Polyelectrolyte Concentration Research Articles

Mixed Adsorption Mono- and Multilayers of ß-Lactoglobulin Fibrils and Sodium Polystyrene Sulfonate

The formation of beta-lactoglobulin (BLG)/sodium polystyrene sulfonate (PSS) complexes decelerates the change in the surface properties of the mixed solutions with the surface age and increases the steady-state dilational surface elasticity in a narrow PSS concentration range. At the same time, the changes in the surface properties are accelerated in the dispersions of BLG fibrils with and without PSS due to the influence of small peptides coexisting with fibrils. A decrease in the peptide concentration as a result of the dispersion purification leads to slower changes in the surface properties at low PSS concentrations. The increase in the polyelectrolyte concentration results in an increase in the steady-state surface elasticity due to the fibril/PSS complex formation and in very slow changes in the surface properties if the polyelectrolyte exceeds a certain critical value. The latter effect is a consequence of the formation of large aggregates and of an increase in the electrostatic adsorption barrier. The consecutive adsorption of BLG fibrils and PSS leads to the formation of regular multilayers at the liquid–gas interface. The multilayer properties change noticeably with an increase in the number of layers from four to six in agreement with previous results on the multilayers of PSS with an oppositely charged synthetic polyelectrolyte, presumably due to the heterogeneity of the first PSS layer. The dynamic elasticity of the multilayers approaches 250 mN/m, indicating that they can effectively stabilize foams and emulsions.

Unveiling the Electrostatically Driven Collapsing and Relaxation of Polyelectrolyte-Colloid Complexes: A Tunable Pathway to Colloidal Assembly.

Polyelectrolyte-colloid (PEC) complexes, ubiquitous across diverse fields, exhibit remarkable phase transitions, mimicking intricate biological assemblies. While the role of electrostatic forces in the PEC complex assembly is undeniable, achieving a holistic comprehension remains an elusive goal. This study unveils a fascinating phenomenon: the formation of highly collapsed coacervate structures in PEC complexes at elevated polyelectrolyte concentrations, followed by the swelling of complexes at even higher concentrations. Employing anionic silica colloids and cationic chitosan as a model system, small-angle X-ray/neutron (SAXS/SANS) elucidates the transition from a bead-on-a-necklace-like phase to a dense packed coacervate state (with volume fraction ∼0.62) until 3 wt % concentration of the polyelectrolyte. However, beyond 3 wt %, swelling of the dense collapsed assembly is observed. This structural evolution of PEC complexes as a function of chitosan concentration is attributed to the interplay of electrostatically driven interactions and the Donnan effect. Notably, the critical concentration for coacervation, Cs*, demonstrates a linear dependence on the initial colloid concentration. Interestingly, a complete expansion of the coacervate is observed at a high polyelectrolyte concentration, particularly for dilute colloid solutions (2 wt %). Furthermore, the addition of an electrolyte sheds light on the delicate interplay of forces. While a low electrolyte concentration partially screens charges, leading to a shift in phase diagram, higher concentrations trigger complete coacervate dissolution beyond the critical electrolyte concentration of 0.2 M, due to the complete screening of electrostatic charges.

Effect of shear rate, temperature, and salts on the viscosity and viscoelasticity of semi‐dilute and entangled xanthan gum

