Microcapsules prepared from a polycondensate‐based cement dispersant via layer‐by‐layer self‐assembly on melamine‐formaldehyde core templates

Novel microcapsules were prepared from colloidal core–shell particles by acid dissolution of the organic core. Weakly crosslinked, monodisperse and spherical melamine‐formaldehyde polycondensate particles (diameter ～ 1 μm) were synthesized as core template and coated with multilayers of an anionic polyelectrolyte via layer‐by‐layer deposition technique. As polyelectrolytes, an anionic naphthalenesulfonate formaldehyde polycondensate that is a common concrete superplasticizer and thus industrially available, and cationic poly(allylamine hydrochloride) were used. Core removal was achieved by soaking the core–shell particles in aqueous hydrochloric acid at pH 1.6, resulting in hollow microcapsules consisting of the polyelectrolytes. Characterization of the template, the core–shell particles, and the microcapsules plus tracking of the layer‐by‐layer polyelectrolyte deposition was performed by means of zeta potential measurement and scanning electron microscopy. The microcapsules might be useful as microcontainers for cement additives. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhanced mechanical properties of multilayer nano‐coated electrospun nylon 6 fibers via a layer‐by‐layer self‐assembly

We reported the mechanical properties of the polyelectrolyte multilayer nano‐coated electrospun fiber mats with different number of layers. Multilayer nano‐coatings composed of layers of PSS and PAH were successfully deposited onto electrospun nylon 6 fibers via layer‐by‐layer self‐assembly. Compared with pure nylon 6 fibers, the morphology of polyelectrolyte multilayer coated nylon 6 fibers was uniform and smooth. The mechanical properties of polyelectrolyte multilayer coated random and aligned nylon 6 fibers were remarkably enhanced. Moreover, it was found that the higher degree of alignment resulted in higher tensile strength, suggesting the combined effects of the alignment, the surface nanocoating and the formation of internal networks of polyelectrolytes on nylone 6 fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal effect of polymer layers deposition on polypropylene nonwoven fabric

To prepare various types of multilayers, polyelectrolytes poly(acrylic acid), poly(allylamine hydrochloride), and poly(dimethyl aminoethyl methacrylate) were prepared and deposited onto polypropylene nonwoven fabrics produced in the melt‐blowing process. Each type of external layer deposited was dyed for identification. Utilizing the layer‐by‐layer method to deposit polyelectrolyte layers considerably strengthens the thermal resistance of the modified fabric (the difference in T_50% is over 40°C). The effect is connected with the type and number of layers. Thermal effects were also observed in both dynamic and isothermal analyses under air atmosphere. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polymer clay self‐assembly complexes on paper

Layer‐by‐layer (LBL) self‐assembly was used to form polymer/clay complexes on paper to enhance its wet strength properties. Initially, alternating layers of poly(allylamine hydrochloride) (PAH) and Kaolin clay were sequentially deposited on quartz substrate and characterized by UV/Vis/NIR spectroscopy as a model system. The same procedure was then applied to a paper test sheet to form multilayered coatings, which were examined with scanning electron microscopy. The wettability of the LBL coated paper test sheet was shown to change from hydrophilic to hydrophobic with increased number of multilayers and if the terminating layer was Kaolin clay. The wet strength of the coated test sheet was improved by more than 270% over the uncoated test sheet with 16 bilayers of PAH/kaolin complex on the surface. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Self‐assembly of novel architectural nanohybrid multilayers and their selective separation of solvent‐water mixtures

A new architectural nanohybrid multilayer has been explored and built on various substrates. The building blocks of positive and negative charged polyelectrolyte‐coated nanoparticles (NPs) could be obtained by tuning the electrical properties of the amphoteric oxide NPs in acid and basic environments. The nanohybrid films were, thereafter, formed by layer‐by‐layer (LbL) assembly of polycation‐ and polyanion‐coated NPs. It was demonstrated that this approach could incorporate single component NPs into both polycation and polyanion layers, and in turn improve the NP loading, maintain good dispersion of NPs within the film. For separation applications, a dynamic LbL assembly was attempted as a means of fabricating such nanohybrid multilayers on both 2‐D and 3‐D polymeric porous substrates. The nanohybrid multilayer membrane renders both much higher selectivity and flux in the separation of solvent‐water mixtures. Moreover, such assembly of nanohybrid multilayers allows us to efficiently simplify the procedures by reducing 30–40‐fold process cycles. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Rapid assembly of polyelectrolyte multilayer membranes using an automatic spray system

