Location: Plant Polymer Research
2018 Annual Report
Objectives
The goal of this research project is to use a wide range of technological approaches in the utilization of agricultural byproducts and feedstocks to improve functionalities of protein/carbohydrate particles for elastomer, coating, agricultural, medical, and cosmetic applications. Over the next 5 years, we will focus on the following objectives:
Objective 1: Enable the commercial production of new products based on functionalized particles for applications in elastomeric composites and latex coatings.
Objective 2: Enable new commercial processes to produce marketable biochar particles for rubber composite filler applications.
Objective 3: Enable the commercial production of new products based on nano- or micro-particles for controlled-release of chemicals.
Objective 4: Enable the commercial production of new products based on biodegradable nanoparticles from starch, and expand their end-use applications.
Objective 5: Enable the commercial production of new products based on micro-and nano-sized particles of lignin and cellulose.
Approach
The aim of this research is to develop biobased particle technologies that produce functional particles using renewable agricultural byproducts and feedstocks. The characteristics of the functional particles include size, shape, aggregate structure, and surface functionalities that can be changed for the particles to function as reinforcements in polymer matrices, hydrocolloids for modifying rheological and surface properties, and controlled-release vehicles for delivering chemicals. The outcome of this research will contribute to the utilization of voluminous byproducts generated by the biofuel and food industries, reduction of greenhouse gases responsible for climate change from carbon black production, and sustainability of the global economy. Currently, carbon black is the dominant filler in rubber products. Our previous research on biobased particles has produced natural rubber composites with useful mechanical properties. Further development will be on the regulation of particle connectivity and interface adhesion. Our masterbatch process will be extended to the rheology and films of latex coatings. Carbonized biomaterials as feedstock will also be developed as rubber filler with emphasis on the methods of biochar production to address performance, quality, and supply issues. We have produced nanoparticles of amylose complexes with steam jet cooking technology and will improve particle functionality for composite, coating, and medical applications. We will also develop nano-size cellulose/lignin for composite and cosmetic applications. For controlled-release applications using biobased particles, the functional particles to deliver chemicals, specifically pesticides, will be developed to solve wash-away issues and reduce pesticide consumption. The resulting technologies will be transferred to users who use these products.
Progress Report
For FY18, we have met our milestones. Our accomplishments and progress are documented in peer-reviewed scientific publications, patent application, invention disclosure, material transfer agreements and cooperative agreement.
Rubber components are used in various applications such as rubber cushion, soundproof insulation, automobile tires, etc. Most rubber parts require reinforcement particles in order to give sufficient mechanical strength. Particles produced from soybean were found to be able to increase rubber strength significantly. Further improvement of rubber properties reinforced with soy protein nanoparticles were made with the incorporation of inorganic particles, which improve the strength of rubber under highly stretched conditions as well as the length of stretch. Improvement was also made with the rolling resistance, which indicates how much energy can be saved when a rubber tire tread is rotating. Compared to carbon black reinforced rubber, the current development shows superior ability to reduce rolling resistance and save energy. These results show that the rubber composites developed have the potential to be used in tire tread as well as a variety of molded rubber objects for damping applications.
The biochar objective is to make rubber composites for the tire industry that replace carbon black filler (fossil fuel based) with biochar (from renewable biomass) as much as possible without detrimental effects in the final composite. To do this, in FY18 the surface chemistry of biochar was modified so that it would have less surface charge and therefore mix better with styrene-butadiene rubber. A renewable, heat-treated starch was used to coat the biochar particles and make them less charged. The resulting coated biochar particles showed improvement in both rubber composite strength and elongation properties compared to the unmodified biochar. This surface chemistry modification would be applicable to other charged biochars as well. This biochar modification method is currently being explored in combination with previous research objectives to improve biochar in other ways to maximize the replacement of carbon black with biochar.
