Performance of concrete containing recycled masks used for personal protection during coronavirus pandemic.

After the coronavirus outbreak, a tremendous amount of personal protective equipment has been produced and used by the health service and every human. Proper medical waste management becomes an important problem, which must be solved with a minimal environmental impact. The presented manuscript introduces the recycling process, during which personal protection masks are transformed into polypropylene fibers being an addition to a concrete mixture. The designed recycling procedure provides the entire disinfection of probably contaminated medical wastes, is straightforward, and potentially enables one to modify the properties of the final product. The applied dosage referred to 1 mask per 1 L of concrete. The final product of face masks processing was studied using Fourier-transform infrared spectroscopy, thermogravimetric analysis, surface free energy, contact angle measurements, and melt flow index. The analysis indicated that polypropylene is its main component. Two concrete mixtures were composed, i.e., with the addition of processed masks and the reference one. The following properties were determined to compare the modified concrete with the reference one: compressive and tensile strength, frost resistance, water transport properties, resistance to high temperature. The obtained results indicated that the addition of processed masks slightly increased the compressive strength (by about 5%) and decreased the tensile strength (by about 3%). Simultaneously, it was reported that the addition did not affect material properties related to concrete durability as frost resistance, water permeability, and fire performance. The results evinced, that the addition of processed facemasks into concrete did not deteriorate its properties. Therefore, it is a possible way of the protective masks processing and reusing with the high recycling capacity. Further study should be conducted to optimize the dosing and to modify the properties of PP strings to improve hardened concrete properties.

Biocomposites of Epoxidized Natural Rubber/Poly(lactic acid) Modified with Natural Fillers (Part I).

The study aimed to prepare sustainable and degradable elastic blends of epoxidized natural rubber (ENR) with poly(lactic acid) (PLA) that were reinforced with flax fiber (FF) and montmorillonite (MMT), simultaneously filling the gap in the literature regarding the PLA-containing polymer blends filled with natural additives. The performed study reveals that FF incorporation into ENR/PLA blend may cause a significant improvement in tensile strength from (10 ± 1) MPa for the reference material to (19 ± 2) MPa for the fibers-filled blend. Additionally, it was found that MMT employment in the role of the filler might contribute to ENR/PLA plasticization and considerably promote the blend elongation up to 600%. This proves the successful creation of the unique and eco-friendly PLA-containing polymer blend exhibiting high elasticity. Moreover, thanks to the performed accelerated thermo-oxidative and ultraviolet (UV) aging, it was established that MMT incorporation may delay the degradation of ENR/PLA blends under the abovementioned conditions. Additionally, mold tests revealed that plant-derived fiber addition might highly enhance the ENR/PLA blend's biodeterioration potential enabling faster and more efficient growth of microorganisms. Therefore, materials presented in this research may become competitive and eco-friendly alternatives to commonly utilized petro-based polymeric products.

Comparison of Aging Resistance and Antimicrobial Properties of Ethylene-Norbornene Copolymer and Poly(Lactic Acid) Impregnated with Phytochemicals Embodied in Thyme (Thymus vulgaris) and Clove (Syzygium aromaticum).

The effects of plant-based extracts on the solar aging and antimicrobial properties of impregnated ethylene-norbornene (EN) copolymer and poly(lactic acid) (PLA) were investigated. In this study, the impregnation yield of polyolefin, lacking in active centers capable of phytochemical bonding, and polyester, abundant in active sides, was measured. Moreover, two different extracts plentiful in phytochemicals-thyme (TE) and clove (CE)-were employed in the solvent-based impregnation process. The effect of thymol and eugenol, the two main compounds embodied in the extracts, was studied as well. Interestingly, oxidation induction times (OIT) for the impregnation of EN with thyme and clove extracts were established to be, respectively, 27.7 and 39.02 min, which are higher than for thymol (18.4 min) and eugenol (21.1 min). Therefore, an aging experiment, mimicking the full spectrum of sunlight, was carried out to investigate the resistance to common radiation of materials impregnated with antioxidative substances. As expected, the experiment revealed that the natural extracts increased the shelf-life of the polymer matrix by inhibiting the degradation processes. The aging resistance was assessed based on detected changes in the materials' behavior and structure that were examined with Fourier-transform infrared spectroscopy, contact angle measurements, color quantification, tensile tests, and hardness investigation. Such broad results of solar aging regarding materials impregnated with thyme and clove extracts have not been reported to date. Moreover, CE was found to be the most effective modifying agent for enabling material with antimicrobial activity against Escherichia coli to be obtained.

