Publications

Abstract

The combination of lyotropic liquid crystals (LLCs) and low-molecular-weight gelators (LMWGs) for the formation of lyotropic liquid crystal gels (LLC gels) leads to a versatile and complex material combining properties of both parent systems. We gelled the calamitic nematic NC phases of a binary and ternary system using the LMWG 3,5-bis-(5-hexylcarbamoyl-pentoxy)-benzoic acid hexyl ester (BHPB-6). This binary system consists of the surfactant N,N-dimethyl-N-ethyl-1-hexadecylammonium bromide (CDEAB) and water, whereas the ternary system consists of the surfactant N,N,N-trimethyl-N-tetradecylammonium bromide (C14TAB), the cosurfactant n-decanol, and water. Though containing similar surfactants, the gelled NC phases of the binary and ternary systems show differences in their visual and gel properties. The gelled NC phase of the binary system remains clear for several days after preparation, whereas the gelled NC phase of the ternary system turns turbid within 24 h. We investigated the time evolution of the gel strength with oscillation rheology measurements (a) within the first 24 h and (b) up to two weeks after gel formation. The shape of the fibers was investigated over different time scales with freeze fracture electron microscopy (FFEM). We demonstrate that despite their similarities, the two LLC gels also have distinct differences.

Abstract

Surfactants play essential roles in many commonplace applications and industrial processes. Although significant progress has been made over the past decades with regard to model-based predictions of the behavior of surfactants, important challenges have remained. Notably, the characteristic time scales of surfactant exchange among micelles, interfaces, and the bulk solution typically exceed the time scales currently accessible with atomistic molecular dynamics (MD) simulations. Here, we circumvent this problem by introducing a framework that combines the general thermodynamic principles of self-assembly and interfacial adsorption with atomistic MD simulations. This approach provides a full thermodynamic description based on equal chemical potentials and connects the surfactant bulk concentration, the experimental control parameter, with the surfactant surface density, the suitable control parameter in MD simulations. Self-consistency is demonstrated for the nonionic surfactant C12EO6 (hexaethylene glycol monododecyl ether) at an alkane/water interface, for which the adsorption and pressure isotherms are computed. The agreement between the simulation results and experiments is semiquantitative. A detailed analysis reveals that the used atomistic model captures well the interactions between surfactants at the interface but less so their adsorption affinities to the interface and incorporation into micelles. Based on a comparison with other recent studies that pursued similar modeling challenges, we conclude that the current atomistic models systematically overestimate the surfactant affinities to aggregates, which calls for improved models in the future.

Abstract

Hypothesis In the phase diagram of the system H2O/NaCl – AOT (sodium bis(2-ethylhexyl) sulfosuccinate) a homogeneous L3 channel can be detected at T = 25 °C as a function of the surfactant and the NaCl mass fraction. Our hypothesis is that a structural transition from a sponge-like to an onion-like structure occurs in this channel. Experiments We (a) determined the relevant part of the phase diagram, (b) carried out electrical conductivity and viscosity measurements, (c) visualized the nanostructure with freeze-fracture electron microscopy (FFEM) and freeze fracture direct imaging (FFDI), (d) determined the characteristic length scales from Small Angle Neutron Scattering (SANS) curves. Findings We detected a narrow one-phase L3 channel in which the conductivities decrease, while the viscosities increase with increasing surfactant and salt mass fractions. Together with the FFEM/FFDI images and the SANS curves we provide experimental evidence for a structural transition from a sponge-like to an onion-like structure: all structures as well as their coexistences are thermodynamically stable.

Abstract

Switchable materials in general and CO2-switchable materials in particular are of great interest in environmental research. The replacement of common non-switchable materials (solutions, solvents, surfactants, etc.) with their switchable counterparts has a great potential to make processes more environmentally friendly by enhancing reusability and circularity and thus reducing energy costs and material consumption. Inspired by this, the present work deals with the surface and foaming properties of aqueous solutions of a non-switchable surfactant in presence of a CO2-switchable additive. A 1 : 1 and a 1 : 5 (molar ratios) mixture of the non-switchable surfactant C14TAB (tetradecyltrimethylammonium bromide) and the CO2-switchable additive TMBDA (N,N,N,N-tetramethyl-1,4-butanediamine) were investigated. It was found that surface properties, foamability, and foam stability can be changed by switching the additive with CO2 as a trigger. This observation can be explained by the fact that TMBDA is surface active in its unprotonated, i.e. neutral form, which disturbs the tight packing of the surfactant molecules on the surface. As a consequence, foams generated with surfactant solutions containing the neutral TMBDA are less stable than their TMBDA-free counterparts. On the other hand, the switched diprotonated additive is a 2 : 1 electrolyte with hardly any surface activity and thus does not affect surface and foam properties.

Abstract

CO2-switchable materials in general and CO2-switchable surfactants in particular are of great interest in environmental research. There is a great potential to make processes more environmentally friendly by enhancing reusability and circularity and thus reducing material costs and energy consumption by replacing common non-switchable surfactants with their switchable counterparts. Inspired by this, the present work deals with the surface and foaming properties of aqueous solutions of the novel anionic CO2-switchable tail surfactant sodium 4-(methyl(octyl)amino)butane-1-sulfonate. In the presence of N2, the unprotonated surfactant is able to stabilize foams. By switching, i.e. by protonating the CO2-responsive trialkyl amine group in the surfactants hydrocarbon chain, the amphiphilic nature of the surfactant is reduced which is indicated by an increase of the plateau surface tension and a higher CMC compared to the non-protonated surfactant. Furthermore, the ability of the protonated surfactant to stabilize foams is reduced.

Abstract

Bioassays are widely used in healthcare to detect and quantify biomarkers, such as molecules or enzymes, which are crucial in monitoring diseases and health conditions. In developed countries, healthcare professionals use specialized reagents and equipment’s to perform these bioassays. However, in less-industrialized countries, the creation of low cost, fast, and technically simple bioassays is required. Herein, we propose a simple approach for detecting biochemical markers using host–guest complexes containing a surfactant. When the biochemical marker is present, the host–guest complex is disrupted, releasing the surfactant and producing foam. The read-out mechanism relies on the change of foam volume as function of biomarker concentration. This change is quantifiable by the naked eye and can be measured with a simple ruler. We claim that the use of foams as sensing tool is an attractive, inexpensive, fast, and easy to handle on-site detection method.

Abstract

ABSTRACTLyotropic liquid crystal gels (LLC gels) are versatile materials which combine the anisotropy of a liquid crystal with the mechanical stability of a gel. We succeeded in gelling the rare calamitic nematic NC phase of two different micellar LLC systems with the low molecular weight gelator (LMWG) 3,5-bis-(5-hexylcarbamoyl-pentoxy)-benzoic acid hexyl ester (BHPB-6). The systems of choice are: (1) a binary LLC system with the surfactant N,N-dimethyl-N-ethyl-1-hexadecylammonium bromide (CDEAB) and water; (2) a ternary LLC system with the surfactant N,N,N-trimethyl-N-tetradecylammonium bromide (C14TAB), n-decanol, and water. The obtained gels show optical birefringence and no macroscopic flow. Freeze fracture electron microscopy (FFEM) images show ribbon-like gel fibres that form the gel network and can stack into thicker bundles, while small-angle X-ray scattering (SAXS) confirms the coexistence of the nematic NC phase and the gel network. The growth of the gel network was monitored with time-resolved SAXS measurements. Additionally, significant gel ageing effects were observed in rheology measurements, showing that the gel strengthens with time. With this study, we considerably broaden the pool of available surfactant-based LLC gels and pave a way to macroscopically aligned LLC gels with the goal to apply them as stimuli-responsive actuators and sensors.

