, the capsules were 2-10 times smaller than the interstitial voids of the beds. The droplets were larger when we used thicker beds and larger glass beads, and these effect correlated with the pore Reynolds number (Rep). Two breakup mechanisms were identified: spontaneous droplet snap-off dominated the system at low Reps, and localized shear forces dominated the system at higher Rep.
Critical Casimir forces for colloidal assembly
Nguyen, V.D. ; Dang, M.T. ; Nguyen, T.A. ; Schall, P. - \ 2016
Journal of Physics-Condensed Matter 28 (2016). - ISSN 0953-8984
assembly - colloids - critical Casimir effect - hydrophobic effect - nanoparticles
Critical Casimir forces attract increasing interest due to their opportunities for reversible particle assembly in soft matter and nano science. These forces provide a thermodynamic analogue of the celebrated quantum mechanical Casimir force that arises from the confinement of vacuum fluctuations of the electromagnetic field. In its thermodynamic analogue, solvent fluctuations, confined between suspended particles, give rise to an attractive or repulsive force between the particles. Due to its unique temperature dependence, this effect allows in situ control of reversible assembly. Both the force magnitude and range vary with the solvent correlation length in a universal manner, adjusting with temperature from fractions of the thermal energy, k B T, and nanometre range to several ten kT and micrometer length scale. Combined with recent breakthroughs in the synthesis of complex particles, critical Casimir forces promise the design and assembly of complex colloidal structures, for fundamental studies of equilibrium and out-of-equilibrium phase behaviour. This review highlights recent developments in this evolving field, with special emphasis on the dynamic interaction control to assemble colloidal structures, in and out of equilibrium.
Adsorption of charged and neutral polymer chains on silica surfaces: The role of electrostatics, volume exclusion, and hydrogen bonding
Spruijt, E. ; Biesheuvel, P.M. ; Vos, W.M. de - \ 2015
Physical Review. E, Statistical nonlinear, and soft matter physics 91 (2015). - ISSN 2470-0045 - 11 p.
polyelectrolyte adsorption - double-layer - free-energy - poly(vinylpyrrolidone) - relaxation - desorption - stability - kinetics - colloids - density
We develop an off-lattice (continuum) model to describe the adsorption of neutral polymer chains and polyelectrolytes to surfaces. Our continuum description allows taking excluded volume interactions between polymer chains and ions directly into account. To implement those interactions, we use a modified hard-sphere equation of state, adapted for mixtures of connected beads. Our model is applicable to neutral, charged, and ionizable surfaces and polymer chains alike and accounts for polarizability effects of the adsorbed layer and chemical interactions between polymer chains and the surface. We compare our model predictions to data of a classical system for polymer adsorption: neutral poly(N-vinylpyrrolidone) (PVP) on silica surfaces. The model shows that PVP adsorption on silica is driven by surface hydrogen bonding with an effective maximum binding energy of about 1.3kBT per PVP segment at low pH. As the pH increases, the Si-OH groups become increasingly dissociated, leading to a lower capacity for H bonding and simultaneous counterion accumulation and volume exclusion close to the surface. Together these effects result in a characteristic adsorption isotherm, with the adsorbed amount dropping sharply at a critical pH. Using this model for adsorption data on silica surfaces cleaned by either a piranha solution or an O2 plasma, we find that the former have a significantly higher density of silanol groups.
Natural nanoparticles in soils and their role in organic-mineral interactions and cooloid-facilitated transport
Regelink, I.C. - \ 2014
Wageningen University. Promotor(en): Rob Comans, co-promotor(en): Liping Weng. - Wageningen : Wageningen University - ISBN 9789462571501 - 221
bodem - bodemchemie - interacties - colloïden - transportprocessen - deeltjes - soil - soil chemistry - interactions - colloids - transport processes - particles
Mineral nanoparticles are naturally present in the soil and play an important role in several soil processes. This thesis uses a combination of novel analytical techniques, among which Field-Flow-Fractionation, to study nanoparticles in soil and water samples. The results show that nanoparticles can be as small as a few nanometer only and play an important role in the transport of phosphorus and trace metals in the environment. Furthermore, Fe-(hydr)oxide nanoparticles play an important role in sequestration of organic matter and phosphate in soils. The adsorption interactions between phosphorus and organic matter have important implications for the predictions of phosphorus-fertility status of the soil because phosphorus becomes more soluble in soils rich in organic matter. Moreover, this thesis shows that Fe-(hydr)oxide nanoparticles form strong aggregates with organic matter and thereby improve aggregate stability and water retention in soils.
