Progress 09/01/23 to 08/31/24
Outputs
Target Audience:Our audiences were mainly scientists, R&D engineers, business owners, extension educators, and undergraduate and graduate students in the field of bioproduct development, bioplastics and textiles industries. Scientific and engineering results of pilot-scale fabrication of physically reinforced keratin fibers were shared via publications inthree refereed journals, onepatent and one PhD dissertation. Changes/Problems:With the extension of the project to end on August 31, 2025, we should complete all planned successfully. What opportunities for training and professional development has the project provided?The P.I. has embedded basic and advanced knowledge of keratin chemistry and manipulation of keratin structures into courses TMFD 999, Doctoral Dissertation, TMFD 896, Independent Study, and TMFD 905, Advanced Problems. Graduate students who had a strong interest in utilizing biobased materials, fiber chemistry, and textile fibers not only learned the knowledge in classrooms but also had lab experience in the real-time spinning of keratin fibers. We also trained undergraduate students to learn and conduct basic knowledge of fiber spinning, yarn spinning, and fabric knitting. With the training, one undergraduate student won the competition in Nebraska's Undergraduate Creative Activities and Research Experience (UCARE). How have the results been disseminated to communities of interest?
Nothing Reported
What do you plan to do during the next reporting period to accomplish the goals?We will complete the production of filament yarns and fabrics made of 50/50 silk/keratin blends and pure keratin. Also, we will develop apparel prototypes composed of keratin blends and pure keratin. Finally, the dyeability evaluations of keratin textiles with both acid and reactive dyes will be completed.
Impacts
What was accomplished under these goals?
We have conducted two physical reinforcement, chitin nanoparticles with controlled deacetylation and in-situ formation of CaCO3 nanoparticles, for continuously spun keratin fibers. We utilize chitin nanoparticles with controlled deacetylation and develop novel wet-spun keratin/chitin fibers on a pilot scale with strong interactions between keratin fibers and chitin nanoparticles. Inspired by chitin-protein interaction in crab shells, we reported the development of wet stable keratin composite fibers with similar fineness to silk and better toughness than wool. On the continuous spinning line, small amount of chitin nanoparticles with controlled amine content enhanced keratin molecular entanglement, improved fiber drawability, induced the formation of ß-sheet conformation, and incorporated external crosslinkages. As a result, keratin composite fibers with chitin nanoparticles had fineness, tenacity, breaking elongation, and toughness, and wet properties from 2.1 to 0.9 denier, 1.1 to 2.2 g/den, 11% to 19%, 21 to 50 J/cm3, and 0.6 to 1.2 g/den, respectively. We further fabricated the continuously spun keratin composite fibers into filament yarns and a sweater. Keratin composite fibers exhibited excellent processibility throughout the entire garment-making process. We have also developed novel and in-situ formed CaCO3 nanoparticles to provide similar strength and wet properties of feather-derived fibers to wool. Transformation of feather wastes to high-quality protein fibers can alleviate the environmental concerns of synthetic textile fibers. Many reinforcements, though necessary to develop quality protein products, are ineffective, toxic, and costly. CaCO3 is potentially a good fiber reinforcement because of the strong calcium-protein interaction. However, many protein/CaCO3 composites, suffering from nanoparticle aggregation and the disruption of protein interactions, are very brittle and wet unstable. In this work, we have developed a novel technology for the dispersant-free and in-situ formation of CaCO3 nanoparticles, enabling precise control over size and distribution within keratin fibers and thus minimizing nanoparticle aggregation and protein disruption. For in-situ formation, Ca2+ was first evenly distributed and anchored in continuously spun keratin fibers. Then keratin fibers were treated under different carbonate buffers so that CaCO3 nanoparticles were in-situ formed in fibers. Without any external dispersing agents, fine and evenly distributed CaCO3 nanoparticles bonded with carboxylic acid, amine, and hydroxyl groups in keratin exerted desirable reinforcement. As a result, with only 1% in-situ formed CaCO3 nanoparticle, keratin fibers had 49%, 47%, 43%, and 47% increases in dry tenacity, dry strain, dry toughness, and wet tenacity, respectively. The continuously spun feather-derived fibers have similar strength and wet properties to wool. We first prepared chitin nanoparticles with consistent particle size and distribution while varying deacetylation levels. We initially subjected chitin to acidic hydrolysis to remove most of its amorphous regions. Subsequently, chitin nanoparticles underwent deacetylation in an alkaline environment. Due to the negligible solubility of chitin and hydrolysis of glycosidic bonds in chitin under alkaline conditions, the particle size