Dispensers for pheromonal pest control.

The detrimental effects of pesticides on the environment and human health have motivated the development of alternative pest control strategies. Pheromonal pest control is one alternative strategy that is attractive because most pheromones used commercially are non-toxic. Pheromones are also effective at low concentrations, and insects are slower to develop resistance to them compared to pesticides. Pheromones can be used to control pests by attracting them towards traps, repelling them from crops, or disrupting their mating behaviour. Viability of pheromonal control strategies must be evaluated on a case-by-case basis and depends on the target species, the pheromone being used, the specific control strategy, the method of dispensing pheromone, other pest control strategies pheromones being used alongside, and many other factors. The efficacy of pheromonal control has been demonstrated in commercial applications such as the control of palm weevils using traps releasing their male aggregation pheromone. Mating disruption using female sex pheromones has also been widely applied for control of both the codling moth Cydia Pomonella and the european grapevine moth Lobesia Botrana (Bangels and Beliën, 2012; Lucchi et al., 2018). Pheromones are volatiles that both degrade quickly in the environment and can be rapidly dispersed by wind. Consequently, administering pheromones to fields requires the use of dispensers that emits pheromone continuously or intermittently. Septum dispensers, membrane dispensers and solid matrix dispensers are best suited to treating smaller areas of cropland since they need to be installed by hand, a labor-intensive process. For treating a large area with pheromones, sprayable formulations and aerosol dispensers are alternative dispensing technologies that can be employed. The characteristics of these different dispenser designs are discussed as well as the kinetics governing pheromone release. Possible areas for future work in pheromone dispenser technology include examining new integrated strategies that employ pheromones alongside other pest control techniques in unique ways. The combination of pheromonal control with physical exclusion or predator release are examples of integrated strategies that are promising but have yet to be widely commercialized. Most commercial pheromonal dispensers are also noted to be impossible or impractical to reuse, apart from aerosol devices. Creating new types of rechargeable dispenser might have some cost saving benefits and would be an interesting area for future innovation in this field.

Physicochemical Limitations of Capillary Models Applied to High-Concentration Polymer Solutions.

Advances in binder jet printing (BJP) require the development of new binder-powder systems, for example, to increase compatibility with better performance metal alloys or to increase the strength of parts using stronger binders. The dynamics of binder absorption are principally understood through capillary models. However, validation of these models in BJP has focused on variation of powder properties. Using a design-of-experiments approach and an optical observation method to track absorption of droplets, this study tests the influence of fluid properties on absorption time against the predictions of capillary models. Properties specific to polymeric binders, such as molecular weight and entanglement state, are also considered. Capillary models are found to be generally accurate in predicting absorption time in dilute systems; however, these predictions are not accurate for highly concentrated binder solutions. The effect of polymer entanglement becomes prevalent as the solution concentration increases, which can also potentially occur as a result of increased evaporation due to powder bed heating. Specifically, concentrated solutions close to the onset of entanglement will absorb much more slowly than predicted. Future models of BJP systems must account for the possibility of polymer entanglement throughout the absorption process. Improved models will provide a more accurate understanding of the flow and solidification of the binder in the powder, allowing faster development of new binders for improved performance in printing.

Rheological insights on the evolution of sonicated cellulose nanocrystal dispersions.

Cellulose nanocrystals (CNCs) are promising biomaterials, but their tendency to agglomerate when dried limits their use in several applications. Ultrasonication is commonly used to disperse CNCs in water, bringing enough energy to the suspension to break agglomerates. While the optimized parameters for sonication are now well defined for small volumes of low concentration CNC suspensions, a deeper understanding of the influence of the dispersing process is needed to work with larger volumes, at higher concentrations. Herein, rheology is used to define the distribution and dispersion states upon ultrasonication of a 3.2 wt% CNC suspension. After considering the importance of the measurement sampling volume, the behavior of a more concentrated suspension (6.4 wt%) is examined and compared with a never-dried suspension of the same concentration to validate the dispersion state.