The layer‐by‐layer (LbL) assembly of polyelectrolyte multilayers on to a porous supporting membrane is able to create various new composite membranes. However, the low efficiency and long time required for such procedures limit practical applications. In this study, an automatic spray system has been constructed for the rapid assembly of polyelectrolyte multilayers on to nanoporous supporting membranes. The compounds polyacrylic acid and poly(ethyleneimine), used as a model polyelectrolyte pair, were alternately sprayed on to a polyacrylonitrile ultrafiltration membrane. Experiments proved that the composite membrane obtained in this way had a good pervaporation dehydration performance. In addition, the process times were dramatically decreased, by as much as 80 folds, when compared with classical dip‐LbL methods. Such an automated system can easily be converted to the assembly of various organic species. Therefore, it is a versatile and highly efficient system for manufacturing composite multilayer membranes for many separation applications. © 2012 American Institute of Chemical Engineers AIChE J, 59: 250–257, 2013     

Dynamic pressure‐driven covalent assembly of inner skin hollow fiber multilayer membrane

A covalent assembly was accomplished onto hollow fibers via a dynamic pressure‐driven layer‐by‐layer (LbL) technique. The covalent crosslinking multilayers were successfully formed onto the inner surfaces of hollow fiber porous substrates during the alternatively filtration of polyethyleneimine (PEI) and glutaraldehyde (GA) solutions. The formation of covalent bond between PEI and GA was confirmed using fourier transform infrared (FTIR) spectra. The thickness increment on a quartz slide clearly suggested the stepwise growth of multilayer at nanometer scale. The regular alternation of zeta potentials demonstrated that the successful formation of GA‐crosslinked PEI multilayers on the hollow fibers. The multilayer membranes showed excellent pervaporation performances for the dehydration of different solvent–water mixtures. The selectivity and permeability can be controlled by varying the PEI layer number. More importantly, the covalent assembled multilayer membrane rendered much higher stabilities compared with those from electrostatically LbL assembly, which offers much opportunity for practical applications. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Quaternized microgels as soft templates for polyelectrolyte layer-by-layer assemblies

A cationic microgel with quaternized amine groups was prepared and used as a soft template for layer-by-layer (LbL) assemblies. The presence of quaternized amine groups inside the microgels was necessary to prevent rearrangements and subsequent bridging between the coated microgels, which were observed for the precursor microgels containing protonated primary amino groups. Sequentially, negatively charged polyelectrolyte poly(sodium styrene sulfonate) (PSS) and positively charged polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) were added to a suspension of quaternized microgels. This leads to an odd-even effect with respect to particle size and surface charge of the formed microgel–polyelectrolyte complexes (MPECs). MPECs with an even number of layers exhibit positive surface charge due to PDADMAC as the outermost layer and are larger compared to complexes with an odd number of layers, which are negatively charged having PSS in the outermost layer. Taking into account previous results (Macromolecules,2009,42, 1229), these observations show that electrostatic interactions are the major force for the odd-even effect in polyelectrolyte multilayers on microgels: the cationic groups of PDADMAC compete with the cationic moieties of the microgel for binding with the sulfonate groups of PSS. Concomitantly, a fluctuating size of the MPECs is induced by an osmotic pressure modulation within the microgel. In contrast, surface tension effects invoked by a possible varying hydrophilicity of the different terminal layers are negligible.     

Interfacial properties of polyelectrolyte-cellulose systems. IV. Electrokinetic properties of carboxymethylcellulose fibers with adsorbed multilayers of cationic polyelectrolyte

Zeta potential measurements by the streaming current method were performed on carboxymethylcellulose (CMC) with and without irreversibly adsorbed multilayers of cationic polyelectrolyte. Factors affecting the electrokinetic properties such as the amount of adsorbed polymer, polymer molecular weights (M_n 50,000 and 200,000), ionic strength (10^?5 ～ 10^?2M KCl), and pH of the streaming medium (KCl solutions) were examined. The negative zeta potential of CMC decreased to the point of monolayer formation and increased from that point to the saturated multilayer formation. The polarity of the zeta potential was negative throughout every adsorption stage. The negative zeta potential increase was attributed to: (a) binding of anions (Cl^? and OH^?) to the outermost layer of the multilayer from KCl solutions and (b) change in chemical potentials of counterions in a diffuse double layer due to expansion of the double layer in the presence of the adsorbed multilayer on CMC. The results suggest that the carboxyl groups under the monolayer are undetectable electrokinetically; however, the negative charge, due to unneutralized carboxyl groups under the monolayer, appears to cause further adsorption forming a saturated multilayer. When the effect of unneutralized carboxyls of CMC are shielded at higher levels of adsorption, the outermost layer of the multilayer becomes a potential-determining layer.     