remained largely unchanged during deacetylation. The particle size distribution of chitin nano-sized particles with different amine content, DD, was approximately 85±20 nm. Chitin nanoparticles with higher deacetylation exhibited slightly smaller particle sizes, but there was no statistically significant difference compared to those with lower deacetylation. Chitin nano-sized particles with desirable amine contents significantly enhanced the unfolding of feather keratin molecules in solution, increasing the entanglement of protein molecules and greatly improving the spinnability of keratin solutions. As the deacetylation level of chitin increased, the binding energy between chitin and keratin rapidly rose from 20 kcal/mol to 120 kcal/mol. When the deacetylation level reached above 50%, the affinity between keratin and chitin gradually leveled off. We also evaluated the effect of chitin nanoparticles on keratin unfolding. We determined the gyration radius (Rg) of the protein, a measure of its compactness, using the protein's rheological properties. Protein unfolding significantly altered the compactness and Rg of keratin. With increasing deacetylation of chitin, the Rg of keratin gradually increased from 3.4 nm to 3.9 nm. While the increase in Rg was smaller for chitin with a deacetylation degree of 8% compared to higher deacetylation levels, it was still significantly higher than that of keratin without chitin. These Rg results align with the calculations of chitin-protein affinity. Consequently, the fineness of protein fibers was further reduced. After the addition of chitin nanoparticles, the fiber fineness can be reduced from 2.1 to 0.9 denier, which was even lower than that of typical silk fibers. Keratin composite fibers had substantial ordered structures. Compared to keratin fibers, keratin composite fibers exhibited higher crystallinity and more beta-sheet structures. The increased entanglement between keratin molecules was facilitated by chitin nanoparticles, allowing for greater drawing ratios of protein fibers. Fiber drawing encouraged better alignment of protein molecules, ultimately resulting in the formation of more ordered structures. Chitin nanoparticles enhanced interaction with keratin, resulting in keratin composite fibers with a fineness of less than 1 denier, a nearly 100% increase in tenacity, and a 250% increase in breaking elongation. We have also developed novel and in-situ formed CaCO3 nanoparticles to provide similar strength and wet properties of feather-derived fibers to wool. Transformation of feather wastes to high-quality protein fibers can alleviate the environmental concerns of synthetic textile fibers. Many reinforcements, though necessary to develop quality protein products, are ineffective, toxic, and costly. CaCO3 is potentially a good fiber reinforcement because of the strong calcium-protein interaction. However, many protein/CaCO3 composites, suffering from nanoparticle aggregation and the disruption of protein interactions, are very brittle and wet unstable. In this work, we have developed a novel technology for the dispersant-free and in-situ formation of CaCO3 nanoparticles, enabling precise control over size and distribution within keratin fibers and thus minimizing nanoparticle aggregation and protein disruption. For in-situ formation, Ca2+ was first evenly distributed and anchored in continuously spun keratin fibers. Then keratin fibers were treated under different carbonate buffers so that CaCO3 nanoparticles were in-situ formed in fibers. Without any external dispersing agents, fine and evenly distributed CaCO3 nanoparticles bonded with carboxylic acid, amine, and hydroxyl groups in keratin exerted desirable reinforcement. As a result, with only 1% in-situ formed CaCO3 nanoparticle, keratin fibers had 49%, 47%, 43%, and 47% increases in dry tenacity, dry strain, dry toughness, and wet tenacity, respectively. The continuously spun feather-derived fibers have similar strength and wet properties to wool.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Mu, B.N., and Yang*, Y.Q., "Densely crosslinked protein bioplastics with superior stretchability and desirable wet stability via quality protein restoration." Food Packaging and Shelf Life 40 (2023): 101225.
- Type:
Journal Articles
Status:
Published
Year Published:
2024
Citation:
Mu, B.N., Yu, X.Q. and Yang*, Y.Q. Continuously spun biocomposite fibers from feather keratin and chitin with better toughness than wool via enhanced protein unfolding and conformation organization. Chemical Engineering Journal. 482, 148850. 8 pgs. (February 2024).
- Type:
Journal Articles
Status:
Published
Year Published:
2024
Citation:
Hassan, F., Mu, B.N., and Yang*, Y.Q. Natural polysaccharides and proteins-based films for potential food packaging and mulch applications: A review. International Journal of Biological Macromolecules. 260, 129628. 29 pgs. (February 2024).
- Type:
Theses/Dissertations
Status:
Submitted
Year Published:
2024
Citation:
Faqrul Hassan (August 2024). Sorption thermodynamics, kinetics, colorfastness, and strength retention of feather derived artificial keratin fibers for industrial applications. Ph.D. Dissertation, The University of Nebraska - Lincoln.
