Solvent-free formation of cyclodextrin-based pseudopolyrotaxanes of polyethylene glycol: kinetic and structural aspects

Pseudopolyrotaxanes (PPRs) are supramolecular structures consisting of macrocycles able to thread on a linear polymer chain in a reversible, non-covalent way, often referred to in the literature as "molecular necklaces". While the synthesis and reaction mechanisms of these structures in solution have been widely described, their solvent-free production has received little attention, despite the advantages that this route may offer. We propose in this work a kinetic mechanism that describes the PPR formation in the solid phase as a process occurring in two consecutive stages. This mechanism has been used to investigate the spontaneous formation of a PPR that occurs when grinding alpha-Cyclodextrin (alpha-CD) with polyethylene glycol (PEG). In the threading stage, the inclusion of the polymer and subsequent release of the water molecules lodged in the cavity of the macrocycle cause vibrational changes that are reflected in the time-dependence of the FTIR-ATR spectra, while the further assembly of PPRs to form crystals produces characteristic reflections in the XRD patterns, due to the channel-like arrangement of CDs, that can be used to track the formation of the adduct in crystalline form. The effects that working variables have on the kinetics of the reaction, such as temperature, feed ratio, molar mass of the polymer and the introduction of an amorphous block in the polymer structure, have been investigated. The rate constants of the threading step increase with the temperature and the activation energy of the process increases at lower proportions of CD to PEG. This is attributed to the lower degree of covering of the polymer chain with CDs that reduces the hydrogen-bonding driven stabilization between adjacent macrocycles. The formation of crystalline PPR, which takes place slowly at room temperature, is markedly promoted at higher temperatures, with lower proportions of CD favoring both the formation and the growth of the crystals. The molar mass of the polymer does not modify the typical channel-like arrangement of packed PPRs but the conversion into crystalline PPR diminishes when using PEG1000 instead of PEG400. At a microscopic level, the crystals arrange into lamellar structures, in the order of hundreds of nm, embedded in an amorphous-like matrix. The introduction of a polypropylene oxide block in the structure of the polymer (Pluronic L62) renders poorer yields and a considerable loss of crystallinity of the product of the reaction. The methodology here proposed can be applied to the general case of inclusion complexes of CDs with drugs in the solid phase, or to multicomponent systems that contain polymers as excipients in pharmaceutical formulations along with CDs

Obtaining of repair lime mortars by mixing aerial lime and nanosilica

This work deals with the effect of the nanosilica addition on the performance of aerial lime mortars. Several lime mortars were prepared and modified upon the addition of 3, 6, 10 and 20 wt.% of nanosilica. The presence of nanosilica increased the water demand of the fresh mixtures and reduced the appearance of superficial cracks after the spreading of the mortars onto a porous stone. Setting time underwent a delay when the amount of nanosilica ranged from 3 to 10 wt.%. However, samples with 20 wt.% of nanosilica showed a shortened setting time compared to plain lime mortars. Nanosilica reacted with Ca(OH)2 particles, yielding C-S-H compounds and, acting as a nanofiller, nanosilica also caused a pore blockage in the mesoporous range. These facts resulted in an increase in both compressive strength and durability after undergoing freezing-thawing processes. Overall, the addition of nanosilica clearly improves several characteristics of the aerial lime mortars in order to prepare enhanced mixtures to be used for restoration works

Long-term mechanical resistance and durability of air lime mortars with large additions of nanosilica

The performance of air lime mortars modified by the incorporation of large amounts of nanostructured colloidal silica ¿ nanosilica, NS - (6, 10 and 20 wt.% with respect to lime) was the main objective of this work. Fresh mixture properties (water demand, setting time and plastic shrinkage), mechanical strengths up to one year and specimens¿ durability after accelerated ageing conditions (climatic chamber, freeze-thaw cycles and sulfate attack by MgSO4 corrosion test) were evaluated. NS was seen to have a strong pozzolanic activity in air lime media. Although the addition of NS gave rise to an increase in volume contraction, the superficial cracking caused by the drying shrinkage was reduced. A noticeable increase in the compressive strength values was observed in the NS-bearing mortars owing to the NS filler effect and the C-S-H formation, as proved by SEM examination and MIP analysis. A honeycomb-shaped network of C-S-H phases appeared as the prevailing microstructure in mortars with large NS additions. In the face of accelerated ageing processes, the presence of NS made the mortars more durable, delaying the progress of decay

Solidification/stabilization of toxic metals in calcium aluminate cement matrices

The ability of calcium aluminate cement (CAC) to encapsulate toxic metals (Pb, Zn and Cu) was assessed under two curing conditions. Changes in the consistency and in the setting time were found upon the addition of the nitrates of the target metals. Both Pb and Cu caused a delay in CAC hydration, while Zn accelerated the stiffening of the mortar. Compressive strengths of the metal-doped mortars, when initially cured at 60ºC/100% RH, were comparable with that of the free-metal mortar. Three different pore size distribution patterns were identified and related to the compounds identified by XRD and SEM. Sorbent capacities of CAC for the toxic metals were excellent: a total uptake was achieved for up to 3 wt.% loading of the three metals. In this way, CAC mortars were perfectly able to encapsulate the toxic metals, allowing the use of CAC for waste management as proved by the leaching tests