Self‐healing properties of layer‐by‐layer assembled multilayers

The review is focused on the formation and the self‐healing properties of polymer and hybrid multilayers formed via the layer‐by‐layer approach. In the first part of the review the recent developments in the construction of polymer multilayers are highlighted. In the second part the design and the self‐healing properties of inorganic ? polymer hybrid multilayers are described. It is shown that self‐healing multilayers have a broad spectrum of applications including corrosion protection, as elements of antifouling and antimicrobial coatings and bio‐inspired superhydrophobic interfaces. It is demonstrated that dynamic functional interfaces have a complex hierarchical organization of non‐covalently bonded polymers and colloidal particles. Mechanisms of self‐healing behavior of the multilayers and the role of water and external stimuli (pH, ionic strength and temperature, light) in swelling of multilayers and rearrangement of polymer segments are discussed. Future trends, perspectives and research strategies for the design of ‘smart’ self‐assemblies with self‐healing properties are proposed. © 2015 Society of Chemical Industry     

Synthesis,characterization, and self‐assembly of cationic coumarin side‐chain polymer

In this study, the synthesis of a novel cationic coumarin‐containing polymer (C‐CPA) was presented. C‐CPA was examined optically using photoluminescence (PL) spectroscopy. The optical data suggested that they were promising blue‐emitting materials mainly due to the coumarin chromophore on the side chain. Moreover, the synthesized cationic polymer was suitable for layer‐by‐layer electrostatic self‐assembly thin film deposition from dilute polymer solution and multilayers were fully characterized by UV–vis spectroscopy, PL spectroscopy and atomic force microscope. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyelectrolyte multilayers of poly(vinylamine hydrochloride‐co‐N‐vinylformamide) with variable primary amine content and a weak polyacid poly(acrylic acid)

Poly(vinylamine hydrochloride‐co‐N‐vinylformamide) [poly(VAm‐co‐NVF)] with variable VAm content, and a weak polyacid poly(acrylic acid) were assembled on a quartz crystal microbalance (QCM) substrate from their aqueous solutions, thus forming polyelectrolyte multilayers. The effects of varying the VAm content on assembly profiles and film structures were analyzed by quantitative QCM analysis, attenuated total reflection spectra techniques, and atomic force microscopic observation. At a VAm content of less than 40% of the total number of poly(VAm‐co‐NVF) units, the layer‐by‐layer assembly did not proceed, and the frequency shift of the QCM zigzagged with the step number. Above 40% VAm content, the frequency increased continuously with an increasing number of steps. The assembly amount was also maximal at 40% VAm content. The films obtained swelled with water molecules, and this swelling was followed by an increase in thickness in the aqueous phase. The results obtained were compared to those obtained from a combination of poly(VAm‐co‐NVF) and a strong polyacid, poly(sodium styrenesulfonate). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3927–3933, 2006     

Intumescent flame retardant TPO composites: Flame retardant properties and morphology of the charred layer

Intumescent flame retardant thermoplastic polyolefin (TPO) composites were prepared to study the relationships between their structure of charred layer (including of the multicellular intumescent layer and the charry layer) and flame retardant properties. They were characterized using the LOI and UL‐94 test, which indicated that the best fire retardant behavior (V‐0 rating and LOI reach to 28.1%) was obtained at the formulation of TPO/ammonium dihydrogen phosphate/starch (100/60/20). Thermal gravimetric analysis demonstrated that the presence of ammonium dihydrogen phosphate/starch promoted the esterification and carbonization process in lower temperature range while enhancing the thermal stability of intumescent flame retardant TPO in high‐temperature range. Scanning electron microscope and optical microscope were shown that, with combustion time prolonged, the intumescent layers obtained greater number of cells, and the charry layer became more compact while the size of the carbon granules became smaller on the surface. Introduction of starch had an obvious effect on the structure of the intumescent and charry layers. The charry layer of the composites with the content of 20 phr starch was more compact and uniform than that of the composites with 50 phr. The weight ratio of ammonium dihydrogen phosphate to starch in the intumescent flame retardant was fixed as 3 : 1 which cooperated with each other well to promote a compact charry layer and to obtain the better flame retardancy performance. Therefore, the better the charred layers produced, and the better flame retardant properties they obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Multilayer thin films of colloidal gold and silica nanoparticles: Effect of polyelectrolyte coating

