Synthesis and characterization of multiple cross-linking UV-curable waterborne polyurethane dispersions

A series of multiple cross-linking ultraviolet (UV) curable waterborne polyurethane dispersions (UV-PUDs) were synthesized by modification of diglycidyl ether of bisphenol-A-based epoxy resin (E51) through ring-opening by 3-aminpropyltriethoxysilane (APTES). Initially, APTES-E51 was synthesized using APTES to open the epoxy groups of E51. Then, APTES-E51 was incorporated into the chains of polyurethane, and multiple cross-linking UV-PUDs were produced. The chemical structures were confirmed by the Fourier-transform infrared spectroscopy (FTIR) and the effect of the APTES-E51 content on the UV-PUDs properties was investigated. The average particle size of UV-PUDs was determined by dynamic light scattering (DLS). The result showed that the average particle size increased with increasing APTES-E51 content and the stability of the UV-PUD storage diminished when the content of APTES-E51 was 10.0%. After modification by APTES-E51, the water absorption of the UV-cured films decreased and the water contact angle (CA) increased significantly. Thermogravimetry analysis (TGA) of the UV-cured films illustrated that APTES-E51 modified UV-curable waterborne polyurethane could exhibit good thermal stability. In addition, mechanical property of the cured films showed that the incorporation of APTES-E51 also improved tensile strength of the cured films. We can obtain good storage stability, satisfied water resistance, and high thermal stability and tensile strength when the APTES-E51 content of the UV-PUD was 9.1%.     

Characterization of colloidal polymer particles through stability ratio measurements

We propose a general methodology for the estimation of the doublet formation rate constant (proportional to the stability ratio of primary particles) in colloidal dispersions from measurements obtained by common optical techniques, such as dynamic light scattering, static light scattering (nephelometry) or turbidimetry. In contrast to previous approaches relying on the initial slopes of the measured quantities, such as the mean hydrodynamic radius, scattered light intensity or turbidity, we introduce a transformation of the measurables to properly scaled quantities, which grow linearly in time with a slope proportional to the doublet formation rate. Analysis of systematic and random errors allows one to control the error in the estimated value of the aggregation rate. Using this approach, we measured the aggregation rate constant of colloidal polymer particles prepared by surfactant-free emulsion copolymerization of styrene and 2-hydroxyethyl methacrylate (HEMA). It was found that the stability ratio at constant ionic strength decreases with increasing dilution of the original polymer latex. This can be explained by the presence of non-reacted stabilizing species (most likely oxidized HEMA) that desorb from the particle surface upon latex dilution and thus diminish the repulsive interactions between particles. In order to check if the stability of latex particles is influenced by reversibly adsorbed species it is always necessary to perform aggregation experiments at various dilutions.     

Enhanced flocculation of colloidal dispersions by polymer mixtures

Bridging flocculation and electrolyte coagulation of negatively charged colloidal dispersions in the presence and absence, respectively, of uncharged polymers and polymer mixtures were studied. The relative coagulation and flocculation rates of particles in the presence of electrolyte and small polymer amounts were measured and the stability ratios have been calculated at various ionic strengths. Also, the structure of polymer layers formed in individual adsorption of polymers and in simultaneous competitive adsorption from binary polymer mixtures at particle/solution interfaces was investigated. The electrophoretic mobility and the diffusion coefficient of particles with and without adsorbed polymer were measured by laser Doppler-electrophoresis and photon correlation spectroscopy, respectively, and the electrophoretic and the hydrodynamic thickness of adsorbed polymer layers have been calculated. It was found that the adsorbed polymers may enhance or diminish the rate of successsful encounters between particles, even at low surface coverages, depending on the magnitude of the interparticle electrostatic repulsion. In addition, competitive adsorption of chemically different polymers for particle surfaces may result in considerable alteration in the conformation of macromolecules in the mixed adsorption layer. Close correlation was found between the effectiveness of polymers as flocculants and the thickness of adsorbed polymer layers formed at optimum polymer dosages on the particle surfaces. Binary mixtures of suitable polymers proved to be very efficient flocculants for the dispersions. The enhanced flocculating effect of some mixtures can be ascribed to extended polymer layers formed in competitive adsorption of chemically different macromolecules at particle/solution interfaces. These findings have relevance in many environmental technologies and offer a way of improving the effectiveness of solid–liquid separation processes.     

