Douglas A Loy
- Professor, Materials Science and Engineering
- Professor, Chemistry and Biochemistry
- Professor, BIO5 Institute
- Professor, James E Rogers College of Law
- Member of the Graduate Faculty
Biography
Douglas Anson Loy is Full Professor at the University of Arizona. Loy is known world-wide for his contributions to polymer synthesis and sol-gel science: his discovery and development of bridged polysilsesquioxanes, thermally reworkable thermosets, polymeric sunscreens and antioxidants, high temperature stable polyarylene polyelectrolyte membranes, and new polymers for additive manufacturing. Prior to the University of Arizona, he was a Distinguished Member of Technical Staff at Sandia National Labs and a Team Leader at Los Alamos National Lab. He holds 26 U.S. patents with another 10 applications in progress. He was one of the co-founders of Energy Materials Corporation with a focus on new fuel cell membranes. He has published 130 peer reviewed publications that have been cited more than 7400 times (Hirsch Index 37). He is a member of the University of Arizona’s Bio5 Center and is an Arizona Center for Accelerated BioMedical Innovation (ACABI) Fellow in recognition of his contributions to new materials development for medical applications. His discovery and work in bridged polysilsesquioxanes have led to more than 8000 publications by his peers and hundreds of millions of dollars per year in new product sales (based on liquid chromatographic materials alone). His inventions of removable or reworkable thermosets while at Sandia Labs have been widely used to encapsulate electronics in aerospace applications. He developed a new class of fuel cell membranes with a significantly higher maximum operational temperature and higher ion conductivity (than the standard, Nafion) that will permit fuel cells to operate with technical grade hydrogen. Loy’s polymeric sunscreens and antioxidants reduce the use of harmful additives to plastics and significantly reduce exposure to and environmental contamination by potentially harmful organic sunscreens. Loy is a member of the American Chemical Society, the Materials Research Society, the Association for the Advancement of Science, and Sigma Xi.
Degrees
- Ph.D. Chemistry
- University of California Irvine, Irvine, California
- Bridged polysilsesquioxanes, aryl bridged siliconates and polysiliconates
- M.S. Chemistry
- Northern Arizona University, Flagstaff, Arizona
- Synthesis of Tannin-like polymers
- B.S. Chemistry
- University of Arizona, Tucson, Arizona
Work Experience
- University of Arizona, Tucson, Arizona (2005 - Ongoing)
- Los Alamos National Laboratory (2003 - 2005)
- Sandia National Laboratories (1991 - 2003)
Awards
- Employee Recognition Award for Meritorious Achievement for “Cermet Fabrication and Product Realization Team"
- Sandia National Laboratories, Winter 1999
- Fellow of National Academy of Inventors
- National Academy of Inventors, Spring 2022 (Award Nominee)
- University of Arizona Patent Medal
- The University of Arizona, Spring 2022
- University of Arizona, Spring 2022
- Catalyst Award, 1st Place
- University of Arizona, Chemistry and Biochemistry Department, Spring 2018
- Arizona Center for Accelerated BioMedical Innovation (ACABI) Fellow
- Arizona Center for Accelerated BioMedical Innovation, Fall 2017
- Catalyst Award (5th Place)
- Chemistry and Biochemistry Department, University of Arizona, Spring 2017
- I2 Expo Inventor of the Year Physical Sciences
- Tech Launch Arizona, Spring 2017
- Foreign Expert
- Harbin Institute of Technology, Harbin, Peoples Republic of China, Summer 2015
- Visiting Scientist - Peoples Republic of China Foreign Expert
- Harbin Institute of Technology, PRC, Summer 2014
- MSE Faculty Fellow
- MSE Department, University of Arizona, Spring 2012
- College of Engineering Teaching Award
- COE, University of Arizona, Spring 2009
- Distinguished Member of Technical Staff
- Sandia National Laboratories, Albuquerque, NM, Fall 2001
Interests
Teaching
Sol-gel science (MSE 425/525), Polymer Science for Engineers (MSE 460/560), Proposal writing for engineers (Eng 502), Advanced Topics in Organic Chemistry (Chem 546), Polymer Chemistry (CHM 543B), Organic Chemistry (CHM 241a&b), Materials Science for Engineers (MSE 331R), Materials Chemistry (MSE 110), 3D printing (MSE 220)
Research
3D Printing, sol-gel science, hydrogels, polysilsesquioxanes, nanoparticles, aerogels, sunscreens, tetrazine based materials, new polymer electrolyte synthesis, Diels Alder polymerizations, reversible and reworkable polymers, adhesives for art conservation, anti-fouling coatings, solid state and gel storage of fuels for fuel cells.
Courses
2025-26 Courses
-
Directed Research
BIOC 392 (Spring 2026) -
Dissertation
CHEM 920 (Spring 2026) -
Dissertation
MSE 920 (Spring 2026) -
Exchange Chemical Info
CHEM 695B (Spring 2026) -
Independent Study
MSE 399 (Spring 2026) -
Independent Study
MSE 499 (Spring 2026) -
Materials Sci Polymers
MSE 460 (Spring 2026) -
Materials Sci Polymers
MSE 560 (Spring 2026) -
Research
MSE 900 (Spring 2026) -
Thesis
MSE 910 (Spring 2026) -
3-D Printing and the Environ
MSE 220 (Fall 2025) -
Directed Research
BIOC 392 (Fall 2025) -
Directed Research
CHEM 392 (Fall 2025) -
Dissertation
CHEM 920 (Fall 2025) -
Dissertation
MSE 920 (Fall 2025) -
Exchange Chemical Info
CHEM 695B (Fall 2025) -
Lecture Organic Chem
CHEM 241A (Fall 2025) -
Research
MSE 900 (Fall 2025) -
Sol-Gel Science
MSE 425 (Fall 2025) -
Sol-Gel Science
MSE 525 (Fall 2025)
2024-25 Courses
-
Dissertation
MSE 920 (Spring 2025) -
Exchange Chemical Info
CHEM 695B (Spring 2025) -
Materials Sci Polymers
MSE 460 (Spring 2025) -
Materials Sci Polymers
MSE 560 (Spring 2025) -
Research
CHEM 900 (Spring 2025) -
Research
MSE 900 (Spring 2025) -
Thesis
MSE 910 (Spring 2025) -
Dissertation
CHEM 920 (Fall 2024) -
Dissertation
MSE 920 (Fall 2024) -
Exchange Chemical Info
CHEM 695B (Fall 2024) -
Fund Materials for Engr
MSE 331R (Fall 2024) -
Materials Sci Polymers
MSE 460 (Fall 2024) -
Research
MSE 900 (Fall 2024)
2023-24 Courses
-
Dissertation
CHEM 920 (Spring 2024) -
Dissertation
MSE 920 (Spring 2024) -
Exchange Chemical Info
CHEM 695B (Spring 2024) -
Lecture Organic Chem
CHEM 241A (Spring 2024) -
Materials Sci Polymers
MSE 460 (Spring 2024) -
Materials Sci Polymers
MSE 560 (Spring 2024) -
Research
CHEM 900 (Spring 2024) -
Research
MSE 900 (Spring 2024) -
Thesis
MSE 910 (Spring 2024) -
Dissertation
CHEM 920 (Fall 2023) -
Dissertation
MSE 920 (Fall 2023) -
Exchange Chemical Info
CHEM 695B (Fall 2023) -
Research
CHEM 900 (Fall 2023) -
Research
MSE 900 (Fall 2023) -
Sol-Gel Science
MSE 425 (Fall 2023) -
Sol-Gel Science
MSE 525 (Fall 2023)
2022-23 Courses
-
Dissertation
CHEM 920 (Spring 2023) -
Dissertation
MSE 920 (Spring 2023) -
Exchange Chemical Info
CHEM 695B (Spring 2023) -
Independent Study
MSE 599 (Spring 2023) -
Materials Sci Polymers
MSE 460 (Spring 2023) -
Materials Sci Polymers
MSE 560 (Spring 2023) -
Research
CHEM 900 (Spring 2023) -
Research
MSE 900 (Spring 2023) -
Senior Capstone
MSE 498 (Spring 2023) -
3-D Printing and the Environ
MSE 220 (Fall 2022) -
Dissertation
CHEM 920 (Fall 2022) -
Dissertation
MSE 920 (Fall 2022) -
Exchange Chemical Info
CHEM 695B (Fall 2022) -
Honors Independent Study
MSE 399H (Fall 2022) -
Independent Study
MSE 399 (Fall 2022) -
Lecture Organic Chem
CHEM 241A (Fall 2022) -
Research
CHEM 900 (Fall 2022) -
Research
MSE 900 (Fall 2022) -
Senior Capstone
MSE 498 (Fall 2022) -
Thesis
CHEM 910 (Fall 2022)
2021-22 Courses
-
Lecture Organic Chem
CHEM 241A (Summer I 2022) -
Dissertation
CHEM 920 (Spring 2022) -
Dissertation
MSE 920 (Spring 2022) -
Exchange Chemical Info
CHEM 695B (Spring 2022) -
Honors Thesis
CHEM 498H (Spring 2022) -
Independent Study
MSE 499 (Spring 2022) -
Materials Sci Polymers
MSE 460 (Spring 2022) -
Materials Sci Polymers
MSE 560 (Spring 2022) -
Research
CHEM 900 (Spring 2022) -
Research
MSE 900 (Spring 2022) -
Senior Capstone
MSE 498 (Spring 2022) -
Thesis
MSE 910 (Spring 2022) -
Dissertation
CHEM 920 (Fall 2021) -
Dissertation
MSE 920 (Fall 2021) -
Exchange Chemical Info
CHEM 695B (Fall 2021) -
Honors Thesis
CHEM 498H (Fall 2021) -
Independent Study
MSE 399 (Fall 2021) -
Lecture Organic Chem
CHEM 241A (Fall 2021) -
Research
CHEM 900 (Fall 2021) -
Research
MSE 900 (Fall 2021) -
Senior Capstone
MSE 498 (Fall 2021) -
Sol-Gel Science
MSE 425 (Fall 2021) -
Sol-Gel Science
MSE 525 (Fall 2021) -
Sol-Gel Science
OPTI 425 (Fall 2021) -
Sol-Gel Science
OPTI 525 (Fall 2021) -
Solid State Chemistry
MSE 110 (Fall 2021) -
Thesis
MSE 910 (Fall 2021)
2020-21 Courses
-
Lecture Organic Chem
CHEM 241A (Summer I 2021) -
Chemistry Majors Colloquium
CHEM 395A (Spring 2021) -
Dissertation
CHEM 920 (Spring 2021) -
Exchange Chemical Info
CHEM 695B (Spring 2021) -
Independent Study
MSE 399 (Spring 2021) -
Internship
MSE 493 (Spring 2021) -
Materials Sci Polymers
MSE 460 (Spring 2021) -
Materials Sci Polymers
MSE 560 (Spring 2021) -
Research
CHEM 900 (Spring 2021) -
Research
MSE 900 (Spring 2021) -
Senior Capstone
MSE 498 (Spring 2021) -
Thesis
MSE 910 (Spring 2021) -
3-D Printing and the Environ
MSE 220 (Fall 2020) -
Dissertation
CHEM 920 (Fall 2020) -
Dissertation
MSE 920 (Fall 2020) -
Exchange Chemical Info
CHEM 695B (Fall 2020) -
Lecture Organic Chem
CHEM 241A (Fall 2020) -
Research
CHEM 900 (Fall 2020) -
Research
MSE 900 (Fall 2020) -
Senior Capstone
MSE 498 (Fall 2020) -
Solid State Chemistry
MSE 110 (Fall 2020)
2019-20 Courses
-
Lecture Organic Chem
CHEM 241A (Summer I 2020) -
Chemistry Majors Colloquium
CHEM 395A (Spring 2020) -
Dissertation
CHEM 920 (Spring 2020) -
Dissertation
MSE 920 (Spring 2020) -
Exchange Chemical Info
CHEM 695B (Spring 2020) -
Honors Independent Study
MSE 499H (Spring 2020) -
Independent Study
MSE 399 (Spring 2020) -
Materials Sci Polymers
MSE 460 (Spring 2020) -
Materials Sci Polymers
MSE 560 (Spring 2020) -
Research
CHEM 900 (Spring 2020) -
Research
MSE 900 (Spring 2020) -
Senior Capstone
BIOC 498 (Spring 2020) -
Senior Capstone
MSE 498 (Spring 2020) -
Thesis
CHEM 910 (Spring 2020) -
Dissertation
CHEM 920 (Fall 2019) -
Dissertation
MSE 920 (Fall 2019) -
Exchange Chemical Info
CHEM 695B (Fall 2019) -
Independent Study
MSE 499 (Fall 2019) -
Lecture Organic Chem
CHEM 241A (Fall 2019) -
Research
CHEM 900 (Fall 2019) -
Research
MSE 900 (Fall 2019) -
Senior Capstone
BIOC 498 (Fall 2019) -
Sol-Gel Science
MSE 425 (Fall 2019) -
Sol-Gel Science
MSE 525 (Fall 2019) -
Sol-Gel Science
OPTI 425 (Fall 2019)
2018-19 Courses
-
Chemistry Majors Colloquium
CHEM 395A (Spring 2019) -
Dissertation
CHEM 920 (Spring 2019) -
Dissertation
MSE 920 (Spring 2019) -
Exchange Chemical Info
CHEM 695B (Spring 2019) -
Materials Sci Polymers
MSE 460 (Spring 2019) -
Materials Sci Polymers
MSE 560 (Spring 2019) -
Research
CHEM 900 (Spring 2019) -
Research
MSE 900 (Spring 2019) -
Solid State Chemistry
MSE 110 (Spring 2019) -
Dissertation
CHEM 920 (Fall 2018) -
Dissertation
MSE 920 (Fall 2018) -
Exchange Chemical Info
CHEM 695B (Fall 2018) -
Lecture Organic Chem
CHEM 241A (Fall 2018) -
Research
CHEM 900 (Fall 2018) -
Research
MSE 900 (Fall 2018)
2017-18 Courses
-
Chemistry Majors Colloquium
CHEM 395A (Spring 2018) -
Directed Research
CHEM 492 (Spring 2018) -
Dissertation
CHEM 920 (Spring 2018) -
Dissertation
MSE 920 (Spring 2018) -
Exchange Chemical Info
CHEM 695B (Spring 2018) -
Fund Materials for Engr
MSE 331R (Spring 2018) -
Materials Sci Polymers
MSE 460 (Spring 2018) -
Materials Sci Polymers
MSE 560 (Spring 2018) -
Research
CHEM 900 (Spring 2018) -
Research
MSE 900 (Spring 2018) -
Directed Research
CHEM 392 (Fall 2017) -
Dissertation
CHEM 920 (Fall 2017) -
Dissertation
MSE 920 (Fall 2017) -
Exchange Chemical Info
CHEM 695B (Fall 2017) -
Research
CHEM 900 (Fall 2017) -
Research
MSE 900 (Fall 2017) -
Sol-Gel Science
MSE 425 (Fall 2017) -
Sol-Gel Science
MSE 525 (Fall 2017) -
Sol-Gel Science
OPTI 425 (Fall 2017)
2016-17 Courses
-
Lecture Organic Chem
CHEM 241B (Summer I 2017) -
Adv Organic Chemistry
CHEM 546 (Spring 2017) -
Dissertation
CHEM 920 (Spring 2017) -
Dissertation
MSE 920 (Spring 2017) -
Exchange Chemical Info
CHEM 695B (Spring 2017) -
Materials Sci Polymers
MSE 460 (Spring 2017) -
Materials Sci Polymers
MSE 560 (Spring 2017) -
Research
CHEM 900 (Spring 2017) -
Research
MSE 900 (Spring 2017) -
Thesis
MSE 910 (Spring 2017) -
Directed Research
CHEM 492 (Fall 2016) -
Dissertation
CHEM 920 (Fall 2016) -
Dissertation
MSE 920 (Fall 2016) -
Exchange Chemical Info
CHEM 695B (Fall 2016) -
Independent Study
MSE 499 (Fall 2016) -
Research
CHEM 900 (Fall 2016) -
Research
MSE 900 (Fall 2016) -
Research Proposal Prep
MSE 502 (Fall 2016) -
Sol-Gel Science
MSE 425 (Fall 2016) -
Sol-Gel Science
MSE 525 (Fall 2016) -
Thesis
MSE 910 (Fall 2016)
2015-16 Courses
-
Lecture Organic Chem
CHEM 241B (Summer I 2016) -
Adv Organic Chemistry
CHEM 546 (Spring 2016) -
Directed Research
CHEM 492 (Spring 2016) -
Dissertation
CHEM 920 (Spring 2016) -
Exchange Chemical Info
CHEM 695B (Spring 2016) -
Materials Sci Polymers
MSE 460 (Spring 2016) -
Materials Sci Polymers
MSE 560 (Spring 2016) -
Research
CHEM 900 (Spring 2016) -
Research
MSE 900 (Spring 2016) -
Thesis
CHEM 910 (Spring 2016) -
Thesis
MSE 910 (Spring 2016)
Scholarly Contributions
Books
- Loy, D. A. (1995). Environmentally friendly polysilane photoresists.
- Loy, D. A. (1995). HEXYLENE-BRIDGED AND PHENYLENE-BRIDGED POLYSILOXANE NETWORK MATERIALS.
- Loy, D. A. (1995). HYPERVALENT SPIRO POLYSILICONATE AND POLYGERMYLATE IONOMERS - NOVEL LADDER AND NETWORK MATERIALS.
- Loy, D. A. (1994). PLASMA OXIDATION OF HYDROCARBON TEMPLATES IN BRIDGED POLYSILSESQUIOXANES - POROUS MATERIALS BY DESIGN.
- Loy, D. A. (1994). ROLE OF PRESSURE IN THE STUDY OF FULLERENES.
Chapters
- Loy, D. A. (2017). Mesoporous Polysilsesquioxanes: Preparation, Properties, and Applications. In Handbook of Sol-Gel Science and Technology. Springer.
- Loy, D. A. (2012). Synthesis and Characterization of Semi-Fluorinated Polyarylene Copolymers. In Advances in Fluorine-Containing Polymers.
- Loy, D. A. (2008). Polymer-silica nanocomposite aerogels with enhanced mechanical properties using chemical vapor deposition (CVD) of cyanoacrylates. In Organic/Inorganic Hybrid Materials - 2007.
- Loy, D. A. (2005). Collapse of porosity during drying of alkylene-bridged polysilsesquioxane gels. Influence of the bridging group length. In Organic/Inorganic Hybrid Materials-2004.
- Loy, D. A. (2005). Evolution of porosity and morphology in alkylene-bridged polysilsesquioxane xerogels as a function of gel aging time. In Organic/Inorganic Hybrid Materials-2004.
- Loy, D. A. (2002). Soluble, high molecular weight polysilsesquioxanes with carboxylate functionalities. In Organic/Inorganic Hybrid Materials-2002.
- Loy, D. A. (1999). Dialkylenecarbonate-bridged polysilsesquioxanes. Hybrid organic-inorganic sol-gels with a thermally labile bridging group. In Organic/Inorganic Hybrid Materials Ii.
- Loy, D. A. (1999). Maleimide functionalized siloxane resins. In Organic/Inorganic Hybrid Materials Ii.
- Loy, D. A. (1999). Porosity in polysilsesquioxane xerogels. In Organic/Inorganic Hybrid Materials Ii.
- Loy, D. A. (1999). Sol-gel chemistry by ring-opening polymerization. In Organic/Inorganic Hybrid Materials Ii.
- Loy, D. A. (1996). Controlling porosity in bridged polysilsesquioxanes through elimination reactions. In Better Ceramics through Chemistry Vii: Organic/Inorganic Hybrid Materials.
- Loy, D. A. (1996). Intramolecular condensation reactions of alpha, omega-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. In Better Ceramics through Chemistry Vii: Organic/Inorganic Hybrid Materials.
- Loy, D. A. (1996). Investigation of hydrolysis and condensation in organically modified sol-gel systems: Si-29 NMR and the INEPT sequence. In Better Ceramics through Chemistry Vii: Organic/Inorganic Hybrid Materials.
- Loy, D. A. (1996). Origin of porosity in arylene-bridged polysilsesquioxanes. In Better Ceramics through Chemistry Vii: Organic/Inorganic Hybrid Materials.
- Loy, D. A. (1996). Sol-gel polymerization of tetraalkoxygermanium and organotrialkoxygermanium monomers. In Microporous and Macroporous Materials.
- Loy, D. A. (1995). Comparison of bridged polysilsesquioxane xerogels prepared from methoxy- and ethoxy-silyl monomers. In Advances in Porous Materials.
- Loy, D. A. (1995). Porosity in hexylene-bridged polysilsesquioxanes. Effects of monomer concentration. In Advances in Porous Materials.
- Loy, D. A. (1995). The effect of O-2 intercalation on the rotational dynamics and the ordering transition of C-60. In Science and Technology of Fullerene Materials.
- Small, J. H., Shea, K. J., Loy, D. A., & Jamison, G. M. (1995). Hypervalent Spiro Polysiliconate and Polygermylate Ionomers: Novel Ladder and Network Materials. In ACS Symposium Proceedings: Silicone Materials. American Chemical Society. doi:10.1021/BK-1995-0585.CH019
- Loy, D. A. (1994). ENGINEERING OF POROSITY IN AMORPHOUS MATERIALS - PLASMA OXIDATION OF HYDROCARBON TEMPLATES IN POLYSILSESQUIOXANES. In Better Ceramics through Chemistry Vi.
- Loy, D. A. (1994). HYDROCARBON-BRIDGED POLYSILOXANE AND POLYSILSESQUIOXANE NETWORK MATERIALS. In Better Ceramics through Chemistry Vi.
Journals/Publications
- Hong, Z., Hong, Z., Zhang, Z., Zhang, Z., You, R., You, R., Chen, J., Chen, J., Li, S., Li, S., Wang, Y., Wang, Y., Sun, Y., Sun, Y., Song, B., Song, B., Ji, Z., Ji, Z., Loy, D. A., , Loy, D. A., et al. (2025). Dual-head multi-photon polymerization 3D printing for parallel additive manufacturing organic/inorganic materials in optics. Additive Manufacturing, 103. doi:10.1016/j.addma.2025.104772More infoRapid 3D laser printing based on two-photon polymerization (TPP) is a promising technique for fabricating high-resolution structures, but its scalability is often hindered by challenges in parallelization and material versatility. In this study, we present a high-precision, multi-head 3D printing system that integrates advanced optical and material control to address these limitations. By employing a dual-head setup with independent focal length adjustments and paired linear polarizers, our system enables simultaneous multi-material printing and rapid iteration of fabrication parameters, significantly enhancing prototyping efficiency. We demonstrated this system's versatility by successfully fabricating diverse microstructures, and compatible with organic and inorganic components. The system can achieve a minimum feature size of sub-100 nm and the highest printing speeds of 20 mm/s with a numerical aperture (NA) of 1.3 or 0.8, balancing precision and efficiency for industrial-scale applications. Additionally, its capability to perform multi-parameter, full-field-of-view additive manufacturing facilitates a wide range of design possibilities. The potential of this technique is further illustrated through two optical applications: an 8 × 8 convex lens array and diffractive optics for high-resolution holography. The lenses exhibit exceptional surface quality and uniformity with a roughness of less than 4 nm and a peak-to-valley surface deviation is around 200 nm, while the diffractive optics achieve sub-wavelength feature resolution, demonstrating the system's suitability for advanced optical component manufacturing. This study advances the state of additive manufacturing by addressing key challenges in parallelization, scalability, and material diversity.
- Hong, Z., Ye, P., Loy, D. A., & Liang, R. (2025). Integrated 3D Printing of Transparency-on-Demand Glass Microstructure. Advanced Optical Materials, 13(Issue 18). doi:10.1002/adom.202500390More infoGlass is essential in optics and photonics due to its exceptional optical, mechanical, thermal, and chemical properties. Additive manufacturing has emerged as a novel method for fabricating complex glass elements in recent years, yet achieving locally controlled transparency in glass micro-objects remains a significant challenge. An innovative method, termed Transparency-on-Demand Glass Additive Manufacturing, to control the transparency of 3D printed glass elements using polymeric silsesquioxane (PSQ) and two-photon polymerization is presented. By precisely manipulating key parameters such as laser power, scanning speed, part thickness, and pyrolysis heating rate, the desired transparency levels are achieved. This study reveals that monomer conversion during printing, structure thickness, and pyrolysis heating strategy significantly influence PSQ oxidation, resulting in varying transparency in the final glass product. This method enables the creation of high-precision, variable-transparency glass micro-components, providing a scalable and efficient solution for producing complex glass structures with tailored optical transparency. This technique paves the way for integrated manufacturing of controllable-transparency glass micro-structures, unlocking new possibilities for advanced optical and photonic applications.
