Composition effects on ion transport in a polyelectrolyte gel with the addition of ion dissociators

The polymerization of lithium 2-acrylamido-2-methyl-1-propane sulphonic acid with N,N′-dimethylacrylamide has yielded polyelectrolyte gels which have the favourable property of being single ion conductors. The use of single ion conductors ensures that the transport number of lithium is close to unity. The mobility of the lithium ion is still quite low in these systems, resulting in low ionic conductivity. To increase ionic conductivity more charge carriers can be added however competing effects arise between increasing the number of charge carriers and decreasing the mobility of these charge carriers. In this paper the monomer ratio of the copolymer polyelectrolyte is varied to investigate the effect increasing the number of charge carriers has on the ionic conductivity and lithium ion and solvent diffusivity using pfg-NMR. Ion dissociators such as TiO₂ nano-particles and a zwitterionic compound based on 1-butylimidazolium-3-(N-butanesulfonate) have been added in an attempt to further increase the ionic conductivity of the system. It was found that the system with the highest ionic conductivity had the lowest solvent mobility in the presence of zwitterion. Without zwitterion the mobility of the solvent appears to determine the maximum ionic conductivity achievable.     

The additive effect of zwitterion and nano-particles on ion dissociation in polyelectrolytes

To realise the battery potential of gel polyelectrolytes greater ion dissociation, ultimately leading to higher conductivities, must be achieved. Higher conductivities will result through increasing the ion-dissociating properties of the gel polyelectrolyte. The poor degree of ion dissociation arises as the active ion tends to remain in close proximity to the backbone charge. Nano-particle inorganic oxides, and zwitterionic compounds have been shown to act as dissociation enhancers in certain polyelectrolyte systems. In an attempt to further increase ion dissociation the addition of both TiO₂ nano-particles and a zwitterionic compound based on 1-butylimidazolium-3-N-(butanesulphonate) were added to the gel polyelectrolyte system poly (Li-2-acrylamido-2-methyl-1-propane sulphonate-co-N,N′-dimethylacrylamide), poly(Li-AMPS-co-DMAA) to determine if a synergistic effect occurs. Two different solvents were used to determine the breadth of applicability of the additive effect. The use of both dissociators resulted in the maximum ionic conductivity being achieved at lower nano-particle concentrations when compared to an identical system without zwitterion.     

Hydrolytic processes and condensation reactions in the cellulose solvent system N,N-dimethylacetamide/lithium chloride. Part 2: degradation of cellulose

Certain cellulose samples, especially those of higher molecular weight, are initially insoluble in N,N-dimethylacetamide (DMAc, 1)/lithium chloride, which is a very common solvent system for cellulosic materials. According to a common protocol, heating or refluxing these samples in DMAc, or in DMAc containing dissolved LiCl, represents one of several so-called ‘activation’ procedures, which are aimed at facilitating subsequent dissolution. In the present work, it is shown that the improved solubility achieved by this method is not only caused by a better activation or improved accessibility of the pulp, but also by a progressing degradation of the cellulosic material (DP loss).The degradation of cellulose in DMAc or DMAc/LiCl is due to two separate chemical processes. The first one, involving N,N-dimethylacetoacetamide (2) which is the primary condensation product of DMAc, causes a slow degradation by thermal endwise peeling. The glucose units peeled off the reducing end are released as furan structures (3). The mechanism appears to be a thermal cleavage of the glycosidic bond, which becomes quite selective towards the proximal anhydroglucose unit by a neighbor group-assisted effect according to quantum-chemical calculations. Due to its stepwise and thus slow mechanism, this pathway contributes only insignificantly to the overall cellulose degradation.The second degradation mechanism causes random chain cleavage and thus pronounced and rather fast changes in the molecular weight distribution. It involves N,N-dimethylketeniminium ions (5), whose presence in DMAc/LiCl at temperatures above 80 °C—the coalescence temperature of DMAc as determined by dynamic NMR—was unambiguously demonstrated by specific trapping in a thermal [2+2]-cycloaddition with lipophilic olefins. The keteniminium ion is an extremely reactive electrophile, which is able to directly cleave glycosidic bonds. The detrimental effect of this intermediate on the integrity of cellulosic pulps was confirmed by addition of an external degrading agent of the keteniminium type. Also the precursor compound, a ketene aminal, was confirmed to be present in heated DMAc or DMAc/LiCl by trapping with allyl alcohol in a spontaneous Claisen-type rearrangement.     

