Perfluoroalkoxy Research Articles

Improved Reactor Productivity for the Safe Photo‐Oxidation of Citronellol Under Visible Light LED Irradiation

AbstractA simple continuous flow photochemical reactor was optimized for the safe photo‐oxidation of citronellol into precursors of rose oxide, a flagrance of commercial value. The reactor productivity was increased by a factor of 4 compared to the current literature for a conversion above 99 % and in safe conditions (up to 0.72 mM min−1 mLreactor−1). The reactor was based on a classical design described by Booker‐Milburn et al., i. e. multiple loops of perfluoroalkoxy (PFA) tubing wrapped tightly around a visible LED lamp under slug flow conditions. The influence of the type of visible white LED light (6500 K vs. 3000 K), of photosensitizers (tetraphenylporphyrin vs. methylene blue), of solvent (CH2Cl2 vs. MeOH), concentration of citronellol (0.1 M vs. 2 M) and of mass efficiency of the reactors (PFA tubing of 0.75 mm to 0.25 mm) was paramount to increase the productivity of the reactor.

A platform for accelerated continuous-flow radical polymerization of acrylates and styrene with copper-wire threads

Accelerated Cu(0)-mediated homo-/block (co)polymerization of the vinyl monomers is conducted via continuous-flow process with a copper metal-wire catalyst threaded through perfluoroalkoxy alkane (PFA) tube.

Preliminary study on alginate/NIPAM hydrogel-based soft microrobot for controlled drug delivery using electromagnetic actuation and near-infrared stimulus.

Currently, microrobots are receiving attention because of their small size and motility, which can be applied to minimal invasive therapy. Additionally, various microrobots using hydrogel with the characteristics of biocompatibility and biodegradability are also being developed. Among them, microrobots that swell and deswell in response to temperature changes caused by external near infrared (NIR) stimuli, focused ultrasound, and an alternating magnetic field, have been receiving a great amount of interest as drug carriers for therapeutic cell delivery. In this study, we propose a spring type medical microrobot that can be manipulated by an electromagnetic actuation (EMA) system and respond to an external stimulus (NIR). Additionally, we verified its feasibility with regard to targeting and drug delivery. There exist various methods of fabricating a spring type microrobot. In this study, we adopted a simple method that entails using a perfluoroalkoxy (PFA) microtube and a syringe pump. Moreover, we also used a hydrogel mixture composed of natural alginate, N-Isopropylacrylamide (NIPAM) for temperature responsiveness, and magnetic nanoparticles (MNPs) for electromagnetic control. Then, we fabricated a spring type alginate/NIPAM hydrogel-based soft microrobot. Additionally, we encapsulated doxorubicin (DOX) for tumor therapy in the microrobot. To verify the feasibility of the proposed spring type hydrogel-based soft microrobot's targeting and drug delivery, we developed an EMA and NIR integrated system. Finally, we observed the swelling and deswelling of the soft microrobot under NIR stimulation and verified the EMA controlled targeting. Moreover, we implemented a control function to release the encapsulated anticancer drug (DOX) through the swelling and deswelling of the soft microrobot by NIR, and evaluated the feasibility of cancer cell therapy by controlling the release of the drug from the soft microrobot.

Chemically Resistant Perfluoroalkoxy Nanoparticle-Packed Porous Substrates and Their Use in Colorimetric Sensor Arrays.

To create printing substrates for colorimetric sensor arrays, chemically resistant membranes are prepared by coating cellulose filter paper with perfluoroalkoxy (PFA) polymer nanoparticles. A water-based fluorothermoplastic polymer dispersion was diluted with an organic solvent that causes weak aggregation of polymer nanoparticles. The resulting solution improved adhesion between the polymer and the cellulose membrane, providing a more mechanically stable substrate. These PFA polymer-coated substrates demonstrated superior chemical resistance against strong alkalines and had relatively uniform nanoporous structures that substantially improved the printability of a colorimetric sensor array. Finally, colorimetric sensor arrays printed on these substrates were evaluated for the detection of four different toxic industrial chemicals (e.g., ammonia, hydrogen sulfide, nitrogen dioxide, and sulfur dioxide) at or below their permissible exposure limits.

