Influence of dispersion of fibrillated cellulose on the reinforcement of coated papers.

The use of cellulose micro/nanofibrils (CMNFs) as reinforcement paper additive at industrial scale is delayed due to inconsistent results, suggesting a lack of proper consideration of some key parameters. The high influence of fibrillated nanocellulose dispersion has been recently identified as a key parameter for paper bulk reinforcement but it has not been studied for surface coating applications yet. This paper studies the effect of CMNF dispersion degree prior to their addition and during mixing with starch on the reinforcement of paper by coating. Results show that this effect depends on the type of CMNFs since it is related to the surface interactions. For a given formulation, a correlation is observed between the CMNF dispersion and the CMNF/starch mixing agitation with the rheology of the coating formulation which highly affects the paper properties. The optimal dispersion degree is different for each nanocellulose, but the best mechanical properties were always achieved at the lowest viscosity of the coating formulation. In general, the initial state of the nanocellulose 3D network, influences the mixing and smooth application of the coating and affects the reinforcement effect. Therefore, the CMNF industrial implementation in coating formulations will be facilitated by the on-line control of formulations prior to their surface application.

On Hair Care Physicochemistry: From Structure and Degradation to Novel Biobased Conditioning Agents.

Hair is constantly exposed to various adverse external stimuli, such as mechanical or thermal factors, that may cause damage or cause it to lose its shine and smooth appearance. These undesirable effects can be minimized by using hair conditioners, which repair the hair and restore the smooth effect desired by the consumer. Some of the currently used conditioning agents present low biodegradability and high toxicity to aquatic organisms. Consumers are also becoming more aware of environmental issues and shifting their preferences toward natural-based products. Therefore, developing novel, sustainable, natural-based derivatives that can act as conditioning agents in hair care products and thus compete with the traditional systems obtained from non-renewable sources is highly appealing. This paper presents the key physicochemical aspects of the hair conditioning process, including hair structure and degradation, and reviews some of the new alternative conditioning agents obtained from natural resources.

Heavy Metals Removal from Aqueous Solutions by Multiwall Carbon Nanotubes: Effect of MWCNTs Dispersion.

Carbon nanotubes (CNTs) are one of the most studied nanoparticles due to their physical, chemical and electronic properties. However, strong Van der Waals bonds, which promote CNTs aggregation are usually present, affecting their unique properties. Avoiding CNTs aggregation is one of the main difficulties when using these nanoparticles. Regarding the adsorption capacity of CNTs, the tendency of CNTs to aggregate decreases the surface area available to retain contaminants. One way to overcome this issue is by changing the surface energy of CNTs through chemical (covalent and noncovalent methods) or mechanical stabilization, but there is not yet a unique solution to solve this problem. In this work, a chemical noncovalent method (addition of surfactants) combined with mechanical energy (ultrasounds) was applied for CNTs stabilization, and the influence in heavy metal ions removal, Pb (II), Cu (II), Ni (II) and Zn (II), an area of high environmental relevance, was evaluated. It was proved that high amounts of metals could be removed from water during the first eighteen hours. Competitive adsorption between heavy metals, during adsorption tests with the simultaneous presence of all ions, was also studied and it was possible to prove that the electronegativity and atomic radius of cations influence their removal. Pb (II) and Cu (II) were the metals removed in higher percentages, and Ni (II) and Zn (II) were the metals less removed during competitive adsorption. Finally, the results obtained show that MWCNTs, if adequately dispersed, present a good solution for the treatment of water contaminated with highly toxic heavy metals, even when using very low concentrations of Multiwall Carbon Nanotubes (MWCNTs).

Characterization of Two Cactus Formulation-Based Flocculants and Investigation on Their Flocculating Ability for Cationic and Anionic Dyes Removal.

Dye invasion in wastewaters is undeniably one of the crucial environmental concerns in addition to the supplement of toxic synthetic chemical flocculants used for color removal using the conventional coagulation-flocculation process. With the aim to improve the flocculation stage in terms of reagents safety and ensure dyes removal, the present study explores the flocculating effectiveness of two natural, stable, and eco-friendly cactus formulations, namely 60 °C oven-dried (DP) and lyophilized (LP) cladodes. Both formulations were assessed to treat cationic (Methylene blue; MB) and anionic (Methyl Orange; MO) dye solutions as a substitution attempt for the currently questioned employed synthetic chemical flocculants. Obtained results demonstrate that, in conjunction with alum as coagulant, the lyophilized powder (LP) bio-based flocculant appears to be the most efficient cactus formulation, showing a significant color (83%) and a turbidity (69%) abatement for the cationic dye (MB) and, respectively, 63% and 62% for the anionic one (MO). Additionally, the flocculation activity of the LP formula remained high over an eight-month period of storage. Moreover, based on the Fourier transform infrared (FTIR) spectroscopic analysis and the chemical characterization of cactus formulations, the occurring flocculation mechanisms of the dye removal are presumed to be based on both adsorption and bridging phenomena. Further, the significant color and turbidity decline achieved upon the addition of the lyophilized cactus cladodes powder (LP), enhancing thus the coagulation performance of the alum-based coagulant, proved the effectiveness of this bio-flocculant compared to the commonly used chemical flocculant (polyacrylamide). Hence, it was suggested that lyophilized cactus cladodes as a natural flocculant could be one of the effective surrogates to chemical flocculants conventionally used in wastewater treatment for the sake of a safer and sustainable environment.

