Peroxidic perfluoropolyether for the covalent binding of perfluoropolyether chains on carbon black surface

Peroxidic perfluoropolyethers (PFPEs) are suitable tools for the covalent linkage of fluorinated groups on substrates containing aromatic moieties. Thus the thermal decomposition process of such fluorinated peroxides allowed the covalent linkage of PFPE radicals to the polycyclic aromatic structure of a graphitic carbon black. Contact angle measurements on molded pellets made with modified carbon black powders revealed a gradual enhancement of the hydrophobicity, which follows the increase of the fluorine content on the surface according to XPS experiments. BET analyses also revealed variations of the surface area of carbonaceous samples. Products and by-products were also evaluated by mass balances of decomposed portions of PFPE residues, respectively, PFPE chains bonded on carbon black and PFPE fluids obtained by homocoupling side-reactions. Modified carbonaceous materials were analyzed by solid state ¹⁹F-MAS NMR and the results are in agreement with the proposed radical mechanism.     

Some physicochemical properties of perfluoropolyether surfactants

Two series of surface active agents have been obtained, starting from intermediate products of HFP and TFE photooxidation :

Structural, physical and chemical properties have been summarized.Surface activity of the products in aqueous solution was examinated in terms of c.m.c. and H.L.B.Molecular cross section areas, derived from surface tension and Langmuir trough measurements, have been related to structural parameters.     

Superhydrophobic behavior of a perfluoropolyether lotus-leaf-like topography

We demonstrate the fabrication of 2-D arrays of nanopillars made from perfluoropolyether derivatives using a porous anodic aluminum oxide membrane as a template. Pretexturing the aluminum prior to anodization enables one to engineer multiple morphological length scales and thereby synthesize a lotus-leaf-like topography. Both nanopillars on a flat surface and on a lotus-leaf-like topology exhibit superhydrophobicity, low contact angle hysteresis, and self-cleaning.     

Soft lithography using acryloxy perfluoropolyether composite stamps

This paper describes composite patterning elements that use a commercially available acryloxy perfluoropolyether (a-PFPE) in various soft lithographic techniques, including microcontact printing, nanotransfer printing, phase-shift optical lithography, proximity field nanopatterning, molecular scale soft nanoimprinting, and solvent assisted micromolding. The a-PFPE material, which is similar to a methacryloxy PFPE (PFPE-DMA) reported recently, offers a combination of high modulus (10.5 MPa), low surface energy (18.5 mNm(-1)), chemical inertness, and resistance to solvent induced swelling that make it useful for producing high fidelity patterns with these soft lithographic methods. The results are comparable to, and in some cases even better than, those obtained with the more widely explored material, high modulus poly(dimethylsiloxane) (h-PDMS).     

Small-angle neutron scattering of mixed ionic perfluoropolyether micellar solutions

Aqueous mixed micellar solutions of perfluoropolyether carboxylic salts with ammonium counterions have been studied by small-angle neutron scattering. Two surfactants differing in the tail length were mixed in proportions n2/n3 = 60/40 w/w, where n2 and n3 are the surfactants with two and three perfluoroisopropoxy units in the tail, respectively. The tails are chlorine-terminated. The mixed micellar solutions, in the concentration range 0.1-0.2 M and thermal interval 20-40 degrees C, show structural characteristics of the interfacial shell that are very similar to ammonium n2 micellar solutions previously investigated; thus, the physics of the interfacial region is dominated by the polar head and counterion. The shape and dimensions of the micelles are influenced by the presence of the n3 surfactant, whose chain length in the micelle is 2 A longer than that of the n2 surfactant. The n3 surfactant favors the ellipsoidal shape in the concentration range 0.1-0.2 M with a 1/2 ionization degree of n2 micelles. The very low surface charge of the mixed micelles is attributed to the increase in hydrophobic interactions between the surfactant tails, due to the longer n3 surfactant molecules in micelles. The closer packing of the tails decreases the micellar curvature and the repulsions between the polar heads, by surface charge neutralization of counterions migrating from the Gouy-Chapman diffuse layer, leading to micellar growth in ellipsoids with greater axial ratios.     