Evidence-based guidelines for the ultrasonic dispersion of cellulose nanocrystals.

Nanoparticles possess unique, size-driven properties. However, they can be challenging to use as they easily agglomerate - their high surface area-to-volume ratio induces strong interparticle forces, generating agglomerates that are difficult to break. This issue prevails in organic particles as well, such as cellulose nanocrystals (CNCs); when in their dried form, strong hydrogen bonding enhances agglomeration. Ultrasonication is widely applied to prepare CNC suspensions, but the methodology employed is non-standardized and typically under-reported, and process efficiency is unknown. This limits the ability to adapt dispersion protocols at industrial scales. Herein, numerical simulations are used in conjunction with validation experiments to define and optimize key parameters for ultrasonic dispersion of CNCs, allowing an operating window to be inferred.

Orienting Cellulose Nanocrystal Functionalities Tunes the Wettability of Water-Cast Films.

Cellulose nanocrystal (CNC)-based materials display apparently erratic wetting behaviors with contact angle (CA) variations as large as 30° from sample to sample. This work hypothesizes that it is the orientation of CNC amphiphilic functionalities at the interface with air that causes the variability in CA. By exploiting relationships with the Hansen solubility parameter theory, a set of surface tension parameters is proposed for both the polar and the non-polar surfaces of cellulose Iß nanocrystals. These coefficients elucidate the wettability of CNC materials by establishing a correlation between the wetting properties of the air/sample interface and its chemical composition in terms of non-polar moieties. Advancing/receding CA experiments suggest that, while spin-coating CNC suspensions yield purely polar films, oven-casting them produces amphiphilic surfaces. We proposed a mechanism where the state of dispersion (individual or agglomerated) in which CNCs reach the air/water interface during casting is the determining factor: while individual nanocrystals find it more stable to orient their non-polar surfaces toward the interface, the aspect ratio of CNC agglomerates favors an orientation of their polar surfaces. This represents the first compelling evidence of CNC orientation at an interface and can be applied to Pickering emulsions and nanocomposites and to the production of CNC materials with tuned wettability.

Self-assembly behaviors of colloidal cellulose nanocrystals: A tale of stabilization mechanisms.

HYPOTHESIS: In solvent casting, colloidal nanocrystal self-assembly patterns are controlled by a mix of cohesive and repulsive interactions that promote destabilization-induced self-assembly (DISA) or evaporation-induced self-assembly (EISA). Tuning the strength and nature of the stabilization mechanisms may allow repulsive interactions to govern self-assembly during the casting of colloidal cellulose nanocrystal (CNC) suspensions. EXPERIMENTS: We propose a tool to classify the level of electrostatic and solvation-induced stabilizations based on two solvent parameters only: dielectric constant, ε, and chemical affinity for CNCs, in terms of Hansen Solubility Parameters, Ra. These criteria are applied to study CNC self-assembly in solvent casting experiments in various media and binary mixtures. FINDINGS: In solvent casting of suspensions stabilized through a combination of electrostatic and solvation effects, the primarily governing mechanism is EISA, which leads to the formation of chiral nematic domains and optically active thin films. In electrostatically-stabilized suspensions, EISA and DISA are in competition and casting may yield anything from a continuous film to a powder. In other suspensions, DISA prevails and evaporation yields a powder of CNC agglomerates. By classifying media according to their stabilization mechanisms, this work establishes that the behavior of CNC suspensions in solvent casting may be predicted from solvent parameters only.

One-step processing of highly viscous multiple Pickering emulsions.