Essential oils are highly volatile substances isolated by a physical process from odoriferous plants. Certain essential oils are used as natural pesticides for pests, specifically insects and select arthropods. Many essential oils have shown a broad spectrum of biological activities, including growth inhibition against bacteria, fungi and yeasts. Since essential oils are volatile, encapsulation is needed to delay their evaporation and elongate their effective time. Zein, a corn prolamin protein, is a food ingredient. Because of its high hydrophobicity, zein has been investigated in the food and pharmaceutical industries for encapsulation and sustained release of inner materials. Although zein has been used for encapsulation of essential oils, systematic investigation to understand the optimum conditions for the production of zein microcapsules has not been investigated. Therefore, the current research was focused on finding the optimum conditions for the production of microcapsules that carry essential oils, food ingredients, or similar chemicals by varying the experimental conditions systematically. The size of prepared microcapsules was much smaller than one micrometer (1/1000 millimeter).
Water soluble starch complexes were prepared by adding the sodium salt of palmitic acid to hot, jet-cooked solutions of high amylose corn starch. Starch is comprised of repeating glucose units, and high amylose corn starch contains 70% of a straight chain component (amylose) and 30% of a highly branched component (amylopectin). Complexes were formed from sodium palmitate and the amylose component of starch when water solutions of starch and sodium palmitate were mixed. Amylose-sodium palmitate complexes are soluble in water and do not precipitate from water solutions. When silver nitrate is added to water solutions of the amylose complex, the sodium palmitate component of the complex is converted to silver palmitate. Addition of glucose to the solution converts the silver component of the starch-silver palmitate complex to microscopic nanoparticles of metallic silver. When these starch complexes with their associated nanoparticles of silver are freeze dried, the nanoparticles do not aggregate but remain as nanometer-size particles in the freeze dried products. These freeze dried products are stable and can be stored for prolonged periods of time. The nanoparticles of silver remain associated with the starch complexes when they are re-dissolved in hot water, and they will not aggregate to form larger particles of metallic silver with reduced antibacterial properties. The ability to easily prepare and dry these starch-based products with their associated nanoparticles of silver for prolonged storage, and to easily reconstitute these materials by dissolving in water, will facilitate the addition of antibacterial silver products to consumer items such as clothing, bandages and ointments.
Three methods of preparation of micro-sized-lignin were developed. The untreated lignin particle sizes are several tens of microns. Three high shearing methods were investigated and evaluated to reduce the particle size of the lignin. One high mechanical shearing method was ball milling. The particle sizes were observed by optical microscope and scanning electron microscope. After ball milling, the sizes of the lignin particles were reduced into several microns. The second method of high shearing was freeze milling. Freeze milling shears the lignin particles at low temperature. The sizes of the lignin particles were also reduced to several microns after freeze milling. The third method was high-pressure high-temperature homogenization. This method also reduced the lignin particle size into microns. The particle size distributions of the lignin for the three shearing methods are under investigation. The length of milling time for both milling methods were studied to evaluate the particle size on milling time. The plastic-like materials made with commercial lignin and micro-sized-lignin were developed. Several plasticizers and molding methods have been evaluated. The mechanical properties of lignin plastic-like materials are being conducted.
Our research contributes to the national economy by creating new applications and potential markets for agricultural materials.
Accomplishments
1. Reducing rolling resistance of rubber tire treads with biobased nanoparticles. Rolling resistance is an important property in rubber tire tread. The lower the rolling resistance, the greater the energy can be saved when a tire is rotating. Carbon black is one of the most common particles used in rubber products, and produces tires with greater rolling resistance when compared to soy-based nanoparticles. ARS scientists in Peoria, Illinois, have produced better rubber composites reinforced with soy-based nanoparticles and inorganic nanoparticles to significantly reduce the rolling resistance of this rubber composite when used as tire tread material. It also improves the mechanical strength of the rubber composite significantly under highly stretched conditions as well as its ability to stretch compared to using soy-based nanoparticles alone. This development will increase the consumption and value of soybean products, save energy when used in tire tread applications, and improve the functionality of rubber products.
