07/16/2025
By Kwok Fan Chow

The Kennedy College of Science, Department of Chemistry, invites you to attend a Ph.D. Dissertation defense by Saurabh Ankush Karande entitled “High-Throughput Functionalization of Fabrics with Metal Oxides and Metal-Organic Frameworks for Chem-Bio Protection.”

Degree: Doctoral
Location: Olney Hall, Room 518 and Zoom Meeting: ID 751 5124 7420; Passcode: 9EYyw3
Date: Friday, July 25, 2025
Time: 10 a.m.

Committee

  • Chair: Prof. James E. Whitten, Department of Chemistry, University of Massachusetts Lowell
  • Prof. Ramaswamy Nagarajan, Department of Plastics Engineering, University of Massachusetts Lowell
  • Prof. Yuyu Sun, Department of Chemistry, University of Massachusetts Lowell
  • Prof. James Reuther, Department of Chemistry, University of Massachusetts Lowell

Abstract:
Attachment of reactive nanoparticles to fabrics and fibers is crucial for applications such as filtration, sensors, and photocatalysis. One important application is chemical-biological (chem-bio) protection, which is vital in safeguarding military personnel, first responders, and industrial workers from hazardous threats, including toxic chemical warfare agents (CWAs). This research presents novel, scalable, high-throughput methods to functionalize fabrics—such as polypropylene (PP), cotton, nylon, and nylon-cotton (NYCO) blend with metal oxide nanoparticles (MONPs) and metal-organic frameworks (MOFs), for demonstrating protective capabilities against nerve agents, as evaluated using a nerve agent simulant, dimethyl methyl phosphonate (DMMP).

Open-air plasma treatment was employed to functionalize fabrics for nanoparticle deposition on PP. Plasma introduces oxygen-rich functional groups converting the carbon backbone into hydroxyl, carbonyl, and carboxylic acid surface groups, as confirmed by X-ray photoelectron spectroscopy (XPS). Plasma-treated and untreated fabrics were then spray-coated with ethanolic colloidal suspensions of MONPs including ZnO, MgO, In₂O₃, CeO₂, SnO₂, SiOₓ, TiO₂, and WO₃. Field emission scanning electron microscopy (FE-SEM) and XPS analysis revealed significantly enhanced nanoparticle adhesion on plasma-treated samples. Notably, MONPs with basic character (e.g., ZnO, MgO) showed better adhesion, while more acidic oxides adhered poorly. Photocatalytic application of ZnO-functionalized PP was successfully demonstrated by ultraviolet light-induced decomposition of methyl paraoxon.

Furthermore, NYCO, commonly used in soldier uniforms, was studied along with its components—cotton and nylon—to evaluate the effect of plasma treatment. Open-air plasma was employed to activate these fabrics such that they covalently bond to ZnO and UiO-66-NH₂ MOF particles. Plasma consistently enhanced the surface concentration of these nanoparticles, as confirmed by SEM and XPS. To assess durability, functionalized fabrics were subjected to washing. While particles were largely removed during laundering, plasma treatment showed improved retention compared to untreated samples. These MOF-functionalized NYCO fabrics demonstrated nearly three times longer DMMP permeation times compared to untreated fabrics, confirming their enhanced chemical protection capability.

A multifunctional fabric was successfully fabricated by electrospinning thermoplastic polyurethane (TPU) nanofibers incorporated with Zr-based UiO-66-NH₂ MOF and tannic acid (TA), a flame retardant, directly onto plasma-treated NYCO with the goal of imparting chem-bio protection and fire retardancy. SEM confirmed uniform fiber morphology and good particle dispersion. Vertical flammability tests revealed reduced char lengths (6 inches) and shorter after-flame times (5 seconds), indicating effective flame resistance. Filtration tests confirmed the fabric’s ability to block bacteria and viruses (100–200 nm) due to its fine pores and high surface area.

Finally, chemical performance was tested using a custom-built apparatus employing a 10.6 eV photoionization detector (PID) to measure DMMP vapor permeation. Vapor was generated by bubbling ultra-high purity, dry air through liquid DMMP at 400 ml/min at ambient temperature (~20 °C). MOF-functionalized fabrics demonstrated significantly extended breakthrough times (up to 5.2 minutes), nearly ten times longer than untreated NYCO (30 seconds), attributed to the high surface area, large pores, and reactive Zr sites in the MOFs.

All interested students and faculty members are invited to attend.