text:
Permeable polyaniline articles for gas separation
Immersion precipitation of solutions having 15%-30% (w/w) and various molecular weights of the emeraldine base form of polyaniline in polar aprotic solvents are shown to form integrally skinned asymmetric membranes and fibers having skin layers <1 μm thick which exhibit improved rates of gas transport while preserving good selectivity. These membranes can be further transformed by an acid doping process after fabrication to achieve excellent permeation rates and high selectivities for particular gas separations. Prior to the use of concentrated EB solutions, the formation of integrally skinned asymmetric membranes was not possible, since films and fibers made from <5% w/w polyaniline solutions were found to disintegrate during the IP process.
Wang, Hsing-lin (Los Alamos, NM)
Mattes, Benjamin R. (Sante Fe, NM)
The Regents of The University of California (Los Alamos, NM)
427/337, 427/385.5, 524/236, 528/422, 528/501
C08G73/02; C08J3/09; D01F6/76; H01B1/12; (IPC1-7): B05D3/10; C08G73/00; C08K5/17
427/336, 524/236, 528/501, 528/422, 427/385.5, 427/337
5358556 Membranes having selective permeability 1994-10-25 Kaner et al.
5278213 Method of processing neutral polyanilines in solvent and solvent mixtures 1994-01-11 Han et al.
4818254 Semi-permeable membranes consisting predominantly of polycarbonates derived from tetrahalobisphenols 1989-04-04 Anand et al. 55/316
E. J. Oh et al., "Polyaniline Dependency of Selected Properties on Molecular Weight." Synthetic Metals, 55-57, 977-982 (1993).*
"Membrane Separation Systems", U.S. Department of Energy, DE 90-011771 (1990).
J. Haggin, "New Generation of Membranes Developed for Industrial Separations", Chem. Eng. News 66, 7 (1988).
R. W. Baker, "Membrane Separation Systems: A Research & Development Needs Assessment", U.S. Department of Energy, DE 90-011770 (1990).
M.R. Anderson et al., "Conjugated Polymer Films For Gas Separations", Science 252, 1412 (1991).
L. Rebattet et al., "Effect of Doping Treatment on Gas Transport Properties and on Separation Factors of Polyaniline Membranes", J. Appl. Polym. Sci. 57, 1595 (1995).
J. M. S. Henins and M. R. Tripodi, "Composite Hollow-Fiber Membranes for Gas Separation: The Resistance Model Approach", J. Membr. Sci. 8, 233 (1981).
T. Vikki et al., "Thermoreversible Gels of Polyaniline: Viscoelastic and Electrical Evidence on Fusible Network Structures", Macromol. 30, 4064 (1997).
S. Kuwabata and C.R. Martin, "Investigation of the Gas-Transport Properties of Polyaniline", J. Membrane Sci. 91, 1 (1994).
Yoon, Tae H.
Freund, Samuel M.
Cottrell, Bruce H.
Parent Case Data:
CROSS REFERENCE TO OTHER APPLICATIONS
The present continuation-in-part patent application claims the benefit of application Ser. No. 09/668,556 filed on Sep. 22, 2000, now U.S. Pat. No. 6,429,282 which is a continuation-in-part of Ser. No. 09/334,719 filed on Jun. 16, 1999, now U.S. Pat. No. 6,123,883 which is a Divisional of Ser. No. 08/926,338 filed on Sep. 05, 1997, now U.S. Pat. No. 5,981,695 which is a file wrapper continuation patent application of Ser. No. 08/658,928 filed on May 31, 1996 now abandoned.
1. A method for preparing a gas-selective, permeable integrally skinned asymmetric membrane (ISAM) which comprises the steps of: (a) forming a solution including the emeraldine base form of polyaniline having between 15% and 30% by weight of polyaniline; (b) pouring the solution onto a substrate forming thereby a membrane; and, (c) immersing the membrane in a nonsolvent for polyaniline; thereby causing the emeraldine base form of polyaniline to precipitate forming an ISAM having a permeable dense skin in the vicinity of the surface of contact of the membrane with the nonsolvent and a lower density porous support portion wherein a gel inhibitor is added to the solution of the emeraldine base form of polyaniline before said step of pouring the solution.
2. The method as described in claim 1, wherein the emeraldine base form of polyaniline comprises polyaniline having MW≧53,000.
3. The method as described in claim 1, wherein the nonsolvent for polyaniline comprises water.
4. The method as described in claim 1, wherein the gel inhibitor is selected from the group consisting of primary, secondary and tertiary amines.
5. The method as described in claim 1, further including the step of drying the membrane after said step of immersing the membrane in a nonsolvent for polyaniline.
6. A method for preparing a gas-selective, permeable integrally skinned asymmetric membrane (ISAM) which comprises the steps of: (a) forming a solution of the emeraldine base form of polyaniline having between 15% and 30% by weight of polyaniline; (b) pouring the solution onto a substrate forming thereby a membrane; (c) immersing the membrane in a nonsolvent for polyaniline, thereby causing the emeraldine base form of polyaniline to precipitate forming an ISAM having a permeable dense skin in the vicinity of the surface of contact of the membrane with the nonsolvent, and a lower density porous support portion; and, caulking the dense skin after said step of immersing the membrane in a nonsolvent for polyaniline.
7. The method as described in claim 6, wherein the caulking compound comprises silicon elastomer.
8. The method as described in claim 7, wherein the silicon elastomer comprises polydimethylsiloxane.
9. The method as described in claim 1, further comprising the step of adjusting the thickness of the membrane after said step of pouring the solution onto a substrate.
10. The method as described in claim 1, further comprising the step of heating the ISAM in order to improve gas selectivity.
11. The method as described in claim 1, further comprising the step of acid doping the ISAM in order to improve gas selectivity.
12. A method for preparing a gas-selective, permeable integrally skinned asymmetric membrane (ISAM) which comprises the steps of: (a) forming a solution including the emeraldine base form of polyaniline having between 15% and 30% by weight of polyaniline and a polymer other than polyaniline; (b) pouring the solution onto a substrate forming thereby a membrane; and, (c) immersing the membrane in a nonsolvent for polyaniline, thereby causing the emeraldine base form of polyaniline to precipitate forming a blended polymer ISAM having a permeable dense skin in the vicinity of the surface of contact of the membrane with the nonsolvent, and a lower density porous support portion.
13. The method as described in claim 12, wherein said polymer other than polyaniline comprises polysulfone.
STATEMENT REGARDING FEDERAL RIGHTS
This invention was made with government support under Contract No. W-7405-ENG-36 awarded by the U.S. Department of Energy to The Regents of The University of California. The government has certain rights in the invention.
The present invention relates generally to gas separation and, more particularly to the use of integrally skinned asymmetric permeable polyaniline membranes and hollow fibers for separating gases.
Membrane-Based Chemical Separation (MBCS) systems have experienced rapid growth in U.S. industries (e.g., Monsanto, DuPont, Dow, and Union Carbide) over the past two decades and are used to separate and purify many high volume chemicals. Broadly stated, a membrane is a barrier material that allows for selective transport. High-profile chemical separations achieved with state of the art commercial membrane systems include: (1) size dependent particle removal filtration from fluid streams; (2) water desalination by reverse osmosis; (3) organic/organic separations and solvent dehydration by pervaporation; and (4) gas separations for hydrogen recovery, nitrogen production, and acid gas removal from natural gas streams. New materials with higher rates and selectivities are required by industry to advance MBCS technologies. MBCS systems permit: (a) high throughput and high selectivity to efficiently concentrate individual components from complex mixtures; (b) small numbers of mechanical parts; and (c) low capital and operating costs due to significantly reduced energy requirements. Because of these advantages, MBCS systems occupy an important place in separation technologies and are attractive for commercial process operations.
The process of separating pure components from a mixture of gases is of great industrial importance. Current gas separation technologies have several shortcomings which include high capital costs, poor energy efficiency, and generation of secondary pollution. Two principal gas separation techniques in use today are cryogenic distillation and pressure-swing gas adsorption. Membrane-based separations have more recently been proven to be economically competitive with these methods while possessing several advantages including reduced energy costs and large reductions in secondary pollution. Moreover, improvements in membrane separation systems may lead to significant savings for the energy industry. Advanced membrane systems for enriched oxygen and nitrogen production alone could save 0.4 quad units of energy per year. See, e.g., "Membrane Separation Systems", U.S. Department of Energy, DE 90-011771 (1990). New membrane systems needed to advance gas separation technology should be: (a) environmentally stable; (b) easy to manufacture and maintain; (c) low in cost; and, most importantly, (d) capable of combining high gas selectivity with high gas flux.
Air separation systems based on gas selective polymer membranes have now been commercialized by several U.S. companies. These are important separations since nitrogen and oxygen are the second and third largest commodity chemicals produced in the United States. See, e.g., J. Huggin, Chem. Eng. News 66, 7 (1988). The first commercial air separation systems used conventional engineering polymers for O2/N2 separations with selectivities in the range of 2-4. Current technology employs membranes with separation factors of 6-7, and an oxygen permeability of 2 Barrers. See, e.g., U.S. Pat. No. 4,818,254 for "Semi-Permeable Membranes Consisting Predominantly Of Polycarbonates Derived From Tetrahalobisphenols" which issued to Joginder N. Anand et al. on Apr. 4, 1989. A recent report prepared by the U.S. Department of Energy states that if stable membranes are developed with an oxygen/nitrogen separation factor of 20 and an oxygen permeability of 10 Barrers, such systems would completely displace present day cryogenic air separations. A membrane with these qualities would readily allow compressed air to be enriched to >75% oxygen or produce nitrogen of >99.9% purity. Energy costs saved in oxygen and nitrogen production, and those saved from enhanced combustion processes, would equal the energy equivalent to 105 to 106 barrels of oil per day. See, e.g., "Membrane Separation Systems: A Research Needs Assessment" by W. Koros, U.S. Department of Energy, DE 90-011770 (1990). Other important commercial gas separations include the recovery of hydrogen and the separation of nitrogen, helium, hydrogen, and carbon dioxide from natural gas.
The conjugated polymer polyaniline is stable in both its undoped and doped states and has a simple and completely reversible acid/base doping chemistry. Permeability tests on thick (25 to 50 μm) as-cast polyaniline films have shown that gases of different kinetic diameters permeate at different rates leading to high selectivity ratios for important gas pairs such as oxygen/nitrogen, hydrogen/nitrogen, and carbon dioxide/methane. See, e.g., "Conjugated Polymer Films For Gas Separations" by M. R. Anderson et al., Science 252, 1412 (1991). By partially doping polyaniline, a highly selective membrane was formed. Two recent papers have confirmed that partially doped polyaniline has the highest known oxygen/nitrogen selectivity and lies above an "upper bound" permselective behavior for both glassy and rubbery polymers. See, e.g., S. Kuwabata and C. R. Martin, J. Membrane Sci. 91, 1 (1994) and L. Rebattet et al., J. Appl. Polym. Sci. 57, 1595 (1995). The commercial potential for gas-selective polyaniline membranes has been limited, however, since there are no reports where a sufficiently thin skin (<1 μm) has been generated to achieve commercially significant gas transport rates. Since gas flux is inversely proportional to the thickness of a barrier membrane, the thinnest possible nonporous polymer layer is desired. Suitable membranes must also be able to withstand pressures of up to 100 atmospheres or more. Separations are therefore generally carried out using asymmetric membranes in which a thin layer or skin of polymer is grown on a porous structural support (asymmetric composite), or where both the thin separating layer and the porous support are the same polymer (integrally skinned asymmetric membrane or ISAM).
Accordingly, it is an object of the present invention to provide a robust, stable permeable polyaniline membrane having a significant gas transport rate and significant gas transport selectivity.
Another object of the present invention is to provide a robust, stable permeable polyaniline hollow fiber having a significant gas transport rate and significant gas transport selectivity.
Still another object of the invention is to provide a robust, stable permeable polyaniline membrane having a significant gas transport rate and oxygen/nitrogen, hydrogen/nitrogen and carbon dioxide/methane gas selectivities.
Yet another object of the present invention is to provide a robust, permeable polyaniline hollow fiber having a significant gas transport rate and oxygen/nitrogen, hydrogen/nitrogen and carbon dioxide/methane gas selectivities.
Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
To achieve the foregoing and other objects, and in accordance with the purposes of the present invention, as embodied and broadly described herein the method for preparing gas-permeable, integrally skinned, asymmetric membranes (ISAMs) hereof includes: forming a solution having between 15% and 30% w/w of the EB form of polyaniline; pouring the solution onto a substrate forming thereby a membrane; and immersing the membrane in a nonsolvent for polyaniline, thereby causing the EB form of polyaniline to precipitate forming an ISAM having a permeable dense skin in the vicinity of the surface of contact of the membrane with the nonsolvent, and a lower density porous support portion.
It is preferred that the nonsolvent for polyaniline includes water.
Preferably, the permeable dense skin is caulked by applying a coating of polydimethylsiloxane thereto.
In another aspect of the present invention in accordance with its objects and purposes, the method for preparing integrally skinned, gas-permeable hollow fibers hereof includes: forming a solution having between 15% and 30% w/w of the EB form of polyaniline; extruding the solution through the outer bore of a hollow fiber spinnerets nozzle; passing the solution through an air-gap; and subsequently directing the extruded solution into a coagulation bath containing a nonsolvent for polyaniline, whereby a hollow fiber having a permeable dense skin in the vicinity of the surfaces thereof which contact the nonsolvent and a lower-density porous interior support portion is formed.
Preferably, the outer surface of the hollow fiber is caulked by applying a coating of polydimethylsiloxane thereto.
Benefits and advantages of the invention include readily prepared, environmentally stable, high-flux, gas-permeable films and hollow fibers, the gas selectivity of the films and fibers being tunable by doping using various acids and doping levels.
The accompanying drawings, which are incorporated in and form a part of the specification, illustrate the embodiments of the present invention and, together with the description, serve to explain the principles of the invention. In the drawings:
FIG. 1 is a graph of the pressure increase on the downstream side of a permeable membrane as a function of time showing typical gas permeation measurement data.
FIG. 2 is a scanning electron microscopy (SEM) photomicrograph of the cross-section of a film made in accordance with the teachings of the present invention showing a thin, nonporous layer located on the surface and a porous substructure generated throughout the bulk of the film. The scale is 1 μm.