The ratio of the lateral correlation length and particle radius determines the density profile of spherical molecules near a fluctuating membrane
Córdoba-Valdés, F. ; Castañeda-Priego, R. ; Timmer, J. ; Fleck, C. - \ 2014
Soft Matter 10 (2014). - ISSN 1744-683X - p. 8475 - 8481.
depletion forces - fluid membranes - lipid bilayers - vesicles - surfaces - colloids - contact - regime
Interactions between membranes and molecules are important for many biological processes, e.g., transport of molecules across cell membranes. However, the detailed physical description of the membrane–biomolecule system remains a challenge and simplified schemes allow capturing its main intrinsic features. In this work, by means of Monte Carlo computer simulations, we systematically study the distribution of uncharged spherical molecules in contact with a flexible surface. Our results show that the distribution for finite size particles has the same simple functional form as the one obtained for point-like particles and depends only on the ratio of the lateral correlation length of the membrane and the radius of the molecules.
Natural amphiphilic proteins as tri-block Janus particles: Self-sorting into thermo-responsive gels
Vries, A. de; Nikiforidis, K. ; Scholten, E. - \ 2014
Europhysics Letters 107 (2014)5. - ISSN 0295-5075 - 6 p.
zein proteins - percolation - hydrogels - colloids
Design of particles for controlled assembly into complex 3D structure has been extensively investigated. However, their use in the preparation of such 3D structures has received less attention due to low availability. Here, we use a Janus-type particle in the form of a tri-block of natural origin, the protein zein, to create such 3D structures in the form of a thermo-responsive gel. Assembly behaviour of the tri-blocks can be initiated onto spherical hydrophobic surfaces, which leads to stacking of the tri-blocks into a space-spanning network. Rheological behaviour is dependent on the interplay between the hydrophobic interactions between the tri-blocks and the solvent quality, and can be used to alter the temperature at which the network collapses and the gel strength decreases by two orders of magnitude, representing a more fluid-like behaviour.
Groepsgedrag op de nanoschaal
Gucht, J. van der - \ 2014
Wageningen : Wageningen University, Wageningen UR - ISBN 9789461739711 - 23
nanotechnologie - colloïden - groepsgedrag - polymeren - nanotechnology - colloids - group behaviour - polymers
Organic monolayers and fluoropolymer brushes : functionalization, stability and tribology
Bhairamadgi, N.S. - \ 2014
Wageningen University. Promotor(en): Han Zuilhof; Cees van Rijn. - Wageningen : Wageningen University - ISBN 9789461739636 - 178
unimoleculaire films - organische verbindingen - organische fluorverbindingen - colloïden - polymeren - adhesie - frictie - oppervlakteverschijnselen - unimolecular films - organic compounds - organofluorine compounds - colloids - polymers - adhesion - friction - surface phenomena
This thesis deals with the adhesion and friction properties of densely grafted and covalently bound fluoropolymer brushes on silicon surfaces with varying thickness and fluorine content. A novel surface-functionalizing method is described using the thiol-yne click (TYC) reaction. The TYC reaction is highly useful for the attachment of functional (bio-)molecules and immobilization of radical initiators onto a surface with high density. Next, the hydrolytic and thermal stability of 24 different types of monolayers on Si(111), Si(100), SiC, SiN, SiO2, CrN, ITO, PAO, Au and stainless steel surfaces was evaluated. Subsequently, based on this outcome, highly stable fluorinated polymers are described as obtained using surface-initiated atom transfer radical polymerization (SI-ATRP) reactions. The effects of thickness and fluorine content on tribological properties of these layers were studied. The adhesion and friction properties were investigated using colloidal probe atomic force microscopy under dry and ambient conditions. The solvent-free lubricating properties of obtained fluoropolymer brushes have been characterized in detail, and demonstrate their potential for e.g., MEMS/NEMS devices.
