A Preliminary Study of Thermosets from Epoxy Resins Made Using Low-Toxicity Furan-Based Diols.

Glycidyl ethers are prepared from a series of furan-based diols and cured with a diamine to form thermosets. The furan diols demonstrate lower toxicity than bisphenol-A in a prior study. The diglycidyl ethers show improved thermal stability compared to the parent diols. Cured thermosets are prepared at elevated temperature using isophorone diamine (IPDA). Glass transition temperatures are in the range of 30-54 °C and depend on the structure of the furan diol. Coatings are prepared on steel substrates and show very high hardness, good adhesion, and a range of flexibility. Properties compare favorably with a control based on a bisphenol-A epoxy resin. The study demonstrates that epoxy resins based on furan diols, which have been shown to have lower toxicity than bisphenol-A, can form thermosets having properties comparable to a standard epoxy resin system; and thus, are viable as replacements for bisphenol-A epoxy resins.

Energy renormalization for temperature transferable coarse-graining of silicone polymer.

The bottom-up prediction of thermodynamic and mechanical behaviors of polymeric materials based on molecular dynamics (MD) simulation is of critical importance in polymer physics. Although the atomistically informed coarse-grained (CG) model can access greater spatiotemporal scales and retain essential chemical specificity, the temperature-transferable CG model is still a big challenge and hinders widespread application of this technique. Herein, we use a silicone polymer, i.e., polydimethylsiloxane (PDMS), having an incredibly low chain rigidity as a model system, combined with an energy-renormalization (ER) approach, to systematically develop a temperature-transferable CG model. Specifically, by introducing temperature-dependent ER factors to renormalize the effective distance and cohesive energy parameters, the developed CG model faithfully preserved the dynamics, mechanical and conformational behaviors compared with the target all-atomistic (AA) model from glassy to melt regimes, which was further validated by experimental data. With the developed CG model featuring tremendously improved computational efficiency, we systematically explored the influences of cohesive interaction strength and temperature on the dynamical heterogeneity and mechanical response of polymers, where we observed consistent trends with other linear polymers with varying chain rigidity and monomeric structures. This study serves as an extension of our proposed ER approach of developing temperature transferable CG models with diverse segmental structures, highlighting the critical role of cohesive interaction strength on CG modeling of polymer dynamics and thermomechanical behaviors.

Amphiphilic Balance: Effect of the Hydrophilic-Hydrophobic Ratio on Fouling-Release Surfaces.

This study demonstrated the importance of identifying the optimal balance of hydrophilic and hydrophobic moieties in amphiphilic coatings to achieve fouling-release (FR) performance that surpasses that of traditional hydrophobic marine coatings. While there have been many reports on fouling-release properties of amphiphilic surfaces, the offered understanding is often limited. Hence, this work is focused on further understanding of the amphiphilic surfaces. Poly(ethylene glycol) (PEG) and polydimethylsiloxane (PDMS) were used to create a series of noncross-linked amphiphilic additives that were then added to a hydrophobic-designed siloxane-polyurethane (SiPU) FR system. After being characterized by ATR-FTIR, XPS, contact angle analysis, and AFM, the FR performance was evaluated by using different marine organisms. The assessments showed that the closer the hydrophilic and hydrophobic moieties in a system reached a relatively equalized level, the more desirable the FR performance of the coating system became. A balanced ratio of hydrophilicity-hydrophobicity in the system at around 10-15 wt % of each component had the best FR performance and was comparable to or better than commercial FR coatings.

Silicone elastomers and the Persson-Brener adhesion model.

Many modern anti-icing and anti-fouling coatings rely on soft, low surface energy elastomeric materials such as polydimethylsiloxane for their functionality. While the low surface energy is desirable for reducing adhesion, very little work considers the larger contribution to adhesive failure caused by the viscoelastic nature of elastomers. Here we examine several different siloxane elastomers using a JKR adhesion test, which was operated over a range of different speeds and temperatures. Additionally, we characterize the dynamic mechanical modulus over a large range of frequencies for each material. We note that surface energies of the materials are all similar, but variation in adhesion strength is clear in the data. The variation at low speeds is related to elastomer architecture but the speed dependence itself is independent of architecture. Qualitative correlations are noted between the JKR adhesion measurements and the dynamic moduli. Finally, an attempt is made to directly compare moduli and adhesion through the recent Persson-Brener model. Approximations of the model are shown to be inaccurate. The full model is found to be accurate at low speeds, although it fails to precisely capture higher speed behaviour.

Biobased, Macro-, and Nanoscale Fungicide Delivery Approaches for Plant Fungi Control.