Iridescent Colors from Films Made of Polymeric Core-Shell Particles

Summary Brilliant and angle-dependent iridescent colors were obtained from polymer films produced via colloidal crystallization of monodisperse core-shell particles by drying aqueous dispersions. By variation of the particle size, the brilliant color could be varied throughout the visible spectrum. The color effects of the smooth thin films exhibit excellent thermal and water stability. The morphology of the core-shell particles and the properties of the corresponding films were characterized by dynamic light scattering (DLS), atomic force microscopy (AFM), differential scanning calorimetry (DSC), and reflection spectrum measurements. The results indicate that the brilliance of the film is strongly dependent on size and quality of the crystalline domains.     

Comparison of two cationic polymeric flocculant architectures on the destabilization of negatively charged latex suspensions

Flocculation studies between cationic polymers and oppositely charged colloidal particles are reported in which both flocculation kinetics and floc structures are systematically investigated. The flocculation rate constant, stability ratio and kinetics laws are experimentally determined using particle counting for two polymer architectures; a cationic linear polymer and a two-branched polymer. Comparisons are also made using NaCl at different ionic concentrations for the destabilization of the colloidal particles. Detailed measurements of electrophoretic mobility and kinetics rate constants on varying the polymer dosage are reported. Results suggest that the polymer architecture plays important roles on the polymer dosage for the rapid destabilization of the colloidal suspension. The branched polymer at optimal dosage exhibits the highest flocculation rate constant, whereas on the other hand, the linear polymer concentration range of flocculation is larger. In both cases, polymer flocculation is more efficient by a factor of 5-6 than charge screening effects due to the presence of salt. Analysis of the stability ratio indicates that tele-bridging flocculation and electrostatic forces dictate the stability of the charged latex particle suspension. It is shown that the fractal concepts which are valid for aggregation processes are also applicable here and branched polymers as well as linear polymers yield to the formation of compact flocs in comparison to those obtained with salt.     

UV-curable PUDs based on sustainable acrylated polyol: Study of their hydrophobic and oleophobic properties

UV-curable polyurethane dispersions (UV-PUDs) are fast expanding commercial applications since they combine benefits of both water-borne as well as UV-curing technologies while addressing many technical, environmental and performance benefits. Varying the compositions and cross-link density of UV-PUD polymeric chain backbone can control the film properties of UV-PUDs. There are many design restrictions posed by availability of commercial materials. In the present research work we demonstrate synthesis and application of a multi-functional acrylate polyol derived from soybean oil, as soft-segment of UV-PUDs. A series of UV-PUDs have been designed for high performance coatings that are specifically hydrophobic and oil-resistant. To this end, UV-PUDs based on acrylated soy-polyol have been further modified by siloxane and perfluoro compounds and their films with varying cross-link density have been investigated. The UV-PUD films were characterized for their film properties, particle size, contact angle and solvent swelling ratio. The outcome of this study provides useful insights into design considerations for hydrophobic and oil-resistant UV-curable coatings.     

Synthesis of a water-soluble chain transfer agent and its application in gel dispersions

Pre-crosslinked gel particles, colloidal dispersion gels, and polymer microspheres are often used as profile-controlling and flooding agents to displace residual crude oil from formations. The preparation process of these profile-controlling and flooding agents is complicated. In order to simplify the preparation steps, a water-soluble chain transfer (RAFT) agent, S,S′-bis(2-propionic acid) trithiocarbonate (PATTC), was synthesized, and then, hydrogel dispersions were prepared by one-pot RAFT polymerization. The structure of PATTC was confirmed by infrared spectroscopy and nuclear magnetic resonance. The effects of reaction conditions on the viscosity and viscosity-average molecular weight of hydrogel dispersions were explored, the rheology, viscoelasticity, particle size, temperature responsiveness, and salinity responsiveness of hydrogel dispersions were measured, and the seepage properties of hydrogel dispersions in porous medium were analyzed. The results show that at higher shear rates, the polyacrylamide gel dispersions exhibited Newtonian fluid characteristics. Viscoelasticity tests further confirmed that the polyacrylamide gel dispersions were successfully synthesized. The particle size of the hydrogel dispersions is 1–75 μm, its viscosity is less affected by temperature and salinity, and its residual resistance coefficient is higher than that of the polyacrylamide solution under similar apparent viscosity.     