Non-Stick Coatings in Aluminium Molds for the Production of Polyurethane Foam

The manufacturing of polyurethane foam is a process of great industrial importance in the automotive and furniture sector. The operation of demolding is the most delicate, since the foam sticks firmly to the walls of the mold onto which it has spread. In order to avoid the use of demolding agents, the proposal is to coat the inside of the molds with non-stick coatings. In this work, three types of different coatings were studied: fluoropolymers, ceramics, and elastomers. After carrying out different tests in the laboratory, two fluoropolymer coatings (PFA (perfluoroalkoxy) and PTFE (polytetrafluoroethylene)) were selected for a test at the industrial level and, after 1500 cycles of demolding, it was experimentally proven that the PFA coating is the most adequate for the use studied.

Preparation of Graphene-Perfluoroalkoxy Composite and Thermal and Mechanical Properties.

Perfluoroalkoxy (PFA) material exhibits perfect corrosion resistance under both acid or alkaline circumstances; thus, steel heat exchangers are being substituted by those made of PFA in high corrosion atmospheres. However, the low thermal conductivity of PFA degrades its heat transfer efficiency. Based on the extremely high heat conductivity of graphene, a novel grapheme-PFA composite was proposed to simultaneously meet the demands of heat transfer and corrosion resistance. Ultrasonic dispersion technology was used to disperse the aggregated graphene in the composite. Graphene–PFA composites with different graphene contents and using different dispersing solvents were prepared with a hot pressing method, and thermal conductivity, abrasion resistance, crystallization and pyrolysis properties were investigated. The thermal conductivity of PFA composites with graphene content of 20 wt % reached 5.017 W (m·k)−1, which is 21.88 times that of pure PFA. The relationship between the abrasion loss and the friction coefficient of the composites with different graphene contents was obtained. A thermogravimetric analyzer was used to investigate the crystallization and pyrolysis behavior of the composites; correspondingly, the temperature range that composites work in was determined. The heat conduction mechanism was analyzed through the thermal conductivity model of composite materials. The composite material is expected to play an important role in the development of high-performance thermal equipment.

Understanding and modeling of triboelectric-electret nanogenerator

Recently, electrostatic kinetic energy harvesters regained strong attention through the development of new triboelectric generators for harvesting green and renewable energy. These devices use a triboelectric dielectric layer as electret for polarizing their capacitance and they behave similarly to electret generators. However, triboelectric-based electret nanogenerators (T-ENG) have specificities arising from the contact electrification phenomenon and leading to different performances. For better understanding T-ENG, we investigated their electrical modeling with lumped-elements and multiphysics simulation in light of last researches on electret generators. To take into account T-ENG specificities, we experimentally measured the amplitude of the triboelectric effect on perfluoroalkoxy alkane films. This approach allowed fully simulating T-ENG and the model was found in agreement with experimental results. Understanding and verifying the model is capital, but to go further toward the application of T-ENG, we reused two electret circuits to extract the T-ENG model parameters in view of facilitating their realistic modeling and practical development into application.

A fast and low-cost microfabrication approach for six types of thermoplastic substrates with reduced feature size and minimized bulges using sacrificial layer assisted laser engraving

Since polydimethylsiloxane (PDMS) is notorious for its severe sorption to biological compounds and even nanoparticles, thermoplastics become a promising substrate for microdevices. Although CO2 laser engraving is an efficient method for thermoplastic device fabrication, it accompanies with poor bonding issues due to severe bulging and large feature size determined by the diameter of laser beam. In this study, a low-cost microfabrication method is proposed by reversibly sealing a 1 mm thick polymethylmethacrylate (PMMA) over an engraving substrate to reduce channel feature size and minimize bulges of laser engraved channels. PMMA, polycarbonate (PC), polystyrene (PS), perfluoroalkoxy alkane (PFA), cyclic-olefin polymers (COP) and polylactic acid (PLA) were found compatible with this sacrificial layer assisted laser engraving technique. Microchannel width as small as ∼40 μm was attainable by a laser beam that was 5 times larger in diameter. Bulging height was significantly reduced to less 5 μm for most substrates, which facilitated leak proof device bonding without channel deformation. Microdevices with high aspect ratio channels were prepared to demonstrate the applicability of this microfabrication method. We believe this fast and low-cost fabrication approach for thermoplastics will be of interest to researchers who have encountered problem with polydimethylsiloxane based microdevices in their applications.