FIG. 3 is a SEM photomicrograph of a typical EB ISAM hollow fiber showing a thin, nonporous layer located on the outer surface of the fiber and a porous substructure generated throughout the bulk interior of the fiber.
FIG. 4 is a graph of O2/N2 selectivity as a function of polyaniline skin thickness. The scale is 500 μm.
Briefly, the present invention includes the use of solutions having 15%-30% (w/w) and various molecular weights of the emeraldine base form of polyaniline in polar aprotic solvents for forming gas permeable integrally skinned asymmetric membranes and hollow fibers (ISAMs). As described in detail in the above-identified Cross-Referenced Applications, organic bases added to these solutions are found to enhance polymer solubility and inhibit otherwise rapid gelation. Permeable flat membranes and hollow-fibers having gas-selective skin layers <1 μm thick have been generated by immersion precipitation (IP) which exhibit improved rates of gas transport while preserving good selectivity. These membranes can be further transformed by an acid doping process after fabrication to achieve excellent gas permeation rates and high selectivities for particular gas separations. Prior to the use of concentrated EB solutions the formation of integrally skinned asymmetric flat membranes and hollow fibers were not possible, since films and fibers made from <5% w/w polyaniline solutions would disintegrate during the IP process.
Immersion precipitation of highly concentrated polyaniline solutions results in ISAMs due to the solvent-nonsolvent exchange process. A thin, dense, skin layer forms at the interface between the liquid film (before solidification) and the nonsolvent, such as water on a more porous substrate layer, and is useful for separating certain gas mixtures into more concentrated gas components. However, in virtually all syntheses of such films, the resulting ISAM has defects in the skin surface. When the total defect area is greater than about 0.1% of the total surface area of the skin, the membrane cannot be used for gas separations since the selectivity is approximately unity. This is because the entire gas mixture will preferentially flow through the defect sites rather than through the dense skin which would otherwise permit smaller molecules to diffuse more rapidly than larger molecules. J. M. S. Henis and M. R. Tripodi (See, e.g., "Composite Hollow-Fiber Membranes for Gas Separation: The Resistance Model Approach", J. Membr. Sci. 8, 233 (1981)) proposed the use of polydimethylsiloxane, a high flux polymeric material layer to fill the defect sites on the skin surface. The effect is achieved by spraying one surface of a membrane, or by dipping a hollow fiber into the liquid polydimethylsiloxane. In this manner, the effect of defects on the skin surface can be minimized, thereby permitting intrinsic selectivity of the permeable membrane to be exercised.
The mechanism for gas separation in a dense membrane is similar to that for gas separation using molecular sieves wherein gases are separated by their kinetic diameter (effective size). The kinetic diameter represents the minimum pore size that will allow sorption to occur for a specific gas molecule; that is, the gas molecules dissolve in and then diffuse through the membrane matrix. Thus, the permeation mechanism consists of three steps: (1) adsorption on the upstream boundary; (2) activated diffusion through the membrane; and (3) desorption from the downstream boundary. This solution-diffusion mechanism is usually driven by a pressure difference between the upstream and downstream sides of the membrane. Differences in permeability may result from diffusivity and the physiochemical interactions (solubility) of the permeant within the polymer matrix, which determines the amount of gas that may be accommodated per unit volume. The permeability of a given homogeneous membrane under steady-state conditions can be obtained from the relationship: P=DS, where P is the bulk permeability, D is the diffusion coefficient and S is the solubility coefficient. Permeability measurements are typically made using the manometric time-lag analysis in which permeable membrane is located between two closed chambers, one chamber being pressurized with the diffusing gas and the other chamber, initially evacuated, increases in pressure as the gas diffuses. A typical graph of the downstream pressure as a function of time is shown in FIG. 1 hereof. The time axis intercept at steady state yields the diffusion coefficient, D, and the slope of the steady state line is equal to P, from which the solubility coefficient S can be obtained.
The permeability of a membrane is defined as the volume of gas permeates per unit transmembrane driving force per membrane thickness, per time period. The permeability unit in this patent application is in Barrers, where 1 Barrer is 10−10 [cm3. STP·cm/cm2·s·cmHg]. Permeance is defined the permeability divided by the membrane thickness and is the volume of the gas permeate per unit transmembrane driving force, per time period in units of 10−10 [cm3·STP/cm2·s·cmHg]. The membrane selectivity for certain gas pairs is defined as the ratio of permeability of fast gas vs. permeability of slow gas.
Permeability measurements on ISAMs and hollow fibers made in accordance with the present invention were performed using the pressure decay for pure gases. Measurements were made for He, H2, O2, N2, CO2, Ar and CH4.
High-molecular weight (MW≧120,000) Polyaniline was synthesized by oxidative polymerization at −45° C. Medium-molecular weight polyaniline (100,000≦MW<120,000) was purchased from NESTE Oy, while Low-molecular weight polyaniline (MW<100,000) was prepared by oxidative polymerization at ≧0° C. It is preferred to use high-molecular weight EB for forming immersion precipitation films and hollow fibers.
Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings.
In a first embodiment of the present invention, ISAMs were prepared from the EB form of polyaniline by the phase inversion process. A nonsolvent gel inhibitor (GI) is added to a solvent for polyaniline EB to prevent gelation once the EB is added. One particularly good solvent for polyaniline EB, N-methyl pyrrolidinone (NMP), is used extensively in what follows hereinbelow. The resulting solution is poured onto a glass plate forming a wet film. Approximate film thickness is determined by passing an adjustable Gardner blade over the wet film. The membrane is subsequently immersed in a water bath which causes the polymer to precipitate with a permeable thin skin and an underlying porous substructure. This substructure is formed by percolation pathways produced by the rapid solvent exchange between the polymer solvent (NMP) and the water in the coagulation bath. The membrane is then immersed in a methanol bath to extract residual solvent, dried in a vacuum oven, coated with a layer of silicon elastomer, and tested for gas permeation.
FIG. 2 shows different regions of the films cross-section as visualized by scanning electron microscopy (SEM). It is clear from the SEM output that there is a thin nonporous layer located on the surface with a porous substructure situated throughout the bulk of the film. The casting knife setting was adjusted to give a wet film thickness in the range from 25 to 40 mil. Each wet film sample was either exposed to a controlled relative humidity chamber containing 75% to 90% water or immersed immediately after casting into a coagulation bath, typically water. The dielectric properties of the coagulation bath were controlled by adding inorganic salts or alcohol to effect the rates of demixing during precipitation.
In another embodiment of the present invention, polyaniline and its derivatives are dissolved in solvent/nonsolvent systems at concentrations high enough (18-30%) to enable the production of hollow fibers. Briefly, the polymer solution is extruded through the outer bore of a hollow fiber spinnerrette nozzle, while a nonsolvent for the polymer, such as water, is simultaneously co-injected through the inner bore of the nozzle. The extruded solution is then passed through an air-gap and into a coagulation bath which precipitates the polymer forming a dense, gas-permeable skin and porous substructure (asymmetric wall structure). The asymmetry can be controlled to give structures with: a) a thin "pin-hole" free skin resting on top of a porous substructure (ISAM); b) a nanoporous structure; c) an ultraporous structure; or microporous structures. The fiber is taken up through a series of baths which removes the solvents and nonsolvents via the uptake reel of a Leesona winder. Typically, solution compositions that yield good flat sheet ISAMs are easily modified to suitable compositions for hollow fiber production. Hollow fibers spun from conjugated polymers have been fabricated into test modules suitable for field testing. FIG. 3 shows the SEM output from a typical EB ISAM hollow fiber.
Having generally described the invention, the following EXAMPLES provide greater detail. Gel inhibitors used in these EXAMPLES include primary, secondary and tertiary amines as follows: the primary amine: n-Butylamine; the secondary amines: 2,5-Dimethyl-3-pyrroline, 3,3-Dimethylpiperidine, Heptamethyleneimine, Diisopropylamine, Hexamethyleneimine, N-ethylbenzylamine, Piperazine, 2,6-Dimethylmorpholine, Piperidine, and Dibutylamine; the tertiary amines: N-Methylpiperidine, N,N′-Dimethylpiperazine, and Triethylamine; and an amine having a bifunctional group: Diethylnipecotinamide.
Gas permeability of ISAMs prepared from highly concentrated, high-molecular weight (MW≧120,000) polyaniline emeraldine base solutions using secondary amines as gel inhibitors:
To a solution of 1.416 g of NMP and 171 mg of piperazine, 300 mg of high-molecular weight (HMW) polyaniline EB prepared at −45° C. was added, the resulting mixture stirred for a few minutes and placed in an oven at 58° C. for approximately 5 min. until a homogeneous solution was formed. The mass content of HMW EB in this solution was ˜15.9% w/w. Once the solution was formed, it was spread onto a glass plate and the wet film was drawn by setting the draw-down blade at 0.006 in. The film was then immersed in 15° C. water nonsolvent. The IP film was kept in the water for 24 h, air dried for a few hours and then placed overnight in a vacuum oven. A 100% silicon elastomer caulking layer was then applied to the membrane surface and allowed to dry overnight before the membrane was placed inside the test cell held at 27° C. for measurements of the gas permeation properties. Table 1 shows that the membrane selectivities for O2/N2 fall in the range between 6 and 8. This is consistent with the selectivity of an EB dense membrane.
Gel-Inhibitor
EB mass
content He H2 N2 O2 CO2 CH4 H2/N2 O2/N2 CO2/CH4
2,5-dimethyl-3- 69526 103876 1778 12566 62938 1474 58.4 7.07 42.70
pyrroline
(15.8%)
N-ethylbenzyl- 76834 119483 2443 14964 71083 2501 48.9 6.13 28.4
amine (15.6%)
Piperazine 49017 73541 934 7167 33969 944 78.7 7.67 36.0
2,6-dimethyl- 54890 87131 2994 17784 66355 2944 29.1 5.94 22.5
morpholine Micron
Piperidine 53570 77485 7389 926 28743 885 83.7 7.98 32.48
Dibutylamine 44812 63013 1272 7802 34240 2183 49.5 6.00 15.7
Hexamethylene- 37890 48533 2431 414 8800 1015 117.0 5.87 8.67
imine (21.7%)
Mixture of 43892 55397 3435 487 14195 778 113.66 7.05 18.24
thiomorpholine
(0.390 g) and
2-methyl-
aziridine (0.290 g)
Gas permeability of the ISAM membrane prepared from >20% w/w of medium-molecular weight (100,000≦MW<120,000) EB polyaniline solutions from a commercial manufacturer thereof (See, e.g., T. Vikki et al., Macromol. 30, 4064 (1997)):
To a solution of 3.166 g of NMP and 150 mg of 3,3-dimethylpiperidine, 911 mg of medium-molecular weight EB polyaniline (from NESTE Oy, Inc.) was added, the mixture stirred for several minutes and placed in an oven at 60° C. for approximately 20 min. until a homogeneous solution was formed. The mass content of NESTE EB in this solution was ˜21.6% w/w. The solution was poured onto a glass plate and the wet film was drawn by setting the draw down blade to 0.006 in. It was then immersed in water at 15° C. where it was kept for 24 h. The IP film was air dried for several hours and placed in a vacuum oven overnight. A 100% silicon elastomer caulking layer was applied to the membrane surface and dried overnight before being placed inside the test cell to measure the gas permeation properties at 27° C. Table 2 shows the results of these measurements. It may be observed that the selectivity for O2/N2 gas pairs from these membranes is between approximately 7 and 9.
Gel-Inhibitor Average
EB Mass Skin H2/ O2/ CO2/
Content He H2 N2 O2 CO2 CH4 Thickness N2 N2 CH4
n-butylamine 77114 120737 2646 18276 96398 2701 0.088 μm 46 6.90 35.7
Triethylamine 61545 98837 2601 18039 81233 1962 0.098 μm 38 6.94 41.4
3,3-dimethyl- 75914 114646 1969 14676 60018 1730 0.125 μm 58 7.45 34.7
piperidine
Heptamethylene- 66418 96976 1290 9843 42215 1086 0.188 μm 75 7.60 38.9
imine
Diisopropyl- 58078 68537 416 3724 14414 356 0.547 μm 165 8.95 40.5
The gas permeability for various skin thickness for polyaniline membranes prepared from solutions in which GIs were used with NMP solvent was investigated. FIG. 4 is a graph of the O2/N2 selectivity versus polyaniline membrane skin thickness and shows that selectivity of O2/N2 is an approximately linear function of the thickness of the membrane. The average skin thickness is estimated to vary between 0.088 μm and 0.547 μm. and was derived from the average value of the apparent skin thickness from the permeance of CO2, O2, N2 and CH4 (Apparent skin thickness=[Permeance of dense film/Permeance of ISAM]× known thickness of dense film). Low gas fluxes were observed for He and H2 yielding abnormally high apparent skin thickness values. As a result, the permeance of these gases was thought to be largely limited by the caulking layer and, therefore, apparent skin thickness values derived therefrom expected to be unreliable.
Gas permeability of ISAMs prepared from >20% w/w low-molecular weight (64,000<MW≦100,000) polyaniline EB solutions:
EB polyaniline was synthesized at approximately 0° C. To a solution of 3.030 g of NMP and 0.390 g of N-methylpiperidine, 909 mg of low-molecular weight (LMW) EB was added, the mixture was stirred for a few minutes and placed in an oven at 60° C. for approximately 10 min. until a homogeneous solution was formed. The mass content of LMW EB in this solution was 21.0% w/w. The solution was then spread onto a glass plate, the wet film drawn by setting the Gardner draw-down blade to 0.006 in. and immersed in water at 20° C. where it was kept for 24 h. The film was air dried for several hours before it was placed overnight in a vacuum oven. A 100% silicon elastomer was used to caulk the membrane which was then allowed to dry overnight to solidify the elastomer. The resulting film was placed into a test cell at 27° C. to measure the gas permeation properties thereof. The results of these measurements are set forth in Table 3 hereof.
Gel-Inhibitor He H2 N2 O2 CO2 CH4 H2/N2 O2/N2 CO2/CH4
N-methylpiperidine 44606 69070 1123 6736 32797 1344 61.5 6.00 24.4
N,N′-dimethyl- 16211 20652 313 1651 6881 364 65.98 5.27 18.90
piperazine
Bifunctional Groups (Combined Amide and Amine Structures in a Single Molecule) Used as Gel Inhibitors:
To a solution of 3.074 g of NMP and 302 mg of N,N-Diethylnipecotinamide, 894 mg of (NESTE) EB was added, the mixture stirred for several minutes and then placed an oven at 60° C. for approximately 45 min. The resulting solution was found to be viscous. The mass content of polyaniline EB in the solution was −20.9% w/w. The solution was spread onto a glass plate and the wet film was drawn by setting the draw down blade at 0.006 in. It was then immersed in water at 15° C. where it was kept for 24 h. The film was then dried for several hours and placed overnight in a vacuum oven. A 100% silicon elastomer caulking layer was applied to the membrane surface and dried overnight before being placed in the test cell at 27° C. to measure the gas permeation properties. The results are shown in Table 4.