AbstractXanthan gum, a naturally‐occurring, high‐molecular‐weight, anionic polyelectrolyte, exhibits significant drag‐reducing properties at low concentrations in water, suggesting promising applications in geothermal networks. The flow behavior of xanthan solutions are explored, specifically at concentrations in the semi‐dilute (1000 ppm by mass) and entangled (4000 ppm) regimes as well as in both water and various salt solutions across a temperature range of 5–85°C. The viscosity and viscoelastic properties of xanthan solutions examine relationships between polyelectrolyte concentration, temperature, and salt concentration. Viscosity decreases by two orders of magnitude in 4000 ppm xanthan solutions in deionized water and with 50 mM NaCl (in the high salt limit) as the temperature increases from 5 to 85°C. Next, the addition of salts affects viscosity differently in the two concentration regimes. Specifically, at 25°C, the zero‐shear rate viscosity upon salt addition decreases by 63% for 1000 ppm solutions (from 0.54 to 0.2 Pa s) but increases by 280% for 4000 ppm solutions (from 28 to 107 Pa s). At 1000 ppm, salt ions cause chain collapse, reducing viscosity; At 4000 ppm, entanglements led to structural changes, resulting in higher viscosity. Furthermore, three salts commonly found in geothermal waters, namely NaCl, Na2CO3, and NaHCO3, exhibited similar changes in viscosity and shear thinning behavior in the entangled regime across temperatures from 5 to 85°C.

Spontaneous Formation of Solid Shell Polymeric Multicompartments at All-Aqueous Interfaces.

Multicompartmental capsules have demonstrated value in fields ranging from drug release, mimetics of artificial cells, to energy conversion and storage. However, the fabrication of devices with different compartments usually requires the use of toxic solvents, and/or the adaptation of technically demanding methods, including precision microfluidics and multistep processes. The spontaneous formation of multi-core capsules resulting from polyelectrolyte complexation at the interface of a prototypic all-aqueous two-phase system is described here. The variation of polyelectrolyte concentration and complexation time are described as simple working parameters capable of driving the formation of compartments at different yields, as well as tailoring their morphology. The mild processing technology enables the encapsulation of animal cells, which are capable of invading capsule walls for specific processing conditions.

Harvesting Enhanced Blue Energy in Charged Nanochannels Using Semidiluted Polyelectrolyte Solution.

Blue energy generation in nanochannels based on salinity gradients is currently the most promising method in the area of nonconventional energy production. We used a semidiluted pure sodium carboxymethylcellulose (NaCMC)-KCl aqueous solution to study the characteristics of blue energy generation within a charged nanochannel. We solve the corresponding equations for ionic transport using a numerical technique based on the finite element method. Our analysis focused on the electric double layer (EDL) potential field, open circuit current, diffuse potential, electric conductance, maximum generated pore power, and maximum energy conversion efficiency by varying concentrations of the salt in the left-side reservoir and the bulk polyelectrolyte. The results indicate that as the polyelectrolyte concentration increases, the extent of EDL overlap considerably reduces. With an increase in polyelectrolyte concentration, the open circuit current increases, while the diffuse potential reduces. It was observed that both electrical conductance and maximal pore power improve considerably with higher polyelectrolyte concentrations. Interestingly, our modeling framework demonstrates a power density substantially higher (up to 16.31 W/m2) than earlier configurations and surpasses the established commercial limit (5 W/m2). Furthermore, our findings reveal that the reservoir salt concentration significantly affects the rate of decline in the maximum energy conversion efficiency as the polyelectrolyte concentration increases. The research paves the way for the development of high-power-density devices with several practical applications.

Critical adsorption and charge reversal in polyelectrolyte solutions: Analytical mean-field theory.

An analytical linearized mean-field theory is presented to describe the adsorption behavior of polyelectrolytes near charged colloidal surfaces with additional short-ranged non-electrostatic interactions. The coupling between the polyelectrolyte segment density and electrostatic potential is explicitly accounted for in a self-consistent manner. This coupling gives rise to highly non-linear behavior, such as oscillations of the electrostatic potential. We derive analytical expressions for the critical surface charge density σc, after which adsorption takes place, and recover the well-known σc∼ns3/2 scaling regime, where ns is the salt concentration. In addition, the theory yields a new ns1 scaling regime if the surface is hard and a unified ns1 scaling regime if the surface also possesses some short-ranged attraction with the polyelectrolyte. Furthermore, we derive an analytical expression to describe the critical polyelectrolyte concentration φc to achieve complete charge reversal, which is found to scale as φc ∼ σ2/(f2c2), where c is related to the magnitude of short-ranged interactions and f is the average charge per monomer of the polyelectrolyte. It is observed that within our theory, complete charge reversal can only take place if the short-ranged interactions are sufficiently strong to completely compensate for the entropy loss of adsorption.