Abstract

In dilute water-surfactant systems L3 phases are found in which bilayers interconnect to form a sample-spanning sponge-like structure. From our previous study of the system water/NaCl-AOT (sodium bis(2-ethylhexyl) sulfosuccinate) we know that a transition of this sponge-like structure to an oil-continuous foam-like structure occurs upon addition of minute amounts of oil (about 3 wt%, α = 0.03) in the L3 channel at a constant surfactant mass fraction of γ = 0.15 and T = 25 °C. The aim of the present study was to verify if the same transition occurs at γ = 0.25. To achieve this goal, we determined the relevant part of the phase diagram and studied the electrical conductivities and viscosities within the narrow one-phase L3 channel. Although the electrical conductivities and viscosities change qualitatively like those observed at γ = 0.15 we did not observe a sponge-like structure at γ = 0.25 in the oil-free system (α = 0) with freeze-fracture electron microscopy (FFEM) and freeze fracture direct imaging (FFDI). Together with the FFEM/FFDI images and SANS/SAXS curves we provide experimental evidence for a structural transition with decreasing oil content from a thermodynamically stable foam-like to a thermodynamically stable onion-like nanostructure at γ = 0.25 rather than to a sponge-like structure as is the case at γ = 0.15.

Abstract

Even though it has been known for a long time that traces of perfluorinated vapors suppress gas exchange (coarsening) between the bubbles of aqueous foams, its stabilizing impact on foam coalescence has been evidenced only recently. While previous work has demonstrated this effect for different surfactant types, we investigate here the influence of the surfactant concentration. We compared the foam properties of aqueous solutions of the non-ionic surfactant dodecyldimethylphospine oxide (C12DMPO) in the absence and presence of perfluorohexane (PFH) in the gas phase. In order to decouple foam coarsening and coalescence, we accompany the foam stability experiments with (a) lifetime statistics of individual, vertical foam films pulled from the same solutions and (b) surface tension measurements in controlled gas environments. All measurements show a clear increase of foam and film stability in the presence of PFH, its effect being most pronounced above the cmc of the surfactant. The surface tension measurements show a clear co-adsorption of the PFH up to the formation of macroscopic films at saturation. We complete the analysis by showing that alkane vapors also have a stabilizing effect for the same surfactant solutions, yet much less pronounced than that of PFH. The precise origin of the stabilizing action of these hydrophobic vapors remains to be elucidated.

Abstract

This paper completes previous studies on the phase behaviour and microstructure of the quaternary microemulsion water – cyclohexane – n-octyl-β-D-glucoside (β-C8G1) – geraniol. The properties of this system are almost insensitive to temperature, while they can be tuned easily by adding an alcohol as co-surfactant. The addition of the alcohol changes the composition of the interfacial film, which, in turn, is the tuning parameter for the quaternary system. Studies of the phase behaviour together with SANS and NMR measurements allow drawing a quantitative picture of how the domain size ξ, the curvature H, and the interfacial tension σab depend on the composition of the interfacial film. The SANS data of both oil-in-water and water-in-oil droplet microemulsions recorded near the emulsification failure boundary were evaluated with the Generalised Indirect Fourier Transformation (GIFT), revealing a growth towards cylindrical structures when approaching the respective critical end point. We will show that the general behaviour of ternary and quaternary systems is equal if the appropriate tuning parameters are chosen. In addition, we will show that it is possible to apply the scaling description derived for temperature-dependent ternary systems to composition-dependent quaternary systems: plotting the reduced domain size, the reduced curvature and the reduced interfacial tension against the proper reduced tuning parameter, i.e., either the reduced temperature or the reduced interfacial composition, leads to one master curve for all systems.

Abstract

The use of low-cost sensors for air quality measurements has become very popular in the last few decades. Due to the detrimental effects of particulate matter (PM) on human health, PM sensors like photometers and optical particle counters (OPCs) are widespread and have been widely investigated. The negative effects of high relative humidity (RH) and fog events in the mass concentration readings of these types of sensors are well documented. In the literature, different solutions to these problems – like correction models based on the Köhler theory or machine learning algorithms – have been applied. In this work, an air pre-conditioning method based on a low-cost thermal dryer for a low-cost OPC is presented. This study was done in two parts. The first part of the study was conducted in the laboratory to test the low-cost dryer under two different scenarios. In one scenario, the drying efficiency of the low-cost dryer was investigated in the presence of fog. In the second scenario, experiments with hygroscopic aerosols were done to determine to which extent the low-cost dryer reverts the growth of hygroscopic particles. In the second part of the study, the PM10 and PM2.5 mass concentrations of an OPC with dryer were compared with the gravimetric measurements and a continuous federal equivalent method (FEM) instrument in the field. The feasibility of using univariate linear regression (ULR) to correct the PM data of an OPC with dryer during field measurement was also evaluated. Finally, comparison measurements between an OPC with dryer, an OPC without dryer, and a FEM instrument during a real fog event are also presented. The laboratory results show that the sensor with the low-cost dryer at its inlet measured an average of 64 % and 59 % less PM2.5 concentration compared with a sensor without the low-cost dryer during the experiments with fog and with hygroscopic particles, respectively. The outcomes of the PM2.5 concentrations of the low-cost sensor with dryer in laboratory conditions reveal, however, an excess of heating compared with the FEM instrument. This excess of heating is also demonstrated in a more in-depth study on the temperature profile inside the dryer. The correction of the PM10 concentrations of the sensor with dryer during field measurements by using ULR showed a reduction of the maximum absolute error (MAE) from 4.3 µg m−3 (raw data) to 2.4 µg m−3 (after correction). The results for PM2.5 make evident an increase in the MAE after correction: from 1.9 µg m−3 in the raw data to 3.2 µg m−3. In light of these results, a low-cost thermal dryer could be a cost-effective add-on that could revert the effect of the hygroscopic growth and the fog in the PM readings. However, special care is needed when designing a low-cost dryer for a PM sensor to produce FEM similar PM readings, as high temperatures may irreversibly change the sampled air by evaporating the most volatile particulate species and thus deliver underestimated PM readings. New versions of a low-cost dryer aiming at FEM measurements should focus on maintaining the RH at the sensor inlet at 50 % and avoid reaching temperatures higher than 40 ∘C in the drying system. Finally, we believe that low-cost dryers have a very promising future for the application of sensors in citizen science, sensor networks for supplemental monitoring, and epidemiological studies.

Abstract

Hydrogel foams provide an aqueous environment that is very attractive for the immobilization of enzymes. To this end, functional polymers are needed that can be converted into hydrogel foams and that enable bioconjugation while maintaining high enzyme activity. The present study demonstrates the potential of biotinylated gelatin methacryloyl (GM10EB) for this purpose. GM10EB is synthesized in a two-step procedure with gelatin methacryloyl (GM10) being the starting point. Successful biotinylation is confirmed by 2,4,6-trinitrobenzene sulfonic acid and 4'-hydroxyazobenzene-2-carboxylic acid/avidin assays. Most importantly, a high methacryloyl group content (DM) is maintained in GM10EB, so that solutions of GM10EB show both a sufficiently low viscosity for microfluidic foaming and a pronounced curing behavior. Thus, foamed and nonfoamed GM10EB hydrogels can be prepared via radical crosslinking of the polymer chains. Within both sample types, biotin groups are available for bioconjugation, as is demonstrated by coupling streptavidin-conjugated horseradish peroxidase to the hydrogels. When assessing the substrate conversion rate rA in foamed hydrogels by enzymatic conversion of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), a value for rA 12 times higher than the value for nonfoamed hydrogels of the same mass is observed. In other words, rA can be successfully tailored by the hydrogel morphology.