|
Progress 09/01/22 to 08/31/23
Outputs
Target Audience:Our audiences were mainly scientists, R&D engineers, business owners, extension educators, and undergraduate and graduate students in the field of bioproduct development. Scientific and engineering results of pilot-scale fabrication of chemically reinforced keratin fibers were shared via two presentations at the 27th Annual Green Chemistry & Engineering Conference and the Fall 2023 National Meeting of American Chemical Society (ACS). Changes/Problems:It is highly possible that we need extensions due to the disruptions by COVID-19. COVID-19 disrupted our collaboration plans with our partners. Therefore, we have to conduct yarn formation and build pilot-scale yarn fabrication facilities in our labs. Also, we have to independently develop knitted fabrics and apparel prototypes composed of keratin fibers. We planned to develop yarns in our partners Jiangsu Sunshine Group and Shandong Daiyin Textile Group and keratin fabrics and garments in another partner, Brown Sheep Company, Inc, respectively. However, since COVID-19 disrupted our collaboration, we have to design and make yarns, fabrics, and garments ourselves in our labs. In the extension year, we will complete the production of filament yarns and fabrics made of 50/50 silk/keratin blends and pure keratin. Also, we will develop apparel prototypes composed of keratin blends and pure keratin. COVID-19 disrupted our research progress. Since COVID-19 led to a 6-month complete campus shutdown, and two-year reduced lab work due to strict social distancing and personnel sickness, research progress, particularly the fabrication of enough keratin fibers for pure keratin and blend yarns, has been delayed. Therefore, we have to continue the fabrication of keratin fibers on a pilot scale in the next reporting period for yarns and fabrics made of 50/50 silk/keratin and pure keratin during the next reporting period. We may not be able to evaluate the dyeability of feather-derived keratin fibers by the end of the next reporting period. We have to study the physical fiber reinforcement, accumulation of keratin/silk, and pure keratin filaments and make prototype garments in the next reporting period. Therefore, we may not be able to complete the dyeability evaluation of keratin fibers. Specifically, we may have to delay the study of thermodynamics and kinetics of dyeing keratin fibers and the comparison of that to other common protein fibers, including wool and silk. Furthermore, the evaluation of colorfastness of dyed keratin fibers may also be delayed. What opportunities for training and professional development has the project provided?The P.I. has embedded basic and advanced knowledge of keratin chemistry and manipulation of keratin structures into courses TMFD 999, Doctoral Dissertation, TMFD 896, Independent Study, and TMFD 905, Advanced Problems. Graduate students who had a strong interest in utilizing biobased materials, fiber chemistry, and textile fibers not only learned the knowledge in classrooms but also had lab experience in the real-time spinning of keratin fibers. How have the results been disseminated to communities of interest?The latest research progress has been disseminated via oral presentations at the 27th Annual Green Chemistry & Engineering Conference and the Fall 2023 National Meeting of American Chemical Society (ACS). Many conference attendees from academic and industrial fields contacted us for potential collaborations. Our research accomplishments were also disseminated to communities of interest via media coverage UNL professor, researchers acknowledged for sustainable fiber achievement. The Daily Nebraskan. November 11, 2022. https://www.dailynebraskan.com/culture/unl-professor-researchers-acknowledged-for-sustainable-fiber-achievement/article_27633c1c-614a-11ed-89ac-b39f1c99d114.html What do you plan to do during the next reporting period to accomplish the goals?We will further improve the toughness of keratin fibers via the incorporation of green and sustainable nanoparticles. Specifically, chitin nanoparticles with controlled deacetylation and calcium carbonate nanoparticles will be blended with protein molecules. We will complete the production of filament yarns and fabrics made of 50/50 silk/keratin blends and pure keratin. Also, we will develop apparel prototypes composed of keratin blends and pure keratin.
Impacts
What was accomplished under these goals?
We have further improved the mechanical and wet properties of fibers via post-treatment of spun fibers, built pilot-scale yarn fabrication facilities in our lab, and successfully made a knitted sweater and a prototype scarf from 50/50 keratin/rayon. We further improve the quality of spun keratin fibers by recovering additional intermolecular crosslinkages, brought by fiber reduction and oxidation. With fiber reduction and oxidation, the dry strength, dry strain, and wet strength were improved by 20%, 25%, and 40%, respectively. The keratin fibers had a dry stress of 120-140 MPa, dry strain of 10-15%, dry toughness of 18-22 J/cm3, wet stress of 70-100 MPa, wet strain of 22-28%, and wet toughness of 22-28 J/cm3. To maximize the recovery of disulfide bonds, spun fibers were reduced by sodium sulfite and then oxidized by hydrogen peroxide three times. The mechanism of recovery of intermolecular disulfide bonds in keratin fiber via sulfite reduction followed by oxidation is illustrated below. Keratin extraction using thiol reducing agent Keratin-S-S-Keratin + Cys-SH - - > Keratin-S-S-Cys (impossible to crosslink) + Keratin-SH Limited intermolecular crosslinkages in fibers after oxidation Keratin-SH + Keratin-SH + [O] - - > Keratin-S-S-Keratin (intermolecular disulfide bonds) Keratin-SH + Cys-SH + [O] - - > Keratin-S-S-Cys (not intermolecular disulfide bonds) Further fiber reduction Keratin-S-S-Cys + [H] - - > Keratin-SH Fiber re-oxidation Keratin-SH + Keratin-SH + [O] - - > Keratin-S-S-Keratin (intermolecular disulfide bonds) First, we used a reducing agent, cysteine, to break initial disulfide bonds in feather keratin (Keratin) in keratin extraction. Cysteine (Cys) can cap keratin molecules, Keratin-S-S-Cys, to prevent the re-establishment of disulfide crosslinkages. As a result, extracted keratin can easily dissolve to form spinning dope with the aid of a small amount of reducing agents. However, after the formation of fibers, very limited intermolecular disulfide bonds could be built due to the existence of Keratin-S-S-Cys. Therefore, we conducted further fiber reduction and oxidation. In the fiber reduction process, capped cysteine on keratin was removed by reducing Keratin-S-S-Cys. The