Progress 06/15/17 to 09/14/21
Outputs
Target Audience:Target audience includes researchers and educators with broad backgrounds and expertise in agricultural science, materials science, engineering, polymer materials and biomaterials. The research results have been disseminated in national and international conferences including ACS Regional Meetings (MWRM), SPE ANTEC Conference, MRS Spring Meeting and Gordon Research Conference. This research project was also presented at Mechanical Engineering Seminar, which is open to all faculty, staffs and students at Wichita State University. The research supported by this grant was also selected to present at Capitol Graduate Research Summit (CGRS) for the State government, education officials, industry and the general public in the State of Kansas. This research received BioKansas Award at CGRS in 2020. Another important target audience is students, including both undergraduate and graduate students. During this reporting period, two first-generation college students: a female student, and an African-American student, were highly involved in this project. Both students had great interests in renewable biomaterials. These research findings have also been incorporated into a course on polymer materials and engineering, and were introduced during the discussion on natural polymers. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project created excellent training and learning opportunities for five different graduate students and undergraduate students in total at Wichita State University. The students have received training on (1) material fabrication for the proposed protein-based materials, including solution processing methods, compression molding, and chemical modifications of nanomaterials; (2) operations of research facilities required for this project, such as SEM, XRD, FTIR, rheological analysis, ferroelectric and dielectric testing; and (3) data analysis skills such as organizing, displaying, and fitting the data collected, using EXCEL, MATLAB and ORIGIN software. This research project also provided the opportunity for the graduate students to attend academic conferences and regional education symposium to improve their presentation skills and expose this project to broad audiences including researchers, government officials, industry, and general public with diverse backgrounds and experiences.? How have the results been disseminated to communities of interest?The results based on the progress in this reporting period have been presented in USDA/NIFA Nanotechnology for Agricultural and Food Systems Grantees Conference,Graduate Research and Scholarly Projects (GRASP Symposium, Wichita State University), ACS Midwest Regional Meetings, SPE ANTEC Conferences, and MRS Meetings. The research supported by this grant was also selected to present at Capitol Graduate Research Summit (CGRS) for the State government, education officials, industry and the general public in the State of Kansas. This research received BioKansas Award at CGRS in 2020. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
The goal of this research project is to explore and extend the applications of renewable and green plant protein materials for dielectric energy storage applications via engineering plant proteins at nanoscale to achieve desired dielectric energy storage performances. Progress on Objective 1: This objective is to learn how denaturation and processing parameters affect the solid-state aggregated protein structures and dielectric polarization behaviors. Various denaturation processes including both physical denaturation (heat and sonication) and chemical denaturation (sodium dodecyl sulfate (SDS) and 2-Mercaptoethanol (2ME), etc.) were applied to soy protein isolate (SPI). The denatured SPIs were made into thin sheet samples for structure and property analyses. The protein aggregation in the solid SPI sheet samples were characterized by Small Angle X-ray Scattering (SAXS) method. Different aggregation domains with different sizes and size distributions were identified, depending on the denaturation processes. The surface properties of these SPI sheet samples, analyzed using water contact angle measurement, were sensitive to the different aggregated protein structures, showing largely different water contact angles ranging from 0o to 60o. Such variation in protein aggregation further led to distinct dielectric polarization behaviors. The highest dielectric polarizability was comparable to the important dielectric polymers, such as poly(vinylidene fluoride) (PVDF). The results support the hypotheses of this research project, demonstrating the diversity and significance of solid-state aggregated protein structures in materials functionalities. It was also found that, after downsizing the aggregated protein structures to nanoscale, the morphological differences of these nanoscale soy proteins were not as evident as the micron-scale, but these nanoscale soy protein structures, fabricated via different processes, showed distinctive effects on both mechanical and dielectric properties of the nanocomposites. The knowledge of their structural differences, and relationships with processing parameters, is important to both objectives 2 and 3. Progress on Objective 2: This objective is to study how nanomaterials with tailored surface properties and structures affect the aggregated protein structures, and to create soy protein nanocomposites with desired energy performances. Pristine boron nitride nanomaterials (BNNMs) were used to modify SPI. The lack of surface modification of BNNMs led to poor dispersion, according to Scanning Electron Microscopic (SEM) analysis, leading to unsatisfactory impact on the dielectric polarizability of SPI. It was found that polydopamine (PDA) was a very effective surfactant for BNNMs. The in-situ polymerization of dopamine and surface modification can take place simultaneously, forming stable PDA coating on the surface of BNNMs. The resulting surface modified-BNNMs (s-BNNMs) exhibited greatly enhanced solubility in protein solutions. The surface modification via PDA led to enhanced interfacial interactions. 