Abstract

The scaffold pore size influences many critical physical aspects of tissue engineering, including tissue infiltration, biodegradation rate, and mechanical properties. Manual measurements of pore sizes from scanning electron micrographs using ImageJ/FIJI are commonly used to characterize scaffolds, but these methods are both time-consuming and subject to user bias. Current semi-automated analysis tools are limited by a lack of accessibility or limited sample size in their verification process. The work here describes the development of a new MATLAB algorithm, PoreScript, to address these limitations. The algorithm was verified using three common scaffold fabrication methods (e.g., salt leaching, gas foaming, emulsion templating) with varying pore sizes and shapes to demonstrate the versatility of this new tool. Our results demonstrate that the pore size characterization using PoreScript is comparable to manual pore size measurements. The PoreScript algorithm was further evaluated to determine the effect of user-input and image parameters (relative image magnification, pixel intensity threshold, and pore structure). Overall, this work validates the accuracy of the PoreScript algorithm across several fabrication methods and provides user-guidance for semi-automated image analysis and increased throughput of scaffold characterization.

Abstract

The present study is about the foaming and defoaming properties of the CO2-switchable surfactant N,N-dimethyltetradecylamine (C14DMA) and its advantages compared with the non-switchable counterpart tetradecyltrimethylammonium bromide (C14TAB). In the absence of CO2, C14DMA is a water insoluble organic molecule without any surface activity thus being unable to stabilize foams. In the presence of CO2, the head group becomes protonated which transforms the water insoluble molecule into a cationic surfactant. Comparing the surface properties and foamability of C14DMA and C14TAB one finds a very similar behavior. However, the foam stabilities differ depending on the gas. Foaming the two-surfactant solutions with CO2 leads to very unstable foams in both cases. However, foaming the two surfactant solutions with N2 reveals the switchability of C14DMA: while the volume of foams stabilized with C14TAB hardly changes over 1600 s, the volume of foams stabilized with C14DMA decreases significantly in the same period of time. This difference is due to the fact that the surface activity, that is, the amphiphilic nature, of C14DMA is continuously switching off since CO2 is displaced by N2 thus deprotonating and deactivating the surfactant.

Abstract

Abstract Liquid foams of intermediate stability have been shown to be very efficient in the cleaning of sensitive surfaces because of the synergy between imbibition and foam decay. While we quantified these mechanisms for contaminations with liquid oils in our previous work, we show here their extension to oils containing soot particles in an effort to simulate increasingly realistic contaminations. Using foams with a wide range of liquid fractions and with different stabilities, we show that the main cleaning mechanisms remain very similar, with the oil entraining the soot particles. However, we find much less efficient soot removal when the liquid channels of the foams are small enough to hinder efficient transport of the soot particles.

Abstract

We developed a new, innovative foam-based cleaning method with which the amount of detergent can be reduced by up to 90%. In addition, foams generate physical cleaning mechanisms, namely imbibition and wiping. The combination of imbibition and wiping is so efficient that it is sufficient to simply let the foam sit on the surface for a while before removing it by vacuuming. No additional mechanical action is needed! This publication describes how we managed to clean the historic carriages of kings and emperors of past centuries in the “Marstallmuseum” in Nymphenburg Palace in cooperation with the “Bavarian Administration of State-Owned Palaces, Gardens and Lakes”.

Abstract

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von makroporösen Hydrogelschäumen sowie hieraus erhältlichen makroporösen Mineralplastik-schäumen.

Abstract

The present invention relates to a method for producing macroporous hydrogel foams and to macroporous mineral plastic foams obtainable by said method.

Abstract

This study reports on a novel templating route, which uses foamed emulsions as templates for porous polymers. The concept is based on the generation of a monomer-in-water emulsion, which is subsequently foamed via microfluidics. The monomer of choice is 1,4-butanediol dimethacrylate (1,4-BDDMA). After polymerization of the foamed emulsion, one obtains open-cell polymer foams with porous pore walls. Foamed emulsions and polymer foams are generated. It is shown that foamed emulsion templating in combination with microfluidics is well-suited to synthesize 1) monodisperse poly(1,4-BBDMA) foams with controllable pore sizes and 2) their polydisperse counterparts with controllable polydispersities. Monodisperse templates with different bubble sizes and thus polymer foams with different pore sizes ranging from about 100–400 μm in diameter are synthesized. Microfluidics is also used for the generation of polydisperse poly(1,4-BDDMA) foams with polydispersities between 18\% and 27\% but the same mean pore sizes as the monodisperse ones, i.e., we have access to polymer foams that only differ in their polydispersity.

Abstract

The influence of gelatin methacryloyl hydrogel morphology on the sorption and release behavior of metoprolol was studied for both equilibrium and non-equilibrium conditions. For samples examined in equilibrium conditions, no influence of the sample morphology was observed. The maximum sorption capacity qmax was determined to be 530 μmol g–1. Furthermore, up to 100\% of the sorbed drug was released from both foamed and non-foamed samples upon immersion into salt solutions, which demonstrates the regenerability of the material. By contrast, the sample morphology strongly influenced the sorption and release kinetics. We found that the sorption and release rate coefficients k increased up to 10 times for foamed hydrogels as compared to non-foamed hydrogels. Furthermore, k increased with increasing ion concentration in the sorption and release medium. This effect was more pronounced for non-foamed hydrogels. The obtained results indicate that the sorption and release rate can be controlled by the morphology of the sorbents and, to some extent, by the ion concentration of the surrounding medium.

Abstract

Hypothesis While tailoring the pore diameters in hydrogel foams has been demonstrated in numerous studies, fine control over the diameters of the pore openings is still a challenge. We hypothesise that this can be achieved by controlling the size of the thin films which separate the bubbles in the liquid foam template. If this is the case, systematic changes of the template’s gas fraction ϕ (the higher ϕ, the larger are the thin films) will lead to corresponding changes of the pore opening diameter. Experiments Since the size of the thin films depends on both bubble size 〈Db〉 and gas fraction ϕ, we need to decouple both parameters to control the film size. Thus, we generated foams with constant bubble sizes via microfluidics and adjusted the gas fractions via two different techniques. The foams were solidified using UV light. Subsequently, they were analysed with confocal fluorescence microscopy. Findings We were able to change the pore opening diameter 〈dp〉 at a constant pore diameter 〈Dp〉 by adjusting the gas fraction of the foam template. The obtained 〈dp〉/〈Dp〉 ratios are between those obtained theoretically for disordered foams and FCC ordered foams, respectively.

Abstract

Polymerizing a water-in-styrene high internal phase emulsion (HIPE) and subsequently expanding the polyHIPE through heating could present an environmentally friendly alternative to the synthesis of industrially expanded polystyrene foams where pentane is used as blowing agent. The polyHIPE has to have a closed-pore morphology to build up enough pressure during heating so that the polystyrene matrix expands before the water escapes. We found that the polyHIPE has to contain only small amounts of the crosslinker DVB to keep the Tg of the polystyrene matrix low and thus to ensure better expandability. In addition, the water volume fraction Φdisp should be as high as possible to obtain polymer foams with low densities. To find a HIPE with a suitable composition for expansion, we systematically varied Φdisp, the DVB concentration cDVB, and the surfactant concentration csurf. We investigated each composition by studying the stability of the HIPE before polymerization, by analyzing the morphology of the polyHIPEs with scanning electron microscopy, and by examining the water release rates of the polyHIPEs. To have a highly porous polystyrene foam, Φdisp must be ≥ 74 vol%. However, no suitable composition was found with this high Φdisp which is why we suggest that a stepwise, systematic reduction of Φdisp at the expense of the porosity could be a solution to this dilemma.

