Atomic Force Microscopy and Molecular Dynamic Simulation of Adsorption of Polyacrylamide with Different Chemistries onto Calcium Carbonate.

This study investigates the interaction of polyacrylamide (PAM) of different functional groups (sulfonate vs. carboxylate) and charge density (30% hydrolysed vs. 10% hydrolysed) with calcium carbonate (CaCO3) via atomic force microscopy (AFM) and partly via molecular dynamic (MD) simulations. The PAM used were F3330 (30% hydrolysed), AN125 (25% sulfonated), and AN910 (% hydrolysed). A total of 100 ppm of PAMs was prepared in 0.1% NaCl, 3% NaCl, and 4.36% NaNO3 to be employed in AFM experiments, while oligomeric models (30 repeating units) of hydrolysed polyacrylamide (HPAM), sulfonated polyacrylamide (SPAM), and neutral PAM (NPAM) were studied on a model calcite surface on MD simulations. AFM analysis indicated that F3330 has a higher average adhesion and interaction energy with CaCO3 than AN125 due to the bulky sulfonate side group of AN125 interfering with SPAM adsorption. Steric repulsion of both PAMs was similar due to their comparable molecular weights and densities of the charged group. In contrast, AN910 showed lower average adhesion and interaction energy, along with slightly longer steric repulsion with calcite than F3330, suggesting AN910 adopts more loops and tails than the slightly flatter F3330 configuration. An increase in salt concentration from 0.1% to 3% NaCl saw a reduction in adhesion and interaction energy for F3330 and AN125 due to charge screening, while AN910 saw an increase, and these values increased further at 4.36% NaNO3. MD simulations revealed that the salt ions in the system formed salt bridges between PAM and calcite, indicating that the adhesion and interaction energy observed from AFM are likely to be the net balance between PAM charged group screening and salt bridging by the salt ions present. Salt ions with larger bare radii and smaller hydrated radii were shown to form stronger salt bridges.

Atomic Force Microscopy of Hydrolysed Polyacrylamide Adsorption onto Calcium Carbonate.

In this work, the interaction of hydrolysed polyacrylamide (HPAM) of two molecular weights (F3330, 11-13 MDa; F3530, 15-17 MDa) with calcium carbonate (CaCO3) was studied via atomic force microscopy (AFM). In the absence of polymers at 1.7 mM and 1 M NaCl, good agreement with DLVO theory was observed. At 1.7 mM NaCl, repulsive interaction during approach at approximately 20 nm and attractive adhesion of approximately 400 pN during retraction was measured, whilst, at 1 M NaCl, no repulsion during approach was found. Still, a significantly larger adhesion of approximately 1400 pN during retraction was observed. In the presence of polymers, results indicated that F3330 displayed higher average adhesion (450-625 pN) and interaction energy (43-145 aJ) with CaCO3 than F3530's average adhesion (85-88 pN) and interaction energy (8.4-11 aJ). On the other hand, F3530 exerted a longer steric repulsion distance (70-100 nm) than F3330 (30-70 nm). This was likely due to the lower molecular weight. F3330 adopted a flatter configuration on the calcite surface, creating more anchor points with the surface in the form of train segments. The adhesion and interaction energy of both HPAM with CaCO3 can be decreased by increasing the salt concentration. At 3% NaCl, the average adhesion and interaction energy of F3330 was 72-120 pN and 5.6-17 aJ, respectively, while the average adhesion and interaction energy of F3530 was 11.4-48 pN and 0.3-2.98 aJ, respectively. The reduction of adhesion and interaction energy was likely due to the screening of the COO- charged group of HPAM by salt cations, leading to a reduction of electrostatic attraction between the negatively charged HPAM and the positively charged CaCO3.

Molecular Dynamics Simulation of Polyacrylamide Adsorption on Calcite.

