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1. Corporate Responsibility: A Green Initiative to Reduce Chlorobenzene Based Chemistries in Semiconductor Processing

   https://doi.org/10.1557/adv.2019.20  

   Farrell, Monique J. ; Frey, Kevin ; Mason, John ( January 2019 , MRS Advances)

   ABSTRACT Climate change and an increase in endangered species, are examples of technological advances negatively impacting the environment. As technology demands increase, an earnest effort to reduce the environmental impact of processing and manufacturing related activities is critical. From a business perspective, minimizing or removing toxic process chemicals is a high impact area that can increase work environment safety and decrease waste management costs. This work presents processing considerations when transitioning to greener alternative polymer resist solvents, for applications in nanomanufacturing with sustainability considerations. Within government contracting, process modifications that change product form, fit, or function require qualification and atmore »minimum justification. This work presents the conversion from a chlorobenzene to anisole based solvent using a 495 kMW polymetheyl methacrylate polymer resin, without impacting form fit or function of the intended device. Resist conversion is of interest as the difference in the substituents of the two solvents, impact the effective toxicity of the polymer resists. Specifically, the oral median lethal dose (LD 50 ) in rats for chlorobenzene is 1110 mg/kg, while anisole is 3700 mg/kg. Therefore, developing a process utilizing anisole and replacing chlorobenzene addresses safety concerns and contributes to green initiatives worldwide. Within this work electron beam lithography fabricated transistor components consisting of a double layered source, and gate were converted from a chlorobenzene to anisole based process; while maintaining process of record specifications. The purpose of this work is to provide a starting platform for individuals seeking to convert from a chlorobenzene solvent to an anisole based resist for sub-micron lithography steps.« less
2. Novel perfluorinated nanofiltration membranes for isolation of pharmaceutical compounds

   https://doi.org/10.1016/j.seppur.2020.117944  

   Chau, John ; Sirkar, Kamalesh K ; Pennisi, Kenneth J ; Vaseghi, Gazelle ; Derdour, Lotfi ; Cohen, Benjamin ( January 2021 , Separation and purification technology)

   Polymeric membranes for separation of pharmaceutical intermediates/products by organic solvent nanofiltration (OSN) have to be highly resistant to many organic solvents including high-boiling polar aprotic ones, e.g., N- methyl-2-pyrollidone (NMP), dimethylsulfoxide (DMSO), dimethylformamide (DMF). Unless cross-linked, few polymers resist swelling or dissolution in such solvents; however particular perfluoropolymers are resistant to almost all solvents except perfluorosolvents. One such polymer, designated AHP1, a glassy amorphous hydrophobic perfluorinated polymer, has been studied here. Additional perfluoropolymers studied here are hydrophilically modified (HMP2 and HMP3) versions to enhance the flux of polar aprotic solvents. OSN performances of three types of membranes including the hydrophilicallymore »modified ones were studied via solvent flux and solute rejection at pressures up to 5000 kPa. The solutes were four active pharmaceutical ingredients (APIs) or pharmaceutical intermediates having molecular weights (MWs) between 432 and 809 Da and three dyes, Oil Blue N (378 Da), Sudan Black B (456 Da), Brilliant Blue R (826 Da). Solvents used were: ethyl acetate, toluene, n- heptane, iso-octane, DMSO, tetrahydrofuran (THF), DMF, acetone, NMP, methanol. Test cells included stirred cells and tangential flow cells. Pure solvent fluxes through three membrane types were characterized using a particular parameter employing various solvent properties. All three membranes achieved high solute rejections around 91–98% at ambient temperatures. HMP2 membrane achieved 95% solute rejection for an API (809 Da) in DMSO at a high temperature, 75 ◦C. A two-stage simulated nanofiltration process achieved 99%+ rejection of a pharmaceutical intermediate (MW, 432 Da) in 75v% NMP-25v% ethyl acetate solution.« less
3. Nanoparticle filtration through microporous ECTFE membrane in an alcoholic solution

   https://doi.org/https://doi.org/10.1016/j.seppur.2018.08.022  

   Na Yao, Boris Khusid ( October 2018 , Separation and purification technology)