newly formed Keratin-SH can be further oxidized to form intermolecular disulfide bonds, known as Keratin-S-S-Keratin. Via the fiber reduction and oxidation, 89% of disulfide bonds were recovered. The improved properties of keratin fibers facilitate the fabrication of yarns and garments. We have built up pilot-scale yarn fabrication facilities in our lab and produced 50/50 keratin/rayon filaments needed for fabric and prototype garments made on a pilot scale. Via the combination of keratin and rayon fibers, and increased yarn sizes and twists on a pilot scale, the total amount of keratin-based filaments was about 400 grams. Due to the limited number of fibers extruded from a spinneret and the minimal requirement of yarn sizes for sweater fabrication, we used two steps to make keratin/rayon filament yarns. First, we combine four bobbins, two with keratin filaments and two with rayon filaments, via our continuous spinning line to make blended keratin/rayon yarns. At this stage, the filaments were fine, and the twists of filaments were not high. Therefore, we further combined four bobbins of blended yarns on an electric eel wheel nanomachine so that the yarn size and degrees of twists were further improved. The resultant blended yarns were ready for the fabrication of prototype garments. We have also overcome all the technical challenges of fabric formation. We have successfully made a knitted sweater and a prototype scarf from 50/50 keratin/rayon. The PI demonstrated the knitted sweater at the 2023 PD meeting in Kansas City. We have also evaluated the effects of the fineness of keratin/rayon yarns on the properties of fabric formation. In detail, we are making several small pieces of fabrics from yarns with different diameters for property evaluations.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2023
Citation:
Mu, B.N, Hassan, F., Xu, L., and Yang*, Y.Q. Novel protein fibers from feathers for textiles. Paper ID: 3889254. June 14 (2:05-2:25pm) in Session of Material and Chemical Innovations in Apparel and Footwear. (2:00-5:05pm) at 27th Annual Green Chemistry & Engineering Conference. Long Beach, CA, June 13-15, 2023.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2023
Citation:
Mu, B.N., Yu, X.Q., Xu, L, and Yang*, Y.Q. Keratin/chitin composite fibers with enhanced elongation, water stability, strength, and elastic modulus. Session of Advances in Renewable Materials, Division of Cellulose and Renewable Materials. ACS Fall 2023, San Francisco, CA, United States, August 13-17, 2023, PAPER ID: 3920583 (August 15, 2023, 2:55PM-3:20 PM)
|
Progress 09/01/21 to 08/31/22
Outputs
Target Audience:Our audiences were mainly scientists, R&D engineers, business owners, extension educators, and undergraduate and graduate students in the field of bioproduct development. Scientific and engineering results of pilot-scale fabrication of chemically reinforced keratin fibers were shared via publication of a peer-reviewed paper in a top-tiered sustainable materials journal and three presentations at the fall 2022 international meeting of American Chemical Society (ACS). Changes/Problems:We need at least one year of no-cost extension due to the disruptions by COVID-19. COVID-19 disrupted our collaboration plans with our partners. Therefore, we have to conduct yarn formation and build pilot-scale yarn fabrication facilities in our labs. Also, we have to independently develop knitted fabrics and apparel prototypes composed of keratin fibers. We planned to develop yarns in our partners Jiangsu Sunshine Group and Shandong Daiyin Textile Group and keratin fabrics and garments in another partner, Brown Sheep Company, Inc, respectively. However, since COVID-19 disrupted our collaboration, we have to design and make yarns, fabrics, and garments ourselves in our labs. In the extension year, we will complete the production of filament yarns and fabrics made of 50/50 silk/keratin blends and pure keratin. Also, we will develop apparel prototypes composed of keratin blends and pure keratin. COVID-19 disrupted our research progress. Since COVID-19 led to a 6-month complete campus shutdown, two-year reduced lab works due to strict social distance and personnel sickness, research progress, particularly the fabrication of enough keratin fibers for pure keratin and blend yarns, has been delayed. We only completed the accumulation of keratin fibers for 50/50 rayon/keratin yarns by the end of third year. Therefore, we have to continue the fabrications of keratin fibers on a pilot scale in the next reporting period for yarns and fabrics made of 50/50 silk/keratin and pure keratin during the next reporting period. COVID-19 delayed our dissemination plan. Due to COVID-19, several important travels have been canceled since 2020. As a result, we need an extension to provide oral or poster presentations to disseminate our research results. What opportunities for training and professional development has the project provided?The P.I. has embedded basic and advanced knowledge of keratin chemistry and manipulation of keratin structures into courses of TMFD 405/805, Advanced Textiles, TMFD 499, Undergraduate Research, TMFD 828, Coloration, and TMFD 999, Doctoral dissertation, respectively. Graduate and undergraduate students who had a strong interest in the utilization of biobased materials, fiber chemistry, and textile fibers not only learned the knowledge in classrooms, but also had a lab experience in real-time spinning of keratin fibers. Due to the travel restrictions from COVID-19, we attended the first conference, ACS Fall 2022, in August 2022 to present our research progresses. How have the results been disseminated to communities of interest?Our patent application regarding the spinning of keratin fibers has been licenced to a company. We have trained their technicians for quick technology transfer and commercialization. Due to confidentiality, we are not allowed to disclose the company's name. Please refer to Jeewan Jyot (jjyot@nutechventures.org) at NUtech Ventures for more information about the company. Our research accomplishments were also disseminated to communities of interests via Media coverage Are chicken feathers a greener alternative to polyester and nylon? By Natalie Berkhout. Poultry World. February 8, 2022. https://www.poultryworld.net/Home/General/2022/2/Are-chicken-feathers-a-greener-alternative-to-polyester-and-nylon-850716E/ Feather-based fibers could recycle poultry processing waste. Elizabeth Doughman, Managing Editor of Poultry Future. WATTPoultry.com. February 4, 2022. https://www.wattagnet.com/blogs/51-poultry-tech-trends/post/44440-feather-based-fibers-could-recycle-poultry-processing-waste