- Lin, D., Ning, H., Liu, Y., Qin, W., Liu, J., & Loy, D. (2025). Mechanism of promoting okara insoluble to soluble dietary fiber by high-pressure homogenization-microbial fermentation. Bioresource Technology, 416(Issue). doi:10.1016/j.biortech.2024.131774More infoThis study investigated the conversion of okara insoluble dietary fiber (IDF) to soluble dietary fiber (SDF) using high-pressure homogenization (HPH) combined with microbial fermentation. The conversion mechanism was analyzed from four aspects: correlation, proteomics, component and structure under. Results indicated a negative correlation between pH and SDF yield (r = -0.9885, p < 0.05), while cellulase and xylanase showed a positive correlation with SDF yield (p < 0.05). Proteomic analysis identified 22 key enzymes involved in IDF degradation. According to the composition and structure, the combined treatment effectively reduced the aggregation of IDF, promoting its transformation into SDF. HPH treatment primarily acted on the hemicellulose fractions in the amorphous region, while microbial fermentation broke hydrogen bonds between hydroxyl groups in the crystalline regions of cellulose, enhancing the conversion of more exposed cellulose. This study provided theoretical support for the development and utilization of okara IDF.
- You, R., Chen, J., Wang, Y., Zhang, Z., Sun, Y., Song, B., Loy, D. A., Ji, Z., Hong, Z., & Liang, R. (2025). Cost-Effective Motionless Color Coded Ptychography for High-Throughput Biomedical Imaging. ACS Photonics, 12(Issue 6). doi:10.1021/acsphotonics.5c00693More infoHigh-throughput imaging methods are essential for various biomedical applications such as digital pathology, drug screening, and early stage cancer detection. Over the past few decades, numerous lensless techniques have emerged to provide high-throughput imaging with significantly more cost-effective hardware compared to conventional optical microscopy systems. Most lensless systems require sophisticated multiheight mechanical motions for phase retrieval, combined with subpixel shifts to reconstruct high-resolution images. These setups often involve bulky mechanical stages. Alternative approaches utilizing multiwavelength techniques can achieve similar physical shifts needed for phase retrieval but sacrifice color information in the process. We propose a novel coded ptychography lensless system capable of recovering high-resolution holographic images by using a single wavelength without any mechanical motion. Additionally, we leveraged an RGB LED matrix for color lensless imaging. Our compact lensless system demonstrates its capabilities by imaging various mouse tissues and organisms and oral cells offering a large field of view 30 mm2 with a resolution of 1.95 μm.
- You, R., Hong, Z., Chen, J., Zhang, Z., Wang, Y., Sun, Y., Song, B., Loy, D. A., Ji, Z., & Liang, R. (2025). Extremely Compact 3D Printed Glass Ternary Diffractive Optical Element for Holographic Images. Advanced Optical Materials, 13(Issue 22). doi:10.1002/adom.202501074More infoThe design and fabrication of compact and versatile holographic structures are critical for advancing next-generation technologies, ranging from augmented and virtual reality (AR/VR) devices to optical holographic data storage. While significant progress is made in holographic design and fabrication, existing methods often involve trade-offs between size, holographic image quality, and manufacturing complexity. Binary or few-level holographic structures, though simple to design and fabricate, are prone to twin-image artifacts, limiting their performance. In contrast, common spatial light modulators (SLMs) achieve higher fidelity but are bulky and unsuitable for compact applications. In this work, a novel approach is presented and holographic diffractive optical elements (DOEs) are proved by integrating a ternary phase design with high-resolution glass 3D printing. Utilizing the ternary design achieves the minimal quantization required to suppress twin images, balancing optical performance and fabrication simplicity. Glass DOEs are fabricated with nanometer-scale precision using additive manufacturing, achieving excellent agreement between simulated and experimental holographic results. Comparative thermal resistance tests demonstrated the superior durability of glass DOEs, which maintained structural integrity and holographic performance under extreme conditions, outperforming organic alternatives. By combining innovative phase design with the inherent material advantages of glass—thermal resistance, mechanical durability, and optical clarity—this study highlights the transformative potential of 3D-printed glass DOEs.
- Figueroa Romero, G., Maldonado, S., Arciniaga, L., Gonzales, D., Villalobos, E., Potter, B., Muralidharan, K., Loy, D., Szivek, J., & Margolis, D. (2024). Polymer-ceramic composites for fused deposition modeling of biomimetic bone scaffolds. Results in Engineering, 23(Issue). doi:10.1016/j.rineng.2024.102407More infoCurrent surgical treatments for segmental bone loss do not reliably result in healing, typically necessitate multiple surgeries, and may result in amputation. Although we have demonstrated that polybutylene terephthalate (PBT) scaffolds can regenerate large critical size bone defects, the material is non-resorbable and may lead to problems including acting as a nidus for infection. New strategies have emerged that use resorbable polymers, ceramics, and composite materials to produce patient specific scaffolds that stimulate rapid bone formation without retention of foreign material. This work describes the production of a composite polymer ceramic material composed of polylactic acid (PLA) and tricalcium phosphate (TCP) that can be used with additive manufacturing techniques to rapidly produce scaffolds with custom geometries. The technique we describe can be used to produce composite materials with a ratio of up to 50-50 PLA-TCP that is suitable for fused deposition modeling and does not necessitate the use of solvents. In this study the properties of PBT, PLA, 75-25 PLA-TCP, and 50-50 PLA-TCP materials are compared. PLA and PLA-TCP materials had a higher compressive elastic modulus compared to PBT, while composite PLA-TCP materials had a higher tensile elastic modulus compared to PLA and PBT. Cell culture experiments demonstrated that all materials were non-toxic to cells. Optimal printing parameters are provided for using pure polymer and composite materials for fused deposition modeling. The results of this study demonstrate that resorbable polymer ceramic materials with a high ceramic composition can be produced for additive manufacturing without necessitating solvents.
- Qin, W., Zou, L., Hou, Y., Wu, Z., Loy, D., & Lin, D. (2024). Characterization of novel anthocyanins film @ carbon quantum dot nanofiber intelligent active double-layer film, physicochemical properties and fresh-keeping monitoring in Ictalurus punctatus fish. Chemical Engineering Journal, 496(Issue). doi:10.1016/j.cej.2024.154041More infoAnthocyanins and carbon quantum dots (CQDs) were produced from highland barley bran to lower the waste of the cereal. This study successfully prepared a polyvinyl alcohol/soy protein isolate/anthocyanin@ polyvinyl alcohol/chitosan quaternary ammonium salt/CQDs nanofiber smart double-layer film (PSA@PHC). We explored the functions of anthocyanin film (PSA) and CQDs nanofiber film (PHC) as the inner and outer layers through structural characterization and property determination. The results showed that as the CQDs in nanofiber film rose, the diameter of the nanofibers expanded by 42.82 ± 9.37 nm, the free radical scavenging ability of DPPH and ABTS was 77.95 ± 2.53 % and 93.15 ± 0.70 %, respectively. When exposed to a xenon lamp, the bilayer film's CQDs generated reactive oxygen species, enhancing the inhibition of S. aureus and E. coli by 67.70 ± 0.54 % and 29.90 ± 1.87 %, respectively. The potential applications for PSA@PHC smart active double-layer film in food packaging were highly promising due to its outstanding properties. In terms of its application to the preservation and freshness monitoring of Ictalurus punctatus fish, the double layer film could extend the shelf life for 2 d and enable effective monitoring.
- Rahman, M. H., Hayes, A. K., Muralidharan, K., Loy, D. A., & Shafae, M. (2024). Additive manufacturing of hydrogel-based lunar regolith pastes: A pathway toward in-situ resource utilization and in-space manufacturing. Journal of Manufacturing Processes, 118(Issue). doi:10.1016/j.jmapro.2024.03.024More infoAdditive Manufacturing (AM), combined with efficient in-situ resource utilization, has the potential to enable sustained presence on the Moon through in-situ production and replacement of construction blocks, engineered parts, and devices in the lunar terrain. As an initial step toward realizing this vision, this work proposes a new material formulation utilizing lunar regolith simulants (LHS-1), water, and a hydrophilic hydrogel-forming polymer (Pluronic F127) to produce a hydrogel-based lunar regolith paste suitable for material extrusion AM. This formulation enables the use of water as another potential lunar in-situ resource for the first time in the literature, considering the recent confirmation of large quantities of water-ice in the shadowed craters around the lunar poles and the presence of water on the sunlit surface of the Moon. To systematically investigate the viability of the proposed hydrogel-based lunar regolith material feedstock and the application of material extrusion AM, this work introduces a three-stage design of experiment (DOE) framework to achieve two fundamental objectives. First, the viable range of lunar regolith simulant in the hydrogel-based material formulation is identified using a categorical quality evaluation of single and multi-layer material depositions. Second, the material printability window is established in terms of printing speed and extrusion rate for different viable material compositions through hierarchically designed experiments. The observed porosity of the sintered parts decreased with increasing regolith content in the material composition, while the density and compressive strength increased with higher regolith content. For material compositions consisting of 25–40 vol% regolith simulants, the observed porosity of the sintered parts decreased from 6.4 to 2.18 %, their density increased from 0.78 to 0.89 g/cm3, and their average compressive strength ranged between 0.68 and 1.32 MPa. Finally, the printability of the material was demonstrated by producing various prototype hand tools and lab-scale construction blocks with varying geometrical complexities. This work represents a crucial step toward in situ resource utilization and sustainable in-space manufacturing, sets the stage for future investigations, and the introduced DOE driven framework offers a pathway toward systematically identifying the optimal material compositions and the corresponding process parameters to enable high-quality prints.
- Ye, P., Hong, Z., Loy, D., & Liang, R. (2024). Solvent-Free Silsesquioxane Self-Welding for 3D Printing Multi-Refractive Index Glass Objects. Advanced Optical Materials, 12(23). doi:10.1002/adom.202400783More infoThe growing interest in 3D printing of silica glass has spurred substantial research efforts. The prior work utilizing a liquid silica resin (LSR) demonstrated high printing accuracy and resolution. However, the resin's sensitivity to moisture posed limitations, restricting the printing environment. On the other hand, polyhedral oligomeric silsesquioxane (POSS)-based materials offer excellent water stability and sinterless features. Yet, they suffer from relatively high shrinkage due to the presence of additional organic monomers. In this study, a polymeric silsesquioxane (PSQ) resin is presented with reduced shrinkage, enhanced moisture stability, and the retention of sinterless features, providing a promising solution for achieving high-resolution 3D printing of glass objects. Leveraging the two-photon polymerization (2PP) method, nanostructures are realized with feature sizes below 80 nm. Moreover, the tunability of the refractive index is demonstrated by incorporating zirconium moieties into the resin, facilitating the fabrication of glass micro-optics with varying refractive indices. Importantly, the self-welding capability observed between two individual components provides a flexible approach for producing micro-optics with multiple components, each possessing distinct refractive indices. This research represents a significant advancement in the field of advanced glass manufacturing, paving the way for future applications in micro- and nano-scale glass objects.
- Hong, Z., Liang, R., Loy, D. A., Sun, Y., & Ye, P. (2023). Bio‐Inspired Compact, High‐Resolution Snapshot Hyperspectral Imaging System with 3D Printed Glass Lightguide Array. Advanced Optical Materials, 11(9), 2300156. doi:10.1002/adom.202300156More infoTo address the major challenges to obtain high spatial resolution in snapshot hyperspectral imaging, 3D printed glass lightguide array has been developed to sample the intermediate image in high spatial resolution and redistribute the pixels in the output end to achieve high spectral resolution. Curved 3D printed lightguide array can significantly simplify the snapshot hyperspectral imaging system, achieve better imaging performance, and reduce the system complexity and cost. We have developed two-photon polymerization process to print glass lightguide array, and demonstrated the system performance with biological samples. This new snapshot technology will catalyze new hyperspectral imaging system development and open doors for new applications from UV to IR.
- Ye, P., Hong, Z., Loy, D. A., & Liang, R. (2023). UV-curable thiol-ene system for broadband infrared transparent objects. Nature Communications, 14(Issue 1). doi:10.1038/s41467-023-44273-0More infoConventional infrared transparent materials, including inorganic ceramic, glass, and sulfur-rich organic materials, are usually processed through thermal or mechanical progress. Here, we report a photo-curable liquid material based on a specially designed thiol-ene strategy, where the multithiols and divinyl oligomers were designed to contain only C, H, and S atoms. This approach ensures transparency in a wide range spectrum from visible light to mid-wave infrared (MWIR), and to long-wave infrared (LWIR). The refractive index, thermal properties, and mechanical properties of samples prepared by this thiol-ene resin were characterized. Objects transparent to LWIR and MWIR were fabricated by molding and two-photon 3D printing techniques. We demonstrated the potential of our material in a range of applications, including the fabrication of IR optics with high imaging resolution and the construction of micro-reactors for temperature monitoring. This UV-curable thiol-ene system provides a fast and convenient alternative for the fabrication of thin IR transparent objects.
- Hong, Z., Ye, P., Loy, D. A., & Liang, R. (2022). High-Precision Printing of Complex Glass Imaging Optics with Precondensed Liquid Silica Resin. Advanced science (Weinheim, Baden-Wurttemberg, Germany), 9(18), e2105595.More info3D printing of optics has gained significant attention in optical industry, but most of the research has been focused on organic polymers. In spite of recent progress in 3D printing glass, 3D printing of precision glass optics for imaging applications still faces challenges from shrinkage during printing and thermal processing, and from inadequate surface shape and quality to meet the requirements for imaging applications. This paper reports a new liquid silica resin (LSR) with higher curing speed, better mechanical properties, lower sintering temperature, and reduced shrinkage, as well as the printing process for high-precision glass optics for imaging applications. It is demonstrated that the proposed material and printing process can print almost all types of optical surfaces, including flat, spherical, aspherical, freeform, and discontinuous surfaces, with accurate surface shape and high surface quality for imaging applications. It is also demonstrated that the proposed method can print complex optical systems with multiple optical elements, completely removing the time-consuming and error-prone alignment process. Most importantly, the proposed printing method is able to print optical systems with active moving elements, significantly improving system flexibility and functionality. The printing method will enable the much-needed transformational manufacturing of complex freeform glass optics that are currently inaccessible with conventional processes.
- Lin, D., Li, Y., Huang, Y., Qin, W., Loy, D. A., Chen, H., Zhang, Q., & Wu, Z. (2022). Properties of polyvinyl alcohol films reinforced by citric acid modified cellulose nanocrystals and silica aerogels. Carbohydrate polymers, 298, 120116.More infoIn this study, citric acid modified cellulose nanocrystals (MCNC) and silica aerogel (SA) were used as reinforcing agents and added to polyvinyl alcohol (PVA) in different proportions to prepare composite films with excellent mechanical and barrier properties. After modification with citric acid, MCNC successfully contained ester bonds. SEM and FTIR results showed that MCNC and SA were uniformly dispersed in the PVA matrix and formed a compact structure. XRD results showed that there were physical interactions between the reinforcing agents and PVA, which improved the thermal stability of the film. Meanwhile, the composite film obtained good barrier properties after adding 0.5 % MCNC and 1.5 % SA. The carbon dioxide permeability decreased by 66.01 % and the oxygen permeability decreased by 69.46 % (23 °C, 50 % RH) and 40.14 % (38 °C, 90 % RH). The tensile strength increased to 43.79 MPa. Therefore, the composite film can be widely used in the packaging of food, medicine, etc.
- Lin, D., Loy, D. A., Zhang, Q., Chen, H., Qin, W., Li, S., & Xiao, L. (2022). Effects of fructooligosaccharide and soybean protein isolate in the microencapsulation of walnut oil. Industrial Crops and Products. doi:10.1016/j.indcrop.2021.114431More infoThe purpose of this study was to evaluate the effects of different proportions of fructooligosaccharide/soy isolate protein as wall materials on the physical properties and structural characterization of walnut oil microcapsules. Different ratios of oligofructose/soy protein isolate microcapsules were prepared to encapsulate walnut oil. The protective effect of microcapsules on walnut oil was evaluated by accelerated oxidation experiment. The microcapsules were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. The results show that fructooligosaccharide had no effect on the two-level structure of soy protein isolate, but its encapsulation efficiency could be improved by reducing the particle size of the emulsion and increasing the viscosity of the emulsion. In addition, fructooligosaccharide can improve the encapsulation efficiency by maintaining the structure of the protein during the freeze-drying process. The addition of fructooligosaccharide reduces the water content and hygroscopicity of the microcapsules. The accelerated oxidation results show that microencapsulation can significantly improve the oxidation stability of walnut oil. After accelerated oxidation, the peroxide value and thiobarbituric acid value of walnut oil in the control group were significantly higher than those of microencapsulated walnut oil ( p < 0.05). The peroxide value of unencapsulated walnut oil is 2.8 times higher than that of encapsulated walnut oil. The results show that fructooligosaccharide/soy isolate protein could be used as the wall material of microcapsules to embed sensitive, active substances. • Fructooligosaccharide reduces the particle size of soy protein isolate emulsion. • Fructooligosaccharides increase the viscosity of soy protein isolate emulsion. • The decrease of the particle size and the increase of the viscosity are beneficial to the stability of the emulsion. • Fructooligosaccharides improve the efficiency of microencapsulation by improving emulsion stability. • The use of SPI and FOS to encapsulate walnut oil can significantly improve the oxidative stability of walnut oil.
- Lin, D., Xiao, L., Qin, W., Loy, D. A., Wu, Z., Chen, H., & Zhang, Q. (2022). Preparation, characterization and antioxidant properties of curcumin encapsulated chitosan/lignosulfonate micelles. Carbohydrate polymers, 281, 119080.More infoIn this work, chitosan/lignosulfonate composite micelles (CS-LS) were successfully prepared through polyelectrolyte self-assembly. Curcumin was encapsulated in CS-LS to obtain CUR-CS-LS. The results showed that the average diameter of CS-LS and CUR-CS-LS were 239 nm and 286 nm, respectively. The results show that the aromatic rings of lignosulfonate are assembled into the hydrophobic core of micelles through π-π interactions, and chitosan binds outside the hydrophobic core as a hydrophilic shell through electrostatic interactions. Curcumin is encapsulated in the hydrophobic core through hydrophobic interactions. Encapsulation improves the thermal stability and pH stability of curcumin. Compared with free curcumin, the retention efficiency of curcumin in CUR-CS-LS increased by approximately 6.66 and 6.46 times under the same heat treatment and pH conditions, respectively. Encapsulation also increases the antioxidant activity of curcumin in aqueous solution. In addition, the release mechanism of curcumin is diffusion and matrix swelling. These findings explain that CS-LS may be an effective promising delivery system for encapsulating hydrophobic biologically active substances.
- Loy, D. A. (2022). The structure, properties and potential probiotic properties of starch-pectin blend: A review. Food Hydrocolloids, 129, 107644.
- Wu, Z., Li, Y., Tang, J., Lin, D., Qin, W., Loy, D. A., Zhang, Q., Chen, H., & Li, S. (2022). Ultrasound-assisted preparation of chitosan/nano-silica aerogel/tea polyphenol biodegradable films: Physical and functional properties. Ultrasonics sonochemistry, 87, 106052.More infoIn this study, chitosan(CS), nano-silicon aerogels(nSA) and tea polyphenols(TP) were used as film-forming materials and processed with ultrasonication to form films using the tape-casting method. The effects of ultrasonication time, temperature and frequency on the properties of CS/nSA/TP film were explored via material property testing. The results of response surface showed that the maximum tensile strength of the film was 4.036 MPa at ultrasonication time(57.97 min), temperature(37.26 °C) and frequency(30 kHz). The maximum elongation at break of the film was 279.42 % at ultrasonication time(60.88 min), temperature(39.93 °C) and frequency(30 kHz). Due to cavitation and super-mixing effects, ultrasonication may make the surface of the film smoother and easier to degrade. After ultrasonication, TPs were protected by the 3D network structure composed of CS and nSA. Ultrasonication improved the antioxidant and antibacterial properties of the film. These results show that ultrasonication is an effective method to improve the properties of films.
- Kang, K. S., Phan, A., Olikagu, C., Lee, T., Loy, D. A., Kwon, M., Paik, H. J., Hong, S. J., Bang, J., Parker, W. O., Sciarra, M., de Angelis, A. R., & Pyun, J. (2021). Segmented Polyurethanes and Thermoplastic Elastomers from Elemental Sulfur with Enhanced Thermomechanical Properties and Flame Retardancy. Angewandte Chemie (International ed. in English), 60(42), 22900-22907.More infoThe production of elemental sulfur from petroleum refining has created a technological opportunity to increase the valorization of elemental sulfur by the creation of high-performance sulfur based plastics with improved thermomechanical properties, elasticity and flame retardancy. We report on a synthetic polymerization methodology to prepare the first example of sulfur based segmented multi-block polyurethanes (SPUs) and thermoplastic elastomers that incorporate an appreciable amount of sulfur into the final target material. This approach applied both the inverse vulcanization of S with olefinic alcohols and dynamic covalent polymerizations with dienes to prepare sulfur polyols and terpolyols that were used in polymerizations with aromatic diisocyanates and short chain diols. Using these methods, a new class of high molecular weight, soluble block copolymer polyurethanes were prepared as confirmed by Size Exclusion Chromatography, NMR spectroscopy, thermal analysis, and microscopic imaging. These sulfur-based polyurethanes were readily solution processed into large area free standing films where both the tensile strength and elasticity of these materials were controlled by variation of the sulfur polyol composition. SPUs with both high tensile strength (13-24 MPa) and ductility (348 % strain at break) were prepared, along with SPU thermoplastic elastomers (578 % strain at break) which are comparable values to classical thermoplastic polyurethanes (TPUs). The incorporation of sulfur into these polyurethanes enhanced flame retardancy in comparison to classical TPUs, which points to the opportunity to impart new properties to polymeric materials as a consequence of using elemental sulfur.
- Liang, R., Loy, D. A., Ye, P., & Hong, Z. (2021). Three-dimensional printing of glass micro-optics. Optica, 8(6), 904. doi:10.1364/optica.422955
- Loy, D. A., Kang, K., Phan, A., Olikagu, C., Lee, T., Kwon, M., Paik, H., Hong, S. J., Bang, J., Parker, W. O., Sciarra, M., Angelis, A. R., & Pyun, J. (2021). Segmented Polyurethanes and Thermoplastic Elastomers from Elemental Sulfur with Enhanced Thermomechanical Properties and Flame Retardancy. Angewandte Chemie, 133(42), 23082-23089. doi:10.1002/ange.202109115
- Stahl, C., Frederick, K., Chaudhary, S., Morton, C. J., Loy, D., Muralidharan, K., Sorooshian, A., & Parthasarathy, S. (2021). Comparison of the Filtration Efficiency of Different Face Masks Against Aerosols. Frontiers in medicine, 8, 654317.More infoThe severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic can spread through virus-containing aerosols ( ≤ 5 μm) and larger airborne droplets. Quantifying filtration efficiency of different kinds of masks and linings for aerosols that fall within the most penetrating particle size (80-400 nm) is critical to limiting viral transmission. The objective of our experiment was to compare the "real-world" filtering efficiency of different face masks for fine aerosols (350 nm) in laboratory simulations. We performed a simulated bench test that measured the filtering efficiency of N95 vs. N99 masks with elastomeric lining in relation to baseline ("background") aerosol generation. A mannequin head was placed within a chamber and was attached to an artificial lung simulator. Particles of known size (350 ± 6 nm aerodynamic diameter) were aerosolized into the chamber while simulating breathing at physiological settings of tidal volume, respiratory rate, and airflow. Particle counts were measured between the mannequin head and the lung simulator at the tracheal airway location. Baseline particle counts without a filter (background) were 2,935 ± 555 (SD) cm, while the N95 (1348 ± 92 cm) and N99 mask with elastomeric lining (279 ± 164 cm;
- Loy, D. A., Runge, K., Momayez, M., Muralidharan, K., & Rao, P. (2020). Direct foaming driven synthesis and thermophysical characterization of silica-alumina foams: Applications for thermal insulation. Journal of Ceramics International, 46(8), 10431-10441. doi:https://doi.org/10.1016/j.ceramint.2020.01.042
- Muralidharan, K., Muralidharan, K., Loy, D. A., Loy, D. A., Runge, K. A., Loy, D. A., Rao, P. R., Momayez, M., Muralidharan, K., Rao, P. R., Runge, K. A., Momayez, M., & Loy, D. A. (2020). Direct foaming driven synthesis and thermophysical characterization of silica-alumina foams: Applications for thermal insulation. Ceramics International, 46(8), 10431-10441. doi:10.1016/j.ceramint.2020.01.042More infoAbstract Using earth-abundant materials such as quartz and corundum powders as precursors, we have developed a simple, but effective low energy direct foaming based method for synthesis of thermally insulating porous foams with thermal conductivity as low as 0.08 W/mK. Specifically, the adopted synthesis procedure provides a straightforward avenue for obtaining closed-cell silica-alumina foams, with densities ranging from 1.7 to 0.22 g/cc. The ability to tune the densities is achieved by controlled addition of blowing agents (H2O2) and surfactants (stearic acid) respectively. The thermal conductivity of these foams decreased monotonically with increasing porosity (or decreasing densities), and the density-thermal conductivity relationship is governed by a power law. In addition, morphological and structural characterization was performed via optical and electron microscopy, x-ray diffraction, and nuclear magnetic resonance, and the results from these studies are also discussed in the context of structural evolution of the foams as a function of porosity. While this work represents a straightforward and simple path towards obtaining silica-alumina foams with very low density, the developed method is directly applicable to obtaining a wider variety of multicomponent ceramic foams.