Gel-Inhibitor He H2 N2 O2 CO2 CH4 Thickness H2/N2 O2/N2 CO2/CH4
Diethylnipecotin- 46092 59010 926 5534 17396 905 0.327 μm 64 5.98 19.2
The results of EXAMPLES 1-4 hereof indicate that polyaniline EB having various molecular weights can be used for fabricating Integrally Skinned Asymmetric Membrane (ISAMS) suitable for gas separations. Primary, secondary and tertiary amines were used as gel inhibitors to process concentrated polyaniline solutions enabling fabrication of these membranes.
Gas Permeability of ISAMs Prepared from 20% w/w Polyaniline EB/solvent Solutions without the Use of Gel Inhibitors:
To a solution of 2.873 g of NMP, 680 mg of NESTE Oy polyaniline EB powder was added in less than 5 s. The mixture was vigorously stirred for several minutes. The mass content of polyaniline EB in this solution was ˜19.1% w/w. The solution was found to have a gelation time less than 10 min. at room temperature, and heating the solution in an oven at 60° C. caused instantaneous gelation. Prior to gelation, the solution was poured onto a glass plate and the wet film was drawn by setting the draw down blade to 0.006 in. The wet film was immersed in water at 17° C. and kept there for 24 h. The film was air dried for several hours and placed overnight in a vacuum. A 100% silicon elastomer caulking layer was applied to the membrane surface and dried overnight before the film was placed inside the test cell at 27° C. to measure the gas permeation properties. The results are shown in Table 5. Two solvents were used to prepare 20% w/w polyaniline EB/solvent IP films. The observed gas permeance indicates that IP films prepared from polyaniline EB/NMP solutions exhibit no selectivity for any of the tested gas pairs. IP films prepared from polyaniline EB/TMU (Tetramethylene Urea) solutions, however, were observed to have a selectivity of 2.4 for the O2/N2 gas pair. This is likely due to the selectivity of the silicon elastomer caulking layer and not the selectivity generated by the polyaniline EB dense skin, since no selectivity was observed for H2/N2 and CO2/CH4. The polyaniline EB/solvent solution generally appeared to be pasty which is indicative of an inhomogeneous solution.
Sample He H2 N2 O2 CO2 CH4 H2/N2 O2/N2 CO2/CH4
IP film from 368894 546117 127849 122975 196310 153308 4.27 0.96 1.28
19.1% w/w
EB/NMP solution
IP film from 20% 66825 111515 28884 70233 408549 84461 1.67 2.43 4.84
w/w EB/tetra-
methylurea
Permeance of the 767400 1287400 613000 1277300 6397100 2029400 1.68 2.08 3.15
100 μm caulking
layer (silicon
elastomer)
Gas Permeation Properties of ISAM Prepared from 20% w/w Polyaniline EB in Different Solvents Using Heptamethyleneimine as Gel Inhibitor:
To a solution of 3.155 g of 1,3-dimethyl-3,4,5,6-2(IH)tetrahydropyrimidinone and 0.309 g of heptamethyleneimine, 0.885 g of NESTE Oy EB polyaniline was added, the mixture was stirred for several minutes and placed in an oven at 60° C. for approximately 10 min. The heated mixture was again stirred until a homogeneous solution was formed. The solution was then poured onto a glass slide and draw down blade (Gardner blade) set to 0.006 in. Once the wet film was drawn, it was immersed in a water bath at 17° C. where it kept for 48 h. The film was then air dried for 24 h and placed in a vacuum oven for 24 hours. A 100% silicon elastomer was used to caulk the membrane surface which was then air dried overnight until the elastomer solidified. The membrane was loaded in the test cell at 27° C. to measure the gas permeation properties. The results are shown in Table 6. It is important to note that the above procedure is not the optimum procedure for process polyaniline EB ISAM membranes. As was shown hereinabove, the as-cast membranes should be extracted using methanol and then heated at 120° C. for 2 h in order to produce optimum permeation properties. See Table 9 hereof.
Solvent He H2 N2 O2 CO2 CH4 H2/N2 O2/N2 CO2/CH4
1,3-dimethyl- 67644 108036 1611 12717 70021 1410 67 7.89 49.7
3,4,5,6-tetrahydro-
2(IH)-pyrimidinone
n-methyl-2- 66418 96976 1290 9843 42215 1086 75 7.60 38.9
pyrrolidinone
(NMP)
n-methylcaprolactam 109240 161274 3096 18769 92850 5192 52 6.06 17.9
Dimethylacetamide 101753 154800 5415 31078 141172 7494 29 5.74 18.8
Tetramethylurea 62052 104343 5182 26559 132474 7555 20 5.13 17.5
Dimethylpropioamide 63243 110520 10697 43362 241424 21876 10 4.05 11.0
EXAMPLE 6 demonstrates that preparing the 20% w/w EB polyaniline solutions with different solvents permits the formation of ISAMs having different gas permeation properties. Table 6 is arranged such that the order O2/N2 selectivity goes from the highest to the lowest. The permeance of the O2, N2, CO2, and CH4 follows the inverse of the general trend observed for the permeance of the O2/N2 and CO2/CH4. The selectivity of the O2/N2 gas pairs varies from 8 to 4, and that for N2 changes from 1611 to 10697. Oxygen permeance changes from 12717 to 43362, while CH4 permeance changes from 1410 to 21876 and CO2 permeance changes from 70021 to 241424.
For some of the membranes described in Table 6, the permeance either He or H2 appears to be lower when compared with the permeance of CO2. Known permeabilities of the silicone caulking layer are: He: 76.74; H2: 128.74; O2: 127.73; N2: 61.3; CO2: 639.71 and CH4: 202.94, while the permeability of dense film EB is He: 4.29; H2: 4.28; O2: 0.15; N2: 0.0165; CO2: 0.72; and CH4: 0.0078. Thus, the He permeability of the silicon elastomer is a factor of 18 times that of the EB; that for H2 is a factor 29; that for O2 is a factor of 846; that for N2 is a factor of 3715; that for CO2 is a factor of 888; and that for CH4 is a factor of 2.6×104, and with a sufficiently thick caulking layer, the permeability of He and H2 will be significantly impacted.
The O2/N2 separation factor of the membrane is not likely to be affected by the caulking layer since the permeance of the N2 and O2 of the polyaniline EB membrane are both within the range that the high flux silicon elastomer can provide. In addition, the CO2 permeability of the caulking layer is so high that the thick caulking layer does not affect the measurements. It is also possible that the various films have different skin thickness as different solvents were used, or the surface porosity of the membranes are different from one another. Calculations of the average skin thicknesses based on the N2 and O2 yield values from 0.18 μm to approximately 0.038 μm.
Effect of GI/EB Molar Ratio on the Permeation Properties of Polyaniline ISAMs:
The EB/NMP/HPMI films were prepared using NESTE Oy EB powder. The GI/EB molar ratio is about twice that for the previous EXAMPLES. That is, EB=0.890 g (2.46×10−3 mole), HPMI=0.596 g (5.29×10−3 mole), NMP=3.15 g, EB polyaniline mass content of 19.2% w/w, and the GI/EB ratio=0.00527/0.00246=2.14, for the first film, while EB=1.790 g (4.494×10−3 mole), HPMI=0.593 g (5.27×10−3 mole), NMP=6.237 g, yielding a polyaniline EB mass content of 20.8% w/w, and the GI/EB ratio=0.00527/0.00494=1.07. At 27° C., the results for gas permeance for the various gases is listed in Table 7. It is observed that there is little effect on the permeation properties of the polyaniline ISAM films when the GI/EB molar ratio is varied from 1.07 to 2.14 in the solution. However, higher GI/EB molar ratios generally result in longer gelation times and lower solution viscosities.
He H2 N2 O2 CO2 CH4 H2/N2 O2/N2 CO2/CH4
Permeance of as- 66418 96976 1290 9843 42215 1086 75.2 7.63 38.9
cast asymmetric
GI/EB = 2.14
Permeance of as- 81068 106767 1235 9372 37558 1258 86.5 7.59 29.9
Effect of Polyaniline EB Mass Content in Solution on the Gas Permeation Properties of ISAMs:
ISAMs have been prepared from 20.74% w/w and 25.00% w/w concentrations of polyaniline EB in NMP/HPMI solutions. In the first, 1.774 g of NESTE EB powder (4.90×10−3 moles) was added to a solution of 6.191 g of NMP and 0.589 g of heptamethyleneimine (5.21×10−3 moles) to generate a 20.74% w/w EB solution in NMP/HPMI having a GI/EB molar ratio of 1.06. After vigorously stirring the mixture for 1 min., it was heated in an oven at 60° C. Every 5 min., the solution was removed from the oven and again stirred. This procedure was repeated at least 6 times until a flowable, homogeneous liquid was formed. The solution was poured onto a glass plate and a wet film drawn with the Gardner blade set at 0.006 in. The membrane was then immersed into water at 18° C. for 24 h. The films were then dried using paper towels to remove the excess water, air dried for several hours and placed in a vacuum oven for greater than 48 h at 10−2 Torr to remove residual moisture.
In the second procedure, 2.50 g of NESTE EB powder (6.91×10−3 mole) was added to a solution of 6.300 g of NMP and 1.203 g of heptamethyleneimine (1.06×10-2 moles) to make a 25.00% w/w polyaniline EB solution in NMP/HPMI having a GI/EB molar ratio of 1.53. The mixture was vigorously stirred for 1 min. to ensure the powder was sufficiently wet, and then heated in an oven at 60° C. Every 10 min. the solution was removed from the oven and again stirred. This procedure was repeated 5 times after which it was observed that the solution viscosity was lower than the viscosity of the starting mixture. The solution was then poured onto a glass plate and the Gardner blade set at 0.005 in. The drawn wet film was immersed into a water bath at 18° C. for 24 h. The IP films were then dried using paper towels to remove the excess water, air dried for several hours and placed in a vacuum oven to pump for greater than 48 h at 10−2 Torr to remove residual moisture. The films were then tested at 27° C. for their gas permeance characteristics. The results are set forth in Table 8 hereof. The ISAM film having 25.00% w/w EB/NMP/HPMI was found to have a smaller permeance when compared to the ISAM film prepared with 20.74% w/w, while the selectivity for O2/N2 and H2/N2 for the 25.00% w/w EB/NMP/HPMI film was observed to be better than that for the with 20.74% w/w. This is due to either the greater thickness or reduced surface defects on the membrane prepared from 25.00% w/w EB solution.
Av. Skin
Thickness He H2 N2 O2 CO2 CH4 H2/N2 O2/N2 CO2/CH4
Permeance of the 0.139 μm 71547 104317 1068 9233 44732 899 98 8.6 49.8
as-cast asymmetric
membrane from
20.7% w/w solution
Permeance of the 0. μm 82039 103458 690 5861 26436 584 150 8.49 45.3
5.0% w/w solution
Effect of Post Treatment on the Gas Permeation Properties of Polyaniline EB ISAMs:
Post membrane treatment of polyaniline EB ISAMs have significant impact on the final gas permeation properties of the membrane. Comparison is made between the as-cast membrane; the as-cast membrane thermally treated at 120° C. for 2 h; the as-cast membrane immersed in methanol for 48 h; the as-cast membrane immersed in methanol for 48 h and subsequently thermally treated at 120° C. for 2 h; and the as-cast membrane thermally cured at 120° C. for 2 h followed by immersion in methanol for 48 h. All membranes were later caulked with silicon elastomer and left to air dry overnight and then loaded in the test cell at 27° C. for the measurement of gas permeation properties. The results are set forth in Table 9 hereof. All samples were taken from the same membrane and the procedure for preparing the as-cast membrane is described hereinabove. From these results, the two most favorable method for processing are: (1) treating the as-cast film in an oven at 120° C. for 2 h followed by caulking the film with silicon elastomer; or (2) extracting the film with methanol and thermally curing the film. It should be mentioned at this point that 4 independent repetitions of these procedures were carried out whereby polyaniline EB ISAMs from 20% w/w EB solution were prepared. The permeability results for O2, N2, CO2 and CH4 were found to be reproducible. Slight variations in the gas permeance for He and H2 were observed, however. Perhaps, this reflects slight variations in the thickness of the caulking layer that was applied to the membrane surface.
Thick- H2/ O2/ CO2/
He H2 N2 O2 CO2 CH4 ness N2 N2 CH4
Permeance of the as- 66418 96976 1290 9843 422150 1086 0.27 μm 75 7.6 38.9
cast membrane
Permeance of as-cast 134749 171388 1156 9670 35736 768 0.20 μm 148 8.4 46.5
membrane, thermally
cured at 120° C.
Permeance of as-cast 107924 146358 1370 10262 40291 1124 0.20 μm 107 7.5 35.9
membrane, methanol
Permeance of as-cast 105024 125861 795 6842 24814 610 0.27 μm 158 8.6 40.7
treated then thermally
Permeance of as-cast 87821 138618 1749 13884 59558 1460 0.20 μm 79 7.9 40.8
cured at 120° C., then
methanol treated
Effect of Temperature on the Permeation Properties of the EB ISAMS:
Gas permeation properties of the EB ISAMs were measured at 24° C. and 28° C. for a membrane prepared from 25% w/w EB/NMP/HPMI solution in accordance with the procedure described hereinabove. The results are set forth in Table 10, hereof. It was observed that the gas permeance is higher at higher temperature when compared with that for lower temperature, while the selectivity for O2/N2 and CO2/CH4 improves as the temperature decreases. This result is consistent with the previous study where the measurements on the thermally cured dense film (≧40 μm) show improved selectivity as the temperature decreases (See, Wang et al. Synth. Metals 102, 1333 (1999))
Permanence of the 82039 103458 690 5861 26436 584 150 8.49 45.3
membrane at 28° C.
Permanence of the 79296 96313 647 5664 24372 506 149 8.75 48.2
Effect of the Caulking Layer on the Gas Permeation Properties of Polyaniline EB ISAMs:
The ISAM employed was prepared from a 20% EB/NMP/Heptamethyleneimine solution. The polyaniline EB powder was purchased from NESTE Oy. The thickness of the membrane was not determined and the diameter of the film was 1 in. The draw down blade was set at 0.006 in. After the film was drawn, it was immersed into water at 15° C. for 24 h. The film was then placed in a vacuum for 24 h and subsequently heated in an oven at 120° C. for 2 h. After cooling to room temperature, the film was immersed in methanol for 48 h, placed under vacuum for 48 h, and a 1% silicon elastomer was applied to the skin surface. The film was placed in a vacuum for another 24 h before it was loaded in the test cell at 25° C. After the measurement of the gas permeability of is this IP film, a second coating 1% of silicon elastomer in cyclohexane solution was applied, the film placed under vacuum for 24 h and the gas permeability remeasured. The same film was again caulked with layer of 5% silicon elastomer in cyclohexane solution, placed in a vacuum 24 h and the gas permeability tested. The results are shown in Table 11 hereof. In this Example, dilute silicon elastomer solutions were used to caulk the surface defects in order to minimize the thickness of this layer. This minimizes the impact of the caulking layer on gas permeances, especially those for He and H2. Selectivity of all gas pairs are observed to be similar to those for thermally cured dense films (≧40 μm) that are defect free.
Permeance dense 713.5 710.4 2.46 26.0 119.6 1.40 290 10.6 86
Permeance of as-cast 604810 807535 155267 149310 154955 217420 3.9 0.96 0.71
asymmetric membrane
(uncaulked)
Permeance of 199478 176441 2772 8233 28131 3397 72 3.0 8.3
membrane (caulked
with 1% silicon
Permeance of 159642 145209 481 4362 17536 348 331 9.1 50.4
elastomer and then
5% silicon elastomer)
Ratio of permeance of 224 204 196 168 147 249
IP film/dense film
Estimated film 0.25 0.27 0.29 0.33 0.38 0.23
thickness (microns)
The permeance of the film also decreases as the thickness of the coating layer increases. The gas permeance for He and H2 decreases little after a thin layer of the silicon elastomer coating was applied to the skin surface; however, the permeance for O2, N2, CO2 and CH4 drops more significantly than that for the faster gases. The estimated average thickness of the skin layer is approximately 0.27 μm. From the data, it may be observed that the best caulking method is to apply a first layer by painting a 1% silicon elastomer in cyclohexane solution on the polyaniline EB membrane, followed by a second layer over the first layer by painting a 5% silicon elastomer in cyclohexane solution on the caulked membrane.