   Organic solvent filtration is an important industrial process. It is widely used in pharmaceutical manufacturing, chemical processing industry, semiconductor industry, auto assembly etc. Most of the particle filtration studies reported in open literature dealt with aqueous suspension medium. The current work has initiated a study of cross-flow solvent filtration behavior of microporous ethylene chlorotrifluoroethylene (ECTFE) membranes using 12 nm silica nanoparticles suspended in an aqueous solution containing 25% ethanol. In the constant pressure mode of operation of cross-flow microfiltration (MF), permeate samples were collected at different time intervals. The permeate particle size distribution (PSD) results for different experiments were identical.more »Particle agglomerates having less than 100 nm size can pass through the membrane; some fouling was observed. The governing fouling mechanisms for tests operated using 3.8×10−3 kg/m3 (3.8 ppm) at 6.9×103 Pag and 1.4×104 Pag were pore blocking. For tests conducted using 3.8×10−3 kg/m3 (3.8 ppm) at 27.6×103 Pag (4 psig) and 1.9×10−3 kg/m3 (1.9 ppm) at 6.9×103, 13.8×103 and 27.6×103 Pag (1, 2 and 4 psig), the mechanism was membrane resistance control. Less particles got embedded in membrane pores in experiments operated using suspensions with lower or higher particle concentrations with a higher transmembrane pressure. This is in good agreement with the values of the shear rate in the pore flow and scanning electron microscope images of the membrane after MF. In the dead-end mode of operation of solvent filtration using methanol, ethanol and 2-propanol, the permeate flux behavior follows Jmethanol > Jethanol > J2-propanol at all testing pressures. The values of permeance (kg/m2-s-Pa) determined from the slope of the linear plot of filtration flux vs. the applied pressure difference across the membrane, were 3.9×10−4, 2.3×10−4 and 3.0×10−5 for methanol, ethanol and 2-propanol, respectively. Further exploration was made on solvent sorption results reported earlier. The critical temperature of selected solvents shows a better correlation with solvent sorption rather than the solubility parameter.« less
4. Polymer blend-filled nanoparticle films via monomer-driven infiltration of polymer and photopolymerization

   https://doi.org/10.1039/C7ME00099E  

   Qiang, Yiwei ; Manohar, Neha ; Stebe, Kathleen J. ; Lee, Daeyeon ( January 2018 , Molecular Systems Design & Engineering)

   Incorporation of nanoparticles into polymer blend films can lead to a synergistic combination of properties and functionalities. Adding a large concentration of nanoparticles into a polymer blend matrix via conventional melting or solution blending techniques, however, is challenging due to the tendency of particles to aggregate. Herein, we report a straightforward approach to generate polymer blend/nanoparticle ternary composite films with extremely high loadings of nanoparticles based on monomer-driven infiltration of polymer and photopolymerization. The fabrication process consists of three steps: (1) preparing a bilayer with a nanoparticle (NP) layer atop a polymer layer, (2) annealing of the bilayer with amore »vapour mixture of a monomer and a photoinitiator, which undergoes capillary condensation and imparts mobility to the polymer layer and (3) exposing this film to UV light to induce photopolymerization of the monomer. The monomer used in this process is chemically different from the repeat unit of the polymer in the bilayer and is a good solvent for the polymer. The second step leads to the infiltration of the plasticized polymer, and the third step results in a blend of two polymers in the interstices of the nanoparticle layer. By varying the thickness ratio of the polymer and nanoparticle layers in the initial bilayers and changing the UV exposure duration, the volume fraction of the two polymers in the composite films can be adjusted. This versatile approach enables the design and engineering of a new class of nanocomposite films that contain a nanoscale-blend of two polymers in the interstices of a nanoparticle film, which could have combinations of unique mechanical and transport properties desirable for advanced applications such as membrane separations, conductive composite films and solar cells. Moreover, these polymer blend-filled nanoparticle films could serve as model systems to study the effect of confinement on the miscibility and morphology of polymer blends.« less
5. Microfluidic Synthesis of Elastomeric Microparticles: A Case Study in Catalysis of Palladium-Mediated Cross-Coupling

   Bennett, Jeffrey A ; Genzer, Jan ; Abolhasani, Milad ( October 2018 , 2018 AIChE Annual Meeting)