In situ FTIR study of the decomposition of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide ionic liquid during cathodic polarization of lithium and graphite electrodes

In this work we analyzed the cathodic reactions of an important ionic liquid (IL) based electrolyte solution, namely lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)/N-methyl-N-methylpyrrolidinium (BMP) TFSI. In situ FTIR spectroscopy was used for the analysis of gaseous products of the electrochemical decomposition of this IL solution during cathodic polarization of lithium metal and graphite electrodes. The main volatile product of the reductive decomposition of the anion in these BMPTFSI solutions is trifluoromethane. BMP cations decompose to mixtures of tertiary amines and hydrocarbons. The composition of the products is influenced by the nature of the anode material. Graphite possesses a catalytic activity in the electroreduction process of BMP cations which occurs along with their intercalation into the graphite structure. The liquid phase after cathodic polarization of graphite electrodes was analyzed by multinuclear NMR spectroscopy coupled with FTIR spectroscopy. ¹⁵N NMR and FTIR spectra revealed an increase in the Li cations content in the electrolyte solution, as a result of BMP cations decomposition during repeated cycling of graphite electrodes.     

Synthesis and characterization of two ionic liquids with emphasis on their chemical stability towards metallic lithium

Two room temperature ionic liquids (RTILs) without acidic protons, based on different cationic species (1-n-butyl-2,3-dimethylimidazolium) (BMMI) and N-n-butyl-N-methylpiperidinium (BMP) using (CF₃SO₂)₂N⁻ (TFSI) as anion, were prepared by quaternization of their respective amines with an appropriate alkyl halide, followed by ion exchange reaction. All relevant properties of these ionic liquids, such as, thermal stability, density, viscosity, electrochemical behavior, ionic conductivity and self-diffusion coefficients for both ionic species, were determined at different temperatures. In spite of their ionic conductivity being lower than 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonylimide) (BMITFSI), the absence of an acidic proton in both compounds is crucial to maintain their chemical stability towards metallic lithium and, thereby, to make possible the safe assembly of lithium ion batteries. Both ionic liquids without acidic protons do not react with metallic lithium; on the other hand, the formation of carbene species when BMITFSI was exposed to Li was confirmed by ¹H and ¹³C nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS).     

Gel electrolytes based on lithium modified silica nano-particles

In this work lithium modified silica (Li-SiO₂) nano-particles were synthesized and used as a single ion lithium conductor source in gel electrolytes. It was found that Li-SiO₂ exhibited good compatibility with DMSO, DMA/EC (a mixture of N,N-dimethyl acetamide and ethylene carbonate) and the ionic liquid, N-methyl-N-propyl pyrrolidinium bis(trifluoromethylsulfonyl) amide ([C₃mpyr][NTf₂]). Several gel electrolytes based on Li-SiO₂ were obtained. These gel electrolytes were investigated by DSC, solid state NMR, conductivity measurements and cyclic voltammetry. Conductivities as high as 10⁻³ S/cm at room temperature were observed in these nano-particle gel electrolytes. The results of electrochemical tests showed that some of these materials were promising for using as lithium conductive electrolytes in electrochemical devices, with high lithium cycling efficiency evident.     

Swelling and mechanical behavior of poly(N-isopropylacrylamide)/Na-montmorillonite layered silicates composite gels

Clay-polymer hydrogel composites have been synthesized based on poly(N-isopropylacrylamide) (PNIPAM) gels containing 0.25-4 wt% of the expandable smectic clay Na-montmorillonite layered silicates (Na-MLS). The morphology of the composite gels has been studied using a polarized optical microscope. The size of Na-MLS aggregates increases with Na-MLS concentration. The swelling ratio of the Na-MLS/PNIPAM composite in water is increased at the low Na-MLS concentration but decreases as the concentration increases. Correspondingly, the shear modulus of the gel is found to exhibit a distinct minimum against clay concentration. For Na-MLS concentrations ranging from 2.0 to 3.2 wt%, the composite gels have larger swelling ratio and stronger mechanical strength than those for a pure PNIPAM. The presence of Na-MLS does not affect the value of the lower critical solution temperature (LCST) of the PNIPAM. However, the gel volume change at the LCST is first increased and then decreased upon the increase of the Na-MLS. No pH induced phase transition is observed for the Na-MLS/PNIPAM composites. The experimental results can be explained by considering that Na-MLS is physically entrapped inside rather than chemically bonded into the gel.     

