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The polymerization of the pre-formed hydrophilic block followed by the chain extension with a hydrophobic monomer in water and the final formation and adsorption of nanolatexes onto surfaces with a 2D or 3D distribution of charged groups. [Display omitted] It is theoretically predicted and hypothesized that the charge density and size of spherical nanoparticles are the key factors for their adsorption onto oppositely charged surfaces. It is also hypothesized that the morphology and charge of the surface are of great importance. In-plane 2D (silica) or a volumetric 3D (regenerated TEMPO-oxidized cellulose model surfaces) distribution of charged groups is expected to influence charge compensation and, thus, the adsorption behavior. In this work, self-stabilized nanolatexes with a range of cationic charge densities and sizes were synthesized through reversible addition − fragmentation chain-transfer (RAFT) polymerization coupled with polymerization-induced self-assembly (PISA). Their adsorption onto silica and anionic cellulose model surfaces was investigated using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). Experiments and theory agree and show that the size of the nanolatex and the difference in charge density compared to the substrate determine the charge compensation and, thus, the surface coverage. Highly charged or large nanolatexes overcompensate the surface charge of non-porous substrates leading to a significant repulsive zone where other particles cannot adsorb. For porous substrates like cellulose, the vertical distribution of charged groups in the 3D volume prevents overcompensation and thus increases the adsorption. This systematic study investigates the isolated effect of surface charge and size and paves the way for on-demand particles specifically designed for a surface with particular characteristics. [ABSTRACT FROM AUTHOR]

Abstract: This paper compares the influence of the molecular weight of polylelectrolytes forming polyelectrolyte multilayers (PEM) on wood fibers on adhesion and paper strength. Sheets were made from fibers treated with poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) of molecular mass 70,000 and 240,000, respectively, and of poly(dimethyldiallylammonium chloride) (PDADMAC)/poly(styrene sulfonate) (PSS) of molecular mass 30,000 and 80,000, respectively. The results were compared to what has recently been reported for PEM formation on fibers using a low-molecular-mass combination of PAH and PAA and a high-molecular-mass combination of PDADMAC/PSS. There was a less significant improvement in the case of the low-molecular-mass PDADMAC/PSS and the high-molecular-mass PAH/PAA. The adsorbed amounts of PAH and PDADMAC were also determined, showing a lower adsorbed amount of the low-molecular-mass PAH than of the high-molecular-mass PDADMAC. The amount of low-molecular-mass PDADMAC was similar to that found for high-molecular-mass PDADMAC/PSS. Individual fibers were partly treated and studied, showing a less significant decrease in wettability with low-molecular-mass PDADMAC/PSS than with the high-molecular-mass combination. The effect of the molecular weight on the adhesion was discussed in terms of the structure and wettability of the PEMs. [Copyright &y& Elsevier]

Abstract: The electrostatic interaction between quarternised hyperbranched polymers (polyesteramides) and a silicon oxide (SiO2) surface has been studied via adsorption studies with quartz crystal microbalance instrument with dissipation (QCM-D). Frequency shift (Δf) results show that the increase in both pH and salt concentration positively affect the adsorbed amount of these polymers, calculated by Sauerbrey equation, on the QCM crystal. The adsorbed amount of HA1 (with lower molecular weight and higher charge density) was lower than that of HA2 (with higher molecular weight and lower charge density) in all experiments. It was also observed that there are no significant changes in the dissipation after adsorption of these polymers. This indicated that both hyperbranched polymers formed rigid adsorbed layers on the negative SiO2 surface. Additionally, the results were compared with adsorption of poly-DADMAC and the results showed that the hyperbranched polymers formed thicker and more rigid layers as compared with the poly-DADMAC. [Copyright &y& Elsevier]

Abstract: Polydimethyldiallylammonium chloride (PDADMAC) and polystyrene sulfonate (PSS) have been used to build-up polyelectrolyte multilayers (PEMs) on chemical soft wood fibres and on SiO2 at various electrolyte concentrations. Adsorption onto SiO2 was studied using a stagnation point adsorption reflectometer (SPAR), and the adsorbed amount of PDADMAC and PSS on the fibres was determined using nitrogen analysis and Schöniger burning, respectively. The adsorption onto the two substrates was then compared. Paper testing showed that the tensile index (TI) increased by about 90% when 11 layers had been adsorbed, and that there was a correlation between the adsorbed amount and the increase in TI. It was also shown that the particular polymer present in the outermost layer significantly influenced the TI, and that PDADMAC produced a higher TI. A correlation between the adsorbed amount and the TI was also found. Individual fibres were partly treated with a PEM and analysed using a dynamic contact angle analyser (DCA) and environmental scanning electron microscopy (ESEM). [Copyright &y& Elsevier]