In this report, two polymeric matrix systems at macro and nanoscales were prepared for efficacious fungicide delivery. The macroscale delivery systems used millimeter-scale, spherical beads composed of cellulose nanocrystals and poly(lactic acid). The nanoscale delivery system involved micelle-type nanoparticles, composed of methoxylated sucrose soyate polyols. Sclerotinia sclerotiorum (Lib.), a destructive fungus affecting high-value industrial crops, was used as a model pathogen against which the efficacy of these polymeric formulations was demonstrated. Commercial fungicides are applied on plants frequently to overcome the transmission of fungal infection. However, fungicides alone do not persist on the plants for a prolonged period due to environmental factors such as rain and airflow. There is a need to apply fungicides multiple times. As such, standard application practices generate a significant environmental footprint due to fungicide accumulation in soil and runoff in surface water. Thus, approaches are needed that can either increase the efficacy of commercially active fungicides or prolong their residence time on plants for sustained antifungal coverage. Using azoxystrobin (AZ) as a model fungicide and canola as a model crop host, we hypothesized that the AZ-loaded macroscale beads, when placed in contact with plants, will act as a depot to release the fungicide at a controlled rate to protect plants against fungal infection. The nanoparticle-based fungicide delivery approach, on the other hand, can be realized via spray or foliar applications. The release rate of AZ from macro- and nanoscale systems was evaluated and analyzed using different kinetic models to understand the mechanism of AZ delivery. We observed that, for macroscopic beads, porosity, tortuosity, and surface roughness governed the efficiency of AZ delivery, and for nanoparticles, contact angle and surface adhesion energy were directing the efficacy of the encapsulated fungicide. The technology reported here can also be translated to a wide variety of industrial crops for fungal protection. The strength of this study is the possibility of using completely plant-derived, biodegradable/compostable additive materials for controlled agrochemical delivery formulations, which will contribute to reducing the frequency of fungicide applications and the potential accumulation of formulation components in soil and water.

Studying the Effect of Pre-Polymer Composition and Incorporation of Surface-Modifying Amphiphilic Additives on the Fouling-Release Performance of Amphiphilic Siloxane-Polyurethane Coatings.

Combining amphiphilic fouling-release (FR) coatings with the surface-active nature of amphiphilic additives can improve the antifouling/fouling-release (AF/FR) properties needed to offer broad-spectrum resistance to marine biofoulants. This work is focused on further tuning the amphiphilic character of a previously developed amphiphilic siloxane-polyurethane (SiPU) coating by varying the amount of PDMS and PEG in the base system. Furthermore, surface-modifying amphiphilic additives (SMAAs) were incorporated into these amphiphilic FR SiPU coatings in varying amounts. ATR-FTIR, contact angle and surface energy measurements, and AFM were performed to assess changes in surface composition, wettability, and morphology. AF/FR properties were evaluated using laboratory biological assays involving Cellulophaga lytica, Navicula incerta, Ulva linza, Amphibalanus amphitrite, and Geukensia demissa. The surfaces of these coatings varied significantly upon changes in PDMS and PEG content in the coating matrix, as well as with changes in SMAA incorporation. AF/FR properties were also significantly changed, with formulations containing the highest amounts of SMAA showing very high removal properties compared to other experimental formulations, in some cases better than that of commercial standard FR coatings.

Grooming of fouling-release coatings to control marine fouling and determining how grooming affects the surface.

Grooming may be an effective technique to control marine biofouling without damaging the coating or discharging active ingredients into the environment. This study assessed the grooming performance of three experimental biocide-free siloxane polyurethane (SiPU) fouling-release coatings. Coatings were statically immersed in Port Canaveral, Florida, and groomed every two weeks for five months using three different brush types. The ungroomed panels became heavily fouled with biofilm, tubeworms, barnacles, and bryozoans. Two of the brushes were able to control the fouling with a coverage of <5%. The commercial silicone elastomer coating was damaged from grooming procedures, while the SiPU coatings were not. Laboratory biological assays were carried out and mirrored the grooming results. Through surface characterization techniques, it was concluded that the coatings were unaffected by the grooming procedures. This study shows that marine fouling on durable SiPU fouling-release coatings can be controlled via grooming without damage or changing the surface properties.

Towards Upcycling Biomass-Derived Crosslinked Polymers with Light.

Photodegradable, recyclable, and renewable, crosslinked polymers from bioresources show promise towards developing a sustainable strategy to address the issue of plastics degradability and recyclability. Photo processes are not widely exploited for upcycling polymers in spite of the potential to have spatial and temporal control of the degradation in addition to being a green process. In this report we highlight a methodology in which biomass-derived crosslinked polymers can be programmed to degrade at ≈300 nm with ≈60 % recovery of the monomer. The recovered monomer was recycled back to the crosslinked polymer.

