The synthesis of stimulus-responsive poly(N-isopropylacrylamide-co-N-isopropylmethacrylamide)/chitosan core/shell nanohydrogels made by batch emulsion polymerization in the presence of chitosan (CS) micelles is reported. The ratio of monomers required to obtain copolymers with a volume phase transition temperature (TVPT) in the range of the temperatures observed in the human body in response to an infection (38 to 40 °C) was estimated with the Fox equation. The conversion was determined by gravimetry; mean particle size, size distribution, and thermal response were measured by quasi-elastic light scattering (QLS). The core/shell structure was confirmed by TEM, and FTIR showed the presence of N-isopropyl acrilamide (NIPA), N-isopropyl methacrylamide (NIPMA), and CS in the nanohydrogels. The nanohydrogels were loaded with the drug doxycycline hyclate, and their release kinetic profile was determined at pH = 2.0 and 7.4 at their volume phase transition temperatures (TVPT). A higher amount of drug was released at acidic pH. Some mathematical models described in the literature were used to fit the experimental drug release data.

The main objective of this work is to demonstrate the agreement between the two-fluid linear Langevin formulation and that described by the extended irreversible thermodynamics (EIT). The two-fluid model, originally proposed by de Gennes, has been widely analyzed by many authors in various flow situations, especially to compare predictions with experimental data of the structure factor in many complex flows. The canonical Langevin equations together with the fluctuation-dissipation theorem ensure consistent thermodynamic behavior for constitutive equations. Therefore, agreement between the EIT formulation and the two-fluid Langevin equations demonstrates the thermodynamic consistency of the EIT formulation. Extension of this analysis to include normal stresses is also considered.

In this work, we analyze the kinetics of the entanglement-disentanglement process of complex fluids coupled to a rheological constitutive equation of state within an irreversible thermodynamics framework. In the context of the coupling between the kinetics and the mechanical phenomena, we assume that the rate constants are functions of the affinities that contain the chemical potentials, which are themselves functions of the extended Gibbs free energy containing the irreversible dissipation terms. Although the derived model has a simple mathematical structure, it is able to predict complex flow behaviors, including shear-thickening, shear-thinning, and more complex flow histories such as shear-banding. As special case, we derive the constitutive equations of the Bautista-Manero-Puig (BMP) model in which the material constants have a thermodynamic basis and have been successfully used for the last two decades to predict the behavior of complex fluids such as the ones examined here.

In this work, we examine the shear-banding flow in polymer-like micellar solutions with the generalized Bautista-Manero-Puig (BMP) model. The couplings between flow, structural parameters, and diffusion naturally arise in this model, derived from the extended irreversible thermodynamics (EIT) formalism. Full tensorial expressions derived from the constitutive equations of the model, in addition to the conservation equations, apply for the case of simple shear flow, in which gradients of the parameter representing the structure of the system and concentration vary in the velocity gradient direction. The model predicts shear-banding, concentration gradients, and jumps in the normal stresses across the interface in shear-banding flows.

A simple but comprehensive model considering homogeneous and micellar nucleation, coagulation, entry of radicals to particles and to micelles and radicals' exit from particles, is presented. The model is validated, in a starved semicontinuous heterophase polymerization of ethyl methacrylate, at three monomer addition rates. The model accurately describes the overall and instantaneous conversion, the average particle density and diameter, and the number and weight average molar masses evolutions over time. It is found that even though the average number of radicals is much smaller than 0.5, the system is not 0‐1. An empirical function was used to describe the gel effect. The homogeneous nucleation was the prevailing mechanism for particle formation and large exit rates of radicals were observed. POLYM. ENG. SCI., 60: 223–232, 2019. © 2019 Society of Plastics Engineers

The trajectories of chaotic fluctuations in dilute micellar solutions, which typically occur during the creation and destruction of shear‐induced structures in the flow inception of a 0.4 wt % cetyltrimethylammonium tosilate aqueous solution and an aqueous solution of 3 mM cetyyltrimethylammonium bromide‐sodium salicylate, are predicted here with an improved Bautista–Manero–Puig model. To determine the constancy of the model parameters with time, we applied successfully an integro‐differential approach. This methodology revealed that all the model parameters, but the elastic modulus is constant. The nature of the predicted fluctuations was analyzed by employing the exponent of Lyapunov. This analysis demonstrates that the fluctuations are chaotic deterministic in Regimes I and IV, whereas they are random in Region II. We found that the predictions of the modified model follow the experimental data and reveal that these fluctuations are related to the creation of elastic structures at the inception of shear flow. © 2018 American Institute of Chemical Engineers AIChE J , 64: 3735–3745, 2018

Correction for Porous monoliths synthesized via polymerization of styrene and divinyl benzene in nonaqueous deep-eutectic solvent-based HIPEs' by M. G. Perez-Garcia et al., RSC Adv., 2015, 5, 23255-23260.