Abstract

Hypothesis In previous studies we looked at the foam stability of various surfactants with C12 alkyl chains but different head groups and found that stable foams are only generated if the head groups are capable of forming hydrogen bonds with each other. Despite the consistency of the experimental data with the conclusions drawn from it we had no direct proof for our hypothesis that H-bonds are formed between surfactant head groups. Experiments To fill this gap, i.e. to demonstrate intersurfactant H-bond formation, we chose the non-ionic sugar surfactant n-dodecyl-β-d-maltoside (β-C12G2) and used molecular dynamics (MD) simulations as well as grazing-incidence X-ray (GIX) scattering and diffraction to study the surfactant-loaded air-water interface. Findings (1) In a densely packed monolayer, close to the critical micelle concentration (cmc), each head group of the sugar surfactant is involved in ∼5 intersurfactant H-bonds with other head groups and in ∼5 H-bonds with water molecules. (2) The number of intersurfactant H-bonds decreases, while the number of surfactant-water H-bonds increases with increasing distance between the head groups (below the cmc). (3) Even at very large distances (well below the cmc) there are still intersurfactant H-bonds, which we ascribe to the formation of clusters at the surface. (4) GIX scattering revealed that a homogeneous surfactant monolayer is formed at full coverage (around the cmc), i.e. cluster formation only happens below the cmc.

Abstract

Hypothesis We synthesised monodisperse macroporous polymers via polymerisation of water-in-monomer droplet emulsions and obtained non-spherical pores with layered pore walls. We hypothesise that this morphology is caused by surfactant diffusion and phase separation during polymerisation. Experiments We varied the surfactant mass fraction of the emulsions and polymerised the templates with a water-soluble initiator. From the resulting macroporous polymers we determined the shape of the pores and thickness of the layers via scanning election microscopy. The response of the monomer/surfactant mixture to polymerisation was studied by a ternary phase diagram that simulated polymerisation. Findings The emergence of non-spherical pores with layered pore walls is indeed caused by surfactant diffusion and phase separation. During polymerisation the surfactant molecules diffuse either to the water/monomer interface or deeper into the continuous monomer phase. The first process results in non-spherical pores, while the second process generates layered pore walls.

Abstract

Using microfluidics, we were able to synthesize monodisperse water-in-monomer emulsions with styrene and divinylbenzene (DVB) as monomers. When polymerizing and drying these emulsions, we found that the structure of the resulting macroporous polymer strongly depends on the type of initiator. With the oil-soluble azobisisobutyronitrile (AIBN), an open-cell structure with spherical pores was obtained. However, with the water-soluble potassium peroxydisulfate (KPS), a closed-cell structure with rhombic dodecahedron-shaped pores and thick, layered pore walls was formed. In the latter case, a yet unexplained mechanism counteracts the capillary pressure arising from surface minimization: the surface area of a rhombic dodecahedron is ˜þinspace10\% larger than that of a sphere. In our previous work, we suggested that the underlying mechanism may be osmotic transport of DVB from the plateau borders to the films. We argued that this transport also explains the layered pore walls, i.e., the formation of two outer poly-DVB-rich layers and one inner polystyrene-rich layer. In order to prove or disprove this mechanism, we carried out additional experiments. However, none of those experiments corroborated our hypothesis of osmotic transport! This study provides clear experimental evidence that our previously suggested mechanism via which spherical droplets become polyhedral pores is incorrect. We will describe (a) the rationale behind the additional experiments, (b) our expectations, and (c) our findings. Last but not least, we will discuss all of this in the light of the proposed osmotic transport.

Abstract

We describe a route to synthesize a mechanically stable, non-flammable poly(acrylic acid)–calcium salt (the so-called mineral plastic) foam whose structure can be tailored. Main steps of the foam synthesis are: (1) foaming of the PAA-containing solution, (2) gelation of the continuous foam phase, and (3) drying of the hydrogel foam. The main challenge was to formulate an aqueous solution with a large amount of poly(acrylic acid), PAA, and calcium to yield a mechanically stable foam. The resulting PAA-based solid foams with pore sizes of around 220 μm can easily be dissolved, i.e. recycled, in an acidic solution.

Abstract

Hypothesis The micrometer-sized gas bubbles of a liquid foam with a dispersed gas phase of > 74 vol% are polyhedral and surrounded by a continuous aqueous phase. The structure of a water-rich microemulsion with a water phase of > 74 vol% normally consists of oil droplets in water or is bicontinuous. We hypothesize that at these high water contents polyhedral water droplets in oil can also exist. Experiments We (a) carried out phase studies on the water-rich side of the phase diagram of the quaternary system water/NaCl – hexyl methacrylate – AOT, because AOT is known for its propensity to form water-in-oil structures and hexyl methacrylate can be polymerized, (b) measured the electrical conductivities and viscosities, and (c) visualized the nanostructure with freeze-fracture electron microscopy (FFEM). Findings We found narrow 1-phase regions emanating from the L3 phase of the oil-free water/NaCl – AOT system by adding small amounts of oil. In these regions the conductivities become extremely low and the viscosities are extremely high. In addition, FFEM images clearly show the foam-like nanostructure.

Abstract

Gelled non-toxic microemulsions have great potential in transdermal drug delivery: the microemulsion provides an optimum solubilizing capacity for drugs and promotes drug permeation through the skin barrier, while the gel network provides mechanical stability. We have formulated such a gelled non-toxic microemulsion consisting of H2O – isopropyl myristate (IPM) – Plantacare 1200 UP (technical-grade alkyl polyglucoside with an average composition of C12G1.4) – 1,2-octanediol in the presence of the low molecular weight gelator (LMWG) 1,3:2,4-dibenzylidene-d-sorbitol (DBS) at an oil-to-water ratio of ϕ = 0.50. The study at hand aimed to develop gelled non-toxic microemulsions that can contain both oil- and water-soluble drugs and are either water- or oil-based, depending on the application. To accomplish this, we varied the oil-to-water ratio from being water-rich to oil-rich, i.e. 0.2 ≤ ϕ ≤ 0.8. Phase studies were carried out along the middle phase trajectory, and a suitable LMWG was identified for all ϕ-ratios. Electrical conductivity measurements showed that the structure can be tuned from water- to oil-continuous by adjusting the amount of 1,2-octanediol and ϕ-ratios. The existence of the gel network was visualized by freeze-fracture electron microscopy (FFEM) at three different ϕ-ratios. We found that all systems from ϕ = 0.35 to ϕ = 0.80 form strong gels with nearly the same rheological behavior, while the system with ϕ = 0.20 is a much weaker gel. We attribute this behavior on the one hand to the microemulsion microstructure and on the other hand to the solvent-dependent gelation properties of DBS, which can be described by the Hansen solubility parameters (HSPs).

