A smart friction control strategy enabled by CO2 absorption and desorption.

Intelligent control of friction is an attractive but challenging topic and it has rarely been investigated for full size engineering applications. In this work, it is instigated if it would be possible to adjust friction by controlling viscosity in a lubricated contact. By exploiting the ability to adjust the viscosity of the switchable ionic liquids, 1,8-Diazabicyclo (5.4.0) undec-7-ene (DBU)/ glycerol mixture via the addition of CO2, the friction could be controlled in the elastohydrodynamic lubrication (EHL) regime. The friction decreased with increasing the amount of CO2 to the lubricant and increased after partial releasing CO2. As CO2 was absorbed by the liquid, the viscosity of the liquid increased which resulted in that the film thickness increased. At the same time the pressure-viscosity coefficient decreased with the addition of CO2. When CO2 was released again the friction increased and it was thus possible to control friction by adding or removing CO2.

Lignin from Hardwood and Softwood Biomass as a Lubricating Additive to Ethylene Glycol.

Ethylene glycol (EG)-based lubricant was prepared with dissolved organosolv lignin from birch wood (BL) and softwood (SL) biomass. The effects of different lignin types on the rheological, thermal, and tribological properties of the lignin/EG lubricants were comprehensively investigated by various characterization techniques. Dissolving organosolv lignin in EG results in outstanding lubricating properties. Specifically, the wear volume of the disc by EG-44BL is only 8.9% of that lubricated by pure EG. The enhanced anti-wear property of the EG/lignin system could be attributed to the formation of a robust lubrication film and the strong adhesion of the lubricant on the contacting metal surface due to the presence of a dense hydrogen bonding (H-bonding) network. The lubricating performance of EG-BL outperforms EG-SL, which could be attributed to the denser H-bonding sites in BL and its broader molecular weight distribution. The disc wear loss of EG-44BL is only 45.7% of that lubricated by EG-44SL. Overall, H-bonding is the major contributor to the different tribological properties of BL and SL in EG-based lubricants.

Comparative Study of the Effect of Defects on Selective Adsorption of Butanol from Butanol/Water Binary Vapor Mixtures in Silicalite-1 Films.

A promising route for sustainable 1-butanol (butanol) production is ABE (acetone, butanol, ethanol) fermentation. However, recovery of the products is challenging because of the low concentrations obtained in the aqueous solution, thus hampering large-scale production of biobutanol. Membrane and adsorbent-based technologies using hydrophobic zeolites are interesting alternatives to traditional separation techniques (e.g., distillation) for energy-efficient separation of butanol from aqueous mixtures. To maximize the butanol over water selectivity of the material, it is important to reduce the number of hydrophilic adsorption sites. This can, for instance, be achieved by reducing the density of lattice defect sites where polar silanol groups are found. The density of silanol defects can be reduced by preparing the zeolite at neutral pH instead of using traditional synthesis solutions with high pH. In this work, binary adsorption of butanol and water in two silicalite-1 films was studied using in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy under equal experimental conditions. One of the films was prepared in fluoride medium, whereas the other one was prepared at high pH using traditional synthesis conditions. The amounts of water and butanol adsorbed from binary vapor mixtures of varying composition were determined at 35 and 50 °C, and the corresponding adsorption selectivities were also obtained. Both samples showed very high selectivities (100-23 000) toward butanol under the conditions studied. The sample having low density of defects, in general, showed ca. a factor 10 times higher butanol selectivity than the sample having a higher density of defects at the same experimental conditions. This difference was due to a much lower adsorption of water in the sample with low density of internal defects. Analysis of molecular simulation trajectories provides insights on the local selectivities in the zeolite channel network and at the film surface.

Adsorption of Butanol and Water Vapors in Silicalite-1 Films with a Low Defect Density.

Pure silica zeolites are potentially hydrophobic and have therefore been considered to be interesting candidates for separating alcohols, e.g., 1-butanol, from water. Zeolites are traditionally synthesized at high pH, leading to the formation of intracrystalline defects in the form of silanol defects in the framework. These silanol groups introduce polar adsorption sites into the framework, potentially reducing the adsorption selectivity toward alcohols in alcohol/water mixtures. In contrast, zeolites prepared at neutral pH using the fluoride route contain significantly fewer defects. Such crystals should show a much higher butanol/water selectivity than crystals prepared in traditional hydroxide (OH-) media. Moreover, silanol groups are present at the external surface of the zeolite crystals; therefore, minimizing the external surface of the studied adsorbent is important. In this work, we determine adsorption isotherms of 1-butanol and water in silicalite-1 films prepared in a fluoride (F-) medium using in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. This film was composed of well intergrown, plate-shaped b-oriented crystals, resulting in a low external area. Single-component adsorption isotherms of 1-butanol and water were determined in the temperature range of 35-80 °C. The 1-butanol isotherms were typical for an adsorbate showing a high affinity for a microporous material and a large increase in the amount adsorbed at low partial pressures of 1-butanol. The Langmuir-Freundlich model was successfully fitted to the 1-butanol isotherms, and the heat of adsorption was determined. Water showed a very low affinity for the adsorbent, and the amounts adsorbed were very similar to previous reports for large silicalite-1 crystals prepared in a fluoride medium. The sample also adsorbed much less water than did a reference silicalite-1(OH-) film containing a high density of internal defects.The results show that silicalite-1 films prepared in a F- medium with a low density of defects and external area are very promising for the selective recovery of 1-butanol from aqueous solutions.