- Carothers, K. J., Carothers, K. J., Glass, R. S., Glass, R. S., Pyun, J., Char, K., Mackay, M. E., Frederick, K. M., Griebel, J. J., Loy, D. A., Kleine, T. S., Karayilan, M., Karayilan, M., Kleine, T. S., Griebel, J. J., Loy, D. A., Glass, R. S., Mackay, M. E., Frederick, K. M., , Pyun, J., et al. (2019). Chalcogenide hybrid inorganic/organic polymer resins: Amine functional prepolymers from elemental sulfur. Journal of Polymer Science Part A, 58(1), 35-41. doi:10.1002/pola.29480
- Song, W., Li, Z., Li, Y., You, H., Qi, P., Liu, F., & Loy, D. A. (2018). Facile sol-gel coating process for anti-biofouling modification of poly (vinylidene fluoride) microfiltration membrane based on novel zwitterionic organosilica. JOURNAL OF MEMBRANE SCIENCE, 550, 266-277.
- Bagge, R. E., Mauldin, T. C., Boday, D. J., Kobilka, B. M., & Loy, D. A. (2017). Transforming Polybutadiene with Tetrazine Click Chemistry into Antioxidant Foams That Fluoresce with Oxidation. CHEMISTRY OF MATERIALS, 29(18), 7953-7960.
- Loy, D. A. (2017). Transforming Polybutadiene with Tetrazine Click Chemistry into Antioxidant Foams That Fluoresce with Oxidation. Chemistry of Materials.
- Loy, D. A. (2017). UV Fluorescent Epoxy Adhesives from Noncovalent and Covalent Incorporation of Coumarin Dyes. ACS Applied Materials & Interfaces.
- Loy, D. A., Bagge, R. E., Mauldin, T. C., Boday, D. J., & Kobilka, B. M. (2017). Transforming Polybutadiene with Tetrazine Click Chemistry into Antioxidant Foams That Fluoresce with Oxidation. Chemistry of Materials, 29(18), 7953-7960. doi:10.1021/acs.chemmater.7b02973
- Loy, D. A., Odegaard, N., Frederick, K., McFadden, P. D., Argüello, L. A., Zhang, Y., & Vandiver, P. (2017). UV Fluorescent Epoxy Adhesives from Noncovalent and Covalent Incorporation of Coumarin Dyes. ACS Applied Materials & Interfaces, 9(11), 10061-10068. doi:10.1021/acsami.6b13218
- McFadden, P. D., Frederick, K., Argueello, L. A., Zhang, Y., Vandiver, P., Odegaard, N., & Loy, D. A. (2017). UV Fluorescent Epoxy Adhesives from Noncovalent and Covalent Incorporation of Coumarin Dyes. ACS APPLIED MATERIALS & INTERFACES, 9(11), 10061-10068.
- Frederick, K. M., Boday, D. J., Unangst, J., Stover, R. J., Li, Z., Budy, S., & Loy, D. A. (2016). Photochemical strengthening of silica aerogels modified with coumarin groups. JOURNAL OF NON-CRYSTALLINE SOLIDS, 432, 189-195.
- Loy, D. A. (2016). Photochemical strengthening of silica aerogels modified with coumarin groups. Journal of Non-Crystalline Solids.
- Muriithi, B., & Loy, D. A. (2016). Proton Conductivity of Nafion/Ex-Situ Sulfonic Acid-Modified Stöber Silica Nanocomposite Membranes As a Function of Temperature, Silica Particles Size and Surface Modification. Membranes, 6(1).More infoThe introduction of sulfonic acid modified silica in Nafion nanocomposite membranes is a good method of improving the Nafion performance at high temperature and low relative humidity. Sulfonic acid-modified silica is bifunctional, with silica phase expected to offer an improvement in membranes hydration while sulfonic groups enhance proton conductivity. However, as discussed in this paper, this may not always be the case. Proton conductivity enhancement of Nafion nanocomposite membranes is very dependent on silica particle size, sometimes depending on experimental conditions, and by surface modification. In this study, Sulfonated Preconcentrated Nafion Stober Silica composites (SPNSS) were prepared by modification of Stober silica particles with mercaptopropyltriethoxysilane, dispersing the particles into a preconcentrated solution of Nafion, then casting the membranes. The mercapto groups were oxidized to sulfonic acids by heating the membranes in 10 wt % hydrogen peroxide for 1 h. At 80 °C and 100% relative humidity, a 20%-30% enhancement of proton conductivity was only observed when sulfonic acid modified particle less than 50 nm in diameter were used. At 120 °C, and 100% humidity, proton conductivity increased by 22%-42% with sulfonated particles with small particles showing the greatest enhancement. At 120 °C and 50% humidity, the sulfonated particles are less efficient at keeping the membranes hydrated, and the composites underperform Nafion and silica-Nafion nanocomposite membranes.
- Muriithi, B., & Loy, D. A. (2016). Proton conductivity of Nafion/ex-situ sulfonic acid-modified Stober silica nanocomposite membranes as a function of temperature, silica particles size and surface modification.. Membranes (Basel, Switzerland), 6(1), 12/1-12/14.
- Tolbert, S. H., McFadden, P. D., & Loy, D. A. (2016). New Hybrid Organic/Inorganic Polysilsesquioxane-Silica Particles as Sunscreens. ACS APPLIED MATERIALS & INTERFACES, 8(5), 3160-3174.
- Tolbert, S. H., McFadden, P. D., & Loy, D. A. (2016). New Hybrid Organic/Inorganic Polysilsesquioxane-Silica Particles as Sunscreens. ACS Applied Materials and Interfaces, 8(Issue 5). doi:10.1021/acsami.5b10472More infoEffectiveness of organic sunscreens is limited by phototoxicity and degradation. Both of which can be significantly reduced by encapsulation in hollow particles or covalent incorporation into the solid structure of particles, but direct comparisons of the two methods have not been reported. In this study, physical encapsulation and covalent incorporation of sunscreens were compared with 1 mol % salicylate and curcumeroid sunscreens. 2-Ethylhexyl salicylate was physically encapsulated in hollow silica nanoparticles prepared by oil-in-water (O/W) microemulsion polymerizations (E-Sal). Some of these particles were coated with an additional shell or cap of silica to reduce leaking of sunscreen (cap-E-Sal). Covalent incorporation involved co-polymerizing tetraethoxysilane (TEOS) with 0.2 mol % of new salicylate and curcuminoid sunscreen monomers with triethoxsilyl groups. Particles were prepared with the salicylate attached to the silica matrix through single silsesquioxane groups (pendant; P-Sal) and two silsesquioxane groups (bridged; B-Sal). Particles based on a new curcuminoid-bridged monomer were also prepared (B-Curc). Sunscreen leaching, photodegradation, and sunscreen performance were determined for the E-Sal, cap-E-Sal, P-Sal, B-Sal, and B-Curc particles. Covalent attachment, particularly with bridged sunscreen monomers, reduced leaching and photodegradation over physical encapsulation, even with capping.
- Boday, D. J., Muriithi, B., Stover, R. J., & Loy, D. A. (2015). Polyaniline nanofiber-silica composite aerogels. JOURNAL OF NON-CRYSTALLINE SOLIDS, 358(12-13), 1575-1580.
- Budy, S., Jin, J., Loy, D., & Iacono, S. (2015). Synthesis and characterization of semifluorinated polyarylene copolymers. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 249.
- Hu, L. J., Lin, D. R., Loy, D. A., Xing, B., & You, H. (2015). Mechanisms of Competitive Adsorption Organic Pollutants on Hexylene-Bridged Polysilsesquioxane.. Materials (Basel, Switzerland), 8(9), 5806-5817. doi:10.3390/ma8095275More infoHexylene-bridged periodic mesoporous polysilsesquioxanes (HBPMS) are a promising new class of adsorbent for the removal of organic contaminants from aqueous solutions. These hybrid organic-inorganic materials have a larger BET surface area of 897 m2·g-1 accessible through a cubic, isotropic network of 3.82-nm diameter pores. The hexylene bridging group provides enhanced adsorption of organic molecules while the bridged polysilsesquioxane structure permits sufficient silanols that are hydrophilic to be retained. In this study, adsorption of phenanthrene (PHEN), 2,4-Dichlorophenol (DCP), and nitrobenzene (NBZ) with HBPMS materials was studied to ascertain the relative contributions to adsorption performance from (1) direct competition for sites and (2) pore blockage. A conceptual model was proposed to further explain the phenomena. This study suggests a promising application of cubic mesoporous BPS in wastewater treatment.
- Jamison, G. M., Wheeler, D. R., Loy, D. A., & Ziller, J. W. (2015). Double phosphaalkyne insertion to a tungsten alkylidene: Formation of a diphosphametallabicyclobutane. ORGANOMETALLICS, 24(10), 2245-2247.
- Lin, D. R., Hu, L. J., Xing, B. S., You, H., & Loy, D. A. (2015). Mechanisms of Competitive Adsorption Organic Pollutants on Hexylene-Bridged Polysilsesquioxane. Materials (Basel, Switzerland), 8(9), 5806-5817.More infoHexylene-bridged periodic mesoporous polysilsesquioxanes (HBPMS) are a promising new class of adsorbent for the removal of organic contaminants from aqueous solutions. These hybrid organic-inorganic materials have a larger BET surface area of 897 m2·g-1 accessible through a cubic, isotropic network of 3.82-nm diameter pores. The hexylene bridging group provides enhanced adsorption of organic molecules while the bridged polysilsesquioxane structure permits sufficient silanols that are hydrophilic to be retained. In this study, adsorption of phenanthrene (PHEN), 2,4-Dichlorophenol (DCP), and nitrobenzene (NBZ) with HBPMS materials was studied to ascertain the relative contributions to adsorption performance from (1) direct competition for sites and (2) pore blockage. A conceptual model was proposed to further explain the phenomena. This study suggests a promising application of cubic mesoporous BPS in wastewater treatment.
- Loy, D. A. (2015). Controlling nanostructure in periodic mesoporous hexylene-bridged polysilsesquioxanes. Journal of Non-Crystalline Solids.
- Loy, D. A., Obrey-DeFriend, K. A., Wilson Jr., K. V., Minke, M., Baugher, B. M., Baugher, C. R., Schneider, D. A., Jamison, G. M., & Shea, K. J. (2015). Influence of the alkoxide group, solvent, catalyst, and concentration on the gelation and porosity of hexylene-bridged polysilsesquioxanes. JOURNAL OF NON-CRYSTALLINE SOLIDS, 362, 82-94.
- Tolbert, S. H., Loy, D. A., Tolbert, S. H., & Loy, D. A. (2015). Fluorescent hybrid organic–inorganic particles: influence of physical encapsulation versus covalent attachment on leaching and UV stability. Journal of the Ceramic Society of Japan, 123(1441), 785-792. doi:10.2109/jcersj2.123.785
- Wang, H., Liu, L. i., Huang, Y., Wang, D. i., Hu, L., & Loy, D. A. (2015). Enhancement Corrosion Resistance of (gamma-Glycidyloxypropyl)-Silsesquioxane-Titanium Dioxide Films and Its Validation by Gas Molecule Diffusion Coefficients Using Molecular Dynamics (MD) Simulation. POLYMERS, 6(2), 300-310.
- Boday, D. J., Stover, R. J., Muriithi, B., & Loy, D. A. (2014). Mechanical properties of hexylene- and phenylene-bridged polysilsesquioxane aerogels and xerogels. JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, 61(1), 144-150.
- Boday, D. J., Stover, R. J., Muriithi, B., & Loy, D. A. (2014). Strong, low density, hexylene- and phenylene-bridged polysilsesquioxane aerogel-polycyanoacrylate composites. JOURNAL OF MATERIALS SCIENCE, 46(19), 6371-6377.
- Boday, D. J., Tolbert, S., Keller, M. W., Li, Z., Wertz, J. T., Muriithi, B., & Loy, D. A. (2014). Non-hydrolytic formation of silica and polysilsesquioxane particles from alkoxysilane monomers with formic acid in toluene/tetrahydrofuran solutions. JOURNAL OF NANOPARTICLE RESEARCH, 16(3).
- Budy, S. M., & Loy, D. A. (2014). Highly Sulfonated Polyelectrolytes Through Friedel-Crafts Sulfonylation of Polyarylenes. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 52(10), 1381-1384.
- Canosa, E. M., Frederick, K. M., Loy, D. A., Vandiver, P., & Odegaard, N. (2014). Thermally re-workable epoxy adhesives for use in artifact repair. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 248.
- Chung, W. J., Simmonds, A. G., Griebel, J. J., Kim, E. T., Suh, H. S., Shim, I., Glass, R. S., Loy, D. A., Theato, P., Sung, Y., Char, K., & Pyun, J. (2014). Elemental Sulfur as a Reactive Medium for Gold Nanoparticles and Nanocomposite Materials. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 50(48), 11409-11412.
- Hu, Y., Geng, W., You, H., Wang, Y., & Loy, D. A. (2014). Modification of a phenolic resin with epoxy- and methacrylate-functionalized silica sols to improve the ablation resistance of their glass fiber-reinforced composites. Polymers, 6(Issue 1). doi:10.3390/polym6010105More infoFunctionalized silica sols were obtained by the hydrolytic condensation of (γ-methacryloxypropyl)trimethoxysilane (MPMS), (γ-glycidyloxypropyl)trimethoxysilane (GPMS) and tetraethoxysilane (TEOS). Three different sols were obtained: MPS (derived from MPMS and TEOS), GPS-MPS (derived from GPMS, MPMS and TEOS), and GPSD (derived from GPMS, TEOS and diglycidyl ether of bisphenol A, DGEBA). These silica sols were mixed with a phenolic resin (PR). Ethylenediamine was used as a hardener for epoxy-functionalized sols and benzoyl peroxide was used as an initiator of the free-radical polymerization of methacrylate-functionalized silica sols. Glass fiber-reinforced composites were obtained from the neat PR and MPS-PR, GPS-MPS-PR and GPSD-PR. The resulting composites were evaluated as ablation resistant materials in an acetylene-oxygen flame. A large increase in the ablation resistance was observed when the PR was modified by the functionalized silica sols. The ablation resistance of the composites decreased as follows: GPSD-PR > MPS-PR > GPS-MPS-PR > PR.
- Li, Z., Tolbert, S., & Loy, D. A. (2014). Hybrid Organic-Inorganic Membranes on Porous Supports by Size Exclusion and Thermal Sintering of Fluorescent Polyphenylsilsesquioxane Nanoparticles. MACROMOLECULAR MATERIALS AND ENGINEERING, 298(7), 715-721.
- Lin, D., Hu, L., Xing, B., You, H., & Loy, D. A. (2014). Mechanisms of Competitive Adsorption Organic Pollutants on Hexylene-Bridged Polysilsesquioxane. MATERIALS, 8(9), 5806-5817.
- Loy, D. A. (2014). Comparison of new periodic, mesoporous, hexylene-bridged polysilsesquioxanes with Pm3n symmetry versus sol-gel polymerized, hexylene-bridged gels. Journal of Non-Crystalline Solids.
- Loy, D. A. (2014). Comparison of new periodic, mesoporous, hexylene-bridged polysilsesquioxanes with Pm3n symmetry versus sol–gel polymerized, hexylene-bridged gels. Journal of Non-Crystalline Solids.
- Loy, D. A. (2014). Computational and experimental determinations of the UV adsorption of polyvinylsilsesquioxane-silica and titanium dioxide hybrids. Bio-Medical Materials and Engineering.
- Loy, D. A. (2014). Enhancement Corrosion Resistance of (gamma-Glycidyloxypropyl)-Silsesquioxane-Titanium Dioxide Films and Its Validation by Gas Molecule Diffusion Coefficients Using Molecular Dynamics (MD) Simulation. Polymers.
- Loy, D. A. (2014). Highly Sulfonated Polyelectrolytes Through Friedel-Crafts Sulfonylation of Polyarylenes. Journal of Polymer Science Part a-Polymer Chemistry.
- Loy, D. A. (2014). Hybrid organic-inorganic membranes from size exclusion deposition of fluorescent, octylene-bridged polysilsesquioxane particles. Journal of Non-Crystalline Solids.
- Loy, D. A. (2014). Influence of alkylene-bridging group length on mesostructure and porosity in cubic (Pm3n) periodic mesoporous bridged polysilsesquioxanes. Journal of Porous Materials.
- Loy, D. A. (2014). Methylene-bridged polysilsesquioxanes: substitution of a methylene spacer within a silicate matrix. Journal of Materials Science.
- Loy, D. A. (2014). Modification of a Phenolic Resin with Epoxy- and Methacrylate-Functionalized Silica Sols to Improve the Ablation Resistance of Their Glass Fiber-Reinforced Composites. Polymers.
- Loy, D. A. (2014). Non-hydrolytic formation of silica and polysilsesquioxane particles from alkoxysilane monomers with formic acid in toluene/tetrahydrofuran solutions. Journal of Nanoparticle Research.
- Loy, D. A. (2014). Proton conductivity of Nafion/ex situ Stober silica nanocomposite membranes as a function of silica particle size and temperature. Journal of Materials Science.
- Loy, D. A., & Budy, S. M. (2014). Highly sulfonated polyelectrolytes through friedel-crafts sulfonylation of polyarylenes. Journal of Polymer Science Part A: Polymer Chemistry, 52(10), 1381-1384. doi:10.1002/pola.27139
- Muriithi, B., & Loy, D. A. (2014). Proton conductivity of Nafion/ex situ Stober silica nanocomposite membranes as a function of silica particle size and temperature. JOURNAL OF MATERIALS SCIENCE, 49(4), 1566-1573.
- Muriithi, B., & Loy, D. A. (2014). Proton conductivity of Nafion/ex situ Stöber silica nanocomposite membranes as a function of silica particle size and temperature. Journal of Materials Science, 49(Issue 4). doi:10.1007/s10853-013-7839-yMore infoIn the first systematic study of the influence of the size of silica particles on ion exchange capacity (IEC) and proton conductivity of Nafion-silica nanocomposite membranes, thin films cast from mixtures of silica particles (5 wt%) with varying diameters ranging from 10 to 400 nm and Nafion in alcohol were examined. IECs decreased exactly as expected with the dilution of Nafion and its sulfonic acid groups with added silica. At 80 C, the proton conductivity was also less with silica particles. However, at higher temperatures (120 C), there was a 58 % improvement in proton conductivity at low relative humidity and a 45 % improvement at higher relative humidity for nanocomposite membranes prepared with silica particles
- Rahimian, K., Loy, D. A., & Wheeler, D. R. (2014). Soluble, high molecular weight polysilsesquioxanes with carboxylate functionalities. MACROMOLECULES, 35(7), 2452-2454.
- Wang, H., Lin, D., Wang, D., Hu, L., Huang, Y., Liu, L., & Loy, D. A. (2014). Computational and experimental determinations of the UV adsorption of polyvinylsilsesquioxane-silica and titanium dioxide hybrids. Bio-medical materials and engineering, 24(1), 651-7.More infoSunscreens that absorb UV light without photodegradation could reduce skin cancer. Polyvinyl silsesquioxanes are known to have greater thermal and photochemical stability than organic compounds, such as those in sunscreens. This paper evaluates the UV transparency of vinyl silsesquioxanes (VS) and its hybrids with SiO2(VSTE) and TiO2(VSTT) experimentally and computationally. Based on films of VS prepared by sol-gel polymerization, using benzoyl peroxide as an initiator, vinyltrimethoxysilane (VMS) formulated oligomer through thermal curing. Similarly, VSTE films were prepared from VMS and 5-25 wt-% tetraethoxysilane (TEOS) and VSTT films were prepared from VMS and 5-25 wt-% titanium tetrabutoxide (TTB). Experimental average transparencies of the modified films were found to be about 9-14% between 280-320 nm, 67-73% between 320-350nm, and 86-89% between 350-400nm. Computation of the band gap was absorption edges for the hybrids in excellent agreement with experimental data. VS, VSTE and VSTT showed good absorption in UV-C and UV-B range, but absorbed virtually no UV-A. Addition of SiO2 or TiO2 does not improve UV-B absorption, but on the opposite increases transparency of thin films to UV. This increase was validated with molecular simulations. Results show computational design can predict better sunscreens and reduce the effort of creating sunscreens that are capable of absorbing more UV-B and UV-A.
- Zhao, L., Loy, D. A., & Shea, K. J. (2014). Photodeformable spherical hybrid nanoparticles. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 128(44), 14250-14251.
- Boday, D. J., DeFriend, K. A., Wilson Jr., K. V., Coder, D., & Loy, D. A. (2013). Formation of polycyanoacrylate - Silica nanocomposites by chemical vapor deposition of cyanoacrylates on aerogels. CHEMISTRY OF MATERIALS, 20(9), 2845-2847.
- Garza, G., Li, P., & Loy, D. (2013). Micro-fluidic Assisted Passive Direct Methanol Fuel Cells. INTERNATIONAL MECHANICAL ENGINEERING CONGRESS AND EXPOSITION - 2012, VOL 9, PTS A AND B, 563-570.
- Hu, Y. u., Zhang, X., You, H., & Loy, D. (2013). Nanoindentation and nanoscratch profiles of thinner POSS films modified with titanium tetrabutoxide. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 246.
- Lin, D., Hu, L., & Loy, D. (2013). Hexylene-bridging periodic mesoporous silsesquioxane with Pm3n symmetry. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 246.
- Lin, D., Hu, L., Xing, B., & Loy, D. (2013). Adsorption of organic pollutants by different synthesized bridge polysilsesquioxane. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 246.
- Lin, D., Hu, L., You, H., & Loy, D. (2013). Effect of the reaction conditions on powder X- ray diffraction patterns and nitrogen adsorption of hexane BPS materials. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 246.
- Loy, D. A. (2013). Adsorption of organic pollutants by different synthesized bridge polysilsesquioxane. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2013). Asymmetric Membranes by Wet Phase Inversion of Phenylated Polyphenylene. Journal of Applied Polymer Science.
- Loy, D. A. (2013). Effect of the reaction conditions on powder X- ray diffraction patterns and nitrogen adsorption of hexane BPS materials. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2013). Foreign experts teaching "Network and Chemistry" at Harbin Institute of Technology. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2013). Hexylene-bridging periodic mesoporous silsesquioxane with Pm3n symmetry. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2013). Hybrid Organic-Inorganic Membranes on Porous Supports by Size Exclusion and Thermal Sintering of Fluorescent Polyphenylsilsesquioxane Nanoparticles. Macromolecular Materials and Engineering.
- Loy, D. A. (2013). Influence of the alkoxide group, solvent, catalyst, and concentration on the gelation and porosity of hexylene-bridged polysilsesquioxanes. Journal of Non-Crystalline Solids.
- Loy, D. A. (2013). Nanoindentation and nanoscratch profiles of thinner POSS films modified with titanium tetrabutoxide. Abstracts of Papers of the American Chemical Society.
- Loy, D. A., Beach, J. V., Baugher, B. M., Assink, R. A., Shea, K. J., Tran, J., & Small, J. H. (2013). Dialkylenecarbonate-bridged polysilsesquioxanes. Hybrid organic-inorganic sol-gels with a thermally labile bridging group. ORGANIC/INORGANIC HYBRID MATERIALS II, 576, 99-104.
- Tolbert, S. H., & Loy, D. A. (2013). Fluorescent hybrid organic-inorganic particles: influence of physical encapsulation versus covalent attachment on leaching and UV stability. JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, 123(1441), 785-792.
- Tolbert, S., Muriithi, B., & Loy, D. (2013). Preparation and investigation of N,N-bis(triethoxysilylpropyl)dansylamide modified silica spheres as a new active ingredient for sunscreens. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 244.
- Boday, D. J., Keng, P. Y., Muriithi, B., Pyun, J., & Loy, D. A. (2012). Mechanically reinforced silica aerogel nanocomposites via surface initiated atom transfer radical polymerizations. JOURNAL OF MATERIALS CHEMISTRY, 20(33), 6863-6865.
- Budy, S. M., & Loy, D. A. (2012). Synthesis and characterization of sulfonated polyarylene. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 244.
- Budy, S. M., Nichol, G. S., & Loy, D. A. (2012). 2,2 '',3,3 '',4,4 '',5,5 ''-Octaphenyl-1,1 ':4 ',1 ''-terphenyl and 2 ',3 ',5 ',6 '-tetrafluoro-2,2 '',3,3 '',4,4 '',5,5 ''-octaphenyl-1,1 ':4 ',1 ''-terphenyl. ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY, 68, O23-O27.
