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.

Chitosan/gallnut tannins composite fiber with improved tensile, antibacterial and fluorescence properties.

Natural extracts gallnut tannins (GTs) were used as functional components to prepare chitosan/gallnut tannins (CS/GTs) composite fiber by blended solution spinning. Chitosan fiber has great potential to be used as absorbent suture and dressing due to its good biocompatibility. However, the weak mechanical properties limited its application. Chitosan and GTs were blended in aqueous solution of acetic acid to spin the composite fiber. The results indicated that CS/GTs fiber can be easily prepared due to the appropriate rheology characteristics for blended solution. Compared with pure chitosan fiber, CS/GTs fiber with 10% GTs showed lower hydrophilicity and higher dry, wet breaking strength by more than 40% due to ionic cross-linking between chitosan and GTs. The bacterial reduction to Staphylococcus aureus increased from 49.0 to 99.7% and about double green and red fluorescent intensity were observed for CS/GTs fiber. GTs have great potentiality in improving the properties of chitosan fiber.

Hybrid Nanocomposites of Cellulose/Carbon-Nanotubes/Polyurethane with Rapidly Water Sensitive Shape Memory Effect and Strain Sensing Performance.

In this work, a fast water-responsive shape memory hybrid polymer based on thermoplastic polyurethane (TPU) was prepared by crosslinking with hydroxyethyl cotton cellulose nanofibers (CNF-C) and multi-walled carbon nanotubes (CNTs). The effect of CNTs content on the electrical conductivity of TPU/CNF-C/CNTs nanocomposite was investigated for the feasibility of being a strain sensor. In order to know its durability, the mechanical and water-responsive shape memory effects were studied comprehensively. The results indicated good mechanical properties and sensing performance for the TPU matrix fully crosslinked with CNF-C and CNTs. The water-induced shape fixity ratio (Rf) and shape recovery ratio (Rr) were 49.65% and 76.64%, respectively, indicating that the deformed composite was able to recover its original shape under a stimulus. The TPU/CNF-C/CNTs samples under their fixed and recovered shapes were tested to investigate their sensing properties, such as periodicity, frequency, and repeatability of the sensor spline under different loadings. Results indicated that the hybrid composite can sense large strains accurately for more than 103 times and water-induced shape recovery can to some extent maintain the sensing accuracy after material fatigue. With such good properties, we envisage that this kind of composite may play a significant role in developing new generations of water-responsive sensors or actuators.

Degradation and regeneration of feather keratin in NMMO solution.

Chicken feather, a potential source of keratin, is often disposed as waste material. Although some methods, i.e., hydrolysis, reduction, and oxidation, have been developed to isolate keratin for composites, it has been limited due to the rising environmental concerns. In this work, a green solvent N-methylmorpholine N-oxide (NMMO) was used to extract keratin from chicken feather waste. Eighty-nine percent of keratin was extracted using 75% NMMO solution. However, the result from size exclusion HPLC showed that most of the keratin degraded into polypeptide with molecular weight of 2189 and only 25.3% regenerated keratin was obtained with molecular weight of 14,485. Analysis of amino acid composition showed a severe damage to the disulfide bonds in keratin during the extraction procedure. Oxidization had an important effect on the reconstitution of the disulfide bonds, which formed a stable three-dimensional net structure in the regenerated keratins. Besides, Raman spectra, NMR, FT-IR, XRD, and TGA were used to characterize the properties of regenerated keratin and raw chicken feather. In the end, a possible mechanism was proposed based on the results.

Biodegradable sizing agents from soy protein via controlled hydrolysis and dis-entanglement for remediation of textile effluents.

Fully biodegradable textile sizes with satisfactory performance properties were developed from soy protein with controlled hydrolysis and dis-entanglement to tackle the intractable environmental issues associated with the non-biodegradable polyvinyl alcohol (PVA) in textile effluents. PVA derived from petroleum is the primary sizing agent due to its excellent sizing performance on polyester-containing yarns, especially in increasingly prevailing high-speed weaving. However, due to the poor biodegradability, PVA causes serious environmental pollution, and thus, should be substituted with more environmentally friendly polymers. Soy protein treated with high amount of triethanolamine was found with acceptable sizing properties. However, triethanolamine is also non-biodegradable and originated from petroleum, therefore, is not an ideal additive. In this research, soy sizes were developed from soy protein treated with glycerol, the biodegradable triol that could also be obtained from soy. The soy sizes had good film properties, adhesion to polyester and abrasion resistance close to PVA, rendering them qualified for sizing applications. Regarding desizing, consumption of water and energy for removal of soy size could be remarkably decreased, comparing to removal of PVA. Moreover, with satisfactory degradability, the wastewater containing soy sizes was readily dischargeable after treated in activated sludge for two days. In summary, the fully biodegradable soy sizes had potential to substitute PVA for sustainable textile processing.