In this work, a simple comprehensive mathematical model, to understand the main mechanisms occurring in the semicontinuous heterophase inverse polymerization of acrylamide, is reported. A Mayo‐Lewis extended model, including nucleation and coagulation, is assessed with experimental conversion, particle density and inferred average number of radicals versus time‐data at 60°C, at three monomer addition rates. It was found that: (1) the average number of radicals is much smaller than 0.5 contrary to most of inverse emulsion and microemulsion polymerization reports, this number increased steadily along the experiments, (2) coagulation does exist in this process, and (3) the exit rate coefficient was found to present a high value, agreeing with other authors that claim a large exit rate. Conversion, the bell‐shaped number of particles' evolution and number average radicals' concentration, versus time data, are well described by the proposed model. POLYM. ENG. SCI., 58:2219–2226, 2018. © 2018 Society of Plastics Engineers

The rheological behavior of micellar solutions is analyzed under nonhomogeneous velocity and stress flow conditions. The framework is based on the extended irreversible thermodynamics and the transient network formulation coupled to the underlying kinetics embodying two relevant processes: formation of wormlike chains from a free micellar solution through a thermally activated process and their flow induced degradation. The second kinetic process consists in the formation of entanglements from the free wormlike chains and their flow‐induced breakage. These processes are modeled in a coupled kinetic scheme constituted by a set of reversible kinetic equations describing the evolution in average of the three microstates (free short rod‐like micelles, free wormlike chains, and entangled wormlike chains) that reflect the complexity of macromolecular interactions. The predictions of the shear stress and first normal stress difference as a function of shear‐rate under banded flow are in good agreement with experimental data. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2277–2292, 2018

Temperature- and pH-responsive core/shell nanoparticles were prepared by semicontinuous heterophase polymerization of N-isopropylacrylamide (NIPA) in the presence of chitosan micelles for drug delivery purposes. Micelles of chitosan, formed in an acetic acid aqueous solution at 70°C containing potassium persulfate, were fed with N-isopropylacrylamide (NIPA) at a controlled rate, to produce PNIPA/chitosan core/shell nanoparticles of about 350 nm. Then, the crosslinking agent, glutaraldehyde, was added to crosslink the nanoparticles. These nanocomposites were temperature- and pH-responsive, which make them suitable as controlled drug releasing agents. The nanoparticles exhibit thermoreversibility to heating-and-cooling cycles and show different responses depending on the releasing medium’s pH. Drug delivery tests were performed, employing as a model drug, doxycycline hyclate.

In this contribution a methodology to compute and classify shear-induced structural and phase transitions in surfactant/water mixtures from rheological measurements is presented. Non-linear rheological experiments, considering variations in surfactant concentration and temperature, are analyzed. In particular, the parameters of the BMP (Bautista-Manero-Puig) model, obtained from the fitting of the shear stress versus shear rate data, which are functions of surfactant concentration and temperature, allow classifying structural and phase transition boundaries. To test this methodology, we consider the analysis of the shear-induced structural and phase transitions of two micellar systems, cetyltrimethylammonium tosylate (CTAT)/water as a function of CTAT concentrations and Pluronics P103/water as a function of temperature. We found that the CTAT/water system presents a first-order phase transition at 30 ° C, and around 31 to 32 wt.% from isotropic to nematic phases, whereas a 20 wt.% Pluronics P103 aqueous micellar solution has two second-order (structural) phase transitions, one from spherical to cylindrical micelles at 33.1 ° C, and another one from cylindrical micelles to a nematic phase at 35.8 ° C and one first-order phase transition around 37.9 ° C at high shear rates near to the cloud point previously reported. The proposed methodology is also able to identify the instability regions where the wormlike micelles are broken, producing the typical shear banding behavior.

The aim of this work was to determine the detailed phase behavior of the sodium dodecyl sulfate/aniline hydrochloride/water system as a function of concentration of sodium dodecyl sulfate (SDS), aniline hydrochloride (AHC) to sodium dodecyl sulfate molar ratio (R = [AHC]/[SDS]) and temperature. Phase behavior information was obtained via polarizing microscopy, differential scanning calorimetry (DSC), cryo-scanning electron microscopy (Cryo-SEM) and oscillatory linear rheological measurements with good agreement among these techniques. It is well known that SDS in water forms spherical micelles at concentrations lower than 40 wt% and temperatures above its Krafft temperature (T k = 16–21 °C). In this region, the SDS/water system exhibits Newtonian rheological behavior, which is characteristic of spherical micellar solutions. The addition of the hydrotrope, aniline hydrochloride, to SDS aqueous solutions produces a viscosity increase in this system as R augments, and a maximum of about five orders of magnitude was found at R = 0.47 for 5 wt% SDS at 20 °C. Moreover, the system shows a transition from viscous to strong viscoelastic behavior. These changes in the rheological behavior are produced by the transitions from sphere to rodlike micelles, which are induced by the hydrophobicity of AHC causing it to be absorbed into the core and the hydrophilic interface of the micelles, which screens the repulsions between the charged head groups.