- Budy, S. M., Nichol, G. S., & Loy, D. A. (2012). 2,2'',3,3'',4,4'',5,5''-Octaphenyl-1,1':4',1''-terphenyl and 2',3',5',6'-tetrafluoro-2,2'',3,3'',4,4'',5,5''-octaphenyl-1,1':4',1''-terphenyl. Acta crystallographica. Section C, Crystal structure communications, 68(Pt 1), o23-7.More infoThe title compounds, C(66)H(46), (I), and C(66)H(42)F(4), (II), are polyphenylated arylenes synthesized by one-step Diels-Alder cycloaddition reactions. In both structures, all molecules lie on crystallographic inversion centers. In the case of (I), there are two half-molecules present in the asymmetric unit, (IA) and (IB); the geometry of each half-molecule differs principally in the magnitudes of the dihedral angles between mean planes fitted through the central aryl ring and the pendant phenyl rings. The crystal used was a non-merohedral twin, with a refined twin scale factor of 0.460 (8). The dihedral angle between the plane of the central tetrafluorinated ring and the adjacent tetraphenylated ring in (II) is 83.87 (4)°, significantly greater than the dihedral angles of 49.89 (12) and 54.38 (10)° found in the two half-molecules in (IA) and (IB), respectively, and attributed to intermolecular C-H···F hydrogen bonding in (II). Intermolecular C-H···π bonding is found in (I). Two interactions have the C-H bond oriented towards the centroid (Cg) of a butadiene fragment of a phenyl ring; both H···Cg distances are approximately 2.68 Å and the interactions connect adjacent molecules into stacks in the c-axis direction. The composition of the stacks alternates, i.e. (IA)-(IB)-(IA)-(IB) etc. A third, weaker, C-H···π interaction and a phenyl-phenyl close contact connect each end of the long molecular axes of (IB) with an adjacent molecule of (IA) into chains which run perpendicular to the (140) and ( ̅140) planes. C-H···F interactions in (II) have the most profound influence on the molecular and crystal structure, the main effect of which is the above-mentioned increase in the dihedral angle between the plane of the central tetrafluorinated ring and the adjacent tetraphenylated ring. C-H···F interactions have refined H···F distances of 2.572 (15) and 2.642 (16) Å, with approximate C-H···F angles of 123 and 157°, respectively. These form a hydrogen-bonded ribbon structure which propagates in the b-axis direction.
- Li, Z., Tolbert, S. H., & Loy, D. A. (2012). Hybrid organic-inorganic membranes from size exclusion deposition of fluorescent, octylene-bridged polysilsesquioxane particles. JOURNAL OF NON-CRYSTALLINE SOLIDS, 403, 88-96.
- Lin, D., Hu, L., Li, Z., & Loy, D. A. (2012). Influence of alkylene-bridging group length on mesostructure and porosity in cubic (Pm3n) periodic mesoporous bridged polysilsesquioxanes. JOURNAL OF POROUS MATERIALS, 21(1), 39-44.
- Loy, D. A. (2012). 2,2 '',3,3 '',4,4 '',5,5 ''-Octaphenyl-1,1 ':4 ',1 ''-terphenyl and 2 ',3 ',5 ',6 '-tetrafluoro-2,2 '',3,3 '',4,4 '',5,5 ''-octaphenyl-1,1 ':4 ',1 ''-terphenyl. Acta Crystallographica Section C-Crystal Structure Communications.
- Loy, D. A. (2012). Mechanical properties of hexylene- and phenylene-bridged polysilsesquioxane aerogels and xerogels. Journal of Sol-Gel Science and Technology.
- Loy, D. A. (2012). Polyaniline nanofiber-silica composite aerogels. Journal of Non-Crystalline Solids.
- Loy, D. A. (2012). Preparation and investigation of N,N-bis(triethoxysilylpropyl)dansylamide modified silica spheres as a new active ingredient for sunscreens. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2012). Processing, Morphology, and Water Uptake of Nafion/Ex situ Stober Silica Nanocomposite Membranes As a Function of Particle Size. Acs Applied Materials & Interfaces.
- Loy, D. A. (2012). Synthesis and characterization of sulfonated polyarylene. Abstracts of Papers of the American Chemical Society.
- Muriithi, B., & Loy, D. A. (2012). Processing, morphology, and water uptake of Nafion/ex situ Stöber silica nanocomposite membranes as a function of particle size. ACS applied materials & interfaces, 4(12), 6766-73.More infoBecause of the bicontinuous phase structure of Nafion with small hydrophilic channels, formation of composites with silica colloids to improve thermal stability, hydration, and proton conductivity should be influenced by size and surface functionality of the colloids. To test this hypothesis, we prepared batches of silica particles between 20 and 400 nm in diameter with narrow polydispersities using a modified Stöber procedure. Some particles were subsequently surface-modified using mercaptopropyltriethoxysilane. Enough particles were mixed with Nafion in alcohols to achieve 5 wt % silica in the final membranes, which were made by casting and drying. Membrane top and bottom surface and cross-section morphologies were examined with AFM and SEM to determine how the particles were dispersed. We discovered that casting the membranes from dispersions with viscosities less than 65 cPs led to larger particles floating to the top surface of the membrane where they were easily dislodged from the dry membrane. Membranes cast from more viscous solutions exhibited homogeneous distributions of particles. Water uptake was over 60% higher in nanocomposites with unmodified silica particles than for Nafion and about 15% higher than for Nafion with in situ generated silica particles, but showed no trend in water uptake correlating with particle size. Surface silated particles of all sizes appeared to have reduced water uptake relative to Nafion alone.
- Zhang, X., Hu, L., & Loy, D. (2012). Foreign experts teaching "Network and Chemistry" at Harbin Institute of Technology. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 246.
- Chung, W. J., Simmonds, A. G., Griebel, J. J., Kim, E. T., Suh, H. S., Shim, I. B., Glass, R. S., Loy, D. A., Theato, P., Sung, Y. E., Char, K., & Pyun, J. (2011). Elemental sulfur as a reactive medium for gold nanoparticles and nanocomposite materials. Angewandte Chemie (International ed. in English), 50(48), 11409-12.
- Hu, Y. u., Geng, W., You, H., Wang, Y., & Loy, D. A. (2011). Modification of a Phenolic Resin with Epoxy- and Methacrylate-Functionalized Silica Sols to Improve the Ablation Resistance of Their Glass Fiber-Reinforced Composites. POLYMERS, 6(1), 105-113.
- Khiterer, M., Loy, D. A., Cornelius, C. J., Fujimoto, C. H., Small, J. H., McIntire, T. M., & Shea, K. J. (2011). Hybrid polyelectrolyte materials for fuel cell applications: Design, synthesis, and evaluation of proton-conducting bridged polysilsesquioxanes. CHEMISTRY OF MATERIALS, 18(16), 3665-3673.
- Li, Z., & Loy, D. A. (2011). Preparation of colloidal silsesquioxane particles from bridged monomer under acidic conditions. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 241.
- Li, Z., & Loy, D. A. (2011). Preparation of dense hybrid membranes from ultraviolet treatment of poly(chloroethylsilsesquioxane) particles. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 242.
- Lin, D., Hu, L., You, H., Tolbert, S. H., & Loy, D. A. (2011). Comparison of new periodic, mesoporous, hexylene-bridged polysilsesquioxanes with Pm3n symmetry versus sol-gel polymerized, hexylene-bridged gels. JOURNAL OF NON-CRYSTALLINE SOLIDS, 406, 139-143.
- Loy, D. A. (2011). Elemental Sulfur as a Reactive Medium for Gold Nanoparticles and Nanocomposite Materials. Angewandte Chemie-International Edition.
- Loy, D. A. (2011). Enhancing mechanical properties of silica aerogels. Journal of Non-Crystalline Solids.
- Loy, D. A. (2011). Photochemical strengthening of silica aerogels modified with coumarins. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2011). Preparation of colloidal silsesquioxane particles from bridged monomer under acidic conditions. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2011). Preparation of dense hybrid membranes from ultraviolet treatment of poly(chloroethylsilsesquioxane) particles. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2011). Strong, low density, hexylene- and phenylene-bridged polysilsesquioxane aerogel-polycyanoacrylate composites. Journal of Materials Science.
- Loy, D. A. (2011). Titanium oxide sol-gel films with tunable refractive index. Optical Materials Express.
- Loy, D. A., Boday, D. J., Stover, R. J., Barton, J., Budy, S. M., & Li, Z. (2011). Photochemical strengthening of silica aerogels modified with coumarins. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 241.
- Obrey, K. A., Wilson, K. V., & Loy, D. A. (2011). Enhancing mechanical properties of silica aerogels. Journal of Non-Crystalline Solids, 357(Issue 19-20). doi:10.1016/j.jnoncrysol.2011.06.014More infoLow-density monolithic silica and hexylene-bridged polysilsesquioxane aerogels were chemical vapor deposition (CVD) treated with hexamethyldisilazane or hexachlorodisilane silylating agents producing TMS (trimethylsilane) or Si layers on the aerogel. Reinforcing the weak aerogels by controlled deposition process improved their compressive strength and preserved their properties characteristic of low-density aerogels. When the silica and hexylene-bridged polysilsesquioxane aerogels were CVD treated with hexamethyldisilazane, the compressive modulus more than doubled in some cases. However, when treating hexylene-bridged aerogels with hexachlorodisilane the compressive modulus increased six fold. Not only did CVD treatment of the aerogels improve the compressive modulus, but the low densities, high surface areas, high porosities, and the transparency of the aerogels were not significantly affected. © 2011 Elsevier B.V. All rights reserved.
- Obrey, K., Wilson, K. V., & Loy, D. A. (2011). Enhancing mechanical properties of silica aerogels. JOURNAL OF NON-CRYSTALLINE SOLIDS, 357(19-20), 3435-3441.
- Loy, D. A. (2010). Mechanically reinforced silica aerogel nanocomposites via surface initiated atom transfer radical polymerizations. Journal of Materials Chemistry.
- Loy, D. A. (2010). Sol-gel polymerization of bridged polysilsesquioxanes to afford membranes for gas separations. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2010). Tailoring and controlling the physical properties of silica aerogel-polymer nanocomposites with surface initiated-ATRP. Abstracts of Papers of the American Chemical Society.
- Muriithi, B., & Loy, D. A. (2010). Processing, Morphology, and Water Uptake of Nafion/Ex situ Stober Silica Nanocomposite Membranes As a Function of Particle Size. ACS APPLIED MATERIALS & INTERFACES, 4(12), 6765-6772.
- Boday, D. J., Stover, R. J., Muriithi, B., Keller, M. W., Wertz, J. T., Defriend Obrey, K. A., & Loy, D. A. (2009). Strong, low-density nanocomposites by chemical vapor deposition and polymerization of cyanoacrylates on aminated silica aerogels. ACS Applied Materials and Interfaces, 1(Issue 7). doi:10.1021/am900240hMore infoStrong polymer?silica aerogel composites were prepared by chemical vapor deposition of cyanoacrylate monomers onto amine-modified aerogels. Amine-modified silica aerogels were prepared by copolymerizing small amounts of (aminopropyl)triethoxysilane with tetraethoxysilane. After silation of the aminated gels with hexamethyldisilazane, they were dried as aerogels using supercritical carbon dioxide processing. The resulting aerogels had only the amine groups as initiators for the cyanoacrylate polymerizations, resulting in cyanoacrylate macromolecules that were higher in molecular weight than those observed with unmodified silica and that were covalently attached to the silica surface. Starting with aminated silica aerogels that were 0.075 g/cm 3 density, composite aerogels were made with densities up to 0.220 g/cm 3 and up to 31 times stronger (flexural strength) than the precursor aerogel and about 2.3 times stronger than an unmodified silica aerogel of the same density. © 2009 American Chemical Society.
- Boday, D. J., Stover, R. J., Muriithi, B., Keller, M. W., Wertz, J. T., Defriend Obrey, K. A., & Loy, D. A. (2009). Strong, low-density nanocomposites by chemical vapor deposition and polymerization of cyanoacrylates on aminated silica aerogels. ACS applied materials & interfaces, 1(7), 1364-9.More infoStrong polymer-silica aerogel composites were prepared by chemical vapor deposition of cyanoacrylate monomers onto amine-modified aerogels. Amine-modified silica aerogels were prepared by copolymerizing small amounts of (aminopropyl)triethoxysilane with tetraethoxysilane. After silation of the aminated gels with hexamethyldisilazane, they were dried as aerogels using supercritical carbon dioxide processing. The resulting aerogels had only the amine groups as initiators for the cyanoacrylate polymerizations, resulting in cyanoacrylate macromolecules that were higher in molecular weight than those observed with unmodified silica and that were covalently attached to the silica surface. Starting with aminated silica aerogels that were 0.075 g/cm(3) density, composite aerogels were made with densities up to 0.220 g/cm(3) and up to 31 times stronger (flexural strength) than the precursor aerogel and about 2.3 times stronger than an unmodified silica aerogel of the same density.
- Loy, D. A. (2009). CHED 76-Seeing is believing: Using digital cameras in the laboratory to assist students. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). COLL 179-Inherently fluorescent silica-silsesquioxane nanoparticles for membrane integrity testing. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). COLL 202-Preparation of silsesquioxane colloidal particles from bridged monomers under acidic conditions. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). COLL 286-Ex situ Stoeber silica-Nafion (R) nanocomposite membranes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). COLL 86-Anhydrous synthesis of silica and hybrid polysilsesquioxane spheres. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). POLY 374-Mechanical property analysis of bridged polysilsesquioxane aerogels and subsequent reinforcing with poly(methyl cyanoacrylate). Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). POLY 68-Sulfonated polyarylene using Lewis acid catalysts: Synthesis and characterization. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). Polyaniline nanofiber/silica aerogel composites with improved strength and sensor applications. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). Preparation and characterization of ex-situ silica-Nafion (R) nanocomposite membranes with different size particles for application in PEM fuel cells. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). Preparation of Platinum Catalyst on Silver Membranes for PEMFC with Green Electroless Deposition. Proton Exchange Membrane Fuel Cells 9.
- Loy, D. A. (2009). Preparation of inherently fluorescent silica-silsesquioxane nanoparticles. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). Silica aerogel polymer nanocomposites using ATRP from surface bound initiators. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). Strong, Low-Density Nanocomposites by Chemical Vapor Deposition and Polymerization of Cyanoacrylates on Aminated Silica Aerogels. ACS APPLIED MATERIALS & INTERFACES.
- Loy, D. A. (2009). Sulfonated polyarylenes using Lewis acid catalysts for PEMFC. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2009). Sulfonated polyarylenes via Friedel-Crafts catalysis: Synthesis and characterization. Abstracts of Papers of the American Chemical Society.
- Taubert, J., & Loy, D. A. (2009). Preparation of Platinum Catalyst on Silver Membranes for PEMFC with Green Electroless Deposition. PROTON EXCHANGE MEMBRANE FUEL CELLS 9, 25(1), 1345-1352.
- Wang, H., Lin, D., Wang, D. i., Hu, L., Huang, Y., Liu, L. i., & Loy, D. A. (2009). Computational and experimental determinations of the UV adsorption of polyvinylsilsesquioxane-silica and titanium dioxide hybrids. BIO-MEDICAL MATERIALS AND ENGINEERING, 24(1), 651-657.
- Boday, D. J., Loy, D. A., DeFriend, K. A., Wilson Jr., K. V., & Coder, D. (2008). Polymer-silica nanocomposite aerogels with enhanced mechanical properties using chemical vapor deposition (CVD) of cyanoacrylates. ORGANIC/INORGANIC HYBRID MATERIALS - 2007, 1007, 153-158.
- Himmelhuber, R., Gangopadhyay, P., Norwood, R. A., Loy, D. A., & Peyghambarian, N. (2008). Titanium oxide sol-gel films with tunable refractive index. OPTICAL MATERIALS EXPRESS, 1(2), 252-258.
- Loy, D. A. (2008). Formation of polycyanoacrylate - Silica nanocomposites by chemical vapor deposition of cyanoacrylates on aerogels. CHEMISTRY OF MATERIALS.
- Loy, D. A. (2008). PMSE 6-Preparation and characterization of fluorescent silica and silsesquioxane nanoparticles. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2008). POLY 294-Hybrid organic-inorganic aerogels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2008). POLY 451-Improvement of unmodified and amine modified silica aerogels by chemical vapor deposition of cyanoacrylates. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2008). Photoresponsive hybrid materials: Synthesis and characterization of coumarin-dimer-bridged polysilsesquioxanes. CHEMISTRY OF MATERIALS.
- Loy, D. A. (2008). Photoresponsive hybrid materials: synthesis and characterization of coumarin-dimer-bridged polysilsesquioxanes. Chemistry of Materials.
- Loy, D. A. (2008). Polymer-silica nanocomposite aerogels with enhanced mechanical properties using Chemical Vapor Deposition (CVD) of cyanoacrylates. Organic/Inorganic Hybrid Materials - 2007.
- Loy, D. A., Zhao, L., Vaupel, M., & Shea, K. J. (2008). Photoresponsive Hybrid Materials: Synthesis and Characterization of Coumarin-Dimer-Bridged Polysilsesquioxanes. Chemistry of Materials, 20(5), 1870-1876. doi:10.1021/cm702804r
- Zhao, L., Vaupel, M., Loy, D. A., & Shea, K. J. (2008). Photoresponsive hybrid materials: Synthesis and characterization of coumarin-dimer-bridged polysilsesquioxanes. CHEMISTRY OF MATERIALS, 20(5), 1870-1876.
- Zhou, O., Kniaz, K., Fischer, J. E., Murphy, D. W., Zhu, Q., Zhou, O., Williams, J., Wang, H., Schirber, J. E., Samara, G. A., Rossiensky, M., Murphy, D., Morosin, B., Loy, D. A., Kortan, A. R., Kniaz, K., Fischer, J. E., & Assink, R. A. (2008). Role of pressure in the study of fullerenes. High‐pressure science and technology, 309(1), 639-642. doi:10.1063/1.46414More infoAlthough fullerenes and their compounds are very new and exhibit new phenomena, pressure has already been an important factor in the characterization and study of these materials. In order to illustrate this, we will review collaborative studies on: i) the effect of pressure on alkali and alkaline earth doped C60 superconductors, ii) the effect of pressure and pressure medium on the ordering temperature of C60, and iii) the role of pressure in the study of the feasibility of using C60 as ‘‘lattice sieves’’ for separation of gases.
- Boday, D. J., Coder, D., Defriend, K. A., Loy, D. A., & Wilson, K. V. (2007). Polymer-Silica Nanocomposite Aerogels with Enhanced Mechanical Properties Using Chemical Vapor Deposition (CVD) of Cyanoacrylates. MRS Proceedings, 1007(1), 153-158. doi:10.1557/proc-1007-s09-05More infoAerogels were structurally modified using chemical vapor deposition (CVD) of cyanoacrylate monomers to afford polycyanoacrylate-aerogel nanocomposites. Silica aerogels are low density, high surface area materials whose applications are limited by their fragility. Cyanoacrylate CVD allowed us to deposit a film of organic polymer throughout fragile porous monoliths within hours. Our experiments have shown that polymerization of the cyanoacrylate monomers was initiated by the adsorbed water on the surface of the silica permitting the nanocomposites structures to be formed with little or no sample preparation. We found that the strength of the polycyanoacrylate-aerogel nanocomposites increased thirty two-fold over the untreated aerogels with only a three-fold increase in density and an eight-fold decrease in surface area. Along with the improvement in mechanical properties, the aerogels became less hydrophilic than un-modified aerogels. Polycyanoacrylate-coated aerogels were placed directly into water and did not suffer catastrophic fragmentation as observed with un-modified silica aerogels.
- Boday, D. J., Stover, R. J., Muriithi, B., Keller, M. W., Wertz, J. T., Obrey, K., & Loy, D. A. (2006). Strong, Low-Density Nanocomposites by Chemical Vapor Deposition and Polymerization of Cyanoacrylates on Aminated Silica Aerogels. ACS APPLIED MATERIALS & INTERFACES, 1(7), 1364-1369.
- LOY, D. A., ASSINK, R. A., JAMISON, G. M., MCNAMARA, W. F., PRABAKAR, S., & SCHNEIDER, D. A. (2006). CHARACTERIZATION OF POLY(XYLYLENES) WITH SOLID-STATE C-13 NUCLEAR-MAGNETIC-RESONANCE SPECTROSCOPY. MACROMOLECULES, 28(17), 5799-5803.
- Lin, D., Hu, L., Tolbert, S. H., Li, Z., & Loy, D. A. (2006). Controlling nanostructure in periodic mesoporous hexylene-bridged polysilsesquioxanes. JOURNAL OF NON-CRYSTALLINE SOLIDS, 419, 6-11.
- Loy, D. A. (2006). Creating macroporous voids in silica aerogels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2006). Hybrid polyelectrolyte materials for fuel cell applications: Design, synthesis, and evaluation of proton-conducting bridged polysilsesquioxanes. CHEMISTRY OF MATERIALS.
- Loy, D. A. (2006). Mesoscopically ordered organosilica and carbon-silica hybrids with uniform morphology by surfactant-assisted self-assembly of organo bis-silanetriols. CHEMICAL COMMUNICATIONS.
- Loy, D. A. (2006). Photodeformable spherical hybrid nanoparticles. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
- Loy, D. A. (2006). Utilization of thermally cleavable surfactants based on furan and maleimide Diels-Alder adducts as removable templates. Abstracts of Papers of the American Chemical Society.
- Loy, D. A., Khiterer, M., Cornelius, C. J., Fujimoto, C. H., Small, J. H., McIntire, T. M., & Shea, K. J. (2006). Hybrid Polyelectrolyte Materials for Fuel Cell Applications: Design, Synthesis, and Evaluation of Proton-Conducting Bridged Polysilsesquioxanes. Chemistry of Materials, 18(16), 3665-3673. doi:10.1021/cm060440a
- Pang, J., Yang, L., Loy, D. A., Peng, H., Ashbaugh, H. S., Mague, J., Brinker, C. J., & Lu, Y. (2006). Mesoscopically ordered organosilica and carbon-silica hybrids with uniform morphology by surfactant-assisted self-assembly of organo bis-silanetriols. Chemical communications (Cambridge, England), 1545-7.More infoLong-range molecularly ordered organosilica and carbon-silica hybrids with uniform morphology have been synthesized by surfactant-assisted hydrolysis and self-assembly of biphenyl bridged organosilane, followed by thermal polycondensation and carbonization.
- Zhao, L., Loy, D. A., & Shea, K. J. (2006). Photodeformable spherical hybrid nanoparticles. Journal of the American Chemical Society, 128(44), 14250-1.More infoWe report the first synthesis of spherical nanoparticles of a bridged polysilsesquioxane. The hard, brittle nanoparticles are prepared by a simple sol-gel polymerization without surfactants or templates. Particle size ranges from 50 to 100 nm. The organic component of these hybrid nanoparticles is composed of a photolabile coumarin dimer. Irradiation with UV light dissociates the photodimer resulting in rupture of the cross-links and subsequent deformation and eventual "melting" of the nanoparticles.
- Zhao, L., Loy, D. A., & Shea, K. J. (2006). Photodeformable spherical hybrid nanoparticles. Journal of the American Chemical Society, 128(Issue 44). doi:10.1021/ja066047nMore infoWe report the first synthesis of spherical nanoparticles of a bridged polysilsesquioxane. The hard, brittle nanoparticles are prepared by a simple sol-gel polymerization without surfactants or templates. Particle size ranges from 50 to 100 nm. The organic component of these hybrid nanoparticles is composed of a photolabile coumarin dimer. Irradiation with UV light dissociates the photodimer resulting in rupture of the cross-links and subsequent deformation and eventual "melting" of the nanoparticles. Copyright © 2006 American Chemical Society.
- BRINKER, C. J., SEHGAL, R., HIETALA, S. L., DESHPANDE, R., SMITH, D. M., LOY, D., & ASHLEY, C. S. (2005). SOL-GEL STRATEGIES FOR CONTROLLED POROSITY INORGANIC MATERIALS. JOURNAL OF MEMBRANE SCIENCE, 94, 85-102.
- JAMISON, G. M., LOY, D. A., & SHEA, K. J. (2005). BRIDGED POLYGERMSESQUIOXANES - ORGANICALLY MODIFIED GERMANIUM OXIDE MATERIALS. CHEMISTRY OF MATERIALS, 5(9), 1193-1195.
- Long, T. M., Simmons, B. A., McElhanon, J. R., Kline, S. R., Wheeler, D. R., Loy, D. A., Rahimian, K., Zifer, T., & Jamison, G. M. (2005). Metathesis depolymerization for removable surfactant templates. Langmuir : the ACS journal of surfaces and colloids, 21(20), 9365-73.More infoCurrent methodologies for the production of meso- and nanoporous materials include the use of a surfactant to produce a self-assembled template around which the material is formed. However, post-production surfactant removal often requires centrifugation, calcination, and/or solvent washing which can damage the initially formed material architecture(s). Surfactants that can be disassembled into easily removable fragments following material preparation would minimize processing damage to the material structure, facilitating formation of templated hybrid architectures. Herein, we describe the design and synthesis of novel cationic and anionic surfactants with regularly spaced unsaturation in their hydrophobic hydrocarbon tails and the first application of ring closing metathesis depolymerization to surfactant degradation resulting in the mild, facile decomposition of these new compounds to produce relatively volatile nonsurface active remnants.
- Loy, D. A. (2005). Anisotropic porosity of hybrid organic/inorganic polyisocyanate sol-gel films. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2005). Collapse of porosity during drying of alkylene-bridged polysilsesquioxane gels: influence of the bridging group length. Organic/Inorganic Hybrid Materials-2004. (Materials Research Society Symposium Proceedings Vol.847).
- Loy, D. A. (2005). Double phosphaalkyne insertion to a tungsten alkylidene: Formation of a diphosphametallabicyclobutane. ORGANOMETALLICS.
- Loy, D. A. (2005). Evolution of porosity and morphology in alkylene-bridged polysilsesquioxane xerogels as a function of gel aging time. Organic/Inorganic Hybrid Materials-2004. (Materials Research Society Symposium Proceedings Vol.847).
- Loy, D. A. (2005). Hierarchical mesoporous carbon/silica nanocomposites from phenyl-bridged organosilane. ADVANCED MATERIALS.
- Loy, D. A. (2005). Ionomeric poly(phenylene) prepared by diels-alder polymerization: Synthesis and physical properties of a novel polyelectrolyte. MACROMOLECULES.