Towards colloidal size control by precipitation
Lebouille, J.G.J.L. - \ 2014
Wageningen University. Promotor(en): Martien Cohen Stuart; Frans Leermakers; R. Tuinier. - Wageningen : Wageningen University - ISBN 9789461738677 - 151
micellen - colloïden - nanotechnologie - deeltjesgrootte - deeltjesgrootteverdeling - micelles - colloids - nanotechnology - particle size - particle size distribution
Many active ingredients like drugs, preservatives and vitamins are hydrophobic. In most applications for food and pharma, however, they need to be functional in aqueous environments. In order to facilitate their usage in aqueous environments one needs a way to enable the dispersion of hydrophobic compounds into submicron particles in water in a controlled manner. We investigated the stabilization by surfactants and encapsulation into micelles of hydrophobic compounds using the nanoprecipitation method. The research described in this thesis is about building more understanding of the nanoprecipitation method in relation to the relevant physical chemical parameters. The theoretical results led to predictions that were compared to experimental data. For water-soluble surfactants as stabilizers in the nanoprecipitation process a new theory was developed to relate the process parameters to the final particle size. For non-water-soluble surfactants self-consistent field theory was used in order to unravel the structure-function relationship between used copolymer chemistry and the form and morphology of the obtained particles, spherical micelles and their size.
We analyzed new and existing experiments on the nanoprecipitation method using water-soluble surfactants as stabilizers in a systematic manner. These were interpreted in terms of a new theory that links the process and material properties to the final particle size. The nanoprecipitation procedure consists of quenching a polymer solution from a good to a poor solvent containing surfactant solution. Three characteristic time scales can be identified which affect the final particle size. First, the mixing time (τmix) was identified; the time needed to mix the polymer solution (polymer in good solvent) into the surfactant solution (poor solvent). Second, the coalescence time (τcls) was identified; the time needed for the collapsed polymer chains to coalesce into bigger droplets and subsequently to harden out into particles with long term storage stability. Last, the protection time (τpro) was identified; the time that the surfactant molecules need to completely cover the coalescing droplets and by this stop the coalescence of the collapsed polymer chains/droplets. The two latter characteristic times are intrinsic properties of the used solvents, surfactants and polymers and cannot be changed without addition of extra/new molecules. However, the mixing time is the only parameter which can be changed without modifying the material properties of the system. The mixing time can be easily varied by the method of mixing the good and the poor solvent. Using a pipette to mix the two solutions will result in a 'slow' mixing time regime and utilizing for instance an impingent jet mixer can result in a 'fast' mixing regime. For both mixing regimes a clear analytical expression could be derived enabling more efficient experimentation in order to obtain a specific final particle size. For the 'slow' mixing regime the relation between final particle size ()was found only to be dependent of the used polymer concentration (cmp) as ~cmpThe practical interpretation of this analytical expression is rather simple; an eight times higher polymer concentration will result in a two times bigger final particle size. For the 'fast' mixing regime the analytical expression can be interpreted also in an easy way; the faster the mixing the smaller the final particle size. Below a certain value for the mixing time the final particle size attains a plateau value; even faster mixing will not further decrease the final particle size. When using water-soluble surfactants the release of the cargo, which in practice often takes place after significant dilution, is expected to be fast. In order to increase the release of the encapsulated compound(s) in time we incorporated the surfactant functionality into a non-water soluble triblock copolymer. This results, even upon huge dilution, in an extended release profile in time.
We employed self-consistent field theory for non-water-soluble surfactants in order to relate the (block copolymer) surfactant chemistry to the size and composition of the resulting spherical equilibrium micelles. The surfactants, triblock copolymers synthesized via ring-opening polymerization, were employed in the nanoprecipitation process in order to make spherical micelles. The theoretical predictions were compared to the experimental results and it was concluded that self-consistent field theory is an accurate theoretical tool to predict the size of spherical micelles given a certain chemistry and composition of the copolymers and the conditions required to form these micelles.
We experimentally studied whether hydrophobic compounds (polymers, different active ingredients or a mixture of the two) were added in order to verify whether these spherical micelles could be loaded by these compounds. We investigated the encapsulation behavior of these micelles for hydrophobic compounds both theoretically and experimentally and considered the influence of the size for the micelles. From both the theoretical predictions and the experimentally obtained data it followed that these micelles can be used for encapsulation of hydrophobic compounds. Moreover, the theoretical predictions matched with the experimentally obtained data. It was concluded that self-consistent field predictions can be used to predict the size and stability of spherical micelles with encapsulated hydrophobic compounds.