By measuring adsorption using a stagnation point reflectometer, it was shown that multilayers consisting of cationic polymers and dissolved and colloidal material released from wood fibres into process waters are formed on an anionic silica surface. The similarity of this experiment to the papermaking process was established.It was established using the “JKR-method” that this multilayer adsorption had a profound effect on the adhesion, in air, of an elastic polydimethyl siloxane (PDMS) probe to these surfaces. The adhesion of PDMS to a bare silica surface showed a large hysteresis, with a much stronger adhesion measured upon the separation of the two surfaces compared with the value obtained from gradually pressing them together. It was suggested that this hysteresis was due to specific interactions (hydrogen bonding) that develop over time. The first adsorbed layer, a cationic poly(dimethyldiallylammoniumchloride) (polyDMDAAC), decreased the magnitude of the hysteresis and gave a relatively low adhesion, which may be due to the fact that these specific interactions were blocked. The subsequent build up of layers of lipophilic wood extractives in the form of colloidal particles and cationic polymer increased the adhesion. This was interpreted as being due to the build up of a soft layer on the stiff mineral surface causing additional energy dissipation upon separation, even though the molecular adhesion was still decreased compared with the bare silica. This was supported by the fact that none of the individual components of the multilayer increased the adhesion when applied in a relatively thin layer on the silica, and by the fact that a thick deposition of cast coated wood extractives gave a very high adhesion. Stearic acid was chosen as a model substance for extractives and deposited onto silica from vapour phase. This resulted in a partial coverage of the surface where the stearic acid was present as patches of different size. This gave a significant reduction of the adhesion. The solid stearic acid melted and was redistributed when confined between the PDMS and the silica. This gave a thinner and more uniform layer. The application of a “monolayer” of C18-tails covalently bound to the silica by siloxane links, gave a very significant reduction of the magnitude of the adhesion hystersis. It is concluded that the distribution of the contaminants over the surface is very significant for the adhesion properties.This is relevant to practical papermaking with respect to: (i) the build up of deposits on process equipment and its effect on adhesion to these surfaces; (ii) fibre–fibre adhesion and thereby paper strength, a phenomenon that can never be studied without directly measuring the adhesion, which makes specific solutions to the practical problems possible. [Copyright &y& Elsevier]

The adsorption of cationic polyacrylamide and silica nanoparticle systems onto a model surface has been compared with the adsorption and flocculation of a fiber suspension. An increase in ionic strength affects the polyelectrolyte adsorption in different ways in these two systems. With a silica surface, an increase in the ionic strength leads to a continuous increase in the adsorption. On a cellulose fiber, the adsorption increases at low ionic strength (1–10 mM NaCl) and then decreases at higher ionic strength (10–100 mM NaCl). When polyelectrolyte is added to the fiber suspension, flocculation occurs with an optimum around a polyelectrolyte addition of 0.4 mg g−1. Above this addition level the flocculation effect is reduced and dispersion occurs when more than 1.2 mg g−1 polyelectrolyte is added. This behavior suggests a bridging flocculation, the dispersion being explained by electrosteric stabilization of the suspension. Addition of silica nanoparticles to the fiber suspension leads to a greater degree of flocculation than in a single polyelectrolyte system. The adsorption of nanoparticles to a polyelectrolyte-covered silica surface increases both the adsorbed amount and the thickness of the adsorbed film. A more extended silica particle, giving a more extended polyelectrolyte–silica film, also results in a higher degree of fiber flocculation. [Copyright &y& Elsevier]

Abstract: The influence of mixing procedure on the properties of polyelectrolyte complexes (PECs) was investigated using two complexation techniques, polyelectrolyte titration and jet mixing, the latter being a new method for PEC preparation. For the low-molecular-weight polyelectrolytes polyacrylic acid (PAA) and polyallyl amine hydrochloride (PAH), shorter mixing times produced smaller PECs, whereas for higher molecular weights of the same polyelectrolytes, PEC size first decreased with decreasing mixing time to a certain level, after which it started increasing again. This pattern was likely due to the diffusion-controlled formation of “pre-complexes”, which, in the case of low-molecular-weight polymers, occurs sufficiently quickly to form stable complexes; when polyelectrolytes are larger, however, non-equilibrium pre-complexes, more prone to aggregation, are formed. Comparing the techniques revealed that jet mixing produced smaller complexes, allowing PEC size to be controlled by mixing time, which was not the case with polyelectrolyte titration. Higher polyelectrolyte concentration during jet mixing led to the formation of larger PECs. It was also demonstrated that PEC size could be changed after preparation: increasing the pH of the PEC dispersion led to an irreversible increase in PEC size, whereas lowering the pH did not influence PEC size. The adsorption behavior of PECs formed from weak polyelectrolytes on model substrates was studied using QCM-D, SPAR, and AFM imaging; the results indicated that increasing the pH increased the amount of PECs adsorbed to model surfaces. However, the amount of PECs adsorbed to the model surfaces was low compared with other systems in all studied cases. [ABSTRACT FROM AUTHOR]