The rheology of aqueous alumina suspensions in the presence of hydroxyethylcellulose as binder

The rheological behaviour of aqueous colloidal alumina dispersions stabilised by the dispersant Darvan C, an ammonium salt of polymethacrylic acid, was investigated in presence of hydroxyethyl cellulose (HEC) at room temperature. Measurements were taken under both oscillatory and steady shear. It was found that the polymer induces flocculation of the particles probably due to a depletion mechanism. The flocculation process results in the creation of a particle network, which restricts particle movements and gives rise to a wide distribution of relaxation times. At high HEC concentrations, two sets of relaxation times can be distinguished, one at low and the other at high frequencies. At high solids content and high HEC concentrations, the response of the system becomes predominantly elastic at low frequencies. The behaviour is similar to an entangled network of high molecular weight uncross-linked polymer solution. Thus, HEC causes the formation of ‘topological restraints' comprised of chains of particles that give rise to a wider distribution of relaxation times with significantly lower terminal relaxation times. In addition, similarly to a polymer solution, complete superposition occurs of the apparent and dynamic viscosity in accordance to the Cox–Merz rule. Taking into account the combined data, a Cross type of formulation was found to fit the behaviour of all dispersions that can be represented in terms of a single dimensionless parameter. The behaviour of the adjustable parameters of this empirical model suggests a diffusion controlled cluster–cluster aggregation process that induces a more closed packed particle arrangement at high shear rates. ©     

SELF-DIFFUSION IN POTENTIALS OF MEAN FORCE IN WEAKLY- AND STRONGLY-INTERACTING DISPERSIONS

Studies of interactions in dispersions have traditionally focused on the stability and transport properties of such systems at extreme dilution, that is, at concentrations for which colloidal and hydrodynamic interactions are significant between at most two particles at a given time. In practice, however, dispersions of interest often do not satisfy this restriction, and, consequently, many-body colloidal interactions and hydrodynamic coupling have important roles in the observed macroscopic behavior. This paper presents an analysis of the effects of many-body interactions on the self-diffusion coefficient in interacting dispersions. Self-diffusion coefficients have been determined for dilute-gas dispersions and for Yukawa dispersions interacting through appropriate potentials of mean force. It is shown that the diffusion coefficients change negligibly with attraction for typical magnitudes of the Hamaker constant in an otherwise repulsion-dominated (i.e., stable) dispersion. The results show that, for thin electrical double layers, dilute dispersions can be approximated by hard-sphere dispersions, even for large values of surface potentials. However, for thick double layers (i.e., thickness comparable to particle radius), while the short-time diffusion coefficient is affected only negligibly, the long-time coefficient can decrease considerably because of the 'memory' effects—even for moderate or low values of the surface potentials. Corresponding results are presented for both dilute-gas dispersions and dispersions with significant local structures. The long-time diffusion coefficients in the latter are effectively linear in volume fraction (up to about 0.2)for thin double layers and are given with reasonable accuracy by the dilute-gas approximation.     

Colloidal properties and gelation of aqueous dispersions of conductive poly(benzimidazobenzophenanthroline) derivatives

Poly(benzimidazobenzophenanthroline), BBL, is a practically insoluble conductive polymer. It can be gradually dispersed in water, however by dialysis and sonication, i.e. during the purification and dilution right after synthesis. Dispersions with higher solids content and colloidal stability were prepared by first turning the polymer amphiphilic adding poly(ethylene oxide), PEO, into BBL chain ends (BBL–PEO). Dynamic light scattering and zeta potential measurements showed that the dispersions consist of negatively-charged particles with a broad size distribution. These dispersions were found to be sensitive to ionic strength. Salting out occurred within a NaCl concentration range of 0.5–4 mM and some samples showed re-entrant behavior with redispersion upon further salt addition. Addition of a non-ionic surfactant was found to enhance the stability of BBL–PEO dispersions against salting-out. Upon increasing the polymer concentration the dispersions form gels upon resting. The strength of the gels depends on the total polymer concentration as well as the proportions of BBL and PEO in the BBL–PEOs. The gel formation was attributed to a formation of a network of nano-wire-type aggregates, which was verified with electron cryo-microscopy.     