Corrosion‐resistant coating development with potential application in equipment of low‐temperature waste heat recovery

AbstractIn order to improve corrosion resistance of a condensing heat exchanger, a fluoropolymer, perfluoroalkoxy alkane (PFA), fine powder in 30 wt% aqueous slurry was coated on metal coupons and a coating of high quality finish was obtained. The coating was characterized by microscopy and thickness measurements. The thickness of the coating can be controlled by the number of layers used for the application of wet spray. Hot acid bath corrosion tests showed that the coated coupon possesses the highest adhesion strength and excellent corrosion resistance (1.8–6.7 × 10−3 mm/year), comparable to super alloys such as Inconel (1.1–26.2 × 10−3 mm/year) and Hastelloy (0.3–19.8 × 10−3 mm/year). A heat transfer coefficient analysis showed that across a heat transfer metal tube coated with PFA, the heat transfer resistance of the gas side film is one order of magnitude larger than the resistance from the coated layer. The developed coating could provide an alternative material solution for condensing heat exchangers used in low‐grade waste heat recovery.

Mass-producible hydrophobic perfluoroalkoxy/nano-silver coatings by suspension flame spraying for antifouling and drag reduction applications

To exploit marine metal materials with antifouling and drag reduction properties, we constructed hydrophobic perfluoroalkoxy (PFA)/nano‑silver (Ag) coatings onto aluminum substrates by suspension flame spray deposition of PFA/AgNO3 composites. Silver nanoparticles were formed in situ within PFA coating during the suspension flame spraying. The successful construction of PFA/nano-Ag coatings was revealed by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and contact angle measurements, respectively. The additional silver nanoparticles play the significant role in regulating the sliding angle of the PFA-based coatings. The silver nanoparticles-loaded hydrophobic PFA coatings synergistically inhibited the adhesion of bacteria, while only PFA coatings with lower content of silver display drag reduction property. The simple and cost-effective approach is of great promise in mass-production of antifoulant-loaded hydrophobic coatings on general substrates for potential antifouling and drag reduction applications.

Effects of Dilution Systems in Olfactometry on the Recovery of Typical Livestock Odorants Determined by PTR-MS.

The present study provides an elaborate assessment of the performance of olfactometers in terms of odorant recovery for a selection of odorants emitted from livestock houses. The study includes three different olfactometer dilution systems, which have been in use at accredited odor laboratories. They consist of: (i) a custom-built olfactometer made of glass tubes, (ii) a TO8 olfactometer, and (iii) an Olfacton dilution system based on a mass flow controller. The odorants include hydrogen sulfide, methanethiol, dimethyl sulfide, acetic acid, butanoic acid, propanoic acid, 3-methylbutanoic acid, 4-methylphenol, and trimethylamine. Furthermore, n-butanol, as the reference gas in the European standard for olfactometry, EN13725, was included. All measurements were performed in real time with proton-transfer-reaction mass spectrometry (PTR-MS). The results show that only dimethyl sulfide was almost completely recovered in all cases, while for the remaining compounds, the performance was found to vary significantly (from 0 to 100%) depending on the chemical properties of the compounds, the concentration levels, the pulse duration, and the olfactometer material. To elucidate the latter, the recovery in different locations of the TO8 olfactometer and in tubes of different materials, that is, poly-tetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), stainless steel and SilcoTek-coated steel, were tested. Significant saturation effects were observed when odorants were in contact with stainless steel.

Performance evaluation of a high-pressure microwave-assisted flow digestion system for juice and milk sample preparation.

Acid digestion is usually required for metal determination in food samples. However, this step is usually performed in batch mode which is time consuming, labor intensive, and may lead to sample contamination. Flow digestion can overcome these limitations. In this work, the performance of a high-pressure microwave-assisted flow digestion system with a large volume reactor was evaluated for liquid samples high in sugar and fat (fruit juice and milk). The digestions were carried out in a coiled perfluoroalkoxy (PFA) tube reactor (13.5mL) installed inside an autoclave pressurized with 40bar nitrogen. The system was operated at 500W microwave power and 5.0mLmin-1 carrier flow rate. Digestion conditions were optimized with phenylalanine, as this substance is known to be difficult to digest completely. The combinations of HCl or H2O2 with HNO3 increased the digestion efficiency of phenylalanine, and the residual carbon content (RCC) was around 50% when 6.0% V/V HCl or H2O2 was used in combination with 32% V/V HNO3. Juice samples were digested with 3.7molL-1 HNO3 and 0.3molL-1 HCl, and the RCC was 16 and 29% for apple and mango juices, respectively. Concentrated HNO3 (10.5molL-1) was successfully applied for digesting milk samples, and the RCCs were 23 and 25% for partially skimmed and whole milk, respectively. Accuracy and precision of the flow digestion procedure were compared with reference digestions using batch mode closed vessel microwave-assisted digestion and no statistically significant differences were encountered at the 95% confidence level. Graphical abstract Application of a high-pressure microwave-assisted flow digestion system for fruit juice and milk sample preparation.

