Harmonized Life-Cycle Inventories of Nanocellulose and Its Application in Composites.

Cellulose nanocrystals (CNC) and nanofibers (CNF) have been broadly studied as renewable nanomaterials for various applications, including additives in cement and plastics composites. Herein, life cycle inventories for 18 previously examined processes are harmonized, and the impacts of CNC and CNF production are compared with a particular focus on GHG emissions. Findings show wide variations in GHG emissions between process designs, from 1.8-1100 kg CO2-eq/kg nanocellulose. Mechanical and enzymatic processes are identified as the lowest GHG emission methods to produce CNCs and CNFs. For most processes, energy consumption and chemical use are the primary sources of emissions. However, on a mass basis, for all examined production methods and impact categories (except CO emissions), CNC and CNF production emissions are higher than Portland cement and, in most cases, are higher than polylactic acid. This work highlights the need to carefully consider process design to prevent potential high emissions from CNCs and CNF production despite their renewable feedstock, and results show the magnitude of conventional material that must be offset through improved performance for these materials to be environmentally favorable.

Rheology of 3D printable ceramic suspensions: effects of non-adsorbing polymer on discontinuous shear thickening.

Concentrated suspensions of particles at volume fractions (ϕ) ≥ 0.5 often exhibit complex rheological behavior, transitioning from shear thinning to shear thickening as the shear stress or shear rate is increased. These suspensions can be extruded to form 3D structures, with non-adsorbing polymers often added as rheology modifiers to improve printability. Understanding how non-adsorbing polymers affect the suspension rheology, particularly the onset of shear thickening, is critical to the design of particle inks that will extrude uniformly. In this work, we examine the rheology of concentrated aqueous suspensions of colloidal alumina particles and the effects of adding non-adsorbing polyvinylpyrrolidone (PVP). First, we show that suspensions with ϕalumina = 0.560-0.575 exhibited discontinuous shear thickening (DST), where the viscosity increased by up to two orders of magnitude above an onset stress (τmin). Increasing ϕalumina from 0.550 to 0.575 increased the viscosity and yield stress in the shear thinning regime and decreased τmin. Next, PVP was added at concentrations within the dilute and semi-dilute non-entangled regimes of polymer conformation (ϕPVP = 0.005-0.050) to suspensions with constant ϕalumina = 0.550. DST was observed in all cases and increasing ϕPVP increased the viscosity and yield stress. Interestingly, increasing ϕPVP also increased τmin. We posit that the free PVP chains act as lubricants between alumina particles, increasing the stress needed to induce thickening. Finally, we demonstrate through direct comparisons of suspensions with and without PVP how non-adsorbing polymer addition can extend the extrusion processing window due to the increase in τmin.

Performance of Advanced Waterborne Wood Coatings Reinforced with Cellulose Nanocrystals.

The main objective of this study was to examine the impact of cellulose nanocrystals (CNCs) in advanced waterborne wood coatings such as polycarbonate urethane (PCU) and hybrid alkyd varnish (HAV) in terms of coating performance, mechanical properties, optical properties, and water permeation and uptake properties. The influence of CNCs on the overall quality of the various waterborne wood coatings was investigated by incorporating different percentages of CNCs. Varying CNC content in coating formulations showed that CNCs are effective for waterborne wood coatings; CNCs offer both higher scratch and impact resistance as compared to neat coatings and have a significant reduction in water vapor permeation through a film with little increase in water vapor uptake at high concentrations. It was observed that the CNC darkened and reduced gloss in the coatings and viscosified the dispersion. These research findings suggest that CNCs are well-dispersed at lower concentrations, but at high concentrations, agglomeration occurred. Thus, while CNCs can give better mechanical and permeation performances at contents of up to 5 wt %, at 1 wt % CNCs can still provide modest scratch and chip resistance improvement without loss of optical properties (gloss and color) while retaining a similar water uptake. Overall, it can be concluded that CNCs have the potential to be used as a reinforcement filler in high-performance waterborne wood coatings.

