Tailoring Electrical Properties in Carbon Nanomaterial Patterns with Multimaterial Aerosol Jet Printing.

Multimaterial aerosol jet printing offers a unique capability to freely mix inks with different chemical compositions in the aerosol phase, enabling one-step digital fabrication with tailored compositions or functionally graded structures, including in the x-y plane. Here, in situ mixing of two carbon nanomaterial inks with distinct electrical properties is demonstrated. By tailoring the mixing ratio of the constituent inks, electrical conductivity is modulated by 130×, and sheet resistance values for a single pass span approximately 2 orders of magnitude. The ability to manufacture components with tailored electrical properties offers significant value for hybrid and flexible electronic device applications, such as microelectronics packaging. Moreover, grading properties within a part provides a new dimension of design freedom for complex assemblies.

Co-conversion of wood and polyvinyl chloride to valuable chemicals and high-quality solid fuel.

Polyvinyl chloride (PVC)-containing waste streams are difficult to recycle due to high chlorine content in PVC. Toxic dioxins or corrosive hydrogen chloride (HCl) vapor released from improper management of PVC-containing wastes can cause severe environmental pollution and human health problems. While PVC is usually treated as contamination and burden in waste recycling, a novel recycling approach was developed in this study to leverage PVC as an asset. Specifically, red oak and PVC were co-converted in γ-Valerolactone, a green biomass-derivable solvent. During the co-conversion, PVC-derived HCl in the solvent acted as an acid catalyst to produce up to 14.4% levoglucosenone and 14.3% furfural from red oak. On the other hand, dechlorinated PVC hydrocarbons and lignin fraction of red oak reacted each other to form chlorine-free solid fuels with high thermal stability. The higher heating value of the solids was up to 36.2 MJ/kg, which is even higher than the heating value of anthracite coal. After the co-conversion, more than 80% of PVC-contained chlorine turned into chloride ion and the rest formed 5-chlorovaleric acid. 5-chlorovaleric acid crystals were further recovered from the post-reaction liquid with a purity of 91.2%.

Towards producing high-quality lignin-based carbon fibers: A review of crucial factors affecting lignin properties and conversion techniques.

The production of low-cost and high-quality carbon fibers (CFs) from biorenewable lignin precursors has been of worldwide interest for decades. Although numerous works have been reported and the proposed "1.72 GPa/172 GPa" target set by the Department of Energy (DOE) has been closely met in a few studies, most lignin-based CFs (LCFs) have poor strength properties compared to industrial PAN (polyacrylonitrile)-based CFs. The production of LCFs involves several steps, and the final quality of LCFs is governed by both lignin's properties and the manufacturing processes. Therefore, understanding the key factors of producing high quality LCF is of high importance. In this review, we firstly outlined several lignin's properties (e.g., impurities, thermal properties, molecular structure) that may play important role in determining its processability and suitability as carbon fiber precursor. Secondly, conversion strategies include spinning, stabilization and carbonization, and corresponding parameters influencing the final quality of LCF are comprehensively analyzed. Last, additional characterization methods are proposed as a means to facilitate analyzing of lignin and LCF. This review attempts to provide insights towards high-quality LCF production from both material and manufacturing aspects.

Upcycling polyamide containing post-consumer Tetra Pak carton packaging to valuable chemicals and recyclable polymer.

Billion tons of post-consumer Tetra Pak cartons are discarded annually as land and ocean wastes, creating significant environmental problems and resource losses. Recycling of the carton wastes is hindered by its multi-material compositions and low values of the recycled products. In this study, a novel upcycling of the cartons was investigated. A post-consumer carton consisting of paper, polyolefin, and polyamide was directly converted in 210-230 °C tetrahydrofuran containing 10-20 mM acid to produce up to 19.2% of levoglucosenone and 8.6% of furfural by selectively decomposing paper fraction. The remaining solids containing mostly intact polyethylene and polyamide but also a smaller fraction of paper-derived char were separated using a solvent-dissolution method. The xylene-soluble fraction was a recycled polymer similar to the original polyethylene, which was verified by its functional groups, the composition of the pyrolysis products, and the melt rheology results. The xylene-insoluble fraction was a mixture of polyamide and paper-derived char. Upon pyrolysis, caprolactam was produced as the only major vapor product. The remaining, thermally stable paper-derived char could be used as a high-quality solid fuel. Overall, the demonstrated recycling method could potentially maximize the values of the products recovered from carton wastes.

Tunable Wettability of Biodegradable Multilayer Sandwich-Structured Electrospun Nanofibrous Membranes.

