Wettability of Graffiti Coatings by Green Nanostructured Fluids.

Green nanostructured fluids (GNFs), specifically water-in-oil nanoemulsions (w/o NEs), were investigated as professional "brush on, wipe off" nanodetergents for the effective removal of various challenging graffiti coatings. The efficacy of the advanced nanodetergents in eradicating resilient graffiti coatings was evaluated using various methods to assess the surface properties of forming graffiti coatings. The surface properties of these coatings were examined by assessing their wettability by water, surface free energy, and topography to obtain information on the intermolecular interactions with the nanodetergent during the wetting and graffiti removal process. Our findings revealed significant variations in the coating removal rate and efficacy of green nanostructured fluids, which are stabilized using surfactants derived from saccharides or amino acids. A water-in-oil nanoemulsion, stabilized by caprylyl/capryl glucoside, demonstrated exceptional efficiency at cleaning graffiti paints based on alkyd resin and containing various additives such as nitrocellulose or bitumen, from any hard surface within a short time period. However, a w/o NE, stabilized by sodium cocoyl glycinate, also showed effective removal of graffiti paints containing durable bitumen, albeit at a slower rate on. These green nanostructured fluids can be used as specific nanodetergents for the comprehensive removal of various graffiti coatings, but require a specified action time to prevent damage to the original substrate beneath the paint coating.

Surface Properties of Graffiti Coatings on Sensitive Surfaces Concerning Their Removal with Formulations Based on the Amino-Acid-Type Surfactants.

Water-in-oil (w/o) nanoemulsions stabilized with amino acid surfactants (AAS) are one example of nanotechnology detergents of the "brush on, wipe off"-type for removing graffiti coatings from different sensitive surfaces. The high-pressure homogenization (HPH) process was used to obtain the nanostructured fluids (NSFs), including the non-toxic and eco-friendly components such as AAS, esterified vegetable oils, and ethyl lactate. The most effective NSF detergent was determined by response surface methodology (RSM) optimization. Afterwards, several surface properties, i.e., topography, wettability, surface free energy, and the work of water adhesion to surfaces before and after their coverage with the black graffiti paint, as well as after the removal of the paint layers by the eco-remover, were determined. It was found that the removal of graffiti with the use of the NSF detergent is more dependent on the energetic properties and microporous structure of the paint coatings than on the properties of the substrates on which the layers were deposited. The use of NSFs and knowledge of the surface properties could enable the development of versatile detergents that would remove unwanted contamination from various surfaces easily and in a controlled way.

Synthesis of hydroxyapatite for biomedical applications.

The current need for long lasting implants and bone substitutes characterized by biocompatibility, bioactivity and mechanical properties, without the immune rejection is a great challenge for scientists. These bone substitute structures should be prepared for individual patients with all details controlled on the micrometer level. Similarly, nontoxic, biocompatible targeted drug delivery systems which allow controlling the rate and time period of the drug delivery and simultaneously eliminating toxic and side effects on the healthy tissues, are of great interest. Extensive attempts have been made to develop a simple, efficient, and green method to form biofunctional scaffolds and implant coatings possessing the above mentioned significant biocompatibility, bioactivity and mechanical strength. Moreover, that could also serve as drug delivery systems. Hydroxyapatite (HA) which is a major mineral component of vertebrate bones and teeth is an excellent material for these purposes. In this literature review the biologically inspired scaffolds, bone substitutes, implants characterized by mechanical strength and biocompatibility, as well the drug delivery systems, based on hydroxyapatite are discussed.

Properties of Langmuir and solid supported lipid films with sphingomyelin.