The polymerization of several alkyl methacrylates in nanoemulsions made by the phase inversion temperature method is presented here. The temperature versus surfactant concentration fish-like phase diagrams for a fixed mixture of alkyl methacrylate/squalane (SQ) of 95/5 w/w, Brij 56 and water were elaborated. Reaction rates were extremely fast (ca. 100% conversion in less than 3 min), and only two reaction rate intervals were observed, which is typical of nanoemulsion polymerization. It suggests that chain transfer to monomer is the main termination mechanism. The addition of squalane inhibits monomer diffusion from small droplets to larger ones and prevents the diffusion of monomer from non-reacting droplets to reacting ones, which guarantees that each monomer droplet acted as a nanoreactor. Polymer particles have similar size than the original nanoemulsion droplets indicating that the nanodroplets act as templates for the formation of the polymer nanoparticles. Reaction rates, as well as kinetics and nanoparticle characterizations by quasielastic light scattering (QLS), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC), are reported. Spheroidal nanoparticles with similar sizes and narrow distribution were observed by TEM for poly(ethyl methacrylate), poly(butyl methacrylate), and poly(hexyl methacrylate). The large molar masses and the narrow molar mass distributions were obtained by gel permeation chromatography.

In this work, we study the diffusion of the interface between bands in wormlike micellar solutions that exhibit shear banding flow regimes, namely, systems undergoing coexistence of states of different shear rates along a constant stress plateau. The migration of the interface between bands possessing different birefringence levels is predicted by the BMP (Bautista-Manero-Puig) model in which a structural parameter (the fluidity) presents two states with differing order separated by an interface. The mechanical potential derived from the constitutive equations and a diffusion term for the structure evolution equation predict various time scales of interface migration at the inception of shear flow and under shear-rate changes along the plateau stress. It is shown that the extremes of the plateau (binodals) correspond to the minima in the mechanical potential as a function of fluidity or shear rate. We also predict the dependence of the diffusive length scale on the applied shear rate.

In this work, the linear viscoelastic properties of the sodium dodecylsulfate/aniline hydrochloride/water system were examined in detail as a function of aniline hydrochloride (AHC) to sodium dodecyl sulfate (SDS) molar ratio (R = [AHC]/[SDS]), SDS concentration and temperature. SDS aqueous solutions undergo a structural transition from sphere to rodlike micelles and subsequently to a viscoelastic network of wormlike micelles induced by the hydrotrope AHC at low and intermediate R molar ratios (i.e., R = 0.1-0.6 for 5 wt.% SDS), which screens the repulsions between the neighboring charged head groups. The rheological response indicates that at low R molar ratios and constant surfactant concentration, the rheological behavior of the system is predominantly viscous (G' < G"). However, upon increasing R, the elastic behavior predominates (G' > G") and a maximum of the absolute value of the zero frequency complex viscosity (|eta(0)*|) is observed, which suggest that the micellar length also goes through a maximum. The region of the elastic behavior diminishes at even greater R molar ratios and a predominantly viscous behavior appears again. This drop in |eta(0)*| can be attributed to the transition from linear to branched wormlike micelles that conform the tridimensional viscoelastic network. The dynamic behavior of the system was analyzed in terms of the Granek-Cates theory, which indicates that the viscoelastic network is in the slow-breaking limit. Under these conditions, reptation is found to be the controlling relaxation mechanism for this system.

The shear thickening behavior of dilute micellar solutions of hexadecyltrimethylammonium-type surfactants with different counterions (tosylate, 3- and 4-fluorobenzoate, vinylbenzoate and salicylate) and of n-alkyltetradecylammonium bromide (CnTAB), with n = 14, 16 and 18, is examined here. These solutions undergo a shear thickening transition due to the formation of shear-induced structures (SISs) in the shear range studied. Here we report a relationship between the shear thickening intensity and the differences in the hydrophobicity of counterions according to the Hofmeister-like anion series, which leads to a master flow diagram. This master flow diagram is produced by plotting a normalized shear thickening intensity (Iη - 1)/(Imax - 1) versus CD/CD,max, where Iη is the shear-thickening intensity, defined as the largest viscosity obtained in the shear-thickening transition (STT) at a given surfactant concentration CD divided by the Newtonian viscosity η0, and Imax is the largest intensity value obtained in the STT at a surfactant concentration CD,max. The master flow diagram is built using several cetyltrimethylammonium-type surfactants with different counterions, according to a Hofmeister-like series, and by n-alkyltetradecylammonium bromide surfactants with different alkyl chain lengths.