Tuning size and loading is mandatory for passive targeting applications because the particle size mainly determines the biologic faith. In order to enable active targeting, utilizing a targeting moiety and (specific) receptor interaction is needed while maintaining the stealthy nature of the spherical particles. We performed a theoretical self-consistent field study on spherical block copolymer micelles to investigate whether it is feasible to hide the targeting moiety within the micellar corona while maintaining receptor interaction. We determined the maximum interaction distance wherefrom targeting moiety receptor connection can be established and the required energy barrier at different distances. The outcome of these calculations was used to design a (theoretical) optimized system for active targeting.
We used self-consistent field theory to calculate the size, loading and targeting capability of triblock copolymer based micelles enabling both passive and active targeting and verified our calculation results experimentally. Although the active targeting predictions were not verified experimentally we established a design for passive and active targeting micellar applications for, for instance, drug delivery applications while maintaining the stealthy nature of these micelles.
Colloids at liquid interfaces: dynamics and organization
Ershov, D.S. - \ 2014
Wageningen University. Promotor(en): Jasper van der Gucht, co-promotor(en): Martien Cohen Stuart. - Wageningen : Wageningen University - ISBN 9789461738943 - 127
colloïden - oppervlaktechemie - grensvlak - oppervlakteverschijnselen - capillairen - vloeistoffen (liquids) - colloids - surface chemistry - interface - surface phenomena - capillaries - liquids
This thesis deals with spherical microparticles trapped at liquid interfaces. It focuses on two aspects of their behavior: firstly, the effect of the curvature of a liquid interface on interparticle interactions and their organization; secondly, the mobility of particles at visco-elastic interfaces.
In Chapter 2of this thesis we showed that it is possible to induce capillary interactions between spherical microparticles with homogeneous surface chemistry by tailoring the curvature of the liquid interface. If the interfacial curvature is anisotropic, the constraint of constant contact angle along the contact line can only be satisfied if the interface is deformed locally. These deformations create excess surface area, which changes when two particles approach each other. This leads to a change in the surface free energy, which manifests itself as a capillary interaction between the particles.
To study the effect of curvature on the interactions between particles, we created oil-water interfaces of different shape (ellipsoid, dumbbell, torus and squares) and added spherical negatively charged particles that adsorbed at these interfaces. On all these interfaces, we observed quadrupolar capillary interactions that organized the particles into square lattices. The order of this organization increased with increasing curvature anisotropy, indicating that capillary interactions are stronger as well. By contrast, on flat interfaces or on spherical droplets with homogeneous curvature, no attractive interaction was observed and only at very high surface coverage did the particles order in a hexagonal lattice, as a result of repulsive interactions.
In Chapter 3we studied the interface deformations around particles at curved interfaces and the resulting capillary interactions theoretically. We used the finite element method to solve the Young-Laplace equation for the shape of the interface around a particle and calculated the interaction potential between the particles numerically.
The main finding of these calculations is that for an anisotropically curved interface, with two different local principal curvatures, the particle deforms the interface in two ways simultaneously: concave deformation along one principal direction and convex – along the other, thus creating a deformation field with quadrupolar symmetry. Two particles with such deformations interact favorably only if the overlapping deformations are similar (concave-concave, convex-convex), which occurs when they approach each other along one of the two principal directions. Since the two local principal directions are always perpendicular, particles interacting along them will tend to arrange into a square pattern.
As a consequence of the quadrupolar deformation field, two particles approaching each other along a line forming 45 degrees with the principal axes will repel each other (which is confirmed by our observations), because in this case the deformation fields overlap with four different “petals” (2 pairs of concave-convex), and the excessive surface area doesn’t reduce upon approaching, but increases. A system of two particles oriented at an angle with respect to the principal axis is therefore subjected to a torque rotating the axis of the system so that it gets aligned with one of the two principal directions. The torque magnitude reaches its maximum when the system’s axis is at an angle of 45 degrees with respect to the principal direction and decreases to 0 when the axis is aligned with one of the principal directions.
The family of interaction potentials we obtained allows for calculating the minimum deviatoric curvature needed to initialize capillary interactions strong enough to compete with thermal energy, so that a stable organization can be expected. The calculated value was very close to the deviatoric curvature where ordering was observed experimentally in Chapter 2.
In Chapter 4we studied the mobility of 3 mm polystyrene particles in a monolayer of 1.5 mm core-shell microparticles deposited at flat air-water interfaces; all the particles present in the system were stabilized by negative charges.
