Progress 07/01/24 to 06/30/25

Outputs
Target Audience:This project will deliver technology to the textiles, non-wovens, and paper industries as a chemical additive to improve material performance. During the first year of the project, multiple key audiences were engaged, including undergraduate students and professionals from several scientific and technical disciplines. These interactions not only broadened the impact of the research but also facilitated knowledge transfer and interdisciplinary collaboration. Students (Paper Science and Engineering): Two undergraduate and two graduate student researchers were actively involved in laboratory work, gaining hands-on experience with textile coating and emulsion formulation. Through this participation, the students developed foundational skills in solvent treatment and emulsion techniques and an understanding of sustainable material processing. Textile Industry Professionals: The project facilitated meaningful engagement with textile chemistry professionals through meetings and presentations. These interactions allowed for the exchange of technical insights and collaborative discussions on optimizing processing conditions for bio-based coatings. These include both Cotton Inc. employees and HeiQ (surfactant/emulsion company) employees. Wood, Fiber, and Pulping Chemistry Experts: Findings were presented to international audiences specializing in cellulosic fiber treatment. The research on epoxidized oil-based coatings for cotton fabrics and paper provided a platform for advancing sustainable alternatives within the fiber modification and coating communities. Mechanical Engineering Professionals: The project also connected with engineers exploring 3D printing applications of epoxidized cottonseed oil (ECSO). These discussions opened new pathways for applying ECSO in additive manufacturing, broadening the potential impact of the material beyond traditional textiles and paper. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project allowed for three presentations (1 oral, 2 posters) at the Fall 2024 American Chemical Society (ACS) National Meeting in Denver, CO August 18-22, 2024 (1 poster presentation) and at the 2025 International Symposium on Wood, Fiber, and Pulping Chemistry (ISWFPC) June 2-6, 2025, in Raleigh, NC. ACS meetings are international gatherings of experts from a wide range of fields that are all in some way related to chemistry. In particular importance to this project, experts in polymer science and chemistry, cellulose, and materials science attended this conference and were able to provide feedback on the poster and techniques demonstrated within. Kanipe, T.; Meza, L.; Park, S.; Chang, H.; Farrell, M.; Venditti, R. "Developing a Chemical Platform Based on Cottonseed Oil to Develop Functional Finishes for Cellulosic Materials." Poster Presentation at American Chemical Society Fall Meeting in Denver, CO, August 18-22, 2024. The ISWFPC is a biannual conference that gathers some of the world's leading experts in the pulp and paper world. One session of the conference is dedicated solely to product development related to cellulose-based materials. This is incredibly relevant to the project, given that we are developing coatings and finishes that are meant for cellulosic materials. Additionally, other work related to epoxides is common, given the uniqueness of the epoxide ring-opening reaction and its propensity for forming tunable resin materials. Kanipe, T.; Meza, L.; Park, S.; Chang, H.; Farrell, M.; Venditti, REpoxidized Cottonseed Oil for Sustainable Textile Finishing: Enhancing Cotton Fabric Performance with Bio-Based Modifications." Poster Presentation at International Symposium on Wood, Fiber, and Pulping Chemistry in Raleigh, NC, June 2-6, 2025. Additionally, the opportunity to work with textile experts at Cotton Incorporated (Cary, NC) is a direct result of this project. Taylor Kanipe is currently working through a internship at Cotton Incorporated research laboratories and is acquiring valuable training in industrial research. How have the results been disseminated to communities of interest?Dissemination of research findings has been a key component of the project, ensuring that progress and results reach relevant academic, industrial, and professional communities. Multiple avenues have been used to engage stakeholders and foster interdisciplinary dialogue. Regular internal meetings have been held with project stakeholders and collaborators to discuss progress, troubleshoot challenges, and align research goals. Close collaboration with experts at Cotton Incorporated has served as a critical channel for industry-focused dissemination. With a concentration of expertise in cotton, cottonseed oil, textile chemistry, and associated markets, Cotton Incorporated has provided a unique environment for real-time feedback, technical discussions, and strategic insight. Project members regularly share experimental results and processing data with these in-house experts, helping to guide practical applications and industrial relevance. Undergraduate researchers not only gained hands-on experience but also acted as knowledge multipliers, sharing findings in meetings with their graduate student advisors and undergraduate research symposia. These activities contributed to a broader educational impact and peer-to-peer dissemination within the student community, increasing awareness of sustainable textile research and bio-based materials. Results have been actively shared with the academic community through presentations at regional, national, and international conferences. The interdisciplinary nature of the project, which spans textile