Batch microemulsion polymerization is a process that allows the synthesis of oil-soluble and water-soluble nanoparticles, nanocomposites and nanogels smaller than ca. 50nm with larger molecular weights (ca. 107g/mol); however, the large amounts of surfactant required by this process to produce small amounts of polymer have hindered its industrial scaling. Semicontinuous O/W and W/O microemulsion polymerizations allow increasing the polymer content without adding more surfactant to the original reacting formulation. The several schemes of semicontinuous microemulsion polymerization that have been proposed, semibatch, semicontinuous feeding or lot additions of monomer to the reacting microemulsion, are reviewed here. Semicontinuous inverse microemulsion polymerization, which is a process to synthesized water-soluble polymer nanoparticles that have important applications as superabsorbents and flocculants, are also reviewed. Moreover, alternative processes, denoted by our group as normal and inverse semicontinuous heterophase polymerizations, which allows the synthesis of even larger concentration of polymer employing smaller amounts of surfactant compared to microemulsion polymerization, are examined.

The synthesis, by two sequential inverse microemulsion polymerizations, of interpenetrating polymer networks (IPN) formed by polyacrylamide (PAM) and poly(acrylic acid) (PAA) and their response to changes in pH and temperature are reported here. The temperature and pH responses of the IPN nanoparticles are compared with those of polyacrylamide and random copolymers of polyacrylamide and poly(acrylic acid) P(AM-co-AA) nanoparticles also made by inverse microemulsion polymerization. We found that only the IPN nanogels exhibited a sharp swelling increase with temperature associated with its Upper Consolute Solution Temperature, driven by hydrogen bonding interactions, and with pH, driven by electrostatic repulsions of the PAA carboxylic groups, especially at pHs larger than the pK(a) of the PAA. The sigma-potentials of the PAM, P(AM-co-AA) and IPN nanogels were measured as a function of pH and temperature, to determine the effects of these two variables, which in turn, affected the swelling of the nanogels. Field emission scanning electron microscopy revealed that the IPN nanogels were spheroidal with sizes similar to those determined by dynamic light scattering.

We report the preparation of polyethyl cyanoacrylate PECA nanoparticles by semicontinuous heterophase polymerization carried out at monomer starved conditions at three monomer addition rates. Particles in the nanometer range were obtained, the size of which diminishes with decreasing monomer addition rate as shown by the fact that particles with mean diameters of ca. 42 and 30 nm were obtained at the faster and intermediate dosing rates, respectively, whereas two populations of particles, one of 15.5 and the other of 36 nm in mean diameters, were produced at the slower dosing rate. The obtained molecular weights were from 2,200 to 3,500 g/mol, depending on the addition rate, which are typical of the anionic polymerizations of cyanoacrylates in aqueous dispersions at low pHs. The rifampicin RIF loading into the nanoparticles was successful since the entire drug added was incorporated. The drug release study carried out at pH of 7.2 indicated a faster release from the free RIF at intermediate and larger release times as expected since, in the nanoparticles, first the drug has to diffuse through the nanoparticle structure. The comparison of several drug release models indicates that the RIF release from PECA nanoparticles follows that of Higuchi.

The steady and transient nonlinear rheological behaviors of dilute rod-like micellar solutions are predicted here with a particular case of the generalized Bautista–Manero–Puig (BMP) model that consists of the upper-convected Maxwell constitutive equation and a dissipative power-dependent kinetic equation, which takes into account the formation and disruption of shear-induced structures (SISs). This model has been derived using the extended irreversible thermodynamic (EIT) formalism. In steady shear, the model predicts a Newtonian region at low shear rates and a characteristic shear rate (\( {\dot{\upgamma}}_{\mathrm{c}} \)) at which shear thickening develops. In the shear thickening region, the model predicts either a reentrant zone, which is caused by multi-valued shear stresses when the data are collected with a shear stress-controlled mode or a continuous increase in the shear stress-shear rate flow curve, when the data are collected with a shear rate-controlled mode; in this region, two coexisting phases are predicted. The coexisting phases at the same shear rate in the two-phase envelope and the spinodal-like region were evaluated from the extended Maxwell equal-area criterion, which was calculated from the equal values of the two minima of the plot of the extended Gibbs free energy versus shear rate. At higher shear rates, the model predicts a transition to shear thinning, and under transient flows, an induction time and a saturation time are obtained from the predicted and the experimental data as detailed in the text. The magnitudes of both, the induction and the saturation times, diminish as the shear rate departs from \( {\dot{\upgamma}}_{\mathrm{c}} \), but only the induction time decreases according to a power law with shear rate. The conditions under which these rheological responses arise are derived and justified in detail with the BMP model. The model predictions are compared with experimental data of two dilute micellar solutions. The model parameters were determined from a set of independent experiments without fitting.