Characterization of Thermal, Mechanical and Tribological Properties of Fluoropolymer Composite Coatings

Perfluoroalkoxy (PFA) is a potential polymer coating material for low-temperature waste heat recovery in heat exchangers. Nonetheless, poor thermal conductivity, low strength and susceptibility to surface degradation by erosion/wear pose restrictions in its application. In this study, four types of fillers, namely graphite, silicon carbide, alumina and boron nitride, were introduced to enhance the thermal, mechanical and tribological properties in PFA coatings. The thermal diffusivity and specific heat capacity of the composites (reinforced with 20 wt.% filler) were also measured using laser flash and differential scanning calorimetry techniques, respectively. The results indicated that the addition of graphite or boron nitride increased the thermal conductivity of PFA by at least 2.8 orders of magnitude, while the composites with the same weight fraction of alumina or silicon carbide showed 20-80% rise in thermal conductivity. The micromechanical deformation and tribological behavior of composite coatings, electrostatically sprayed on steel substrates, were investigated by means of instrumented indentation and scratch tests. The deformation response and friction characteristics were investigated, and the failure mechanisms were identified. Surface hardness, roughness and structure of fillers influenced the sliding performance of the composite coatings. PFA coatings filled with Al2O3 or SiC particles showed high load-bearing capacity under sliding conditions. Conversely, BN- and graphite-filled PFA coatings exhibited lower interfacial adhesion to steel substrate and were prone to failure at relatively lower applied loads.

Exploring the Fundamentals of Microreactor Technology with Multidisciplinary Lab Experiments Combining the Synthesis and Characterization of Inorganic Nanoparticles

Multidisciplinary lab experiments combining microfluidics, nanoparticle synthesis, and characterization are presented. These experiments rely on the implementation of affordable yet efficient microfluidic setups based on perfluoroalkoxyalkane (PFA) capillary coils and standard HPLC connectors in upper undergraduate chemistry laboratories. Fundamental principles and concepts as well as practical tips for the rapid deployment of microfluidics are presented. In-line membrane separation, the segmented-flow regime, high-temperature experiments, and in-line analytical techniques are illustrated by the preparation of inorganic nanoparticles (silver, gold, and cadmium selenide or telluride) in microreactors. Besides microfluidics, analytical techniques for nanoparticle analysis are also illustrated.

Flexible perfluoroalkoxy films filled with carbon nanotubes and their electric heating property

ABSTRACTCarbon nanotubes (CNTs) filled perfluoroalkoxy (PFA) films with the thicknesses of about 10 μm have been prepared via blade coating. Both of the CNTs and PFA are aqueous dispersion, which are favorable for the uniform dispersion of fillers into the matrix. The morphology, direct current (DC) resistivity, electrothermal property, and thermal diffusivity of the composite films were studied. We find out that the fraction of CNTs played a vital role in the heating property and thermal transferring capacity of the composite films. Under the input voltage of 110 V, the temperature of PFA composite film with 15 wt % CNT reached to 200 °C, and the thermal diffusivity was about 3.3 mm2/s. We believe these CNTs/PFA films are promising alternatives to work as flexible electric heating devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44782.

Microstructure Formation on Polytetrafluoroethylene (PTFE) and Perfluoroalkoxy (PFA) Bulk Plates by a Magnetron Enhanced Reactive Ion Etching System

Microstructure Formation on Polytetrafluoroethylene (PTFE) and Perfluoroalkoxy (PFA) Bulk Plates by a Magnetron Enhanced Reactive Ion Etching System

Practical limitations of single particle ICP-MS in the determination of nanoparticle size distributions and dissolution: case of rare earth oxides

The applicability of single particle ICP-MS (SP-ICP-MS) for the analysis of nanoparticle size distributions and the determination of particle numbers was evaluated using the rare earth oxide, La2O3, as a model particle. The composition of the storage containers, as well as the ICP-MS sample introduction system were found to significantly impact SP-ICP-MS analysis. While La2O3 nanoparticles (La2O3 NP) did not appear to interact strongly with sample containers, adsorptive losses of La3+(over 24h) were substantial (>72%) for fluorinated ethylene propylene bottles as opposed to polypropylene (<10%). Furthermore, each part of the sample introduction system (nebulizers made of perfluoroalkoxy alkane (PFA) or glass, PFA capillary tubing, and polyvinyl chloride (PVC) peristaltic pump tubing) contributed to La3+ adsorptive losses. On the other hand, the presence of natural organic matter in the nanoparticle suspensions led to a decreased adsorptive loss in both the sample containers and the introduction system, suggesting that SP-ICP-MS may nonetheless be appropriate for NP analysis in environmental matrices. Coupling of an ion-exchange resin to the SP-ICP-MS led to more accurate determinations of the La2O3 NP size distributions.