Process improves strength, color of feather-based fibers. Phys.org Process improves strength, color of feather-based fibers (phys.org) January 12, 2022. Credit: Shutterstock. Nebraska in the national news: January 2022 Nebraska Today University of Nebraska-Lincoln (unl.edu) Process improves strength, color of feather-based fibers. in Pocket Science: Exploring the 'What,' 'So what' and 'Now what' of Husker research. by Scott Schrage. Nebraska Today. January 12, 2022. Process improves strength, color of feather-based fibers Nebraska Today University of Nebraska-Lincoln (unl.edu) Researchers develop process for improving feather quality, performance. By Marie Donlon. Engineering360. January 12, 2022. Researchers develop process for improving feather quality, performance Engineering360 (globalspec.com) What do you plan to do during the next reporting period to accomplish the goals?We will focus on the accumulation of keratin fibers via pilot-scale spinning and design pilot-scale yarn fabrication facilities in our labs. We will continue to accumulate keratin fibers for silk/keratin and pure keratin yarns and fabric formation. In the grant proposal, pilot-scale fabrication of keratin fibers should have been completed by the third year. However, due to the research disruption by COVID-19, we only completed the accumulation of keratin fibers for 50/50 rayon/keratin yarns. Therefore, we have to continue the fabrications of keratin fibers on a pilot scale to produce enough protein fibers for 50/50 silk/keratin and pure keratin yarns during the next reporting period. We will learn yarn formation and build pilot-scale yarn fabrication facilities in our labs. In the grant proposal, pilot-scale fabrication of keratin yarns, fabrics and garments would be conducted in our partners' plants. However, due to the disruption of COVID, we have to cancel proposed collaborations and make yarns ourselves in our labs.In the next year, we plan to produce enough 50/50 rayon/keratin filament yarns and make a 50/50 rayon/keratin fabric to evaluate our ability of yarn formation.
Impacts
What was accomplished under these goals?
We have completed pilot-scale extraction of keratin from various chicken feathers, determination of conditions for pilot-scale fabrication of keratin fibers and accumulation of keratin fibers for rayon/keratin blend yarns in the third year of research. Our success in pilot-scale keratin extraction and fiber spinning helps the fast transference of our technology into the industry production. In addition to efficient colorant separation from various chicken feathers for the pilot-scale extraction of keratin, we successfully extracted keratin from different kinds of chicken feathers with high yield and purity. Our keratin extraction system was applied on a 30-gallon tumbling reactor heated with steam in our lab for pilot-scale protein extraction. Results showed that pilot-scale keratin extraction fitted various feather kinds and obtained a high extraction yield, about 70%, and protein purity, about 95%. Also, we refined the drying conditions for keratin. Initially, we used freeze drying to prepared fluffy keratin powders for easy dissolution in spinning dopes. Here, we simply oven-dried keratin followed by milling to make fine keratin particles. The resultant products also easily dissolved in spinning dopes. Besides, we have separated colors from colored feathers in the pilot scale protein extraction. Pilot-scale extraction, cost-effective oven drying and efficient color removal from feathers ensured an easy and quick industry transference of our spinning technology. Though our research progresses have been disrupted by COVID-19, we have optimized conditions of continuous fiber spinnings for better properties and easier spinning operations and accumulated keratin fibers enough for 50/50 rayon/keratin filament yarns. Overall, we reduced the use of chemicals both in spinning dope and coagulation baths. As a result, fiber properties were further improved, and fiber washings were simplified. For spinning dope, we have reduced the use of inorganic salts by 80%. Initially, we used 0.2 M carbonate buffer to maintain the pH of spinning dope. However, the high salt concentration prevented desirable protein dissolution and molecular entanglements. As a result, the spinnability of spinning dope would be reduced. Here, we replaced carbonate buffer with 0.4% sodium hydroxide solution, providing the same spinning dope pH. Due to the replacement, protein concentration and spinnability were both improved. Because of the changes in the composition of spinning dopes, we also changed the chemicals in coagulation bath for desirable fiber stretchability and solidified speed. In the coagulation bath, the sodium sulfate was reduced from 15% to 10%, and the pH was increased from 2 to 4. We also found that adding 1 g/L sodium dodecyl sulfate into the coagulation bath substantially improved the stretchability of fibers. Via the optimization of spinning dope and coagulation bath, the drawability was improved by 150%. Furthermore, we incorporated the chemical crosslinking into the continuous spinning line. Specifically, filaments underwent multiple dippings and squeezings for the establishment of crosslinkages brought by saccharide aldehydes. The pH of the dipping solution, containing saccharide aldehydes, was adjusted to 5 with acetic buffer. Concentrations of saccharide aldehydes in fibers were controlled by squeezings. Filaments with desirable amounts of saccharide aldehydes reached the heating roller to form aldimine crosslinkages in fibers. The temperature of the heating roller was controllable for optimized crosslinking. Finally, filaments were washed in a bath with pH of 4 adjusted by hydrochloric acid. Final breaking strength and breaking elongation of keratin fibers from pilot-scale wet spinning were 215 MPa and 20%.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2022
Citation:
Mu, Bingnan, et al. "Pilot-scale spinning and sucrose-tetra-aldehydes-crosslinking of feather-derived protein fibers with improved mechanical properties and water resistance." Sustainable Materials and Technologies 31 (2022): e00367.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Mu, B.N. (presenter), Xu, Lan, and Yang, Y.Q. Ductile keratin/chitin composites from improved matrix-reinforcement compatibility and amide crosslinkages via controlled degree of chitin deacetylation. Session of Advances in Packaging Recycling and Sustainability under Division of Agricultural and Food Chemistry (AGFD). ACS Fall 2022, Chicago, IL, United States, August 21-25, 2022 (August 23, 2022, 4:50PM-5:15 PM).