In this exploratory chapter we made an attempt to characterize the mechanical properties of such monolayers by analyzing the mobility of the larger tracer particles in the monolayer. With increasing particle density of the monolayer, we observed that the mean-square displacement of the tracer particles was reduced, which can be interpreted as an increase of the viscosity of the monolayer. At very high densities the motion of the particles became subdiffusive and confined, pointing at elasticity of the monolayer. We also studied correlated movements between neighboring particles in an attempt to do two-point interfacial microrheology. A comparison between the one-point and two-point methods shows clear indications of heterogeneous dynamics of the tracer particles. Our results therefore call for a further development of two-point microrheology at interfaces.
In Chapter 5we used tracer particles to study the properties of thin cross-linked actin networks deposited at the surface of oil droplets. These networks are a model system for the intracellular actin cortex. We used the generalized Stokes-Einstein relation to extract the complex frequency-dependent shear modulus of such networks from the movement of the added tracer particles. We studied the effects of the length of actin filaments and the cross-linker concentration on the mechanical properties of these layers.
The advantage of this system is that actin networks are freely accessible from the water phase, and therefore can be subjected to in-situ addition of cross-linkers, enzymes or other chemicals of interest. Using this, we managed to show strong stiffening after addition of myosin motor proteins and ATP, which we ascribed to contraction of the actin-myosin network.
Heteroaggregation and sedimentation rates for nanomaterials in natural waters
Quik, J.T.K. ; Velzeboer, I. ; Wouterse, M. ; Koelmans, A.A. ; Meent, D. van de - \ 2014
Water Research 48 (2014)1. - ISSN 0043-1354 - p. 269 - 279.
sedimentatie - zwevende deeltjes - aggregatie - nanotechnologie - emissie - schatting - colloïden - waterstroming - zeewater - oppervlaktewaterkwaliteit - sedimentation - suspended solids - aggregation - nanotechnology - emission - estimation - colloids - water flow - sea water - surface water quality - engineered nanomaterials - silver nanoparticles - carbon nanotubes - manufactured nanoparticles - aggregation kinetics - aquatic environments - ceo2 nanoparticles - organic-matter - fate - exposure
Exposure modeling of engineered nanomaterials requires input parameters such as sedimentation rates and heteroaggregation rates. Here, we estimate these rates using quiescent settling experiments under environmentally relevant conditions. We investigated 4 different nanomaterials (C60, CeO2, SiO2-Ag and PVP-Ag) in 6 different water types ranging from a small stream to seawater. In the presence of natural colloids, sedimentation rates ranged from 0.0001md-1 for SiO2-Ag to 0.14md-1 for C60. The apparent rates of heteroaggregation between nanomaterials and natural colloids were estimated using a novel method that separates heteroaggregation from homoaggregation using a simplified Smoluchowski-based aggregation-settling equation applied to data from unfiltered and filtered waters. The heteroaggregation rates ranged between 0.007 and 0.6Lmg-1 day-1, with the highest values observed in seawater. We argue that such system specific parameters are key to the development of dedicated water quality models for ENMs.
Principles of interactions in non-aqueous electrolyte solutions
Lyklema, J. - \ 2013
Current Opinion in Colloid and Interface Science 18 (2013)2. - ISSN 1359-0294 - p. 116 - 128.
nonpolar-solvents - aerosol ot - ionic association - micelle formation - apolar solvents - media - conductance - stability - water - colloids
In this paper a review is presented on the molecular interactions in non-aqueous media of low dielectric permittivity. Qualitative and quantitative distinctions with aqueous solutions are emphasized. The reviewed themes include dispersion forces, dissociation and association equilibria, discrimination between electrostatic and non-electrostatic interactions, ionic specificity, conductivity, electrokinetics and colloid interaction. Distinctions between so-called primitive and non-primitive interpretations and between individual and collective behavior are discussed; in these respects the colloid stability phenomena behave differently from the corresponding ones in aqueous solvents. (c) 2013 Elsevier Ltd. All rights reserved.