chemistry, pulp and paper science, materials engineering, and bio-based coatings, has led to participation in a diverse range of conferences. This strategy ensures that findings are communicated to a variety of audiences, including chemists, engineers, materials scientists, and sustainability researchers. These forums also provide opportunities for networking, collaboration, and enhancing the visibility of the project's contributions to sustainable material innovation. What do you plan to do during the next reporting period to accomplish the goals?Objective 1: Further characterization of cottonseed oil samples and other oilseed oil samples is needed. An in-depth characterization can be achieved in multiple ways. To profile the fatty acid profile, typically triglycerides are converted into fatty acid methyl esters. These are small molecules that are suitable for gas chromatography analysis. The major drawbacks of this method involve the preparation of the FAMEs as well as the lack of information regarding how the different fatty acids are arranged into the triglycerides that make up cottonseed oil. Advanced FTIR with complex deconvolution of peaks assigned to specific chemical functional groups will be conducted. Objective 2: Analysis and optimization of the epoxidation reaction will continue. Namely, the analysis of the 12 systems in which the epoxidation reaction conditions are altered via statistical designs will begin, and the optimum conditions for different degrees of epoxidation will be determined. Full epoxidation of cottonseed oil will be optimized first before working to develop proper conditions to produce multifunctional molecules. Objective 3: The next steps involve completing the emulsification of remaining formulations through sonication, ensuring consistent mixing parameters and timing. Stability assessments, such as visual observation, droplet size analysis, or phase separation tracking, will be performed over time to evaluate the effects of surfactant concentration, additive presence, and emulsifier distribution. Additional formulations may be tested by adjusting the Tween/Span ratio or adding alternative additives. Based on the results, optimized emulsions will be chosen for further functional testing or scale-up trials. Objective 4: Emulsion applied ECSO to fabric evaluation studies will continue. Burst strength, softness, and wrinkle resistance will be evaluated for emulsion-treated fabric samples. Similarly, samples will undergo laundering trials to determine the durability of the fabric finish. In future emulsion trials, different catalytic systems will be explored to optimize performance and cost. Objective 5: Emulsion applications or ECSO to paper will build on the knowledge gained from fabric studies. As paper and cotton fabric are both made from cellulose, they are the same on a chemical level. Where these materials differ is in the macrostructure, which thus lends fabric and paper vastly different qualities. Informed decision-making based on the fabric study results will be used in paper trials to optimize ECSO emulsions for use in paper products. Objective 6: The interaction between ECSO and different amines will be studied to determine the tunability of ECSO-amine and then evaluate treatments of these materials on fabric properties, particularly for textile applications.

Impacts
What was accomplished under these goals? Durable press finishes are widely used to improve the wrinkle resistance of cotton fabrics, but traditional formulations often contain formaldehyde-based chemicals that pose health and environmental risks. In addition, many of these finishes are derived from petroleum-based materials. This project seeks to develop a renewable, safer alternative by chemically modifying cottonseed oil (CSO) into epoxidized cottonseed oil (ECSO), which can then be formulated into aqueous emulsions for application on fabric and paper. The long-term goal is to produce bio-based treatments that are effective, sustainable, and formaldehyde-free. Objective 1: Fully characterize the chemical composition of cottonseed oil We conducted chemical characterization on refined CSO samples using titration-based techniques. The iodine value (IV), a measure of unsaturation, was found to be high (111 g iodine/100 g oil), confirming the presence of multiple double bonds available for epoxidation. Free fatty acid (FFA) content was measured at 0.06%, indicating minimal degradation and confirming that the oil was fresh and suitable for modification. Oxirane oxygen content (Oo%) was confirmed to be approximately 0%, as expected for unmodified CSO. These metrics collectively verify that the oil possesses the chemical structure and quality necessary for downstream epoxidation and formulation steps. Over a 2.5 year storage period over 90% of the epoxy rings of the freshly made ECSO are still present. Objective 2: Optimize epoxidation reaction conditions To evaluate and optimize the epoxidation process, we designed a response surface methodology using Design Expert software. Independent variables included reaction temperature, time, and hydrogen peroxide concentration. Preliminary epoxidation reactions are ongoing, and the goal is to assess conversion by tracking changes in IV and the formation of epoxide groups via Oo% titrations. These reactions will also explore the use of alumina in place of traditional acid catalysts, which could allow for a more environmentally friendly and reusable catalyst system. Early results suggest that higher peroxide concentrations and temperatures favor higher epoxidation extents, but further data collection is needed to build reliable predictive models. Objective 