Pure keratin membrane and fibers from chicken feather.

In this research, keratin was extracted from the disposable chicken feather using l-cysteine as reducing agent. Then, it was re-dissolved in the sodium carbonate-sodium bicarbonate buffer, and the pure keratin membrane and fiber were fabricated by doctor-blade casting process and wet spinning method, respectively. Scanning electron microscopy (SEM), fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were used to characterize the chemical and physical properties of resulting powder, membrane and fiber. Compared with the raw chicken feather, the regenerated keratin materials retain its chemical structure and thermal stability, their relative crystallinity is a little different depend on the shaping method, which leads to the difference in moisture regain. The mechanical results show that tensile strength of the keratin membrane researches 3.5MPa, have potential application in biomedical fields. However, the keratin fiber presents low tenacity, i.e. 0.5cN/dtex, this problem should be solved in order to apply the new fiber in textile and material science.

Effects of monomers and homopolymer contents on the dry and wet tensile properties of starch films grafted with various methacrylates.

Starch grafted with four different methacrylates was compression molded to form thermoplastic films with good strength and water stability. Starch is an inexpensive and biodegradable polymer but is nonthermoplastic and needs to be chemically modified to make starch suitable for various applications. In this research, starch was grafted with four methacrylates (methyl, ethyl, butyl, and hexyl), and the effect of the length of the alkyl ester group on grafting parameters, thermoplasticity, and properties of thermoplastic films developed have been studied. Influence of grafting conditions on % grafting efficiency, % homopolymers, and % monomer conversion were studied, and the grafted starch was characterized using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and nuclear magnetic resonance ((1)H NMR). At similar grafting ratios, butyl methacrylate (BMA) provided better strength and elongation to the starch films than the other three methacrylates. Grafting of methacrylates appears to be an economical approach to develop thermoplastic products from starch.

Development and characterization of thermoplastic films from sorghum distillers dried grains grafted with various methacrylates.

Distillers Dried Grains (DDG) obtained during production of ethanol from grain sorghum were grafted with methacrylates and compression molded into films with good dry and wet tensile properties. Since sorghum DDG contains up to 45% proteins that are indigestible by animals, it is necessary to find alternative applications to make sorghum ethanol economically competitive. In this research, sorghum DDG was grafted with methyl, ethyl, and butyl methacrylates, the grafted DDG was compression molded into films, and the properties of the grafted DDG and films were studied. At a grafting ratio of 40%, butyl methacrylate (BMA) grafted films had a strength of 4.8 MPa and elongation of 1.8% when dry and 3.1 MPa and 8.1% when wet, indicating that the films had good strength and wet stability. Films developed from grafted DDG show the potential to overcome the brittleness and poor water stability of biopolymer-based films and be useful for various applications.

Bio-thermoplastics from grafted chicken feathers for potential biomedical applications.

This research demonstrated the feasibility of using bio-thermoplastics developed from chicken feathers grafted with acrylates and methacrylates as scaffolds for tissue engineering. Keratin, the major protein in feathers, is a highly crosslinked biopolymer that has been reported to be biocompatible. However, it is difficult to break the disulfide bonds and make keratin soluble to develop materials for tissue engineering and other medical applications. Previously, keratin extracted from feathers using alkaline hydrolysis has been made into scaffolds but with poor water stability and mechanical properties. In this study, thermoplastic films were compression molded from chicken feathers grafted with 6 different acrylate monomers. The influence of the concentration and structures of grafted monomers on grafting parameters and the tensile strength, water stability and cytocompatibility of grafted feathers compression molded into films were investigated. It was found that the grafted feather films were water stable and had good strength and better supported cell growth than poly(lactic acid) films. Grafted feathers demonstrated the potential to be used for fabrication of biomaterials for various biomedical applications.