Effect of Heat Treatment on the Gas Permeation Properties of the Polyaniline EB ISAMs:
To a solution of 3.155 g 1,3-Dimethyl,3,4,5,6-tetrahydro-2(H)-pyrimidinone and 0.309 g of heptamethyleneimine (2.73×10−3 moles), 0.885 g of NESTE EB powder (2.44×10−3 moles) was added to generate a 20.3% w/w EB/1,3-Dimethyl,3,4,5,6-tetrahydro-2(H)-pyrimidinone/HPMI solution having a GI/EB molar ratio of 1.12. After vigorously stirring the mixture for 1 min. the mixture was placed inside an oven at 58° C. for 7 min. which resulted in homogeneous solution. The solution was poured onto a glass plate and the Gardner blade set to 0.006 in. Once the wet film was drawn, it was immersed into a water bath at 18° C. for 24 h. The film was dried using paper towels to remove the excess water, air dried for several hours and placed in a vacuum oven for greater than 48 h at 10−2 Torr to ensure that residual moisture was removed. This membrane was later heat treated at various temperature by placing it in an oven under a flow of Ar gas. The membrane surface was then caulked with 100% silicon elastomer before being loaded in the test cell at 30° C. for measurement of its gas permeation properties. The results are set forth in Table 12 hereof. The membrane heat treated at temperatures below 150° C. shows slight improvement in the selectivities of all gas pairs and a slight decrease in gas permeance for most gases (CO2, O2, N2, and CH4). The membrane heat treated at 200° C. for 2 h shows a dramatic decrease on gas permeance for all gases. This is likely due to the formation of a more rigid polymer backbone structure induced by thermal crosslinking between the polymer chains.
As-cast membrane 67644 108036 1611 12717 70021 1410 67 7.89 50
As-cast membrane heat 84820 126780 1435 11719 49643 965 88 8.17 51
treated at 150° C. for 4 h
As-cast membrane heat 42150 56791 428 3509 15118 310 132 8.20 49
As-cast membrane heat 33565 42743 466 3694 16983 362 92 7.67 47
treated at 250° C. for 25
Effect of Acid Doping on the Gas Permeation Properties of Polyaniline EB ISAMs:
Measurements were obtained from 1.3 in. diameter polyaniline EB membranes dissected from the same larger membrane in order to eliminate the discrepancies arising from separate sample preparations. Membrane doping is achieved by immersing the membranes in two liters of aqueous acid solution at 25° C. for 48 h. The membranes were then air dried for several hours before being placed in a vacuum oven for 48 h to remove residual moisture. The membrane surface was subsequently caulked with 100% silicon elastomer before being loaded in the test cell at 22° C. where the gas permeation properties were measured. The results are set forth in Table 13 hereof.
Permeance of asymmetric 71546 104317 1068 9233 44732 899 98 8.6 49.8
membrane as cast
Permeance of asymmetric 38579 52718 209 2338 9132 146 252 11.2 62.5
membrane 0.00100 M HCl
doped
Permeance of asymmetric 55569 54713 77 877 3389 64.6 710 11.4 52.5
membrane 0.0050 M HCl
Permeance of asymmetric 39755 44242 53.3 796 2980 47.3 830 15.0 63
Permeance of asymmetric 44683 38873 35.8 497 1877 45.6 1087 14.1 41.5
membrane 0.0175 M HO
doped average #1 & #2
Permeance of asymmetric 18760 15248 21.5 195 750 48 709 9.1 15.6
membrane 4M HCl doped
Five months later, the 0.010 M HCl-doped ISAM was retested. The results are set forth in Table 14 hereof. Doping the IP film with different concentration of HCl aqueous solution are shown to alter the permeation properties of the ISAMs. Higher doping levels give the lowest gas permeance.
Permeance of asymmetric 39570 31703 22.7 350 1202 30 1397 15.4 40
membrane doped-dedoped-
redope by 0.01M HCL
operating temperature 30° C.
5 months later retest the 42047 31049 36.5 396.4 1266 58.9 851 10.9 21.5
same film operating
temperature 30° C.
The as cast membranes are observed to have the highest gas permeance, while the partially doped samples have intermediate permeance.
Partial doping of the polyaniline EB ISAMs gives higher CO2/CH4 selectivity (63), H2/N2 selectivity (1089), and O2/N2 selectivity (15.0) when compared to the selectivity for the as-cast membranes: (49.8) for CO2/CH4, (98) for H2/N2, and (8.6) for O2/N2. However, the higher selectivity was achieved by sacrificing the overall gas permeance of the membrane.
Still 5 months later, the 0.010 M HCl-doped EB ISAM was retested at higher temperature (30° C.). The permeance for He, H2, O2 and CO2 were essentially the same; however, the permeances for slower gases N2 and CH4 are different and increased 50% and 100%, respectively, as compared to the first measurements. The selectivity for O2/N2 is still as high as 10.9 and that for H2/N2 is 851. A series of studies using HBr as the dopant was also performed for polyaniline EB ISAMs. The results are set forth in Table 15 hereof. Doping the IP film with different concentrations of HBr in aqueous solution can alter the permeation properties of ISAMs. It is clear that higher doping levels give the lowest gas permeance. The as cast membranes have the highest gas permeance, while the partially doped samples have intermediate permeance. It was also observed that O2/N2 selectivity increases when the EB membrane was doped using 0.010 M HBr in aqueous solution. The gas permeance was observed to drop by one order of magnitude, while selectivity of O2/N2 increase from 7.6 to 10.5.
Permeance of the as 66418 96976 1290 9843 42215 1086 75.2 7.63 38.87
Permeance of 0.010 M 34020 33073 102.3 1.072 4234 1.09 332.6 10.48 38.84
HBr doped asymmetric
Permeance of 0.100 M 19409 21297 46.3 335 1344 73.7 460.0 7.30 18.23
Permeance of 4 M HBr 16415 14288 19.0 194 709 27.6 751.2 10.23 25.69
doped asymmetric
Investigation of trifluoroacitic acid as a dopant for polyaniline EB ISAMs was also performed. The results are set forth in Table 16 hereof. It was found that the permeance of the membrane decreased slightly when the EB membrane was doped using 0.010 M CF3COOH. As the concentration of the trifluoroacetic acid was increased, the gas permeance of the doped EB membrane was also found to increase. Selectivity for O2/N2 remained unchanged, while selectivity for CO2/CH4 increased from 38.87 (as cast) to 52.21.
Permeance of the as- 66418 96976 1290 9843 42215 1086 75.2 7.63 38.87
Permeance of 0.010 M 87705 98847 829 6533 23210 518 119.2 7.88 44.80
CF3COOH doped
Permeance of 0.0175 M 119083 120188 1015 7399 25788 634 118.4 7.29 40.68
Permeance of 1.0 M 66662 81494 1380 9931 53462 1024 59.1 7.20 52.21
Effect of Dopant Size on the Fully Doped Polyaniline EB ISAMs:
Table 17 sets forth the gas permeation properties for fully doped polyaniline EB ISAMs for various dopants. Complete doping of ISAMs is achieved by immersing these membranes in various 4 M aqueous acid solutions. These dopants include organic and inorganic acids which have been listed in the order of their sizes from small to large. Fully doped polyaniline EB ISAMs show a decrease in gas permeance when compared to the as cast polyaniline EB ISAMs with the exception of trifluoroacetic acid (CF3COOH) where the gas permeance for all gases increases slightly as the EB ISAM was fully doped by this acid. HCl and HBr-fully doped polyaniline EB ISAMs have an H2/N2 selectivity of greater than 720 and an O2/N2 selectivity of greater than 9.2. CF3COOH-doped polyaniline EB ISAMs exhibit a CO2/CH4 selectivity of 52.2 and a gas permeance of 53462 (10−10 cc STP/cm2 s cm Hg). There appears to be no general trend relating the dopant size to the permeance of the EB membrane.
Dopant Size, A3 He H2 N2 O2 CO2 CH4 H2/N2 O2/N2 CO2/CH4
As-cast 0.00 71547 104320 1068.0 9233.0 44732 899.0 97.6 8.65 49.76
HF 9.8500 9036 7744 23.6 167.0 576 47.0 328.1 7.08 12.26
HCl 28.840 18760 15248 21.0 195.0 750 48.0 726.1 9.29 15.63
HBr 31.060 16415 14288 19.0 194.4 709 27.6 751.2 10.22 25.69
HCOOH 54.050 12480 9104 30.4 154.7 705 67.0 299.5 5.09 10.52
CH3COOH 77.640 18534 14147 41.4 303.6 2188 117.0 341.6 7.33 18.70
CF3COOH 87.020 66662 81494 1380.0 9931.0 53462 1024.0 59.1 7.20 52.21
ClCH2COOH 99.550 4658 2992 16.7 80.0 464 46.4 179.2 4.79 10.00
Cl2CHCOOH 121.40 7208 5391 33.0 253.0 1397 54.400 163.4 7.67 25.68
CCl3COOH 143.50 14910 10233 78.0 733.0 3775.0 154.00 131.2 9.40 24.51
Gas Separation ISAMs Prepared from Polyaniline EB and Polysulfone (PS) Blends:
To a solution of 3.010 g of NMP and 0.308 g HPMI (2.72×10−3 moles), 0.893 g (2.47×10−3 moles) of NESTE (EB) powder was added to make a 21.2% w/w EB/NMP/HPMI mixture having a GI/EB molar ratio of 1.10. After vigorously stirring the mixture for 1 min., the mixture was placed in an oven at 58° C. for 30 min. which resulted in a homogeneous solution. In a separate vial, 2.0 g of polysulfone, (Udel Amoco PS, P-350ONT-11) was added to 8.0 g of NMP solvent to generate a 20% w/w PS solution which was placed inside the oven at 58° until the PS completely dissolved in the NMP solvent. After both solutions were cooled to room temperature (22° C.), 1.0 g of the PS solution was added to 4.0 g of EB solution, stirred for one min. and placed in the oven at 58° C. for 5 min. to obtain a homogeneous solution. This solution was poured on a glass plate and the Gardner blade set to 0.006 in. Once the wet film was drawn, it was immersed in a water bath at 18° C. for 24 h. The IP film was dried using paper towels to remove excess water, air dried for several hours and placed in a vacuum oven for greater than 48 h at 10−2 Torr to ensure removal of residue moisture. The final composition of this membrane contained 80% w/w polyaniline EB and 20% w/w of PS. This membrane was caulked with 100% silicon elastomer and placed in the test cell at 30° C. where its gas permeation properties were measured.
For another blend, 0.878 g (2.43×10−3 moles) of NESTE (EB) powder was added to 2.995 g tetramethylurea (TMU) and 0.308 HPMI (2.72×10−3 moles) solution to make a 21.0% w/w EB/TMU/HPMI mixture having a GI/EB molar ratio of 1.12. After vigorously stirring the mixture for 1 min., the mixture was placed in an oven at 58° C. for 30 min. which resulted in an homogeneous solution. In a separate vial, 2.0 g of PS (Udel Amoco PS, P-350ONT-11) was added to 8.0 g of TMU solvent to generate a 20% w/w PS solution which was placed in the 58° C. oven until the PS completely dissolved in the TMU. After both solutions were cooled to room temperature (22° C.), 1.0 g of PS solution was added to 4.0 g of EB solution, stirred for 1 min. and placed in the 58° C. oven for 5 min. to obtain an homogeneous solution. This solution was poured on a glass plate and the Gardner blade set to 0.006 in. Once the wet film was drawn, it was immersed in water bath at 18° C. water bath for 24 hours. The IP film was dried using paper towels to remove the excess water, air dried for several hours and placed in a vacuum oven for greater than 48 h at 10−2 Torr to remove residual. The final composition of this membrane contained 80% w/w of polyaniline EB and 20% w/w of PS. The membrane was caulked with 100% silicon elastomer and loaded in the test cell at 30° C. where its gas permeation properties were measured. The results are set forth in Table 18 hereof.
Permeance of the as- 60030 92737 2614 16538 79977 2785 35.5 6.33 28.7
cast EB/PS
membrane from NMP
Permeance of the as- 62052 104340 5182 26559 132474 7555 20.1 5.13 17.5
membrane from TMU
ISAMs prepared from the above-described EB and PS blend solutions exhibited good O2 and N2 gas permeance and O2/N2 selectivities of 6.33 and 5.13, respectively.
The foregoing description of the invention has been presented for purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application to thereby enable others skilled in the art to best utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto.
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PART 1: VORTICE If you're familiar with the PTY nightlife scene, you've probably been to a Vortice or two. Vortice is the name for a party Mairena and her two friends have been organizing and hosting since 2004. Nowadays, the party is thrown thrice a year, always at a different Panama City venue.
When Vortice started, Mairena was in charge of advertising and decorating the parties, but is now its creative director. Vortice has been going on for eight years, but the party people are definitely not sick of it. Mairena explains why Vortice is always held at different places: "We want people to remember the experience of the party, not the place." True, true.
The theme of last month's Vortice (which was awesome, we might add) was mod. "I love pop art and I love Andy Warhol and the New York scene of the 60s, so I'm very in touch with that. And I was so picky," Mairena explained, giggling. "I hired a friend [to do decorating], and I was like I want that like that, and I want that like that!"Look out for Vortice's annual Halloween party, which Mairena says is always their most crazy. "It's always a costume party. Always big, big, big, ones, and we do them in big big big places." Well, that settles it. There's our reason for re-visiting Panama next fall.
PART 2: LATERAL: Mairena and her friend Carla Garcia de Los Rios (who currently runs Hoja de Bijao) hit on the idea for Lateral in December 2010. They imagined a publication that would cover creative types not just from Panama but from all over Latin America.
"Everytime you hear about a very good designer they are from Spain, or the States, or England. I don't want to say no to that but I started thinking okay, we have a lot of good designers here too," Mairena said.
The name's a reference to both the creative lifestyles Mairena seeks to cover and the original side-project status of Lateral. "The thing that's right al lado de tuyo," Mairena said about the title, "I used to work 9 to 6. My projects were my lateral activity – not work based." Plus she said she wanted the name to be some meaningful and more importantly, to be in Spanish. " The first print edition was published in 2011.
I happened upon Lateral's website one late night right before I moved to Panama City, when I was panicking just a little bit that there wouldn't be any kind of art and culture scene in the city. Lateral, with its killer design and well-written coverage, was the best reassurance I could have found.
After two print editions, Mairena realized that shipping paper copies was not the best way to create a cross-countries magazine. "I shipped stuff to Costa Rica and Guatemala, but it was like too much money and time," Mairena said. "I thought to myself, what I should do? and I was like no, I'm going digital. It isn't only about the money, it's about getting your information out there." Lateral's website just relaunched with a new design just last week.
Mairena is also starting a local gallery in collaboration with Hotel Decapolis. Starting in June, the restaurant Brava Pizza & Espuma will project works from a different digital artist every month 'til January.
MM: So we want to tell you a little about an event we're doing on June 9th at Terrae. It's a clothing trade called Ropa Vieja, where everyone brings their old clothes, we organize it and then you can take what you like. So what do you have lingering in the back of your closet?
MB: I like things a lot. I'm not a coleccionista, but I like things. I have so many pieces of jewelry, so many little things. I have a lot of accessories that I don't use that much now, but I still have because I think it's coming back.
MM: We ask everyone about their recommendations in Panama City, so, anything that you would recommend in Panama City?
MB: I love Via Argentina. I think it [has a] very not-Panama style, in that people live there, but there are [also] a lot of coffee shops, like in Mexico City or Buenos Aires. You can feel the soul of the city. I love walking around, here [in Panama] you don't see that so much. The classic stores like Espacio Vintage, La Botica. You should definitely put in Sak's.
MM: [Redacted 10 minute story of Eve buying a full red linen suit for under $5 and Christina getting a $400 silk blazer for $8.] Oh my god we love Sak's. And Dorian's.