0.5wt% s-BNNMs showed similar reinforcement effects to 20wt% p-BNNMs. The enhanced interfacial interactions were observed in their dielectric relaxation behaviors, with alpha relaxation and interfacial relaxation shifting to the lower frequency. The surface modification also suppressed the dielectric polarization Dielectric properties were studied at various temperatures up to the melting temperature of the polymer matrix. In opposite to most polymeric systems, both p-BNNM and s-BNNM suppressed the dielectric loss in the nanocomposites. The concentration dependent suppression was more evident in the case of s-BNNM. Such findings also suggest the potential of BNNMs and polydopamine surface modification in fabrication of low loss dielectric materials for energy and electronic-related applications. It was also found that s-BNNM shown the best solubility in aqueous solutions, therefore, a modified fabrication process was used. In this process, thiols were used to denature proteins to create uniform protein solutions to interact with s-BNNMs. The resulting nanocomposites showed uniform dispersion and compatible interfaces between s-BNNMs and matrix. The thiols could be easily removed in ethanol bath with weak sonication treatment. The soy protein /s-BNNM nanocomposite showed improved dielectric polarization, within a wide temperature range, without substantially increasing the dielectric loss or causing earlier breakdown at high electric fields. Progress on Objective 3: This objective is to study the relationships between aggregated protein structures and polymer/protein interactions, and to create hybrid dielectric materials. Two polymers, that is, hydrophobic PVDF and hydrophilic PEO, were intentionally selected. Both denatured SPIs and the polymer matrix played critical roles in defining microstructures and dielectric properties of polymer /SPI films. Results showed that PEO-SPI interactions led to distinguishable phase morphologies of PEO/SPI films, and favored low crystallinity of PEO and high β-film content in SPI. Such interactions reduced the dielectric polarizability of the PEO/SPI films, compared with pure PEO, and improved the charging-discharging efficiency. Similar to PEO, a remarkable reduction of crystallinity of PVDF was observed. PVDF-SPI interactions led to more intricate phase structures of the resulting PVDF-SPI films, tuning the dielectric hysteresis behaviors of PVDF. The morphologies of nanoscale soy proteins achieved under different conditions in this study were not distinguishable from each other using conventional characterization methods, such as XRD and SEM. It was found that the combined use of dynamic rheological and dielectric relaxation analyses could provide useful knowledge of these "look-alike" nanoscale soy proteins. The results suggest that, despite the resemblance of their morphologies, the nanoscale soy proteins proved largely different, subjected to the processes. In this work, dimethyl sulfoxide (DMSO) and distilled water (H2O) were applied to create different nanoscale soy proteins. With the modification by 0.5wt% SPIs, both the storage modulus (G') and loss modulus (G") of PEO melt increased by roughly 2 orders, suggesting effective PEO-SPI interactions. The differences between SPI-DMSO and SPI-H2O were remarkably reflected by the dielectric relaxation analysis. 1wt% SPI led to highest dielectric constant (ε'), suggesting that PEO-SPI interactions favor interfacial polarizations. Increasing SPI loading led to formation of SPI network structures consisting of nanoscale soy proteins. SPI-DMSO exhibited extraordinary network forming capability. With 10wt% SPI-DMSO, the moduli of the composites had a 6-order increase compared to pure PEO. The formation of network structures also suppressed dielectric polarization. The hybrid nanocomposites were fabricated. In addition to soy protein, wheat gluten was added to fabricate the hybrid nanocomposites. While the addition of wheat gluten did not lead to very noticeable improvement of dielectric polarization. The presence of wheat gluten did have positive effects on the processing of the hybrid nanocomposites, as well as their toughness. Soy protein is more brittle than wheat gluten, particularly after dehydration treatment. The modification of soy protein by BNNMs led to greater brittleness, although positively impacting dielectric properties. The presence of wheat gluten noticeably toughened the nanocomposites. The changes in dielectric relaxation behaviors caused by wheat gluten suggested favorable interactions between wheat gluten and soy protein, which might partially account for the improved toughness, however, the variation in relaxation mechanisms seemed to have little effects on the dielectric polarizability.
Publications
- Type:
Journal Articles
Status:
Other
Year Published:
2022
Citation:
Zhao Heng Tan and McCord Cox, Effects of surface modification of boron nitride nanoparticles on the dielectric properties of protein-based nanocomposites, to be submitted
|
Progress 06/15/20 to 06/14/21
Outputs
Target Audience:Target audience includes students, researchers and educators with backgrounds and expertise in agricultural science, materials science & engineering, nanotechnology, polymer materials and biomaterials. This research project was also presented at Graduate Research and Scholarly Projects (GRASP 2021) Symposium at Wichita State University, which is open to all faculty, staffs, students and non-WSU members. One manuscripton the research findings in this period is currently under review. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project created excellent training and learning opportunities for the new graduate student who participates this project starting from spring 2020. The student has received training on (1) material fabrication for the proposed protein-based materials, including solution processing methods, compression molding, and chemical modifications of nanomaterials; (2) operations of research facilities required for this project, including ferroelectric and dielectric testing; and (3) data analysis skills such as organizing, displaying, and fitting the data collected using Excel, Origin and Matlab softwares. 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?
Nothing Reported
Impacts
What was accomplished under these goals?