Low Fouling Polyelectrolyte Layer-by-Layer Self-Assembled Membrane for High Performance Dye/Salt Fractionation: Sequence Effect of Self-Assembly.

Layer-by-layer (LbL) self-assembly of oppositely charged polyelectrolytes (PEs) is usually performed on a conventional ultrafiltration base substrate (negative zeta potential) by depositing a cationic PE as a first layer. Herein, we report the facile and fast formation of high performance molecular selective membrane by the nonelectrostatic adsorption of anionic PE on the polyvinylidene fluoride (PVDF, zeta potential -17 mV) substrate followed by the electrostatic LbL assembly. Loose nanofiltration membranes have been prepared via both concentration-polarization (CP-LbL, under applied pressure) driven and conventional (C-LbL, dipping) LbL self-assembly. When the first layer is poly(styrene sodium) sulfonic acid, the LbL assembled membrane contains free -SO3- groups and exhibits higher rejection of Na2SO4 and lower rejection of MgCl2. The reversal of salt rejection occurs when the first layer is quaternized polyvinyl imidazole (PVIm-Me). The membrane (five layers) prepared by first depositing PStSO3Na shows higher rejection of several dyes (97.9 to >99.9%), higher NaCl to dye separation factor (52-1800), and higher dye antifouling performance as compared to the membrane prepared by first depositing PVIm-Me (97.5-99.5% dye rejection, separation factor ∼40-200). However, the C-LbL membrane requires a longer time of self-assembly or higher PE concentration to reach a performance close to the CP-LbL membranes. The membranes exhibit excellent pressure, pH (3-12), and salt (60 g L-1) stability. This work provides an insight for the construction of low fouling and high-performance membranes for the fractionation of dye and salt based on the LbL self-assembly sequence.

Underwater Fabrication of Carbon Nanotube/Coacervate Composites.

Soft conductive materials are of interest for a wide range of applications, but their syntheses have remained difficult. Herein, we present a convenient route for underwater fabrication of a composite made of carbon nanotubes (CNTs) and mussel-inspired complex coacervates. The key to success of this method is that CNTs were solubilized very effectively in protocoacervates, which are high-concentration solutions of polyelectrolytes at a pH where only one of them is charged, thereby impeding coacervate formation. Composite materials were formed by the simple injection of CNT-dispersed protocoacervate solutions into water under ambient conditions. The method is simple, fast, and ecofriendly, and composites of CNT-complex coacervate in the form of films or bulk materials were obtained. The composites demonstrated electrical conductivity and tunable mechanical properties, which depended on the concentration of polyelectrolytes and the CNT:protocoacervate ratio. Hence, the composites can be manipulated to attain diverse properties, for examples, tunable reduced modulus (15 to 32 GPa) and hardness (0.3 to 0.7 GPa) as well as an electrical conductivity of up to 4 × 103 S m-1.

Distribution of polyelectrolytes and counterions upon polyelectrolyte complexation

HypothesisUnderstanding polyelectrolyte complexation remains limited due to the absence of a systematic methodology for analyzing the distribution of components between the polyelectrolyte complex (PEC) and the dilute phases. ExperimentsWe developed a methodology based on NMR to quantify all components of solid-like PECs and their supernatant phases formed by mixing different ratios of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid)-sodium salt (PAA). This approach allowed for determining relative and absolute concentrations of polyelectrolytes in both phases by 1H NMR studies. Using 23Na and 35Cl NMR spectroscopy we measured the concentration of counterions in both phases. FindingsRegardless of the mixing ratio of the polyelectrolytes the PEC is charge-stoichiometric, and any excess polyelectrolytes to achieve charge stoichiometry remains in the supernatant phase. The majority of counterions were found in the supernatant phase, confirming counterion release being a major thermodynamic driving force for PEC formation. The counterion concentrations in the PEC phase were approximately twice as high as in the supernatant phase. The complete mass balance of PEC formation could be determined and translated into a molecular picture. It appears that PAH is fully charged, while PAA is more protonated, so less charged, and some 10% extrinsic PAH-Cl- pairs are present in the complex.