Phone Camera Nano-Biosensor Using Mighty Sensitive Transparent Reusable Upconversion Paper.

Lycopene, a natural colorant and antioxidant with a huge growing market, is highly susceptible to photo/thermal degradation, which demands real-time sensors. Hence, here a transparent upconversion nanoparticles (UCNPs) strip having 30 mol % Yb, 0.1 mol % Tm, and ß-NaYF4 UCNPs, which shows an intense emission at 475 nm, has been developed. This strip has been found to be sensitive to lycopene with a detection limit as low as 10 nM using a smartphone camera, which is due to static quenching that is confirmed by the lifetime study. In comparison to previous paper strips, here the transparent strip has minimal scattering with maximum sensitivity in spite of not using any metal quenchers. An increase in strip hydrophobicity during the fabrication process complements the strip to selectively permeate and present an extraction-free substitute analysis for chromatography. Hydrophobicity endows the strip with the capability to reuse the strip with ∼100% luminescence recovery.

Structure-Property Relationship of Cellulose Nanocrystal-Polyvinyl Alcohol Thin Films for High Barrier Coating Applications.

CO2 and O2 gas permeability are paramount concerns in food packaging. Here, the permeability of cellulose nanocrystals (CNCs) and polyvinyl alcohol (PVA) coatings was explored as it relates to varied CNC content. Specifically, this work focuses on the role of PVA in rheology and barrier performance of the CNC films. Results show that shear-casted CNC films are transparent and have a high-order parameter, which is attributed to the shear-thinning behavior of the CNCs. The barrier performance of the CNC films improved because of the synergistic effect of having both alignment of CNCs and a lower free volume. The CNC-PVA films exhibited excellent barrier performance as compared to traditional engineered polymers, even much higher than high barrier ethylene-vinyl alcohol copolymer films. Furthermore, the moisture sensitivity of the films was greatly diminished with the addition of PVA. Overall, the results show applicability of CNC-PVA coating formulations for high barrier packaging applications.

Influence of alignment and microstructure features on the mechanical properties and failure mechanisms of cellulose nanocrystals (CNC) films.

The mechanical properties of cellulose nanocrystal (CNC) films critically depend on many microstructural parameters such as fiber length distribution (FLD), fiber orientation distribution (FOD), and the strength of the interactions between the fibers. In this paper, we use our coarse-grained molecular model of CNC to study the effect of length and orientation distribution and attractions between CNCs on the mechanical properties of neat CNCs. The effect of misalignment of a 2D staggered structure of CNC with respect to the loading direction was studied with simulations and analytical solutions and then verified with experiments. To understand the effect of FLD and FOD on the mechanical performance, various 3D microstructures representing different case studies such as highly aligned, randomly distributed, short length CNCs and long length CNCs were generated and simulated. According to the misalignment study, three different failure modes: sliding mode, mixed mode, and normal mode were defined. Also, comparing the effects of FOD, FLD, and CNC interaction strength, shows that the adhesion strength is the only parameter that can significantly improve the mechanical properties, regardless of loading direction or FOD of CNCs.

Alignment of Cellulose Nanofibers: Harnessing Nanoscale Properties to Macroscale Benefits.

In nature, cellulose nanofibers form hierarchical structures across multiple length scales to achieve high-performance properties and different functionalities. Cellulose nanofibers, which are separated from plants or synthesized biologically, are being extensively investigated and processed into different materials owing to their good properties. The alignment of cellulose nanofibers is reported to significantly influence the performance of cellulose nanofiber-based materials. The alignment of cellulose nanofibers can bridge the nanoscale and macroscale, bringing enhanced nanoscale properties to high-performance macroscale materials. However, compared with extensive reviews on the alignment of cellulose nanocrystals, reviews focusing on cellulose nanofibers are seldom reported, possibly because of the challenge of aligning cellulose nanofibers. In this review, the alignment of cellulose nanofibers, including cellulose nanofibrils and bacterial cellulose, is extensively discussed from different aspects of the driving force, evaluation, strategies, properties, and applications. Future perspectives on challenges and opportunities in cellulose nanofiber alignment are also briefly highlighted.