Thermal Behavior of Green Cellulose-Filled Thermoplastic Elastomer Polymer Blends.

A recently developed cellulose hybrid chemical treatment consists of two steps: solvent exchange (with ethanol or hexane) and chemical grafting of maleic anhydride (MA) on the surface of fibers. It induces a significant decrease in cellulose moisture content and causes some changes in the thermal resistance of analyzed blend samples, as well as surface properties. The thermal characteristics of ethylene-norbornene copolymer (TOPAS) blends filled with hybrid chemically modified cellulose fibers (UFC100) have been widely described on the basis of differential scanning calorimetry and thermogravimetric analysis. Higher thermal stability is observed for the materials filled with the fibers which were dried before any of the treatments carried out. Dried cellulose filled samples start to degrade at approximately 330 °C while undried UFC100 specimens begin to degrade around 320 °C. Interestingly, the most elevated thermal resistance was detected for samples filled with cellulose altered only with solvents (both ethanol and hexane). In order to support the supposed thermal resistance trends of prepared blend materials, apparent activation energies assigned to cellulose degradation (EA1) and polymer matrix decomposition (EA2) have been calculated and presented in the article. It may be evidenced that apparent activation energies assigned to the first decomposition step are higher in case of the systems filled with UFC100 dried prior to the modification process. Moreover, the results have been enriched using surface free energy analysis of the polymer blends. The surface free energy polar part (Ep) raises considering samples filled with not dried UFC100. On the other hand, when cellulose fibers are dried prior to the modification process, then the blend sample's dispersive part of surface free energy is increased with respect to that containing unmodified fiber. As polymer blend Ep exhibits higher values reflecting enhanced material degradation potential, the cellulose fibers employment leads to more eco-friendly production and responsible waste management. This is in accordance with the rules of sustainable development.

Ecologically Modified Leather of Bacterial Origin.

The research presented here is an attempt to develop an innovative and environmentally friendly material based on bacterial nanocellulose (BNC), which will be able to replace both animal skins and synthetic polymer products. Bacterial nanocellulose becomes stiff and brittle when dried, so attempts have been made to plasticise this material so that BNC can be used in industry. The research presented here focuses on the ecological modification of bacterial nanocellulose with vegetable oils such as rapeseed oil, linseed oil, and grape seed oil. The effect of compatibilisers of a natural origin on the plasticisation process of BNC, such as chlorophyll, curcumin, and L-glutamine, was also evaluated. BNC samples were modified with rapeseed, linseed, and grapeseed oils, as well as mixtures of each of these oils with the previously mentioned additives. The modification was carried out by passing the oil, or oil mixture, through the BNC using vacuum filtration, where the BNC acted as a filter. The following tests were performed to determine the effect of the modification on the BNC: FTIR spectroscopic analysis, contact angle measurements, and static mechanical analysis. As a result of the modification, the BNC was plasticised. Rapeseed oil proved to be the best for this purpose, with the help of which a material with good strength and elasticity was obtained.

Analysis of classical techniques precision on the measurement of cellulose moisture gain/loss.

The precision of the four classical techniques (Karl-Fischer titration, (thermo)gravimetric method, Fourier-transform infrared (FT-IR) and near infrared (NIR) spectroscopies) commonly used in the analysis of cellulose moisture absorption/desorption has been deeply investigated regarding the reproducibility of these processes. Based on multiple repeated experiments, cellulose water content values obtained with Karl-Fischer titration and (thermo)gravimetric method were plotted as a function of time. Then, the cautious peak-by-peak analysis of the absorbance and wavenumber shifts visible in IR spectra has been carried out. The collected data was described using boxplots that provided valuable information on the experimental points spread. It has been successfully proven that gravimetric methods allow for precise drawing of moisture absorption and desorption curves, while Karl-Fischer titration, ATR FT-IR and NIR techniques provide the possibility of the moisture absorption/desorption processes description by linear mathematical models (R2 >90%). Therefore, this study provides a systematic comparison between various analytical methods.