Rheo-SAXS study of a shear-thinning hydrogel containing clay nanoplatelets

Shear-induced orientation of clay nanoplatelets within a physically cross-linked hydrogel based on ionenes, positively charged polyelectrolytes, is studied here. Small angle X-ray scattering measurements (SAXS) are performed under shear within a Couette cell cylinder (rheo-SAXS). As the SAXS signal is dominated by that of the clay component, we follow the evolution of the orientational distribution of the clay nanoplatelets within the hydrogel as a function of shear. We investigate the effect of the clay volume fraction, polyelectrolyte concentration, clay charge location and clay charge density by screening three different types of clay: Wyoming and Arizona montmorillonites and Idaho beidellite. The orientational field of clay nanoplatelets in the gel is shown to strongly depend on the clay charge location and shear rate, whereas it is independent of the clay volume fraction. Approaching the critical gelation concentration of the polyelectrolyte system, these features change drastically.

Electrodeposition modification of heterogeneous cation exchange membrane using expanded polystyrene waste: Enhanced electrochemical properties and electrodialytic performance

In this study, surface modification of a cation exchange membrane based on polyvinyl chloride was accomplished via electrochemical deposition of post-sulfonated waste-expanded polystyrene aiming to enhance its electrochemical properties and electrodialytic performance. The membrane was synthesized by the phase inversion method, modified with different concentrations of polyelectrolyte, characterized by FTIR and SEM analyses, and applied for electrodialytic desalination of NaCl solution. Deposition of sulfonated polystyrene with polyelectrolyte concentration of 2 g/l, current of 8 mA/cm2, and period time of 30 min caused a reduction in electrical resistance up to 52 %. Furthermore, the sodium ionic flux through electrodialytic desalination was improved by 58 % as a result of the promotion of the electrochemical properties of the membrane.

Quantitative turbidimetric characterization of stabilized complex coacervate dispersions.

Stabilizing complex coacervate microdroplets is desirable due to their various applications, such as bioreactors, drug delivery vehicles, and encapsulants. Here, we present quantitative characterization of complex coacervate dispersion stability inferred by turbidimetry measurements. The stability of the dispersions is shown to be modulated by the concentrations of comb polyelectrolyte (cPE) stabilizers and salt. We demonstrate cPEs as effective stabilizers for complex coacervate dispersions independent of the chemistry or length of the constituent polyelectrolytes, salts, or preparation routes. By monitoring the temporal evolution of dispersion turbidity, we show that cPEs suppress microdroplet coalescence with minimal change in microdroplet sizes over 48 hours, even at salt concentrations up to 300 mM. The number density and average microdroplet size are shown to be controlled by varying the cPE and salt concentrations. Lastly, turbidity maps, akin to binodal phase maps, depict an expansion of the turbid two-phase region and an increase in the salt resistance of the coacervates upon the introduction of cPEs. The coacervate salt resistance is shown to increase by >3×, and this increase is maintained for up to 15 days, demonstrating that cPEs impart higher salt resistance over extended durations.

Nanofiltration membrane performance of layer-by-layer membranes with different polyelectrolyte concentrations