INVITED REVIEW STABILITY OF COLLOIDAL DISPERSIONS

The stability of colloidal dispersions has traditionally attracted considerable attention in the chemical literature because of its origins in the physical chemistry of electrostatic and steric interactions between surfaces immersed in liquids. Moreover, progress in the physics and chemistry of stability phenomena has a direct impact on chemical engineering research, since stability of dispersions plays an important role in the rheology and transport properties of charged particles in liquids, separation processes (such as membrane filtration and solid/liquid separation), deposition and particulale fouling phenomena and numerous other processing operations. This paper presents a discussion of physical and chemical factors that affect colloidal stability and, in addition, presents an overview of the status of current research needs in this area. In addition to electrostatic and steric effects, some recent studies on the role of bulk motion of the supporting liquid on stability are also discussed. The emphasis throughout is on the stability of dilute dispersions, in which simultaneous interactions between more than two particles are negligible. Some major research needs in the above areas are also identified.     

Viscometric properties of poly(dimethylsiloxane) filled with spherical silica particles

The shear viscosity and primary normal stress coefficient were measured for colloidal dispersions of monodisperse silica spheres in poly(dimethylsiloxane). The viscometric properties of the dispersions were a function of the shear rate, particle diameter, and the volume fraction of particles. Dimensional analysis of rheological properties of colloidal dispersions of spherical particles in a second-order fluid was performed, and the experimental data were analyzed in terms of the appropriate dimensionless groups. The reduced shear viscosity of the colloidal dispersions was a function of the volume fraction of particles and the reduced shear stress (or reduced shear rate). The reduced primary normal stress coefficient was a function of the volume fraction of particles, the reduced shear rate, and the Weissenberg number.     

Stability of pigment and resin dispersions in waterborne paint

The stability of a colloidal dispersion in a waterborne paint system, which consists of dispersed pigment and polymeric particles (dispersion or emulsion) along with a water-soluble acrylic polymer, was investigated. It was found that adsorption of appropriate ultrafine particles to the relevant particles could stabilize these particles against flocculation, leading to lower viscosity and yield value. The gloss and smoothness of the resultant films are notably improved. As the stability of the colloidal particles in an aqueous system is strongly dependent on the electrostatic effect, the effect was evaluated by measuring the ζ-potentials of the relevant colloidal particles. The ζ-potential is the electric potential on the outside of the surface layer, which includes the counterions around the particle. The ζ-potentials of a series of pigments in a solution of a water-soluble polymer were determined. By arranging the pigments according to their ζ-potentials, an order of basicity-acidity was established for pigments in a waterborne system, and the order was found to be different from that of solventborne systems, thought to be due to adsorbed counterions. After dispersing the pigment sufficiently with an appropriate polymer dispersant, ultrafine particles (of size under 0.05 μm) of lower refractive indexes were adsorbed to the surface of the pigments and polymeric particles. The adsorption layer of ultrafine particles can modulate the ζ-potentials of various colloidal particles to bring them into a certain range, so that the co-flocculation tendency between different colloids is remarkably diminished providing quite stable paint compositions by both electrostatic and steric hindrance effects.     