Contributions to the thermodynamics of polymer hydrogel systems

In this work, an extended version of a quasichemical thermodynamic model is presented. The swelling behavior of crosslinked acrylamide polymer gels and N-substituted derivatives, such as N-isopropylacrylamide and N-tert-butylacrylamide has been compared to predictions from such model which takes into account the specific hydrogen bonding interactions encountered in these systems. The calculated volume transition temperature of the poly(N-isopropylacrylamide) gel is 0.8 °C lower than the experimental value and the predicted solvent volume fraction in the collapsed and swollen gel states are about 2% larger than the corresponding experimental data measured at the transition point. Applying the same energy parameters obtained from regressing poly(N-isopropylacrylamide) gel swelling pressure data, the model has also been capable to correctly represent the major features found in the swelling behavior of linear poly(N-tert-butylacrylamide) and poly(N-tert-butylacrylamide) gels, after the model parameters that characterize the molecular structure were changed in accord to each polymer repetitive unit.     

On the water swelling behaviour of poly(N-isopropylacrylamide) [P(N-iPAAm)], poly(methacrylic acid) [P(MAA)], their random copolymers and sequential interpenetrating polymer networks (IPNs)

Thermo- and pH-responsive stimuli hydrogels based on N-isopropylacrylamide (N-iPAAm) and methacrylic acid (MAA) have been synthesized and their swelling behaviour studied as a function of composition, pH and temperature. Copolymers varying in composition have been obtained by copolymerizing these two monomers and interpenetrating polymer networks (IPNs) of P(MAA) and P(N-iPAAm) by the sequential method. Temperature and pH have been changed in the ranges from 25 to 40 °C and from 2 to 9, respectively. The swelling behaviour of the hydrogels depends on the nature of the polymer and the environmental conditions, namely pH and temperature. Copolymer gels under basic conditions exhibit higher degree of swelling than the homopolymer ones. The disruption of the complexes dominates the kinetic swelling of MAA enriched gels under basic conditions. The hydrogen bond formation between carboxyl and amide groups has been made clear through the dynamic swelling behaviour of copolymers under acidic conditions. IPNs reduce their ability to swell in water with increasing P(N-iPAAm) content because of the formation of hydrophobic interpolymer complexes through hydrogen bonding. Lower critical solution temperature occurs only in the enriched N-iPAAm copolymers under acidic conditions when the MAA carboxyl groups are unionized.     

Thermo- and pH-sensitivity of aqueous poly(N-vinylpyrrolidone) solutions in the presence of organic acids

The phase transition in poly(N-vinylpyrrolidone) (PVP) aqueous solutions is shown to occur at heating upon addition of organic acids such as isobutyric, isovaleric, and, especially, trichloroacetic (TCA) ones. The cloud point temperature (T_c) of PVP solutions drops from 70 to 6 °C when the TCA concentration rises from 0.2 to 0.3 mol/l. A decrease in T_c is even more drastic when HCl is also added though HCl addition to the system without TCA does not result in phase separation. These phenomena are explained by the reversible coordination between the non-ionized form of TCA and PVP units via hydrogen bonding. An increase in the medium acidity depresses TCA dissociation, resulting in an increase in PVP-TCA associate concentration. Calculations based on the pK_a values of TCA confirm this suggestion. The similar behavior is observed with poly(N-vinylcaprolactam) systems. The amount of TCA bound to PVP has been determined by means of separation of the precipitate by centrifugation at temperatures above T_c and subsequent titration of TCA in the polymer with NaOH. It is shown that the precipitate contains one TCA molecule per 3-6 VP units, this value decreasing down to 1.25-2 upon HCl addition to the system.     

Synthesis of thermosensitive poly(N-alkylacrylamide) gels and core-shell type gels

When the poly(acrylic acid) (PAA) gel-1,8-diazabicyclo-[5,4,0]-7-undecene salt (DAA) was placed in N-methyl-2-pyrrolidone containing an excess of alkylamine and triphenylphosphine, selective amidation took place from the outside to give the corresponding poly(N-alkylacrylamide) gel containing a C3 alkyl chain through a DAA-poly(N-alkylacrylamide) type gel capsule consisting of a hydrophilic unreacted core part and an amidated shell layer. The amidation proceeded by a reaction mechanism similar to the unreacted-core model. Thermal properties of the resulting poly(N-alkylacrylamide) gels such as deswelling behavior and equilibrium swelling ratio in water as a function of temperature were measured. The release of methyl orange from a poly(N-alkylacrylamide) gel and the gel capsule was also examined. PAA-poly(N-alkylacrylamide) type gel capsules containing a PAA core part and thermosensitive poly(N-alkylacrylamide) shell layer, prepared by the neutralization of DAA-poly(N-alkylacrylamide) type gel capsules, showed on-off chemical release characteristics in response to stepwise temperature changes across the LCST.     