- Loy, D. A. (2005). Metathesis depolymerization for removable surfactant templates. LANGMUIR.
- Loy, D. A. (2005). Methylene-bridged polysilsesquioxanes: Substitution of a methylene spacer within a silicate matrix. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2005). Nanostructure in polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2005). Nonshrinking, photopolymerizable polycarbosiloxanes through ring-opening polymerization of disilaoxacyclopentane monomers. CHEMISTRY OF MATERIALS.
- Loy, D. A. (2005). Thermally cleavable surfactants based on furan-maleimide Diels-Alder adducts. LANGMUIR.
- Loy, D. A., Baugher, B. M., Baugher, C. R., Schneider, D. A., & Rahimian, K. (2005). Substituent effects on the sol-gel chemistry of organotrialkoxysilanes. CHEMISTRY OF MATERIALS, 12(12), 3624-3632.
- Loy, D. A., Carpenter, J. P., Alam, T. M., Shaltout, R., Dorhout, P. K., Greaves, J., Small, J. H., & Shea, K. J. (2005). Cyclization phenomena in the sol-gel polymerization of alpha,omega-bis(triethoxysilyl) alkanes and incorporation of the cyclic structures into network silsesquioxane polymers. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 121(23), 5413-5425.
- Loy, D. A., Small, J. H., DeFriend, K. A., Wilson, K. V., Minke, M., Baugher, B. M., Baugher, C. R., Schneider, D. A., & Shea, K. J. (2005). Evolution of porosity and morphology in alkylene-bridged polysilsesquioxane xerogels as a function of gel aging time. Organic/Inorganic Hybrid Materials-2004, 847, 99-106.
- McElhanon, J. R., Zifer, T., Kline, S. R., Wheeler, D. R., Loy, D. A., Jamison, G. M., Long, T. M., Rahimian, K., & Simmons, B. A. (2005). Thermally cleavable surfactants based on furan-maleimide Diels-Alder adducts. Langmuir : the ACS journal of surfaces and colloids, 21(8), 3259-66.More infoTwo new surfactant molecules are reported that contain thermally labile Diels-Alder adducts connecting the hydrophilic and hydrophobic sections of each molecule. The two surfactants possess identical hydrophobic dodecyl tail segments but have phenol and carboxylic acid hydrophilic headgroups, respectively. Deprotonation with potassium hydroxide affords the formation of water-soluble surfactants. Room temperature aqueous solutions of both surfactants exhibit classical surface-active agent behavior similar to common analagous alkylaryl surfactant molecules. Critical micelle concentrations have been determined for each surfactant through dynamic surface tension and dye solubilization techniques. Small-angle neutron scattering measurements of the aqueous surfactant solutions indicate the presence of spherical micelles with radii of 16.5 angstroms for the carboxylate and 18.8 angstroms for the phenolate. When these surfactants are exposed to elevated temperatures (>50 degrees C), the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments. Aqueous solutions of each surfactant subsequently exhibit a loss of all surface-active behavior and the micellar aggregates are no longer detectable.
- RAMAN, N. K., & BRINKER, C. J. (2005). ORGANIC TEMPLATE APPROACH TO MOLECULAR-SIEVING SILICA MEMBRANES. JOURNAL OF MEMBRANE SCIENCE, 105(3), 273-279.
- SMALL, J. H., SHEA, K. J., & LOY, D. A. (2005). ARYLENE-BRIDGED AND ALKYLENE-BRIDGED POLYSILSESQUIOXANES. JOURNAL OF NON-CRYSTALLINE SOLIDS, 160(3), 234-246.
- Baugher, B. M., Schneider, D. A., Loy, D. A., & Rahimian, K. (2004). Porosity in polysilsesquioxane xerogels. ORGANIC/INORGANIC HYBRID MATERIALS II, 576, 105-110.
- Baugher, C. R., Baugher, B. M., Defriend, K. A., Loy, D. A., Minke, M., Schneider, D. A., Shea, K. J., Small, J. H., & Wilson, K. V. (2004). COLLAPSE OF POROSITY DURING DRYING OF ALKYLENE-BRIDGED POLYSILSESQUIOXANE GELS. INFLUENCE OF THE BRIDGING GROUP LENGTH. MRS Proceedings, 847, 165-170. doi:10.1557/proc-847-ee9.9More infoThe introduction of organic substituents into sol-gel materials can often result in networks that collapse during drying to afford non-porous xerogels. This can prove useful if non-porous coatings or membranes are the ultimate objectives. Collapse of porosity is also manifested in bridged polysilsesquioxanes with flexible bridging groups. Alkylene-bridged polysilsesquioxanes are hybrid xerogels whose organic bridging group is an integral constituent of the network polymer that can be systematically varied to probe the influence of its length on the xerogels' porosity and morphology. Our previous studies have shown that hexylene-bridged polysilsesquioxane xerogels prepared from 1, 6-bis(triethoxysilyl)hexane under acidic conditions are nonporous while the pentylene-bridged polysilsesquioxanes prepared under the same conditions are porous. We also discovered that the more reactive 1, 6-bis(trimethoxysilyl)hexane monomer could polymerize under acidic conditions to afford porous xerogels. Here, we have extended our study of bis(trimethoxysilyl)alkanes to include the heptylene (C7), octylene (C8), nonylene(C9) and decylene (C10) bridges so as to ascertain at what bridging group length the porosity collapses. The morphology of the resulting xerogels was characterized by nitrogen sorption porosimetry and electron microscopy. Solid state NMR was used to structurally characterize the materials.
- Loy, D. A. (2004). Alkylene-bridging group length in bridged silsesquioxanes and its effects on gel morphology. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Bridged polysilsesquioxane xerogels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). CVD modification of low-denisty silica and bridged polysilsesquioxane aerogels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Effect of pH on the gelation time of hexylene-bridged polysilsesquioxanes. CHEMISTRY OF MATERIALS.
- Loy, D. A. (2004). Effects of pH on the gelation time in the sol-gel polymerization of 1,6-bis(trimethoxysilyl)hexane. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Encapsulant based on meta-substituted phenylene bridged byclic siloxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Influence of aging time on the porosity, morphology and structure of hexylene-bridged polysilsesquioxane gels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Inorganic-organic composites for use as polyelectrolyte membranes in fuel cell applications. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Nature of the alkoxide group, solvent, catalyst, and monomer concentration on the gelation and porosity of hexylene-bridged polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Polysilsesquioxanes as solid electrolytes for proton exchange membrane fuel cell applications. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Sol-gel polymerization of polyisocyanates. Anisotropic porosity of hybrid organic-inorganic films. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Structure of arylene-bridged polysilsesquioxane xerogels and aerogels. CHEMISTRY OF MATERIALS.
- Loy, D. A. (2004). Surface modification of low density silica and bridged polysilsesquioxane aerogels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2004). Thermally cleavable surfactants based on furan-maleimide Diels-Alder adducts. Abstracts of Papers of the American Chemical Society.
- Loy, D. A., Jamison, G. M., McClain, M. D., & Alam, T. M. (2004). Spontaneous polymerization of phenylphosphaethyne. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 37(2), 129-133.
- Simmons, B. A., McElhanon JR, ., Loy, D. A., Jamison, G. M., Long, T. M., Wheeler, D. R., Kline SR, ., Rahimian, K., Zifer, T., & Even, W. R. (2004). Thermally cleavable surfactants based on furan-maleimide Diels-Alder adducts.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 227, U874-U874.
- Wilson, K. V., Baugher, C. R., Small, J. H., Baugher, B. M., Shea, K. J., Defriend, K. A., Schneider, D. A., Loy, D. A., Minke, M., Minke, M., Schneider, D. A., Loy, D. A., Defriend, K. A., Shea, K. J., Baugher, C. R., Small, J. H., Baugher, B. M., & Wilson, K. V. (2004). Evolution of Porosity and Morphology in Alkylene-Bridged Polysilsesquioxane Xerogels as a Function of Gel Aging Time. MRS Proceedings, 847(1), 99-106. doi:10.1557/proc-847-ee10.3More infoAging of silica gels before drying is known to result in significant changes in xerogel morphology, porosity and properties. In this study, the influence of aging gels on the porosity and morphology of alkylene-bridged polysilsesquioxane xerogels was examined. Gels of hexylene-, heptylene, octylene, nonylene, and decylene-bridged polysilsesquioxanes were prepared by the sol-gel polymerization of the respective bis(trimethoxysilyl)alkane monomers under acidic or basic conditions in methanol and in tetrahydrofuran. The gels were aged 3, 7, 14, 28, 35, 42, 49, and 56 days before drying to afford xerogels. The xerogels were characterized by nitrogen sorption porosimetry. Xerogels prepared in THF were non-porous. Those prepared and aged under basic conditions in methanol or tetrahydrofuran exhibited coarsening of porosity with aging time. With the exception of the hexylene-bridged gels, those prepared and aged in acidic methanol showed little change with aging. The surface area of the hexylene-bridged xerogels nearly tripled with aging times of up to several weeks, then decreased, for the gels aged for more than two weeks, to around 100 meters squared per gram.
- Loy, D. A. (2003). A parallel colorimetric method for the rapid discovery and optimization of heterogeneous hydrodesulfurization catalysts. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
- Loy, D. A. (2003). Metathesis depolymerization for removable surfactant templates. Abstracts of Papers of the American Chemical Society.
- Shea, K. J., & Loy, D. A. (2003). A mechanistic investigation of gelation. The sol-gel polymerization of precursors to bridged polysilsesquioxanes. ACCOUNTS OF CHEMICAL RESEARCH, 34(9), 707-716.
- Staiger, C. L., Loy, D. A., Jamison, G. M., Schneider, D. A., & Cornelius, C. J. (2003). A parallel colorimetric method for the rapid discovery and optimization of heterogeneous hydrodesulfurization catalysts. Journal of the American Chemical Society, 125(33), 9920-1.More infoA spectrophotometric based, parallel approach to screen heterogeneous catalysts for hydrodesulfurization has been developed. The method utilizes optical changes resulting from the hydrodesulfurization of 1,1'-binaphthothiophene to 1,1'-binaphthyl to determine catalyst activity. Hydrodesulfurization of 1,1'-binaphthothiophene to 1,1'-binaphthyl results in a loss of conjugation in the binaphthyl ring system. This results in a blue shift of more than 60 nm in the UV-vis spectrum. Since only small amounts of the HDS catalyst and 1,1'-binaphthothiophene are required, a large number of catalysts may be screened simultaneously. The synthesis of the 1,1'-binaphthothiophene and conditions for HDS catalyst screening are described.
- ASSINK, R. A., SCHIRBER, J. E., LOY, D. A., MOROSIN, B., & CARLSON, G. A. (2002). INTERCALATION OF MOLECULAR-SPECIES INTO THE INTERSTITIAL SITES OF FULLERENE. JOURNAL OF MATERIALS RESEARCH, 7(8), 2136-2143.
- LOY, D. A., JAMISON, G. M., ASSINK, R. A., MYERS, S., & SHEA, K. J. (2002). HEXYLENE-BRIDGED AND PHENYLENE-BRIDGED POLYSILOXANE NETWORK MATERIALS. HYBRID ORGANIC-INORGANIC COMPOSITES, 585, 264-277.
- Loy, D. A. (2002). Discovery and optimization of hydrodesulfurization catalysts using a combinatorial approach. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2002). Gas separation by thin film diels-alder polyphenylenes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2002). Removable foams based on an epoxy resin incorporating reversible Diels-Alder adducts. JOURNAL OF APPLIED POLYMER SCIENCE.
- Loy, D. A. (2002). Soluble, high molecular weight polysilsesquioxanes with carboxylate functionalities. Organic/Inorganic Hybrid Materials - 2002. Symposium (Materials Research Society Symposium Proceedings Vol.726).
- Loy, D. A. (2002). Soluble, high molecular weight polysilsesquioxanes with carboxylate functionalities. MACROMOLECULES.
- Loy, D. A. (2002). Synthesis and sol-gel chemistry of bis(diethoxymethylsilylpropyl)urea. Abstracts of Papers of the American Chemical Society.
- Loy, D. A., Cornelius, C. J., Apblett, C. A., Ingersoll, D., Brozik, S. M., Okandan, M., Kravitz, S. H., Schubert, W. K., Schubert, W. K., & Cornelius, C. J. (2002). Biofuel Cell LDRD. Sandia Report. doi:10.2172/801401
- BAUGHER, B. M., LOY, D. A., PRABAKAR, S., ASSINK, R. A., SHEA, K. J., & OVIATT, H. (2001). Porosity in hexylene-bridged polysilsesquioxanes. Effects of monomer concentration. ADVANCES IN POROUS MATERIALS, 371, 253-259.
- Loy, D. A. (2001). A mechanistic investigation of gelation. The sol-gel polymerization of precursors to bridged polysilsesquioxanes. ACCOUNTS OF CHEMICAL RESEARCH.
- Loy, D. A. (2001). Bridged polysilsesquioxanes. Molecular-engineered hybrid organic-inorganic materials. CHEMISTRY OF MATERIALS.
- Loy, D. A. (2001). Bridged polysilsesquioxanes: Molecular engineering of hybrid organic-inorganic materials. MRS BULLETIN.
- Loy, D. A. (2001). Butylene-bridged disilaoxacyclopentanes, liquid precursors for non-shrinking polycarbosiloxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Chemical modification of olefinic groups in bridged polysilsesquioxane gels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Chemistry of epoxy-functionalized organotrialkoxysilanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Engineering permeability and selectivy properties from polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Functional bridged polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Hybrid organic-inorganic materials. MRS BULLETIN.
- Loy, D. A. (2001). Sol-gel chemistry of 3-isocyanatopropyltriethoxysilane. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Sol-gel chemistry of amino-functionalized organotrialkoxysilanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Sol-gel chemistry of methacryloxy- and styryl-functionalized organotrialkoxysilanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Sol-gel chemistry of polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Sol-gel polymerization and thermal deprotection of protected 3-isocyanatopropyltriethoxysilanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Surface area and porosity engineering of alkylene-bridged methoxysilanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Synthesis and characterization of functional mesostructured silica films. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2001). Synthesis of siloxanes and silsesquioxanes for 157 nm lithography. Abstracts of Papers of the American Chemical Society.
- Loy, D. A., Mather, B., Straumanis, A. R., Baugher, C., Schneider, D. A., Sanchez, A., & Shea, K. J. (2001). Effect of pH on the gelation time of hexylene-bridged polysilsesquioxanes. CHEMISTRY OF MATERIALS, 16(11), 2041-2043.
- Rahimian, K., & Loy, D. A. (2001). Sol-gel chemistry by ring-opening polymerization. ORGANIC/INORGANIC HYBRID MATERIALS II, 576, 63-67.
- Schaefer, D. W., Beaucage, G., Loy, D. A., Shea, K. J., & Lin, J. S. (2001). Structure of arylene-bridged polysilsesquioxane xerogels and aerogels. CHEMISTRY OF MATERIALS, 16(8), 1402-1410.
- Shea, K. J., & Loy, D. A. (2001). Bridged polysilsesquioxanes. Molecular-engineered hybrid organic-inorganic materials. CHEMISTRY OF MATERIALS, 13(10), 3306-3319.
- Shea, K., & Loy, D. (2001). Functional bridged polysilsesquioxanes.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 222, U428-U428.
- Alam, T. M., Alam, T., Baugher, B. M., Loy, D. A., Rahimian, K., & Schneider, D. A. (2000). Sol-Gel Chemistry of Trialkoxysilanes. MRS Proceedings, 628(1), 1-6. doi:10.1557/proc-628-cc6.35More infoHydrolysis and condensation of trialkoxysilanes, HSi(OMe)3 and HSi(OEt)3, has been used to prepare polyhydridosilsesquioxaes for dielectric applications. In this study we examined the ability of trimethoxysilane (TMS) and triethoxysilane (TES) to undergo sol-gel polymerization to afford gels. Sol-gel polymerization experiments were conducted under acidic (HCl), basic (NaOH), and neutral conditions in methanol or ethanol. Gels prepared with basic catalysts were exothermic with the evolution of hydrogen gas. Gel times are compared with silica gels prepared from tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS). Gels were worked up under aqueous conditions to afford xerogels. Surface area analyses by nitrogen sorption porosimetery revealed that the materials were mostly mesoporous materials with surface areas in the hundreds of square meters per gram. Solid state 29Si CP MAS NMR was used to determine the amount of hydrido group remaining in the xerogels. Gels prepared under acidic conditions were essentially polysilsesquioxanes with very little loss of hydride functionalities. In gels prepared under basic conditions the hydride groups were completely gone leaving silica gels. Gels prepared with neutral water lost approximately 66% of the hydride groups.
- LOY, D. A., SMALL, J. H., & SHEA, K. J. (2000). ARYLENE-BRIDGED AND ALKYLENE-BRIDGED SILICONATES. ORGANOMETALLICS, 12(4), 1484-1488.
- Long, T. M., Simmons, B. A., McElhanon JR, ., Kline SR, ., Wheeler, D. R., Loy, D. A., Rahimian, K., Zifer, T., & Jamison, G. M. (2000). Metathesis depolymerization for removable surfactant templates. LANGMUIR, 21(20), 9365-9373.
- Loy, D. A. (2000). Bridged polysilsesquioxanes: A molecular-based approach for the synthesis of functional hybrid materials. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Evaporation-induced self-assembly of hybrid bridged silsesquioxane film and particulate mesophases with integral organic functionality. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
- Loy, D. A. (2000). Investigation of the transmission of substituent effects by Si-29 NMR. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2.
- Loy, D. A. (2000). Molecular engineering with bridged polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Polymerization chemistry of functionalized organotrialkoxysilanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Polymethylsilsesquioxanes through base-catalyzed redistribution of oligomethylhydridosiloxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Polysilsesquioxanes through base-catalyzed redistribution of oligomethylhydridosiloxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Porosity in polysilsesquioxane xerogels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Sol-gel chemistry of 3-isocyanatopropyltriethoxysilane. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Sol-gel chemistry of epoxy-functionalized organotrialkoxysilanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Sol-gel chemistry of methacryloxy- and styryl-functionalized organotrialkoxysilanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Structural modification of sol-gel materials through retro Diels-Alder reaction. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (2000). Substituent effects on the sol-gel chemistry of organotrialkoxysilanes. CHEMISTRY OF MATERIALS.
- Loy, D. A., Ulibarri, T. A., Curro, J. G., Saunders, R. S., Derzon, D. K., & Guess, T. R. (2000). Final report for the designed synthesis of controlled degradative materials LDRD. Sand report. doi:10.2172/751361More infoThe main goal of this research was to develop degradable systems either by developing weaklink-containing polymers or identifying commercial polymeric systems which are easily degraded. In both cases, the degradation method involves environmentally friendly chemistries. The weaklinks are easily degradable fragments which are introduced either randomly or regularly in the polymer backbone or as crosslinking sites to make high molecular weight systems via branching. The authors targeted three general application areas: (1) non-lethal deterrents, (2) removable encapsulants, and (3) readily recyclable/environmentally friendly polymers for structural and thin film applications.
- Rahimian, K., Loy, D. A., Rahimian, K., & Loy, D. A. (2000). Solventless sol-gel chemistry through ring-opening polymerization of bridged disilaoxacyclopentanes. MRS Proceedings, 628(1), 1-6. doi:10.1557/proc-628-cc6.43More infoDisilaoxacyclopentanes have proven to be excellent precursors to sol-gel type materials. These materials have shown promise as precursors for encapsulation and microelectronics applications. The polymers are highly crosslinked and are structurally similar to traditional sol-gels, but unlike typical sol-gels they are prepared without the use of solvents and water, they have low VOC's and show little shrinkage during processing.
- Rahimian, K., Loy, D. A., Rahimian, K., & Loy, D. A. (2000). Solventless sol-gel chemistry through ring-opening polymerization of bridged disilaoxacyclopentanes. MRS Proceedings, 628, 619-620. doi:10.1557/proc-628-cc6.4More infoDisilaoxacyclopentanes have proven to be excellent precursors to sol-gel type materials. These materials have shown promise as precursors for encapsulation and microelectronics applications. The polymers are highly crosslinked and are structurally similar to traditional sol-gels, but unlike typical sol-gels they are prepared without the use of solvents and water, they have low VOC's and show little shrinkage during processing.
- Shaltout, R., Loy, D., McClain, M., Prabakar, S., Greaves, J., & Shea, K. J. (2000). Structural modification of sol-gel materials through retro Diels-Alder reaction.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 219, U357-U357.
- Shea, K. J., & Loy, D. A. (2000). A Mechanistic Investigation of Gelation. The Sol-Gel Polymerization of Bridged Silsesquioxane Monomers. Accounts of Chemical Research.More infoThe study of a homologous series of silsesquioxane monomers has uncovered striking discontinuities in gelation behavior. An investigation of the chemistry during the early stages of the polymerization has provided a molecular basis for these observations. Monomers containing from one to four carbon atoms exhibit a pronounced tendency to undergo inter or intramolecular cyclization. The cyclic intermediates have been characterized by {sup 29}Si NMR, chemical ionization mass spectrometry and isolation from the reaction solution. These carbosiloxanes are local thermodynamic sinks that produce kinetic bottlenecks in the production of high molecular weight silsesquioxanes. The formation of cyclics results in slowing down or in some cases completely shutting down gelation. An additional finding is that the cyclic structures are incorporated intact into the final xerogel. Since cyclization alters the structure of the building block that eventually makes up the xerogel network, it is expected that this will contribute importantly to the bulk properties of the xerogel as well.
- Yamanaka, S. A., Charych, D. H., Loy, D. A., & Sasaki, D. Y. (2000). Solid phase immobilization of optically responsive liposomes in sol-gel materials for chemical and biological sensing. LANGMUIR, 13(19), 5049-5053.
- Alam, T. M., Assink, R. A., & Loy, D. A. (1999). Hydrolysis and esterification in organically modified alkoxysilanes: A Si-29 NMR investigation of methyltrimethoxysilane. CHEMISTRY OF MATERIALS, 8(9), 2366-2374.
- Boday, D. J., & Loy, D. A. (1999). Strengthening silica aerogels with surface initiated ATRP cross-linked poly(methyl methacrylate). JOURNAL OF NON-CRYSTALLINE SOLIDS, 427, 114-119.
- Jamison, G. M., Saunders, R. S., Wheeler, D. R., Alam, T. M., McClain, M. D., Loy, D. A., & Ziller, J. W. (1999). Isolation and characterization of the molybdenum alkylidyne complex [(F3C)Me(2)CO]Mo-2(C-t-Bu)[N(Ar)P=C(H)(CMe(2)Ph)] and its conversion to a phosphamolybdacyclobutene. ORGANOMETALLICS, 15(15), 3244-3246.
- Jamison, G. M., Saunders, R. S., Wheeler, D. R., McClain, M. D., Loy, D. A., & Ziller, J. W. (1999). Cycloaddition of phosphaalkynes to high-oxidation-state metal alkylidenes: Synthesis and characterization of a unique phosphametallacyclobutene via an alkoxide ligand shift. ORGANOMETALLICS, 15(1), 16-18.
- Loy, D. A. (1999). Cyclization phenomena in the sol-gel polymerization of alpha,omega-bis(triethoxysilyl) alkanes and incorporation of the cyclic structures into network silsesquioxane polymers. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
- Loy, D. A. (1999). Dialkylene carbonate-bridged polysilsesquioxanes. Hybrid organic-inorganic sol-gels with a thermally labile bridging group. CHEMISTRY OF MATERIALS.
- Loy, D. A. (1999). Maleimide functionalized siloxane resins. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1999). Phenylene-bridged cyclic siloxanes as precursors to nonshrinking sol-gel systems and their use as encapsulants. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION.
- Loy, D. A. (1999). Polymerization of the Z and E isomers of bis(triethoxysilyl)-2-butene. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1999). Shrinking sol-gel type polymers by ring opening polymerization. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1999). Sol-gel polymerization of organotrialkoxysilanes. Effect of the organic substituent on gelation. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1999). Spontaneous polymerization of phenylphosphaethyne. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY.
- Loy, D. A. (1999). Tailored porous materials. CHEMISTRY OF MATERIALS.
- Loy, D. A., Rahimian, K., & Samara, M. (1999). Phenylene-Bridged Cyclic Siloxanes as Precursors to Nonshrinking Sol-Gel Systems and Their Use as Encapsulants. Angewandte Chemie (International ed. in English), 38(4), 555-557.More infoA new class of thermally robust sol-gel polymers have been prepared from the disilaoxacyclopentane derivative 1 by ring-opening polymerization to form nonshrinking polysiloxanes. This reaction, which does not need solvent or water, can be used for, amongst other things, the encapsulation of an electronic microchip.
- Loy, D. A., Rahimian, K., & Samara, M. (1999). Phenylen‐verbrückte, cyclische Siloxane als Vorstufen nichtschrumpfender Sol‐Gel‐Systeme und deren Nutzung als Kapselmaterial. Angewandte Chemie, 111(4), 515-516. doi:10.1002/(sici)1521-3757(19990215)111:4<515::aid-ange515>3.0.co;2-mMore infoEine neue Klasse thermisch widerstandsfahiger Sol-Gel-Polymere ist uber das Disilaoxacyclopentanderivat 1 zuganglich, da dessen Ringoffnungspolymerisation Polysiloxane ohne Schrumpfungsprobleme liefert. Damit kann diese Reaktion, bei der auf Wasser oder andere Losungsmittel verzichtet werden kann, unter anderem genutzt werden, um elektronische Bauteile einzukapseln.