The goal of this research project is to explore and extend the applications of renewable and green plant protein materials for dielectric energy storage applications via engineering plant proteins at nanoscale to achieve desired dielectric energy storage performances. The research findings in the previous reporting period revealed the significant contributions of surface modification of boron nitride nanomaterials (s-BNNM) with polydopamine in tuning the dielectric properties of polymer nanocomposites. This report, covering the research progress in the fourth year, successfully applied the s-BNNM to protein-based nanocomposites via a modified material fabrication process, achieving further improvement in dielectric performances, in comparison to the pristine BNNM (p-BNNM). The work in this period primarily focused on the proposed objectives 2 and 3. Progress on Objective 2: This objective is to study how nanomaterials with tailored surface properties and structures affect the aggregated protein structures, and to create soy protein nanocomposites with desired energy performances. In the previous reporting period, p-BNNM was successfully incorporated into soy protein to fabrication soy protein/p-BNNM nanocomposites. In current reporting period, the major challenge to achieve this objective was fabrication of protein-based nanocomposites with s-BNNM via previously used fabrication process, due to the poor solubility of s-BNNM in DMSO. It was found that s-BNNM showed the best solubility in aqueous solutions; therefore, to fabricate soy protein /s-BNNM nanocomposites with uniform s-BNNM dispersion, a modified fabrication process was used. In this process, thiols were used to denature proteins in distilled water, and to create uniform and consistent protein solutions to interact with s-BNNM without affecting the quality of surface coating on s-BNNMs. The resulting nanocomposites showed uniform dispersion and compatible interfaces between s-BNNM and protein matrix. The thiols could be easily removed in ethanol bath with weak sonication treatment. The soy protein /s-BNNM nanocomposite exhibited improved dielectric polarization, within a wide temperature range, without substantially increasing the dielectric loss or causing earlier breakdown at high electric fields. Meanwhile, in comparison to soy protein/p-BNNM nanocomposites, the surface modification of BNNMs seemed to signify the effects of concentration of nanomaterials on the materials properties. Progress on Objective 3: This objective is to study the relationships between aggregated protein structures and polymer/protein interactions, and to create hybrid dielectric materials. In the current reporting period, the hybrid nanocomposites were fabricated. In addition to soy protein, wheat gluten, another plant protein abundant in nature, was added to fabricate the hybrid nanocomposites. While the addition of wheat gluten did not lead to very noticeable improvement of dielectric polarization in the resulting hybrid nanocomposites. The presence of wheat gluten did have positive effects on the processing of the hybrid nanocomposites, as well as their toughness. Soy protein is more brittle than wheat gluten, particularly after dehydration treatment. The modification of soy protein by BNNMs led to greater brittleness, although positively impacting dielectric properties. The brittleness certainly made the sample preparation, characterization, and materials application more difficult. The presence of wheat gluten noticeably toughened the nanocomposites. The changes in dielectric relaxation behaviors caused by wheat gluten suggested favorable interactions between wheat gluten and soy protein, which might partially account for the improved toughness. However, the variation in relaxation mechanisms seemed to have little effects on the dielectric polarizability, according to the polarization data. The presence of gluten also substantially reduced the shrinkage and distortion of soy protein-based materials during drying process, which further benefited the sample preparation and characterization in this study.
Publications
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2020
Citation:
https://soar.wichita.edu/handle/10057/19756
- Type:
Journal Articles
Status:
Submitted
Year Published:
2021
Citation:
McCord Cox and Bin Li, Dielectric polarization of soy protein composites: effects of process and temperature
|
Progress 06/15/19 to 06/14/20
Outputs
Target Audience:Target audience includes students, researchers and educators with backgrounds and expertise in agricultural science, materials science & engineering, nanotechnology, polymer materials and biomaterials. The research results have been disseminated in ACS Regional Meetings (MWRM 2019). A conference paper and oral presentation were accepted by ANTEC 2020 (Society of Plastics Engineering). The research supported by this grant was also selected to present at Capitol Graduate Research Summit (CGRS) for the State government, education officials, industry and the general public in the State of Kansas. This research received BioKansas Award at CGRS in 2020.It was later presented at Graduate Research and Scholarly Projects (GRASP 2020) Symposium at Wichita State University, which is open to all faculty, staffs, students and non-WSU members. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project created excellent training and learning opportunities for the new graduate student who participates this project starting from spring 2020. The student has received training on (1) material fabrication for the proposed protein-based materials, including solution processing methods, compression molding, and chemical modifications of nanomaterials; (2) operations of research facilities required for this project, such as SEM, XRD, FTIR, rheological analysis, ferroelectric and dielectric testing; and (3) data analysis skills such as organizing, displaying, and fitting the data collected. This research project also provided the opportunity for the graduate students to attend academic conferences and regional education symposium to improve their presentation skills and expose this project to broad audiences including researchers, government officials, industry, and general public with diverse backgrounds and experiences. How have the results been disseminated to communities of interest?The results based on the progress in current reporting period have been presented in several domestic and international conferences, including 2019 ACS Midwest Regional Meeting, 2020 ANTEC Conference and 2020Capitol Graduate Research Summit. This summit exposes state government, local industry, and general public to quality research performed in the State of Kansas, during which, this USDA-funded researchwas awarded 2020 BioKansas Award. In addition, the research was also presented at 2020 Graduate Research and Scholarly Projects (GRASP) Symposium at Wichita State University. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