Abstract

Gelled non-toxic bicontinuous microemulsions have great potentials in transdermal drug delivery. The bicontinuous microemulsion provides optimum drug solubilisation and promotes skin permeation, while the gel network provides mechanical stability and an easy application. For the first time, we have formulated such a gelled non-toxic bicontinuous microemulsion consisting of H2O, isopropyl myristate (IPM), the non-ionic sugar-based surfactant Plantacare 1200 UP (C12G1.4), 1,2-octanediol, and the low molecular weight gelator 1,3:2,4-dibenzylidene-D-sorbitol (DBS). In this study, we solubilised both hydrophobic and hydrophilic model drugs in the non-toxic bicontinuous microemulsion, namely lidocaine and diclofenac sodium salt. We found that the microemulsion allows for the solubilisation of designated amounts of both model drugs in the same formulation. Interestingly, the combination of both drugs led to the unexpected stabilisation of a scattering one-phase formulation without adding the surfactant Plantacare 1200 UP. Furthermore, the drug-loaded microemulsions were gelled by DBS without altering the phase behaviour. Finally, we found the rheological behaviour of the drug-free and drug-loaded microemulsions to be quite similar. These results suggest that the drug-containing gelled bicontinuous microemulsion is an orthogonal self-assembled system with a high potential for the use in transdermal drug delivery.

Abstract

Hypothesis Foamed surfactant solutions can clean surfaces! We hypothesise that the cleaning efficiency depends on the liquid fraction and on the stability of the foam. We also hypothesise that the cleaning efficiency is the better the smaller the average bubble size is. Experiments The double syringe technique was used to generate foams with varying liquid fractions but the same, very small bubble sizes with and without perfluorohexane in the gas phase. We performed cleaning tests in which the foams were applied to glass substrates contaminated with a fluorescent oil. Findings We found that unstable foams clean better than stable foams. Three cleaning mechanisms were identified: (1) imbibition at low liquid fractions, (2) wiping, i.e., shifting of the contact line between oil, foam and glass, at all liquid fractions, and (3) drainage at high liquid fractions. The change of the liquid fraction and of the foam stability lead to different combinations of these mechanisms and thus to different cleaning results.

Abstract

Abstract Controlling the stability of liquid foams is of the utmost importance for a wide range of applications. For decades, fluorocarbon vapors have been added to the gas phase of foams to ensure long-term stability against bubble coarsening. However, it is shown here for the first time that they also have an unexpected and pronounced effect on bubble coalescence. This effect is quantified in detail for foams stabilized by the nonionic surfactant hexaethylene glycol monododecyl ether (C12E6) at controlled fluorocarbon (perfluorohexane (C6F14)) concentrations, but it is observed for all investigated surfactants. Measuring surface tensions of the foaming solution with increasing fluorocarbon concentration, a synergy between the fluorocarbon and the surfactant is found which can be explained by a) the formation of mixed layers of both species at the gas/water interface at low fluorocarbon concentrations and b) the formation of a macroscopic fluorocarbon film if the gas phase is saturated with fluorocarbon vapor. The precise mechanism responsible for reducing coalescence, that is, film rupture, remains to be elucidated.

Abstract

Eine Alternative zu organischen Kunststoffschäumen für die Wärmedämmung von Gebäuden können Mineralkunststoffe sein. Sie sind nicht brennbar und im Gegensatz zu Silica‐Aerogelen oder Steinwolle gut zu recyceln.

Abstract

Hypothesis It is possible to generate fairly monodisperse liquid foams by a dispersion cell, which was originally designed for the generation of fairly monodisperse emulsions. If this is the case, scaling-up the production of monodisperse liquid and solid foams will be no longer a problem. Experiments We used the dispersion cell - a batch process - and examined the influence of stirrer speed, membrane pore diameter and injection rate on the structure of the resulting liquid foams. We used an aqueous surfactant solution as scouting system. Once the experimental conditions were known we generated gelatin-based liquid foams and methacrylate-based foamed emulsions. Findings We found that (a) the bubble size of the generated liquid foams can be adjusted by varying the membrane pore diameter, (b) no stirrer should be used to obtain monodisperse foams, and (c) the bubble size is not influenced by the air injection rate. Since (i) the output for all investigated systems is up to two orders of magnitude larger compared to microfluidics and (ii) the membrane technology can very easily be scaled-up if run in a continuous process, the use of membrane foaming is expected to be heavily used for the generation of monodisperse liquid and solid foams, respectively.

Abstract

Emulsion and foam templating allow the synthesis of tailor-made polymer foams. A complementary templating route is foamed emulsion templating. The concept is based on the generation of a monomer-in-water emulsion which is subsequently foamed. After polymerization of the foamed emulsion, one obtains open-cell polymer foams with porous pore walls. In the paper at hand, we generated foamed emulsions and synthesized polymer foams which are based on the monomer 1,4-butanediol dimethacrylate (1,4-BDDMA). The main challenge was to find the optimal composition of the emulsion by varying the components systematically. We will discuss that the composition of the monomer-in-water emulsion is key for the stability of the foamed emulsion and thus for the structure of the resulting polymer foam. The final composition of the continuous phase was found to be 65 vol% 1,4-BDDMA, 30 vol% water and 5 vol% glycerol. We foamed and polymerized this emulsion to check the foamed emulsion's suitability as a template for solid polymer foams. We generated a foamed emulsion with a mean bubble diameter of 151 μm ± 90 μm and obtained a highly porous poly(1,4-BDDMA) foam with a pore mean diameter of 366 μm ± 91 μm. Furthermore, the polymer foam has a “sub-porosity” within the pore walls.

Abstract

Polymer foams are becoming increasingly important in industry, especially biodegradable polymer foams are in demand. Depending on the application, polymer foams need to have characteristic properties, which include connectivity and polydispersity. We show how polymer foams with tailor-made structures can be synthesized from water-in-monomer emulsions which were generated via microfluidics. As monomer we used 1,4-butanediol dimethacrylate (1,4-BDDMA). Firstly, we synthesised monodisperse open- and closed-cell poly(1,4-BDDMA) foams with either spherical or hexagonal pore shapes by varying the locus of initiation. Secondly, we were able to control the pore diameters and obtained polymer foams of both connectivities and pore shapes with pore sizes from ∼70 μm up to ∼120 μm by means of one microfluidic chip. Finally, we synthesized poly(1,4-BDDMA) foams with controllable polydispersity. Here, the mean droplet diameter was the same as that of the monodisperse counterparts in order to be able to compare the properties of the resulting polymer foams.

Abstract

Gelled non-toxic bicontinuous microemulsions have a great potential for transdermal drug delivery as the microemulsion facilitates the solubilization of both hydrophilic and hydrophobic drugs, while the gel network provides mechanical stability and thus an easy application on the skin. In our previous study, we formulated a gelled non-toxic bicontinuous microemulsion: we gelled the system H2O–isopropyl myristate (IPM)–Plantacare 1200 UP (C12G1.4)–1,2-octanediol with the low molecular weight organogelator 1,3:2,4-dibenzylidene-d-sorbitol (DBS). However, a large amount of Plantacare 1200 UP (12 wt %) is needed to form a bicontinuous microemulsion. To solve this problem, we studied a new class of surfactants, namely, alkanoyl methylglucamides (MEGA), which have been rarely used for the formulation of microemulsions. The phase behavior of microemulsions stabilized by MEGA-8/10, MEGA-12/14-PC, and MEGA-12/14-HC was compared with that of systems stabilized by alkyl polyglucosides. We found that even with 2 wt % MEGA-12/14-HC, a bicontinuous microemulsion can be formed, which is 1/6 of the amount of Plantacare 1200 UP. The bicontinuous microstructure of the non-toxic microemulsion H2O–IPM–MEGA-12/14-HC–1,2-octanediol was confirmed by small-angle neutron scattering. Furthermore, the phase boundaries remained unchanged when gelled by DBS. The rheological properties of the gel were studied by oscillatory shear rheometry. Finally, freeze-fracture electron microscopy images show the coexistence of gel fibers and bicontinuous oil and water domains. These results suggest that the new gelled non-toxic bicontinuous microemulsion is an orthogonal self-assembled system.