Modification of surface properties of polyethylene by perfluoropolyether blending

The preparation of a stabile blend from thermoplastic polymer and lubricating additive was studied with high density polyethylene (HDPE) and perfluoropolyether (PFPE). PFPE was melt blended within HDPE by injection molding. The chemical composition of the mixtures, the relative amount of PFPE on the surface, and the nature of the surface were studied by three surface sensitive methods: attenuated total reflectance infrared (ATR‐IR) spectroscopy, secondary ion mass spectroscopy (SIMS), and contact angle (CA) measurement. All the blends exhibited improved hydrophobicity. CA and SIMS gave a maximum response when about 2.0 wt % PFPE was added, whereas ATR‐IR spectroscopy gave maximum response for an addition of about 3.0 wt %. No changes in surface properties were observed when samples were reanalyzed about 1–4 months after preparation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2252–2258, 2005     

Temperature and pressure dependence of the viscosities of perfluoropolyether fluids

The viscosities of two structurally different perfluoropolyether fluids were determined at a series of temperatures and pressures, from 25 to 100°C and from 1 to 1000 bars. Flow activation energies and volumes as well as their temperature and pressure coefficients were derived. An attempt was made to relate measured and derived quantities to the compound structures.     

Mixed micelles of homologous perfluoropolyether anionic surfactants in water

The mixtures of sodium and ammonium salts of three homologous perfluoropolyether carboxylic acids having Cl-terminated perfluoroalkyl group (Cl-PFPE) and differing in the average molecular weight (MW) were examined. The surfactants, namely n2, n3 and n4, have two, three and four PFPE units, respectively. Each surfactant was studied alone and in mixture with the other surfactants with the same counterion. NMR chemical shifts were measured for each surfactant and for the mixtures in different concentrations. For a given mixture the micelle composition, X_i, can be determined from the observation of the chemical shifts of the micellar components. It was found that Cl-PFPE surfactant mixtures form in water mixed micelles which contain the surfactants in equilibrium with monomeric species. The analysis of NMR chemical shift variations allowed evaluating the partition of the various surfactants in the mixed aggregates as a function of the total concentration. Composition of mixed micelles resembles ideal mixing predictions particularly at high surfactant concentrations.     

Interaction of perfluoropolyether peroxide PFPEP-4 with polyfluoroaromatic compounds

Russian Chemical Bulletin - The interaction of perfluoropolyether peroxides with perfluoro- and polyfluoroaromatic compounds (C6F6, C6F5H, C6F5Cl, and C6F5CF3) was investigated. It was found that...     

A study of the thermal decarboxylation of three perfluoropolyether salts

The thermal decarboxylation of three dicarboxylic perfluoropolyether potassium salts of relatively short chain length has been investigated and the products and kinetics of the main reactions have been defined. From the rate constants and Arrhenius parameters data, the second decarboxylation appears to be quantitatively rather close to the first.     

润滑油的电化学分析研究进展

文章综合评述了电导法、介电常数法、气敏传感器、伏安法和阻抗谱技术在石油产品分析中的应用,石油产品的特定电学或电化学效应与其性能关系密切,采用这些电化学分析技术进行润滑油分析不失为一种便利与可靠的选择.因此,电化学分析法在石油产品分析中有着很好的发展潜力.     

Ultraviolet-based bonding for perfluoropolyether low aspect-ratio microchannels and hybrid devices

Producing solvent-resistant microfluidic devices is a challenge for analytical chemistry and biochemistry. We demonstrate a simple and low-cost fabrication approach for the realization of solvent-resistant microchannels based on perfluoropolyether elastomers, exhibiting very low aspect ratios (0.01). The strength of the microchannels sealing is evaluated through the maximum internal pressure (1.52 MPa) prior to device failure, due to delamination at the bonded interface. This approach allows the elastic properties of silicone elastomers, suitable for high quality external connections, to be combined with the non-swelling character of perfluoropolyethers.     