In poorly consolidated carbonate rock reservoirs, solids production risk, which can lead to increased environmental waste, can be mitigated by injecting formation-strengthening chemicals. Classical atomistic molecular dynamics (MD) simulation is employed to model the interaction of polyacrylamide-based polymer additives with a calcite structure, which is the main component of carbonate formations. Amongst the possible calcite crystal planes employed as surrogates of reservoir rocks, the (1 0 4) plane is shown to be the most suitable surrogate for assessing the interactions with chemicals due to its stability and more realistic representation of carbonate structure. The molecular conformation and binding energies of pure polyacrylamide (PAM), hydrolysed polyacrylamide in neutral form (HPAM), hydrolysed polyacrylamide with 33% charge density (HPAM 33%) and sulfonated polyacrylamide with 33% charge density (SPAM 33%) are assessed to determine the adsorption characteristics onto calcite surfaces. An adsorption-free energy analysis, using an enhanced umbrella sampling method, is applied to evaluate the chemical adsorption performance. The interaction energy analysis shows that the polyacrylamide-based polymers display favourable interactions with the calcite structure. This is attributed to the electrostatic attraction between the amide and carboxyl functional groups with the calcite. Simulations confirm that HPAM33% has a lower free energy than other polymers, presumably due to the presence of the acrylate monomer in ionised form. The superior chemical adsorption performance of HPAM33% agrees with Atomic Force Microscopy experiments reported herein.

Non-linear response of colloid monolayers at high-frequency probed by ultrasound-driven microbubble dynamics.

HYPOTHESIS: High-frequency interfacial rheology of complex interfaces remains challenging yet it is central to the performance of multiphase soft matter products. We propose to use ultrasound-driven bubble dynamics to probe the high-frequency rheology of a colloid monolayer used as model system with controlled interactions and simultaneous monitoring of the microstructure. We hypothesize that by comparing the response of colloid-coated bubbles with that of a bare bubble under identical experimental conditions, it is possible to detect the non-linear response of the monolayer and use it to extract interfacial rheological properties at 104s-1. EXPERIMENTS: Using high-speed video-microscopy, the dynamics of colloid-coated bubbles were probed to study the micromechanical response of the monolayer to high-frequency deformation. Protocols analogous to stress-sweep and frequency-sweep were developed to examine the stress-strain relationships. A simple model, motivated by the observed non-linear responses, was developed to estimate the interfacial viscoelastic parameters. FINDINGS: The estimated elastic moduli of colloid monolayers at 104s-1 are about an order of magnitude larger than those measured at 1 s-1. The monolayers exhibit non-linear viscoelasticity for strain amplitudes as small as 1%, and strain-softening behaviour. These findings highlight the applicability of acoustic bubbles as high-frequency interfacial probes.

Adsorption of Hydrolysed Polyacrylamide onto Calcium Carbonate.

Carbonate rock strengthening using chemical techniques is a strategy to prevent excessive fines migration during oil and gas production. We provide herein a study of the adsorption of three types of hydrolysed polyacrylamide (HPAM) of different molecular weight (F3330S, 11-13 MDa; F3530 S, 15-17 MDa; F3630S, 18-20 MDa) onto calcium carbonate (CaCO3) particles via spectrophotometry using a Shimadzu UV-2600 spectrometer. The results are compared to different adsorption isotherms and kinetic models. The Langmuir isotherm shows the highest correlation coefficient (R2 > 0.97) with equilibrium parameters (RL) ranging between 0 and 1 for all three HPAMs, suggesting a favorable monolayer adsorption of HPAM onto CaCO3. The adsorption follows pseudo-second order kinetics, indicating that the interaction of HPAM with CaCO3 is largely dependent on the adsorbate concentration. An adsorption plot reveals that the amount of HPAM adsorbed onto CaCO3 at equilibrium increases with higher polymer molecular weight; the equilibrium adsorbed values for F3330S, F3530S and F3630S are approximately 0.24 mg/m2, 0.31 mg/m2, and 0.43 mg/m2, respectively. Zeta potential analysis shows that CaCO3 has a zeta potential of +12.32 mV, which transitions into negative values upon introducing HPAM. The point of zero charge (PZC) is observed at HPAM dosage between 10 to 30 ppm, in which the pH here lies between 9-10.