Substitutional impurity-induced vitrification in microgel crystals
Higler, R. ; Appel, J. ; Sprakel, J.H.B. - \ 2013
Soft Matter 9 (2013). - ISSN 1744-683X - p. 5372 - 5379.
medium-range order - metallic glasses - liquids - spheres - scattering - colloids - packing
We study the effect of larger substitutional impurities on the structure of soft microgel crystals. At the size ratio we employ, rsmall/rlarge = 0.67, we observe the unexpected co-crystallisation of the large impurities with the base crystal, at low fractions of impurity particles. A single impurity takes the place of 4 tetrahedrally coordinated small particles within the lattice. However, as this is accompanied by local deformations of the particles, this distortion-minimizing structure transforms into a random surrounding of the impurity particle at higher fractions of large substitutional impurities. The distortions in the lattice become longer ranged through this transformation, and ultimately result in vitrification of the sample
Structure of binary mixed polymer Langmuir layers
Bernardini, C. - \ 2012
Wageningen University. Promotor(en): Martien Cohen Stuart; Frans Leermakers. - S.l. : s.n. - ISBN 9789461732149 - 200
polymeren - colloïden - colloïdale eigenschappen - oppervlakteverschijnselen - polymers - colloids - colloidal properties - surface phenomena
The possibility of preparing 2D stable emulsions through mixing of homopolymers in a Langmuir monolayer is the core topic of this thesis. While colloid science has achieved well established results in the study of bulk dispersed systems, accounts on properties of mixed monomolecular films are fewer, and seldom systematic. The aim of this investigation is to contribute to a deeper understanding of the subject, in order to explore opportunities to apply the acquired knowledge to the fabrication of technologically relevant materials. In particular, this study focused on a possibly applicable, innovative strategy for the manipulation of the morphology and the patterning of mixed Langmuir monolayers: the possibility to stabilize and control a dispersion of homopolymers through the addition of a lineactant (the equivalent of a surfactant in three dimensional systems), able to adsorb preferentially at the interfacial contact line of polymer domains, thereby lowering the interfacial energy (line tension) in the system and favoring an effective dispersion of one component into the other.
The state of the art of the preparation and investigation of 2D colloids is the subject of Chapter 2, which is a comprehensive review on several systems able to yield phase–separated Langmuir monolayers, and includes a general definition of the concept of a 2D colloid, the most relevant instrumental techniques and experimental tools available, a summary of several systems suitable for preparing 2D colloid dispersions, an introduction to the concept of lineactant, and several examples, both experimental and theoretical, in which compounds acting as lineactants have been investigated. This review clearly shows that the polymer–based mixtures are a poorly explored subject, when compared to amphiphiles of natural origin, and so the rest of the thesis has been devoted to the investigation of polymer–based Langmuir monolayers.
This investigation has been carried out with two parallel approaches: classical experiments at the Langmuir trough and morphological characterization of the Langmuir monolayers with the Brewster Angle Microscope have been performed, along with Self–Consistent Field modeling of the same systems. The setup of the SCF model and comparison of SCF calculation with experimental data from the reference experiments are dealt with in Chapter 3. Surface pressure isotherms at the air/water interface were reproduced for four different polymers, poly–l–lactic acid (PLLA), poly (dimethylsiloxane) (PDMS), poly (methyl methacrylate) (PMMA), and poly (isobutylene) (PiB). The polymers are all insoluble in water, but display a different degree of amphiphilicity; therefore the four isotherms differed strongly. The polymers were described through a SCF model on a united atom level, taking the side groups on the monomer level into account. In line with experiments, the model shown that PiB spread in a monolayer which smoothly thickened at a very low surface pressure and area/monomer value. The monolayer made of PMMA had an autophobic behavior: a PMMA liquid did not spread on top of the monolayer of PMMA at the air/water interface. A thicker PMMA layer only formed after the collapse of the film at a relatively high pressure. The isotherm of PDMS had regions with extreme compressibility which were linked to a layering transition. Finally, PLLA wetted the water surface and spread homogeneously at larger areas per monomer. The classical SCF approach features only short–range, nearest–neighbor interactions. For the correct positioning of the layering and for the thickening of the polymer films, a power–law van der Waals contribution was taken into account in this model. Two–gradient SCF computations were performed to model the interface between two coexistent PDMS films at the layering transition, and an estimation of the length of their interfacial contact was obtained, together with the associated line tension value. The SF–SCF molecularly detailed modeling of PLLA, PDMS, PMMA, and PiB monolayers, spread at the air/water surface, has proven to be consistent with experimental data: the incorporation in the model of a detailed molecular description of the monomeric features of the four compounds examined has been crucial to reproducing the features of the adsorption and pressure/area isotherms.