The goal of this research project is to explore and extend the applications of renewable and green plant protein materials for dielectric energy storage applications via engineering plant proteins at nanoscale to achieve desired dielectric energy storage performances. The research findings in the previous reporting period revealed the profound and distinctive effects of nanoscale soy protein structures on the dielectric properties and mechanical properties in polymeric materials, as well as the successful tuning of dielectric and mechanical properties of polymeric materials via surface modification of boron nitride nanomaterials (BNNM) with polydopamine, a nature-inspired synthetic polymer coating. The surface modified BNNM (s-BNNM) led to desirable dielectric properties in the resulting nanocomposites with low loss. This report, covering the research progress in the third year of this four-year project, addresses the continuing efforts and achievements on the application of nanotechnology in creating plant protein based dielectric materials with desirable dielectric properties. An in-depth understanding of effects of BNNMs on dielectric and mechanical properties of the nanocomposites has been achieved, revealing the enhanced thermal stability of dielectric performances. Even close to the melting point of the polymer, the nanocomposites still showed greatly suppressed dielectric loss, which is not frequently found in nanocomposites and is ideal for dielectric applications within a broad temperature range. The pristine BNNM (p-BNNM) and s-BNNM have been incorporated into soy protein to fabricate the soy protein nanocomposites, with their dielectric properties having been investigated, and the dependence of dielectric parameters on both BNNMs and processing conditions was found. Progress on Objective 1: This objective is to learn how denaturation and processing parameters affect the solid-state aggregated protein structures and dielectric polarization behaviors. Based on previous findings, the nanoscale soy protein structures, fabricated via different processes, showed distinctive effects on both mechanical and dielectric properties of the nanocomposites, although they did not exhibit substantial morphological differences according to microscopic observations. The knowledge of their structural differences, and relationships with processing parameters, is important to both objectives 2 and 3. Continuous efforts are being made on this challenging issue via small angle x-ray scattering and rheological approaches. Progress on Objective 2: This objective is to study how nanomaterials with tailored surface properties and structures affect the aggregated protein structures, and to create soy protein nanocomposites with desired energy performances. In the previous reporting period, the surface modification was successful, and the resulting s-BNNM materials with a polydopamine coating was able to suppress the dielectric loss of the nanocomposites. In the current period, dielectric properties were studied at various temperatures up to the melting temperature of the polymer matrix. In opposite to most polymeric systems, instead of a significant increase in dielectric loss at high temperatures close to melting, both p-BNNM and s-BNNM suppressed the dielectric loss in the nanocomposites. The concentration dependent suppression was more evident in the case of s-BNNM, due to the surface modification via polydopamine, suggesting excellent thermal stability of the dielectric performances. Such findings also suggest the potential of BNNMs and polydopamine surface modification in fabrication of low loss dielectric materials for energy and electronic-related applications. p-BNNM have also been incorporated into soy protein to fabricate soy protein/p-BNNM nanocomposites, using a novel filtration-assisted method. Although p-BNNM was dispersed using high intensity sonication treatment, aggregates of p-BNNM nanoparticles were still observed, due to the lack of proper surface modification. p-BNNM had weak effects on dielectric constant within testing temperature range up to 150oC. Soy protein materials exhibited three relaxation behaviors: Relaxation III (fastest) occurs at low temperature & high frequency; Relaxation II (slowest) occurs at high temperature & low frequency; while Relaxation I is in between. Compression molding led to condensed materials structures and suppressed Relaxation II, while the two faster relaxation mechanisms were hardly affected, suggesting that I and III are mostly related to primary protein structures, while II is related to tertiary and quaternary protein structures. Relaxation II was also subjected to p-BNNMs, showing complex concentration dependences. Such complexity should come from the non-uniform dispersion of p-BNNMs. The nanocomposites were ground and polished to thin sheet samples for hysteresis testing up to 160kV/cm. The maximum electric field was limited by the sample thickness and high voltage amplifier. Without surface modification or uniform dispersion, p-BNNM had very limited effects on the hysteresis behaviors. All samples showed high hysteresis efficiency with very little energy loss, which is desirable for energy storage application. Meanwhile, the polarization only moderately declined when the temperature increased to 150oC, showing relatively thermally stable dielectric polarizability of both soy protein and soy protein/p-BNNM nanocomposites. Currently, the soy protein/s-BNNM nanocomposites are being fabricated and studied. Meanwhile, a new amplifier was purchased to investigate the dielectric hysteresis behaviors at a higher electric field. Progress on Objective 3: This objective is to study the relationships between aggregated protein structures and polymer/protein interactions, and to create hybrid dielectric materials. In the current reporting period, the research activities related to Objective 3 were parallel with Objective 1. In order to fabricate desirable hybrid nanocomposites, the knowledge on the nanoscale soy protein structures is necessary. However, their characterization remains a challenge, since conventional morphological analysis and structural analysis were not able to explain the distinctive dielectric and mechanical properties in resulting materials, due to their morphological similarities. This is an ongoing and continuous effort, with small angle x-ray scattering and rheological analysis employed currently.
Publications
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2020
Citation:
Paige Feikert and Bin Li,The Contributions of Soy Protein Quaternary Structures on Viscoelastic Properties of Polyethylene Oxide/Soy Protein Composites, Graduate Research and Scholarly Projects (GRASP) Symposium,Wichita State University, Wichita, KS
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Paige Feikert and Bin Li, Viscoelastic Properties of Polydopamine-Modified Boron Nitride/Polyethylene Oxide Nanocomposites, virtual poster presentation, ANTEC 2020, Society of Plastics Engineers
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Paige Feikert and Bin Li, The Contributions of Soy Protein Quaternary Structures on Viscoelastic Properties of Polyethylene Oxide/Soy Protein Composites, Capitol Graduate Research Summit (CGRS),Topeka, KS
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Paige Feikert and Bin Li, Effects of Soy Protein on Dynamic Relaxation of Polymer Materials Toward Design and Fabrication of Functional Polymer/Plant Protein Composites, American Chemicals Society MWRM 2019, Wichita, KS
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2020
Citation:
Paige Feikert and Bin Li, Tailoring interfacial properties of polyethylene oxide/boron nitride nanocomposites via polydopamine. (Paper not presented because of COVID-19), ANTEC 2020, Society of Plastics Engineers.