Colloidal Defect-Free Silicalite-1 Single Crystals: Preparation, Structure Characterization, Adsorption, and Separation Properties for Alcohol/Water Mixtures.

In this work, colloidal silicalite-1 single crystals are for the first time synthesized using fluoride as mineralizing agent at near neutral pH. SEM, TEM, DLS, XRD, solid-state (29)Si MAS NMR, and adsorption/desorption experiments using nitrogen, water, n-butanol, and ethanol as adsorbates were used to characterize the crystals. The single crystals have a platelike habit with a length of less than 170 nm and an aspect ratio (length/width) of about 1.2, and the thickness of the crystals is less than 40 nm. Compared with silicalite-1 crystals grown using hydroxide as mineralizing agent, the amount of structural defects in the lattice is significantly reduced and the hydrophobicity is increased. Membrane separation and adsorption results show that the synthesized defect-free crystals present high selectivity to alcohols from alcohol/water mixtures. The n-butanol/water adsorption selectivities were ca. 165 and 14 for the defect-free crystals and a reference sample containing defects, respectively, illustrating the improvement in n-butanol/water selectivity by eliminating the polar silanol defects.

Adsorption of water and butanol in silicalite-1 film studied with in situ attenuated total reflectance-Fourier transform infrared spectroscopy.

Biobutanol produced by, e.g., acetone-butanol-ethanol (ABE) fermentation is a promising alternative to petroleum-based chemicals as, e.g., solvent and fuel. Recovery of butanol from dilute fermentation broths by hydrophobic membranes and adsorbents has been identified as a promising route. In this work, the adsorption of water and butanol vapor in a silicalite-1 film was studied using in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy to better understand the adsorption properties of silicalite-1 membranes and adsorbents. Single-component adsorption isotherms were determined in the temperature range of 35-120 °C, and the Langmuir model was successfully fitted to the experimental data. The adsorption of butanol is very favorable compared to that of water. When the silicalite-1 film was exposed to a butanol/water vapor mixture with 15 mol % butanol (which is the vapor composition of an aqueous solution containing 2 wt % butanol, a typical concentration in an ABE fermentation broth, i.e., the composition of the gas obtained from gas stripping of an ABE broth) at 35 °C, the adsorption selectivity toward butanol was as high as 107. These results confirm that silicalite-1 quite selectively adsorbs hydrocarbons from vapor mixtures. To the best of our knowledge, this is the first comprehensive study on the adsorption of water and butanol in silicalite-1 from vapor phase.

The facile assembly of nanocrystals by optimizing humidity.

The ambient humidity and the nature of substrates are considered coordinately in the assembly of nano-sized crystals. The nanocrystal monolayers show large-area uniformity without any aggregates. Zeolite and hematite monolayers with thicknesses of 20-100 nm and excellent orientations are produced.

Nanoporous membranes with cellulose nanocrystals as functional entity in chitosan: removal of dyes from water.

Fully biobased composite membranes for water purification were fabricated with cellulose nanocrystals (CNCs) as functional entities in chitosan matrix via freeze-drying process followed by compacting. The chitosan (10 wt%) bound the CNCs in a stable and nanoporous membrane structure with thickness of 250-270 µm, which was further stabilized by cross-linking with gluteraldehyde vapors. Scanning electron microscopy (SEM) studies revealed well-individualized CNCs embedded in a matrix of chitosan. Brunauer, Emmett and Teller (BET) measurements showed that the membranes were nanoporous with pores in the range of 13-10nm. In spite of the low water flux (64 Lm(-2) h(-1)), the membranes successfully removed 98%, 84% and 70% respectively of positively charged dyes like Victoria Blue 2B, Methyl Violet 2B and Rhodamine 6G, after a contact time of 24h. The removal of dyes was expected to be driven by the electrostatic attraction between negatively charged CNCs and the positively charged dyes.

A uniformly oriented MFI membrane for improved CO2 separation.

Membrane separation of CO2 from natural gas, biogas, synthesis gas, and flu gas is a simple and energy-efficient alternative to other separation techniques. But results for CO2 -selective permeance have always been achieved by randomly oriented and thick zeolite membranes. Thin, oriented membranes have great potential to realize high-flux and high-selectivity separation of mixtures at low energy cost. We now report a facile method for preparing silica MFI membranes in fluoride media on a graded alumina support. In the resulting membrane straight channels are uniformly vertically aligned and the membrane has a thickness of 0.5 µm. The membrane showed a separation selectivity of 109 for CO2/H2 mixtures and a CO2 permeance of 51×10(-7) mol m(-2) s(-1) Pa(-1) at -35 °C, making it promising for practical CO2 separation from mixtures.