Nanofiltration membranes produced with polyelectrolytes via the layer-by-layer technique are frequently researched, but misunderstood parameter is the polyelectrolyte concentration. Higher polyelectrolyte (PE) concentrations are known to produce thicker PE layers, but its effect on the membrane performance has only been studied in a limited fashion, leading to premature conclusions. In this work, two well-known strong polyelectrolytes, PDADMAC and PSS were used to prepare membranes using coating solutions with polyelectrolyte concentrations of 0.01, 0.1, 1.0, 2.5 and 5.0 wt% and two different salt concentrations in the coating solution of 0.05 and 1 M, as higher salt concentrations lead to thicker PE layers. The membrane performance of the prepared membranes is researched in terms of pure water permeability (PWP), molecular weight cut-off (MWCO) and the retention of different salts. In the first bilayer, membranes coated with a 0.05 M salt solution showed lower PWPs and MWCOs and higher salt retentions by increasing the PE concentration. After a certain number of coated bilayers, the MWCO and salt retentions reach a plateau for all PE concentrations; but the plateau value was obtained earlier by coating with a higher PE concentration. The membranes coated with the 1 M salt concentration had lower or comparable retention rates, except for MgCl2, than those coated with 0.05 M salt. The higher salt concentration resulted in more abundant PDADMAC in the membrane, which promotes the MgCl2 retentions for all bilayers. In conclusion, we found that the polyelectrolyte concentration significantly alters the membrane performance, but after coating 7 bilayers, the same size exclusion plateaus are reached.

Parametric Study of Colloidal Particle Confinement near a Surface in the Presence of DLVO and Structural Interactions Using Brownian Dynamic Simulations.

Total internal reflection microscopy (TIRM) has become a crucial technique for understanding the surface interactions and dynamics of Brownian colloidal particles near a surface. However, for select colloidal systems, experimental limitations associated with TIRM can occlude exploration of nano- and submicrometer colloids dispersed in complex or structured fluids. It should be possible to use Brownian dynamic simulations to quantify, explore, or circumvent these limitations to extend the TIRM technique further. A Brownian dynamics algorithm based on the Langevin equation was utilized to identify favorable colloidal systems for conducting TIRM experiments in electrolyte and nonadsorbing polyelectrolyte solutions. In electrolyte solution, the motion of polystyrene and silica particles of nanometer- and micrometer-sized radii was simulated near a glass slide in the presence of retarded van der Waals and electric double-layer forces to develop potential energy profiles. In the case of nonadsorbing polyelectrolyte solutions, a structural force was also implemented into the simulation, and the influence of structural interactions on particle confinement was explored as a function of particle size, particle density, and polyelectrolyte concentration. In electrolyte solutions, our results were able to identify the minimum particle size required for TIRM experiments as well as insight into particle selection based on material density. For structural or oscillatory forces, our results show that prior to conducting TIRM experiments, Brownian dynamics simulation can be used to select the appropriate particle size, material, and polyelectrolyte concentration range where the colloidal particle can sample multiple structural energy wells without confinement. These results provide insight into the colloidal system suitable to experimentally study near-surface particle diffusion dynamics for a range of separations in the presence of structural interactions.

Insight of the viscometric behavior of pullulan and curdlan derivative solutions: Effect of the nature and salt concentration

Increasing interest for polysaccharides investigation is based on their friendly behavior with environment and living organisms. The chemical structure, molar mass, chain conformation adopted in different media plays an important role for their performances in various practical applications. In this context, the viscometric behavior of two cationic pullulan and curdlan derivatives has been followed in water and salt solutions. The biopolyelectrolytes contain trimethylammonium propyl carbamate groups and trimethyl-N-(2-hydroxypropyl)ammonium ones attached to the backbone of pullulan and curdlan, respectively. The viscosity data have been interpreted in terms of the Wolf model. From the estimated values of the hydrodynamic parameters expressed by intrinsic viscosity [η], the hydrodynamic interaction parameter (b), etc., the dependence of the polyion conformation on the polyelectrolyte concentration and salt nature and concentration has been revealed; [η] decreased and b increased with increasing salt concentration and counterions valence. The viscosity data obtained in salt solutions allowed the estimation of the stiffness parameter (B), the expansion factors for the viscosity (αη) and for the root mean-square radius of gyration, αS, etc. and the establishment of counterions binding type as an “atmospheric ionic” one for the mononovalent counterions.

