High sorption of reactive dyes onto cotton controlled by chemical potential gradient for reduction of dyeing effluents.

This research uses soybean oil/water dual-phase solvents system (SWDS) to achieve high dye fixation as well as minimal discharge of waste effluents. Reactive dyeings are one of the most serious pollution sources and few dyeing technologies developed could successfully reduce the generation of toxic substances without decreasing dyeing qualities. Through a remarkable increase in chemical potential of dyes in dyeing medium, SWDS remarkably increased the dye concentration in the internal solvent phase. As a result, % exhaustion of dye was 100%, and % fixation of dye was up to 92% in SWDS. Final discharges of dyes and salts from SWDS were decreased by 85% and 100%, respectively, compared to that from the conventional aqueous system. More than 99.5% of initially added biodegradable soybean oil could be recycled for reactive dyeing without treatments. Furthermore, SWDS could be readily applied in jet-dyeing machines on a pilot scale. Via the reuse of soybean oil, SWDS could save up to $0.26 per kg of fabric compared to aqueous dyeings in terms of materials cost.

Natural polysaccharides and proteins-based films for potential food packaging and mulch applications: A review.

Conventional nondegradable packaging and mulch films, after reaching the end of their use, become a major source of waste and are primarily disposed of in landfills. Accumulation of non-degradable film residues in the soil leads to diminished soil fertility, reduced crop yield, and can potentially affect humans. Application of degradable films is still limited due to the high cost, poor mechanical, and gas barrier properties of current biobased synthetic polymers. In this respect, natural polysaccharides and proteins can offer potential solutions. Having versatile functional groups, three-dimensional network structures, biodegradability, ease of processing, and the potential for surface modifications make polysaccharides and proteins excellent candidates for quality films. Besides, their low-cost availability as industrial waste/byproducts makes them cost-effective alternatives. This review paper covers the performance properties, cost assessment, and in-depth analysis of macromolecular structures of some natural polysaccharides and proteins-based films that have great potential for packaging and mulch applications. Proper dissolution of biopolymers to improve molecular interactions and entanglement, and establishment of crosslinkages to form an ordered and cohesive polymeric structure can help to obtain films with good properties. Simple aqueous-based film formulation techniques and utilization of waste/byproducts can stimulate the adoption of affordable biobased films on a large-scale.

High-quality acrylic fibers from waste textiles.

The objective of this work is to develop a closed-loop recycling method specifically tailored for acrylic fibers. Recycling waste acrylic is essential, given the vast volumes of acrylic-containing textiles produced yearly and the strong capability of acrylics to generate toxic microplastics. However, none of the available closed-loop recycling, mechanical recycling, chemical recycling, and direct extrusion technologies work for acrylics. Acrylic fibers are always blended with other textile fibers, making fiber separation via mechanical recycling almost impossible. Polyacrylonitrile, an addition-polymerized thermoplastic material, cannot be depolymerized into its original monomer. Direct extrusion of waste acrylics faces issues of uncontrollable colors on fibers and pollution of spinning lines due to the influence of existing colorants. In our method, acrylic fibers were extracted from waste textiles using a novel approach involving maximized acrylic swelling and dissolution with dimethyl sulfoxide and butanediol. Cationic dyes were effectively removed through cost-effective recycling technology. This work demonstrates that cationic dyes seriously affect the acrylic dissolution, color consistency, and dyeability of regenerated fibers via direct wet extrusion. Such negative impacts of dyes have been eliminated by our cost-effective and closed-loop acrylic recycling technology, which enables the efficient separation of non-acrylic fibers and dyes from acrylic fibers. Our recycling system achieved zero discharges through recycling solvents, dyes, and acrylics. The regenerated acrylic fibers exhibited mechanical properties and dyeability comparable to virgin acrylic fibers. The material and energy costs to produce pure acrylic from waste textiles were only 40 % of those from fossils. This study successfully introduces a closed-loop recycling method for acrylic fibers from waste textiles, addressing key challenges in acrylic fiber recycling. Further research and implementation of this technology are recommended to advance its commercial viability and widespread adoption.

Fine and high-performance protein fibers from meat goat hairs via manipulation of keratin alignment and crosslinkages.

We have converted waste coarse and short hairs of meat goats to high-value, fine, long, and elastic protein fibers via manipulation of keratin alignment and crosslinkages. The shortage of non-petroleum-based fibers has become one of the most prominent concerns. However, few technologies could convert such coarse hairs to fine and flexible fibers for textile uses due to limitations in extensions of fibers, less than 100% of their initial length, and poor flexibility retention of extended fibers, less than 20% of breaking elongation. Limited stretchability and flexibility retention of hair fibers mainly resulted from the difficulty in recovery of crosslinkages in stretched fibers. Here, we used a series of dithiols via multiple cycles of reduction, drawing, and oxidation to produce fine and flexible fibers from coarse and short wool for the first time. Dithiols with long backbones ensured sufficient crosslinkages in proteins after high ratios of drawings. Besides, long crosslinkages brought by dithiols secured sufficient movement between protein molecules and prevented of rupturing chains of protein molecules. As a result, short and coarse hairs of meat goats were turned into long and fine fibers, 350% of their original lengths and 54% of their original diameters, with excellent performance properties, with retentions of 170% of tenacity, and 50% of breaking elongation compared to original hairs. Also, a set of models developed to quantify the effects of extensions of fibers and structures of crosslinkers on the mechanical properties of fibers guides scientists and engineers on property improvement of materials via controlled crosslinkings.