Abstract

Surfactant-based lyotropic liquid crystal gels (LLCGs) are soft materials which combine the anisotropic order of a surfactant-based lyotropic liquid crystal with the mechanical stability of a gel. The most prominent example of a “natural“ LLCG is the biological cell. This review summarizes potential applications of surfactant-based LLCGs and the different strategies via which these materials can be obtained. The main focus, however, is on gelation with low molecular weight gelators (LMWG), which form self-assembled fibrillar networks (SAFiN). We will discuss whether or not the resulting surfactant-based LLCGs are orthogonal self-assembled systems, i.e. systems where the two coexisting structures (lyotropic liquid crystal and SAFiN) form independently.

Abstract

In solid foams, most physical properties are determined by the pore size and shape distributions and the organisation of the pores. For this reason, it is important to control the structure of porous materials. We recently tackled this issue with the help of microfluidic-aided foam templating, which allowed us to generate monodisperse and highly ordered chitosan foams. However, the properties of foams also depend on the properties of the pore wall constituents. In case of chitosan-based foams, the foams have poor absolute mechanical properties, simply due to the fact that the solubility of chitosan in water is very low, so that the relative density of the freeze-dried foams becomes very small. Drawing inspiration from the field of nanocomposites, we incorporated cellulose nanofibres into the foamed chitosan solutions, with a view to strengthening the pore walls in the foam and thus the mechanical properties of the final foam. We report here how the cellulose nanofibres affect the structure of both the liquid foam template and the solid foam. The resulting nanocomposite foams have improved mechanical properties, which, however, are not proportional to the amount of cellulose nanofibres in the composites. One reason for this observation is the disturbance of the porous structure of the solid foams by the cellulose nanofibres.

Abstract

The low-molecular-weight gelator (LMG) 12-hydroxyoctadecanoic acid (12-HOA) is insoluble in water, but can be solubilized in surfactant micelles. We therefore solubilized 12-HOA at 80 °C in an aqueous solution of cetyltrimethylammonium bromide (CTAB) containing spherical micelles. On cooling this system down to room temperature, a hydrogel is obtained. We will refer to this process as “surfactant-mediated gelation” (SMG). The hydrogels were formed at a lower 12-HOA concentration when sodium salicylate (NaSal) was added to the CTAB system, which induced the formation of wormlike micelles. Hydrogels obtained by SMG from spherical and wormlike micelles are referred to as gelled micellar phases (GMs) and gelled wormlike micellar phases (GWLMs), respectively. Optical microscopy and transmission electron microscopy (TEM) showed that 12-HOA forms self-assembled fibrillar networks (SAFiNs) in both GMs and GWLMs. The sol–gel transition temperature, Tsol–gel, of the GWLM samples was higher than that of the GM samples. Dynamic rheological measurements revealed gel properties (G′ > G′′ at all angular frequencies) for both gels; however, a higher viscoelasticity was observed for the GWLM samples, which in turn, was reflected in the higher Tsol–gel. Small- and wide-angle X-ray scattering (SWAXS) showed that micelles and gel fibers coexist in the GM and GWLM samples. Our study demonstrates the gelation of aqueous micellar solutions with water-insoluble LMGs.

Abstract

Abstract Tailoring the morphology of macroporous structures remains one of the biggest challenges in material synthesis. Herein, we present an innovative approach for the fabrication of custom macroporous materials in which pore size varies throughout the structure by up to an order of magnitude. We employed a valve-based flow-focusing junction (vFF) in which the size of the orifice can be adjusted in real-time (within tens of milliseconds) to generate foams with on-line controlled bubble size. We used the junction to fabricate layered and smoothly graded porous structures with pore size varying in the range of 80?800??m. Additionally, we mounted the vFF on top of an extrusion printer and 3D-printed constructs characterized by a predefined 3D geometry and a controlled, spatially varying internal porous architecture, such as a model of a bone. The presented technology opens new possibilities in macroporous material synthesis with potential applications ranging from tissue engineering to aerospace industry and construction.

Abstract

Bicontinuous microemulsions gelled with a low molecular weight gelator have been shown to be an orthogonally self-assembled system. With the mechanical stability provided by the gel network, gelled non-toxic bicontinuous microemulsions have the potential to be an efficient transdermal drug delivery carrier. However, up to now no suitable system has been formulated for transdermal drug delivery. To fill this gap, we formulated and characterized a gelled non-toxic bicontinuous microemulsion suitable for the mentioned application. Starting from a previously studied scouting system, namely, H2O–n-octane–n-octyl β-d-glucopyranoside (β–C8G1)–1-octanol, the co-surfactant and the oil were replaced by non-toxic components. Subsequently, the expensive pure surfactant was replaced by cheap technical-grade surfactants (Plantacare® series) to make the system economical. Having formulated the non-toxic microemulsion H2O–IPM–Plantacare 1200 UP–1,2-octanediol, three low molecular weight gelators were studied with regard to the gelation of both the scouting system and the non-toxic system. The chosen gelators were 12-hydroxyoctadecanoic acid (12-HOA), 1,3:2,4-dibenzylidene-d-sorbitol (DBS), and N,N′-dibenzoyl-l-cystine (DBC). We found that only DBS gels the non-toxic microemulsion. The gelled non-toxic bicontinuous microemulsion H2O–IPM–Plantacare 1200 UP–1,2-octanediol was characterized with oscillatory shear rheometry and small-angle neutron scattering (SANS) at a DBS concentration of 0.3 wt% to verify that the system is indeed a gel and that the microstructure of the microemulsion is not altered by the gel network.

Abstract

On the basis of previous results revealing that intersurfactant H-bonds improve foam stability, we now focus on how foams stabilized by two different N-acyl amino acid surfactants are affected by different salts (NaF, NaCl, NaSCN), which can promote or break intersurfactant H-bonds. The chosen surfactants, namely, sodium N-lauroyl sarcosinate (C12SarcNa) and sodium N-lauroyl glycinate (C12GlyNa), differ only by one methyl group at the nitrogen of the amide bond that blocks intersurfactant H-bonds in the case of C12SarcNa. The salts were chosen because they are kosmotropic (NaF), chaotropic (NaSCN), and in between (NaCl) and thus influence the formation of an H-bond network in different ways. Surface tension measurements showed that the addition of salts decreased the cmcs of both surfactants and increased the packing density, as expected. Moreover, in presence of the salts, the head groups of the H-bond forming surfactant C12GlyNa were more tightly packed at the surface than the C12SarcNa head groups. The effect of the salts on foam stability was studied by analysis of the foam height, the foam liquid fraction, and by image analysis of the foam structure. As expected, the salts had no significant effect on foams stabilized by C12SarcNa, which is unable to form intersurfactant H-bonds. In contrast, the stability of C12GlyNa-containing foams followed the trend NaF > NaCl > NaSCN, which is in agreement with NaF promoting and NaSCN breaking intersurfactant H-bonds. Surface rheology measurements allowed us to correlate foam stability with surface elasticity. This study provides new insights into the importance of H-bond promoters and breakers, which should be used in the future design of tailor-made surfactants.

