The pH-responsive behaviour of poly(acrylic acid) in aqueous solution is dependent on molar mass.

The failure behaviour of glass polyalkenoate cements was investigated using a linear elastic fracture mechanics (LEFM) approach. Cements were based on Drayton gasifier slag and four poly(acrylic acid)s with number average molar masses ranging from 3.03 × 103 to 6.44 × 104. Cement properties were studied at time intervals of one, seven and twenty eight days. Compressive and flexural strengths of the cements increased with increasing molar mass of the poly(acrylic acid)s and time. The Young's modulii increased with time and were independent of poly(acrylic acid) molar mass. Fracture toughness increased with increasing molar mass of the poly(acrylic acid)s. Fracture toughness increases over an ageing time of one week and subsequently decreased over one month. Toughness increased with poly(acrylic acid) molar mass, these increases being most pronounced at higher molar mass. The toughness values decreased with time for the higher molar mass cements, which is consistent with increased crosslinking of the poly(acrylic acid) chains and reducing molecular flow at the crack tip. Plastic zone size increased with poly(acrylic acid) molar mass and decreased with time for lower molar mass cements, remained constant for intermediate molar mass cements and increased with high molar mass cements.

The mean molecular weight and particle size of asphaltene aggregates extracted from Buzurgan feedstock have been evaluated by measuring the diffusivity by means of 1H diffusion-ordered spectroscopy (DOSY) nuclear magnetic resonance (NMR). This technique, recently applied in the petroleum industry, appeared as a key tool to investigate the behavior of asphaltenes diluted in toluene over a wide range of concentrations (from 0.01 to 15 wt %). The results show that the diffusivity is highly dependent upon solute concentration. Indeed, interactions occurring in dilute systems differ from interactions occurring in the semi-dilute regime. In the dilute regime (below 0.25 wt %), physical characterization of the nanoaggregates detected by 1H DOSY NMR could be achieved. An average molecular weight of roughly 6900 g mol−1 (taken at the highest diffusion peak and given as a polystyrene equivalent) with a range of 1500−85000 g mol−1 was obtained, while a mean radius of 15.6 Å was determined from the solute diffusivity at infinite dilution [D∞asp ∼ (2.4 ± 0.1) × 10−10 m2 s−1 for Buzurgan asphaltenes]. Average masses (Mn and Mw) were also calculated from DOSY NMR data and compared to results obtained from size exclusion chromatography (SEC) analyses. We also used DOSY NMR techniques to investigate the molecular dynamics of asphaltenes. A concentration of 0.25 wt % was found to represent the onset of the aggregation process. We believe DOSY NMR allowed us to observe the beginning of aggregation in phase transition. The asphaltene system is very polydisperse. At low concentrations, it is a polydisperse diluted system, but increasing the solute concentration induces a distinction of different aggregates, presenting various sizes in a macroscopic homogeneous phase. When the distinction occurs, there is a zone that is richer in high molecular weight aggregates of asphaltenes, and as a result, a second zone is impoverished in high molecular weight aggregates. In a microscopic point of view, there is a difference in nano or macroaggregate concentration, whereas in a macroscopic point of view, an average density is observed. For the first time, a clear separation between two families of aggregates of asphaltenes is presented in the diffusion dimension for concentrations higher than 3 wt %. 1H DOSY spectra and diffusion profiles confirm these results. The key point of this study resides in the detection and presentation of two classes of aggregates of asphaltenes achieved for concentrated solutions, without any assumption concerning the composition of the mixture.

Polyacrylic acid was synthesized in water by persulfate-initiated polymerization (solution polymerization) of glacial acrylic acid in the absence of a chain-transfer agent. The final product is odorless and colorless. Chelation for calcium ions using a calcium electrode show that our poly(acrylic acid) has a higher chelation capacity than that of existing commercial poly(acrylic acids). A design of experiments was performed to optimize the synthesis conditions to obtain poly(acrylic acid) with a high maximum chelation value. These studies also helped us to gain insight into its high chelation capacity. The chelation capacity for calcium reaches its highest values when polymerization near isothermal conditions is done ∼ 95°C with an acrylic acid concentration of ≤21 wt % and an addition time >1 h. These conditions favor higher molecular weight poly(acrylic acid) with a polydispersity ∼ 4. The dispersion properties of our poly(acrylic acid) are similar to those of the commercial ones. This dual capability of chelation and dispersion is absent in commercial chelants such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and their analogs. At pH > 7, chelation of calcium by our poly(acrylic acid) is much higher than that observed with EDTA. Characterization by NMR, Raman, FTIR, and molecular modeling are included in an attempt to understand structural features that can explain the higher chelation capacity of our atactic poly(acrylic acid).