   Metal-mediated cross-coupling reactions offer organic chemists a wide array of stereo- and chemically-selective reactions with broad applications in fine chemical and pharmaceutical synthesis.1 Current batch-based synthesis methods are beginning to be replaced with flow chemistry strategies to take advantage of the improved consistency and process control methods offered by continuous flow systems.2,3 Most cross-coupling chemistries still encounter several issues in flow using homogeneous catalysis, including expensive catalyst recovery and air sensitivity due to the chemical nature of the catalyst ligands.1 To mitigate some of these issues, a ligand-free heterogeneous catalysis reaction was developed using palladium (Pd) loaded into a polymericmore »network of a silicone elastomer, poly(hydromethylsiloxane) (PHMS), that is not air sensitive and can be used with mild reaction solvents (ethanol and water).4 In this work we present a novel method of producing soft catalytic microparticles using a multiphase flow-focusing microreactor and demonstrate their application for continuous Suzuki-Miyaura cross-coupling reactions. The catalytic microparticles are produced in a coaxial glass capillary-based 3D flow-focusing microreactor. The microreactor consists of two precursors, a cross-linking catalyst in toluene and a mixture of the PHMS polymer and a divinyl cross-linker. The dispersed phase containing the polymer, cross-linker, and cross-linking catalyst is continuously mixed and then formed into microdroplets by the continuous phase of water and surfactant (sodium dodecyl sulfate) introduced in a counter-flow configuration. Elastomeric microdroplets with a diameter ranging between 50 to 300 micron are produced at 25 to 250 Hz with a size polydispersity less than 3% in single stream production. The physicochemical properties of the elastomeric microparticles such as particle swelling/softness can be tuned using the ratio of cross-linker to polymer as well as the ratio of polymer mixture to solvent during the particle formation. Swelling in toluene can be tuned up to 400% of the initial particle volume by reducing the concentration of cross-linker in the mixture and increasing the ratio of polymer to solvent during production.5 After the particles are produced and collected, they are transferred into toluene containing palladium acetate, allowing the particles to incorporate the palladium into the polymer network and then reduce the palladium to Pd0 with the Si-H functionality present on the PHMS backbones. After the reduction, the Pd-loaded particles can be washed and dried for storage or switched into an ethanol/water solution for loading into a micro-packed bed reactor (µ-PBR) for continuous organic synthesis. The in-situ reduction of Pd within the PHMS microparticles was confirmed using energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and focused ion beam-SEM, and TEM techniques. In the next step, we used the developed µ-PBR to conduct continuous organic synthesis of 4-phenyltoluene by Suzuki-Miyaura cross-coupling of 4-iodotoluene and phenylboronic acid using potassium carbonate as the base. Catalyst leaching was determined to only occur at sub ppm concentrations even at high solvent flow rates after 24 h of continuous run using inductively coupled plasma mass spectrometry (ICP-MS). The developed µ-PBR using the elastomeric microparticles is an important initial step towards the development of highly-efficient and green continuous manufacturing technologies in the pharma industry. In addition, the developed elastomeric microparticle synthesis technique can be utilized for the development of a library of other chemically cross-linkable polymer/cross-linker pairs for applications in organic synthesis, targeted drug delivery, cell encapsulation, or biomedical imaging. References 1. Ruiz-Castillo P, Buchwald SL. Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions. Chem Rev. 2016;116(19):12564-12649. 2. Adamo A, Beingessner RL, Behnam M, et al. On-demand continuous-flow production of pharmaceuticals in a compact, reconfigurable system. Science. 2016;352(6281):61 LP-67. 3. Jensen KF. Flow Chemistry — Microreaction Technology Comes of Age. 2017;63(3). 4. Stibingerova I, Voltrova S, Kocova S, Lindale M, Srogl J. Modular Approach to Heterogenous Catalysis. Manipulation of Cross-Coupling Catalyst Activity. Org Lett. 2016;18(2):312-315. 5. Bennett JA, Kristof AJ, Vasudevan V, Genzer J, Srogl J, Abolhasani M. Microfluidic synthesis of elastomeric microparticles: A case study in catalysis of palladium-mediated cross-coupling. AIChE J. 2018;0(0):1-10.« less