What kind of Belwith Cottage are you looking for today?
Sometimes you want razzle-dazzle, and other times you don't. For all those times when you can do without the fanfare, the Belwith Cottage Series is the answer. With smooth lines, elegant finishes and understated designs, these Belwith knobs and pulls create a tasteful and well-dressed atmosphere in moments. Because it's so neutral, you can use this cabinet hardware anywhere from the kitchen to the office. So browse through this Belwith collection, and see why it's one of the favorites across the board.
For those times in life when you're not looking for a whole lot of noise, Belwith pulls offer an unpretentious style that you can love. Solidly fashionable, this cabinet hardware will stand the test of time as well as the ever coming and going trends. Choose from petite Belwith pulls or more prominent options, but always enjoy the simple sophistication that comes along for the ride.
Cottage Belwith knobs have either a smooth surface or slight rim details, so you are really getting the chicness of minimalistic design. The finishes are what give this cabinet hardware real personality. With choices like highlighted bronze, satin rose and satin Dover, it's no wonder that these Belwith knobs are among the most popular in the industry. So order your own Belwith pulls and knobs from the Cottage Collection now because sometimes less really is more.


Manufacturer of oil and gas surface production equipment including custom orders, tanks, flare stacks and more. Ask us how our products can improve your business and increase the safety of your operation.
We can source and supply production surface equipment such as tanks, separators, flare stacks and knockout tanks. Additionally we are a supplier of parts for production tanks (e.g., tank gauges, thief hatches, anodes, skimmer floats) including many brand-names.
Exclusive dealers in British Columbia of the Surtuf secondary containment systems. The system is an engineered secondary containment system designed for its ease of use drop pin connecting panels with single slide in leg system.