Abstract: Individual wood fibres were partly treated with polyelectrolyte multilayers (PEMs) consisting of two different polymer combinations, poly allylamine (PAH)/poly acrylic acid (PAA) and polyethylene oxide (PEO)/PAA in order to study the influence of these polymers on fibre wettability. Single fibres were partly treated and analysed using a so-called dynamic contact analyser (DCA) where the fibres are wet under controlled conditions. When PAH/PAA was used, a stronger influence on fibre wettability was detected when PAH was adsorbed in the outermost layer of the multilayer than when PAA was adsorbed in the outermost layer. The wettability of fibres treated with PAH/PAA PEMs was also influenced by the pH of the adsorption. With the PEO/PAA system, however, the type of polymer adsorbed in the outermost layer caused no detectable difference. Tests of sheets prepared from fibres treated with PEO/PAA showed an increase of about 90% in the tensile index when 9 layers were adsorbed. These and other recently published results from similar experiments using PAH/PAA [S.M. Notley, M. Eriksson, L. Wågberg, J. Colloid Interface Sci. 292 (2005) 29] are compared to the results for the PEM-treated individual fibres. The results indicate that fibres with low wettability contribute to greater paper strength. AFM-force measurements, with the aid of a colloidal probe technique, have also been performed using PAH/PAA, showing that there is also a close correlation between lower wettability of the surfaces and a higher pull-off force between the PEM treated surfaces, i.e. the flat surface and the colloidal probe. This is valid for the two pH strategies that are used for the formation for the PAH/PAA PEMs, which are studied using AFM-force measurements. [Copyright &y& Elsevier]

Abstract: Polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA) have been used to build up polyelectrolyte multilayers (PEM) on wood fibres and on silicon oxide surfaces, under various pH conditions. Consecutive adsorption onto silicon oxide surfaces of PAH and PAA were studied using stagnation point adsorption reflectometry, and the results showed a steady build-up of multilayers. Furthermore, by altering pH, the build-up of the multilayer could be made either linear or exponential in terms of adsorbed amount. Nitrogen analysis of sheets prepared from modified fibres showed that the adsorbed amount of PAH increased throughout PEM build-up, the amount of increase depending on pH during adsorption. Strength measurements of the sheets, i.e., stress at break and strain at break, showed significant improvements ranging from 60 to 200%, depending on both pH during adsorption and type of polyelectrolyte in the outer layer. A good correlation between the adsorbed amount of PAH and the improved strength properties of the paper was also found. [Copyright &y& Elsevier]

Abstract: In this study, thermo-responsive nanofibrillated cellulose (NFC) has been produced by the adsorption of thermo-responsive polyelectrolytes to the NFC. Three block copolymers were synthesized in which the polyelectrolyte block was composed of quaternized poly(2-(dimethylamino)ethyl methacrylate) (qPDMAEMA) and the thermo-responsive block was composed of poly(di(ethylene glycol) methyl ether methacrylate) (PDEGMA). The block copolymers were synthesized employing atom transfer radical polymerization (ATRP) and the PDMAEMA block was utilized as a macroinitiator for the polymerizations of PDEGMA. The length and charge of the PDMAEMA block were kept constant in all three block copolymers, while three different molecular weights of the PDEGMA block was synthesized. The PDMAEMA block was quaternized to introduce positive charges and the block copolymers were subsequently adsorbed onto the negatively charged NFC that was dispersed in water. The lower critical solution temperatures (LCSTs) of the free block copolymers in solution were analyzed by dynamic light scattering (DLS). The composites were analyzed by QCM-D, FT-IR and TGA, which clearly showed an adsorption of the block copolymer onto the NFC. The grafted NFC showed a thermo-responsive behavior in solution upon heating and cooling, thus supporting that the properties of the polyelectrolyte can be transferred to the cellulose. By this methodology, thermo-responsive NFC materials can be produced in a straight-forward manner in water dispersions, without performing any chemical reactions on the NFC. [Copyright &y& Elsevier]