Characterization of the UV-aging and antimicrobial resistance of cellulose / ethylene-norbornene composites.

The aim of this research was to investigate for the first time the possible application range of sustainable cellulose-filled polymer-based materials dedicated for common use in healthcare sector. These products are exposed to contact with solutions of different acidity, microorganisms and are being constantly UV sterilized. Therefore, the impact of plant filler on the microbial growth, UV-aging and pH-resistance of cellulose-filled ethylene-norbornene copolymer (EN) was investigated, as the polymer matrix employed is widely used in healthcare applications. Moreover, two different coupling agents, vinyltrimethoxysilane (VTMS) and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPTMS), were used to promote the adhesion between the polymer matrix and cellulose (hydrophobization of fibres evidenced with increased water contact angle from 15 to 130°). Additionally, UV-aging revealed that the silane-originated functional groups might have possibly acted as free radical scavengers, hence, prolonging composites' shelf-life. Furthermore, incorporation of investigated amount of cellulose did not result in the decreased pH-resistance or improved growth of Escherichia coli.

Original study on mathematical models for analysis of cellulose water content from absorbance/wavenumber shifts in ATR FT-IR spectrum.

The aim of this research was to evaluate the applicability of the attenuated total reflectance Fourier-transform infrared (ATR FT-IR) spectroscopy in the quantitative analysis of the moisture content in cellulose (from 0.5 to 11.0 wt.%). Innovatively, this work describes the variations in both absorbance and wavenumber of 16 absorption bands plotted as a function of cellulose water amount measured with Karl-Fischer titration. Different regression models were investigated (simple linear, semilogarithmic, power) and the adjusted coefficient of determination (R2) was given for each calculation. While model exhibited R2 > 90%, the standard error of calibration (SEC) was presented and an external validation has been performed. Regarding the absorbance-water content relationship, data recorded for sixteen peaks was successfully fitted with linear functions exhibiting R2 > 90%. The highest value of R2 = 98.7% and standard error of prediction SEP = 0.3wt.% have been assigned to the maximum from 3339 to 3327 cm-1 (-OH), proving ATR FT-IR usefulness in quantitative analysis.

Biocomposites of Epoxidized Natural Rubber/Poly(Lactic Acid) Modified with Natural Substances: Influence of Biomolecules on the Aging Properties (Part II).

The aim of this study is to present the possible influence of natural substances on the aging properties of epoxidized natural rubber (ENR) and poly(lactic acid) (PLA) eco-friendly elastic blends. Therefore, the ENR/PLA blends were filled with natural pro-health substances of potentially antioxidative behavior, namely, δ-tocopherol (vitamin E), curcumin, ß-carotene and quercetin. In this way, the material biodeterioration potential was maintained and the material's lifespan was prolonged while subjected to increased temperatures or high-energy UVA irradiation (340 nm). The investigation of the samples' properties indicated that curcumin and quercetin are the most promising natural additives that may contribute to the delay of ENR/PLA degradation under the above-mentioned conditions. The efficiency of the proposed new natural anti-aging additives was proven with static mechanical analysis, color change investigation, as well as mass loss during a certain aging. The aging coefficient, which compares the mechanical properties before and after the aging process, indicated that the ENR/PLA performance after 200 h of accelerated aging might decrease only by approximately 30% with the blend loaded with quercetin. This finding paves new opportunities for bio-based and green anti-aging systems employed in polymer technology.

Application of Fluids in Supercritical Conditions in the Polymer Industry.

This article reviews the use of fluids under supercritical conditions in processes related to the modern and innovative polymer industry. The most important processes using supercritical fluids are: extraction, particle formation, micronization, encapsulation, impregnation, polymerization and foaming. This review article briefly describes and characterizes the individual processes, with a focus on extraction, micronization, particle formation and encapsulation. The methods mentioned focus on modifications in the scope of conducting processes in a more ecological manner and showing higher quality efficiency. Nowadays, due to the growing trend of ecological solutions in the chemical industry, we see more and more advanced technological solutions. Less toxic fluids under supercritical conditions can be used as an ecological alternative to organic solvents widely used in the polymer industry. The use of supercritical conditions to conduct these processes creates new opportunities for obtaining materials and products with specialized applications, in particular in the medical, pharmacological, cosmetic and food industries, based on substances of natural sources. The considerations contained in this article are intended to increase the awareness of the need to change the existing techniques. In particular, the importance of using supercritical fluids in more industrial methods and for the development of already known processes, as well as creating new solutions with their use, should be emphasized.