|
Progress 06/15/18 to 06/14/19
Outputs
Target Audience:Target audience includes students, researchers and educators with backgrounds and expertise in agricultural science, materials science & engineering, nanotechnology, polymer materials and biomaterials. The research results have been disseminated in 2019 USDA/NIFA Nanotechnology for Agricultural and Food Systems Grantees Conference, and an oral presentation has been accepted by and will be given in the ACS Regional Meetings (MWRM 2019). This research project was also presented at Graduate Research and Scholarly Projects (GRASP 2019) Symposium at Wichita State University, which is open to all faculty, staffs, students and non-WSU members. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project continued to create training and learning opportunities for both undergraduate and graduate students. Two new graduate students have been recruited to take on the roles of graduate research assistant. These graduate students received training on (1) basic material processing techniques for the protein-based materials and polymer materials; (2) chemical and physical modifications of nanomaterials; (2) operations of research facilities required for this project, such as SEM, XRD, rheometer, and dielectric testing, etc; and (3) data analysis skills using EXCEL, MATLAB and ORIGIN software. This research project also provided the opportunity for these students to attend academic conferences and symposia to improve their presentation skills and broaden their minds. This project also provided learning opportunity for undergraduate students. In the previous reporting period, based on the proposed research tasks, an experiment on the soy protein-based plastic was developed and incorporated in PD's undergraduate course on polymer materials and engineering. During this reporting period, this experiment was redesigned to increase the students' involvement. How have the results been disseminated to communities of interest?The results based on the progress in this reporting period have been presented in 2019 USDA/NIFA Nanotechnology for Agricultural and Food Systems Grantees Conference and2019 Graduate Research and Scholarly Projects (GRASP) Symposium at Wichita State University. Anoral presentation on the research progress of this projecthas been accepted by ACS Midwest Regional Meeting 2019, which will be given in October 2019. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
The goal of this research project is to explore and extend the applications of renewable and green plant protein materials for dielectric energy storage applications via engineering plant proteins at nanoscale to achieve desired dielectric energy storage performances. This report, covering the second year of this three-year project, addresses the continuing efforts and achievements on acquiring knowledge on aggregated protein structures, particularly at nanoscale, and their relationships with dielectric properties of the resulting protein-based nanocomposites. The nanoscale soy protein was achieved by controlling both treatment of soy protein and protein-polymer interactions. In contrast to largely different dielectric properties, the resulting nanocomposites did not show significantly different microstructures, in terms of crystal structures and phase morphologies. Such contrast suggests the complexity of the nanoscale soy proteins. To identify and understand the structures and properties of nanoscale soy proteins, dynamic rheological analysis and dielectric relaxation analysis have been applied. Meanwhile boron nitride nanomaterials have been successfully modified by polydopamine, which improved dispersion quality and interfacial interactions with soy proteins, showing great potential in fabrication of desired dielectric nanocomposites. Progress on Objective 1: This objective is to learn how denaturation and processing parameters affect the solid-state aggregated protein structures and dielectric polarization behaviors. The research findings in the first year revealed the varied aggregated protein structures and resulting different dielectric polarizability. In the current report period, it was found that, after downsizing the aggregated protein structures to nanoscale, the morphological differences of these nanoscale soy proteins were not as evident as the micron-scale, although the progress on objective 3 revealed their largely different properties. The lack of accurate identification of these nanoscale soy proteins failed to provide direct structure-property relationships to guide the fabrication of desired dielectric nanocomposites. Therefore, the in-depth understanding of these "look-alike" nanoscale soy proteins is crucial to achieving the goal of this project. Currently, the collaborative work on characterization of the nanoscale soy proteins is underway. Progress on Objective 2: This objective is to study how nanomaterials with tailored surface properties and structures affect the aggregated protein structures, and to create soy protein nanocomposites with desired energy performances. Due to the unsatisfactory surface properties of pristine boron nitride nanomaterials (p-BNNMs), the dispersion quality as well as the interfacial interactions needed substantial improvement. The second-year efforts focused on the surface modification of BNNMs. It was found that polydopamine (PDA) was a very facile and effective surfactant for chemically inert BNNMs. The in-situ polymerization of dopamine and surface modification of BNNMs can take place simultaneously, forming stable PDA coating on the surface of BNNMs. The resulting surface modified-BNNMs (s-BNNMs) exhibited greatly enhanced solubility in water and protein solutions. To validate the effects of PDA surface modification, both p-BNNMs and s-BNNMs were dispersed in polyethylene oxide (PEO). The surface modification via PDA led to enhanced interfacial interactions. 