Resin-based dental materials containing 3-aminopropyltriethoxysilane modified halloysite-clay nanotubes for extended drug delivery.

OBJECTIVE: To synthesize and characterize a novel resin-based dental material containing 3-aminopropyltriethoxysilane (APTES) surface-modified halloysite-clay nanotubes (HNTs) for long-term delivery of guest molecules. METHODS: The optimal concentrations of HNT (10, 15, 20 wt.%) and silane (0, 2, 4 vol.%sil) to be incorporated into the resin-based materials were determined (15 wt.%HNT, 4 vol.%sil) after assessment of the mechanical properties (DC%, degree of conversion; FS, flexural strength; FM, flexural modulus; and UTS, ultimate tensile strength). The HNTsil-powder was loaded with chlorhexidine (CHX) to evaluate the effect of the silanization on drug release. Resin-discs were prepared for the following groups: RES (resin), HNT (resin+15 wt.%HNT), HNTsil (resin+15 wt.%HNT silanized), HNT-CHX (resin+15 wt.%HNT loaded with chlorhexidine), HNTsil-CHX (resin+15 wt.%HNTsil-CHX), and 0.2 vol.%CHX (resin+0.2 vol.%CHX solution). Specimens were stored in water for 1, 3, 5, 10, and 15 days at 37 °C. Aliquots from each time point and the final 15-day specimens were evaluated for the zone of inhibition (ZOI) against Streptococcus mutans. CHX release was analyzed using spectrophotometry at absorbance of 300 nm. Data were statistically analyzed (α = 0.05). RESULTS: All materials presented similar DC%. Reduced FS but increased FM was detected for 20 wt.%HNT-4%APTES. Groups with 15 wt.% and 20 wt.%HNT with/without APTES presented higher values of UTS. Agar diffusion data indicates that the HNTsil-CHX had a greater ZOI than all other groups over 15 days. HNTsil-CHX had the highest absorbance for day 1 but presented similar values to other groups every time point after. SIGNIFICANCE: Silanization of nanotubes followed by encapsulation of chlorhexidine is a promising technique for long-term delivery of guest molecules.

Recent Developments in Cellulose Nanomaterial Composites.

Cellulose nanomaterials (CNMs) are a class of materials that have recently garnered attention in fields as varied as structural materials, biomaterials, rheology modifiers, construction, paper enhancement, and others. As the principal structural reinforcement of biomass giving wood its mechanical properties, CNM is strong and stiff, but also nontoxic, biodegradable, and sustainable with a very large (Gton yr-1 ) source. Unfortunately, due to the relatively young nature of the field and inherent incompatibility of CNM with most man-made materials in use today, research has tended to be more basic-science oriented rather than commercially applicable, so there are few CNM-enabled products on the market today. Herein, efforts are presented for preparing and forming cellulose nanomaterial nanocomposites. The focus is on recent efforts attempting to mitigate common impediments to practical commercialization but is also placed in context with traditional efforts. The work is presented in terms of the progress made, and still to be made, on solving the most pressing challenges-getting properties that are competitive with currently used materials, removing organic solvent, solving the inherent incompatibility between CNM and polymers of interest, and incorporation into commonly used industrial processing techniques.

An emerging mobile air pollution source: outdoor plastic liner manufacturing sites discharge VOCs into urban and rural areas.