Multilayer soft lithography of perfluoropolyether based elastomer for microfluidic device fabrication

The compatibility of microfluidic devices with solvents and other chemicals is extremely important for many applications such as organic synthesis in microreactors and drug screening. We report the successful fabrication of microfluidic devices from a novel perfluoropolyether based polymer utilizing the Multilayer Soft Lithography? (MSL) technique with simple, straightforward processing. The perfluorinated polymer SIFEL X-71 8115 is a highly chemically resistant elastomeric material. We demonstrate fabrication of a microfluidic device using an off-ratio bonding technique to bond multiple SIFEL layers, each patterned lithographically. The mechanical properties of the SIFEL MSL valves (including actuation pressures) are similar to PDMS MSL valves of the same geometry. Chemical compatibility tests highlight SIFEL's remarkable resistance to organic solvents, acids and alkalis.     

Microfluidic behaviour of perfluoropolyether fluids in poly(dimethylsiloxane) micro-channels

Two different perfluoropolyether-based fluids, namely the unfunctionalized GALDEN SV90^® and the dihydroxy derivative FOMBLIN Z-DOL^® 2000 were employed as liquid samples in a poly(dimethylsiloxane) (PDMS) microfluidic setup, fabricated by soft-lithography techniques. The results of our investigation were compared with the behaviour of the low viscosity and high-fragility polyurethane structural adhesive (NOA72^®), that is well known as an excellent material for the fabrication of sub-micrometer structures by soft-lithography techniques, and whose structural elastic properties inside restricted geometric systems have been recently investigated.     

Novel conductive nanocomposites from perfluoropolyether waterborne polyurethanes and carbon nanotubes

The exceptional electrical conductivity of carbon nanotubes (CNTs) has been exploited for the preparation of conductive nanocomposites based on a large variety of insulating polymers. Among these, perfluoropolyether‐polyurethanes (PFPE‐PUs) represent a class of highly performing fluorinated materials with excellent water/oil repellency, chemical resistance, and substrate adhesion. The incorporation of highly conductive fillers to this class of highly performing materials allows them to be exploited in new technological and industrial fields where their unique properties need to be combined with the electrical conductivity or the electrostatic dissipation properties of carbon nanotubes. However, no studies have been presented so far on nanocomposites based on PFPE‐PUs and CNTs. In this work, polymer nanocomposites based on waterborne PFPE‐PUs and increasing amounts of carboxylated multiwall CNTs (COOH‐CNTs) were prepared and characterized for the first time. The effect of increasing concentration of COOH‐CNTs on the physical, mechanical, and surface properties of the nanocomposites was investigated by means of rheological measurements, dynamic mechanical analysis, thermal characterization, optical contact angle measurements, and scanning electron microscopy. In addition, electrical measurements showed that the highly insulating undoped PFPE‐PU system undergoes substantial modifications upon addition of COOH‐CNTs, leading to the formation of conductive nanocomposites with electrical conductivities as high as 1 S/cm. The results of this study demonstrate that the addition of COOH‐CNTs to PFPE‐PU systems represents a promising strategy to expand their possible use to technological applications where chemical stability, water/oil repellence and electrical conductivity are simultaneously required. Copyright © 2014 John Wiley & Sons, Ltd.     

Aggregation of perfluoropolyether carboxylic salts in aqueous solutions. Fluorescence probe study

Aqueous solutions of anionic surfactants Cl(C3F6O)nCF2COOX, consisting of n = 2 and 3 perfluoroisopropoxy units and the counterion X = Na+ or NH4+, were studied by the method of fluorescence quenching with the use of (1-pyrenylbutyl)trimethylammonium bromide as a luminophore, and 1,1'-dimethyl-4,4'bipyridinium dichloride (methyl viologen) as a quencher. From the kinetics of fluorescence decay (time-resolved experiments) micellar aggregation numbers, N, and rate constants of the intramicellar quenching were determined for a wide range of surfactant concentrations, on the basis of the model developed by Infelta and Tachiya. The results are discussed in terms of the shape of the aggregates and the degree of counterion binding. The most important conclusions include: (i) a significant increase of N with increasing surfactant concentration suggests that spherical micelles formed at critical micellar concentration (CMC) transform into ellipsoidal aggregates, (ii) the degree of counterion binding to micelles is higher for NH4+ than for Na+, leading to higher N values in the case of the ammonium salt (n = 2), and (iii) at concentrations close to CMC the longer chain surfactant (n = 3) forms loose aggregates suggesting significant permeation with water molecules. An additional finding of this study is that the micelle-bound luminophore and quencher can form a ground-state complex, and for this reason the N values cannot be evaluated properly from the steady-state fluorescence intensity data using the equation proposed by Turro and Yekta.     