Signature of elastic turbulence of viscoelastic fluid flow in a single pore throat.

When a viscoelastic fluid, such as an aqueous polymer solution, flows through a porous medium, the fluid undergoes a repetitive expansion and contraction as it passes from one pore to the next. Above a critical flow rate, the interaction between the viscoelastic nature of the polymer and the pore configuration results in spatial and temporal flow instabilities reminiscent of turbulentlike behavior, even though the Reynolds number Re≪1. To investigate whether this is caused by many repeated pore body-pore throat sequences, or simply a consequence of the converging (diverging) nature present in a single pore throat, we performed experiments using anionic hydrolyzed polyacrylamide (HPAM) in a microfluidic flow geometry representing a single pore throat. This allows the viscoelastic fluid to be characterized at increasing flow rates using microparticle image velocimetry in combination with pressure drop measurements. The key finding is that the effect, popularly known as "elastic turbulence," occurs already in a single pore throat geometry. The critical Deborah number at which the transition in rheological flow behavior from pseudoplastic (shear thinning) to dilatant (shear thickening) strongly depends on the ionic strength, the type of cation in the anionic HPAM solution, and the nature of pore configuration. The transition towards the elastic turbulence regime was found to directly correlate with an increase in normal stresses. The topology parameter, Q_{f}, computed from the velocity distribution, suggests that the "shear thickening" regime, where much of the elastic turbulence occurs in a single pore throat, is a consequence of viscoelastic normal stresses that cause a complex flow field. This flow field consists of extensional, shear, and rotational features around the constriction, as well as upstream and downstream of the constriction. Furthermore, this elastic turbulence regime, has high-pressure fluctuations, with a power-law decay exponent of up to |-2.1| which is higher than the Kolmogorov value for turbulence of |-5/3|.

Layer-by-layer adsorption: Factors affecting the choice of substrates and polymers.

The electrostatic layer-by-layer technique for fabrication of multi-layered structures of various sizes and shapes using flat and colloidal templates coupled with polyelectrolyte layer-forming materials has attracted significant interest among both academic and industrial researchers due to its versatility and relative simplicity of the procedures involved in its execution. Fabrication of the multi-layered structures using the electrostatic layer-by-layer method involves several distinct stages each of which holds great importance when considering the production of a high-quality product. These stages include selection of materials (both template and a pair of construction polyelectrolytes), adsorption of the first polyelectrolyte layer onto the selected templates, formation of the second layer comprised of the oppositely charged polyelectrolyte and guided by the interactions between the two chosen polyelectrolytes, and multi-layering, where a selected number of layers are produced, and which is conditioned by both intrinsic properties of the involved construction materials and external fabrication conditions such as temperature, pH and ionic strength. The current review summarises the most important aspects of each stage mentioned above and gives examples of the materials suitable for utilization of the technique and describes the underlying physics involved.

Layer-by-layer encapsulated nano-emulsion of ionic liquid loaded with functional material for extraction of Cd2+ ions from aqueous solutions.