Simultaneous toughness and stiffness of 3D printed nano-reinforced polylactide matrix with complete stereo-complexation via hierarchical crystallinity and reactivity.

A novel strategy adaptive to 3D printing of stereo-complexed polylactide matrix for simultaneous toughness and stiffness was designed. Stereo-complexation is a potent way to enhance both aqueous stability and heat resistance of polylactide, but also aggravates brittleness problem of polylactide. Though poly(butyleneadipate-co-terephthalate) elastomer with epoxidized compatibilizer improved stiffness and toughness of common polylactide, their effectiveness on mechanical and crystallization properties of stereo-complexed polylactide remained unknown. More importantly, incorporation of above techniques into 3D printing kept a fundamental challenge. Both stereo-complexation of polylactide and covalent coupling of polylactide and poly(butyleneadipate-co-terephthalate) by epoxidized compatibilizer are easy to occur when preparing the filaments for printing, impeding the following 3D printing procedure. The hypothesis for this research is that controlled hierarchical crystallization and reaction in three thermal processes could ensure simultaneous toughness and stiffness, and complete stereo-complexation in polylactide matrices. Reinforcing effects of a selected epoxidized compatibilizer, POSS(epoxy)8, on crystallinities, thermal properties, mechanical properties and morphologies were systematically studied. Such a strategy not only removed the obstacles in incorporating stereo-complexation and coupling techniques of polylactide into 3D printing, but also revealed the mechanism to produce high-performance 3D printed polylactide matrix via hierarchical crystallization and reaction.

Hierarchical crystallization strategy adaptive to 3-dimentional printing of polylactide matrix for complete stereo-complexation.

A novel strategy adaptive to 3D printing of PLA matrix for complete stereo-complexation was designed. Stereo-complexation has been demonstrated for its effectiveness in simultaneously improving aqueous stability and heat resistance of PLA. However, current techniques could not be directly incorporated into 3D printing of stereo-complexed PLA since stereo-complexed crystallites are easily formed before printing. High printing temperatures are thus required but decompose PLA materials at the same time. The hypothesis for this research is that controllable hierarchical crystallization in three thermal processes, the filament preparation, 3D printing and post annealing, could ensure feasibility of the strategy and a 100% stereo-complexation level in PLA matrices. Effects of extrusion, ambient and annealing temperatures on material structures were analyzed via WAXD, DSC and DMA. Resistance to hydrolysis and heat of the 3D printed PLA matrix was evaluated under practical conditions. It was showed that homo-crystallites anchored molecular chains of PLA during the post-annealing process for a high retention of tensile properties, while stereo-complexed crystallites provided stronger intermolecular interactions for improved hydrolytic and thermal resistance. This novel strategy via incorporating controlled hierarchical crystallization into 3D printing would enrich the fabrication and exploration of high-performance 3D printed PLA materials.

Transferring feather wastes to ductile keratin filaments towards a sustainable poultry industry.

Technology for the transformation of waste feathers to quality regenerated filaments has been developed. Regardless of superior properties of natural keratin materials, previously developed regenerated materials from keratin had tensile properties much lower than their natural counterparts due to backbone hydrolysis and inefficient reconstruction of disulfide crosslinkages. In this work, tough keratin filaments have been regenerated from white duck feathers via efficient restoration of disulfide crosslinkages using a dithiol reducing agent. Dithiol substantially reserves free thiol groups in the extraction and formed lengthy intermolecular crosslinkages in regenerated keratin filaments. Due to the high degree of intermolecular reconstruction of disulfide bonds and formation of lengthy crosslinkages via dithiol chain-extension, the keratin filaments exhibited considerable improvements in mechanical properties, especially for ductility and water stability. The tenacity and elongation at break were 160.7 MPa and 14%, respectively. The filaments retained about 80% of the tenacity of natural feathers at either dry or wet conditions and demonstrated stretchability 150% higher than natural feathers. The fiber regeneration technology makes it possible to substitute primary fiber sources by renewable poultry feathers. Successful filament substitution or addition can bring more than 88-billion-dollar revenue. The technology not only contributes to a sustainable fiber and poultry industry but adds substantial values to poultry feathers.

Feasibility of industrial-scale treatment of dye wastewater via bio-adsorption technology.