2. Improvement of biochar surface chemistry with heat-treated starch. Biochar can be made from many different biomass feedstocks and, as a result, many biochars can have a charged surface. Charged particles do not mix well with styrene-butadiene rubber, a primary material for the tire industry. ARS scientists in Peoria, Illinois, have developed heat-treated starch, a renewable material that can be used to coat the biochar particles and improve their mixing and dispersive properties in styrene-butadiene rubber. By coating the biochar particles with heat-treated starch, the surface charges were reduced and the biochar mixed more easily with styrene-butadiene rubber. Rubber composites made with the coated biochar showed increases in strength, elongation, and toughness compared to composites made with uncoated biochar particles. This technology provides a means to modify the surface chemistry of any charged biochar so that its miscibility with styrene-butadiene rubber is improved, as well as its ability to replace carbon black in rubber tires. Carbon black is a non-renewable, fossil fuel-based commodity that has an enormous market in the tire industry (roughly 1.2 million metric tons in 2015), so even partially replacing this fossil fuel-based commodity with renewable biochar would have a significant impact on reducing climate change and reducing our dependence on petroleum.
3. Preparation of insecticides that are not washed away by rain. The problem with existing insecticides is that they are washed away with rain or the morning dew after the application. This situation requires repeated application of insecticides to annihilate the target insects. To resolve this issue, ARS scientists in Peoria, Illinois, have encapsulated insecticides into tiny particles that adhere onto the surface of plant leaves and stay there until they are consumed by the insects. For commercial viability, these particles were prepared by using non-toxic chemicals and low-cost materials. This product will save farmers’ time, effort, and cost for the application of insecticides by eliminating the need for multiple applications, whereby the pollution due to pesticides will also be minimized. Since the toxic chemicals (i.e., insecticides) are surrounded by nontoxic materials, this product is safer to handle than conventional insecticides.
4. Easily re-dispersible nanoparticles of antimicrobial silver for consumer applications. Although silver nanoparticles have excellent antibacterial properties, aggregation of these small particles will reduce their antibacterial activity. An inexpensive method to improve commercial products is therefore needed for preparing silver nanoparticles that can be easily dried for prolonged storage and then re-dispersed in water when needed without the problem of aggregation. ARS scientists in Peoria, Illinois, have developed a method for preparing stable silver nanoparticles by binding a water soluble silver salt to an amylose complex prepared from corn starch and then reducing the bound silver ions to nanoparticles of metallic silver by reaction with glucose. Since the silver ions are bound to starch when they are reduced, aggregation to form larger particles of silver will not take place, and the antibacterial properties will therefore be retained when the products are dried for prolonged storage and then re-dispersed in water. This technology will expand the new uses of starch, increase the value of starch, and create a more effective and lower cost antimicrobial product, which will have economic benefit to starch producers and the manufacturers of antibacterial products.
Review Publications
Sayed, A.M., Kim, S., Behle, R.W. 2017. Characterization of silver nanoparticles synthesized by Bacillus thuringiensis as a nanobiopesticide for insect pest control. Biocontrol Science and Technology. 27(11):1308-1326. http://dx.doi.org/10.1080/09583157.2017.1397597.
Jong, L. 2018. Improved natural rubber composites reinforced with a complex filler network of biobased nanoparticles and ionomer. Materials Chemistry and Physics. 203:156-165.
Jong, L. 2018. Methacrylamide grafted elastomer composites reinforced with biobased particles. Journal Polymer Research. 25:64. https://doi.org/10.1007/s10965-018-1468-8.
Vaughn, S.F., Dinelli, F.D., Jackson, M.A., Vaughan, M.M., Peterson, S.C. 2018. Biochar-organic amendment mixtures added to simulated golf greens under reduced chemical fertilization increase creeping bentgrass growth. Industrial Crops and Products. 111:667-672.
Hay, W.T., Fanta, G.F., Peterson, S.C., Thomas, A.J., Utt, K.D., Walsh, K.A., Boddu, V.M., Selling, G.W. 2018. Improved hydroxypropyl methylcellulose (HPMC) films through incorporation of amylose-sodium palmitate inclusion complexes. Carbohydrate Polymers. 188:76-84.
Vaughn, S.F., Dinelli, F.D., Kenar, J.A., Jackson, M.A., Thomas, A.J., Peterson, S.C. 2018. Physical and chemical properties of pyrolyzed biosolids for utilization in sand-based turfgrass rootzones. Waste Management. 76:98-105.