Durable siloxane-polyurethane coatings for mitigating freshwater mussel fouling.

Siloxane-polyurethane hybrid coatings were assessed for biofouling control caused by freshwater mussels. Invasive species such as zebra (Dreissena polymorpha) and quagga (Dreissena bugensis) mussels have rapidly spread through the waterways in the United States causing major concerns in reservoir infrastructure and freshwater lakes. Current coating solutions such as biocidal anti-fouling coatings are not suitable given the released biocides which may accumulate in reservoirs. Biocide free fouling release coatings based on silicone elastomers do not have adequate mechanical durability. The siloxane-polyurethane (SiPU) coatings were evaluated using model organism laboratory assays and real-life performance was evaluated in the freshwater field environment. Two coating compositions displayed excellent performance in field trials for up to 2+ years. The surface analysis experiments of the coatings indicate that the morphology of the coatings is affected by the formulations' solvent choice. These coatings show great promise in mitigating biofouling predominated by freshwater mussels.

Surface modifying amphiphilic additives and their effect on the fouling-release performance of siloxane-polyurethane coatings.

In this work, surface-modifying amphiphilic additives (SMAAs) were synthesized via hydrosilylation using various polymethylhydrosiloxanes (PMHS) and allyl-terminated polyethylene glycol monomethyl ethers (APEG) of varying molecular weights. The additives synthesized were incorporated into a hydrophobic, self-stratifying siloxane-polyurethane (SiPU) coating system to produce an amphiphilic surface. Contact angle experiments and atomic force microscopy (AFM), in a dry and hydrated state, were performed to assess changes in surface wettability and morphology. The antifouling and fouling-release (AF/FR) performances were evaluated by performing laboratory biological assays using the marine bacterium Cellulophaga lytica, the microalga Navicula incerta, the macroalga Ulva linza, the barnacle Amphibalanus amphitrite, and the marine mussel, Geukensia demissa. Several of the formulations showed improved AF/FR performance vs the base SiPU and performed better than some of the commercial standard marine coatings. Formulations containing SMAAs with a low grafting density of relatively high molecular weight PEG chains showed the best performance overall.

Critical Amphiphilic Concentration: Effect of the Extent of Amphiphilicity on Marine Fouling-Release Performance.

Amphiphilic surfaces, containing both hydrophilic and hydrophobic domains, offer desirable performance for many applications such as marine coatings or anti-icing purposes. This work explores the effect of the concentration of amphiphilic moieties on converting a polyurethane (PU) system to a coating having fouling-release properties. A novel amphiphilic compound is synthesized and added at increasing amounts to a PU system, where the amount of the additive is the only variable in the study. The additive-modified surfaces are characterized by a variety of techniques including ATR-FTIR, XPS, contact angle measurements, and AFM. Surface characterizations indicate the presence of amphiphilic domains on the surface due to the introduction of the self-stratifying amphiphilic additive. The fouling-release properties of the surfaces are assessed with three biological assays using Ulva linza, Cellulophaga lytica, and Navicula Incerta as the test organisms. A change in the fouling-release performance is observed and plateaued once a certain amount of amphiphilicity is attained in the coating system, which we call the critical amphiphilic concentration (CAC).

A Preliminary Environmental Assessment of Epoxidized Sucrose Soyate (ESS)-Based Biocomposite.

Biocomposites can be both environmentally and economically beneficial: during their life cycle they generally use and generate less petroleum-based carbon, and when produced from the byproduct of another industry or recycled back to the manufacturing process, they will bring additional economic benefits through contributing to a circular economy. Here we investigate and compare the environmental performance of a biocomposite composed of a soybean oil-based resin (epoxidized sucrose soyate) and flax-based reinforcement using life cycle assessment (LCA) methodology. We evaluate the main environmental impacts that are generated during the production of the bio-based resin used in the biocomposite, as well as the biocomposite itself. We compare the life cycle impacts of the proposed biocomposite to a functionally similar petroleum-based resin and flax fiber reinforced composite, to identify tradeoffs between the environmental performance of the two products. We demonstrate that the bio-based resin (epoxidized sucrose soyate) compared to a conventional (bisphenol A-based) resin shows lower negative environmental impacts in most studied categories. When comparing the biocomposite to the fossil fuel derived composite, it is demonstrated that using epoxidized sucrose soyate versus a bisphenol A (BPA)-based epoxy resin can improve the environmental performance of the composite in most categories except eutrophication and ozone layer depletion. For future designs, considering an alternative cross-linker to facilitate the bond between the bio-based resin and the flax fiber, may help improve the overall environmental performance of the biocomposite. An uncertainty analysis was also performed to evaluate the effect of variation in LCA model inputs on the environmental results for both the biocomposite and composite. The findings show a better overall carbon footprint for the biocomposite compared to the BPA-based composite at almost all times, demonstrating a good potential for marketability especially in the presence of incentives or regulations that address reducing the carbon intensity of products. This analysis allowed us to pinpoint hotspots in the biocomposite's supply chain and recommend future modifications to improve the product's sustainability.