0.5wt% s-BNNMs showed similar reinforcement effects to 20wt% p-BNNMs. Meanwhile, at the same loadings, the surface modification led to more than 20-fold increases in shear resistance. The enhanced interfacial interactions were also observed in their dielectric relaxation behaviors, with alpha relaxation and interfacial relaxation shifting to the lower frequency. The surface modification also suppressed the dielectric polarization when the concentration of BNNMs was higher than 0.5wt%. The enhanced interactions between s-BNNMs and soy protein did not only improve the solubility of s-BNNMs, but also increased the solution viscosity, which subsequently created new issues in the fabrication of the soy protein/s-BNNMs nanocomposites. The exploration of improved fabrication methods is underway. Progress on Objective 3: This objective is to study the relationships between aggregated protein structures and polymer/protein interactions, and to create hybrid dielectric materials. The morphologies of nanoscale soy proteins achieved under different conditions in this study were not distinguishable from each other using conventional characterization methods, including scanning electron microscope (SEM) and fluorescence imaging and X-ray diffraction (XRD). It was found that the combined use of dynamic rheological and dielectric relaxation analyses could provide useful knowledge of these "look-alike" nanoscale soy proteins. The results suggest that, despite the resemblance of their morphologies, the nanoscale soy proteins proved largely different, subjected to the processes. In this work, dimethyl sulfoxide (DMSO) and distilled water (H2O) were applied to create different nanoscale soy proteins, labeled as SPI-DMSO and SPI- H2O, respectively. With the modification by as low as 0.5wt% SPIs, both the storage modulus (G') and loss modulus (G") of PEO melt increased by roughly 2 orders, suggesting effective PEO-SPI interactions and favorable load bearing capability. The differences between SPI-DMSO and SPI-H2O were remarkably reflected by the dielectric relaxation analysis. 1wt% SPI led to highest dielectric constant (ε'), in comparison to all other compositions, suggesting that PEO-SPI interactions favor interfacial polarizations. However, theε' of PEO/1wt% SPI-H2Ocomposite was two times higher than that of the PEO/1wt% SPI-DMSO composite. Meanwhile, the interactions between PEO and SPI-H2O led to a faster alpha relaxation, which could contribute to stronger dielectric polarizability in PEO/SPI-H2O composites. Increasing SPI loading led to higher G' and G", and weakened frequency dependence of the linear viscoelastic properties. Such composition dependence was due to the formation of SPI network structures consisting of nanoscale soy proteins. SPI-DMSO exhibited extraordinary network forming capability. The dominance of frequency-independent G' and G" in PEO/SPI-DMSO composites indicated a typical solid-like behavior, which started at as low as 5wt% SPI-DMSO loading. Such properties are typically observed in polymer nanocomposites with percolated network structures consisting of rigid nanoparticles. With 10wt% SPI-DMSO, the moduli of the composites had a 6-order increase compared to pure PEO. In contrast, although the increase in moduli was also observed in PEO/SPI-H2O composites, even at 10wt% loading, the network of SPI-H2O has not been well built yet, showing much lower moduli and clear frequency dependence. The formation of network structures also suppressed dielectric polarization. With the increase of SPI loading from 1wt% to 10wt%, a decline in dielectric polarization was found in both groups of composites, and alpha relaxation of the PEO matrix was greatly restrained. While the PEO-SPI interactions alone favored dielectric polarization, the formation of network created substantial resistance to dielectric polarizations, due to greatly restrained chain mobility. Particularly, in the presence of SPI-DMSO, the polarizability of the composites was even weaker than that of pure PEO. Moreover, such SPI-DMSO network structures produced noticeably weakened temperature dependence of dielectric properties. Continuous efforts are being made to explore their interaction mechanisms, in order to acquire profound knowledge on the nanoscale soy proteins and determine optimal process and structural parameters to create hybrid dielectric nanocomposites with desired energy storage performances.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Zhuoyuan Zheng, Olaseeni Olayinka and Bin Li, 2S-Soy Protein-Based Biopolymer as a Non-Covalent Surfactant and Its Effects on Electrical Conduction and Dielectric Relaxation of Polymer Nanocomposites 2018, 4, 87-99
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2019
Citation:
Dielectric polarization and relaxation of soy protein-based biomaterial and its nanocomposites,Ph.D. Dissertation, Wichita State University, March, 2019, http://hdl.handle.net/10057/15904
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2019
Citation:
Wenqing Wang, Paige Feikert and Bin Li,Study of Soy Protein as a Dielectric Modifier for Polymer Materials, Graduate Research and Scholarly Projects (GRASP) Symposium, Wichita State University, 2019
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2019
Citation:
Paige Feikert and Bin Li, Linear Viscoelastic Properties of Soy Protein/Polyethylene Oxide Composites,Graduate Research and Scholarly Projects (GRASP) Symposium, Wichita State University, 2019
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2019
Citation:
Paige Feikert, Wenqing Wang, Zhuoyuan Zheng and Bin Li, Effects of Nanoscale Soy Protein on Dynamic Relaxation of Dielectric Polymer Nanocomposites, 2019 USDA/NIFA Nanotechnology for Agricultural and Food Systems Grantees Conference.
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2019
Citation:
Paige Feikert, Wenqing Wang, Zhuoyuan Zheng and Bin Li,Dielectric and Rheological Analysis of Protein-Modified Nanocomposites,2019 USDA/NIFA Nanotechnology for Agricultural and Food Systems Grantees Conference.