The critical role of the dispersant agents in the preparation and ecotoxicity of nanomaterial suspensions.

This work reports the role of different dispersants, namely, polyethylene glycol (PEG 200 2%), ethylene glycol 5%, ethanol 2%, dimethyl sulfoxide (DMSO 5%), and polyvinyl alcohol (PVA 5%) in the toxicity profile of several commercial nanomaterials (NM), such as hydrophilic and hydrophobic TiO2, hydrophilic SiO2, SiO2 in aqueous suspension (aq), and ZnO towards the bioluminescent bacterium Aliivibrio fischeri. The majority of NM showed tendency to form agglomerates in the different dispersants. Although some particle agglomeration could be detected, DMSO at 5% was the best dispersant for hydrophobic TiO2 NM while PVA at 5% was the most effective dispersant for the other types of NM. Average size was not the most relevant aspect accounting for their toxicity. A remarkable reduction in average size was followed by a decrease in NM toxicity, as demonstrated for SiO2 aq. in PVA 5%. Contrarily, despite of high particle agglomeration, ZnO NM showed a higher toxicity to bacteria when compared with other tested NM. Independently of the average particle size or surface charge, the dispersant either enhanced the toxicity to bacteria or acted as physical barrier decreasing the NM harmful effect to A. fischeri.

Is the aquatic toxicity of cationic polyelectrolytes predictable from selected physical properties?

Cationic acrylamide-based polyelectrolytes (cPAM) are widely used in industry. They can be designed for optimal performance in a specific application, but this opportunity means the environmental safety of all different alternatives needs to be addressed. Both the inclusion of environmental toxicity as a design variable and the establishment of relationships between structure and ecotoxicity are thus current challenges. The aim of this study was to assess whether structural variables such as molecular weight, charge density and the integrative intrinsic viscosity parameter can be used to predict the environmental safety of cPAMs, as well as if these relationships are stable when the biological models change. Five cPAMs comprising molecular weight and charge density gradients were tested against bacteria, microalgae, macrophytes and daphnids. While correlations were found between physical properties of cPAMs as expected, no clear ecotoxicity patterns could be identified. All cPAMs can be classified as harmful to aquatic life on the basis of the responses elicited in the most sensitive organisms, microalgae and daphnids. Unicellular bacteria were the least sensitive eco-receptors possibly due to cell wall structure or the protective effect of the ionic strength of the test medium. The macrophytes were also tolerant to cPAMs exposure, which may be related to exposure avoidance mechanisms. The order of toxicity of cPAMs depended on the test organism, preventing the establishment of stable structure-ecotoxicity relationships. Therefore, the study leads to the overall generalist recommendation of relying on the most sensitively responding test organisms when developing new (eco)safe-by-design cPAMs.

Influence of the stabilizers on the toxicity of metallic nanomaterials in aquatic organisms and human cell lines.

In this study, following a systematic approach, we used aquatic species (bacteria Vibrio fischeri and microalgae Raphidocelis subcapitata) and different human cell lines (Caco-2, HepG2, SV-80 and HaCaT) representing different tissues and exposure pathways, to investigate how two organic stabilizers (PVA and DMSO) used for NMs dispersion influence their physicochemical properties, the persistence of metals in suspension and the toxicity/ecotoxicity of two metallic NMs (nano-Ag and nano-Cu). Although the stabilizers are expected to contribute to improve the dispersion and stability of NMs, the results obtained clearly showed that no similar changes in toxicity and morphological properties of the nano-Ag can be expected after its stabilization with PVA. Thus, regarding human cell lines, the reduction in the average size of the PVA-nano-Ag was followed by a reduction or maintenance of its toxicity, but the opposite was observed for the aquatic species tested since an increase in the average size enhanced its toxicity. As far as nano-Cu is considered DMSO contributed for a better dispersion of this nanomaterial, however this was not translated in a similar toxicity/ecotoxicity modification. In summary, even for nano-Cu, for which few or no data exists regarding its toxicity after stabilization with organic compounds, it was confirmed with consistent data, that the toxicity of metallic NMs is a complex combination of average size, chemical composition, solubilization or persistence in suspension of the metallic forms, interaction with test medium components and sensitivity of test species and cell lines. The combination of all of these factors makes the toxicity of metallic NMs unpredictable and points for the need of an extensive evaluation of each new formulation.