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Mu, B.N. (presenter), Xu, Lan, and Yang, Y.Q. Highly flexible and wet stable keratin films with controlled length of disulfide crosslinkage formed via room temperature reduction-oxidation. Session of Biobased Polymers & Applications under Division of Agricultural and Food Chemistry (AGFD). ACS Fall 2022, Chicago, IL, United States, August 21-25, 2022 (August 21, 2022, 2:00PM-2:25 PM).
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Mu, B.N., Hassan, F., Xu, Lan, and Yang, Y.Q. (presenter). Pilot-scale production of tough and wet stable protein fibers from chicken feathers. Session of Advances in Renewable Materials under Division of Cellulose and Renewable Materials (CELL). ACS Fall 2022, Chicago, IL, United States, August 21-25, 2022 (August 22, 2022, 10:55AM-11:20 AM).
|
Progress 09/01/20 to 08/31/21
Outputs
Target Audience:Our audiences were mainly scientists, R&D engineers, business owners, extension educators, and undergraduate and graduate students in the field of bioproduct development. Scientific and engineering results of reinforcement of keratin fibers and colorant separation for pilot-scale extraction of keratin were shared via publication of peer-reviewed papers in three top-tier journals. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?The PI has embedded basic and advanced knowledge of keratin chemistry and manipulation of keratin structures into courses of TMFD 405/805, Advanced Textiles, TMFD 499, Undergraduate Research, TMFD 830, Fiber, Yarn and Fabric Constructions, and TMFD 999, Doctoral dissertation, respectively. Graduate and undergraduate students who had a strong interest in the utilization of biobased materials, fiber chemistry, and textile fibers not only learned the knowledge in classrooms, but also had a lab experience in real-time spinning of keratin fibers. Due to the COVID-19 and lockdowns, many planned training activities, including one-on-one work, workshops, conferences, seminars, study groups, were canceled. How have the results been disseminated to communities of interest?Since our research is still in its initial stage and due to the COVID-19 pandemic, our dissemination activities are limited in the second year. One of the companies, Dropel Fabrics, has demonstrated considerable interests in our fiber production technology. We have had many communications with Dropel Fabrics, sent multiple samples of our fibers for their evaluations and are at the final stage to sign technology transfer agreements with that company. What do you plan to do during the next reporting period to accomplish the goals?We will focus on the pilot-scale extraction of keratin and the pilot-scale fabrication of keratin fibers and yarns(threads) for the next reporting period. Extraction of colorants and keratin will be optimized for safe, non-destructive, efficient keratin extractions. The separated colorants could be reused as natural colorants for regenerated keratin fibers. For pilot-scale fabrication of keratin fibers, spinning dope, coagulation bath, oxidation bath and washing bath will be carefully investigated. The properties of spinning dope from lab-scale extracted and pilot-scale extracted protein will be compared. The concentrations of protein content, additives and cleavages of disulfide bonds will be controlled to ensure an optimal entanglement of protein chains and solution spinnability. For the coagulation bath, the different compositions will be studied for the fast precipitation of protein. For oxidation bath, the disulfide bonds in keratin fibers must be recovered swiftly so that the spun fibers have a very fine diameter and desirable mechanical properties. The oxidation not only ensures the fast recovery of disulfide bonds, but also avoids damaging the backbones of keratin in the fibers. The drawing ratio of fibers after oxidation should further increase. After oxidation and drawing, the fibers will be washed to remove impurities including salts and oxidation agents. For pilot-scale fabrication of keratin yarns, we will try various yarn spinning techniques including sirofil spinning, ring spinning and twisting.
Impacts
What was accomplished under these goals?