text:
Two Bauer Management Profs In Top 2 Percent Most Cited
Professor Leanne Atwater and Professor Alan Witt Named in Industrial-Organizational Psychology Study of Most Cited In Textbooks
Leanne Atwater and Alan Witt
Two management professors from the C. T. Bauer College of Business professors are among an elite group of most-cited authors in popular industrial-organizational psychology textbooks, according to a study published earlier this year in Industrial and Organizational Psychology (IOP).
Leanne Atwater and Alan Witt are in the top 2 percent of those cited in introductory textbooks aimed at industrial and organizational psychology students taking their first in-depth classes (according to Aguinas et al. in press). The Bauer College faculty emerged as top contributors from a field of more than 8,600 experts cited.
Atwater is a professor of management and the former chair of the Bauer College Department of Management. She is also a former editor of The Leadership Quarterly and the author of numerous refereed papers and books on leadership.
Witt is a professor of psychology at the University of Houston with a joint appointment in Bauer College. Witt's areas of research include organizational politics, customer service, personality, counterproductive work behavior and diversity/equal opportunity.
SOURCE: Aguinis, H., Ramani, R. S., Campbell, P. K., Bernal-Turnes, P., Drewry, J. M., & Edgerton, B. T. (in press). Most frequently cited sources, articles, and authors in industrial-organizational psychology textbooks. Industrial and Organizational Psychology: Perspectives on Science and Practice.
By Julie Bonnin
Posted Under: Bauer Business Minds, Faculty and Staff