Highly Sensitive Raman Spectroscopy with Low Laser Power for Fast In-Line Reaction and Multiphase Flow Monitoring

In process analytics, the applicability of Raman spectroscopy is restricted by high excitation intensities or the long integration times required. In this work, a novel Raman system was developed to minimize photon flux losses. It allows specific reduction of spectral resolution to enable the use of Raman spectroscopy for real-time analytics when strongly increased sensitivity is required. The performance potential of the optical setup was demonstrated in two exemplary applications: First, a fast exothermic reaction (Michael addition) was monitored with backscattering fiber optics under strongly attenuated laser power (7 mW). Second, high-speed scanning of a segmented multiphase flow (water/toluene) with submicroliter droplets was achieved by aligning the focus of a coaxial Raman probe with long focal length directly into a perfluoroalkoxy (PFA) capillary. With an acquisition rate of 333 Raman spectra per second, chemical information was obtained separately for both of the rapidly alternating phases. The experiment with reduced laser power demonstrates that the technique described in this paper is applicable in chemical production processes, especially in hazardous environments. Further potential uses can be envisioned in medical or biological applications with limited power input. The realization of high-speed measurements shows new possibilities for analysis of heterogeneous phase systems and of fast reactions or processes.

Mechanically Robust Silver Nanowires Network for Triboelectric Nanogenerators

The authors develop a mechanically robust silver nanowires (AgNWs) electrode platform for use in flexible and stretchable triboelectric nanogenerators (TENGs). The embedding of an AgNWs network into a photocurable or thermocurable polymeric matrix dramatically enhances the mechanical robustness of the flexible and stretchable TENG electrodes while maintaining a highly efficient triboelectric performance. The AgNWs/polymeric matrix electrode is fabricated in four steps: (i) the AgNWs networks are formed on a hydrophobic glass substrate; (ii) a laminating photocurable or thermocurable prepolymer film is applied to the developed AgNWs network; (iii) the polymeric matrix is crosslinked by UV exposure or thermal treatment; and (iv) the AgNWs‐embedded polymeric matrix is delaminated from the glass substrate. The AgNWs‐embedded polymeric matrix electrodes with four different sheet resistances, controlled by varying the AgNWs network deposition density, are deployed in TENG devices. The authors find that the potential difference between the two contact surfaces of the AgNWs network‐embedded polymer matrix electrodes and the nylon (or perfluoroalkoxy alkane) governs the output triboelectric performances of the devices, rather than the sheet resistance. Both Kelvin probe force microscopy and numerical simulations strongly support these observations.

Simultaneous determination of iron and nickel in fluoropolymers by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry

This paper reports the development of a method of simultaneous determination of iron and nickel in fluoropolymers by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) with direct solid sampling. In order to carry out simultaneous measurements, both the main resonance line of nickel (232.003nm) and the adjacent secondary line of iron (232.036nm) were monitored in the same spectral window. The proposed method was optimized with a perfluoroalkoxy (PFA) sample and was applied to the determination of iron and nickel in fluorinated ethylene propylene (FEP) and modified polytetrafluoroethylene (PTFE-TFM) samples. Pyrolysis and atomization temperatures, as well as the use of Pd and H2 (during pyrolysis) as chemical modifiers, were carefully investigated. Compromise temperatures for pyrolysis and atomization of both analytes were achieved at 800 and 2300°C, respectively, using only 0.5Lmin−1 H2 as chemical modifier during pyrolysis. Calibration curves were performed with aqueous standards by using a single solution which contained both analytes. Limits of detection were 221 and 9.6ngg−1 for iron and nickel, respectively. Analyte concentrations in all samples ranged from 3.53 to 12.4µgg−1 for iron and from 37 to 78ngg−1 for nickel, with relative standard deviation less than 19%. Accuracy was evaluated by comparing these results with those obtained by inductively coupled plasma mass spectrometry after sample digestion by microwave-induced combustion and no significant statistical difference was observed.