In Chapter 4, the same approach was applied to the description of polymer mixtures spread at the air/water interface. The aim of this chapter was to analyze topics such as 2D phase separation and partitioning in mixed polymeric Langmuir monolayers. Two of the four polymers studied in Chapter 3 were selected in order to obtain a mixed Langmuir monolayer. A system consisting of water–insoluble, spreadable, fluid–like polymers was prepared. The polymers were polydimethylsiloxane (PDMS) and polymethylmethacrylate (PMMA), combined, in some cases, with a minority of PDMS–b–PMMA copolymer. Both Langmuir trough pressure/area isotherm measurements and Brewster angle microscopy (BAM) observations were performed, and complemented with molecularly detailed self–consistent field (SCF) calculations. It was shown that PDMS undergoes a layering transition that is difficult to detect by BAM. Addition of PMMA enhanced contrast in BAM, showing a two–phase system: if this consisted of separate two–dimensional (2D) PMMA and PDMS phases, a PDMS–PMMA diblock should accumulate at the phase boundary. However, the diblock copolymer of PDMS–PMMA failed to show the expected “lineactant” behavior, i.e., failed to accumulate at the phase boundary. The calculations pointed to a non-trivial arrangement of the polymer chains at the interface: in mixtures of the two homopolymers, in a rather wide composition ratio, a vertical (with respect to the air/water interfacial plane) configuration was found, with PMMA sitting preferably at the PDMS/water interface of the thicker PDMS film, during the PDMS layering phase transition. This also explained why the diblock copolymer was not a lineactant. Both PMMA and PDMS–b–PMMA were depleted from the thin–thick PDMS film interface, and the line tension between the phases consequently increased in the binary mixtures, as well as in the ternary ones. The results shown in this chapter proved that gaining an accurate control over thin film structures at the microscopic level is a far from trivial task, and the acquisition of fundamental knowledge is necessary in order to interpret experimental data in an appropriate way.
As a consequence, in Chapter 5 an investigation based solely on SCF modeling was carried out, in order to analyze which polymer blends could have the possibility to undergo lateral phase separation in two dimensions. Specifically, the model system investigated consisted of water–supported Langmuir monolayers, obtained from binary polyalkyl methacrylate mixtures (PXMA, where X stands for any of the type of ester side groups used: M, methyl–; E, ethyl–; B, butyl–; H, hexyl–; O, octyl–; L, lauryl–methacrylate). In particular, the conditions which determined demixing and phase separation in the two–dimensional system were addressed, showing that a sufficient chain length mismatch in the ester side group moieties is able to drive the polymer demixing. When the difference in length of the alkyl chain of the ester moieties on the two types of polymers was progressively reduced, from 11 carbon atoms (PMMA/PLMA) to 4 carbons only (POMA/PLMA), the demixing tendency was also reduced; it vanished, indeed, for POMA/PLMA. In the latter case the polymer/subphase interactions affected more the distribution of the polymer coils in the blend monolayer: mixing of the two polymers was observed, but also a partial layering along the vertical direction.
Lineactancy was also considered, by selecting the mixture in which phase separation was best achieved: a third component, namely a symmetrical diblock copolymer of the type PLMA–b–PMMA, was added to a PMMA/PLMA blended monolayer. Adsorption of the diblock copolymer was observed exclusively at the contact line between the two homopolymer domains, together with a concomitant lowering of the line tension. The line tension varied with chemical potential of the diblock copolymer according to the Gibbs’ law, which demonstrated that PLMA–b–PMMA indeed acted as a lineactant (the two–dimensional analog of a surfactant) in the model system made of a binary demixed PMMA/PLMA Langmuir monolayer.
In conclusion, the requirements needed to achieve polymer blend demixing in a Langmuir monolayer are the following: spreadable, insoluble polymers, with the same amphiphilicity degree, combined to a certain chemical mismatch of the side moieties are necessary in order to cause lateral demixing at the air/water interface. The polyalkyl methacrylate example investigated in the chapter represented a suitable model system, since the methacrylate backbone guarantees that the different polymers have the same affinity towards the water subphase, while the different ester moieties drive the occurrence of lateral demixing. The dependency of the lateral demixing on the difference in length between the two ester side groups chosen was demonstrated. A rather complex interplay of forces regulates the distribution of the polymer coils in the monolayer: subtle alterations of this complex balance might favor the dewetting of the mixture in a single domain, together with the layering of the blended polymers along the direction normal to the air/water interface, as well as accumulation of one polymer at the domain edge, instead of the occurrence of the lateral phase separation. Furthermore, the possibility to control emulsification of two–dimensional demixed polymer blends was proven. This was achieved by use of a diblock copolymer, which acted as a lineactant by adsorbing at the contact line of the polymer domains. The calculations demonstrated the possibility to extend the lineactant concept, first elaborated in the context of lipid membrane investigations, to the field of study of polymer thin films.