redpajama_set_name: RedPajamaCommonCrawl


text:
Disney+ Exclusive Clip At New Series 'Loki' Coming May 2021
Jeff Porter Dec 26, 2020
Joe Rogan Thinks This Netflix Series Is "Really Good" –…
Jamie Foxx & The Cast From Disney+'s 'Soul'…
Disney+ 'The Mandalorian' Had An Accidental Crew Cameo!
100 Dias Para Enamorarnos 1000-Lb Sisters 7 LIttle Johnstons 90 Day Fiancé 90210 All My Children American Idol
Disney+'s 'The Mandalorian' Had A 'Deadwood' Reunion You May Have…
Jeff Porter Nov 1, 2020 0
Disney+'s 'The Mandalorian' season 2 opener had a lot of incredible things in it! From the appearance of actor John Leguizamo, the shocking appearance of Temeura Morrison as Boba Fett and more! However, as a fan of 'Deadwood', one more…
Disney+'s 'The Mandalorian' Returns With Boba Fett (Temuera Morrison)! –…
Jeff Porter Oct 31, 2020 0
Is your heart still racing after the season 2 opener of Disney's 'The Mandalorian'? I couldn't stop talking about it. From my love of Timothy Olyphant and William Earl Brown reuniting from their 'Deadwood' days, a special voice cameo from…
Disney+'s 'The Mandalorian' Season 2 Makes Low Key Reference To 'Knights Of…
Disney+'s 'The Mandalorian' paid special homage to a certain quest from the MMORPG 'Star Wars: Knights of the Old Republic' is it's season 2 opener! Among all of the amazing cameos, Timothy Olyphant and the return of Boba Fett, there was…
Disney+'s 'The Mandalorian' Season 2 Starring Pedro Pascal Premieres October 30…
Disney+'s 'The Mandalorian' Starring Pedro Pascal took the world by storm with the first season last year. Now, in 10 days, the phenomenon returns with its second season! To get everyone even more excited, Disney's official Instagram…
'The Mandalorian' Season 2, WandaVision + Everything Coming To Disney+ In November…
There's a lot coming to Disney+, most notably new seasons of 'The Mandalorian', as well as new series from Marvel, including 'WandaVision'. What can we expect to see next month, however? Today, Disney put out a video showcasing the new…
Disney+ Has Assembled The Marvel Cinematic Universe For Your Viewing Pleasure
According to a post from IGN, Disney+ has finally fixed an issue with a terrible interface on its streaming platform for all their Marvel films. The interface was extremely difficult and hard to use, but now, after over a year, fans are…
Everything Coming To Disney+ This Month | October 2020
Jeff Porter Oct 1, 2020 0
Yes! It's finally October and for a lot of us that means 'The Mandalorian' season 2 is releasing! However, the highly anticipated show is releasing with a slew of other great series and films this month on Disney+, including 'X2',…
Disney+'s 'Secret Society of Second-Born Royals' Character Powers and Stunts
Jeff Porter Sep 28, 2020 0
Disney+'s 'Secret Society of Second-Born Royals' follows Sam's adventures at a top-secret training program for a new class of second-born royals tasked with saving the world. The original Disney+ film was released a few days ago on the 25th…
Disney+ 'Nick Fury' Series In Development With Samuel L. Jackson
According to IGN and Variety, Samuel L. Jackson is reportedly returning as the patch wearing Nick Fury for a Disney+ original streaming series. Jackson previously made a minor cameo in the television series 'Agents of Shield', so it's not…
Disney+'s 'WandaVision' Offical Trailer Finally Releases But Leaves Us With More…
Disney+'s 'WandaVision' finally released a trailer for the anticipated Marvel series and it looks to be a mind-melding experience. The trailer left many more questions in our head than it answered and seemed very confusing to a lot of…


Unlike many of the Zeiss-branded lenses sold and designed by Sony, the Batis range is developed and distributed exclusively by Zeiss - a brand known for uncompromising quality and occasionally very high prices, as is the case with the universally acclaimed Otus 55m 1.4.
Is an OLED display really necessary?
Where a vintage lens might have provided guide markings on the barrel to help you focus your image, the two Batis models are fitted instead with a small OLED offering up focus distance and depth of field information in a more convenient illuminated display.
Although the OLED display looks pretty and performs a useful function. It's not actually providing any information which couldn't just as easily be displayed on the camera's screen.
Such indicators are invaluable in the manual, film-based photography, but aren't really necessary on modern digital cameras and that OLED must certainly be pushing the price higher than would be necessary to obtain similar optical results.
One advantage over physical markings is that the display can be read in the dark and, if you want to go old-school and shoot without using the screen, then you can as manual focus override is supported in both lenses.
Zeiss claims the the display has been fitted in response to numerous requests from customers. Perhaps if you are one of those customers you might like to tell me why it's important for you. The OLED a unique feature which is certainly nice to have, but I'm just not sure I'd want to pay more for a lens with such a display.
I expect very high quality from the new Batis lenses, but while the entirely manual Otus lenses are extremely expensive, it at least feels as though the significant financial outlay required is all going towards purchasing the best possible image quality rather than a nice-to-have feature.
Whether or not the OLED is of practical benefit to you, the Batis lenses feature professional-level build quality: Zeiss has released a teaser video which shows an intrepid outdoor photographer trudging through the rain with a decidedly wet camera, demonstrating the weather-sealed lens body.
At twelve seconds, we can see the 25mm Batis 'booting up' to display the the word 'Zeiss', but sadly we don't get to see either the focus distance or depth of field markings in use.
Available now for pre-order, the Batis 1.8/85 is priced at $1,199, with the Batis costing a little more 2/25 at $1,299. Both lenses are due to start shipping on 15th July 2015. The pair may be a little gimmicky, but it's great to see a company daring enough to innovate.
For more details and lens specs, see the Zeiss press release.


text:
Q: LINQ to XML subquery to ListBox I have an XML file that looks something like this:
<?xml version="1.0" encoding="utf-8" ?>
<scripts>
    <script id="1">
        <name>A Script File</name>
        <author>Joe Doe</author>
        <fileDestination>
            <destination>W:\folderolder\</destination>
            <destination>W:\anotherfolder\</destination>
            <destination>W:\athirdfolder\</destination>
        </fileDestination>
    </script>
    <script id="2">
        <name>Another File</name>
        <author>Bobby Doe</author>
        <fileDestination>
            <destination>W:\somefolder\</destination>
            <destination>W:\someotherfolder\</destination>
        </fileDestination>
    </script>
</scripts>

I have a LINQ to XML query that I have worked out with some help from this SO Question.
    var query3 = (from c in xDoc.Descendants("script")
                          select new
                          {
                              Name = (string)c.Element("name").Value,
                              Author = (string)c.Element("author").Value,
                              //Destination = c.Element("fileDestination").Elements().Select(e => (string)c.Element("destination").Value)
                              //Destination = c.Element("fileDestination").Elements().Where(e => (string)c.Element("destination").Value != null).Select(e => (string)c.Element("destination").Value).ToList()
                              Destination = c.Descendants("fileDestination").Elements().Where(e => c.Element("fileDestination").Element("destination").Value != null).Select( e => (string)c.Element("destination").Value)
                          });

The trouble is, (1) I always get a nullreferenceerror and (2) I don't understand how to access the results of the second select. I can do something like:
        txtScriptTitle.Text = query.FirstOrDefault().Name;
        cmboAuthor.Text = query.FirstOrDefault().Author;

to show the results of the first two items, but I can't figure out how to access "Destination".
What I ultimately want to do is perform one LINQ query against the XML document and bind the single results (Name and Author in my example below) to individual text boxes (txtName and txtAuthor) and then bind the results of the subquery to a listbox. Can I do this in a single query?

A: Trying changing your query which populates Destination to
Destination = c.Descendants("destination")
               .Select(e => e.Value)
               .Where(s => !string.IsNullOrEmpty(s))
               .ToList();

That will populate it with a List which you can then bind to your control.

redpajama_set_name: RedPajamaStackExchange


text:
Kaple blahoslaveného císaře Karla I. ve Staré Boleslavi měla podobu postranní kaple v poutním kostele Nanebevzetí Panny Marie, kde je také uloženo vzácné Palladium země české.

Zasvěcení
Proces blahořečení císaře Karla I. byl dokončen 4. října 2004 papežem Janem Pavlem II. Ten stanovil svátek Karla I. z domu rakouského na 21. říjen. Toto datum bylo zvoleno, coby výroční den Karlovy svatby (21. října 1911) se Zitou Bourbonsko-Parmskou. Novomanželé pak po svatbě společně žili na zámku v nedalekém Brandýse nad Labem, kde mladý císař sloužil u vojenské posádky. Ke zdejšímu kraji měl blízký vztah a prožil zde nejkrásnější čas rodinného života.

Popis kaple

Kaple s relikviářem blahoslaveného Karla I. se nacházela v bývalé tzv. "panské" sakristii v přízemí severní věže při presbytáři staroboleslavského kostela Nanebevzetí Panny Marie, který je významný tím, že je zde uloženo Palladium země české. Byla vybudována péčí Modlitební ligy císaře Karla za mír mezi národy a zasvěcena poslednímu císaři a českému králi, jehož relikvie byla v kapli slavnostně uložena při jejím vysvěcení 1. května 2011, v týž den, kdy byl blahořečen papež Jan Pavel II.  Kaple byla zrušena v roce 2018, kdy byl kostel uzavřen z důvodu celkové rekonstrukce, po jeho znovuotevření v roce 2020 již prostor slouží jinému účelu.

Reference

Externí odkazy

 Blahoslavený Karel I. Habsbursko-Lotrinský na stránkách Společnosti přátel historie města Jablonného v Podještědí
 Karel I. Habsburský - Blahoslavený ze Staré Boleslavi na christnet.eu

Karla I.
Stará Boleslav
Stavby v Brandýse nad Labem-Staré Boleslavi
Karla
Stará Boleslav
Náboženství v Brandýse nad Labem-Staré Boleslavi

redpajama_set_name: RedPajamaWikipedia


text:
SOURCE: NY Times
'1917' Turns a Horrific War Into an Uplifting Hero's Journey
tags: World War I, movies, 1917
by Cathy Tempelsman
Cathy Tempelsman is a writer. Her play "The Eleventh Hour" is based on partisan congressional hearings in the United States just after World War I.
I was looking forward to seeing Sam Mendes's film "1917" when it arrived in theaters in December. I have a special interest in the subject — my grandfather fought in World War I, and I've done years of research on the events while writing a play about the war.
I can't argue with Mr. Mendes's artistry. Visually and technically speaking, "1917," which is nominated for 10 Academy Awards, is dazzling. The filmmaking team cleverly manages to make the entire movie seem like one long, continuous take, and I, like many viewers, found myself wondering how certain scenes were shot.
The director's own grandfather inspired him with stories about volunteering to run messages across open, war-ravaged terrain. In an interview, Mr. Mendes said that "1917" called for "a different kind of storytelling." He described the "Great War" as "a chaos of mismanagement and human tragedy on a vast scale."
If only he had told that story. Instead, "1917" left me uneasy. Mr. Mendes paints an uplifting and dangerously misleading picture of the war.
The fictionalized premise is this: General Erinmore (Colin Firth) sends two British soldiers on an urgent mission. They have until dawn to deliver a vital message: The Second Battalion is about to walk into a trap, and the attack must be called off. The general warns one of the soldiers, Lance Corporal Blake (Dean-Charles Chapman), "If you don't get there in time, we will lose 1,600 men — your brother among them."
Read entire article at NY Times


text:
Q: Socket.io socket.broadcast.to not working I have in  my Express server
userbase = {'Fitz': '84Iw3MNEIMaed0GoAAAD'}; //Exapmle user to receive message and associated socket id

//Sending message to Example user
    socket.on('send_msg',function(data_from_client){

       //Testing  for receivers socketId

     console.log(userbase[data_from_client.to_user]);//This returns the socket id for Fitz in userbase successfully i.e 84Iw3MNEIMaed0GoAAAD

      socket.broadcast.to(userbase[data_from_client.to_user]).emit('get_msg',{msg:data_server.msg});
    });

Surprise surprise when I setup a handler for this event on my cliens side for 'get_msg' i get nothing.
.factory('SocketFctry',function(){
  var socket = io('http://localhost:3002')

  return socket;
})

.controller('ChatCtrl', function($scope,SocketFctry) {

 SocketFctry.on('get_msg',function(received_message){
   console.log(received_message);
   $scope.$apply();

 })

});

My other client side handlers are working fine.
 SocketFctry.on('new_user', function(users,my_id){
    console.log(users);
    $scope.online_users = users;
    $scope.$apply();
  })

My version of socket.io is 1.3.7 .Am I missing something here?