- Type:
Journal Articles
Status:
Submitted
Year Published:
2019
Citation:
Paige Feikert, Wenqing Wang and Bin Li, Networking of Soy Protein in Polymer and Its Effects on Rheological and Dielectric Properties of Polymer/Soy Protein Composites submitted, 2019
|
Progress 06/15/17 to 06/14/18
Outputs
Target Audience:Target audience includes researchers and educators with broad backgrounds and expertise in agricultural science, materials science, engineering, polymer materials and biomaterials. The research results have been disseminated in national and international conferences including ACS Regional Meeting(MWRM), SPE ANTEC Conference, MRS Spring Meeting and Gordon Research Conference. This research project was also presented at Mechanical Engineering Seminar, which is open to all faculty, staffs and students at Wichita State University. Another important target audience is students, including both undergraduate and graduate students. During this reporting period, two first-generation college students: a female student, and an African-American student, were highly involved in this project. Both students had great interests in renewable biomaterials. These research findings have also been incorporated into a course on polymer materials and engineering, and were introduced during the discussion on natural polymers. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?This project created excellent training and learning opportunities for both undergraduate and graduate students in the past reporting period, including two undergraduate students, two master students and two Ph.D. students. These graduate students received training on (1) basic material processing techniques for the proposed protein-based materials, including denaturation and modifications of protein materials, solution processing methods, compression molding and modifications of nanomaterials; (2) operations of research facilities required for this project, such as SEM, XRD, FTIR, ferroelectric and dielectric testing, etc; and (3) data analysis skills such as organizing, displaying, and fitting the data collected. This research project also provided the opportunity for these students to attend academic conferences to improve their presentation skills and broaden their minds via interacting with researchers with diverse backgrounds and experiences. How have the results been disseminated to communities of interest?The results based on the progress in the first reporting period have been presented in several domestic and international conferences, including 2017 ACS Midwest Regional Meeting, 2018 MRS Spring Meeting, 2018 ANTEC Conferenceand 2018Gordon Research ConferenceonNanoscale Science & Engineering for Agriculture & Food. Additionally, this research was also presented at ME Graduate Seminar at Wichita State University. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
The goal of this research project is to explore and extend the applications of renewable and green plant protein materials for dielectric energy storage applications via engineering the processes and structures of the plant proteins to simultaneously achieve high energy density and high energy efficiency. To achieve this goal, it is necessary to acquire basic knowledge on the protein structures and resulting properties to provide a key data set for future optimization and design of the proposed plant protein-based materials. However, as of today, the studies on the protein aggregation and functionalities are mostly conducted with intended applications for food and biological systems. In contrast, the solid-state aggregated protein structures and properties towards functional material applications are not well understood. Moreover, proteins have unique chemical and physical structures, with greater diversity and tailorability compared to other biopolymers derived from natural resources, and have not received sufficient attention in current studies on protein-based functonal materials. This report, covering the first year of this three-year project, addresses the progress and achievements on the issues stated above. In addition to conventional analytical studies of solid-state protein structures, more valuable knowledge on the solid-state aggregated soy protein structures was revealed via studying the interactions between soy protein structures and intentionally-selected polymer materials. The study showed diverse material structures and morphologies, as well as distinctive dielectric performances, indicating the diversity of solid-stated aggregated soy protein structures and their crucial roles in the material functionalities and applications. These findings are direct evidence for the multifunctionality of plant protein materials, and provide the foundation for the proposed plant-protein based hybrid nanocomposites for dielectric energy storage applications. In order to achieve the proposed goal of this research project, the following three supporting objectives will be accomplished, with the progress made on these objectives as stated below: Objective 1: to gain knowledge on how denaturation and processing parameters affect the solid-state aggregated protein structures and their relationships with dielectric polarization; Objective 2: to gain knowledge on how nanomaterials with tailored surface properties and structures affect the aggregated protein structures, and to create soy protein nanocomposites with desired energy performances; Objective 3: to gain knowledge on howaggregated protein structures affect polymer/protein interactions, as well as resulting phase structures, and to create hybrid dielectric materials with enhanced energy performances and environment friendliness. Progress on Objective 1: This objective is to learn how denaturation and processing parameters affect the solid-state aggregated protein structures and dielectric polarization behaviors. Various denaturation processes including both physical denaturation (heat and sonication) and chemical denaturation (sodium dodecyl sulfate (SDS) and 2-Mercaptoethanol (2ME), etc.) were applied to soy protein isolate (SPI). The denatured SPIs were made into thin sheet samples for structure and property analyses. The protein aggregation in the solid SPI sheet samples were characterized by Small Angle X-ray Scattering (SAXS) method. Different aggregation domains with different sizes and size distributions were identified, depending on the denaturation processes. The surface properties of these SPI sheet samples, analyzed using water contact angle measurement, were sensitive to the different aggregated protein