- MYERS, S. A., ASSINK, R. A., SCHIRBER, J. E., & LOY, D. A. (1999). The effect of O-2 intercalation on the rotational dynamics and the ordering transition of C-60. SCIENCE AND TECHNOLOGY OF FULLERENE MATERIALS, 359, 505-509.
- SCHIRBER, J. E., ASSINK, R. A., SAMARA, G. A., MOROSIN, B., & LOY, D. (1999). NEGATIVE-PRESSURE EFFECTS IN HIGH-PRESSURE OXYGEN-INTERCALATED C-60. PHYSICAL REVIEW B, 51(21), 15552-15554.
- Schaefer, D. W., Beaucage, G. B., Loy, D. A., Ulibarri, T. A., Black, E., Shea, K. J., & Buss, R. J. (1999). Origin of porosity in arylene-bridged polysilsesquioxanes. BETTER CERAMICS THROUGH CHEMISTRY VII: ORGANIC/INORGANIC HYBRID MATERIALS, 435, 301-306.
- Tran, H. V., Hung, R. J., Loy, D. A., Wheeler, D. R., Byers, J., Conley, W., & Willson, C. G. (1999). Synthesis of siloxanes and silsesquioxanes for 157 nm lithography.. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 221, U337-U337.
- Tran, J. A., Shea, K. J., & Loy, D. A. (1999). Methylene-bridged polysilsesquioxanes: substitution of a methylene spacer within a silicate matrix. JOURNAL OF MATERIALS SCIENCE, 49(14), 5006-5016.
- Loy, D. A. (1998). Arylene-bridged 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentanes as precursors to non-shrinking polysiloxanes. A new route to sol-gel type polymers. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1998). Diels-Alder reaction of cyclopentadiene with ethoxysilyl substituted dienophiles. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1998). Polymerization of bis(triethoxysilyl) ethenes. Impact of substitution geometry on the formation of ethenylene- and vinylidene-bridged polysilsesquioxanes. CHEMISTRY OF MATERIALS.
- Loy, D. A. (1998). Polymerization of the cis and trans isomers of 1,4-bis(triethoxysilyl)-2-butene and comparison of their structural properties. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1998). Polymerization of trialkoxysilanes. Effect of the organic substituent on the formation of gels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1998). Preparation and characterization of phenyl-, benzyl-, and phenethyl-substituted polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1998). Shrinkage and recyclability of poly(1,2-ethylene-bis(dimethylsiloxane)). Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1998). Synthesis and characterization of novel high molecular weight silsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1998). The impact of substitution geometry on the formation of ethenylene bridged polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- SCHIRBER, J. E., SAMARA, G. A., MOROSIN, B., ASSINK, R., LOY, D., WANG, H., WILLIAMS, J., ZHU, Q., KNIAZ, K., & FISCHER, J. E. (1998). ROLE OF PRESSURE IN THE STUDY OF FULLERENES. HIGH-PRESSURE SCIENCE AND TECHNOLOGY - 1993, PTS 1 AND 2, 639-642.
- Schneider, D. A., Loy, D. A., Baugher, B. M., Wheeler, D. R., Assink, R. A., Alam, T. M., & Saunders, R. S. (1998). Preparation and characterization of aryl-substituted polysilsesquioxanes. sand report. doi:10.2172/672121More infoPolymerizations of aryltrialkoxysilanes generally afford soluble oligomeric or polymeric aryl-substituted silsesquioxanes. This is in spite of being based on trifunctional precursors capable of forming highly crosslinked and insoluble network polymers. In this study, soluble phenyl, benzyl, and phenethyl-substituted silsesquioxane oligomers and polymers were prepared by hydrolyzing their respective triethoxysilyl precursor with water or aqueous acid. Additional samples of the polymers were prepared by heating the materials at 100 C or 200 C under vacuum in order to drive the condensation chemistry. One sample of polybenzylsilsesquioxane was heated at 200 C with catalytic NaOH. The resulting materials were characterized using solution {sup 1}H, {sup 13}C, and {sup 29}Si NMR spectroscopy, gel permeation chromatography, and differential scanning calorimetry. Of particular interest was the effect of the aryl substituent, and processing conditions on the molecular weight and glass transition temperatures of the polysilsesquioxanes.
- Jamison, G. M., Loy, D. A., & Curro, J. G. (1997). LDRD final report on chemical functionalization of oligo(hydrido)silanes, economically attractive routes to new photoresponsive materials. Sand Report. doi:10.2172/491421More infoMetathesis-catalyzed polymerizations of primary silanes were performed to generate polysilanes suitable for functionalization with a variety of side groups. Modeling was employed to predict conformations and estimate electronic properties of candidate functionalized polysilanes. Chemical functionalization of oligo(hydrido)silanes with terminal {alpha}, {omega}-dienes under free radical conditions yielded highly crosslinked, nonporous polysilane networks. Ketone reduction with oligo(hydrido)silanes under free radical conditions led to novel poly(phenylalkoxysilanes). Free radical reduction of terminal alkenyl(alkoxy)silanes forms functionalized polysilanes which can be further transformed into sol-gel matrices with the polysilane functionality intact. These gels may be processed into nonporous xerogels or high surface area aerogels.
- Loy, D. A. (1997). Cyclic intermediates isolated from the synthesis of alkylene-bridged polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1997). Direct formation of aerogels by sol-gel polymerizations of alkoxysilanes in supercritical carbon dioxide. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1997). Encapsulation of gold nanoclusters in silica materials via an inverse micelle/sol-gel synthesis. CHEMISTRY OF MATERIALS.
- Loy, D. A. (1997). Hybrid organic-inorganic materials. MRS BULLETIN, 26(5), 364-365.
- Loy, D. A. (1997). Preparation and characterization of polyphenyl-silsesquioxanes. Ladder or branched polymers?. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1997). Preparation of novel fluorinated 1,4-diols. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1997). Preparation of poly(dipropylenecarbonate co-disiloxane) by a condensation polymerization. Thermally degradable polymers. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1997). Solid phase immobilization of optically responsive liposomes in sol-gel materials for chemical and biological sensing. LANGMUIR.
- Loy, D. A. (1997). The impact of monomer structure on the surface area and porosity of polysilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A., Carpenter, J. P., Myers, S. A., Assink, R. A., Small, J. H., Greaves, J., & Shea, K. J. (1997). Intramolecular condensation reactions of alpha,omega-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 118(35), 8501-8502.
- Loy, D. A., Russick, E. M., Yamanaka, S. A., Baugher, B. M., & Shea, K. J. (1997). Direct Formation of Aerogels by Sol - Gel Polymerizations of Alkoxysilanes in Supercritical Carbon Dioxide. Chemistry of Materials, 9(Issue 11). doi:10.1021/cm970326f
- Martino, A., Yamanaka, S. A., Kawola, J. S., & Loy, D. A. (1997). Encapsulation of Gold Nanoclusters in Silica Materials via an Inverse Micelle/Sol-Gel Synthesis. Chemistry of Materials, 9(Issue 2). doi:10.1021/cm9604625More infoNanometer-sized gold particles were encapsulated in the micropores of xerogels and aerogels. The synthesis involves the sequential reduction of a gold salt followed by sol-gel processing in an inverse micelle solution. The inverse micelle solution solubilizes the metal salt and provides a microreactor for the nucleation, growth, and stabilization of the nanometer-sized clusters. Hydrolysis and condensation of an added siloxane precursor produces a wet gel embedding the particles. Characterization of the particle size and composition and the particle growth process was completed with transmission electron microscopy (TEM), electron diffraction, and UV-visible absorption spectrometry. Characterization of the gel surface areas was completed with N2 porosimetry. Material properties determined as a function of the gel precursor (TEOS vs a prehydrolyzed form of TEOS), the water to gel precursor reaction stoichiometry, and surfactant concentration are discussed in terms of the unique solution chemistry occurring in the microheterogeneous inverse micelle solutions.
- SMALL, J. H., SHEA, K. J., LOY, D. A., & JAMISON, G. M. (1997). HYPERVALENT SPIRO POLYSILICONATE AND POLYGERMYLATE IONOMERS - NOVEL LADDER AND NETWORK MATERIALS. HYBRID ORGANIC-INORGANIC COMPOSITES, 585, 248-263.
- Ulibarri, T. A., Bates, S. E., Loy, D. A., Jamison, G. M., Jamison, G. M., Emerson, J. A., & Curro, J. G. (1997). LDRD final report on nanocomposite materials based on hydrocarbon-bridged siloxanes. SAND Report. doi:10.2172/481573More infoSilicones [polydimethylsiloxane (PDMS) polymers] are environmentally safe, nonflammable, weather resistant, thermally stable, low T{sub g} materials which are attractive for general elastomer applications because of their safety and their performance over a wide temperature range. However, PDMS is inherently weak due to its low glass transition temperature (T{sub g}) and lack of stress crystallization. The major goal of this project was to create a family of reinforced elastomers based on silsesquioxane/PDMS networks. Polydimethylsiloxane-based (PDMS) composite materials containing a variety of alkylene-arylene-bridged polysilsesquioxanes were synthesized in order to probe short chain and linkage effects in bimodal polymer networks. Monte Carlo simulations on the alkylene-bridged silsesquioxane/PDMS system predicted that the introduction of the silsesquioxane short chains into the long chain PDMS network would have a significant reinforcing effect on the elastomer. The silsesquioxane-PDMS networks were synthesized and evaluated. Analysis of the mechanical properties of the resulting materials indicated that use of the appropriate silisesquioxane generated materials with greatly enhanced properties. Arylene and activated alkylene systems resulted in materials that showed superior adhesive strength for metal-to-metal adhesion.
- Guo, C., Budy, S. M., & Loy, D. A. (1996). Asymmetric Membranes by Wet Phase Inversion of Phenylated Polyphenylene. JOURNAL OF APPLIED POLYMER SCIENCE, 128(1), 750-753.
- JAMISON, G. M., LOY, D. A., ASSINK, R. A., & SHEA, K. J. (1996). HYDROCARBON-BRIDGED POLYSILOXANE AND POLYSILSESQUIOXANE NETWORK MATERIALS. BETTER CERAMICS THROUGH CHEMISTRY VI, 346, 487-491.
- LOY, D. A., & SHEA, K. J. (1996). BRIDGED POLYSILSESQUIOXANES - HIGHLY POROUS HYBRID ORGANIC-INORGANIC MATERIALS. CHEMICAL REVIEWS, 95(5), 1431-1442.
- Loy, D. A. (1996). Amorphous silica molecular sieving membranes by sol-gel processing. Advanced Materials.
- Loy, D. A. (1996). Bridged polysilsesquioxane-polydimethylsiloxane nanocomposites: A reactivity study. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Characterization of polyxylylenes with solid state C-13 nuclear magnetic resonance spectroscopy. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Comparison of bridged polysilsesquioxane xerogels prepared from methoxy-, ethoxy- and propoxy-silyl monomers. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Cycloaddition of phosphaalkynes to high-oxidation-state metal alkylidenes: Synthesis and characterization of a unique phosphametallacyclobutene via an alkoxide ligand shift. ORGANOMETALLICS.
- Loy, D. A. (1996). Engineering macrostructure in ceramics. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Engineering the macrostructure of thermally induced phase separated polysilane foams. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY.
- Loy, D. A. (1996). Formation and polymerization of cyclic disilsesquioxanes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Hydrolysis and esterification in organically modified alkoxysilanes: A Si-29 NMR investigation of methyltrimethoxysilane. CHEMISTRY OF MATERIALS.
- Loy, D. A. (1996). Identification and characterization of the hydrolysis products in TMOS and MTMS monomers using Si-29 NMR and polarization transfer techniques. MAGNETIC RESONANCE IN CHEMISTRY.
- Loy, D. A. (1996). Intramolecular condensation reactions of alpha,omega-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
- Loy, D. A. (1996). Isolation and characterization of the molybdenum alkylidyne complex [(F3C)Me(2)CO]Mo-2(C-t-Bu)[N(Ar)P=C(H)(CMe(2)Ph)] and its conversion to a phosphamolybdacyclobutene. ORGANOMETALLICS.
- Loy, D. A. (1996). Metal mediated sol-gel chemistry of 1,2-bis(triethoxysilyl)-ethene. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Molybdenum alkylidynes and phosphamolybdacyclobutenes derived from phosphaalkynes and molybdenum alkylidenes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Multiple phosphaalkyne additions to high oxidation state tungsten alkylidenes. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). New hybrid polysilane/polysiloxane nanocomposites. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Oligosilane-siloxane nanocomposites. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Sol-gel synthesis and characterization of tetra-alkoxysilane and bridged-polysilsesquioxane materials in non-polar solvents. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Sol-gel synthesis of hybrid organic-inorganic materials. Hexylene- and phenylene-bridged polysiloxanes. CHEMISTRY OF MATERIALS.
- Loy, D. A. (1996). Synthesis and characterization of amine-containing hybrid organic-inorganic bridged polysilsesquioxane and siloxane stargels. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1996). Thermal oligomerization of phenyl phosphaacetylene. Abstracts of Papers of the American Chemical Society.
- Loy, D. A., Beach, J. V., Baugher, B. M., Assink, R. A., Shea, K. J., Tran, J., & Small, J. H. (1996). Dialkylene carbonate-bridged polysilsesquioxanes. Hybrid organic-inorganic sol-gels with a thermally labile bridging group. CHEMISTRY OF MATERIALS, 11(11), 3333-3341.
- Loy, D. A., Carpenter, J. P., Myers, S. A., Assink, R. A., Small, J. H., Greaves, J., & Shea, K. J. (1996). Intramolecular condensation reactions of alpha, omega-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. BETTER CERAMICS THROUGH CHEMISTRY VII: ORGANIC/INORGANIC HYBRID MATERIALS, 435, 33-41.
- Loy, D. A., Rahimian, K., & Samara, M. (1996). Phenylene-bridged cyclic siloxanes as precursors to nonshrinking sol-gel systems and their use as encapsulants. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 38(4), 555-557.
- Loy, D. A., Small, J. H., DeFriend, K. A., Wilson, K. V., Minke, M., Baugher, B. M., Baugher, C. R., Schneider, D. A., & Shea, K. J. (1996). Collapse of porosity during drying of alkylene-bridged polysilsesquioxane gels. Influence of the bridging group length. Organic/Inorganic Hybrid Materials-2004, 847, 165-170.
- Myers, S. A., Assink, R. A., Loy, D. A., & Shea, K. J. (1996). Investigation of the transmission of substituent effects by Si-29 NMR. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 545-549.
- SAMARA, G. A., HANSEN, L. V., ASSINK, R. A., MOROSIN, B., SCHIRBER, J. E., & LOY, D. (1996). EFFECTS OF PRESSURE AND AMBIENT SPECIES ON THE ORIENTATIONAL ORDERING IN SOLID C60. PHYSICAL REVIEW B, 47(8), 4756-4764.
- SHEA, K. J., LOY, D. A., & SMALL, J. H. (1996). CONDENSED ARYL-BRIDGED SILICONATES - NEW LADDER AND NETWORK IONOMERS. CHEMISTRY OF MATERIALS, 4(2), 255-258.
- Schirber, J. E., Assink, R. A., Morosin, B., Loy, D. A., & Carlson, G. A. (1996). LDRD final report on gas separation by fullerene membranes. sand report. doi:10.2172/270715More infoThis LDRD (Laboratory Directed Research and Development) project was funded for two years beginning in October 1992 (FY93) and was designed as a multidisciplinary approach to determining the structural and physical properties of C{sub 60} intercalated with various gases. The purpose of the study was to evaluate the relative permeation and diffusion of various gases with an ultimate goal of finding an effective filter for gas separations. A variety of probes including NMR, X-ray and neutron diffraction; IR spectroscopy, thermogravimetric analysis and mass spectroscopy were employed on C{sub 60} impregnated with a number of gases including O{sub 2}, N{sub 2}, Ar, Ne, H{sub 2}, NO and CH{sub 4}. In order to increase the absorption and decrease the effective time constraints for bulk samples, these gases were intercalated into the C{sub 60} using pressures to several kbar. The results of these measurements which were quite encouraging for separation of O{sub 2} and N{sub 2} and for H{sub 2} from N{sub 2} led to 17 manuscripts which have been published in peer reviewed journals. The abstracts of these manuscripts are shown below along with a complete citation to the full text.
- Shaltout, R. M., Loy, D. A., & Wheeler, D. R. (1996). Maleimide functionalized siloxane resins. ORGANIC/INORGANIC HYBRID MATERIALS II, 576, 15-20.
- Shea, K. J., & Loy, D. A. (1996). Bridged polysilsesquioxanes: Molecular engineering of hybrid organic-inorganic materials. MRS BULLETIN, 26(5), 368-376.
- Assink, R. A., Jamison, G. M., Loy, D. A., Mcnamara, W. F., Prabakar, S., & Schneider, D. A. (1995). Characterization of Poly(xylylenes) with Solid-State 13C Nuclear Magnetic Resonance Spectroscopy. Macromolecules, 28(17), 5799-5803. doi:10.1021/ma00121a016More infoPoly(xylylenes) are an important class of thermoplastics that are readily prepared by thermolysis of [2.2]paracyclophane or xylene precursors to afford xylylene monomers that condense and polymerize on solid surfaces to give polymer films. As most poly(xylylenes) are insoluble due to a high degree of crystallinity, characterization by solid-state nuclear magnetic resonance spectroscopic techniques is necessary. In this paper we describe the preparation of poly(xylylene) (P1), poly(2-ethylxylylene) (P2), poly(2-chloroxylylene) (P3), poly(2,3-dichloroxylylene) (P4), and poly(α,α,α',α'-tetrafluoroxylylene) (P5) and their characterization using solid-state 13 C cross polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR) spectroscopy.
- Assink, R. A., Loy, D. A., Morosin, B., Samara, G. A., & Schirber, J. E. (1995). Negative pressure effects in high-pressure oxygen-intercalated C60.. Physical review. B, Condensed matter, 51(21), 15552-15554. doi:10.1103/physrevb.51.15552More infoWe have observed unexpected and as yet unexplained negative pressure effects in high-oxygen-pressure-treated C{sub 60} in which the orientational ordering temperature is greatly depressed. Such effects are not observed in identical studies with nitrogen.
- Beach, J. V., Loy, D. A., Hsiao, Y. L., & Waymouth, R. M. (1995). Environmentally friendly polysilane photoresists. MICROELECTRONICS TECHNOLOGY, 614, 355-366.
- Cao, G. Z., Lu, Y. F., Delattre, L., Brinker, C. J., & Lopez, G. P. (1995). Amorphous silica molecular sieving membranes by sol-gel processing. ADVANCED MATERIALS, 8(7), 588-&.
- Fujimoto, C. H., Hickner, M. A., Cornelius, C. J., & Loy, D. A. (1995). Ionomeric poly(phenylene) prepared by diels-alder polymerization: Synthesis and physical properties of a novel polyelectrolyte. MACROMOLECULES, 38(12), 5010-5016.
- Loy, D. A. (1995). ALKYLENE-BRIDGED POLYSILSESQUIOXANE AEROGELS - HIGHLY POROUS HYBRID ORGANIC-INORGANIC MATERIALS. JOURNAL OF NON-CRYSTALLINE SOLIDS.
- Loy, D. A. (1995). BRIDGED POLYSILSESQUIOXANES - HIGHLY POROUS HYBRID ORGANIC-INORGANIC MATERIALS. CHEMICAL REVIEWS.
- Loy, D. A. (1995). CHARACTERIZATION OF MICROENVIRONMENT POLARITY AND SOLVENT ACCESSIBILITY OF POLYSILSESQUIOXANE XEROGELS BY THE FLUORESCENT-PROBE TECHNIQUE. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1995). CHARACTERIZATION OF POLY(XYLYLENES) WITH SOLID-STATE C-13 NUCLEAR-MAGNETIC-RESONANCE SPECTROSCOPY. MACROMOLECULES.
- Loy, D. A. (1995). Computer-aided structure elucidation for arylene-bridged polysilsesquioxanes. Computational Materials Science.
- Loy, D. A. (1995). ENCAPSULATED METAL NANOCLUSTER MATERIALS PREPARED BY A NOVEL INVERSE MICELLE SOL-GEL TECHNIQUE. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1995). ENVIRONMENTALLY BENIGN POLYMER SYNTHESIS - POLYSILANE PHOTORESISTS. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1995). ENVIRONMENTALLY FRIENDLY POLYSILANES - AN ALTERNATIVE ROUTE TO POLYSILANE PHOTORESISTS. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1995). NEGATIVE-PRESSURE EFFECTS IN HIGH-PRESSURE OXYGEN-INTERCALATED C-60. PHYSICAL REVIEW B.
- Loy, D. A. (1995). ORGANIC TEMPLATE APPROACH TO MOLECULAR-SIEVING SILICA MEMBRANES. Journal of Membrane Science.
- Loy, D. A., & Shea, K. J. (1995). Bridged Polysilsesquioxanes. Highly Porous Hybrid Organic-Inorganic Materials. Chem. Rev. (Washington, D. C.), 95(5), 1431.
- Loy, D. A., & Shea, K. J. (1995). Bridged Polysilsesquioxanes. Highly Porous Hybrid Organic-Inorganic Materials. Chemical Reviews, 95(Issue 5). doi:10.1021/cr00037a013
- Loy, D. A., Carpenter, J. P., Yamanaka, S. A., McClain, M. D., Greaves, J., Hobson, S., & Shea, K. J. (1995). Polymerization of bis(triethoxysilyl) ethenes. Impact of substitution geometry on the formation of ethenylene- and vinylidene-bridged polysilsesquioxanes. CHEMISTRY OF MATERIALS, 10(12), 4129-4140.
- Loy, D. A., Jamison, G. M., Baugher, B. M., Myers, S. A., Assink, R. A., & Shea, K. J. (1995). Sol-gel synthesis of hybrid organic-inorganic materials. Hexylene- and phenylene-bridged polysiloxanes. CHEMISTRY OF MATERIALS, 8(3), 656-663.
- Lu, Y. F., Fan, H. Y., Doke, N., Loy, D. A., Assink, R. A., LaVan, D. A., & Brinker, C. J. (1995). Evaporation-induced self-assembly of hybrid bridged silsesquioxane film and particulate mesophases with integral organic functionality. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 122(22), 5258-5261.
- McClain, M. D., Loy, D. A., & Prabakar, S. (1995). Controlling porosity in bridged polysilsesquioxanes through elimination reactions. BETTER CERAMICS THROUGH CHEMISTRY VII: ORGANIC/INORGANIC HYBRID MATERIALS, 435, 277-282.
- McElhanon JR, ., Zifer, T., Kline SR, ., Wheeler, D. R., Loy, D. A., Jamison, G. M., Long, T. M., Rahimian, K., & Simmons, B. A. (1995). Thermally cleavable surfactants based on furan-maleimide Diels-Alder adducts. LANGMUIR, 21(8), 3259-3266.
- Mcelhanon JR, ., Russick, E. M., Wheeler, D. R., Loy, D. A., & Aubert, J. H. (1995). Removable foams based on an epoxy resin incorporating reversible Diels-Alder adducts. JOURNAL OF APPLIED POLYMER SCIENCE, 85(7), 1496-1502.
- Raman, N. K., & Brinker, C. J. (1995). Organic “template” approach to molecular sieving silica membranes. Journal of Membrane Science, 105(3), 273-279. doi:10.1016/0376-7388(95)00067-mMore infoAbstract We demonstrate a “template” approach to prepare microporous inorganic membranes exhibiting high flux combined with high selectivity, overcoming limitations inherent to both conventional inorganic (sol-gel, CVD) and organic membrane approaches. Hybrid organic-inorganic polymers prepared by co-polymerization of tetraethoxysilane (TEOS) and methyltrie-thoxysilane (MTES) were deposited on commercial asymmetric alumina supports. Heat treatments were employed to densify the inorganic matrix and pyrolyze the methyl ligands, creating a continous network of micropores. Resulting membranes exhibited very high CO2 permeance values (2.57×10−3 cm3/cm2 s cm Hg) combined with moderate CO 2 CH 4 selectivities (12.2). Subsequent derivatization of the pore surfaces with monomeric TEOS significantly increased CO 2 CH 4 separation factors (71.5) with only a modest reduction in CO2 permeance (2.04×10−4 cm3/cm2 s cm Hg). Combined CO 2 CH 4 selectivity factors and CO2 fluxes exceeded those of all known organic membranes.
- SAMARA, G. A., SCHIRBER, J. E., MOROSIN, B., HANSEN, L. V., LOY, D., & SYLWESTER, A. P. (1995). PRESSURE-DEPENDENCE OF THE ORIENTATIONAL ORDERING IN SOLID C60. PHYSICAL REVIEW LETTERS, 67(22), 3136-3139.