Ionic liquids can serve as an environmentally-friendly replacement for solvents in emulsions, therefore they are considered suitable to be used as an emulsified medium for various active materials one of which are extractors of metal ions. Increasing the extraction efficiency is considered to be one of the key objectives when working with such extraction systems. One way to improve the extraction efficiency is to increase the contact area between the extractant and the working ionic solution. This can be accomplished by creating a nano-emulsion of ionic liquid containing such an extractant. Since emulsification of ionic liquid is not always possible in the sample itself, there is a necessity of creating a stable emulsion that can be added externally and on demand to samples from which metal ions need to be extracted. We propose a method of fabrication of a highly-stable extractant-loaded ionic liquid-in-water nano-emulsion via a low-energy phase reversal emulsification followed by continuous layer-by-layer polyelectrolyte deposition process to encapsulate the nano-emulsion and enhance the emulsion stability. Such a multilayered stabilized nano-emulsion was tested for extraction of Cd2+ and Ca2+ ions in order to determine its extraction efficiency and selectivity. It was found to be effective in the extraction of Cd2+ ions with near 100% cadmium removal, as well as being selective since no Ca2+ ions were extracted. The encapsulated emulsion was removed from samples post-extraction using two methods - filtration and magnetic separation, both of which were shown to be viable under different circumstances - larger and mechanically stronger capsules could be removed by filtration, however magnetic separation worked better for both smaller and bigger capsules. The long-term stability of nano-emulsion was also tested being a very important characteristic for its proposed use: it was found to be highly stable after four months of storage time.

Fabrication of polyelectrolyte multilayered nano-capsules using a continuous layer-by-layer approach.

The layer-by-layer approach is a highly versatile method for the fabrication of multilayered polymeric films and capsules. It has been widely investigated in research for various polyelectrolyte pairs and core template particles. However, the fabrication of nano-sized capsules at the larger scale is difficult and time consuming, due to the necessity of washing and centrifugation steps before the deposition of each polyelectrolyte layer. This results not only in a very long fabrication time, but also in the partial loss of particles during those intermediate steps. In this study, we introduced a continuous approach for the fabrication of multilayer polyelectrolyte based nano-capsules using calcium phosphate core nanoparticles and a tubular flow type reactor with the potential for synthesizing tens of milligrams of capsules per hour. Adsorption of the polyelectrolyte layer occurred in the tubing where particles and polyelectrolyte solution of choice were mixed, creating a layer of polyelectrolyte on the particles. After this, these newly surfaced-modified particles passed into the next segment of tubing, where they were mixed with a second polyelectrolyte of opposite charge. This process can be continuously repeated until the desired number of layers is achieved. One potential problem with this method concerned the presence of any excess polyelectrolyte in the tubing, so careful control of the amount of polymer added was crucial. It was found that slightly under dosing the amount of added polyelectrolyte ensured that negligible unadsorbed polyelectrolyte remained in solution. The particles created at each deposition step were stable, as they all had a zeta potential of greater than ±25mV. Furthermore the zeta potential measurements showed that charge reversal occurred at each stage. Having achieved the necessary number of polyelectrolyte layers, the calcium phosphate cores were easily removed via dissolution in either hydrochloric or acetic acid.

Microfluidic processing of concentrated surfactant mixtures: online SAXS, microscopy and rheology.

We investigate the effect of microfluidic flow on the microstructure and dynamics of a model surfactant mixture, combining synchrotron Small Angle X-ray Scattering (SAXS), microscopy and rheology. A system comprising a single-chain cationic surfactant, hexadecyl trimethyl ammonium chloride (C16TAC), a short-chain alcohol (1-pentanol) and water was selected for the study due to its flow responsiveness and industrial relevance. Model flow fields, including sequential contraction-expansion (extensional) and rotational flows, were investigated and the fluid response in terms of the lamellar d-spacing, orientation and birefringence was monitored in situ, as well as the recovery processes after cessation of flow. Extensional flows are found to result in considerable d-spacing increase (from approx 59 Å to 65 Å). However, under continuous flow, swelling decreases with increasing flow velocity, eventually approaching the equilibrium values at velocities ≃2 cm s(-1). Through individual constrictions we observe the alignment of lamellae along the flow velocity, accompanied by increasing birefringence, followed by an orientation flip whereby lamellae exit perpendicularly to the flow direction. The resulting microstructures are mapped quantitatively onto the flow field in 2D with 200 µm spatial resolution. Rotational flows alone do not result in appreciable changes in lamellar spacing and flow type and magnitude evidently impact the fluid microstructure under flow, as well as upon relaxation. The findings are correlated with rheological properties measured ex situ to provide a mechanistic understanding of the effect of flow imposed by tubular processing units in the phase behavior and performance of a model surfactant system with ubiquitous applications in personal care and coating industries.