IR Study on Cellulose with the Varied Moisture Contents: Insight into the Supramolecular Structure.

The following article is the first attempt to investigate the supramolecular structure of cellulose with the varied moisture content by the means of Fourier-transform and near infrared spectroscopy techniques. Moreover, authors aimed at the detailed and precise presentation of IR spectra interpretation approach in order to create a reliable guideline for other researchers. On the basis of obtained data, factors indicating biopolymer crystallinity and development of hydrogen interactions were calculated and the peaks representing hydrogen bonding (7500-6000 cm-1, 3700-3000 cm-1, and 1750-1550 cm-1) were resolved using the Gaussian distribution function. Then, the deconvoluted signals have been assigned to the specific interactions occurring at the supramolecular level and the hydrogen bond length, as well bonding-energy were established. Furthermore, not only was the water molecules adsorption observed, but also the possibility of the 3OH⋯O5 intramolecular hydrogen bond shortening in the wet state was found-from (27,786 ± 2) 10-5 nm to (27,770 ± 5) 10-5 nm. Additionally, it was proposed that some deconvoluted signals from the region of 3000-2750 cm-1 might be assigned to the hydroxyl group-incorporated hydrogen bonding, which is, undoubtedly, a scientific novelty as the peak was not resolved before.

Drying of the Natural Fibers as A Solvent-Free Way to Improve the Cellulose-Filled Polymer Composite Performance.

When considering cellulose (UFC100) modification, most of the processes employ various solvents in the role of the reaction environment. The following article addresses a solvent-free method, thermal drying, which causes a moisture content decrease in cellulose fibers. Herein, the moisture content in UFC100 was analyzed with spectroscopic methods, thermogravimetric analysis, and differential scanning calorimetry. During water desorption, a moisture content drop from approximately 6% to 1% was evidenced. Moreover, drying may bring about a specific variation in cellulose's chemical structure. These changes affected the cellulose-filled polymer composite's properties, e.g., an increase in tensile strength from 17 MPa for the not-dried UFC100 to approximately 30 MPa (dried cellulose; 24 h, 100 °C) was observed. Furthermore, the obtained tensile test results were in good correspondence with Payne effect values, which changed from 0.82 MPa (not-dried UFC100) to 1.21 MPa (dried fibers). This raise proves the reinforcing nature of dried UFC100, as the Payne effect is dependent on the filler structure's development within a polymer matrix. This finding paves new opportunities for natural fiber applications in polymer composites by enabling a solvent-free and efficient cellulose modification approach that fulfils the sustainable development rules.

Superiority of Cellulose Non-Solvent Chemical Modification over Solvent-Involving Treatment: Application in Polymer Composite (part II).

The following article debates on the properties of cellulose-filled ethylene-norbornene copolymer (EN) composites. Natural fibers employed in this study have been modified via two different approaches: solvent-involving (S) and newly developed non-solvent (NS). The second type of the treatment is fully eco-friendly and was carried out in the planetary mill without incorporation of any additional, waste-generating substances. Composite samples have been investigated with the use of spectroscopic methods (FT-IR), differential scanning calorimetry (DSC), static mechanical analysis, and surface-free energy measurements. It has been proved that the possible filler-polymer matrix interaction changes may occur due to the performed modifications. The highest reinforcement was evidenced for the composite sample filled with cellulose treated via a NS approach-TS = (34 ± 2) MPa, Eb = (380 ± 20)%. Additionally, a surface free energy polar part exhibited a significant increase for the same type of modification. Consequently, this could indicate easier wetting of the material which may contribute to the degradation process enhancement. Successfully developed cellulose-filled ethylene-norbornene copolymer composite compromises the rules of green chemistry and sustainable development by taking an advantage of renewable natural resources. This bio-inspired material may become an eco-friendly alternative for commonly used polymer blends.

Superiority of Cellulose Non-Solvent Chemical Modification over Solvent-Involving Treatment: Solution for Green Chemistry (Part I).