Soysome: A Surfactant-Free, Fully Biobased, Self-Assembled Platform for Nanoscale Drug Delivery Applications.

A new class of biobased nanocarriers, soysomes, has been discovered and investigated. These nanocarriers are derived from a synthetically accessible, scalable macromolecule, methoxylated sucrose soyate polyol (MSSP), derived from chemical building blocks obtained from soybean oil and sucrose. We observed for the first time that MSSP, when dissolved in an organic solvent of different polarity and slowly added to an aqueous phase at a predetermined rate under "nanoprecipitation" conditions, will form a stable, self-assembled structure with a size range from 100 to 200 nm depending on the polarity difference between the precipitating solvent pairs. Without the aid of poly(ethylene glycol) or any surfactants, these soysomes were found to be stable in water for an extended period and can withstand the destabilizing effect of time, temperature, and pH. We also found that the soysomes were able to encapsulate and release a hydrophobic bioactive compound, such as curcumin. Both MSSP and their self-assembled structures were highly biocompatible and did not trigger cellular toxicity to mammalian cell lines. Our experiments showed that such 100% biobased, noncytotoxic material as MSSP and a related class of products have the potential for use toward the sustainable manufacturing of drug nanocarriers for biomedical applications.

Fouling-Release Performance of Silicone Oil-Modified Siloxane-Polyurethane Coatings.

The effect of incorporation of silicone oils into a siloxane-polyurethane fouling-release coatings system was explored. Incorporation of phenylmethyl silicone oil has been shown to improve the fouling-release performance of silicone-based fouling-release coatings through increased interfacial slippage. The extent of improvement is highly dependent upon the type and composition of silicone oil used. The siloxane-polyurethane (SiPU) coating system is a tough fouling-release solution, which combines the mechanical durability of polyurethane while maintaining comparable fouling-release performance with regard to commercial standards. To further improve the fouling-release performance of the siloxane-PU coating system, the use of phenylmethyl silicones oils was studied. Coatings formulations were prepared incorporating phenylmethyl silicone oils having a range of compositions and viscosities. Contact angle and surface energy measurements were conducted to evaluate the surface wettability of the coatings. X-ray photoelectron spectroscopy (XPS) depth profiling experiments demonstrated self-stratification of silicone oil along with siloxane to the coating-air interface. Several coating formulations displayed improved or comparable fouling-release performance to commercial standards during laboratory biological assay tests for microalgae (Navicula incerta), macroalgae (Ulva linza), adult barnacles (Balanus amphitrite syn. Amphibalanus amphitrite), and mussels (Geukensia demissa). Selected silicone-oil-modified siloxane-PU coatings also demonstrated comparable fouling-release performance in field immersion trials. In general, modifying the siloxane-PU fouling-release coatings with a small amount (1-5 wt % basis) of phenylmethyl silicone oil resulted in improved performance in several laboratory biological assays and in long-term field immersion assessments.

Comparison of laboratory and field testing performance evaluations of siloxane-polyurethane fouling-release marine coatings.

A series of eight novel siloxane-polyurethane fouling-release (FR) coatings were assessed for their FR performance in both the laboratory and in the field. Laboratory analysis included adhesion assessments of bacteria, microalgae, macroalgal spores, adult barnacles and pseudobarnacles using high-throughput screening techniques, while field evaluations were conducted in accordance with standardized testing methods at three different ocean testing sites over the course of six-months exposure. The data collected were subjected to statistical analysis in order to identify potential correlations. In general, there was good agreement between the laboratory screening assays and the field assessments, with both regimes clearly distinguishing the siloxane-polyurethane compositions comprising monofunctional poly(dimethyl siloxane) (PDMS) (m-PDMS) as possessing superior, broad-spectrum FR properties compared to those prepared with difunctional PDMS (d-PDMS). Of the seven laboratory screening techniques, the Cellulophaga lytica biofilm retraction and reattached barnacle (Amphibalanus amphitrite) adhesion assays were shown to be the most predictive of broad-spectrum field performance.