The in situ manufacture of cured-in-place-pipe (CIPP) plastic liners in damaged sewer pipes is an emerging mobile source of anthropogenic air pollution. Evidence indicates volatile organic compounds (VOCs) can be released before, during, and after manufacture. The chemical composition of a popular uncured styrene-based CIPP resin was examined, along with the VOCs that remained in the new cured composite. The roles of curing temperature and heating time in waste discharged into the air were examined. Uncured resin contained approximately 39 wt% VOCs. Multiple hazardous air pollutants were present, however, 61 wt% of the uncured resin was not chemically identified. A substantial mass of VOCs (8.87 wt%) was emitted into the air during manufacture, and all cured composites contained about 3 wt% VOCs. Some VOCs were created during manufacture. Curing temperature (65.5-93.3 °C) and heating time (25-100 min) did not cause different composite VOC loadings. High styrene air concentrations inhibited the detection of other VOCs in air. It is estimated that tens of tons of VOCs may be emitted at a single CIPP manufacturing site. Regulators should consider monitoring, and potentially regulating, these growing mobile air pollution and volatile chemical product sources as they are operating in urban and rural areas often in close proximity to residential and commercial buildings.

Influence of Free Volume Determined by Positron Annihilation Lifetime Spectroscopy (PALS) on Gas Permeability of Cellulose Nanocrystal Films.

Cellulose nanocrystals (CNCs) are of increasing interest for packaging applications because of their biodegradability, low cost, high crystallinity, and high aspect ratio. The objective of this study was to use positron annihilation lifetime spectroscopy (PALS) to investigate the free volume of CNC films with different structural arrangements (chiral nematic vs shear-oriented CNC films) and relate this information to gas barrier performance. It was found that sheared CNC films with higher CNC alignment have lower free volume and hence have more tortuosity than chiral nematic self-assembled films, which lowers gas diffusion throughout the films. The overall barrier performance of the aligned CNC film obtained in this study has a higher barrier performance than high barrier polymer films like PVOH and EVOH. Furthermore, a modified model was developed for single-component CNC films to predict the gas permeability with variation of CNC alignment with validation by the data taken.

Multifunctional Bio-Nanocomposite Coatings for Perishable Fruits.

Hunger and chronic undernourishment impact over 800 million people, which translates to ≈10.7% of the world's population. While countries are increasingly making efforts to reduce poverty and hunger by pursuing sustainable energy and agricultural practices, a third of the food produced around the globe still is wasted and never consumed. Reducing food shortages is vital in this effort and is often addressed by the development of genetically modified produce or chemical additives and inedible coatings, which create additional health and environmental concerns. Herein, a multifunctional bio-nanocomposite comprised largely of egg-derived polymers and cellulose nanomaterials as a conformal coating onto fresh produce that slows down food decay by retarding ripening, dehydration, and microbial invasion is reported. The coating is edible, washable, and made from readily available inexpensive or waste materials, which makes it a promising economic alternative to commercially available fruit coatings and a solution to combat food wastage that is rampant in the world.

High shear capillary rheometry of cellulose nanocrystals for industrially relevant processing.

A microcapillary rheometer was employed to study the rheological characteristics of CNCs at temperatures between 15 °C and 50 °C and aqueous concentrations between 1.5 wt% and 12.1 wt%, at rates up to 8 × 105 s-1. Time-temperature and time-concentration superposition were applied to analyze the data. A master curve of shear rate sweeps at temperatures between 15 °C and 50 °C was successfully generated to a reference temperature of 25 °C with the shift factor plot suggesting an Arrhenius relationship over the entire measured temperature range. Concentration-dependent data indicate a high shear Newtonian plateau at the limit of low concentration. Repeated testing of the same sample volume was implemented to represent extended times at elevated stress, with repeated experiments leading to a permanent decrease in viscosity. Atomic force microscopy (AFM) suggests sensitivity of the CNC geometry to moderate stress in a flow field.

Considerations for emission monitoring and liner analysis of thermally manufactured sewer cured-in-place-pipes (CIPP).