HYPOTHESIS: Solid-stabilized Pickering emulsions have attracted a lot of attention recently due to their surfactant-free character, and exceptional stability. At the moment, how the viscosities of the liquid phases impact the processing of Pickering emulsions remain to be clearly understood - it is however an important parameter to consider when developing chemical engineering processes employing these multiphase liquids. Our first assumption was that the amount of emulsified dispersed phase would drastically decrease as viscosity increases. EXPERIMENTS AND FINDINGS: In this work, we demonstrate that double water-in-oil-in-water (W/O/W) Pickering emulsions are obtained in a single processing step when using very high viscosity silicone oils (≥10,000 cSt) and a single type of sub-µm silica particles modified with two grafted silanes and sodium alginate. The formation of water sub-inclusions proceeds via a phase-inversion mechanism. These sub-inclusions are subsequently stabilized and retained in the oil phase due to its viscosity, limiting sub-inclusions mobility, and the presence of adsorbed particles forming dense layers at oil-water interfaces, acting as barriers. The process we present is simple, requires a minimum number of components, and allows the preparation of multiple emulsions which could then be used to efficiently protect and/or transport a variety of sensitive encapsulated compounds.

The structural amphiphilicity of cellulose nanocrystals characterized from their cohesion parameters.

Cellulose nanocrystals (CNCs), usually considered as isotropically polar nanoparticles, are sheet-like crystalline assemblies of cellulose chains. Here, we link the anisotropy of the CNC structure to an amphiphilic behavior in suspension. The Hansen solubility parameters (HSP: δD;δP;δH) of wood-based H2SO4-hydrolyzed CNCs were measured from sedimentation tests in a wide set of 59 solvents and binary mixtures. Two sets of cohesion parameters corresponding to a polar surface (18.1; 20.4; 15.3) ±â€¯(0.5; 0.5; 0.4) MPa1/2 and to a mildly non-polar one (17.4; 4.8; 6.5) ±â€¯(0.3; 0.5; 0.6) MPa1/2 were determined, with respective solubility radii of 7.8 and 2.1 MPa1/2. The polar sphere is thought to correspond to the (110) & (11¯0) surfaces of cellulose Iß nanocrystals, while the smaller non-polar sphere is coherent with the exposure of (200) surfaces. The HSP graph provides new insights on the amphiphilic nature of CNCs and a mapping of their chemical affinity for solvents and polymer matrices.

VUV Photodeposition of Thiol-Terminated Films: A Wavelength-Dependent Study.

Photoinitiated chemical vapor deposition (PICVD) has become attractive for selective and specific surface functionalization, because it relies on a single energy source, the photons, to carry out (photo-) chemistry. In the present wavelength (λ)-dependent study, thiol (SH)-terminated thin film deposits have been prepared from gas mixtures of acetylene (C2H2) and hydrogen sulfide (H2S) via PICVD using four different vacuum-ultraviolet (VUV) sources, namely, KrL (λpeak = 123.6 nm), XeL (λpeak = 147.0 nm), XeE (λpeak = 172.0 nm), and Hg (λ = 184.9 nm) lamps. Different λ influence the deposition kinetics and film composition, reflecting that photolytic reactions are governed by the gases' absorption coefficients, k(λ). Thiol concentrations, [SH], up to ∼7.7%, were obtained with the XeL source, the highest reported in the literature so far. Furthermore, all films showed islandlike surface morphology, regardless of λ.

Large-Scale Encapsulation of Magnetic Iron Oxide Nanoparticles via Syngas Photo-Initiated Chemical Vapor Deposition.

Photo-initiated chemical vapor deposition (PICVD) has been adapted for use in a jet-assisted fluidized bed configuration, allowing for the encapsulation of magnetic iron oxide nanoparticles on a larger scale than ever reported (5 g). This new methodology leads to a functional coating with a thickness of 1.4-10 nm, confirmed by HRTEM and TGA. XPS and TOF-SIMS characterization confirm that the coating is composed of both aliphatic and polymerized carbon chains, with incorporated organometallic bonds and oxygen-containing moieties. UV-Vis absorbance spectra show that the coating improved dispersion in non-polar solvents, such as n-dodecane. This process represents a first step towards the large-scale, solvent-free post-synthesis processing of nanoparticles to impart a functional coating.

Sodium alginate-grafted submicrometer particles display enhanced reversible aggregation/disaggregation properties.