- Shea, K. J., Russick, E. M., Prabakar, S., Loy, D. A., Jamison, G. M., Baugher, B. M., & Assink, R. A. (1995). Alkylene-bridged polysilsesquioxane aerogels: highly porous hybrid organic-inorganic materials. Journal of Non-crystalline Solids, 186, 44-53. doi:10.1016/0022-3093(95)00032-1More infoAbstract Alkylene-bridged polysilsesquioxane gels were prepared by sol-gel polymerizations of α, ω-bis(triethoxysilyl)alkanes 1–5. The gels were extracted with supercritical carbon dioxide to afford a novel class of hybrid organic-inorganic aerogels. The effect of the length of the alkylene bridging group and catalyst (HCl and NaOH) on the structure was examined. The molecular structure was characterized by solid-state 13C and 29Si cross polarization magic angle spinning nuclear magnetic resonance spectroscopy. The alkylene bridging groups survived sol-gel polymerization to give materials with average degrees of condensation of 79 and 90% for the acid- and base-catalyzed aerogels, respectively. Scanning electron microscopy was used to examine the macroscopic structure of the gels and nitrogen sorption porosimetry was used to measure their surface areas and pore structures. Most of the alkylene-bridged aerogels were mesoporous, high-surface-area materials. As with alkylene-bridged polysilsesquioxane xerogels, the surface area decreased with increasing alkylene bridging group length. Only the base-catalyzed tetradecylene-bridged aerogel was found to be non-porous.
- Shea, K. J., Zhu, H. D., & Loy, D. A. (1995). Characterization of microenvironment polarity and solvent accessibility of polysilsesquioxane xerogels by the fluorescent probe technique. Sand Report.More infoPoly (1, 4 bis(triethoxysilyl)benzene) (PTESB), a representative of a new type of organic-inorganic hybrid polysilsesquioxane material, was characterized by fluorescence spectroscopy for both microenvironmental polarity and solvent accessibility. A dansyl fluorescent molecule was incorporated into the bulk as well as onto the surface of both PTESB and silica materials. Information about the microenvironment polarity and accessibility of PTESB to various organic solvents was determined and compared to that of silica gel. This study found that both the bulk and surface of PTESB are less polar than that of the silica material. The silica material is accessible to polar solvents and water, while YMB is accessible to polar solvents but not to water. The hydrophobicity of PTESB differentiates these new materials from silica gel.
- Whinnery, L. L., Even, W. R., Beach, J. V., & Loy, D. A. (1995). Engineering the macrostructure of thermally induced phase separated polysilane foams. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 34(8), 1623-1627.
- Yamanaka, S. A., Carpenter, J. P., Mcclain, M., & Loy, D. A. (1995). Synthesis and characterization of vinyl-bridged polysilsesquioxane sol-gel materials. Sand Report.More infoVinyl-bridged polysilsesquioxane gels were formed through the use of sol-gel polymerization methods. Acid- and base-catalyzed samples were prepared from both the pure cis-(l) and pure trans-(2) isomers of 1, 2-bis(triethoxysilyl)ethylene. Gelation times of the two isomers were compared. The trans monomer 2 formed gels within a week while the cis monomer I failed to gel-even after several months. Gelation of 1 could be promoted by the addition of a coordinating metal such as palladium. The resulting cis- and trans- vinyl-bridged polysilsesquioxane gels were then processed either by vacuum drying to afford xerogels or by extracting with supercritical carbon dioxide to afford aerogels. These vinylbridged polysilsesquioxanes were characterized by SEM, nitrogen sorption porosimetry, solid State {sub 29}Si and {sub 13}C NMR and x-ray powder diffraction.
- Assink, R. A., Buss, R. J., Loy, D. A., Oviatt, H., & Shea, K. J. (1994). Engineering of porosity in amorphous materials. Plasma oxidation of hydrocarbon templates in polysilsesquioxanes. MRS Proceedings, 346, 825-829. doi:10.1557/proc-346-825More infoArylene- and alkylene-bridged polysilsesquioxanes were prepared by sol-gel processing of bis(triethoxysilyl)-arylene monomers 1--4, and alkylene monomers 5--9. The arylene polysilsesquioxanes were porous materials with surface areas as high as 830 m{sup 2}/g (BET). Treatment with an inductively coupled oxygen plasma resulted in the near quantitative removal of the arylene bridging groups and a coarsening of the pore structure. Solid state {sup 29}Si NMR was used to confirm the conversion of the sesquioxane silicons (T) to silica (Q). The alkylene-bridged polysilsesquioxanes were non-porous. Oxygen plasma treatment afforded silica gels with mesoporosity. The porosity in the silica gels appears to arise entirely from the oxidation of the alkylene spacers.
- LOY, D. A., JAMISON, G. M., BAUGHER, B. M., RUSSICK, E. M., ASSINK, R. A., PRABAKAR, S., & SHEA, K. J. (1994). ALKYLENE-BRIDGED POLYSILSESQUIOXANE AEROGELS - HIGHLY POROUS HYBRID ORGANIC-INORGANIC MATERIALS. JOURNAL OF NON-CRYSTALLINE SOLIDS, 186, 44-53.
- LOY, D. A., SHEA, K. J., BUSS, R. J., & ASSINK, R. A. (1994). PLASMA OXIDATION OF HYDROCARBON TEMPLATES IN BRIDGED POLYSILSESQUIOXANES - POROUS MATERIALS BY DESIGN. INORGANIC AND ORGANOMETALLIC POLYMERS II, 572, 122-133.
- Loy, D. A. (1994). ABSOLUTE HYDROGEN DETERMINATION IN COAL-DERIVED HEAVY DISTILLATE SAMPLES. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1994). ALKYLENE-BRIDGED AND AYLENE-BRIDGED POLYSILOXANE NETWORK MATERIALS. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1994). ALKYLENE-BRIDGED POLYGERM-OXANES AND POLYGERMSILSESQUI-OXANES - NEW HYBRID ORGANIC-INORGANIC MATERIALS. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1994). Role of pressure in the study of fullerenes. AIP Conference Proceedings.
- Loy, D. A. (1994). SOL-GEL STRATEGIES FOR CONTROLLED POROSITY INORGANIC MATERIALS. JOURNAL OF MEMBRANE SCIENCE.
- Loy, D. A. (1994). SYNTHESIS AND CHARACTERIZATION OF ARYLENE-BRIDGED AND ALKYLENE-BRIDGED POLYSILSEQUIOXANE POLYDIMETHYLSILOXANE COMPOSITE-MATERIALS. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1994). SYNTHESIS AND CHARACTERIZATION OF NOVEL SPIRO PENTACOORDINATE AND HEXACOORDINATE ANIONIC POLYSILICONATE AND POLYGERMYLATE IONMERS. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1994). SYNTHESIS AND POLYMERIZATION OF ACRYLAMIDE AND METHACRYLIMIDATE. Abstracts of Papers of the American Chemical Society.
- MOROSIN, B., NEWCOMER, P. P., BAUGHMAN, R. J., VENTURINI, E. L., LOY, D., & SCHIRBER, J. E. (1994). ON THE ORTHORHOMBIC FORM OF C-60 - MOLECULAR-CRYSTALS CONTAINING CS2. PHYSICA C, 184(1-3), 21-23.
- Martino, A., Yamanaka, S. A., Kawola, J. S., & Loy, D. A. (1994). Encapsulation of gold nanoclusters in silica materials via an inverse micelle/sol-gel synthesis. CHEMISTRY OF MATERIALS, 9(2), 423-429.
- Pang, J. B., John, V. T., Loy, D. A., Yang, Z. Z., & Lu, Y. F. (1994). Hierarchical mesoporous carbon/silica nanocomposites from phenyl-bridged organosilane. ADVANCED MATERIALS, 17(6), 704-+.
- Schirber, J. E., Assink, R. A., Myers, S. A., Loy, D. A., Myers, S. A., Loy, D. A., Assink, R. A., & Schirber, J. E. (1994). The Effect of O2 Intercalation on the Rotational Dynamics and the Ordering Transition of C60. MRS Proceedings, 359, 505-509. doi:10.1557/proc-359-505More infoWe have used {sup 13}C magic-angle spinning (MAS) nuclear magnetic resonance (NMR) to characterize the structure and rotational dynamics of C{sub 60} containing oxygen molecules located in the interstitial sites of the fcc lattice. Under normal conditions, a narrow peak at 143.7 ppm is observed for C{sub 60}. When exposed to oxygen at moderate pressures, several additional resonances appear in the {sup 13}C MAS NMR spectrum. These secondary resonances are shifted downfield from the main peak at 143.7 ppm and are due to the Fermi-contact interaction of the paramagnetic oxygen molecules with the {sup 13}C nuclear spins. The presence of oxygen depresses the orientational ordering transition by ca. 20 K as observed by DSC. The spin-lattice relaxation time (T{sub 1}) of each secondary peak shows a minimum near the ordering transition, indicating that this transition is not dependent on the number of oxygen molecules surrounding an individual C{sub 60} molecule. The T{sub 1}, due to paramagnetic relaxation, normalized by the number of surrounding oxygen molecules, is constant. This observation demonstrates that within a given sample, the dynamics of C{sub 60} molecules are independent of the number of surrounding oxygen molecules.
- Shea, K. J., Assink, R. A., Assinkt, R. A., Loy, D. A., Jamison, G. M., Jamison, G. M., Assinkt, R. A., Loy, D. A., Assink, R. A., & Shea, K. J. (1994). Hydrocarbon-bridged polysiloxane and polysilsesquioxane network materials. MRS Proceedings, 346, 487-491. doi:10.1557/proc-346-487More infoHexylene and phenylene-bridged polymethylsiloxane xerogels X-2 and X-4, respectively, were prepared by the sol-gel hydrolysis and condensation of 1, 6-bis(diethoxymethylsilyl)hexane 1 and 1, 4-bis(diethoxymethylsilyl)benzene 2 under acidic and basic conditions. These polymerizations afforded network polymers in the form of wet gels within several hours. The gels were processed to afford xerogels whose characteristics (determined by solid state {sup 13}C and {sup 29}Si CP MAS NMR spectroscopy and nitrogen sorption porosimetry) were compared and contrasted with those of their analogous polysilsesquioxanes. {sup 29}Si CP MAS NMR indicates a high degree of hydrolysis and polycondensation; porosimetry measurements reveal that the materials have significant surface areas, save for the acid-catalyzed hexylene gels X-2.
- Smith, D. M., Ashley, C. S., Sehgal, R., Brinker, C. J., Deshpande, R., Loy, D. A., Hietala, S. L., Hietala, S. L., Deshpande, R., Loy, D. A., Brinker, C. J., Sehgal, R., Ashley, C. S., & Smith, D. M. (1994). Sol-gel strategies for controlled porosity inorganic materials. Journal of Membrane Science, 94(1), 85-102. doi:10.1016/0376-7388(93)e0129-8More infoThe porosity (i.e., pore volume, pore size, and surface area) of ceramic materials prepared by sol-gel processing depends on the size and structure of primary particles or polymers formed by condensation reactions, the organization of these structures, often by aggregation, to form a gel, and the collapse of the gel by drying. This paper reviews these ideas in the context of the formation of thin films suitable for inorganic membranes and introduces a number of specific strategies designed to control pore sizes in the range appropriate for gas separation: ( 1) aggregation of fractals; (2 ) management of capillary pressure, (3) control of condensation rate, and (4) the use of organic or microporous templates in composite thin film structures. These strategies are contrasted with the more traditional particle packing approach to preparing controlled porosity materials.
- Alam, T. M., Assink, R. A., & Loy, D. A. (1993). Investigation of hydrolysis and condensation in organically modified sol-gel systems: Si-29 NMR and the INEPT sequence. BETTER CERAMICS THROUGH CHEMISTRY VII: ORGANIC/INORGANIC HYBRID MATERIALS, 435, 421-426.
- Jamison, G. M., Loy, D. A., & Shea, K. J. (1993). Bridged Polygermsesquioxanes. Organically Modified Germanium Oxide Materials. Chemistry of Materials, 5(9), 1193-1195. doi:10.1021/cm00033a001More infoSol-gel processed polysilsesquioxanes are hybrid organic-inorganic materials with potential applications as photoresists, membranes, or catalytic supports. Hydrolytic conversion of trichloro- or trialkoxysilanes often leads to amorphous or crystalline oligosilsesquioxanes instead of high polymers. In light of the intimate dependence of polysilsesquioxane properties of tightly controlled reaction conditions and processing, recent emphasis has been placed on control of polymer microarchitecture via the introduction of arylene-, acetylene-, and alkylene-bridging groups. Another strategy for modifying the properties of hybrid organic-inorganic polymers is to substitute a group IVA metal, such as germanium, for silicon. The authors report the synthesis and characterization of bifunctional hexylene-bridged organogermanium monomers X[sub 3]Ge-(CH[sub 2])[sub 6]GeX[sub 3] (X = Cl; OEt) and the formation of polymeric materials through sol-gel hydrolysis-condensation of the monomers. 15 refs., 2 figs.
- LOY, D. A., & ASSINK, R. A. (1993). SYNTHESIS OF A C-60-P-XYLYLENE COPOLYMER. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 114(10), 3977-3978.
- LOY, D. A., BAUGHER, B. M., PRABAKAR, S., ASSINK, R. A., & SHEA, K. J. (1993). Comparison of bridged polysilsesquioxane xerogels prepared from methoxy- and ethoxy-silyl monomers.. ADVANCES IN POROUS MATERIALS, 371, 229-234.
- LOY, D. A., BUSS, R. J., ASSINK, R. A., SHEA, K. J., & OVIATT, H. (1993). ENGINEERING OF POROSITY IN AMORPHOUS MATERIALS - PLASMA OXIDATION OF HYDROCARBON TEMPLATES IN POLYSILSESQUIOXANES. BETTER CERAMICS THROUGH CHEMISTRY VI, 346, 825-829.
- Loy, D. A. (1993). ARYLENE-BRIDGED AND ALKYLENE-BRIDGED POLYSILSESQUIOXANES. JOURNAL OF NON-CRYSTALLINE SOLIDS.
- Loy, D. A. (1993). ARYLENE-BRIDGED AND ALKYLENE-BRIDGED SILICONATES. ORGANOMETALLICS.
- Loy, D. A. (1993). BRIDGED POLYGERMSESQUIOXANES - ORGANICALLY MODIFIED GERMANIUM OXIDE MATERIALS. CHEMISTRY OF MATERIALS.
- Loy, D. A. (1993). EFFECTS OF PRESSURE AND AMBIENT SPECIES ON THE ORIENTATIONAL ORDERING IN SOLID C60. PHYSICAL REVIEW B.
- Loy, D. A. (1993). NEW GROUP-XIV OXIDE MATERIALS - POLYGERM AND POLYGERMSILSESQUIOXANES. Abstracts of Papers of the American Chemical Society.
- Loy, D. A. (1993). POROUS MATERIALS BY DESIGN - PLASMA OXIDATION OF HYDROCARBON TEMPLATES IN POLYSILSESQUIOXANES. Abstracts of Papers of the American Chemical Society.
- Loy, D. A., Shea, K. J., & Small, J. H. (1993). Arylene- and alkylene-bridged siliconates. Organometallics, 12(4), 1484-1488. doi:10.1021/om00028a083
- Schirber, J. E., Assink, R. A., Samara, G. A., Hansen, L. V., Morosin, B., Loy, D. A., Morosin, B., Loy, D. A., Hansen, L. V., Samara, G. A., Assink, R. A., & Schirber, J. E. (1993). Effects of pressure and ambient species on the orientational ordering in solid C60.. Physical review. B, Condensed matter, 47(8), 4756-4764. doi:10.1103/physrevb.47.4756More infoThe effects of hydrostatic pressure on the orientational ordering transition in solid C[sub 60] were investigated using helium, nitrogen, and a 50/50 (by volume) mixture of normal and isopentanes as pressure-transmitting media. The different observed responses in these media and for different samples, as well as some irreversible pressure cycling effects, have provided much insight into the ordering process. Highlights of the work include the following: (1) Lattice compression hinders the librational motion of the C[sub 60] molecules in the low-temperature simple cubic (sc) phase, thereby increasing [ital T][sub [ital c]] and stabilizing the sc phase; the effect is large; (2) the pressure dependence of [ital T][sub [ital c]], along with the accurately known volume change at the transition, yield 1.7 kcal/mole and 6.5 cal/K mole for the latent heat and discontinuous change in entropy, respectively, associated with the transition; (3) [ital T][sub [ital c]] and its pressure dependence are influenced by the presence of ambient species in the interstitial lattice sites. Helium appears to diffuse readily into the lattice, whereas N[sub 2] (and O[sub 2]) diffuse less rapidly and occupy octahedral sites; (4) a two-peak structure in differential thermal analysis spectra (also reported in specific-heat measurements) was observed andmore » is believed to be due to the partial occupation of the octahedral sites by species such as N[sub 2] or O[sub 2]; (5) solid C[sub 60] reacts'' with pentane at pressures [ge] 14 kbar and temperatures [gt]475 K to yield an irreversible C[sub 60]/pentane complex similar to that obtained by the cocrystallization of C[sub 60] and normal pentane at 1 bar. These results are discussed in terms of proposed models.« less
- Small, J. H., Shea, K. J., & Loy, D. A. (1993). Arylene- and alkylene-bridged polysilsesquioxanes. Journal of Non-crystalline Solids, 160(3), 234-246. doi:10.1016/0022-3093(93)91267-7More infoAbstract Bis(triethoxysilyl)arylene monomers 1–5 and the 1,6-bis(trimethoxysilyl)hexylene monomer 6 were hydrolytically condensed under sol-gel conditions using both acid and base catalysts to produce their respective arylene- and alkylene-bridged polysilsesquioxane materials (X-1 through X-6). Polymerization reactions yielded gels within 24 h. One notable exception was the acid-catalyzed polymerization of 2,5-bis(triethoxysilyl)thiophene (X-5-S1) which required approximately 1 month to gel. The gels were processed by extracting with low dielectric solvents or by aqueous extraction. Solid state 13C and 29Si CP MAS-NMR, infrared spectroscopy, and gas sorption porosimetry were measured on the xerogels. The materials were transparent, glass-like xerogels with surface areas as high as 1100 m2/g and porosity primarily confined to a micropore region ( A diameters ). Xerogels prepared using the aqueous extraction had surface areas between 500 and 956 m2/g.
- Small, J. H., Shea, K. J., Shea, K. J., Loy, D. A., & Jamison, G. M. (1993). Synthesis and characterization of novel spiro penta- and hexacoordinate anionic polysiliconate and polygermylate ionomers derived from the condensation of ({plus_minus}) 5,5{prime}, 6,6{prime} - Tetrahydroxy-1,1{prime} - spiro-bis(Indane) with trialkoxysilanes, tetraalkoxysilanes, and trialkoxygermanes. Sand Report.More infoSynthesis of hybrid organic-inorganic materials with ionic functionality within the polymer backbone has been achieved. A new family of hypervalent spiro anionic polysiliconates and polygermylates has been prepared. These materials were shown to be thermally stable to moderate temperatures and are completely air and moisture stable. Analysis by solution and solid state NMR verified the presence of the hypervalent functionality. We are currently examining the effect that alteration of the condensing reagent and/or the counterion may have on bulk properties of the ionomeric material.
- ASSINK, R. A., LOY, D. A., SCHIRBER, J. E., & MOROSIN, B. (1992). AN NMR-STUDY OF THE OCCUPATION OF C-60 INTERSTITIAL SITES BY OXYGEN MOLECULES. NOVEL FORMS OF CARBON, 270, 255-260.
- Alam, T. M., Assink, R. A., Prabakar, S., & Loy, D. A. (1992). Identification and characterization of the hydrolysis products in TMOS and MTMS monomers using Si-29 NMR and polarization transfer techniques. MAGNETIC RESONANCE IN CHEMISTRY, 34(8), 603-609.
- Caple, G., Eastman, M. P., Fei, B. H., Loy, D. A., Parkanyi, C., & Yuan, H. L. (1992). Preparation of the precursors of new tannin‐like polymers with potential biological effects. Macromolecular Chemistry and Physics, 193(12), 3037-3044. doi:10.1002/macp.1992.021931210More infoNew acrylate based polymers, with the potential to be converted to polyphenolic polymers — poly[2-(4-benzyloxyphenyl)ethyl acrylate] (4) and poly[3-(4-benzyloxy-3-methoxyphenyl)propyl acrylate] (9) — were prepared from the corresponding monomers 3 and 8 by free-radical polymeri- zation, initiated by 2,2′-azoisobutyronitrile (AIBN). The acrylate monomers, 2-(4-benzyloxy- pheny1)ethyl acrylate (3) and 3-(4-benzyloxy-3-methoxyphenyl)propy1 acrylate (8), were synthes- ized from acryloyl chloride and the corresponding alcohols — 2-(4-benzyloxyphenyl)ethanol(2) and 3-(4-benzyloxy-3-methoxyphenyl)- 1 -propano1 (7), respectively. The monomer 7 was prepared from 3-(4-benzyloxy-3-methoxyphenyl)-1-propene (6) by hydroboration/oxidation and 6 was obtained from eugenol(4-allyl-2-methoxyphenol) as the starting material. The compounds were characterized by 1H NMR, 13C NMR, FTIR, and elemental analyses. The molecular weight of the synthesized polymers was determined by gel-permeation chromatography (GPC).
- LOY, D. A., SHEA, K. J., & RUSSICK, E. M. (1992). PREPARATION OF ARYL-BRIDGED POLYSILSESQUIOXANE AEROGELS. BETTER CERAMICS THROUGH CHEMISTRY V, 271, 699-704.
- Loy, D. A. (1992). ARYLSILSESQUIOXANE GELS AND RELATED MATERIALS - NEW HYBRIDS OF ORGANIC AND INORGANIC NETWORKS. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
- Loy, D. A. (1992). CONDENSED ARYL-BRIDGED SILICONATES - NEW LADDER AND NETWORK IONOMERS. CHEMISTRY OF MATERIALS.
- Loy, D. A. (1992). INTERCALATION OF MOLECULAR-SPECIES INTO THE INTERSTITIAL SITES OF FULLERENE. JOURNAL OF MATERIALS RESEARCH.
- Loy, D. A. (1992). PREPARATION OF THE PRECURSORS OF NEW TANNIN-LIKE POLYMERS WITH POTENTIAL BIOLOGICAL EFFECTS. MAKROMOLEKULARE CHEMIE-MACROMOLECULAR CHEMISTRY AND PHYSICS.
- Loy, D. A. (1992). SYNTHESIS OF A C-60-P-XYLYLENE COPOLYMER. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
- Loy, D. A. (1992). Synthesis of a C -para-xylylene copolymer. Electrical, Optical, and Magnetic Properties of Organic Solid State Materials Symposium.
- Loy, D. A., Russick, E. M., Yamanaka, S. A., Baugher, B. M., & Shea, K. J. (1992). Direct formation of aerogels by sol-gel polymerizations of alkoxysilanes in supercritical carbon dioxide. CHEMISTRY OF MATERIALS, 9(11), 2264-2268.
- Loy, D. A., Shea, K. J., & Small, J. H. (1992). Hypervalent Siliconate Materials. Synthesis and Characterization of Novel Ladder and Network Ionomers. MRS Proceedings, 271. doi:10.1557/proc-271-711More infoABSTRACTThe first representatives of novel materials that contain five- and six-coordinate anionie silicon are reported. Linear (or cyclic) ionomers incorporating pentacovalent siliconate were synthesized by condensation of 1,2,4,5-tetrahydroxybenzene (THB) with alkyl and aryl trialkoxysilylanes. Network ionomers that incorporate pentacovalent siliconates were formed from THB and alkyl and aryl bistrialkoxysilanes. In addition, network ionomers with hexacoordinate silicon result from condensation of TEOS and THB. Spectroscopie evidence is presented to verify the identity of the novel structural features of these materials.
- Pang, J. B., Yang, L., Loy, D. A., Peng, H. S., Ashbaugh, H. S., Mague, J., Brinker, C. J., & Lu, Y. F. (1992). Mesoscopically ordered organosilica and carbon-silica hybrids with uniform morphology by surfactant-assisted self-assembly of organo bis-silanetriols. CHEMICAL COMMUNICATIONS, 1545-1547.
- SHEA, K. J., LOY, D. A., & SMALL, J. H. (1992). HYPERVALENT SILICONATE MATERIALS - SYNTHESIS AND CHARACTERIZATION OF NOVEL LADDER AND NETWORK IONOMERS. BETTER CERAMICS THROUGH CHEMISTRY V, 271, 711-718.
- SHEA, K. J., LOY, D. A., & WEBSTER, O. (1992). ARYLSILSESQUIOXANE GELS AND RELATED MATERIALS - NEW HYBRIDS OF ORGANIC AND INORGANIC NETWORKS. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 114(17), 6700-6710.
- Schirber, J. E., Assink, R. A., Morosin, B., Carlson, G. A., Loy, D. A., Loy, D. A., Carlson, G. A., Morosin, B., Assink, R. A., & Schirber, J. E. (1992). Intercalation of molecular species into the interstitial sites of fullerene. Journal of Materials Research, 7(8), 2136-2143. doi:10.1557/jmr.1992.2136More infoMolecular species were found to diffuse readily into the octahedral interstitial sites of the fcc lattice of C{sub 60}. The {sup 13}C NMR spectrum of C{sub 60} under magic angle spinning (MAS) conditions consisted of a primary resonance at 143.7 ppm and a minor peak shifted 0.7 ppm downfield. The downfield shift obeys Curie's law and is attributed to the Fermi-contact interaction between paramagnetic oxygen molecules and all 60 carbon atoms of rapidly rotating adjacent C{sub 60} molecules. Exposure of C{sub 60} to 1 kbar oxygen for 1.75 h at room temperature resulted in a spectrum of seven evenly spaced resonances corresponding to the filling of 0 to 6 of the adjacent octahedral interstitial sites with oxygen molecules. The distribution of site occupancies about a C{sub 60} molecule provided evidence that the intercalation process is controlled by diffusion kinetics. Exposure to 0.14 kbar hydrogen gas at room temperature for 16 h filled a substantial fraction of the interstitial sites of C{sub 60} and C{sub 70} with hydrogen molecules.