Polymers and oligomers derived from pyrrole and N-hydroxymethylpyrrole: A theoretical analysis of the structural and electronic properties

This work reports a theoretical investigation about the structural and electronic properties of polymers constituted by pyrrole and N-hydroxymethylpyrrole in both neutral and p-doped states. Ab initio quantum mechanical calculations were performed on neutral and positively charged oligomers to evaluate the bond length alternation pattern in the π-system, the molecular conformation, the π-π* transition energies and the ionization potential. Results, which have been extrapolated to infinite polymer chains, allow analyze the influence of N-hydroxyalkylation of polypyrrole on these properties.     

Metal-free isotactic-specific radical polymerization of N-alkylacrylamides with 3,5-dimethylpyridine N-oxide: The effect of the N-substituent and solvent on the isotactic specificity

Radical polymerization of N-methylacrylamide (NMAAm), N-n-propylacrylamide, N-isopropylacrylamide (NIPAAm) and N-benzylacrylamide was investigated in CHCl₃, CH₂Cl₂ and CH₃CN, in the presence of 3,5-dimethylpyridine N-oxide (35DMPNO) to examine the effects of the N-substituent and the solvent on the isotactic specificity induced by 35DMPNO. With addition of 35DMPNO to radical polymerization of N-alkylacrylamides in CHCl₃, isotactic specificity was significantly induced in NIPAAm polymerization but only slightly induced in NMAAm polymerization. Furthermore, mixed solvents of CH₃CN and halomethanes such as CHCl₃ and CH₂Cl₂ enhanced the ability of 35DMPNO to induce isotactic specificity, and poly(NIPAAm) with 74% meso dyad was obtained.     

Cellulose in lithium chloride/N,N-dimethylacetamide, optimisation of a dissolution method using paper substrates and stability of the solutions

Activation and dissolution in lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) of cellulose from paper substrates are studied. The importance of the multiple parameters involved such as salt concentration, sample source and preparation is shown in a literature review. The experiments are carried out in order to perfect the method of activation and dissolution of paper containing different kinds of additives, typically found in historic papers. The suitability and efficiency obtained in the different trials are evaluated. The final procedure involves the activation by solvent exchange, with a water/methanol/DMAc sequence, followed by dissolution in 8% LiCl/DMAc at 4 °C. A study of the stability of the cellulose solutions in the experimental conditions showed that no degradation nor aggregation occurred during the solvation process and even after several months and confirmed the non-aggressiveness of LiCl/DMAc.     

Adsorption of N,N′-dimethylthiourea at a mercury/aqueous solution of NaClO4 interface; dependence on the supporting electrolyte concentration

Adsorption of N,N′-dimethylthiourea (DMTU) on mercury electrode from 0.1, 1 and 5 M NaClO₄ was studied as the function of electrode charge density and adsorbate bulk concentration. In the study, the experimental data obtained from the measurements of differential capacity of double layer were used, the measurements of zero charge potential and surface tension at the zero charge potential. In each system studied the values of the relative surface excess increase with an increase of the concentration of N,N′-dimethylthiourea and NaClO₄. The adsorption parameters were obtained from the Frumkin, virial and modified Flory-Huggins isotherms. It was found that the values of free adsorption energy, interactions constants and integral capacity depends on the supporting electrolyte concentration. The strength of the surface bond formed between N,N′-dimethylthiourea and the electrode surface and the influence of water present on the electrode surface in the obtained results of calculations were discussed.     

Aggregation of biodegradable amphiphilic poly(succinimide-co-N-propyl aspartamide) and poly(N-dodecyl aspartamide-co-N-propyl aspartamide) in aqueous medium and its preliminary drug-released properties

Two series of biodegradable amphiphilic copolymers, poly(succinimide-co-N-propyl aspartamide) (PSI-PA) and poly(N-dodecyl aspartamide-co-N-propyl aspartamide) (PDDA-PA) were synthesized by partial and total aminolysis of polysuccinimide (PSI), respectively. PSI-PA copolymers could self-aggregate in water directly under ultrasonication at room temperature. Differing from PSI-PA copolymers, the aggregates of PDDA-PA need to add PDDA-PA DMF solution into an excessive amount of water. The aggregative properties of PSI-PA and PDDA-PA copolymers have been investigated by dynamic light scattering (DLS) and surface tension measurements. Hydrophilicity of these two copolymers was attributed to the N-propyl aspartamide segments. Due to the stiff structure, succinimide segments preferred to form irregular hydrophobic microdomains, and some aggregates of PSI-PA are bimodal size distribution in water medium, while the more flexible PDDA-PA copolymer chains preferred to form monodispersed spherical aggregates. Elevated temperature could reduce the aggregate size of both PSI-PA and PDDA-PA copolymers due to the breaking of the hydrogen bonding and the releasing of the bonded water molecules. PSI-PA copolymers were surface active, while the surface tension of PDDA-PA copolymers was independent on concentration. The drug-loaded aggregates of PSI-PA also have been prepared and the preliminary release properties have been studied in vitro.     