Colloids and interfaces in life sciences and bionanotechnology
Norde, Willem - \ 2011
CRC Press - ISBN 9781439817186 - 466 p.
colloids - colloidal properties - interface - surface tension - emulsions - foams - rheological properties - textbooks - surface chemistry
Colloidal systems occur everywhere-in soils, seawater, foodstuff, pharmaceuticals, paints, blood, biological cells, and microorganisms. Colloids and Interfaces in Life Sciences and Bionanotechnology, Second Edition, gives a concise treatment of physicochemical principles determining interrelated colloidal and interfacial phenomena. New in the Second Edition: New topics, including phase separations in polymer systems, electrokinetics of charged permeable surface coatings, and polymer brush coatings to control adsorption and adhesion of particles. Emphasis on inter-particle interactions and surface phenomena in (bio)nanotechnology. Full solutions to over 100 updated and additional exercises are presented in the Appendix. Focusing on physicochemical concepts that form the basis of understanding colloidal and interfacial phenomena-rather than on experimental methods and techniques-this book is an excellent primer for students and scientists interested in colloidal and interfacial phenomena, their mutual relations and connections, and the fascinating role they play in natural and man-made systems.
Smart microgels for controlled uptake and release
Li, Y. - \ 2011
Wageningen University. Promotor(en): Martien Cohen Stuart; Willem Norde, co-promotor(en): Mieke Kleijn. - [S.l.] : S.n. - ISBN 9789085859994 - 173
gels - zetmeel - colloïden - lysozym - gecontroleerde afgifte - gels - starch - colloids - lysozyme - controlled release
This dissertation describes a systematic study on oxidized starch microgel particles. It begins with the preparation and characterization of oxidized starch gels in terms of some important physical-chemical properties, with the aim to select an optimum gel for further investigation of protein uptake. The gel with the highest degree of oxidation DO100% is chosen for lysozyme uptake because of its high protein uptake capacity and low swelling capacity. In addition, DO30% gels have been used in many experiments, since DO30% starch allows for preparation of well-defined spherical microgel particles and because it is enzymatically degradable. The two main aspects of interest are the protein binding affinity and protein saturation. Neutral pH and low salt concentration are found to be the optimum protein uptake conditions for high protein saturation. For more detailed studies, spherical microgels with a narrow size distribution have been made by optimizing the preparation process. The mobility of lysozyme molecules inside those microgel particles has been investigated. The main conclusion is that high salt and high pH increase the mobility of lysozyme in the gel particles. It implies that high pH and high salt concentration are potential triggers for lysozyme release from the gel. Subsequently, the kinetics of protein release by high pH and high salt concentration is presented. For the aim of application, the antimicrobial activity of lysozyme containing starch gel particles against some bacterial strains is determined. Finally, the deposition of poly-lysine/poly-glutamic acid complex layer around microgel surface is used to stabilize the microgel particle and optimize our system.
Influence of membrane properties on fouling in submerged membrane bioreactors
Marel, P. van der; Zwijnenburg, A. ; Kemperman, A. ; Wessling, M. ; Temmink, B.G. ; Meer, W. van der - \ 2010
Journal of Membrane Science 348 (2010)1-2. - ISSN 0376-7388 - p. 66 - 74.
waste-water treatment - cross-flow microfiltration - subcritical flux operation - activated-sludge - step method - filtration - ultrafiltration - deposition - morphology - colloids
Polymeric flat-sheet membranes with different properties were used in filtration experiments with activated sludge from a pilot-scale MBR to investigate the influence of membrane pore size, surface porosity, pore morphology, and hydrophobicity on membrane fouling. An improved flux-step method was used to measure both the critical flux and critical flux for irreversibility. Long term experiments were performed to evaluate if influences of membrane properties on short term could be translated to long term fouling behavior. The results showed that a hydrophilic asymmetric membrane with an interconnected pore structure, a nominal pore size of 0.3 µm, and large surface porosity of 27%, provided the best membrane performance with respect to critical flux and critical flux for irreversibility. The dominant fouling mechanism in long term filtration experiments was gel layer formation, which for this membrane was the least severe, and therefore extended the sustainable time.