Biological cell membranes play a crucial role in various biological processes and their functionality to some extent is determined by the hydrophilic/hydrophobic balance. A significant progress in understanding the membrane structure was the discovery of laterally segregated lipid domains, called the lipid rafts. These raft domains are of ordered lamellar liquid-crystalline phase, while rest of the membrane exists in a relatively disordered lamellar liquid-crystalline phase. Moreover, the chemical constitution of the lipid rafts consists of a higher content (up to 50%) of cholesterol (Chol) and sphingomyelin (SM). Sphingomyelin also plays a significant role in the red cells of blood and nerves, in some diseases, as a precursor to ceramides, and other sphingolipid metabolites. In this paper properties of Langmuir and solid supported mixed lipid films of DPPC/SM, DOPC/SM, and Chol/SM are described. Special attention has been paid to wetting properties (hydrophobic/hydrophilic balance) of these films transferred onto a hydrophilic glass surface. To our knowledge such results have not yet been published in the literature. The properties were determined via contact angle measurements and then calculation of the films' apparent surface free energy. The films' wettability and their apparent surface free energy strongly depend on their composition. The energy is affected by both the structure of hydrocarbon chains of glycerophospholipids (DPPC and DOPC) and their interactions with SM. Properties of mixed Chol/SM monolayer depend also on the film stoichiometry. At a low Chol content (XChol=0.25) the interactions between SM and Chol are strong and hence the formation of binary complex is possible. This is accompanied by a decrease in the film surface free energy in comparison to that of pure SM monolayer, contrary to a higher Chol content where the monolayer energy increases. This suggests that cholesterol is excluded from the membrane thus increasing the film hydrophilicity. These results are consistent with the literature data and somehow confirm the hypothesis of lipid raft formation. The roughness of the investigated monolayer surfaces was also determined using optical profilometry. The roughness parameters of the DPPC, SM, and mixed DPPC/SM generally correlate with the changes of their apparent surface free energy, i.e. with the decreasing roughness the apparent surface free energy also decreases. However, this is not the case for mixed DOPC/SM monolayers. Although the roughness increases with SM content the apparent surface free energy decreases. Therefore some other factors, like the presence of unsaturated bonds in the DOPC molecule, influence the film phase state and the energy too. More experiments are needed to explain this hypothesis.

Surface modification of glass plates and silica particles by phospholipid adsorption.

The effect of phospholipid adsorption on the hydrophobicity of glass plates and on the surface charge of silica particles using contact angle and electrophoretic mobility measurements, respectively, was investigated. Deposition of successive statistical monolayers of dipalmitoylphosphatidylcholine (DPPC) on the glass surface showed zig-zag changes of water contact angle, especially on the first few monolayers. This behavior is qualitatively coherent with the oscillations observed in zeta potential values for increasing DPPC concentration. The results indicate that the phospholipid is adsorbed vertically on the plates, exposing alternately its polar head and non-polar hydrocarbon chains in successive layers. On the other hand, experiments conducted on glass plates prior hydrophobized by contact with n-tetradecane suggest that DPPC molecules may to some extent dissolve in the relatively thick n-alkane film and then expose their polar heads over the film surface thus producing polar electron-donor interactions. The effect of both DPPC and dioleoylphosphatidylcholine (DOPC) on the electrokinetic potential of silica spheres confirms adsorption of the phospholipids, leading to a decrease in the (originally negative) zeta potential of silica and even reversal of its sign to positive at acidic pH. Hydrophobic interactions between phospholipid molecules in the medium and those already adsorbed may explain the overcharging. The adsorption of neutral phospholipids may reduce the zeta potential as a consequence of the shift of the electrokinetic or slip plane. The effect is more evident in the case of DOPC, suggesting a less efficient packing of this phospholipid because of the presence of double bonds in its molecule, which in fact is well known.

Effect of temperature on n-tetradecane emulsion in the presence of phospholipid DPPC and enzyme lipase or phospholipase A2.

Zeta potentials and effective diameters of n-tetradecane emulsions in 1 M ethanol were investigated in the presence of 1,2-dipalmitoyl- sn-glycero-3-phosphocholine (DPPC) (1 mg/100 mL), Candida cylindracea lipase (CCL), and phospholipase PLA2 (1 mg/100 mL) at 20, 37, and 45 degrees C. The enzyme was added at the beginning of mechanical emulsion homogenization or 1 min before the end of stirring for 10 min at 10,000 rpm. It was found that DPPC decreases the negative zeta potentials at all three temperatures. The decrease was largest at 20 degrees C and smallest at 45 degrees C. The influence of the enzymes on the zeta potentials depended on the enzyme kind, time of its injection, and temperature. More negative values of the zeta potentials relative to n-C14H30/DPPC droplets were obtained if the lipase was present. Generally, the effective diameters correlate with the zeta potentials, i.e., lower zeta potential corresponds with bigger effective diameter. Possible reasons for the observed changes of the measured parameters are discussed.

