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Amongst all synthetic polymers used in the clothing industry, polyethylene terephthalate (PET) is the most widely used polyester, its fibres representing half the total PET global market (in comparison bottle PET being less than a third). Compared to bottle PET, the recycling of fabric PET fibres represents a challenge, both due to intrinsic structural differences (chain length and crystallinity) and to the presence of various additives (dyes, protection or finishing agents). Effective waste management requires addressing these additives through elimination or recycling processes. This review article aims to give an overview about all the existing means to recycle PET fibres. Textile recycling encompasses primary (closed-loop), secondary (mechanical), tertiary (chemical), and quaternary (incineration with energy recovery) processes. Mechanical recycling faces challenges due to PET's characteristics, including lower molecular weight and additives. Chemical recycling, particularly solvolysis processes (hydrolysis in neutral, acidic, or alkaline media, alcoholysis, glycolysis, aminolysis or enzymatic hydrolysis), offers a more advanced approach and will be described in detail, focusing both on the specific recycling of fibres when available and enlightening the advantages and drawbacks of each method. To discuss the environmental impact of each process, a quantitative analysis was conducted by defining the experimental domain represented by the temperature range and reaction time, and then calculating the energy-saving coefficient, as a green metric adapted to the diversity of textile PET recycling processes and data provided in the literature. This coefficient allows for discussing the relevance of using complex or non-renewable catalysts in processes, the positioning of enzymatic pathways, and the choice of reaction mechanisms applicable to the industry. A prospective approach was employed to identify key criteria for future advancements in green recycling. Subsequently, a comparative analysis of depolymerisation methods will be presented within the context of sustainable development goals (SDGs), green chemistry, and green metrics. Finally, using ε factors, this analysis will facilitate the detection and highlighting of pathways that show the most promise in terms of greening PET recycling. [ABSTRACT FROM AUTHOR]

In a solvent extraction process, the compositions of the phases in thermodynamic equilibrium (described as a Winsor-II regime) must be determined to obtain the extraction isotherms of ions as well as co-extracted water. By comparing the extractions of a series of acids by the malonamide DMDOHEMA (N,N’-dimethyl-N,N’-dioctyl hexylethoxy malonamide) in n-heptane, the specific anion effects regarding third phase formation and the strength of the acid-extractant interaction were investigated. It is shown that third phase formation is driven by hydration enthalpy of acid, while the polar core microstructure is controlled by the pKa of the acids. Upon acid extraction, the promotion of third phase formation follows the series H2SO4≈ H3PO4≈ HClO4> HNO3> HCl > HCOOH, which correlates to hydration enthalpy of acid in the case of monoacids. The combination of IR spectroscopy and DFT calculations revealed two different modes of acid extraction, either by hydrogen bonding (extraction of non-dissociated acid: HA) or by protonation of the extractant (extraction of dissociated acid: H+A−). The strength of the amide-acid interaction (protonation vs. hydrogen bonding) is correlated to the pKa of the acid and is responsible for the microstructure of the solution. [ABSTRACT FROM PUBLISHER]

Non-electrostatic ion-specific effects are strong for anions when water is involved. We study here the thermodynamic equilibrium of a water-in-oil microemulsion stabilized by a surface-active extractant in a Winsor-II regime. Acid extraction isotherms for different anions located differently in the Hofmeister series have been investigated. A Langmuir like model was written for the specific case of acids treated as electrolytes, describing acid extraction as the adsorption of extracted electrolytes on the polar/apolar interface of the aggregates. Except for sulfate, isotherms can be described at first approximation as simple Langmuir-type isotherms when plotted as a function of the acid activity in the aqueous phase. The validity of the model being hence demonstrated, acid extraction free energies could be derived and compared, taking into account the effect of the anion position in the Hofmeister series. The case of phosphate, chloride, and sulfate as kosmotropes can be distinguished. They are significantly extracted, only above a threshold since the sphere-to-rod transition of the reverse aggregates has to be triggered by high chemical potential of the acid required to compensate anion dehydration. [ABSTRACT FROM PUBLISHER]

We show in the case of N,N′-dimethyl-N,N′-dioctyl-2-(2(hexyloxy)ethyl)-malonamide (DMDOHEMA) chosen as a typical oil-soluble extractant with surface activity that the free energy of formation of reverse micelles in the solvent phase strongly depends on the presence of polar solutes. Free energies per molecule vary typically from 0 to 2 kT per molecule (5 kJ mol−1), depending on the kosmotropic/chaotropic nature of the anion extracted. Variations of the reverse aggregation free energy introduced by acids and other co-extracted solutes as deduced from the critical aggregation concentrations cannot be neglected while modelling extraction. With typical aggregation numbers of 4–6, the free energy of formation of one reverse aggregate varies up to 20 kJ mol−1, which is four times the typical difference in free energy of one single cation transfer between a “target” and a non-target ion in practical extraction and stripping industrial processes. [ABSTRACT FROM AUTHOR]