Low molar mass poly(acrylic acid) (PAA) is generally obtained by free radical polymerization of acrylic acid (AA) in aqueous solution, using thermal initiators and some chain transfer agent. However, under such conditions it is rather difficult to efficiently produce molar masses as low as those required for obtaining an effective dispersant. In this work, the semibatch polymerization of AA at 45 °C is considered, using potassium persulfate (KPS) and sodium metabisulfite (KPS/NaMBS), or alternatively KPS and sodium hypophosphite (KPS/NaHP) as redox initiators to produce PAA of controlled low molar masses. These initiation systems allow the production of PAA with Mn as low as 2.0 kDa, relatively narrow molar mass distribution (1.5 < Mw/Mn < 3.0), and low branching degree. Most of the investigated polymerizations reach almost complete conversions (>95%); and it is verified that both reductants, NaMBS and NaHP, also behave as chain transfer agents. Finally, the investigated process with redox couples allowed the production of PAA with acceptable dispersant and antiscaling properties.

The failure behaviour of glass polyalkenoate cements was investigated using a linear elastic fracture mechanics (LEFM) approach. Cements were based on four model glasses with varying reactivity and four poly(acrylic acid)s (PAA)s with number average molar masses (Mn) ranging from 3.25 × 104 to 1.08 × 105. Cement properties were studied at time intervals of one, seven and twenty eight days. Compressive strengths (σc) of the cements increased with increasing fluorine content of the glass, with increased molar mass of the PAA and with ageing time. The Young's moduli increased with time, but were lower for cements based on the fluorine free glass. Moduli values were independant of PAA molar mass. The un-notched fracture strength (σf) of the cement increased with the molar mass of the PAA and with ageing time. Glass composition did not appreciably influence the un-notched fracture strength. The fracture toughness (KIC) increased with the molar mass of the PAA and with ageing time, but reduced with increasing fluorine content of the glass. The toughness (GIC) was dependant on molar mass. The influence of molar mass was not as great as predicted by the reptation chain pull-out model for fracture. The molar mass dependence of toughness was greatest with the lower fluorine content glasses. The plastic zone size at the crack tip increased with the molar mass of the PAA. However the plastic zone size decreased with ageing time for all the cements studied and was smaller for the more reactive higher fluorine content glasses.

The influence of poly(acrylic acid), PAA molar mass and concentration on fracture toughness and toughness of glass polyalkenoate cements was investigated. Fracture toughness and toughness increased with both the molar mass of the PAA and its concentration. The fracture toughness and toughness increased dramatically with concentration for the highest molar mass PAA studied. However the increase in fracture toughness and toughness with PAA concentration was small for the lowest molar mass PAA. The influence of molar mass was greatest at the highest PAA concentration studied and least for the lowest PAA concentration. The toughness results were analysed with a reptation chain pull-out model. The greater dependance of toughness on PAA concentration for high molar mass cements can be explained by the critical molar mass for chain entanglements to form (M e) being concentration dependant and M e decreasing with increasing PAA concentration.

The influence of poly(acrylic acid) molar mass was investigated on cements formed from zinc oxide-apatite mixtures at three aging times; one, seven and 28 days. Cements based on both hydroxyapatite and fluorapatite were investigated. The compressive strength, un-notched fracture strength and fracture toughness increased markedly with poly(acrylic acid) molar mass. The fracture toughness and un-notched fracture strength increased with aging time for the two highest molar mass cements, but decreased with time for the two lowest molar mass cements. The greater chain entanglement density present in the higher molar mass cements is thought to contribute significantly to the cement stability in addition to the crosslinking of the polyacrylate chains by calcium and zinc ions. Substitution of hydroxyapatite by fluorapatite had no significant influence on the mechanical properties of the cements at aging times longer than one day.