Treatment of toxic metal aqueous solutions: encapsulation in a phosphate-calcium aluminate matrix

Polyphosphate-modified calcium aluminate cement matrices were prepared by using aqueous solutions polluted with toxic metals as mixing water to obtain waste-containing solid blocks with improved management and disposal. Synthetically contaminated waters containing either Pb or Cu or Zn were incorporated into phosphoaluminate cement mortars and the effects of the metal’s presence on setting time and mechanical performance were assessed. Sorption and leaching tests were also executed and both retention and release patterns were investigated. For all three metals, high uptake capacities as well as percentages of retention larger than 99.9% were measured. Both Pb and Cu were seen to be largely compatible with this cementitious matrix, rendering the obtained blocks suitable for landfilling or for building purposes. However, Zn spoilt the compressive strength values because of its reaction with hydrogen phosphate anions, hindering the development of the binding matrix

Tradición, versatilidad e innovación en la cal: un material de excelencia

Actas revisadas por pares de los trabajos presentados en las VI Jornadas FICAL organizadas por el Grupo de Investigación MIMED del Departamento de Química de la Facultad de Ciencias, celebradas en la Universidad de Navarra del 28 al 30 de mayo de 2018

Assessment of the interaction of polycarboxylate superplasticizers in hydrated lime pastes modified with nanosilica or metakaolin as pozzolanic reactives

Two polycarboxylate ether copolymers were assessed as superplasticizers (SPs) for hydrated lime pastes modified with two reactive compounds, nanosilica (NS) and ceramic metakaolin (MK). Characterization of the molecular structure of the SPs by Size Exclusion Chromatography, XRD, FTIR and MALDI-TOF (Matrix Assisted Laser Desorption Ionization Time-of-Flight) mass spectrometry was performed. The structures of the polymers were seen to be star- and worm-like shapes. A close relationship was found between the molecular architecture and the flowability of the pastes, being the star-shaped plasticizer the most efficient. Zeta potential assessment allowed us to elucidate a steric hindrance as the main action mechanism for these polymers. The large specific surface area of nanosilica led to a large SPs consumption as compared with metakaolin with lower surface area. However, SPs in MK-lime samples were attached favourably on the C-S-H and aluminate hydrates, so that the dispersing action was greater with respect to NS-lime suspensions

Influence of two polymer-based superplasticizers (poly-naphthalene sulfonate, PNS, and lignosulfonate, LS) on compressive and flexural strength, freeze-thaw, and sulphate attack resistance of lime-metakaolin grouts

A new range of grouts prepared by air lime and metakaolin (MK) as a pozzolanic admixture has been obtained by using as dispersing agents two polymers, namely poly-naphthalene sulfonate (PNS) and lignosulfonate (LS), with the aim of improving the fluidity of the fresh grouts. Fluidity and setting times of the grouts were assessed. Differences in the molecular architecture and in the anionic charge density explained the different adsorption of the polymers and the different performance. The higher anionic charge of PNS and its linear shape explained its better adsorption and effectiveness. The pozzolanic reaction was favoured in grouts with PNS, achieving the highest values of compressive strength (4.8 MPa after 182 curing days). The addition of PNS on lime grouts slightly decreased the frost resistance of the grouts (from 24 freeze-thaw cycles for the polymer-free samples to 19 or 20 cycles with 0.5 or 1 wt % of PNS). After the magnesium sulphate attack, grouts were altered by decalcification of hydrated phases and by formation of hexahydrite and gypsum. A protective role of portlandite against magnesium sulphate attack was clearly identified. Accordingly, the polymer LS, which preserves a significant amount of Ca(OH)2, could be an alternative for the obtaining of grouts requiring high sulphate attack resistance

Hydrophobized lime grouts prepared with microsilica and superplasticizers

This work reports the obtaining of lime-based grouts as repairing materials. Microsilica was added as pozzolanic additive to enhance the compressive strength of the hardened grouts. Sodium oleate, as water repellent admixture, and different superplasticizers were also incorporated to reduce the water absorption and to enhance the injectability of the grouts. Polycarboxylate ether (PCE), polynaphthalene sulfonate (PNS), melamine sulfonate (MMS) and polyacrylic acid (PA) were tested as plasticizing agents. Regarding the fluidity of the grouts, PCE was seen to improve the injectability, followed by PNS, MMS and PA. However, PCE addition was also accompanied by a severe delay in the setting time. The other three superplasticizers did not provoke significant delays in the hardening of the samples. The water contact angle underwent an increase pointing to an effective hydrophobization of the surface as a consequence of the water repellent admixture. The combination with PCE was the most effective in keeping the water repellency in comparison with the control sample (lime grout + oleate). MMS yielded high compressive strengths and durability of the mortars, in the face of freezing-thawing cycles, was enhanced