Abstract

This study deals with the gelation of lyotropic liquid crystals (LLCs) of the binary system H2O–heptaethylene glycol monododecyl ether (C12E7). The Lα and H1 phases are gelled with the organogelator 1,3:2,4-dibenzylidene-d-sorbitol (DBS). The microstructure of the gelled LLCs is compared to those of the binary counterparts, i.e., the pure LLCs and the binary gel ethylene glycol–DBS. We present the first examples of gelled lyotropic liquid crystals (LLCs) formed by two different ways upon cooling: (1) At a DBS mass fraction of η = 0.015, the gel is formed first, followed by LLC formation. (2) At η = 0.0075, the LLC is formed first, followed by gel formation. Addressing LLC and gel formation in different orders, the influence of the LLC on the gel network and vice versa can be examined. Independent of which structure is formed first, the interlayer spacing dLLC of the LLCs is only slightly larger in the presence of the gel network compared to the nongelled counterparts. Likewise, the influence of the LLCs on the gel fibers is independent of the chronology of the gel and LLC formation. For both ways, the gel fibers are twisted and arranged in bundles parallel to the bilayers of the Lα phase and the cylindrical micelles of the H1 phase. Whereas the twisted structure of the gel fibers in ethylene glycol is retained in the presence of the LLCs, the arrangement in bundles is not observed in the binary gels. In the latter case, randomly distributed single fibers which are also slightly thinner are detected. However, we observed the fiber bundles independent of whether the gel network is formed in the isotropic phase or in the LLC and argue that the difference is caused by different interactions of organogelator DBS with the system H2O–C12E7 than with ethylene glycol. In summary, we found that both the surfactant and the gelator molecules self-assemble in the presence of each other, leading to the coexistence of an LLC and a gel network. This is what is called orthogonal self-assembly.

Abstract

Gelled lyotropic liquid crystals (LLCs) are highly tunable multi-component materials. By studying a selection of low molecular weight gelators (LMWGs), we find gelators that form self-assembled gels in LLCs without influencing their phase boundaries. We studied the system H2O/NaCl–Genapol LA070 in the presence of (a) the organogelators 12-hydroxyoctadecanoic acid (12-HOA) and 1,3:2,4-dibenzylidene-d-sorbitol (DBS) and (b) the hydrogelators N,N′-dibenzoyl-l-cystine (DBC) and a tris-amido-cyclohexane derivative (HG1). Visual phase studies and oscillation shear frequency sweeps confirmed that 12-HOA acts as co-surfactant (stabilizing the lamellar Lα phase and destabilizing the hexagonal H1 phase), thus preventing gelation. Conversely, DBS was a potent gelator for LLCs, with the phase boundaries un-influenced by the presence of DBS; gelled lamellar Lα, and softly-gelled hexagonal H1 phases are formed. For the hydrogelator DBC, the LLC phase boundaries were only slightly altered, but no gelled LLCs were formed. For the hydrogelator HG1, however, the phase boundaries were unaffected while gelled lamellar Lα and softly-gelled hexagonal H1 phases were formed. Temperature-dependent rheology measurements demonstrated that by changing the DBS or the HG1 concentration, the sol–gel transition temperature of the gelled lamellar Lα phase can be adjusted such that (a) Tsol–gel is below the Lα-isotropic phase transition (DBS, HG1 mass fraction η = 0.0075) and (b) Tsol–gel is above the gelled Lα-isotropic phase transition (DBS, HG1 η = 0.015). This opens the possibility of temporal materials control by addressing phase transitions in different orders. As this system contains oil and water, both the organogelator DBS and the hydrogelator HG1 can gel these LLCs, but this clearly does not apply to all organogelators/hydrogelators. The study indicates that careful optimization of LMWGs is required to avoid interaction with the surfactant layer and to optimize the Tsol–gel value, which is important for the application of LMWGs in gelled LLCs.

Abstract

In a previous study we investigated the phase behavior of microemulsions consisting of the ionic liquid ethylammonium nitrate (EAN), an n-alkane and a nonionic alkyl polyglycolether (CiEj). We found the same general trends as for the aqueous counterparts, i.e. a transition from an oil-in-EAN microemulsion via a bicontinuous microemulsion to an EAN-in-oil microemulsion with increasing temperature. However, unlike what happens in the corresponding aqueous systems, in EAN-in-oil microemulsions only a very small amount of EAN was detected by NMR-measurements. This is why we investigated the phase behavior and microstructure of EAN-rich n-dodecane-in-EAN microemulsions and oil-rich EAN-in-n-octane microemulsions. We found that the ionic liquid emulsification failure boundary has an extraordinarily small slope, which suggests that the amphiphilic film loses its ability to solubilize EAN with an increase in temperature by only a few degrees. The analysis of the small angle neutron scattering (SANS) curves unambiguously shows that this behavior is due to the fact that the EAN molecules form a substructure with a characteristic length scale of Λ ≈ 8 Å inside the EAN-in-oil droplets. In more detail, the analysis of the SANS data with the GIFT method revealed a transition from spherical to cylindrical structures approaching the respective critical endpoint temperatures. By using the respective form factors and combining them with a Gaussian spatial intensity distribution to account for the EAN sub-structure we were able to describe the scattering curves nearly quantitatively.

Abstract

We study the generation and decay of aqueous foams stabilized by sodium dodecyl sulfate (SDS) in the presence of unmodified cellulose nanofibrils (CNF). Together with the rheology of aqueous suspensions containing CNF and SDS, the interfacial/colloidal interactions are determined by quartz crystal microgravimetry with dissipation monitoring, surface plasmon resonance, and isothermal titration calorimetry. The results are used to explain the properties of the air/water interface (interfacial activity and dilatational moduli determined from oscillating air bubbles) and of the bulk (steady-state flow, oscillatory shear, and capillary thinning). These properties are finally correlated to the foamability and to the foam stability. The latter was studied as a function of time by monitoring the foam volume, the liquid fraction, and the bubble size distribution. The shear-thinning effect of CNF is found to facilitate foam formation at SDS concentrations above the critical micelle concentration (cSDS ≥ cmc). Compared with foams stabilized by pure SDS, the presence of CNF enhances the viscosity and elasticity of the continuous phase as well as of the air/water interface. The CNF-containing foams have higher liquid fractions, larger initial bubble sizes, and better stability. Due to charge screening effects caused by sodium counter ions and depletion attraction caused by SDS micelles, especially at high SDS concentrations, CNF forms aggregates in the Plateau borders and nodes of the foam, thus slowing down liquid drainage and bubble growth and improving foam stability. Overall, our findings advance the understanding of the role of CNF in foam generation and stabilization.

Abstract

This study relates to the release of non-cellulosic components (cell wall heteropolysaccharides, lignin, and extractives) from swollen wood fibers in the presence of an anionic surfactant (sodium dodecyl sulfate, SDS) at submicellar concentrations. Highly surface-active aggregates form between SDS and the leached, non-cellulosic components, which otherwise do not occur in the presence of cationic or nonionic surfactants. The in situ and efficient generation of liquid foams in the presence of the leached species is demonstrated. The foaming capacity and foam stability, as well as the foam’s structure, are determined as a function of the composition of the aqueous suspension. The results indicate that naturally occurring components bound to wood fibers are extractable solely with aqueous solutions of the anionic surfactant. Moreover, they can form surface-active aggregates that have a high foaming capacity. The results further our understanding of residual cell wall components and their role in the generation of foams.