Abstract: In this study, particle polyelectrolyte complexes (PPECs) were formed by mixing cationic polyacrylamide (CPAM) and silica nanoparticles using the jet mixing technique. Within certain limits, the size of the formed PPECs could be controlled. The aim was to prepare PPECs with embedded sacrificial bonds, similar to those found in bones. Examination of PPEC adsorption to silica model surfaces indicated that smaller PPECs adsorbed to a higher level than larger ones, due to the higher diffusion speed of smaller complexes. Adsorption studies of the same components as in the PPECs, but arranged in multilayers, that is, particle polyelectrolyte multilayers (PPEMs), indicated a stable, gradual build-up of material on the surface with smaller nanoparticles, whereas PPEMs comprising elongated nanoparticles appeared to be more loosely adsorbed onto the surface when the nanoparticles were in the outer layer, due to repulsive forces within the adsorbed layer. The AFM colloidal probe technique was used to study the interaction between surfaces treated with PPECs, multilayers, or polyelectrolyte complexes (PECs). The results showed that the expected long-range disentanglement could be achieved with PPECs but that the pull-off forces were generally low. Treatment with PPEMs comprising the same polymer and nanoparticle components produced higher pull-off values, together with disentanglement behaviour, possibly due to better contact between the surfaces. Adhesion experiments with polymer PECs showed significantly higher pull-off values than with the PPECs, probably due to polymer interdiffusion across the surface boundary. [Copyright &y& Elsevier]

Abstract: The wetting of two different model cellulose surfaces has been studied; a regenerated cellulose (RG) surface prepared by spin-coating, and a novel multilayer film of poly(ethyleneimine) and a carboxymethylated microfibrillated cellulose (MFC). The cellulose films were characterized in detail using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM indicates smooth and continuous films on a nanometer scale and the RMS roughness of the RG cellulose and MFC surfaces was determined to be 3 and 6 nm, respectively. The cellulose films were modified by coating with various amounts of an anionic fluorosurfactant, perfluorooctadecanoic acid, or covalently modified with pentadecafluorooctanyl chloride. The fluorinated cellulose films were used to follow the spreading mechanisms of three different oil mixtures. The viscosity and surface tension of the oils were found to be essential parameters governing the spreading kinetics on these surfaces. XPS and dispersive surface energy measurements were made on the cellulose films coated with perfluorooctadecanoic acid. A strong correlation was found between the surface concentration of fluorine, the dispersive surface energy and the contact angle of castor oil on the surface. A dispersive surface energy less than 18 mN/m was required in order for the cellulose surface to be non-wetting () by castor oil. [Copyright &y& Elsevier]

Abstract: Wet and dry adhesion between dextran-coated surfaces were measured aiming to understand the influence of polymer compatibility. The wet adhesion measurements were performed using the atomic force microscope (AFM) colloidal probe technique whereas the dry adhesion measurements were performed using the micro adhesion measurement apparatus (MAMA). Two types of dextrans were used, one cationically modified dextran (DEX) and one that was both cationically and hydrophobically modified (HDEX), leading to three different combinations of polymer-coated surfaces; (1) DEX:DEX, (2) HDEX:DEX, and (3) HDEX:HDEX. DEX increased dry adhesion more than HDEX did, which likely is due to differences in the ability to form specific interactions, especially hydrogen bonding. HDEX gave strong wet adhesion, probably due to its poorer solvency, while DEX contributed to reducing the wet adhesion due to its hydrophilicity. All combinations showed a steric repulsion on approach in aqueous media. Furthermore, when HDEX was adsorbed on either or both surfaces a long range attractive force between the surfaces was detected outside this steric regime. [Copyright &y& Elsevier]

• Anionic PEDOT:PSS adsorbs spontaneously on anionically charged cellulose. • Temperature-dependent QCM-D suggests the larger entropic contribution to adsorption. • Low pH, high ionic strength and multivalent counterions favor PEDOT:PSS adsorption on CNF. • PEDOT:PSS and CNF show higher adhesion at low pH in colloidal probe measurements. • PEDOT:PSS organizes differently on 3D and 2D cellulose surfaces. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a conducting polymer frequently used with cellulose, to develop advanced electronic materials. To understand the fundamental interactions between cellulose and PEDOT:PSS, a quartz crystal microbalance with dissipation (QCM-D) was used to study the adsorption of PEDOT:PSS onto model films of cellulose-nanofibrils (CNFs) and regenerated cellulose. The results show that PEDOT:PSS adsorbs spontaneously onto anionically charged cellulose wherein the adsorbed amount can be tuned by altering solution parameters such as pH, ionic strength and counterion to the charges on the CNF. Temperature-dependent QCM-D studies indicate that an entropy gain is the driving force for adsorption, as the adsorbed amount of PEDOT:PSS increased with increasing temperature. Colloidal probe AFM, in accordance with QCM-D results, also showed an increased adhesion between cellulose and PEDOT:PSS at low pH. AFM images show bead-like PEDOT:PSS particles on CNF surfaces, while no such organization was observed on the regenerated cellulose surfaces. This work provides insight into the interaction of PEDOT:PSS/cellulose that will aid in the design of sustainable electronic devices. [ABSTRACT FROM AUTHOR]