The use of oppositely charged colloidal nanoparticles to build multilayered structures is an approach in thin film science. In this work, uniform spherical nano‐dispersions of gold (ca. 20 nm) and silica (ca. 30 nm) were synthesised with specific volume concentration to achieve colloidal stability. Exploiting the use of self‐assembly, multilayers of these oppositely charged nanoparticles were built using alternate coating with chitosan. Gold nanoparticles have strong optical absorption in visible region of electromagnetic spectrum resulting from its surface plasmon resonance. Silica nanoparticles have low refractive index and absorb light mostly in the ultraviolet (UV) region. The optical absorption band of the fabricated thin films extends from UV to visible region of the electromagnetic spectrum. The spectral characteristics of these thin‐film assemblies are a combination of thickness and the order of the layers in a stack. These films have potential applications as optical elements and in optoelectronics. © 2011 Canadian Society for Chemical Engineering     

Structure and mechanism of formation of polyelectrolyte multilayers

The mechanism of formation and structure of polyelectrolyte multilayers deposited from salt free solutions on a charged substrate was investigated using MD simulation. The minimum energy configuration of the system was investigated by varying the temperature of deposition and lowering the charge of monomers in the polyelectrolyte chains. The PE molecules in the multilayers were found to be kinetically trapped under influence of strong electrostatic interactions. The multilayered structure composed of seven double layers contained many voids and imperfections resulting from freezing of the structure. Simulation results also show that the resulting structure is truly layered and that the layer thickness is not very different from the thermodynamic equilibrium layer thickness. The structure of the layers is fuzzy in nature and molecules show a high level of interpenetration and disorder.     

Development of antimicrobial stainless steel via surface modification with N‐halamines: Characterization of surface chemistry and N‐halamine chlorination

N‐halamine modification of materials enables the development of antimicrobial materials whose activity can be regenerated after exposure to halogenated sanitizers. Surface and bulk modification of polymers by N‐halamines has shown great success, however, modification of inorganic substrates (e.g., stainless steel) remains an area of research need. Herein, we report the covalent surface modification of stainless steel to possess rechargeably antimicrobial N‐halamine moieties. Multilayers of branched polyethyleneimine and poly(acrylic acid) were immobilized onto the surface of stainless steel and the number of N‐halamines available to complex chlorine was quantified. Samples were characterized through contact angle, Fourier transform infrared spectroscopy, ellipsometry, dye assay for amine quantification, and X‐ray photoelectron spectroscopy. Increasing the number of multilayers from one to six increased the number of N‐halamines available to complex chlorine from 0.30 ± 0.5 to 36.81 ± 5.0 nmol cm^?2. XPS and FTIR confirmed successful covalent layer‐by‐layer deposition of the N‐halamine multilayers. The reported layer‐by‐layer deposition technique resulted in a greater than seven‐fold increase of available N‐halamine compared to prior reports of N‐halamine surface modifications. The N‐halamine modified steel demonstrated antimicrobial activity (99.7% reduction) against the pathogen Listeria monocytogenes. Such surface modified stainless steel with increased N‐halamine functionality, and therefore potential for rechargeable antimicrobial activity, supports efforts to reduce cross‐contamination by pathogenic organisms in the food and biomedical industries. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of the tie‐layer thickness on the delamination and tensile properties of polypropylene/tie‐layer/nylon 6 multilayers