Effects of concentration of dispersions on particle sizing during production of fine particles in wet grinding process

Stirred media milling is a prospective technology for producing colloidal dispersions by means of wet grinding process. In the past, many researchers have studied the effects of different operating parameters such as size, shape, nature and quantity of grinding medium, the speed of agitator in grinding chamber, the feed rate of dispersions, etc. in stirred media mills. However, it is still less known how particle sizing which generates valuable information of particle size of the product to interpret, control and optimize the grinding process, is influenced by the concentration of the dispersion during stirred media milling where particles change their size from micron to colloidal range rapidly. One of the reasons of this lack had been our incapability in the past to study the particle size distribution of dispersions without dilution. The recent advent of acoustic attenuation spectroscopy is known to be capable of studying dispersions without dilution, under real process conditions and on line. The study employs acoustic attenuation spectroscopy to investigate the effects of concentration of dispersions of CaCO₃ on its particle sizing during size reduction process in a stirred media mill (LabStar manufactured by NETZSCH). The dispersions of CaCO₃ at 5%, 10%, 20% and 30% (m/m) were studied about six hours under a selected set of operating conditions. Contrary to the existing knowledge obtained through other techniques of particle sizing that are based on the principle of dilution, acoustic attenuation spectroscopy shows that, under certain grinding time at given operating conditions, increase in concentration of dispersion results in better grinding results yielding smaller particles. The causes behind the differences in results of acoustic attenuation spectroscopy and dynamic light scattering have been thoroughly investigated. We find certain limitations of acoustic attenuation spectroscopy in particle sizing. A typical phenomenon which causes misleading trends in particle sizing is multiple scattering in acoustic measurements. Multiple scattering, particularly, influences acoustic results when particles approach to fine size range during size reduction process.     

The colloidal properties of alkaline‐soluble waterborne polymers

Waterborne polymer dispersions are widely used in coatings and graphic arts markets as environmentally friendly and more sustainable alternatives to solvent borne binders. Traditionally, waterborne (meth)acrylic dispersions are prepared by emulsion polymerization using low molar mass surfactants as a key ingredient to control particle size. However, these surfactants can have a negative influence on the performance of coatings such as reduced water resistance and adhesion. To mitigate the negative effects of surfactants, polymer latexes have been developed that employ alkaline‐soluble polymers as the sole stabilizer for a subsequent emulsion polymerization step. In this way surfactant‐free polymer dispersions are obtained. Despite the high commercial impact and relevance of this technology, fundamental studies regarding the physicochemical properties of the alkaline‐soluble polymers are lacking. In this article, the synthesis and colloidal properties of alkaline‐soluble waterborne methacrylic copolymers are reported. The dissolution behavior and colloidal properties of these alkaline‐soluble polymers were studied as function of molar mass, acid content, and pH. The dissolving polymer particles were characterized using static and dynamic light scattering, static and dynamic surface tension measurements, and cryogenic‐transmission electron microscopy analysis. It is concluded that the dissolution mechanism of alkaline‐soluble polymers follows a gradual process. As the pH increases deprotonation of the carboxylic acid groups swells the particle enhancing the further swelling with water. At a certain amount of base, the particles disintegrate into small polymer aggregates while the most water‐soluble polymer chains are dissolved in the water phase. An important learning is that part of the alkaline‐soluble polymer resides in very small particles (<5 nm). The formation of these polymer particles below 5 nm was not reported previously and offers a new insight into the dissolution mechanism of alkaline soluble polymers. The most important parameter steering this process is the acid value of the polymer, while the molar mass plays a modest role. The understanding gained in this study can be used to further advance alkaline‐soluble polymers as stabilizer in surfactant‐free emulsion polymerization technology, improving the performance of a wide range of industrially relevant coatings. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46168.     

INVITED REVIEW STABILITY OF COLLOIDAL DISPERSIONS

The stability of colloidal dispersions has traditionally attracted considerable attention in the chemical literature because of its origins in the physical chemistry of electrostatic and steric interactions between surfaces immersed in liquids. Moreover, progress in the physics and chemistry of stability phenomena has a direct impact on chemical engineering research, since stability of dispersions plays an important role in the rheology and transport properties of charged particles in liquids, separation processes (such as membrane filtration and solid/liquid separation), deposition and particulale fouling phenomena and numerous other processing operations. This paper presents a discussion of physical and chemical factors that affect colloidal stability and, in addition, presents an overview of the status of current research needs in this area. In addition to electrostatic and steric effects, some recent studies on the role of bulk motion of the supporting liquid on stability are also discussed. The emphasis throughout is on the stability of dilute dispersions, in which simultaneous interactions between more than two particles are negligible. Some major research needs in the above areas are also identified.     