Towards an understanding of the release behavior of temperature-sensitive liposomes: a possible explanation of the "pseudoequilibrium" release behavior at the phase transition temperature.

It is generally believed that thermal sensitive liposomes (i.e. vesicles) that contain 1,2-dihexadecanoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethyleneglycol)-2000 (DSPE.2000) maintain a constant permeability to ionic molecules when they are heated to the phase transition temperature of the membrane (Tm). However, DPPC:DSPE.2000 liposome systems have been reported to release encapsulated agent in a "pseudoequilibrium" pattern upon temperature rise, whereby there is a rapid release of encapsulated material followed by no further release. Little effort has been made to determine the mechanism of such release behavior. We aim to explore the potential cause of "pseudoequilibrium" release of DPPC:DSPE.2000 liposome systems in response to temperature rise. Using calcein as a hydrophilic marker, the release pattern of DPPC:DSPE.2000 liposome system at Tm has been carefully determined. The potential mechanism of its release behavior has been further explored using two novel assays (i.e. heating-cooling-reheating assay and incubation assay). Our results show that there is a dramatic enhancement of the permeability of DPPC:DSPE.2000 vesicles to ionized molecules (i.e. calcein) during the initial period of heating to 42 °C. This is believed to result from the opening of the hydrophilic pores at the liquid/solid interface. However, after less than 2 min of incubation at this temperature, no further release of calcein is observed, suggesting that the sizes of pores are reduced, restricting any further movement of calcein molecules. On cooling and reheating the DPPC:DSPE.2000 liposomes to 42 °C, no further release of calcein is observed. The incorporation of MSPC (1-stearoyl-2-hydroxy-sn-glycero-3-phosphocholine) extends the release period of calcein from the DPPC:MSPC:DSPE.2000 vesicles to more than 30 min, suggesting that the lysolipid stabilizes the pores in the lipid membrane.

Preparation and characterization of microgels sensitive toward copper II ions.

An emulsion polymerization technique has been used to prepare chemically crosslinked microgels in aqueous suspension that are sensitive to the presence of copper ions. Poly(N-isopropylacrylamide) (PNIPAM) was copolymerized with different amounts of 1-vinylimidazole (VI), and the resultant microgels exhibited multi-responsive behavior being sensitive to changes in temperature, pH and to the presence of metal ions, particularly copper. These swelling properties of the microgel particles were characterized using dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The effect of temperature showed that the microgel particles shrunk continuously as the temperature was raised, up to a temperature of 50°C, and the volume phase transition temperature, VPTT, has been shifted to higher temperatures (in the range of 35-45°C) compared to pure PNIPAM microgels where the VPTT≈30-35°C. The particle size of these microgels was also investigated as a function of pH; the microgel particles became swollen at low pH and collapsed at high pH, due to the ionization of the VI component of the microgels. Most interesting, however, was the effect of the copper ion concentration in solution. The PNIPAM-co-VI microgels were found to swell with increasing concentration of Cu(2+) up to 0.3g/l of Cu(2+) due to adsorption of the cations inside the particle, which leads to charging up the internal phase of the microgel. However, at higher concentrations of added copper (II) ions, the binding forces of complexation lead to conformational changes to the microgel resulting in weaker polymer-solvent interaction and consequential shrinkage again of the polymer. In addition, the copper (II) uptake was calculated, and the uptake was found to be well described by the Langmuir adsorption isotherm, with up to 2g of copper II being taken up by 1g of microgel.