Surface free energy of sulfur--revisited II. Samples solidified against different solid surfaces.

The apparent surface free energy of yellow and orange samples of sulfur crystallized at the surface of gold, silicon, and Teflon and in air was evaluated from the advancing and receding contact angles of water. The samples were prepared by casting melted rhombic mineralogical specimen sulfur onto the surface of the above-noted solids. Yellow samples were obtained when just melted sulfur (ca. 120 degrees C) was cast onto the surfaces, and the orange ones, when the melted sulfur was heated longer to a higher temperature (ca. 160 degrees C) and then cast onto the surfaces. The obtained results show that the apparent surface free energy depends on which surface it crystallized. The greatest value is for the sample crystallized at the gold surface, which is 35% higher than that crystallized in air. Generally, the surface free energy of orange samples is slightly higher than that of yellow ones. It is believed that the differences in the energy result from changes in the packing and structural orientation of sulfur atoms on the surfaces.

Effects of a static magnetic field on water and electrolyte solutions.

Water and electrolyte solutions were exposed for 5 min to a weak static magnetic field (B = 15 mT). Their conductivity and the amount of evaporated water were then measured as a function of time. Simultaneously, these quantities were determined for magnetically untreated samples, as reference systems. It was found that a magnetic field influences these two parameters and their changes depend on the thermodynamic functions of hydration of these ions. A roughly linear change in conductivity versus 'scaled' functions was obtained. On this basis it was concluded that the magnetic field causes changes in the hydration shells of the ions.

Investigation of the electrokinetic properties of paraffin suspension. 2. In cationic and anionic surfactant solutions.

Electrical phenomena at nonionogenic hydrophobic surfaces (solid or liquid) in water, electrolyte, and/or surfactant solutions still attract research. In part 1 of this paper we described the electrokinetic behavior of paraffin wax suspension in water and electrolyte solutions (NaCl or LaCl3). On the basis of the latest data of water structure near hydrophobic surfaces it was concluded that immobilized water dipoles at the interface can play an essential role in the zeta potential formation. In this paper were investigated the zeta potentials of paraffin wax in cationic surfactants cetyltrimethylammonium bromide, C16H33(CH3)3NBr, and octadecyltrimethylammonium chloride, C18H37(CH3)3NCl, and anionic surfactant sodium dodecyl sulfate, C12H25SO4Na. Also changes in wettability of the paraffin surface due to the surfactant's adsorption were studied via wetting contact angle measurements and calculation of the surface free energy. It was concluded that at a low surfactant concentration (10(-6) M) the water dipole structure still contributes to the zeta potential, but at a higher one the zeta potential is determined by the surfactant molecules' adsorption. A special role of OH- ions is also clearly seen. Moreover, a functional relationship was found between the surface free energy of the surfactant-covered paraffin surface and the zeta potential.

Influence of sodium dodecyl sulfate and static magnetic field on the properties of freshly precipitated calcium carbonate.

Properties of calcium carbonate precipitated from aqueous solutions of CaCl(2) and Na(2)CO(3) in the presence of sodium dodecyl sulfate (SDS) and S-S 0.1 T magnetic field (MF) were studied. The nucleation and precipitation processes of CaCO(3) were investigated by pH and zeta potential measurements at 20 +/- 1 degrees C up to 2 h after mixing the solutions. Also the amounts of calcium carbonate deposited on the glass surfaces and its structure were examined. It was found that SDS influences the kinetics of precipitation, crystallographic forms, and crystal size of CaCO(3). The SDS effects are more pronounced in MF presence. A small amount of SDS accelerates transformation of vaterite into calcite, whereas increasing surfactant concentration moderates such a transformation. On the other hand, in all the systems, MF in the presence of SDS causes a slower transformation of vaterite into calcite. These effects are reflected in pH and zeta potential changes, although there is no clear dependence between the SDS amount present during the precipitation and changes of the parameters investigated. It seems that MF effect is most significant at a defined optimal SDS concentration. The results, however, do not allow suggestion of any detailed mechanism of the field interaction.