In this article, we demonstrate that submicrometer particles with surface-grafted sodium alginate (SA) display enhanced and reversible aggregation/disaggregation properties in aqueous solution. 300 nm silica particles were first functionalized with an aminosilane coupling agent, followed by the grafting of pH-sensitive SA, as confirmed by zeta potential, XPS and FTIR analyses. The SA-modified particles show enhanced aggregation properties at acidic pH compared to unmodified silica, with a 10 times increase in average aggregate diameter. The process is reversible, as the aggregates can be broken and dispersed again when the pH is increased back to 7.0. As a result, the sedimentation rate of SA-modified particles at pH 3.0 is both significantly faster and complete compared to the unmodified particles. This enhanced aggregation is most likely due to the formation of intermolecular hydrogen bonds between neighboring SA-modified particles. This work illustrates how surface-grafted macromolecules of natural origins can be used to tune interparticle interactions, in order to improve separation processes.

Ultrasonication of spray- and freeze-dried cellulose nanocrystals in water.

The structural and rheological properties of aqueous suspensions of spray-dried cellulose nanocrystals (CNCs) were investigated and compared to those of freeze-dried. The cellulose nanocrystals were obtained from sulfuric acid hydrolysis of wood pulp. Ultrasonication was used to disperse cellulose nanocrystals in Milli-Q water and the power applied during ultrasonication was shown to be the controlling parameter for their dispersion, more than total energy. Dynamic light scattering measurements showed a decrease of the average hydrodynamic diameter down to the same limiting value, i.e. ∼75 nm, for both spray and freeze-dried cellulose nanocrystals. Since the same maximum dispersion state was reached for both CNC types, it indicated that the spray drying process did not limit dispersion, provided that sufficient ultrasonication was provided. Moreover, no desulfation occurred during ultrasonication at ambient temperature. Strong ultrasonication also caused a decrease of intrinsic viscosity, along with an increase in maximum packing concentration. These properties were correlated to agglomerates break-up, which released both ions and water in suspension. The ionic strength increase may lead to a thinner electrostatic double layer surrounding the cellulose nanocrystals, reducing their apparent concentration.

Kinetics, Chemistry, and Morphology of Syngas Photoinitiated Chemical Vapor Deposition.

Syngas is the product of gasification processes and is used for the production of petrochemicals. Little attention has been paid to its use in the production of oligomeric thin films under ambient conditions. Herein, the nature of the photoinitiated chemical vapor deposition of films made from syngas using high-wavelength ultraviolet light is discussed, including an exploration of the oligomeric films' structure, synthesis mechanism, and growth kinetics. Specifically, X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry analyses provide insight into the chemical structure, illustrating the effect of photogenerated radicals in the formation of aliphatic, anhydride, and cyclic structures. The films are covalently bonded to the substrate and chemically uniform. Electron and atomic force microscopy identify an islandlike morphology for the deposit. These insights into the mechanism and structure are linked to processing parameters through a study on the effect of residence time and treatment duration on the deposition rate, as determined through profilometry.

Photo Initiated Chemical Vapour Deposition To Increase Polymer Hydrophobicity.

Apple growers face new challenges to produce organic apples and now many cover orchards with high-density polyethylene (HDPE) nets to exclude insects, rather than spraying insecticides. However, rainwater- associated wetness favours the development of apple scabs, Venturia inaequalis, whose lesions accumulate on the leaves and fruit causing unsightly spots. Treating the nets with a superhydrophobic coating should reduce the amount of water that passes through the net. Here we treat HDPE and polyethylene terephthalate using photo-initiated chemical vapour deposition (PICVD). We placed polymer samples in a quartz tube and passed a mixture of H2 and CO through it while a UVC lamp (254 nm) illuminated the surface. After the treatment, the contact angle between water droplets and the surface increased by an average of 20°. The contact angle of samples placed 70 cm from the entrance of the tube was higher than those at 45 cm and 20 cm. The PICVD-treated HDPE achieved a contact angle of 124°. Nets spray coated with a solvent-based commercial product achieved 180° but water ingress was, surprisingly, higher than that for nets with a lower contact angle.