This research aims to develop multilayer sandwich-structured electrospun nanofiber (ENF) membranes using biodegradable polymers. Hydrophilic regenerated cellulose (RC) and hydrophobic poly (lactic acid) (PLA)-based novel multilayer sandwich-structures were created by electrospinning on various copper collectors, including copper foil and 30-mesh copper gauzes, to modify the surface roughness for tunable wettability. Different collectors yielded various sizes and morphologies of the fabricated ENFs with different levels of surface roughness. Bead-free thicker fibers were collected on foil collectors. The surface roughness of the fine fibers collected on mesh collectors contributed to an increase in hydrophobicity. An RC-based triple-layered structure showed a contact angle of 48.2°, which is comparable to the contact angle of the single-layer cellulosic fabrics (47.0°). The polar shift of RC membranes on the wetting envelope is indicative of the possibility of tuning the wetting behavior by creating multilayer structures. Wettability can be tuned by creating multilayer sandwich structures consisting of RC and PLA. This study provides an important insight into the manipulation of the wetting behavior of polymeric ENFs in multilayer structures for applications including chemical protective clothing.

One-pot selective conversion of lignocellulosic biomass into furfural and co-products using aqueous choline chloride/methyl isobutyl ketone biphasic solvent system.

This study investigated simultaneous lignocellulose fractionation and conversion in a one-pot reaction using an aqueous choline chloride/methyl isobutyl ketone (ChCl/MIBK) biphasic solvent system. Under the optimized condition (170 °C, 60 min, 0.6 wt% H2SO4, 10.7 wt% solid loading), the biphasic solvent solubilized 96% xylan in raw switchgrass, which was simultaneously converted to furfural with a yield of 84.04%. The biphasic solvent was also able to selectively extract lignin, which had a high purity (93.1%), and uncondensed moieties (i.e., Hibbert's ketone), as well as decreased molecular weight and polydispersity index. The resultant pulp was enriched with cellulose (73.3%), which can be completely hydrolyzed into glucose within 48 h via enzymatic hydrolysis. Aqueous ChCl was successfully recycled and reused for atleast three cycles with similar performance in switchgrass fractionation. This study demonstrated that aqueous ChCl/MIBK biphasic system was an effective solvent system for co-production of furfural, high quality technical lignin and digestible cellulose for further upgrading.

Production of biofuel precursor chemicals from the mixture of cellulose and polyvinylchloride in polar aprotic solvent.

Polyvinylchloride (PVC) is the major halogen source in municipal solid waste (MSW) and its recycling is problematic. PVC can not only cause various environmental problems by releasing halogens, but also negatively impact other MSW compositions during waste to energy conversion. For instance, co-pyrolysis of biomass with PVC increases solid residue and promotes the formation of CO and CO2 from cellulose. Herein, we report an approach to dehydrochlorinate PVC while simultaneously enhancing the production of valuable chemicals from cellulose. Specifically, cellulose and PVC were co-converted in tetrahydrofuran (THF). It was found that co-conversion of cellulose with PVC significantly increased liquid yield from cellulose and shortened the conversion time compared to converting cellulose alone. Levoglucosan was the major product from cellulose and its highest yield of 40% was achieved with 2.5 wt% of PVC at 335 °C after only 8 min of reaction. We have shown that the in-situ generated HCl derived from PVC decomposition serves as acid catalyst to enhance glycosidic bond cleavage in cellulose. Moreover, using a THF/water co-solvent could further enhance the conversion rate and increased liquid yield to a maximum of 92.55%. Pyrolysis of the solid residue did not release chlorinated organics, suggesting that PVC was fully dechlorinated in THF. The present study may be applied to convert PVC-containing, cellulose rich MSW for higher valued products in environmentally friendly approach.

Quantitative investigation of free radicals in bio-oil and their potential role in condensed-phase polymerization.

We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20)  spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable.

Pyrolytic sugars from cellulosic biomass.

Depolymerization of cellulose offers the prospect of inexpensive sugars from biomass. Breaking the glycosidic bonds of cellulose to liberate glucose has usually been pursued by acid or enzymatic hydrolysis although a purely thermal depolymerization route to sugars is also possible. Fast pyrolysis of pure cellulose yields primarily the anhydrosugar levoglucosan (LG) whereas the presence of naturally occurring alkali and alkaline earth metals (AAEMs) in biomass strongly catalyzes ring-breaking reactions that favor formation of light oxygenates. Here, we show a method of significantly increasing the yield of sugars from biomass by purely thermal means through infusion of certain mineral acids (phosphoric and sulfuric acid) into the biomass to convert the AAEMs into thermally stable salts (particularly potassium sulfates and phosphates). These salts not only passivate AAEMs that normally catalyze fragmentation of pyranose rings, but also buffer the system at pH levels that favor glycosidic bond breakage. It appears that AAEM passivation contributes to 80 % of the enhancement in LG yield while the buffering effect of the acid salts contributes to the balance of the enhancement.