The goal is to develop textile fibers, yarns, fabrics and garments from chicken feathers via engineered pilot-scale production, which determines whether the technology is viable on industrial-scale productions. We propose several dissolution systems and reinforcement methods to improve the properties of regenerated keratin fibers, and to produce keratin fibers from continuous wet-spinning system with acceptable textile processing properties. Through collaborations with the world-leading textile manufacturers, we will demonstrate that chicken feathers could be turned into profitable textile products. We focused on the physical and chemical reinforcements of keratin fibers and pilot-scale extraction of keratin from various chicken feathers in the second year of research. The purpose of reinforcement of keratin fibers is to further improve the mechanical properties and wet stabilities. As a result, keratin fibers after reinforcements could meet the requirements for textile uses. We developed chitin nanoparticles with engineered deacetylation for the physical reinforcement. The physical reinforcement technology can be of sufficient interest to researchers and industrial technologists who focus on developing robust biobased products including fibers, films and foams using green and cost-effective approaches. Keratin films are used first to quantify the reinforcement of nanoparticles. We found out that chitin-nanoparticles with engineered deacetylation not only had improved interfacial interactions but also formed crosslinkages with keratin. As a result, ordered keratin structures with a high degree of entanglement of keratin molecules were substantially formed without the help of coupling agents. Reinforced keratin products had a 230%, 260%, 540% improvement in breaking strain, breaking stress, and ductility, respectively as well as 94% weight retention after being immersed in water for 1 week. We also developed formyl-saccharide-based crosslinkers to chemically reinforce keratin fibers. The chemical reinforcement technology can be of sufficient interest to researchers and industrial technologists who focus on developing biobased crosslinkers, reinforcements under mild conditions, crosslinkings with minimal damages to matrix, and robust biobased products including fibers, films, and foams. First, we addressed the concerns of using formyl-saccharide as crosslinkers, such as generation of formaldehyde, high consumption of modifiers, loss of mechanical properties, yellowing, and decline in dyeability of fibers after crosslinking. In this project, we controlled structures of crosslinkers and incorporated disaccharide-tetra-aldehydes into keratin fibers. No formaldehyde was generated in the whole process. Cytocompatibility of crosslinked products was not altered by formyl-saccharides. Length of crosslinkages controlled properties of fiber products. We achieved the efficient colorant separation from various chicken feathers for the pilot-scale extraction of keratin. The colorant removal technology can be of sufficient interest to researchers and industrial technologists who focus on non-destructive color removal and high value-added textile recycling. When extracting keratin from feathers on a pilot scale, chicken feathers with different colors and from various sources will be added to the extraction bath. To obtain white keratin fibers, colorants on the feathers must be removed without damaging protein structures. Without the color removal, regenerated keratin fibers would have dull shades and limited market values. Since traditional dye extractions focus on finding solvents with high dye solubility, dyes cannot be completely removed from protein materials. We found out that lessening feather density substantially disrupts physical interactions between dyes and feathers, and thus raises the chemical potential of dyes in all parts of feathers higher than that in solutions. Via the minimization of feather density by solvents and temperatures, colorants on feathers were completely removed.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Mu, B., Hassan, F., Wu, Q., & Yang, Y. (2020). Ductile keratin/deacetylated chitin composites with nanoparticle-induced formation of ordered and entangled structures. Composites Science and Technology, 200, 108462 (7 pgs).
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
Mu, B., & Yang, Y. (2022). Complete separation of colorants from polymeric materials for cost-effective recycling of waste textiles. Chemical Engineering Journal, 427. 131570 (11 pgs). (2021 online)
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
Mu, B.N., Wu, Q.M., Xu, L. and Yang*, Y.Q. (2022). A sustainable approach to synchronous improvement of wet-stability and toughness of chitosan films. Food Hydrocolloids. 123. 107138 (8 pgs) (2021 online).
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2020
Citation:
Mu, B. (2020). Establishment of Ordered Keratin Structures and Crosslinkages for Production of High-performance Textile Fibers, Adsorbents and Composites from Chicken Feathers. Ph.D. Dissertation, The University of Nebraska - Lincoln.
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Progress 09/01/19 to 08/31/20
Outputs
Target Audience:Our audiences were mainly scientists, R&D engineers, business owners, extension educators, and undergraduate and graduate students in the field of bioproduct development. Scientific and engineering results on continuous wet-spinning of pure keratin fibers from chicken feathers were shared via publication of a peer-reviewed paper in a top green chemistry journal and oral presentations at two international conferences on green and sustainable development of polymeric materials. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?The PI have embedded basic and advanced knowledge of keratin chemistry and manipulation of keratin structures into courses of TMFD 405 and 805, Advanced Textiles, and TMFD 896, Independent Study, respectively. Graduate and undergraduate students who had a strong interest in the utilization of biobased materials, fiber chemistry, and textile fibers not only learnt the knowledge in classroom, but also had a lab tour to see actual spinning process for keratin fibers. Meanwhile, PI and graduate students in PI's group participated in some academic conferences to share our latest research progress. It was a unique professional training for graduate students who can get feedback on an early version of their latest work, know other people in their field, hear about the latest research and improve the presentation and communication skills. We attended two conferences last year. One was Forth International Symposium on Materials from Renewables in University of Georgia and the other one was 9th International Conference on Advanced Fibers and Polymer Materials in China. ? How have the results been disseminated to communities of interest?Since our research is still in its initial stage, we did not perform many dissemination activities in the first year. We have contacted several companies after obtaining some preliminary results. One of the companies, Dropel Fabrics, has demonstrated considerable interest in our fiber products. We are now in the early contact with Dropel Fabrics, and the company is conducting initial evaluations of our technology. ? What do you plan to do during the next reporting period to accomplish the goals?For the next reporting period, we focus on the reinforcements of keratin fibers, including increasing mechanical properties and wet stabilities. Besides, we will initiate a pilot-scale extraction of keratin from chicken feathers. Addition of biobased nanoparticles into spinning dope is the main physical reinforcement for keratin fibers. We will use partially deacetylated chitin nanoparticles for the reinforcement. Chitosan nanoparticles are known for their good affinity to protein materials. They have a large quantity of amino and hydroxyl groups, which could form strong intermolecular interactions with keratin molecules. However, such a large number of hydrophilic groups also lead to poor water stability of chitosan. Although chitin nanoparticles are stable in an aqueous environment, their compatibility with protein materials is not as good as chitosan nanoparticles. Thereby, chitin will be hydrolyzed to form nanoparticles and then deacetylated to different degrees to achieve a balance between stability to water and compatibility to protein materials. These chitin nanoparticles with varying degrees of deacetylation will be uniformly distributed in keratin spinning dopes to obtain physically reinforced keratin fibers. Effect of concentration, aspect ratio, and crystallinity of the chitin nanoparticles with different degrees of deacetylation on tensile properties, water stability, thermal stabilities, and surface morphologies of keratin fibers will be evaluated. Crosslinking will be used as the chemical reinforcement. Crosslinkers will be screened based on low crosslinking temperature, low toxicity and cost-effectiveness. Sugar-based aldehydes and citric acid are two candidates to be evaluated. In the following year, we will choose an optimal crosslinker and finalize the crosslinking conditions such as chemical concentration, temperature, and pH. Improvements in tensile properties, water stabilities, thermal stabilities, and surface morphologies, as well as crosslinking degree of keratin fibers, will be evaluated.?