STABILIZATION OF WATER-COAL COMPO­SITE FUELS USING CARBON MICRO-NANO­MATERIALS AND AMINO ALCOHOLS

The study investigated the potential of stabilizing composite water-coal fuel (CWCF) by adding carbon micro-nanomaterials obtained through the plasma-chemical conversion of organics-containing wastewater and amino alcohols. The study focused on systems based on anthracite with a solid phase concentration of 62%. Two amino alcohols, 2-amino-­2-methyl-1-propanol (AMP) and 2-amino-­2-ethyl-1,3-propanediol (AEPD) were used at concentrations of 0.25%, 0.5%, 1%, and 2.5% by weight of CWCF.
 The low stability and heterogeneity of coal particle distribution in organic liquids cause an increase in the viscosity of dispersed systems in combined systems. To regulate the rheological properties and stabilize the CWCF, chemicals such as dispersants, plasticizers, and stabili­zers are added. The CWCF 's properties can be improved by using additives such as sodium, calcium, and magnesium lignosulfonates, and naphthalene sulfonic acids. However, these reagents may not provide the desired properties of coal slurries in organomineral environments. Therefore, substitutes for these pro­ducts need to be found.
 Amino alcohols are commonly used as dispersants and stabilizers, especially in the production of water-based paints. They are low in cost, low in toxicity, and serve as anti-corrosive agents and pH stabilizers without causing excessive foaming. To strengthen the spatial structure, reactive particles such as carbon micro- and nanomaterials (CNM) can be introduced into the CWCF. Unlike polyelectrolytes and surfactants, CNM particles can have a varying number of active centers depending on the method of formation. By varying the properties of CNMs, it is possible to increase the number of contact centers and form a spatial grid without increasing the concentration of surfactants and polyelectrolytes. This is because contact interactions are activated during grinding, forming a new surface with energy-saturated active centers. As a result, the concentration of the system can be increased, and the calorific value of the fuel can be increased as well. However, the presence of an organic component can render mechanochemical activation ineffective by shielding active sites with large organic molecules. Therefore, identifying the most effective stabilizer reagents and deve­loping technology for their introduction into the dispersed system is a crucial and intricate problem in obtaining CWCF
 The study revealed that the ξ potential of anthracite particles is 40–45 mV in the pre­sence of amino alcohols. Sedimentation stabi­lity in the presence of highly dispersed carbon additives increases from 5–6 to 10–14 days, i.e., almost twice. The introduction of highly dispersed carbon leads to an increase in the effective viscosity of the systems and can be recommended for controlling the fluidity of the CWCF. The technical and operational requirements are best met by the CWCF containing 0.25% AMR and 1% highly dispersed carbon.

Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions.

We present results from explicit-solvent coarse-grained molecular dynamics (MD) simulations of fully charged, salt-free, and unentangled polyelectrolytes in semidilute solutions. The inclusion of a polar solvent in the model allows for a more physical representation of these solutions at concentrations, where the assumptions of a continuum dielectric medium and screened hydrodynamics break down. The collective dynamic structure factor of polyelectrolytes, S(q,t), showed that at [Formula: see text], where [Formula: see text] is the polyelectrolyte peak in the structure factor S(q) and [Formula: see text] is the correlation length, the relaxation time obtained from fits to stretched exponential was [Formula: see text], which describes unscreened Zimm-like dynamics. This is in contrast to implicit-solvent simulations using a Langevin thermostat where [Formula: see text]. At [Formula: see text], a crossover region was observed that eventually transitions to another inflection point [Formula: see text] at length scales larger than [Formula: see text] for both implicit- and explicit-solvent simulations. The simulation results were also compared to scaling predictions for correlation length, [Formula: see text], specific viscosity, [Formula: see text], and diffusion coefficient, [Formula: see text], where [Formula: see text] is the polyelectrolyte concentration. The scaling prediction for [Formula: see text] holds; however, deviations from the predictions for [Formula: see text] and D were observed for systems at higher [Formula: see text], which are in qualitative agreements with recent experimental results. This study highlights the importance of explicit-solvent effects in molecular dynamics simulations, particularly in semidilute solutions, for a better understanding of polyelectrolyte solution behavior.