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

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

Surface tension-induced gel fracture. Part 2. Fracture of gelatin gels.

The spreading of surfactants on gel layers has been found to be accompanied by an intriguing instability which involves the formation of crack-like patterns on the surface of the gel. In an attempt to extend the findings on the spreading on agar gels presented in part 1 of this series, this paper examines the case of surfactant spreading on gelatin, which is a characteristic example of a protein-based gel. Aqueous solutions of Silwet L-77 of varying concentrations were spread on thick gelatin layers of varying concentrations. The resulting pattern formation was found to have many similarities to the corresponding phenomenon on agar. In terms of spreading dynamics, the values of the spreading exponent, n, of the power law L(t) ~ kt(n), which describes the temporal evolution of the cracks, are similar to those of the agar case, within the predicted limits for surface tension gradient-induced spreading on thick films, highlighting the dominant presence of Marangoni stresses. However, the values of the spreading coefficient, k, are much smaller compared to those measured during the spreading on agar. Further observations are linked with the rheological properties of gelatin, which are also measured in detail.

Development of lysolipid-based thermosensitive liposomes for delivery of high molecular weight proteins.

The purpose of the present investigation was to determine the feasibility of using lysolipid-based thermal sensitive liposomes (145nm) for high molecular weight molecule delivery. Fluorescein isothiocyanate conjugate-albumin was used as a model drug (MW 66kDa). Thermal sensitive liposomes, which encapsulated the protein were prepared using a passive encapsulation methodology involving freeze-thawing cycles followed by extrusion. In vitro release studies at various temperatures indicated rapid release behaviour of the encapsulated protein at 42 and 44.5°C but a good stability at 37.5°C. The current findings suggest that lysolipid-based thermal sensitive liposomes can be used to deliver high molecular weight molecules.

Interaction forces between particles stabilized by a hydrophobically modified inulin surfactant.

The adsorption isotherm of a hydrophobically modified inulin (INUTEC SP1) on polystyrene (PS) and poly(methyl methacrylate) (PMMA) particles was determined. The results show a high affinity isotherm for both particles as expected for a polymeric surfactant adsorption. The interactions forces between two layers of the hydrophobically modified inulin surfactant adsorbed onto a glass sphere and plate was determined using a modified atomic force microscope (AFM) apparatus. In the absence of any polymer, the interaction was attractive although the energy of interaction was lower than predicted by the van der Waals forces. The results between two layers of the adsorbed polymer confirms the adsorption isotherms results and provides an explanation to the high stability of the particles covered by INUTEC SP1 at high electrolyte concentration. Stability of dispersions against strong flocculation could be attributed to the conformation of the polymeric surfactant at the solid/liquid interface (multipoint attachment with several loops) which remains efficient at Na(2)SO(4) concentration reaching 1.5 mol dm(-3). The thickness of the adsorbed polymer layer in water determined both by AFM and rheology measurements, was found to be about 9 nm.

Manipulating forces between surfaces: applications in colloid science and biophysics.

It is the forces between the microscopic constituents of materials which to a large extent determine the macroscopic properties. For example, it is the differences in bonding between the carbon atoms which determines the different physical properties of carbon and graphite. The same is true in colloidal systems. In colloidal systems, there are three common types of long-range interactions between particles: van der Waals forces, electrical double layer forces and steric forces. In this paper, examples as to how these forces can be modified and even manipulated will be given. To convincingly demonstrate these effects, it is necessary to measure these interaction forces. We have achieved this by using the principles of atomic force microscopy (AFM). The principle is simple, a small particle, 5-30 microm, is attached onto a small weak cantilever spring. The interaction between this particle and another particle or a surface is measured by monitoring the deflection of the spring as the two particles are moved together. In this paper, I shall give examples of direct measurements of van der Waals, electrical double layer and steric forces and show how they can be modified and how these modifications affect the properties of bulk suspensions. Similar principles are involved in the interactions of biological materials. However, nature is much cleverer than man such that many of the macromolecules on cell surfaces are able to specifically recognise only one other molecule. An example of this recognition-type interaction, namely, cholera toxin interacting with the glycolipid Gm1, will also be presented. Finally, the adhesion of cells to surfaces of different surface chemistries has been determined; this is of significance in many fields ranging from fouling of filtration membranes on the one hand to the biocompatibility of surgical implants on the other.