A theoretical study on the interaction between N-methylpyrrole and 3,4-ethylenedioxythiophene units in copolymer molecules

Quantum mechanical calculations at the density functional theory level have been used to examine the interaction between 3,4-ethylenedioxythiophene and N-methylpyrrole units when they are directly linked in copolymer chains. Specifically, in this study, which was motivated by experimental observations of electrochemically synthesized copolymers, the conformation and electronic properties of co-oligomers formed by two, three and four units have been examined in both neutral and radical cation states. Results reveal significant differences, especially in the radical cation state, between the co-oligomers and the corresponding individual homo-oligomers, which have also been explored considering the same theoretical method. Furthermore, electronic properties of oligomers have been used to estimate those of poly(3,4-ethylenedioxythiophene), poly(N-methylpyrrole) and the copolymer with alternated structure, which have been compared among them. The overall results allowed to understand the anomalous features detected in copolymers prepared by electrochemical techniques from 3,4-ethylenedioxythiophene and N-methylpyrrole mixtures, which were initially attributed to some type of unfavourable interaction between the two types of monomeric units.     

Phase diagram of a cellulose solvent: N-methylmorpholine-N-oxide-water mixtures

The phase diagram of the N-methylmorpholine-N-oxide-H₂O mixtures from 0 to 100% has been determined. Three crystalline hydrates have been identified, the already known monohydrate, a dihydrate and a hydrate composed of 8 water molecules per NMMO. The melting temperature of the 8H₂O-NMMO hydrate is −47 °C with a melting enthalpy of about 80 J/g. The region between 25 and 55% of water does not show any crystallisation, but a glass transition around −60 to −100 °C.     

Reentrant swelling behavior of thermosensitive N-isopropylacrylamide nano-sized gel particles

The closed-loop phase diagram of poly N-isopropylacrylamide (PNIPA) in a water-N,N-dimethylformamide (DMF) system was measured by thermooptical analysis (TOA). The reentrant swelling behavior of N-isopropylacrylamide (NIPA) nano-sized gel particles in the water-DMF system was measured by using photon correlation spectroscopy (PCS) technique. Theoretically, a modified double lattice model (MDL) can be used to describe the closed-loop phase behavior of linear PNIPA in water-DMF systems. For crosslinked NIPA nano-sized gel particles in a water-DMF system, we combined MDL theory for the mixing contribution and Flory-Erman theory for the elastic contribution. Molecular interaction parameters obtained from the PNIPA solution were used to directly predict the swelling-ratio curves for the NIPA gel. Using our model, the calculated results were in good agreement with the experimental data using only one adjustable parameter.     

Temperature sensitive poly(N-t-butylacrylamide-co-acrylamide) hydrogels: synthesis and swelling behavior

A series of temperature sensitive hydrogels was prepared by free-radical crosslinking copolymerization of N-t-butylacrylamide (TBA) and acrylamide in methanol. N,N′-methylenebis(acrylamide) was used as the crosslinker. It was shown that the swelling behavior of the hydrogels can be controlled by changing the amount of TBA units in the network chains. Hydrogels immersed in dimethylsulfoxide (DMSO)-water mixtures exhibited reentrant swelling behavior, in which the gels first deswell then reswell if the DMSO content of the solvent mixture is continuously increased. In water over the temperature range of 2-64 °C, hydrogels with less than 40[percnt] TBA by mole were in a swollen state while those with TBA contents higher than 60[percnt] were in a collapsed state. Hydrogels with 40-60[percnt] TBA exhibited swelling-deswelling transition in water depending on the temperature. The temperature interval for the deswelling transition of 60[percnt] TBA gel was found to be in the range from 10 to 28 °C, while for the 40[percnt] TBA gel, the deswelling started at about 20 °C and continued until the onset of the hydrolysis of the network chains at around 64 °C. It was shown that the Flory-Rehner theory of swelling equilibrium provides a satisfactory agreement to the experimental swelling data of the hydrogels, provided that the sensitive dependence of the χ parameter on both temperature and polymer concentration is taken into account.