Cured-in-place-pipes (CIPP) are plastic liners chemically manufactured inside existing damaged sewer pipes. They are gaining popularity in North America, Africa, Asia, Europe, and Oceania. Volatile and semi-volatile organic compound (VOC/SVOC) emissions from storm sewer CIPP installations were investigated at a dedicated outdoor research site. Tedlar bag, sorbent tube, and photoionization detector (PID) air sampling was conducted for five steam-CIPP installations and was coupled with composite characterizations. New CIPPs contained up to 2.21 wt% volatile material and only 6-31% chemical mass extracted per CIPP was identified. Each 6.1 m [20 ft] liner contained an estimated 5-10 kg [11-22 lbs] of residual chemical. Extracted chemicals included hazardous air pollutants and suspected and known carcinogens that were not reported by others. These included monomers, monomer oxidation products, antioxidants, initiator degradation products, and a plasticizer. PID signals did not accurately represent styrene air concentration differing sometimes by 10s- to 1000s-fold. Multiple VOCs found in air samples likely affected PID responses. Styrene (>86.4 ppmv) and methylene chloride (>1.56 ppmv) air concentrations were likely greater onsite and phenol was also detected. Additional studies are needed to examine pollutant emissions so process monitoring can be improved, and environment impacts and associated human exposures can be minimized.

An efficient mechanochemical synthesis of alpha-aluminum hydride: Synergistic effect of TiF3 on the crystallization rate and selective formation of alpha-aluminum hydride polymorph.

α-AlH3 is one of the most promising hydrogen storage materials due to its high gravimetric hydrogen capacity and low dehydriding temperature. In present work, a convenient and cost-efficient solid-state mechanochemical reaction is proposed to obtain α-AlH3 nano-composite. With the addition of TiF3, α-AlH3 nano-composite was formed in a short period by milling of LiH and AlCl3. Based on XRD and NMR results, the average grain size of the α-AlH3 in the nano-composite was 45 nm. The reaction pathway as well as the synergistic effect of TiF3 on the solid state reaction between LiH and AlCl3 were confirmed. In the α-AlH3/LiCl nano-composite, TiF3 reduced the temperature of dehydriding reaction and improved dehydrogenation rate of α-AlH3. Within the temperature range between 80 and 160 °C, dehydrogenation of the as-milled α-AlH3 nano-composite showed fast kinetics. At 160 °C, a maximum hydrogen desorption of 9.92 wt% was obtained within 750 s, very close to the theoretical hydrogen capacity of α-AlH3.

Outdoor manufacture of UV-Cured plastic linings for storm water culvert repair: Chemical emissions and residual.

Storm water culverts are integral for U.S. public safety and welfare, and their mechanical failure can cause roadways to collapse. To repair these buried assets, ultraviolet (UV) light cured-in-place-pipes (CIPP) are being installed. Chemical emission and residual material left behind from the installation process was investigated in New York and Virginia, USA. Samples of an uncured resin tube and field-cured styrene-based resin CIPPs were collected and analyzed. Also collected were air and water samples before, during, and after installations. Chemicals were emitted into air because of the installation and curing processes. Particulates emitted into the air, water, and soil contained fiberglass, polymer, and contaminants, some of which are regulated by state-level water quality standards. The uncured resin tube contained more than 70 chemical compounds, and 19 were confirmed with analytical standards. Compounds included known and suspected carcinogens, endocrine disrupting compounds, hazardous air pollutants, and other compounds with little aquatic toxicity data available. Compounds (14 of 19 confirmed) were extracted from the newly installed CIPPs, and 11 were found in water samples. Aqueous styrene (2.31 mg/L), dibutyl phthalate (12.5 µg/L), and phenol (16.7 µg/L) levels exceeded the most stringent state water quality standards chosen in this study. Styrene was the only compound that was found to have exceed a 48 h aquatic toxicity threshold. Newly installed CIPPs contained a significant amount volatile material (1.0 to > 9.0 wt%). Recommendations provided can reduce chemical emission, as well as improve worksite and environmental protection practices. Recommended future research is also described.

Hybrid plasmonic Au-TiN vertically aligned nanocomposites: a nanoscale platform towards tunable optical sensing.