Tisserat, B., Hwang, H.-S., Vaughn, S.F., Berhow, M.A., Peterson, S.C., Joshee, N., Vaidya, B.N., Harry-O'kuru, R. 2018. Fiberboard created using the natural adhesive properties of distillers dried grains with solubles. BioResources. 13(2):2678-2701.
Biswas, A., Kim, S., Gomez, A., Buttrum, M.A., Boddu, V.M., Cheng, H.N. 2018. Microwave-assisted synthesis of sucrose polyurethanes and their semi-interpenetrating polymer networks with polycaprolactane and soybean oil. Industrial and Engineering Chemistry Research. 57: 3227-3234. https://pubs.acs.org/doi/pdf/10.1021/acs.iecr.7b04059.
Jackson, M.A., White, M.G., Haasch, R.T., Peterson, S.C., Blackburn, J.A. 2017. Hydrogenation of furfural at the dynamic Cu surface of CuOCeO2/Al2O3 in vapor phase packed bed reactor. Journal of Molecular Catalysis. 445:124-132. doi: 10.1016/j.mcat.2017.11.023.
Harry-O'kuru, R.E., Biresaw, G., Gordon, S.H., Xu, J. 2018. Physical characteristics of tetrahydroxy and acylated derivatives of Jojoba liquid wax in lubricant applications. Journal of Analytical Methods in Chemistry. https://doi.org/10.1155/2018/7548327.
Hwang, H.-S., Gillman, J.D., Winkler-Moser, J.K., Kim, S., Singh, M., Byars, J.A., Evangelista, R.L. 2018. Properties of oleogels formed with high-stearic soybean oils and sunflower wax. Journal of the American Oil Chemists' Society. 95(5):557-569. https://doi.org/10.1002/aocs.12060.
Boddu, V.M., Kim, S., Adkins, J.E., Weimer, E., Paul, T., Damavarapu, R. 2017. Sensitive determination of nitrophenol isomers by reverse-phase high-performance liquid chromatography in conjunction with liquid-liquid extraction. International Journal of Environmental Analytical Chemistry. 97(11):1053-1064. doi.org/10.1080/03067319.2017.1381235.
Tisserat, B., Reifschneider, L., Gravatt, A., Peterson, S.C. 2017. Wood-plastic composites utilizing wood flours derived from fast-growing trees common to the midwest. BioResources. 12(4):7898-7916.
Liu, S., Chen, D., Xu, J. 2018. The effect of partially substituted lupin, soybean, and navy bean flours on wheat bread quality. Food and Nutrition Sciences. 9:840-854.
Liu, S.X., Chen, D., Xu, J. 2017. Evaluation of gluten-free amaranth and navy bean flour blends on quality of sugar cookies. Journal of Food Research. 6(6):63-73.
Xu, J., Krietemeyer, E.F., Boddu, V.M., Liu, S.X., Liu, W. 2018. Production and characterization of cellulose nanofibril (CNF) from agricultural waste corn stover. Carbohydrate Polymers. 192:202-207. https://doi.org/10.1016/j.carbpol.2018.03.017.
Kim, S., Biswas, A., Boddu, V.M., Hwang, H., Adkins, J.E. 2018. Solubilization of cashew gum from Anacardium Occidentale in aqueous medium. Carbohydrate Polymers. 199:205-209. https://doi.org/10.1016/j.carbpol.2018.07.022.
Peterson, S.C., Kim, S. 2018. Using heat-treated starch to modify the surface of biochar and improve the tensile properties of biochar-filled stryene-butadiene rubber composites. Journal of Elastomers and Plastics. 51(1):26-35. 10.1177/0095244318768636.
Peterson, S.C., Joshee, N. 2018. Co-milled silica and coppiced wood biochars improve elongation and toughness in styrene-butadiene elastomeric composites while replacing carbon black. Journal of Elastomers and Plastics. 50(8):667-676. 10.1177/0095244317753653.
Xu, J., Selling, G.W. 2017. A comparison of the viscoelastic properties of starch-polyacrylamide graft copolymers produced in dimethyl sulfoxide and water. Rheology. 1(2):1000109.