Role of concentration and hydrophobic nature of weak polyelectrolytes on adsorption structure and thermodynamics at oil-water interface: Study of several carboxylate polymers

Intermolecular structure, conformations, solvation and adsorption characteristics of four partially ionized polycarboxylic acids syndiotactic-poly(acrylic acid) (s-PAA), syndiotactic-poly(methacrylic acid) (s-PMA), isotactic-poly(methacrylic acid) (i-PMA) and atactic-poly(ethacrylic acid) (a-PEA) at oil (CCl4) - water interface is studied by molecular dynamics simulations over the range from dilute to monolayer coverage. Linearity and slope of Θ-Γ curves are correlated to conformational invariance and extent of adsorption (partial vs complete) respectively, within the range of concentration of study. Adsorption of i-PMA and a-PEA chains occurs deeper into the oil-side of interface region as driven by the greater hydrophobicity of these polymers. Higher tendency of highly extended s-PMA to desorb from the interface as compared to strong adsorption of compact coiled i-PMA is driven by their solvation behavior dictated by aspects of structural partitioning of chemical groups with respect to the solvents of the two phases. Hydrophobic side-group in the polyelectrolyte chain is responsible for the slower dynamics of the backbone. The observed variation in thickness of adsorbed layer and fractional interface coverage with concentration suggest partial adsorption of chain segments beyond saturation of interface rather than coiling of chains to accommodate additional chains. While a-PEA exhibits greater variation in interfacial tension, the change in electric potential difference across the interface indicates weak adsorption by s-PMA. The influence of the tacticity of PMA on dynamics and distribution of counter-ions is in agreement with experimental results. Results provide a significant advancement in our understanding of polyelectrolyte and polymer adsorption at oil-water liquid interface.

Process validation and a new method for quality control of ultrathin polyelectrolyte multilayer coatings

The properties of polyelectrolyte multilayers are ruled by the process parameters employed during self-assembly. This is the first study in which a design of experiment approach was used to validate and control the production of ultrathin polyelectrolyte multilayer coatings by identifying the ranges of critical process parameters (polyelectrolyte concentration, ionic strength and pH) within which coatings with reproducible properties (thickness, refractive index and hydrophilicity) are created. Mathematical models describing the combined impact of key process parameters on coatings properties were developed demonstrating that only ionic strength and pH affect the coatings thickness, but not polyelectrolyte concentration. While the electrolyte concentration had a linear effect, the pH contribution was described by a quadratic polynomial. A significant contribution of this study is the development of a new approach to estimate the thickness of polyelectrolyte multilayer nanofilms by quantitative rhodamine B staining, which might be useful in all cases when ellipsometry is not feasible due to the shape complexity or small size of the coated substrate. The novel approach proposed here overcomes the limitations of known methods as it offers a low spatial sampling size and the ability to analyse a wide area without restrictions on the chemical composition and shape of the substrate.

Polyaniline/Cashew Gum Composite Electrosynthesized on Gold Surface in Aqueous Acid Medium for Ammonia Colorimetric Detection

The electrosynthesis of polyaniline (PAni) and cashew gum (CG) composite was successfully performed by electrochemical methods (potential scanning and constant potential) in terms of pH, aniline (Ani), and polyelectrolyte concentrations. Study aim was to investigate the performance of a polyaniline-based ammonia sensor under different concentrations of ammonium gas, evidencing a color change from green to blue as in the presence of gas in a sensitive and reversible process. Films grown by cyclic voltammetry and chronoamperometry showed a cauliflower-like morphology, and a visual analysis detected a limit of 0.015 and 0.010 mol l−1, respectively. The sensor demonstrated a fast response time of 20 s, a low detection limit, with a short regeneration time of less than 1 min at room temperature. This polyaniline-based sensor is shown as a portable, sensitive, dimensionally flexible, and cost-effective alternative for food packaging and other devices. The findings of this study contribute to the development of advanced ammonia detection technology.