This review emphasizes the importance of costs in industrial-scale treatment of dye wastewater and provides a way to assess the cost-based feasibility of bio-adsorption technologies. Dye wastewater is one of the major contributors to environmental pollution. Bio-adsorption has attracted considerable attentions in dye wastewater treatment due to its technical feasibility, flexibility and operation simplicity. However, industrial-scale treatment of dye wastewater via bio-adsorption technologies remains stagnant, mainly due to high costs. So far, no review or research articles have systematically discussed the criteria for successful utilization of bio-adsorption technologies on a large scale. This review discusses the major factors affecting adsorption and desorption performance based on basic chemical and physical structures of bio-adsorbents available in literatures. A quantitative relationship has been summarized based on previous studies to assess the cost to utilize a bio-adsorption technology and serve as an access threshold for quality bio-adsorbents to be taken into real applications.

Quantitation of fast hydrolysis of cellulose catalyzed by its substituents for potential biomass conversion.

This paper investigates the accelerated acidic hydrolysis of cellulose by its substituents for potential biomass conversion. Insufficient pretreatments and slow cellulose hydrolysis are major obstacles that impede efficient hydrolysis of cellulose. Substituted cellulose, such as dyed cotton, has large availability. It is susceptible to acidic hydrolysis and can be used for biomass conversion without any pretreatments. To understand the mechanism of accelerated hydrolysis of cellulose by its substituents is a prerequisite for cellulosic biomass conversion with high efficiency. Substituents with different charge properties were synthesized and their interactions with oxocarbenium ions were studied based on Density Functional Theory. Results indicate that hydrolysis rate is affected by field effect from substituents. Such field effect is dominated by amounts of negative charges on substituents and distance between negatively charged groups and oxocarbenium. Hydrolysis rate of dye-substituted cotton is higher than or comparable to that applied with other catalytic approaches.

Poly(l-lactic acid) bio-composites reinforced by oligo(d-lactic acid) grafted chitosan for simultaneously improved ductility, strength and modulus.

PLA bio-composites reinforced by oligo(d-lactic acid) grafted chitosan has been developed for simultaneously improved ductility, strength and modulus. Brittleness problem greatly limits the applications of PLA, a polymer derived from corn. Various methods have been developed to solve the brittleness problem. Unfortunately, these methods have their limitations, such as sacrifice of strength and modulus of PLA, use of toxic chemicals and high costs. Bio-based elastomers such as chitosan also have poor compatibility with PLA, leading to poor mechanical properties. The hypothesis for this research is that CS-g-oligo(D-LA) particles with good ductility could form strong interfacial interactions with PLLA matrix. Reinforcing effect of CS-g-oligo(D-LA) particles on PLLA matrix was systematically studied. Compatibility and intermolecular interactions between CS-g-oligo(D-LA) particles and PLLA matrix were studied by SEM, DSC and 13C NMR analyses. The reinforcing mechanism was summarized. Due to effective transfer of stress from PLLA matrix to the strong but ductile skeletons of CS-g-oligo(D-LA), ductility, strength and modulus of PLLA bio-composites were substantially improved. This novel reinforcing strategy via formation of strong interactions between enantiomeric lactyl units would enrich the fabrication and exploration of high-performance PLA-based bio-composites.

Green and Sustainable Technology for High-Efficiency and Low-Damage Manipulation of Densely Crosslinked Proteins.

A two-step technology using nontoxic and eco-friendly chemicals is developed for the durable setting of densely/highly crosslinked proteins, such as wool and hair. Currently, most technologies for morphological modification are effective only for materials from non-highly-crosslinked proteins and cellulose. Before their morphological change, only water is needed to interrupt hydrogen bonds and ionic linkages, which stabilize the relative positions of molecules in non-highly-crosslinked proteins and cellulose. However, highly crosslinked proteins contain disulfide crosslinks, which are insusceptible to water. Thus, the controlled cleavage of disulfide bonds is required for creating new morphologies of highly crosslinked protein materials, such as hair and wool. Herein, cysteine and citric acid (CA) were used for the two-step setting of highly crosslinked proteins. This recipe showed better morphological change and less mechanical loss than commercial hair styling products. A reaction between CA and keratin was proposed, and verified via NMR and Raman spectra and titration. This technology could be a prospective alternative to achieve durable hair setting, anticrease finishing of wool textiles, and other durable morphological changes needed for highly crosslinked proteins.

Accelerated hydrolysis of substituted cellulose for potential biofuel production: kinetic study and modeling.

In this work, kinetics of substitution accelerated cellulose hydrolysis with multiple reaction stages was investigated to lay foundation for mechanism study and molecular design of substituting compounds. High-efficiency hydrolysis of cellulose is critical for cellulose-based bioethanol production. It is known that, substitution could substantially decrease activation energy and increase reaction rate of acidic hydrolysis of glycosidic bonds in cellulose. However, reaction kinetics and mechanism of the accelerated hydrolysis were not fully revealed. In this research, it was proved that substitution therefore accelerated hydrolysis only occurred in amorphous regions of cellulose fibers, and was a process with multiple reaction stages. With molar ratio of substitution less than 1%, the overall hydrolysis rate could be increased for around 10 times. We also quantified the relationship between the hydrolysis rate of individual reaction stage and its major influences, including molar ratio of substitution, activation energy of acidic hydrolysis, pH and temperature.