Water-dispersible graft copolymer mixtures prepared by electron irradiation. II. Dispersion behavior

Highly viscous systems made up of 70 wt% epoxy resin dissolved in 30% monomer mixture of styrene and acrylic monomers were irradiated with 1.5 MeV electrons to initiate graft copolymerization. The obtained product of graft copolymer mixture was fed into a mixed solvent of n-butanol and cyclohexanone, and was heated 2 h at 70°C to form a predispersion. Then aqueous solution of 2-dimethylaminoethanol or ethanol was added to the predispersion, thus giving a stable dispersion in water or in ethanol. The particle diameter of the aqueous and ethanol dispersions is practically the same, thus suggesting that polymer particles are virtually generated during the predispersing procedure, and at this step the size of the particles is actually determined. The particle diameter increases inversely proportional to the polymer concentration in the predispersion. Furthermore, the particle diameter shows a tendency to decrease with an increase in the hydrophilicity of monomers used in the graft copolymerization. The stopped-flow measurement, on the other hand, reveals a characteristic pH dependence of the dispersion stability to the addition of NaCl. This result is interpreted based on a particle model consisting of a particle core of epoxy resin and its surrounding layer of acrylic copolymer.     

Viscosity of Electrostatically Stabilized Dispersions of Monodispersed, Bimodal, and Trimodal Silica Particles

Effect of particle size and polydispersity on the viscosity and maximum packing fraction of aqueous colloidal dispersions has been studied. For dispersions of mono-sized particles, the results indicate that there is a linear relationship between the log(η) (viscosity) and particle size at a fixed shear rate and volume fraction of solids. However, there is a particle diameter at which there is a decrease in the dependency of viscosity on particle size as the slope of the linear plots of log(η) versus particle diameter changes to a smaller value. Preliminary calculations indicate that this particle size may correspond to a separation distance at which electrostatic energy as compared with the thermal energy of the particles can be ignored. In the case of bimodal dispersions, the viscosity is affected by both absolute size and the ratio of the two sizes. The effect of particle size ratio on the viscosity was investigated using bimodal dispersions of the same size coarse particles, but fines of different sizes. There is a critical volume ratio below which bimodal dispersions of larger size ratios show lower viscosities than systems of smaller size ratios. Above this volume ratio of the two sizes, the trend becomes reversed and the fines will have a dominant effect on the viscosity behavior of the bimodal system. Statistically designed experiments were carried out using trimodal mixtures of monodispersed silica particles and it was shown that tridispersed suspensions demonstrate similar behavior as bidispersed suspensions, with a minimum in viscosity observed as a function of particle volume ratio.     

Molecular weight (M n) and functionality effects on CUP formation and stability

The formation of colloidal unimolecular polymer (CUP) particles from single polymer strands was investigated as a function of molecular weight. The CUP particle size was correlated with the absolute molecular weight and its distribution. The characteristics of the particles were evaluated with respect to viscosity, acid number, size distribution, and stability. The particle size varied from less than 3 nm to above 8 nm representing polymers with molecular weight in the range of 3000–153,000. Lower molecular weight polymers were found to be unstable. Particle size measurements using dynamic light scattering technique indicated a normal distribution which corresponded to the molecular weight distribution of the copolymer. The statistical distribution of the acid groups in the polymer chains played a significant role in the stability of low molecular weight polymers.     

Water resistance of the membranes for UV curable waterborne polyurethane dispersions

The water absorption of the membranes made from UV curable waterborne polyurethane dispersions (UV-PUDs) was investigated systematically and correlated with the nature of the polymer and its gel content after curing. It was found that the water absorption of the membranes was reduced significantly by using polyester polyols, reducing the COOH content and increasing the gel content through a higher CC level. In particular, the membranes made from polyurethanes having hydroxyl-terminated polybutadiene (HTPB) or modified with dihydroxybutyl-terminated polydimethylsiloxane (PDMS) presented a superior water resistance. The results showed a linear relationship between the water absorption and the surface tension of the membrane.