This study examined the effect of the tie‐layer thickness on the delamination behavior of polypropylene/tie‐layer/nylon 6 multilayers. Various maleated polypropylene resins were compared for their effectiveness as tie‐layers. Delamination failure occurred cohesively in all the multilayer systems. Two adhesion regimes were defined according to the change in the slope of the linear relationship between the delamination toughness and the tie‐layer thickness. The measured delamination toughness of the various tie‐layers was quantitatively correlated to the length of the damage zone that formed at the crack tip. In addition, the effect of the tie‐layer thickness on the multilayer tensile properties was correlated with the delamination behavior. The fracture strain of the multilayers decreased with decreasing tie‐layer thickness. An examination of the prefracture damage mechanism of the stretched multilayers revealed a good correlation with the delamination toughness of the tie‐layers. In thick tie‐layers (>2 μm), the delamination toughness was great enough to prevent the delamination of the multilayers when they were stretched. In thin tie‐layers (<2 μm), the delamination toughness of all the tie‐layers was low; consequently, delamination led to premature fracture in the stretched multilayers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Buildup of hyperbranched polymer/alginate multilayers and their influence on protein adsorption and platelet adhesion

A hyperbranched poly(methylene bisacrylamide–aminoethyl piperazine) (HPMA) and lactobionic acid modified hyperbranched poly(methylene bisacrylamide–aminoethyl piperazine) (LA–HPMA), namely, galactosylated HPMA, were assembled with alginate through the application of the layer‐by‐layer technique to fabricate polyelectrolyte multilayer (PEM) films. We monitored the assembly process to reveal the stepwise mass increase with a quartz crystal microbalance with the dissipation technique and by the reversal of the ζ potential. The thickness of PEMs assembled in solutions with different pHs was measured by spectroscopic ellipsometry; it showed a general decreasing tendency along with the pH increase. Postincubation in a buffer solution revealed that the multilayers possessed good stability with a thickness decrease from 5 to 15%. The PEMs showed a limited protein adsorption. Serum, bovine serum albumin, and fibrinogen were adsorbed onto the multilayers with a density within hundreds of nanograms per square centimeter to 1 μg/cm² and showed a relatively smaller adsorption on the multilayers assembled at pH 9. The PEMs assembled with LA–HPMA showed the lowest adhesion and activation of platelets, regardless of the outmost layer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44769.     

Simple method for the layer-by-layer surface modification of multiwall carbon nanotubes

A simplified method for the surface modification of multiwall carbon nanotubes (MWCNTs) using the layer-by-layer (LbL) technique is proposed. In this approach, the minimum polyelectrolyte content was added to the solution in order to eliminate the tedious centrifugation step. The one pot LbL deposition of poly (diallyldimethylammonium chloride) (PDADMAC), and poly (sodium 4-styrenesulfonate), (PSS) is presented. UV–Vis spectroscopy and zeta potential measurements were used to determine the minimum PDADMAC and PSS concentration needed for the deposition of each polyelectrolyte layer. The deposition cycle was repeated until six layers of PDADMAC/PSS were deposited. The film growth was confirmed by transmission electron microcopy and was found to increase as a function of the number of deposited layers with a final thickness of 18 nm. Evidence of the alternate deposition of oppositely charged polyelectrolytes was further investigated by measurement of the zeta potential values which were found to reverse from positive to negative as a function of the number of deposited layers thus confirming the overcompensation of the surface charge at each adsorption step. This simple method could be useful for the fast preparation of large volumes of MWCNTs solutions in a single batch without the need for centrifugation step.     

Adsorption of anionic amphiphilic polyelectrolytes onto amino-terminated solid surfaces

The adsorption behavior of several amphiphilic polyelectrolytes of poly(maleic anhydride-alt-styrene) functionalized with naphthyl and phenyl groups, onto amino-terminated silicon wafer has been studied by means of null- ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The maximum of adsorption, Γ_plateau, varies with the ionic strength, the polyelectrolyte structure and the chain length. Values of Γ_plateau obtained at low and high ionic strengths indicate that the adsorption follows the “screening-reduced adsorption” regime. Large aggregates were detected in solution by means of dynamic light scattering and fluorescence measurements. However, AFM indicated the formation of smooth layers and the absence of aggregates. A model based on a two-step adsorption behavior was proposed. In the first one, isolated chains in equilibrium with the aggregates in solution adsorbed onto amino-terminated surface. The adsorption is driven by electrostatic interaction between protonated surface and carboxylate groups. This first layer exposes naphtyl or phenyl groups to the solution. The second layer adsorption is now driven by hydrophobic interaction between surface and chains and exposes carboxylate groups to the medium, which repel the forthcoming chain by electrostatic repulsion. Upon drying some hydrophobic naphtyl or phenyl groups might be oriented to the air, as revealed by contact angle measurements. Such amphiphilic polyelectrolyte layers worked well for the building-up of multilayers with chitosan.