Abstract

Gelled lyotropic liquid crystals can be formed by adding a gelator to a mixture of surfactant and solvent. If the gel network and the liquid-crystalline phase coexist without influencing each other, the self-assembly is called orthogonal. In this study, the influence of the organogelator 12-hydroxyoctadecanoic acid (12-HOA) on the lamellar and hexagonal liquid crystalline phases of the binary system H2O–C12E7 (heptaethylene glycol monododecyl ether) is investigated. More precisely, we added 12-HOA at mass fractions from 0.015 to 0.05 and studied the resulting phase diagram of the system H2O–C12E7 by visual observation of birefringence and by 2H NMR spectroscopy. In addition, the dynamic shear moduli of the samples were measured in order to examine their gel character. The results show that 12-HOA is partly acting as co-surfactant, manifested by the destabilization of the hexagonal phase and the stabilization of the lamellar phase. The higher the total surfactant concentration, the more 12-HOA is incorporated in the surfactant layer. Accordingly, its gelation capacity is substantially reduced in the surfactant solution compared to the system 12-HOA–n-decane, and large amounts of gelator are required for gels to form, especially in the lamellar phase.

Abstract

HYPOTHESIS: Many efforts have been made to formulate water-IL microemulsions. One of the most intensely studied systems is H2O - 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF6) - 4-octylphenol polyethoxylate (TX-100) and it is not questioned that this system forms microemulsions. The nanostructures observed for traditional microemulsions are postulated with the surfactant being adsorbed at the interface such that the hydrophilic EO sides intrude into the water domains, while the hydrophobic hydrocarbon chains are immersed into BMImPF6. However, the high polarity of BMImPF6 and the observation that BMImPF6 mixes well with oligoethylene oxides but hardly with non-polar solvents like toluene or alkanes are not in line with this picture. EXPERIMENTS: We re-studied the ternary system H2O - BMImPF6 - TX-100 by measuring phase diagrams, determining tie-lines, and carrying out ROESY NMR and PFG NMR measurements. FINDINGS: We found that the hydrophobic part of the surfactant interacts neither with water nor with BMImPF6, while both solvents interact with the hydrophilic part of the surfactant. We suggest that the surfactant is not adsorbed at the interface between water and the IL, but forms normal spherical or elongated micelles or even continuous aggregates with the hydrocarbon chains forming the interior of the aggregates.

Abstract

The critical micelle concentration (cmc), the surface excess (Γ), as well as the micelle aggregation number (m) of the surfactant dodecyldimethylamine oxide (C12DMAO) have been reported to strongly depend on the pH-value of the aqueous surfactant solution. At high ionic strength, the cmc displays a minimum, while both Γ and m have a maximum at a pH-value close to the pKa of the surfactant. These experimental observations have been explained as being due to specific hydrogen bonds between the head groups, which are formed once the surfactant is partly or fully protonated. This investigation addresses the question of whether the pH also affects the foaming properties of C12DMAO solutions. To answer this question we measured the foamability and the foam stability of C12DMAO solutions at a fixed C12DMAO concentration of 5 cmc for five different pH-values, namely pH = 2, 3, 5, 8, and 10. We found that the foamability is hardly affected by the pH-value, while the foam stability strongly depends on the pH. As is the case for the above mentioned properties, the foam stability also displays an extremum in the studied pH-range, namely a maximum at pH = 5. We discuss our results in terms of the hydrogen bond hypothesis and show that this hypothesis indeed is in line with the observed trend for the foam stability. Moreover, we discuss that hydrogen bond formation may rationalize how the molecular structure of a surfactant affects foam stability.

Abstract

The disjoining pressure ∏ as a function of the film thickness h was measured for aqueous solutions of the three non-ionic surfactants n-dodecyl-β-D-maltoside (β-C12G2), hexaethyleneglycol-monododecylether (C12E6), and tetraethyleneglycol-monodecylether (C10E4). For all three systems the film thickness of the Common black film (CBF) at a given pressure decreases with increasing surfactant concentration and from a certain concentration on a Newton black film (NBF) is formed. Moreover, an interpretation of the ∏(h) curves in terms of the DLVO theory leads to the result that the surface charge density decreases with increasing surfactant concentration for all of the surfactants. However, looking at the film stabilities, i. e. the pressure where the film rupture occurs, one sees a striking difference. Whereas the CBFs of β-C12G2 and C12E6 are destabilized with increasing surfactant concentration, the opposite is observed for the CBFs of C10E4. This result will be compared with literature data and discussed in terms of surface elasticities. Stabilization of Foam Films with Non-Ionic Surfactants: Alkyl Polyglycol Ethers Compared with Alkyl Polyglucosides.

Abstract

The foam pressure drop technique allows a characterisation of aqueous foams in a reasonably short time even if the foam is very stable. This technique determines the drainage (decrease of the water content W as a function of time t) and the lifetime sp of a foam at a certain reduced pressure Pr (pressure drop). With Pa being the atmospheric pressure the resulting pressure applied to the measuring cell is DP = Pa – Pr > 0. It is found that the rate of drainage is influenced by the type of foam film, namely Common Thin Film (CTF), Common Black Film (CBF), Newton Black Film (NBF), and Bilayer Film (BF). The type of film the foam consists of also plays a role for the lifetime sp. Measuring sp as a function of DP one obtains characteristic curves for foams consisting of CTFs, CBFs, NBFs, and BFs, respectively. Example experiments are given for some surfactant solutions and discussed with respect to the correlation between single foam films and macroscopic foams.

Abstract

Microemulsion formulations based on non-toxic alkyl glucosides (CmGn) are of interest for applications in pharmaceutical and cosmetic products. In this work we demonstrate the favorable properties of quaternary microemulsions consisting of water - oil - C8G1 - alcohol. As alcohols we used n-octanol as well as the non-toxic geraniol (C10H17OH). Microemulsions with geraniol are potential candidates for pharmaceutical applications. We show for the first time by simultaneous phase behavior, SANS and interfacial tension measurements a quantitative correlation between the curvature and the composition of the interfacial film. We can relate the behavior of quaternary, temperature-insensitive microemulsions based on alkyl glucosides to that of ternary nonionic systems which exhibit a temperature-dependent curvature of the film. Thus, we are able to compare directly the effect of the temperature and the concentration of alcohol in the interfacial film. Both are important tuning parameters for the curvature, helping to formulate microemulsions with the desired properties in practical applications

Abstract

Since foam is made of thin liquid films separated by air, its stability is determined by the properties of these individual films. The stability of well-drained quasi-static foam films is usually discussed in terms of interaction forces. These forces create an excess pressure normal to the film interfaces, which is termed the disjoining pressure II. Measuring II as a function of the distance h between the two interfaces results in so-called disjoining pressure isotherms. A first order interpretation of the experimental data is obtained by using the classical DLVO theory. However, the classical DLVO theory disregards the elasticity of the surfactant monolayers. By means of a DLVO expression which is expanded accordingly, a quantitative description of the disjoining pressure isotherms could be possible. This would be a very important step towards understanding the stability of thin liquid films which would eventually help us to correlate the stability of thin liquid films with that of macroscopic foams.

Abstract

This paper deals with the phase behavior of a quaternary system containing alkyl polyglucosides (APG). After briefly discussing the phase diagrams of the constituent binary and ternary systems we focus on the phase behavior of the quaternary system water-oil-surfactant-alcohol. By varying the surfactant-to-alcohol ratio in this quaternary mixture we observe the phase sequence 2-3-2 with increasing amounts of alcohol. We discuss the role of the alcohol and compare the phase inversion of this quaternary system with that of ternary systems of the type water-oil-alkyl polyglycol ether, CnEm, to stress the different properties and possible applications of these two types of nonionic surfactants.