Morphology of poly(p‐oxybenzoyl) prepared in perfluoropolyether

Solvent effect on the morphology of poly(p‐oxybenzoyl) (POB) prepared by the reaction‐induced phase separation of oligomers was examined by the polymerization of p‐acetoxybenzoic acid in perfluoropolyether Aflunox^TM (AFL2507 and AFL606). Polymerization was carried out at 320°C for 6 hr. POB microspheres were formed in AFL2507 by the liquid–liquid phase separation of oligomers due to the low miscibility of oligomers in AFL2507. The molecular weight of the solvent influenced the morphology, and the polymerization in AFL606 of which the molecular weight was lower than AFL2507 yielded whiskers formed by crystallization of oligomers induced by the increase in miscibility compared with that in AFL2507. The solvent structure and its molecular weight influenced the miscibility of oligomers and ultimately controlled the morphology from whisker to microsphere. Copyright © 2004 John Wiley & Sons, Ltd.     

Adhesion and friction properties of molecularly thin perfluoropolyether liquid films on solid surface

The adhesion and friction properties of molecularly thin perfluoropolyether (PFPE) lubricant films dip-coated on a diamond-like carbon (DLC) overcoat of magnetic disks were studied using a pin-on-disk-type micro-tribotester that we developed. The load and friction forces were simultaneously measured on a rotating disk surface under an increasing/decreasing load cycle and slow sliding conditions. Experiments were performed using two types of PFPE lubricants: Fomblin Z-tetraol2000S with functional end-groups and Fomblin Z-03 without any end-group. The curves of the friction force as a function of the applied load agree with the curves estimated using the Johnson-Kendall-Roberts (JKR) model. The friction forces on the Z-03 films having different thicknesses were not found to decrease drastically; however, the friction forces on the Z-tetraol film were found to decrease drastically when the film thickness is more than ~1.2 nm. This drastic change in the case of the Z-tetraol film is estimated to be affected by the coverage of the lubricant film.     

Tracking lubricants during single screw extrusion of uPVC

Lubrication is one of the most important parameters in unplasticized polyvinyl chloride (uPVC) processing apart from the PVC resin and processing equipment. Lubricants are used in specific ratios to ensure effective fusion of PVC particles. The exact mechanism on how these lubricants interact is not yet fully understood. A widely accepted theory is the interaction mechanism proposed by Rabinovic et al. where lubricants are said to act as surfactants and slip agents. In this study a method for tracking lubricants, by simulating the extrusion process within a single screw extruder, was proposed. A three stage fusion simulation consisted of the feeding zone (stage 1), the compression zone (stage 2) and the metering zone (stage 3). The association interactions between the individual components of a typical uPVC formulation were followed throughout the three stages. External polar and nonpolar lubricants in combination with an internal lubricant was studied. Lubricants were successfully tracked using scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). In conclusion it was found that the use of an internal lubricant promotes dispersion of external lubrication towards PVC. It was also found that there is a competition between the internal lubricant and polar external lubricant.     

Autophobic dewetting of Z-tetraol perfluoropolyether lubricant films on the amorphous nitrogenated carbon surface

The thermodynamic stability of thin films of the perfluoropolyether (PFPE) Z-Tetraol, as a function of molecular weight, on amorphous nitrogenated carbon, CNx, is investigated. An optical surface analyzer is used to image the autophobic dewetting of the Z-Tetraol films. Film dewetting results when the PFPE film thickness applied to the CNx surface exceeds a critical value. This critical dewetting thickness is identified as the monolayer thickness of the adsorbed PFPE film via measurements of the changes in the surface energy as a function of lubricant film thickness. The observed dewetting coincides with the film thickness at which the disjoining pressure goes to zero. The critical dewetting thickness is dependent on the PFPE molecular weight.