Programmed photodegradation of polymeric/oligomeric materials derived from renewable bioresources.

Renewable polymeric materials derived from biomass with built-in phototriggers were synthesized and evaluated for degradation under irradiation of UV light. Complete decomposition of the polymeric materials was observed with recovery of the monomer that was used to resynthesize the polymers.

Thermoset coatings from epoxidized sucrose soyate and blocked, bio-based dicarboxylic acids.

A new 100% bio-based thermosetting coating system was developed from epoxidized sucrose soyate crosslinked with blocked bio-based dicarboxylic acids. A solvent-free, green method was used to block the carboxylic acid groups and render the acids miscible with the epoxy resin. The thermal reversibility of this blocking allowed for the formulation of epoxy-acid thermoset coatings that are 100% bio-based. This was possible due to the volatility of the vinyl ethers under curing conditions. These systems have good adhesion to metal substrates and perform well under chemical and physical stress. Additionally, the hardness of the coating system is dependent on the chain length of the diacid used, making it tunable.

New biobased high functionality polyols and their use in polyurethane coatings.

High-functionality polyols for application in polyurethanes (PUs) were prepared by epoxide ring-opening reactions from epoxidized sucrose esters of soybean oil-epoxidized sucrose soyates-in which secondary hydroxyl groups were generated from epoxides on fatty acid chains. Ester polyols were prepared by using a base-catalyzed acid-epoxy reaction with carboxylic acids (e.g., acetic acid); ether polyols were prepared by using an acid-catalyzed alcohol-epoxy reaction with monoalcohols (e.g., methanol). The polyols were characterized by using gel permeation chromatography, FTIR spectroscopy, (1)H NMR spectroscopy, differential scanning calorimetry (DSC), and viscosity measurements. PU thermosets were prepared by using aliphatic polyisocyanates based on isophorone diisocyanate and hexamethylene diisocyanate. The properties of the PUs were studied by performing tensile testing, dynamic mechanical analysis, DSC, and thermogravimetric analysis. The properties of PU coatings on steel substrates were evaluated by using ASTM methods to determine coating hardness, adhesion, solvent resistance, and ductility. Compared to a soy triglyceride polyol, sucrose soyate polyols provide greater hardness and range of cross-link density to PU thermosets because of the unique structure of these macromolecules: well-defined compact structures with a rigid sucrose core coupled with high hydroxyl group functionality.

Impact of structure and functionality of core polyol in highly functional biobased epoxy resins.

Highly functional biobased epoxy resins were prepared using dipentaerythritol (DPE), tripentaerythritol (TPE), and sucrose as core polyols that were substituted with epoxidized soybean oil fatty acids, and the impact of structure and functionality of the core polyol on the properties of the macromolecular resins and their epoxy-anhydride thermosets was explored. The chemical structures, functional groups, molecular weights, and compositions of epoxies were characterized using nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, gel permeation chromatography (GPC), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI MS). The epoxies were also studied for their bulk viscosity, intrinsic viscosity, and density. Crosslinked with dodecenyl succinic anhydride (DDSA), epoxy-anhydride thermosets were evaluated using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile tests, and tests of coating properties. Epoxidized soybean oil (ESO) was used as a control. Overall, the sucrose-based thermosets exhibited the highest moduli, having the most rigid and ductile performance while maintaining the highest biobased content. DPE/TPE-based thermosets showed modestly better thermosetting performance than the control ESO thermoset.

Synthesis of soybean oil-based thiol oligomers.

Industrial grade soybean oil (SBO) and thiols were reacted to generate thiol-functionalized oligomers via a thermal, free radical initiated thiol-ene reaction between the SBO double bond moieties and the thiol functional groups. The effect of the reaction conditions, including thiol concentration, catalyst loading level, reaction time, and atmosphere, on the molecular weight and the conversion to the resultant soy-thiols were examined in a combinatorial high-throughput fashion using parallel synthesis, combinatorial FTIR, and rapid gel permeation chromatography (GPC). High thiol functionality and concentration, high thermal free radical catalyst concentration, long reaction time, and the use of a nitrogen reaction atmosphere were found to favor fast consumption of the SBO, and produced high molecular weight products. The thiol conversion during the reaction was inversely affected by a high thiol concentration, but was favored by a long reaction time and an air reaction atmosphere. These experimental observations were explained by the initial low affinity of the SBO and thiol, and the improved affinity between the generated soy-thiol oligomers and unreacted SBO during the reaction. The synthesized soy-thiol oligomers can be used for renewable thiol-ene UV curable materials and high molecular solids and thiourethane thermal cure materials.