In the following article, a new approach of cellulose modification, which does not incorporate any solvents (NS), is introduced. It is compared for the first time with the traditional solvent-involving (S) treatment. The analysed non-solvent modification process is carried out in a planetary mill. This provides the opportunity for cellulose mechanical degradation, decreasing its size, simultaneously with ongoing silane coupling agent grafting. Fourier-transform infrared spectroscopy (FT-IR) indicated the possibility of intense cleavage of the glucose rings in the cellulose chains during the mechano-chemical treatment. This effect was proved with dynamic light scattering (DLS) results-the size of the particles decreased. Moreover, according to differential scanning calorimetry (DSC) investigation, modified samples exhibited decreased moisture content and a drop in the adsorbed water evaporation temperature. The performed research proved the superiority of the mechano-chemical treatment over regular chemical modification. The one-pot bio-filler modification approach, as a solution fulfilling green chemistry requirements, as well as compromising the sustainable development rules, was presented. Furthermore, this research may contribute significantly to the elimination of toxic solvents from cellulose modification processes.

Cellulose Modification for Improved Compatibility with the Polymer Matrix: Mechanical Characterization of the Composite Material.

The following article is the presentation attempt of cellulose hybrid chemical modification approach as a useful tool in improving the mechanical properties of plant fiber-filled polymer materials. The treatment process is a prolonged method of the cellulose maleinization and consists of two steps: 1. solvent exchange (altering fiber structure); 2. maleic anhydride (MA) chemical grafting (surface modification). Thanks to the incorporated treatment method, the created ethylene-norbornene copolymer composite specimen exhibited an improved performance, tensile strength at the level of (38.8 ± 0.8) MPa and (510 ± 20)% elongation at break, which is higher than for neat polymer matrix and could not be achieved in the case of regular MA treatment. Moreover, both the Payne effect and filler efficiency factor indicate a possibility of the fiber reinforcing nature that is not a common result. Additionally, the polymer matrix employed in this research is widely known for its excellent resistance to aqueous and polar organic media, good biocompatibility, and the ability to reproduce fine structures which makes it an interesting material regarding healthcare applications. Therefore, plant fiber-based polymer materials described in this research might be potentially applied in this area, e.g., medical devices, drug delivery, wearables, pharmaceutical blisters, and trays.

Cellulose Fibers Hydrophobization via a Hybrid Chemical Modification.

The following article highlights the importance of an indispensable process in cellulose fibers (UFC100) modification which may change the biopolymer properties-drying. The reader is provided with a broad range of information considering the drying process consequences on the chemical treatment of the cellulose. This research underlines the importance of UFC100 moisture content reduction considering polymer composites application with the employment of a technique different than thermal treating. Therefore, a new hybrid chemical modification approach is introduced. It consists of two steps: solvent exchange (with ethanol either hexane) and chemical treatment (maleic anhydride-MA). With the use of Fourier-transform infrared spectroscopy (FT-IR), it has been proven that the employment of different solvents may contribute to the higher yield of the modification process as they cause rearrangements in hydrogen bonds structure, swell the biopolymer and, therefore, affect its molecular packing. Furthermore, according to the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), the improvement in fibers thermal resistance was noticed, e.g., shift in the value of 5% temperature mass loss from 240 °C (regular modification) to 306 °C (while solvent employed). Moreover, the research was broadened with cellulose moisture content influence on the modification process-tested fibers were either dried (D) or not dried (ND) before the hybrid chemical treatment. According to the gathered data, D cellulose exhibits elevated thermal resistance and ND fibers are more prone to the MA modification. What should be emphasized, in the case of all carried out UFC100 treatments, is that a decrease in moisture contend was evidenced-from approximately 4% in case of thermal drying to 1.7% for hybrid chemical modification. This is incredibly promising considering the possibility of the treated fibers application in polymer matrix.

A catalyst-free, temperature controlled gelation system for in-mold fabrication of microgels.

Anisometric microgels are prepared via thermal crosslinking using an in-mold polymerization technique. Star-shaped poly(ethylene oxide-stat-propylene oxide) polymers, end-modified with amine and epoxy groups, form hydrogels, of which the mechanical properties and gelation rate can be adjusted by the temperature, duration of heating, and polymer concentration. Depending on the microgel stiffness, the rod-shaped microgels self-assemble into ordered or disordered structures.