- Schirber, J. E., Morosin, B., Loy, D. A., & Assink, R. A. (1992). An NMR study of the occupation of C sub 60 interstitial sites by oxygen molecules. MRS Proceedings, 270. doi:10.1557/proc-270-255More infoThe 13{sub C} NMR of FCC C{sub 60} under magic angle spinning (MAS) conditions yields linewidths on the order of 1 Hz at fields of 4.7 T. The spectrum consists of a primary resonance at 143.7 ppm and a minor peak shifted 0.7 ppm downfield. The intensity of the minor resonance relative to the primary resonance was found to vary from 0.6 to 5.5 % depending on the sample history. The downfield shift obeys Curie's law and is attributed to the Fermi contact coupling interaction between paramagnetic oxygen molecules and all 60 carbon atoms of rapidly rotating adjacent C{sub 60} molecules. Exposure of the sample to 1 kbar oxygen for 1 3/4 hours resulted in a spectrum of 7 evenly spaced resonances corresponding to 0 to 6 of the adjacent octahedral interstitial sites being filled with oxygen molecules. At ambient pressure, the oxygen diffused out of the lattice on time scales ranging from hours to days.
- Shea, K. J., Loy, D. A., Shea, K. J., & Webster, O. W. (1992). Arylsilsesquioxane gels and related materials. New hybrids of organic and inorganic networks. Journal of the American Chemical Society, 114(17), 6700-6710. doi:10.1021/ja00043a014More infoMolecular building blocks for the preparation of amorphous hybrid organic-inorganic network materials have been synthesized. Hydrolysis and condensation of bis(triethoxysilyl)aryl 1-4 and -ethynyl 5 monomers results in formation of aryl- and ethynyl-bridged polysilsequioxanes in the form of xerogels. The gels were glasslike materials composed of uniform aggregate of particles between 50 and 80 nm in diameter. Atomic force microscopy was used to examine the fine grained aggregate characteristics of phenyl-bridged polysilsesquioxane
- Shea, K. J., Russick, E. M., & Loy, D. A. (1992). Preparation of aryl-bridged polysilsesquioxane aerogels. MRS Proceedings, 271. doi:10.1557/proc-271-699More infoWe report the preparation of a new class of organic/inorganic hybrid aerogels from aryl-bridged polysilsesquioxanes. 1,4- Bis(triethoxysilyl)benzene and 4,4{prime}-bis(triethoxysilyl)- biphenyl were sol-gel processed to form phenyl- and biphenyl-bridged polysilsesquioxane gels. The gels were then dried using supercritical carbon dioxide extraction. It was discovered that aryl-bridged polysilsesquioxane aerogels are indeed formed, but with a pronounced influence on surface area from the reaction conditions used in preparing the initial gels. Specifically, high surface area aerogels (up to 1750 m{sup 2}/g) are obtained from gels prepared with either acid or base catalysts. With reduced concentrations of base catalyst, however, supercritical processing afforded phenyl-bridge xerogel-like materials. The materials were characterized by nitrogen sorption surface analysis and by transmission electron microscopy. 8 refs., 5 figs., 1 tab.
- Small, J. H., Loy, D. A., Shea, K. J., Shea, K. J., Small, J. H., & Loy, D. A. (1992). Condensed aryl-bridged siliconates. New ladder and network ionomers. Chemistry of Materials, 4(2), 255-258. doi:10.1021/cm00020a007
- Barton, T. J., Bull, L. M., Klemperer, W. G., Loy, D. A., McEnaney, B., Misono, M., Monson, P. A., Pez, G., Scherer, G. W., Vartuli, J. C., & Yaghi, O. M. (1991). Tailored porous materials. CHEMISTRY OF MATERIALS, 11(10), 2633-2656.
- Baughman, R. J., Loy, D. A., Morosin, B., Newcomer, P. P., Schirber, J. E., & Venturini, E. L. (1991). On the “orthorhombic form of C60” molecular crystals containing CS2. Physica C-superconductivity and Its Applications, 184(1), 21-23. doi:10.1016/0921-4534(91)91495-pMore infoAbstract Crystals of orthorhombic symmetry obtained on evaporation of CS 2 solutions of C 60 contain solvent molecules rather than representing a new lower density form of pure C 60 . Introduction of I 2 into the CS 2 solutions yields containing solid solutions, i.e. C 60 ·1.5 (CS 2 , I 2 ). Both types of crystals degrade rapidly in X-ray radiation.
- Loy, D. A. (1991). ON THE ORTHORHOMBIC FORM OF C-60 - MOLECULAR-CRYSTALS CONTAINING CS2. PHYSICA C.
- Loy, D. A. (1991). PRESSURE-DEPENDENCE OF THE ORIENTATIONAL ORDERING IN SOLID C60. PHYSICAL REVIEW LETTERS.
- Staiger, C. L., Loy, D. A., Jamison, G. M., Schneider, D. A., & Cornelius, C. J. (1991). A parallel colorimetric method for the rapid discovery and optimization of heterogeneous hydrodesulfurization catalysts. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 125(33), 9920-9921.
- Sylwester, A. P., Schirber, J. E., Samara, G. A., Morosin, B., Loy, D. A., & Hansen, L. V. (1991). Pressure dependence of the orientational ordering in solid C60.. Physical review letters, 67(22), 3136-3139. doi:10.1103/physrevlett.67.3136More infoPressure studies of the molecular orientational ordering in solid ${\mathrm{C}}_{60}$ have exhibited three principal effects: (1) The simple-cubic (sc) to face-centered-cubic (fcc) ordering transition temperature (${\mathit{T}}_{\mathit{c}}$=249 K) increases with pressure at a rate of 10.4\ifmmode\pm\else\textpm\fi{}0.2 K/kbar corresponding to ln${\mathit{T}}_{\mathit{c}}$/d ln${\mathit{a}}_{0}$=-22.8, where ${\mathit{a}}_{0}$ is the lattice parameter; (2) pressure greatly reduces orientational fluctuations of the ${\mathrm{C}}_{60}$ molecules in the ordered low-temperature sc phase; and (3) the results suggest the presence of two ordering transitions instead of one near 249 K. The implications of these results are discussed.
- Loy, D. A. (1990). ARYL-BRIDGED POLYSILSESQUIOXANES - NEW MICROPOROUS MATERIALS. Abstracts of Papers of the American Chemical Society.
- SHEA, K. J., WEBSTER, O., & LOY, D. A. (1990). ARYL-BRIDGED POLYSILSESQUIOXANES - NEW MICROPOROUS MATERIALS. BETTER CERAMICS THROUGH CHEMISTRY IV, 180, 975-980.
- Shea, K. J., Loy, D. A., & Webster, O. W. (1990). Aryl-bridged polysilsesquioxanes. A new class of microporous materials. Chemistry of Materials.
- Webster, O. W., Shea, K. J., & Loy, D. A. (1990). Aryl-Bridged Polysilsesquioxanes - New Microporous Materials.. MRS Proceedings, 180. doi:10.1557/proc-180-975More infoABSTRACTThe first representatives of a new family of microporous, aryl-bridged polysilsesquioxanes have been prepared by sol-gel processing of bis-1,4-(triethoxysilyl)benzene la, bis-4,4′- (triethoxysilyl)biphenyl 2a, bis-4,4′-(triethoxysilyl)terphenyl 3a, and bis-9,10-triethoxysilyl anthracene 4a. The bis(trichlorosilyl) analogs of la and 2a (lb and 2b, respectively) were also examined. The materials produced by hydrolysis and condensation of the monomers provide an opportunity to fully condense to a network with rigid-rod organic spacers interspaced at regular intervals in the silicate-like framework. The xerogels produced upon subsesquent processing of the gels have extremely high surface areas (256–1100 m2/g; BET) with porosities confined to the micropore domain (< 200 nm). Solid state (CP MAS) 13C and 29Si NMR were used to evaluate the extent of hydrolysis and degree of condensation in the xerogels. The porosity and thermal stability of the aryl bridged polysilsesquioxanes may lead to applications as chromatographic absorbents. The transparent materials may also have optical applications arising from both the gels′ high refractive indices and the covalent incorporation of ultraviolet chromophores.
- Webster, O. W., Shea, K. J., & Loy, D. A. (1989). Aryl-bridged polysilsesquioxanes--new microporous materials. Chemistry of Materials, 1(6), 572-574. doi:10.1021/cm00006a003
Proceedings Publications
- Bagge, R., Boday, D., & Loy, D. (2016). Polybiphenylenes by cycloaddition co-polymerizatation of 1,2,4,5-tetrazines with 1,4-diethynylbenzene..
- Bagge, R., Boday, D., & Loy, D. (2016). Tetrazines as polydiene modifiers and blowing agents..
- Frederick, K., Odegaard, N., Vandiver, P., & Loy, D. (2016). Reversible, photocurable epoxy based resins..
- Loy, D., Bagge, R., & Boday, D. (2016). New materials using tetrazines as monomers, or polymer modifiers and blowing agents..
- McFadden, P., Bagge, R., Canosa, E., Loy, D., Odegaard, N., & Vandiver, P. (2016). Thermally re-workable epoxy adhesives for use in artifact repair..
- McFadden, P., Bagge, R., Frederick, K., Canosa, E., Loy, D., Odegaard, N., & Vandiver, P. (2016). Developing epoxies for art conservation: Reworkable and fluorescent adhesives..
- McFadden, P., Frederick, K., Arguello, L., Odegaard, N., Vandiver, P., & Loy, D. (2016). Coumarin-based fluorescent tag for art conservation epoxy visualization..
- Budy, S. M., Jin, J., Loy, D. A., & Iacono, S. T. (2015). Synthesis and characterization of semifluorinated polyarylene copolymers..
- Loy, D. A., & Tolbert, S. (2015). Development of new siloxane modified particles as stabilized active ingredients for sunscreens..
- Canosa, E. M., Frederick, K. M., Loy, D. A., Vandiver, P., & Odegaard, N. (2014). Thermally re-workable epoxy adhesives for use in artifact repair..
- Garza, G., Li, P., & Loy, D. A. (2012). Micro-Fluidic Assisted Passive Direct Methanol Fuel Cells. In Volume 9: Micro- and Nano-Systems Engineering and Packaging, Parts A and B, 563-570.More infoA novel design of micro-fluidic structure has been proposed to facilitate passive methanol supply and ventilation of carbon dioxide in direct methanol fuel cells (DMFC). Experimental study was conducted for three in-house fabricated cells which have different membrane-electrode-assemblies (MEA) and cathode-side air-breathing current collectors. Low rate of passive methanol supply and control was accomplished through capillary-force-driven mass transfer in the in-plane of carbon paper wicks. The low methanol supply rate using this passive method only meets the need of fuel of the electrochemical reaction, and there is almost no surplus methanol that could cross over the membrane. The micro-fluidic structure on the anode plate also makes passive removal of the CO2 gas from the electrochemical reaction. The influence of the concentration of methanol and cell operation temperature was examined and compared in the study. The results reveal very promising performance in the passive DMFCs when a methanol concentration is above 8M.Copyright © 2012 by ASME
- Budy, S. M., & Loy, D. A. (2009). Sulfonated polyarylene using Lewis acid catalysts: Synthesis and characterization. In 238th National Meeting and Exposition of the American Chemical Society, ACS 2009.More infoPolymer electrolytes, or more specifically, proton exchange membranes (PEM)s for fuel cell applications have been a growing area of research and development worldwide in the last decade. DuPont's Nafion® perfluorinated membranes have played an integral role in the success of recent PEM fuel cell technology. However, its high cost, poor performance at temperatures above 100 °C, and relatively high permeability to fuels and oxidizers material has driven researchers to look for alternative materials, including sulfonated polysulfones and polyether-ether-ketones (PEEK). We have looked at sulfonating polyarylenes prepared by Diels-Alder polymerizations as possible PEM fuel cell candidates; high proton conductivity, chemical and thermal stability, and film toughness demonstrated that these materials are promising candidates. However, sulfonation reactions using sulfuric acid, sulfur trioxide, or chlorosulfonic acid can also cause cross-linking through the formation of sulfone links between polymer chains and lead to lower yields of usable ionomers. In this work we have adapted the Friedel-Crafts reactions that cause cross-linking to prepare sulfonated polymers by reacting polyarylenes with 1,3,5-benzenetrisulfonyl chloride.
- Muriithi, B., & Loy, D. A. (2009). Ex situ Stöeber silica-Nafion® nanocomposite membranes. In 238th National Meeting and Exposition of the American Chemical Society, ACS 2009.More infoHigh temperature (100-200 °C) operation of fuel cells alleviates CO poisoning of the electrocatalysts and thermal-management problems associated with current proton exchange membrane (PEM) fuel cell technology. Perfluorosulfonic acid-based membranes have high proton conductivity below 80 °C, but at higher temperatures conductivity and fuel cell performance rapidly dwindle. Incorporation of inorganic fillers into the PEM has been shown to increase its working temperature range and improve its mechanical properties. These include composite materials prepared by in-situ polymerization of tetraalkoxysilanes in Nafion®. However, these studies did not examine the effects of particle size and the surface chemistry of the silica on processing and composite properties. In this work, we prepared and characterized a family of nanocomposites of Nafion® with monodisperse silica spheres with varied particle size and surface chemistry. Silica particles with controlled sizes (20-200 nm diameter) were prepared from tetraethoxysilane by the Stöeber method. Surface modification with mercaptopropyltriethoxysilane afforded hydrophobic thiol-modified silica that, upon oxidation with hydrogen peroxide, were converted into hydrophilic, sulfonic acid modified particles. We were successful in developing procedures for homogeneously dispersing the particles in Nafion® to make 80-100μm thick nanocomposite membranes. Atomic force microscopy and scanning electron microscopy were used to determine the distribution of the silica particles in the membranes and how it is affected by their size and surface chemistry. The results of our morphological studies and the influence of the size and chemical modification of the well-defined silica particles on the properties of the composite membranes, such as water uptake and proton conductivity at high temperatures, will be presented.
- Taubert, J., & Loy, D. (2009). Preparation of platinum catalyst on silver membranes for PEMFC with green electroless deposition. In 9th Proton Exchange Membrane Fuel Cell Symposium (PEMFC 9) - 216th Meeting of the Electrochemical Society, 25.More infoAs an alternative to platinum on carbon electrocatalysts for polymer electrolyte fuel cells, we have deposited platinum on silver membranes using electroless reduction of platinum salts with isopropanol. To speed discovery and optimization of the electroless chemistry, we developed two visual screening experiments to identify which formulations deposited active platinum catalysts. Once an environmentally friendly or green formulation was identified, we optimized the chemistry looking at catalyst activity and morphology as a function of temperature and reactant concentrations. ©The Electrochemical Society.
- Rahimian, K., Lang, D. P., & Lay, D. A. (2000). Polylsilsesquioxanes through base-catalyzed redistribution of oligohydridosiloxanes. In Washington,DC. Meeting, 41.More infoThe use of tetrabutylammonium hydroxide (TBAH) as an excellent catalyst for the disproportionation of alkyl and arylhydridosiloxanes to polysilsesquioxanes is demonstrated. The extent of disproportionation is controlled by the amount of catalyst added or by using solvent. Overall, this methodology gives access to silsesquioxane gels that cannot be accessed by traditional solgel means.
- Loy, D. A., & Baugher, B. M. (1997). Preparation of poly(dipropylenecarbonate-co-disiloxane) by a condensation polymerization. Thermally degradable polymers. In Proceedings of the 1997 ACS San Francisco Meeting, 38.More infoA high molecular weight poly(dipropylenecarbonate-co-disiloxane) was prepared through a simple acid-catalyzed hydrolysis and condensation polymerization reaction of bis(3-dimethylethoxysilylpropylene) carbonate. The polymer was thermally stable to 300 °C. Higher temperatures resulted in the complete degradation of the polymer to monomeric products including three different tetramethyldisiloxane products. The nature of degradation products were markedly dependent on the manner in which the polymer had been processed and were particularly sensitive to traces of acid.
- Loy, D. A., Carpenter, J. P., Myers, S. A., Assink, R. A., Small, J. H., Greaves, J., & Shea, K. J. (1996). Intramolecular condensation reactions of α,ω-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. In Proceedings of the 1996 MRS Spring Symposium, 435.More infoUnder acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane 1 and 1,4-bis(triethoxysilyl)butane 2 were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed with the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to preserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.
- Myers, S. A., Assink, R. A., Schirber, J. E., & Loy, D. A. (1995). Effect of O2 intercalation on the rotational dynamics and the ordering transition of C60. In Proceedings of the 1994 MRS Fall Meeting, 359.More infoWe have used 13C magic-angle spinning (MAS) nuclear magnetic resonance (NMR) to characterize the structure and rotational dynamics of C60 containing oxygen molecules located in the interstitial sites of the fcc lattice. Under normal conditions, a narrow peak at 143.7 ppm is observed for C60. When exposed to oxygen at moderate pressures, several additional resonances appear in the 13C MAS NMR spectrum. These secondary resonances are shifted downfield from the main peak at 143.7 ppm and are due to the Fermi-contact interaction of the paramagnetic oxygen molecules with the 13C nuclear spins. The presence of oxygen depresses the orientational ordering transition by ca. 20 K as observed by DSC. The spin-lattice relaxation time (T1) of each secondary peak shows a minimum near the ordering transition, indicating that this transition is not dependent on the number of oxygen molecules surrounding an individual C60 molecule. The T1 due to paramagnetic relaxation, normalized by the number of surrounding oxygen molecules, is constant. This observation demonstrates that within a given sample, the dynamics of C60 molecules are independent of the number of surrounding oxygen molecules.
- Jamison, G. M., Loy, D. A., & Shea, K. J. (1993). New group XIV oxide network materials: polygerm- and polygermsilsequioxanes. In Proceedings of the American Chemical Society Division of Polymeric Materials - Science and Engineering, 69.More infoAlklylene-bridged polygerm- and polygermsilsesquioxanes have been formed by hydrolysis-condensation of their corresponding (EtO)3 M(CH2)n Ge(OEt)3 monomers under HCl- and NEt3 -catalyzed conditions in ethanol. Solid state 13C and 29Si NMR indicate the retention of the alkylene bridging moiety during poylmerization; infrared analysis suggests the formation of a small amount of olefinic group. The resulting aerogels are mesoporous materials with high surface areas. Incorporation of the short ethylene bridging unit results in higher surface areas than when hexylene bridges are present. The hexylene bridging group also gives rise to desorption hystereses indicating the presence of bottlenecks in their pore structure.
- Loy, D. A., Buss, R. J., Assink, R. A., Shea, K. J., Shea, K. J., Oviatt, H., & Oviatt, H. (1992). Porous materials by design. Plasma oxidation of hydrocarbon templates in polysilsesquioxanes. In MRS.More infoArylene- and alkylene-bridged polysilsesquioxanes were prepared by sol-gel processing of bis(triethoxysilyl)-aryl monomers and decyl monomer. The arylene polysilsesquioxanes were porous materials with surface areas as high as 830 m{sup 2}/g (BET). Treatment with an inductively coupled oxygen plasma resulted in the near quantitative removal of the arylene bridging groups and a coarsening of the pore structure. Solid state {sup 29}Si NMR was used to confirm the conversion of the sesquioxane silicons (T) to silica (Q). The decylene-bridged polysilsesquioxane was a non-porous material. Oxygen plasma treatment afforded a silica gel with a surface area of 294 m{sup 2}/g and a mean pore diameter of 46 {Angstrom}. The porosity in the silica gel appears to arise entirely from the oxidation of the 1,10-decylene spacer.
Presentations
- Hogan, D. E., Maier, R. M., Loy, D. A., & Perez, S. (2023). Complexation Strength of Bioinspired Glycolipids with Ni, PB, and Zn. NIEHS Superfund Research Program Annual Meeting.
- Loy, D. A. (2022, Fall). Iminodiacetic acid modified hydrogels for the removal of heavy metals from water. American Chemical Society Fall Meeting. Chicago, Ill: American Chemical Society.
- Loy, D. A. (2022, Fall). UV-reversible epoxy resins containing photocleavable coumarin dimer crosslinks. ACS Fall 2022. Chicago, Il: ACS.
- Loy, D. A. (2022, May 25). 3D Printing of Glass Imaging Optics with High Precision using a Liquid Silica Resin. ACerS Glass & Optical Materials Division Meeting. Baltimore, MD: American Ceramics Society.
- Maier, R., Babst-Kostecka, A., Loy, D. A., Lokugama, V., Hogan, D. E., & Perez, S. (2022). Zinc removal from water using functionalized hydrogels. University of Arizona ENViSion Research Symposium.
- Loy, D. A. (2014, December 2014). Polymerization of organotrialkoxysilanes: Formation of polyhedral oligomers, networks of rings and ladder‐like structures. Silicone containing polymers and composites workshop. San Diego, California: American Chemical Society.
- Loy, D. A. (2014, January). Polyarylene Electrolytes. Department of Chemical and biological Engineering Colloquium. Lincoln, Nebraska: University of Nebraska.
- Loy, D. A. (2014, January). Polyarylene electrolytes. Chemical and Materials Engineering Department Seminar. University of Nebraska, Lincoln: Chemical and Materials Engineering Department.
- Loy, D. A. (2014, July). Membranes, protective coatings and sunscreens: synthesis and applications of polysilsesquioxanes. Harbin Institute of Technology Colloquium. Weihai, Peoples Republic of China.
Poster Presentations
- Hogan, D. E., Maier, R. M., Loy, D. A., Nanayakkara, R., & Graves, K. (2025).
Uranium adsorption by novel bioinspired hydrogel polymer
. NIEHS Superfund Research 2025 Annual Meeting. - Hogan, D. E., Maier, R. M., Loy, D. A., Root, R. A., & Perez, S. (2025).
Glycolipid metal interactions and ion flotation applications for recovering metals from water
. Society for Mining, Metallurgy, and Exploration Annual Conference. - Hogan, D. E., Maier, R. M., Loy, D. A., Root, R. A., & Perez, S. (2025).
Glycolipid uranium interactions and ion flotation applications for recovering uranium from water
. University of Arizona ENViSion Research Symposium. - Hogan, D. E., Maier, R. M., Loy, D. A., Root, R. A., & Perez, S. (2024). Glycolipid Metal Interactions and Ion Flotation Applications for Recovering Metals from Water. Society for Mining, Metallurgy, and Exploration Arizona Conference.
- Hogan, D. E., Maier, R. M., Loy, D. A., Root, R. A., & Perez, S. (2024, December). Glycolipid Metal Interactions and Ion Flotation Applications for Recovering Metals from Water. . Society for Mining Metallurgy and Exploration Arizona Chapter Annual Conference (SME AZ 2024). Tucson, AZ: SME.
- Hogan, D. E., Maier, R. M., Loy, D. A., & Vidula, L. (2023). A Sustainable Approach To Recover Rare Earth Elements (REE) Using Functionalized Hydrogels. University of Arizona ENViSion Research Symposium. Tucson, AZ.
- Loy, D. A. (2022, Fall). Design of efficient UV-protective dihydropyridazine thin-film coatings. ACS Fall 2022. Chicago, Ill: ACS.
- Loy, D. A. (2022, Fall). Thermoset polymer particle sunscreens using polycondensation technique. ACS Fall 2022. Chicago, Il: ACS.
- Loy, D. A. (2022, Spring). 3D printable thermosets from curable Diels-Alder polymer with benzoxazine moieties. ACS Spring 2022. San Diego, CA: ACS.
- Loy, D. A. (2022, Spring). Chemical Modification of Glycolipids with Polymerizable Acrylate Groups and Their Incorporation into Hydrogels. MRS Spring Meeting. Honolulu, HW: MRS.
- Loy, D. A. (2022, Spring). FDM 3D Printing of Main-Chain Polybenzoxazine with Diels-Alder Moieties. MRS Spring Meeting. Honolulul, Hawaii: MRS.
- Loy, D. A., Maier, R., Hogan, D. E., Twaje, S., Power, A., Perez, S., & Lokugama, V. (2022). Chemical Modification of Glycolipids with Polymerizable Acrylate Groups and Their Incorporation into Hydrogels. Materials Research Society Spring Meeting Symposium.
- Maier, R. M., Babst-Kostecka, A., Loy, D. A., Lokugama, V., Hogan, D. E., & Perez, S. (2022, December). Conditional Stability Constants for Synthetically Derived Glycolipids. NIEHS Superfund Research Program Annual Meeting. Raleigh, NC: NIEHS.
- Maier, R. M., Babst-Kostecka, A., Loy, D. A., Lokugama, V., Hogan, D. E., & Perez, S. (2022, December). Conditional Stability Constants for Synthetically Derived Glycolipids. SME Arizona Conference. Tucson, AZ: Society for Mining, Metallurgy and Exploration.