structures, showing largely different water contact angles ranging from 0o to 60o. Such variation in protein aggregation further led to distinct dielectric polarization behaviors, measured by charge-discharge hysteresis analysis. The highest dielectric polarizability obtained during the first year was comparable to the important dielectric polymers, such as poly(vinylidene fluoride) (PVDF). The results support the hypotheses of this research project, demonstrating the diversity and significance of solid-state aggregated protein structures in materials functionalities. Progress on Objective 2: This objective is to study how nanomaterials with tailored surface properties and structures affect the aggregated protein structures, and to create soy protein nanocomposites with desired energy performances. In the first year of study, pristine boron nitride nanomaterials (BNNMs) were used to modify SPI. The lack of surface modification of BNNMs led to poor dispersion, according to Scanning Electron Microscopic (SEM) analysis, leading to unsatisfactory impact on the dielectric polarizability of SPI. Surface modification of BNNMs is certainly needed, which is currently underway, considering the importance of dispersion quality of the nanomaterials and interfaces to dielectric properties of the nanocomposites. Progress on Objective 3: This objective is to study the relationships between aggregated protein structures and polymer/protein interactions, and to create hybrid dielectric materials. In the first year of study, the main focus was on the relationships between aggregated protein structures and polymer/protein interactions. In addition to different denaturation processes, two polymers, that is, hydrophobic PVDF and hydrophilic poly(ethylene oxide) (PEO), were intentionally selected. Both polymers have received great interests in polymeric electronic materials. SEM, X-Ray Diffraction (XRD), Confocal Laser Scanning Microscopy (CLSM) and Fourier Transform Infrared Spectroscopy (FTIR) were applied to study the microstructures including crystalline structures of the polymers, secondary structures of the SPI and the phase structures. Both denatured SPIs and the polymer matrix played critical roles in defining microstructures and dielectric properties of polymer /SPI films. Results showed that PEO-SPI interactions led to distinguishable phase morphologies of PEO/SPI films, and favored low crystallinity of PEO and high β-film content in SPI. Such interactions reduced the dielectric polarizability of the PEO/SPI films, compared with pure PEO, and substantially improved the charging-discharging efficiency. The distinctive microstructures and dielectric properties directly related to the diverse PEO-SPI interactions, subjected to different denaturation processes. Particularly, sonication treatment of SPI led to very unique parabolic composition dependence of structures and properties, in contrast to other PEO/SPI films showing monotonic composition dependence. Similar to PEO, a remarkable reduction of crystallinity of PVDF was observed, depending on the PVDF-SPI interactions. PVDF-SPI interactions led to more intricate phase structures of the resulting PVDF/SPI films, in addition to the variation in the morphologies of SPI aggregates. The films exhibited solid nonporous structures, when SPI was denatured at 90oC or by SDS. The films exhibited distinctive porous structures when SPI was denatured at 60oC, by sonication, or 2ME, suggesting different PVDF-SPI interactions. SPI was found to be able to tune the dielectric hysteresis behaviors of PVDF to meet various requirements, such as enhancing dielectric polarization, promoting energy storage efficiency, and improving released dielectric energy, depending on the denaturation treatment of SPI. Continuous efforts are being made to achieve this objective and create hybrid dielectric nanocomposites with desired energy storage performances.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Zhuoyuan Zheng and Bin Li, Surface Modification of Hexagonal Boron Nitride Nanomaterials: A Review, Journal of Materials Science, 2018, 53, 66.
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Zhuoyuan Zheng, Susan Ma, Soheil Rashidi, and Bin Li, Study of Denaturation and Composition Dependent Poly(ethylene oxide)-Soy protein Interactions: Structures and Dielectric Polarization, Journal of Applied Polymer Science 2018, 135, 46561.
- Type:
Journal Articles
Status:
Accepted
Year Published:
2018
Citation:
Zhuoyuan Zheng, McCord Cox and Bin Li, Effective Structure Regulation of Poly(vinylidene fluoride) via Soy Protein Isolate: A Morphological Study, Journal of Applied Polymer Science, DOI: 10.1002/app.20180357
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Zhuoyuan Zheng and Bin Li, Modified Dielectric Properties of Poly(vinylidene fluoride) via 2S Fraction of Soy Protein, Journal of Applied Polymer Science, 2018, 135, 46882
- Type:
Journal Articles
Status:
Submitted
Year Published:
2018
Citation:
Zhuoyuan Zheng, Olaseeni Olayinka, and Bin Li, 2S-Soy Protein as a Non-Covalent Surfactant and its Effects on Electrical Conduction and Dielectric Relaxation of Polymer Nanocomposites, Journal of Applied Physics, Submitted, 2018
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2017
Citation:
Zhuoyuan Zheng and Bin Li, Study of Soy Protein Isolate as a Functional Modifier for Polymer Materials, 2017 ACS Midwest Regional Meeting, Lawrence, KS, October, 2017 (Oral Presentation)
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2017
Citation:
McCord Cox, and Zhuoyuan Zheng and Bin Li, Dielectric Properties of Soy Protein Isolate and Its Nanocomposites, 2017 ACS Midwest Regional Meeting, Lawrence, KS, October, 2017 (Poster Presentation)
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2018
Citation:
Zhuoyuan Zheng and Bin Li, Effects of Protein Aggregation on the Structures and Dielectric Energy Storage Performances of Polymer Films, MRS Spring Meeting & Exhibition, Phoenix, April, 2018 (Poster Presentation)
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2018
Citation:
Zhuoyuan Zheng and Bin Li, Structures and Dielectric Properties of Soy Protein Modified Poly(vinylindene fluoride) Films, ANTEC 2018-The Plastics Conference, Orlando, May, 2018 (Poster Presentation)
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2018
Citation:
Zhuoyuan Zheng, McCord Cox and Bin Li; A Study of Soy Protein in Polymer Dielectric Film Applications, Gordon Research Conference on Nanoscale Science & Engineering for Agriculture & Food, South Hadley, MA, 2018 (Poster Presentation)
|
|