Diffusion-ordered spectroscopy (DOSY) NMR was successfully used to characterize amphiphilic block copolymers. A triblock copolymer was prepared by ring-opening polymerisation of a lactide using poly(ethylene glycol) as the initiator. The DOSY NMR experiment is revealed to be a useful analytical method to prove the formation of block copolymers. According to the DOSY map, PLA and PEG blocks exhibited the same diffusion coefficient of 5.623 × 10−10 m2 s−1, consistent with an efficient polymerisation of the lactide. The determination of the critical micelle concentration (CMC) using DOSY NMR experiments has also been reported. The CMC value correlated with those obtained by fluorimetry and static light scattering. The CMC value was found to be 0.11 g L−1. All the results suggest that DOSY NMR is a valuable analytical tool for the polymer community. The good correlation between the results from DOSY, fluorescence and SLS experiments suggests that the DOSY spectroscopy can accurately measure the CMC of amphiphilic copolymer solutions.

Stable amorphous calcium carbonate (ACC) composite particle with a size-controlled monodispersed sphere was obtained by a new simple carbonate controlled-addition method by using poly(acrylic acid) (PAA) (Mw = 5000), in which an aqueous ammonium carbonate solution was added into an aqueous solution of PAA and CaCl2 with a different time period. The obtained ACC composite products consist of about 50 wt % of ACC, 30 wt % of PAA, and H2O. Average particle sizes of the ACC spheres increased from (1.8 +/- 0.4) x 102 to (5.5 +/- 1.2) x 102 nm with an increase of the complexation time of the PAA-CaCl2 solution from 3 min to 24 h, respectively. The ACC formed from the complexation time for 3 min was stable for 10 days with gentle stirring as well as 3 months under a quiescent condition in the aqueous solution. Moreover, the ACC was also stable at 400 degrees C. Stability of the amorphous phase decreased with an increase of the complexation time of the PAA-CaCl2 solution. No ACC was obtained when the lower molar mass PAAs (Mw = 1200 and 2100) were used. In the higher molar mass case (Mw = 25 000), a mixture of the amorphous phase and vaterite and calcite crystalline product was produced. The present results demonstrate that the interaction and the reaction kinetics of the PAA-Ca2+-H2O complex play an important role in the mineralization of CaCO3.

The interactions of nanomaterials with plasma proteins have a significant impact on their in vivo transport and fate in biological fluids. This article discusses the binding of human serum albumin (HSA) to poly(amidoamine) [PAMAM] dendrimers. We use protein-coated silica particles to measure the HSA binding constants (K(b)) of a homologous series of 19 PAMAM dendrimers in aqueous solutions at physiological pH (7.4) as a function of dendrimer generation, terminal group, and core chemistry. To gain insight into the mechanisms of HSA binding to PAMAM dendrimers, we combined (1)H NMR, saturation transfer difference (STD) NMR, and NMR diffusion ordered spectroscopy (DOSY) of dendrimer-HSA complexes with atomistic molecular dynamics (MD) simulations of dendrimer conformation in aqueous solutions. The binding measurements show that the HSA binding constants (K(b)) of PAMAM dendrimers depend on dendrimer size and terminal group chemistry. The NMR (1)H and DOSY experiments indicate that the interactions between HSA and PAMAM dendrimers are relatively weak. The (1)H NMR STD experiments and MD simulations suggest that the inner shell protons of the dendrimers groups interact more strongly with HSA proteins. These interactions, which are consistently observed for different dendrimer generations (G0-NH(2)vs G4-NH(2)) and terminal groups (G4-NH(2)vs G4-OH with amidoethanol groups), suggest that PAMAM dendrimers adopt backfolded configurations as they form weak complexes with HSA proteins in aqueous solutions at physiological pH (7.4).