Tunable plasmonic structure at the nanometer scale presents enormous opportunities for various photonic devices. In this work, we present a hybrid plasmonic thin film platform: i.e., a vertically aligned Au nanopillar array grown inside a TiN matrix with controllable Au pillar density. Compared to single phase plasmonic materials, the presented tunable hybrid nanostructures attain optical flexibility including gradual tuning and anisotropic behavior of the complex dielectric function, resonant peak shifting and change of surface plasmon resonances (SPRs) in the UV-visible range, all confirmed by numerical simulations. The tailorable hybrid platform also demonstrates enhanced surface plasmon Raman response for Fourier-transform infrared spectroscopy (FTIR) and photoluminescence (PL) measurements, and presents great potentials as designable hybrid platforms for tunable optical-based chemical sensing applications.

Cellulose Nanocrystal (CNC) Coatings with Controlled Anisotropy as High-Performance Gas Barrier Films.

Cellulose nanomaterials are promising materials for the polymer industry due to their abundance and renewability. In packaging applications, these materials may impart enhanced gas barrier performance due to their high crystallinity and polarity. In this work, low barrier to superior gas barrier pristine nanocellulose films were produced using a shear-coating technique to obtain a range of anisotropic films. Induction of anisotropy in a nanocellulose film can control the overall free volume of the system which effectively controls the gas diffusion path; hence, controlled anisotropy results in tunable barrier properties of the nanocellulose films. The highest anisotropy materials showed a maximum of 900-fold oxygen barrier improvement compared to the isotropic arrangement of nanocellulose film. The Bharadwaj model of nanocomposite permeability was modified for pure nanoparticles, and the CNC data were fitted with good agreement. Overall, the oxygen barrier performance of anisotropic nanocellulose films was 97 and 27 times better than traditional barrier materials such as biaxially oriented poly(ethylene terephthalate) (BoPET) and ethylene vinyl alcohol copolymer (EVOH), respectively, and thus could be utilized for oxygen-sensitive packaging applications.

Additive Manufacturing and Performance of Architectured Cement-Based Materials.

There is an increasing interest in hierarchical design and additive manufacturing (AM) of cement-based materials. However, the brittle behavior of these materials and the presence of interfaces from the AM process currently present a major challenge. Contrary to the commonly adopted approach in AM of cement-based materials to eliminate the interfaces in 3D-printed hardened cement paste (hcp) elements, this work focuses on harnessing the heterogeneous interfaces by employing novel architectures (based on bioinspired Bouligand structures). These architectures are found to generate unique damage mechanisms, which allow inherently brittle hcp materials to attain flaw-tolerant properties and novel performance characteristics. It is hypothesized that combining heterogeneous interfaces with carefully designed architectures promotes such damage mechanisms as, among others, interfacial microcracking and crack twisting. This, in turn, leads to damage delocalization in brittle 3D-printed architectured hcp and therefore results in quasi-brittle behavior, enhanced fracture and damage tolerance, and unique load-displacement response, all without sacrificing strength. It is further found that in addition to delocalization of the cracks, the Bouligand architectures can also enhance work of failure and inelastic deflection of the architectured hcp elements by over 50% when compared to traditionally cast elements from the same materials.

Surface Functionalization of Carbon Architecture with Nano-MnO2 for Effective Polysulfide Confinement in Lithium-Sulfur Batteries.

Li-S batteries have received tremendous attention owing to their high theoretical capacity (1672 mA h g-1 ), sulfur abundance, and low cost. However, main systemic issues, associated with polysulfide shuttling and low Coulombic efficiency, hinder the practical use of the sulfur electrode in commercial batteries. Herein, we demonstrate an effective strategy of decorating nano-MnO2 (less than 10 wt %) onto the sulfur reservoir to capture the out-diffused polysulfides through chemical interaction and thereby improve the electrochemical performance of the sulfur electrode without increasing the mass burden of total battery configuration. Pistachio shell-derived sustainable carbon (PC) was employed as effective sulfur containers owing to its structural characteristics (interconnected macro channels and micropores). With the aids of the structural benefits of the PC scaffold and the uniform decoration of nano-MnO2 , polysulfide shuttling was significantly suppressed and the cycling performance of the sulfur cathode was dramatically improved over 250 cycles.