Influence of Zn(II) on the adsorption of arsenate onto ferrihydrite.

Addition of iron oxide to arsenic-contaminated soil has been proposed as a means of reducing the mobility of arsenic in the soil. Arsenic and zinc are common coexisting contaminants in soils. The presence of zinc therefore may affect the adsorption properties of arsenic on iron oxide, and may thus affect its mobility in the soil. The influence of Zn(II) on the adsorption of arsenate ions on iron oxide was studied. Batch adsorption experiments indicated that Zn(II) increased the arsenate removal from a solution by ferrihydrite at pH 8. However, ATR-FTIR spectroscopy showed that no adsorption of arsenate on a ferrihydrite film occurred at pD 8 in the presence of Zn(II). Precipitation of zinc hydroxide carbonate followed by arsenate adorption onto the precipitate was found to be a plausible mechanism explaining the arsenate removal from a solution in the presence of Zn(II) at pH/pD 8. The previously suggested mechanisms attributing the enhanced removal of arsenate from solution in the presence of Zn(II) to additional adsorption on iron oxides could not be verified under the experimental conditions studied. It was also shown that at pH/pD 4, the presence of Zn(II) in the system did not significantly affect the adsorption of arsenate on ferrihydrite.

Dynamic properties of water in silicalite-1 powder.

Self-diffusion of D(2)O in partially filled silicalite-1 crystals was studied at 25°C by (2)H nuclear magnetic resonance (NMR) with bipolar field gradient pulses and longitudinal Eddy-current-delay. For the first time, reliable experimental diffusion data for this system were obtained. Analysis of NMR diffusion decays revealed the presence of a continuous distribution of apparent self-diffusion coefficients (SDCs) of water, ranging from 10(-7) to ∼10(-10) m(2)/s, which include values much higher and lower than that of bulk water (∼10(-9) m(2)/s) in liquid phase. The observed distribution of SDC changes with variation of the diffusion time in the range of 10-200 ms. A two-site Kärger exchange model was successfully fitted to the data. Finally, the water distribution and exchange in silicalite-1 pores were described by taking into account (a) a gas-like phase in the zeolite pores, a gas-like phase in mesopores and an intercrystalline gas-like phase and (b) intercrystalline liquid droplets with intermediate exchange rate with the other phases. The other phases experience fast exchange on the NMR diffusion time scale. Diffusion coefficients and mean residence times of water in some of these states were estimated.

Semi-deterministic chemo-mechanical model of boundary lubrication.

A model for tribofilm growth is developed. The model is used in combination with numerical contact mechanics tools to enable evaluation of the combined effects of chemistry and contact mechanics. The model is tuned with experimental data and is thereafter applied to rough surfaces. The growth of the tribofilm is evaluated for 3 different contact cases and short-term tribofilm growth behaviour is analyzed. The results show how tribofilms grow in patches. The model is expected to be used as a tool for analysis of the interaction between rough surfaces.

In situ ATR-FTIR studies on the competitive adsorption of arsenate and phosphate on ferrihydrite.

In the present study, in situ ATR-FTIR spectroscopy was used for the first time to study the competitive adsorption of phosphate and arsenate on ferrihydrite. Deuterium oxide was used as solvent to facilitate the interpretations of recorded infrared spectra. It was found that arsenate and phosphate adsorbed more strongly at lower pD-values, showing similarities in the adsorption behavior as a function of pD. However, arsenate complexes were found to be more strongly adsorbed than phosphate complexes in the pD range studied. About five times higher concentration of phosphate in solution was needed to reduce the absorbance due to pre-adsorbed arsenate to the same relative level as for pre-adsorbed phosphate, which was desorbed using a solution containing equal (molar) concentrations in arsenate and phosphate. At pD 4, two phosphate complexes were adsorbed on the iron oxide, one deuterated and one de-deuterated. When phosphate was pre-adsorbed and arsenate subsequently added to the system, the deuterated phosphate complex desorbed rapidly while the de-deuterated phosphate complex was quite stable. At pD 8.5, only the de-deuterated phosphate complex was adsorbed on the iron oxide. Moreover, the arsenate adsorbed was also predominantly de-deuterated as opposite to the arsenate adsorbed at pD 4. During the substitution experiments the configuration of these complexes on the iron oxide surface did not change. To the best of our knowledge, this is the first time this difference in stability of the different phosphate complexes is reported and shows the power of employing in situ spectroscopy for this kind of studies.

Zeolite coated ATR crystals for new applications in FTIR-ATR spectroscopy.

Thin silicalite-1 films were grown on ATR crystals and used for detection of low amounts of organic molecules in a gas flow by FTIR spectroscopy.