Heavy crude oils are more and more of interest for the oil industry to meet the growing worldwide energy demand. Asphaltenes, which are the heaviest and least reactive molecules in crude oils, have received great attention over the last few decades, because they are responsible for many problems occurring during hydrotreatment and hydroconversion. 1H diffusion-ordered spectroscopy (DOSY) nuclear magnetic resonance (NMR) based on pulsed field gradient (PFG) sequences is a powerful tool to analyze polydisperse samples. The key advantage of such a technique compared to traditional NMR diffusion sequences, such as pulsed field gradient spin−echo (PFGSE), is to obtain both physical and chemical information in a single experiment. 1H DOSY NMR has been carried out on different types of samples to obtain a deeper insight into the physicochemical properties of petroleum samples, because diffusion coefficients are both sensitive to molecular weights and sizes. The application of DOSY NMR to analyze hydrocarbon mixtures and asphaltenes is assessed. It is shown that both solute and solvent diffusion coefficients decrease with an increasing concentration of solute. Different types of intermolecular interactions were observed on petroleum samples depending upon the sample concentration. Dilute and semi-dilute regimes have also been detected. 1H DOSY spectra applied to diesel and asphaltene samples in toluene are presented and interpreted to demonstrate the potential of DOSY techniques to analyze heterogeneous petroleum samples. The data obtained for the diesel sample enable us to establish that monoaromatics were connected to long alkyl chains, whereas di- or triaromatic molecules were linked to shorter hydrocarbon chains. However, a clear conclusion could not be reached for the asphaltene sample because there were only a few aromatic protons that were not detected. This observation is most consistent with a continental model of these asphaltenes.

Previous studies have reported that mixed molar mass polymer matrices show enhanced DNA sequencing fragment separation compared with matrices formulated from a single average molar mass. Here, we describe a systematic study to investigate the effects of varying the amounts of two different average molar mass polymers on the DNA sequencing ability of poly(N,N-dimethylacrylamide) (pDMA) sequencing matrices in microfluidic chips. Two polydisperse samples of pDMA, with weight-average molar masses of 3.5 MDa and 770 kDa, were mixed at various fractional concentrations while maintaining the overall polymer concentration at 5% w/v. We show that although the separation of short DNA fragments depends strongly on the overall solution concentration of the polymer, inclusion of the high-molar mass polymer is essential to achieve read lengths of interest (>400 bases) for many sequencing applications. Our results also show that one of the blended matrices, comprised of 3% 3.5 MDa pDMA and 2% 770 kDa pDMA, yields similar sequencing read lengths (>520 bases on average) to the high-molar mass matrix alone, while also providing a fivefold reduction in zero-shear viscosity. These results indicate that the long read lengths achieved in a viscous, high-molar mass polymer matrix are also possible to achieve in a tuned, blended matrix of high- and low-molar mass polymers with a much lower overall solution viscosity.

A series of well-defined diblock, triblock, and star-block copolymers composed of polystyrene and poly(acrylic acid) were synthesized by controlled/living radical polymerization and used as stabilizers in emulsion polymerization under alkaline conditions. The structure of the copolymers, the size of the blocks, and the composition were varied and their efficiency as stabilizers was correlated with their structural characteristics. The block length was varied from 10 to 30 units for the polystyrene block and from 13 to 266 units for the poly(acrylic acid) block. The copolymers appeared to be efficient stabilizers down to a block copolymer-to-monomer ratio of less than 0.5 wt %. From the comparison of the effect of the different structures and compositions, it was shown that the diblock copolymers were particularly efficient and that the optimal composition was about 10 styrene units and a maximum of 50 acrylic acid units. The triblock and star-block copolymers with external hydrophilic blocks did not behave much differently than diblock copolymers. In contrast, for the triblock copolymers with an internal hydrophilic segment, the efficiency strongly depended on the respective length of both blocks. The evolution of the number of latex particles, Np, with the concentration of surfactant was also studied and Np was shown to be proportional to [surfactant]α over a wide range of surfactant concentrations. The value of α was a function of the block copolymer composition irrespective of the individual block lengths: it was 1 for block copolymers with a poly(acrylic acid) content lower than 75 mol % and decreased to 0.4 when the hydrophilic content was increased. This trend was correlated with the exchange dynamics of the stabilizer. The results obtained with various initiator concentrations, temperatures, and ionic strengths corroborated the previous observation that the important point to explain the evolution of α with the copolymer composition was the competition between nucleation of the micelles and exchange of the block copolymers between the micelles and the continuously created polymer /water interfaces in the system. The time scale of this exchange (which is very fast for small-molecule surfactants) was on the same order of magnitude as the nucleation step for emulsion polymerizations carried out in the presence of block copolymers.

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Assessment of techniques for DOSY NMR data processing