Impacts
What was accomplished under these goals?
For the first year of this project, we focused on the development of keratin fibers from chicken feathers with desirable mechanical properties, low costs and environmental responsibility. We focused on clean, efficient and cost-effective extraction of keratin from chicken feathers, preparation of spinning dopes, and production of regenerated keratin fibers with desirable mechanical properties on a lab scale. We developed and optimized the aqueous keratin extraction system for chicken feathers. The extraction technology can be of sufficient interest to researchers and industrial technoligists who focus on various applications of poultry wastes, since efficient and cost-effective extraction of proteins from poultry wastes using environmentally responsible chemicals is a long-standing challenge. Specifically, urea and sodium dodecyl sulfate were used to swell keratin and stretch the keratin molecule chains. Cysteine was to break chemical crosslinkages in the keratin. Given that urea, sodium dodecyl sulfate, and cysteine can disrupt all original interactions in feather keratin, a minimal amount of alkali was needed. Low alkalinity can better preserve the protein backbones, and, therefore, retain mechanical properties of regenerated keratin products. Using an aqueous system containing 2M urea, 10% sodium dodecyl sulfate, and 10% cysteine based on the weight of feathers at a pH of 10.5, the extraction yield of keratin was as high as 67%. We also developed an aqueous system to dissolve extracted keratin. This step is to help molecular chains of keratin fully stretched and entangled with each other in water. Good dissolution is the prerequisite for the development of quality regenerated keratin products. We tried different combinations of swelling agents and reducing agents to dissolve keratin for desirable spinnability of fibers. To ensure better spinnability of keratin fibers on a continuous spinning line, the disulfide bonds in keratin need to be partially retained to provide keratins with good solubility, highest molecular entanglement and most appropriate molecular weight. The optimized spinning dope is an aqueous system containing 10% sodium dodecyl sulfate and 2% mercaptoethanol based on the weight of keratin powders with a pH of 8. For the continuous formation of keratin fibers, we focused on the development of a technology that can substantially restore the protein secondary and tertiary structures in fibers so that properties of fiber products can be comparable to raw chicken feathers. The fiber regeneration technology could inspire other researchers in the field of industrial applications of poultry wastes, food wastes, and other protein wastes. Successful fiber regeneration on a lab-scale demonstrates the potential value addition to agricultural industries and benefits to the farmers. Technology-wise, we conducted multiple cycles of fiber drawings and oxidations. Drawing helps decrease the diameter of fibers and make ordered protein structures. Oxidations help form the crosslinkages in fibers. Stepwise drawings and oxidations helped fast formation of disulfide crosslinkages between ordered protein structures. As a result, mechanical properties of fibers substantially improved because of high degree of crosslinkages and ordered structures. Total crystallinity, beta-sheet crystallinity, and disulfide crosslinkages in keratin fibers were recovered 78%, 95%, and 71%, respectively, compared to chicken feathers. Because of the efficient secondary structure recovery, keratin was continuously spun into fine fibers with 86%, 64%, 89%, and 91% recoveries in dry tenacity, wet tenacity, dry toughness, and wet toughness, respectively. Fibers after 10 times of drawing had a diameter of around 15 μm, which is lower than those of most natural wool fibers (30 μm) and slightly larger than those of silk fibers (10 μm). A magnified SEM image shows that the fiber surface was smooth. Fine fibers ensure a good hand, breathability, and dyeability. The wet stabilities of keratin fibers after stepwise drawings and oxidations were not desirable. The strength retention of fibers after immersed in water for 1 week was only 40%. Therefore, additional reinforcement is needed. We will focus on the fiber reinforcements next year.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Mu, B., Hassan, F., and Yang, Y., 2020. Controlled assembly of secondary keratin structures for continuous and scalable production of tough fibers from chicken feathers. Green Chemistry. 22(5), pp. 1726-1734.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Yang*, Y.Q., Mu, B.N., Mi, X., Xu, H.L., Hassan, F., and Xu, L. Pure keratin fibers from poultry feathers. 9th International Conference on Advanced Fibers and Polymer Materials. (ICAFPM 2019 Next-Generation Fibers: Shaping a better future), Session H: Natural Fibers and Biomimetic Polymers. Organized by the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials. Shanghai, China. November 19-23, 2019.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Yang*, Y.Q., Mu, B.N., and Hassan, F. Continuous wet spun keratin fibers from chicken feathers. Forth International Symposium on Materials from Renewables (ISMR). October 9-10, 2019 in Athens, GA. Plenary lecture (Invited Speech). University of Georgia and North Dakota State University.
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