Investigation of the electrokinetic properties of paraffin suspension. 1. In inorganic electrolyte solutions.

Although electrical properties of nonionogenic hydrophobic surface (solid or liquid) in water and/or electrolyte solutions have been studied for many decades, they are still not well recognized, especially as for the nature of the charge and potential origin. Similarly, water structure at such a surface is still extensively studied. One such system is paraffin wax/water (electrolyte). The zeta potentials and the particle diameters of this system were investigated in this paper. To obtain the suspension of paraffin in water or electrolyte solution (NaCl or LaCl3), the mixture was heated to ca. 70 degrees C and then stirred during cooling. For thus obtained suspensions, the zeta potential was determined as a function of time at 20 degrees C. Also the pH effect on the zeta potentials was investigated. The zeta potentials were calculated from Henry's equation. The results obtained by us are in agreement with those obtained earlier by others. They confirm that although H+/OH- are not surface charge creating ions, OH- ions to some extent are zeta potential determining for the paraffin surface. By use of the potentials and diameters, the electric charge for a spherical particle in the shear plane was calculated. These values are small in the range of 10(-3) C/m2. On the basis of the findings of water structure near hydrophobic surface and the calculated charges, it is concluded that in fact the potential may be created by immobilized and oriented water dipoles.

Adhesion of in situ precipitated calcium carbonate in the presence and absence of magnetic field in quiescent conditions on different solid surfaces.

Deposition of in situ precipitated calcium carbonate from Na(2)CO(3) and CaCl2 solutions on different substrates, i.e. stainless steel, copper, aluminium, and glass, was investigated at different temperatures, 20 degrees C, 40 degrees C, 60 degrees C and 80 degrees C, both in the absence and presence of S-S 0.1T magnetic field (MF). It was found that in quiescent conditions during 2h the amounts deposited firmly on the surfaces decreased with increasing temperature. If MF was present the deposition was reduced at all temperatures, and depended on the nature of the substrate. The largest MF effect was found on glass at 60 degrees C, which amounted 50% reduction of the deposit. However, at 80 degrees C no deposition was found in the presence of MF on aluminium surface. At this temperature the reproducibility of the experiments was poor, and an additional effect due to the metal surface corrosion (especially that of aluminium and copper) may be thought in alkaline environment of the experiments (pH ca. 10). Based on optical microscope photographs, it was concluded that the amounts of crystallographic forms of CaCO3 depended on the nature of substrate on which the precipitation and then the adhesion took place. To some extent the ratios of CaCO3 forms precipitated were different in the bulk phase than on the substrate surfaces at the same temperature, and this conclusion was based on the X-ray diffractograms. Some possible mechanisms causing MF effects are discussed.

Influence of impurity ions and magnetic field on the properties of freshly precipitated calcium carbonate.

Static magnetic field (MF) effects on the properties of freshly precipitated calcium carbonate have been investigated in the presence of impurity ion Mg(2+), Fe(2+), or SO4(2-). One or both solutions, CaCl2 and Na2CO3, were exposure to MF (0.5T) for 20min at 20 degrees C. Then calcium carbonate was precipitated and zeta potential, pH and light absorbance (lambda=543.3 nm) were measured. The same parameters were also determined for the reference systems in which the solutions were not MF-treated. It was found that in all the systems tested MF effects as determined by the above mentioned parameters had appeared. They depended on the kind of the impurity ion present, as well as on which solution, CaCl2, Na2CO3 or both, MF interacted. For example, if Mg(2+) ion was present in CaCl2 solution, the largest shift in the zeta potential toward higher positive values was observed if Na2CO3 was MF-treated (e.g. from 2 to 12mV) and the same was true as for the maximum in the light absorbance and the pH increase. Interestingly, if (CaCl2 + Mg(2+)) was MF-treated pH of the slurry had decreased. Moreover, a correlation between above mentioned MF effects and the entropy of hydration of the ions has also been found. This points to the changes in the hydrating water structure caused by magnetic field.