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.

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.

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.

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.

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.

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.

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.