Dewetting behavior of aqueous cationic surfactant solutions on liquid films.

Previous experimental work has shown that the spreading of a drop of aqueous anionic surfactant solution on a liquid film supported by a negatively charged solid substrate may give rise to a fingering instability (Afsar-Siddiqui, A. B.; Luckham P, F.; Matar, O. K. Langmuir 2003, 19, 703-708). However, upon deposition of a cationic surfactant on a similarly charged support, the surfactant will adsorb onto the solid-liquid interface rendering it hydrophobic. Water is then expelled from the hydrophobic regions, causing film rupture and dewetting. In this paper, experimental results are presented showing how the surfactant concentration and film thickness affect the dewetting behavior of aqueous dodecyltrimethylammonium bromide solutions. At low surfactant concentrations and large film thicknesses, the film ruptures at a point from which dewetting proceeds. At higher concentrations and smaller film thicknesses, the ruptured region is annular in shape and fluid moves away from this region. At still higher concentrations and smaller film thicknesses, the deposited surfactant forms a cap at the point of deposition that neither spreads nor retracts. This variation in dewetting mode is explained by considering the relative Marangoni and bulk diffusion time scales as well as the mode of assembly of the surfactant adsorbed on the solid surface.

Interaction forces between polyethylene oxide-polypropylene oxide ABA copolymers adsorbed to hydrophobic surfaces.

Block and graft copolymers are frequently used as stabilizing agents in colloidal dispersions. One common material is the range of polymers known as "Pluronics," which is a BASF trade name for ABA block copolymers composed of a propylene oxide anchoring block (B block) and two ethylene oxide buoy or stabilizing blocks (A block); the equivalent ICI (Uneqima) trade name is Synperonic. In the work presented here the interactions between adsorbed layers of these materials immersed in 10(-2) M sodium sulfate solutions are presented. The block copolymers investigated had an approximately fixed molecular weight of around 3250 Da for the anchoring B block, whilst the molecular weight of the stabilizing polyethylene oxide chains varies around 800-6500 Da. Hydrophobic glass surfaces were used as the test substrate. It was found that in the absence of polymer a long ranged attractive interaction is observed, typical for the interaction between hydrophobic surfaces in aqueous media, but that in the presence of the polymers a repulsion was observed. The repulsion became longer ranged as the molecular weight of the ethylene oxide chain increased. On separation of the surfaces, the interaction was slightly longer ranged, suggesting that the two polymer layers intertwine and stretch each other on separation. This effect was more noticeable for the higher molecular weight polymers. The compression data were well described using a scaling analysis for the interaction between polymer brushes.

Investigation of the molecular interactions in a pMDI formulation by atomic force microscopy.

The forces of interaction between inhalable formoterol fumarate dihydrate particles, and the various components of a pressurised Metered Dose Inhaler (pMDI) (e.g. aluminium container, other drug particles and stabilising excipients) were investigated in isolation and combination in the model propellant 2H, 3H perfluoropentane (HPFP). The results obtained offer conclusive proof that the model systems tested have a degree of instability both in the presence and absence of polymer(s). The attractive forces measured following the addition of a mixed homopolymer solution may well be weak enough to be overcome by shaking. The use of homopolymers has inherent difficulties associated with it in the form of bridging interaction. Block or comb copolymers may well be a better option therefore, as they will reduce the possibility of bridging interactions. AFM offers great insight into the behaviour of HFA drug suspensions, and could play a vital role in the future development of suspension formulations.