We report the specific effects of a series of anions(chloride,nitrate, and oxalate) on the solubility and self-assembly of cationiccetylpyridinium surfactants in water. The anion influence on micellizationwas evidenced by tensiometry and determination of Krafft temperatures.Anions strongly affect these parameters, depending on their positionin the lyotropic series as well as on their “bridging”character. Scattering techniques (light, X-rays, and neutrons) wereused to characterize the structures of micelles, and by solving alateral equation of state approach, we show that chaotropic anionscan be considered as adsorbed on the pyridinium head groups, inducinga decrease of the surface polarity and a Krafft temperature shift.Mixing different counteranions in various ratios led to a competitionwith a preferential adsorption at the micellar surface. [ABSTRACT FROM AUTHOR]

An amphiphilic hexapeptide has been used as a model to quantify how specific ion effects induced by addition of four salts tune the hydrophilic/hydrophobic balance and induce temperature-dependant coacervate formation from aqueous solution. The hexapeptide chosen is present as a dimer with low transfer energy from water to octanol. Taking sodium chloride as the reference state in the Hofmeister scale, we identify water activity effects and therefore measure the free energy of transfer from water to octanol and separately the free energy associated to the adsorption of chaotropic ions or the desorption of kosmotropic ions for the same amphiphilic peptide. These effects have the same order of magnitude: therefore, both energies of solvation as well as transfer into octanol strongly depend on the nature of the electrolytes used to formulate any buffer. Model peptides could be used on separation processes based on criteria linked to "Hofmeister" but different from volume and valency.

Transmission microscopy with soft X-rays (TXM) is applied to image in-situ polyelectrolyte assemblies in aqueous environment. The method is element specific and at this stage exhibits a lateral resolution of 20 nm. With the specific examples of hollow capsules and full spheres made of PAH/PSS polyelectrolyte multilayers, it is shown quantitatively that heat treatment irreversibly reduces the water content in the membrane. These experiments complement those reported recently on the polyion system PDADMAC/PSS, which shows a different glass-transition behavior. Finally, the potential and present limitations of TXM are discussed.

A detailed study of the role of solution pH and ionic strength on the swelling behavior of capsules composed of the weak polyelectrolytes poly(4-vinylpyridine) (P4VP) and poly(methacrylic acid) (PMA) with different numbers of layers was carried out. The polyelectrolyte layers were assembled onto silicon oxide particles and multilayer formation was followed by zeta-potential measurements. Hollow capsules were investigated by scanning electron microscopy and atomic force microscopy. The pH-dependent behavior of P4VP/PMA capsules was probed in aqueous media using confocal laser scanning microscopy. All systems exhibited a pronounced swelling at the edges of stability, at pHs of 2 and 8.1. The swelling degree increased when more polymer material was adsorbed. The swollen state can be attributed to uncompensated positive and negative charges within the multilayers, and it is stabilized by counteracting hydrophobic interactions. The swelling was related to the electrostatic interactions by infrared spectroscopy and zeta-potential measurements. The stability of the capsules as well as the swelling degree at a given pH could be tuned, when the ionic strength of the medium was altered.

Hollow microcapsules composed of the weak polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) are templated on silicon oxide particles using the layer-by-layer adsorption. The colloidal template is removed with a buffer system of hydrofluoric acid and ammonium fluoride. With this buffer system, the template can be dissolved in mild pH conditions, where the polymeric layers are still stable. The morphology and the thickness of the resulting capsules are investigated with atomic force microscopy. The resulting hollow capsules show pH-dependent properties. The shells are stable over a broad pH range and swell and immediately dissolve for pH values below 2.3 and above 11. If the molecular weight of the poly(methacrylic acid) is increased, the enhanced entanglement of the polymers results in a reversible swelling of the capsules at low and at high pH. The swelling degree is probed with confocal laser scanning microscopy. In addition to the pH-dependent size variations, the different ionization degree of poly(methacrylic acid) as a function of pH is used for the selective binding of calcium ions.

An approach for the entrapment of a polyanion by polyelectrolyte microcapsules is reported. It is based on a reversal changing of microcapsule wall permeability from neutral to basic pH. Polyelectrolyte microcapsules were templated on latex (polystyrene) particles by the layer-by-layer adsorption of oppositely charged polymers of sodium poly(styrene sulfonate) and poly(allylamine hydrochloride), followed by core removal using tetrahydrofuran. In alkaline conditions, the microcapsules swell and become permeable for polymers. During encapsulation, the addition of salt ions increases the amount of the polymer encapsulated and contributes to its protonation because of redistribution of H+ ions across a semipermeable microcapsule wall. The redistribution of small ions across the microcapsule wall was tuned by adding salt according to the Donnan equilibrium and was characterized by H+ sensitive dyes.

Hollow polyelectrolyte microcapsules made of poly(allylamine hydrochloride) and sodium poly(styrene sulfonate), templated on various cores, manganese and calcium carbonate particles or polystyrene latexes, were investigated. The polyelectrolyte multilayers respond to a change of pH, leading to a swelling of the capsules in basic conditions and a further shrinking when the pH is reduced to acidic. The nature of the core and the subsequent dissolution process have an influence on this pH responsiveness, and the structuring effect of tetrahydrofuran on the multilayers has been demonstrated. Increasing the molecular weight of the polymers or the number of layers causes also a rigidification of the structure and modifies the pH response.

Chiral P-H spirophosphoranes reacted with long-chain prochiral aldimines and, after selective hydrolysis, afforded (alpha-amino)phosphonic acid amphiphiles in both enantiopure forms.