3: Develop stable oil-in-water emulsions of epoxidized cottonseed oil Since ECSO is oil-based and incompatible with water, stable emulsions must be developed for aqueous processing. We prepared emulsions with a fixed water-to-oil ratio (WOR) of 4:1 and tested multiple surfactant loadings (0.5%, 1%, 2%, and 5% wt/vol) using Tween 80 (HLB 15) and Span 20 (HLB 8.6) in a 1.8:1 mass ratio to achieve an overall HLB of 12.7, optimal for stabilizing oil-in-water systems. Surfactants were added from 10% stock solutions to the aqueous phase. Emulsions were tested both with and without additives, 1% NaCl or 1% glycerol (w/v), based on total aqueous volume. Initial mixing trials using an Ultraturrax homogenizer were unsuccessful due to equipment contamination. Subsequent batches were prepared using ultrasonic homogenization (amplitude 35%, pulse 2s on, 3s off, total 12 minutes). Early observations suggest that increasing surfactant concentration improves emulsion stability and that glycerol may contribute additional viscosity that stabilizes the interface. Emulsions were prepared in triplicate for consistency and reproducibility, with systematic labeling to track formulation variables. It has been shown that the conditions of emulsification critically impact the stability of the materials. Objective 4: Apply ECSO emulsions to cotton fabric and assess finish performance ECSO can impart hydrophobic properties to cotton fabric under certain conditions. When ECSO is applied in a solvent system containing hexanes and zinc chloride, the modified oil can bond and polymerize on the surface of the fabrics. This creates a hydrophobic layer on top of the cellulose of the fabric. This was confirmed by water contact angle measurements. Untreated fabrics displayed low contact angles, approximately 0°, which indicated a high degree of hydrophilic, water-loving, behavior. After treatment with ECSO, the water contact angle increased to 125°. Materials with WCA values above 90° are generally considered hydrophobic. The significant increase in the ratio of hydrophobic to hydrophilic groups is likely the explanation for the shift in behavior, though more work is needed to confirm this. Additionally, studies applying ECSO containing emulsions to cotton fabric have initiated. An experimental design testing ECSO concentration, solution pH, cure time, and cure temperature as independent variables has been constructed. Different dependent variables, including color, burst strength, and wrinkle resistance, are being analyzed to determine the efficacy of the different treatment conditions on cotton fabric. Preliminary results indicate that harsher treatment conditions (high temperature, long cure times, high pHs) lead to more significant discoloration and fabric yellowing. Alkaline yellowing, or the yellowing of cellulosic materials when exposed to high pHs, is a known phenomenon and was expected to occur. Low treatment temperatures and times minimized discoloration, even under high pH conditions. Objective 5: Evaluate ECSO coatings on paper for wet strength and water resistance Filter paper was treated using ECSO to evaluate water repellency and potential for wet-strength improvement. Like cotton, paper is composed of cellulose fibers, but with a different macrostructure, wet-laid, shorter wood fibers held by hydrogen bonding. Treatment with ECSO increased WCA from 40° (untreated) to 109°, suggesting that ECSO can form a similar hydrophobic film on paper surfaces. Further testing is underway to assess dry and wet tensile strength and permanence of the hydrophobic barrier after exposure to water. This approach could offer a sustainable, bio-based alternative to synthetic paper coatings used in packaging and food contact materials. Objective 6: Modify ECSO with amines for potential fabric softener applications In early-stage exploratory work, we reacted ECSO with primary fatty amines (dodecylamine, hexadecylamine, and octadecylamine) in the presence of zinc chloride as a Lewis acid catalyst. Unexpectedly, the reaction favored nucleophilic attack at the ester linkage rather than at the epoxide ring, producing fatty amides rather than epoxide-amine adducts. Fatty amides are of interest as phase change materials (PCMs) for thermal energy storage due to their ability to absorb and release heat during melting and solidification. While this route may not yield the intended fabric softener compounds, it opens a new line of investigation into energy storage materials derived from cottonseed oil.

Publications

• Type: Conference Papers and Presentations Status: Other Year Published: 2025 Citation: Venditti, R.: Kanipe, T.; Meza, L.; Park, S.; Chang, H.; Farrell, M.; From Byproduct to Functional Finish: Upgrading Cottonseed Oil for Textile and Paper Applications. Oral Presentation at International Symposium on Wood, Fiber, and Pulping Chemistry in Raleigh, NC, June 2-6, 2025.
• Type: Conference Papers and Presentations Status: Published Year Published: 2024 Citation: Kanipe, T.; Meza, L.; Park, S.; Chang, H.; Farrell, M.; Venditti, R. Developing a Chemical Platform Based on Cottonseed Oil to Develop Functional Finishes for Cellulosic Materials. Poster Presentation at American Chemical Society Fall Meeting in Denver, CO, August 18-22, 2024.
• Type: Conference Papers and Presentations Status: Published Year Published: 2025 Citation: Kanipe, T.; Meza, L.; Park, S.; Chang, H.; Farrell, M.; Venditti, R. Epoxidized Cottonseed Oil for Sustainable Textile Finishing: Enhancing Cotton Fabric Performance with Bio-Based Modifications. Poster Presentation at International Symposium on Wood, Fiber, and Pulping Chemistry in Raleigh, NC, June 2-6, 2025.