A: socket.broadcast().to() send a message to all users that match the to() arguments EXCEPT the user who's socket it is.  So, socket.broadcast.to(socket.id) will never send to the actual socket user.  In fact, by default, it won't send to anyone.
Direct from the socket.io doc:

To broadcast, simply add a broadcast flag to emit and send method
  calls. Broadcasting means sending a message to everyone else except
  for the socket that starts it.

If you want to send to only a single socket, then just use:
socket.emit(...)

If you want to broadcast to a socket.id-type room and you want to include the user who's room it is, then use:
io.to('some room').emit('some event'):

So, you can change this:
socket.broadcast.to(userbase[data_from_client.to_user]).emit('get_msg',{msg:data_server.msg});

to this:
io.to(userbase[data_from_client.to_user]).emit('get_msg',{msg:data_server.msg});

A: Do you have users join a namespace on connection?
socket.join(userbase[data_from_client.to_user]); //'84Iw3MNEIMaed0GoAAAD'

You can try:
socket.in(userbase[data_from_client.to_user]).emit('get_msg', {msg:data_server.msg});


text:
Mission, Vision, and Strategy
Legal and Study Acts
Students Affairs Office
Want to Enroll?
Masters Studies
Application and Registration
Res novae archives
Students and business practice
March-april 2016
Type seach words and click "enter"
Rozman, Til
Courses Management and Law in Employment Relations, Business Law
In 2016, Dr. Til Rozman cum laude defended his doctoral thesis on the issues of normative regulation and business practices of managing corporate groups in the Republic of Slovenia and the EU and was awarded with the title PhD. Rozman has been appointed as an Assistant Professor of Civil and Commercial Law at the University of Ljubljana. Rozman has published several academic articles and has delivered papers at national and international conferences, particularly in the fields of company law, corporate governance and competition law.
Between 2016 and 2019, Rozman was member of two research projects at the Research Centre for Comparative Corporate Law, namely "Socially Responsible Corporate Governance as the Foundation of the new Development Paradigm of Slovenia and EU" and "Corporate Governance of State-Owned Enterprises: Contemporary Issues and Challenges for Slovenia and EU". In 2020, Rozman has joined research project »Holistic approach to business and human rights: a normative reform of Slovenia and international legal order«, carried out by the Faculty of Government and European Studies. In the same year, Rozman has joined Faculty of Law and Business Studies as an assistant professor.
Faculty of Law and Business Studies
P: +386 (0)820 52 300


Image Title: Swivel Dining Chairs Throughout Danube Midcentury Modern Leather Chair Safavieh Design 19. Post Title: Swivel Dining Chairs. Filename: swivel-dining-chairs-throughout-danube-midcentury-modern-leather-chair-safavieh-design-19.jpg. Image Dimension: 488 x 488 pixels. Images Format: jpg/jpeg. Publisher/Author: Jake Cummings. Uploaded Date: Saturday - May 05th. 2018 14:05:31 PM. Category: Architecture. Image Source: decoist.com. Modern Dining Chair Most Inspirations 1. For Chairs Interesting Decorations Cattelan Swivel 3. With Apollo Tilt Com Upholstered Prepare Chet 5. Casual 14. Design Of Within Midcentury At 10. Beetle Rolling Armchairs 1stdibs Throughout Base Decor And 00 19. Whirl Safavieh In Crate Hivemodern Tyler Arms 11. Barrel Callee Amazon Danube Four Alluring 1 By Beardsley 095 W Grey Shipping White Eurway 6. Plans Leather 4. Caster Designs Mulan Free Italia Daytona Reviews 12.


text:
namespace aura {
class Window;
}

namespace ash {
class BackGestureContextualNudgeController;
}

// BackGestureContextualNudgeDelegate observes |window_|'s active webcontent and
// notify when |window_|'s navigation status changes (either the active
// webcontent changed or a navigation happens in the active webcontent.).
class BackGestureContextualNudgeDelegate
    : public ash::BackGestureContextualNudgeDelegate,
      public content::WebContentsObserver,
      public TabStripModelObserver,
      public aura::WindowObserver {
 public:
  explicit BackGestureContextualNudgeDelegate(
      ash::BackGestureContextualNudgeController* controller);
  BackGestureContextualNudgeDelegate(
      const BackGestureContextualNudgeDelegate&) = delete;
  BackGestureContextualNudgeDelegate& operator=(
      const BackGestureContextualNudgeDelegate&) = delete;

  ~BackGestureContextualNudgeDelegate() override;

  // ash::BackGestureContextualNudgeDelegate:
  void MaybeStartTrackingNavigation(aura::Window* window) override;

  // content::WebContentsObserver:
  void DidFinishNavigation(
      content::NavigationHandle* navigation_handle) override;

  // TabStripModelObserver:
  void OnTabStripModelChanged(
      TabStripModel* tab_strip_model,
      const TabStripModelChange& change,
      const TabStripSelectionChange& selection) override;

  // aura::WindowObserver:
  void OnWindowDestroying(aura::Window* window) override;

 private:
  // Stop tracking the navigation status for |window_|.
  void StopTrackingNavigation();

  aura::Window* window_ = nullptr;  // Current observed window.
  ash::BackGestureContextualNudgeController* const controller_;  // Not owned.
};

#endif  // CHROME_BROWSER_UI_ASH_BACK_GESTURE_CONTEXTUAL_NUDGE_DELEGATE_H_

redpajama_set_name: RedPajamaGithub


This page displays sold house prices for Kildare Court in Middlesbrough.
Kildare Court in Middlesbrough TS3 consists predominantly of terraced houses. Properties on Kildare Court typically have values around £100,000 - £150,000, with larger terraced houses and townhouses valued at around £150,000.
Map showing Kildare Court in Middlesbrough.


The objective of this comprehensive consensus statement was to provide practical and independent advice to physicians for treating and managing spinal anesthesia-induced maternal hypotension in both resource-rich and resource-poor environments. This clinical best practices summary was necessary as there has been much variation in the methods used to manage spinal anesthesia-induced hypotension during cesarean section, and maternal hypotension increases risks to both maternal and fetal/neonatal health. While generalized recommendations have been made for the management of this problem by professional organizations, the authors indicated this was the first consensus statement providing specific, pragmatic recommendations for managing spinal anesthesia-induced hypotension.
Obstetric Anesthesia Digest38(4):171-172, December 2018.


I have a mental list of all the things I must see in my lifetime. This week, on a trip from Perth to Shark Bay in Western Australia, I managed to tick three things off that list.
The first 'once in a lifetime' sight was the Wreath Lechenaultia in full bloom.
We nearly missed out on spotting this magical plant. After driving for hours we reached our destination just on sunset. A few minutes later and we would have missed it. I was so excited I didn't even stop to put on my shoes and delighted in tip-toeing barefoot through the Wreaths with tears in my eyes.
I'll be back soon to share my second and third 'once in a lifetime' sights.


text:
Inicio > Catálogo Materiales > Catálogo Hormigón armado > Concrete progress from antiquity to the third millennium
Concrete progress from antiquity to the third millennium
Autor: Idorn, Gunnar
Concrete progress deals with the technology that made concrete the most widely used building material in the world in the course of the past hundred years, and the most indispensable for the global socio-economic development in the new millennium. It offers an insight into many people's dedicated, exploratory concrete research, and into strategic planning and management of research and its transfer to engineering practice
Contenido Concrete progress from antiquity to the third millennium
Concrete progress deals with the technology that made concrete the most widely used building material in the world in the course of the past hundred years, and the most indispensable for the global socio-economic development in the new millennium. It offers an insight into many people's dedicated, exploratory concrete research, and into strategic planning and management of research and its transfer to engineering practice. This book is introduced by retrospectively highlighting the international history of concrete technology and uses. It traces the socio-economic impact of concrete from the magnificent construction epoch of Roman antiquity, to the Industrial Revolution in the nineteenth century, and its continuity between the two World Wars. Then, in more detail, it describes concrete technology progress during the first post World War II decades, which coincided with - and indeed depended on - the demands for concrete to house millions of homeless people and to reconstruct the industrial manufacturing capacity and the infrastructures. The outreach message of Concrete progress is both to cement and concrete professionals in the developing countries, where the creation of new research and engineering skill still is pristine, and to the hidebound research and practice in the rich industrialised, technology satisfied parts of the world. Contents Part 1 Flashlights on history and research Our heritage of cement and concrete technology Field concrete performance - observation and contemplation A new era of concrete researchThe Concrete Research Laboratory - Karlstrup Part 2 Alkali-silica Reaction Introduction and history The dormant decade of ASR research The second phase of ASR research ASR year 2000 Part 3 International Consultant The consultancy basis The durability crisis Alkali-silica reaction Ground, granulated blasted-furnace slag Other consultancy projects Consultant's service in its market-place Part 4 Concrete in the Millennium's Transition The ageing decades of the twentieth century Concrete in the third millennium Progressive concrete research References


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Vijay Singh
MAMARONECK, NEW YORK
Q. How much of this right now is between the ears versus say a week ago given what happened just up the road here?
VIJAY SINGH: Pretty good. I've taken a lot of confidence from there. I'm not in a high, but my golf game just kind of lifted to a level where I feel a lot more at ease playing right now. I'm looking forward to the next three days here.
Q. Compare hitting out of the rough here in the first and second cut to Westchester last week.
VIJAY SINGH: It started different. You can get some nasty lies at Westchester, but the fairways were a lot more generous there. But the rough at Westchester was almost as bad as this in places. But obviously the fairways were twice or three times as wide as this, so you didn't have any problem with it, and a much shorter golf course.
Q. The wind, the conditions last week, did that kind of prepare you more for the wind you had to deal with out here today?
VIJAY SINGH: A little bit. Windy conditions at Westchester was different because the golf course you could still go ahead and be very aggressive with the tee shots and not worry about missing the fairways much. Over here you're always concerned about which side to miss it and where not to hit it.
It's totally a different golf course. The conditions may be a little similar, but the greens are a lot firmer here.
Q. The score that you did post today, does it feel like an under par round?
VIJAY SINGH: It feels like a good round but not an under par round.
Q. (Inaudible).
VIJAY SINGH: I was in it once, but I got away with it.
Q. What hole was it?
VIJAY SINGH: It was I think 12 or no. 12th hole, I think no, 14, sorry.
Q. Good lie?
VIJAY SINGH: I missed the thick rough and got into where the crowds were walking, so I got away with it.
Q. Was it a fair U.S. Open setup in your mind?
VIJAY SINGH: At the moment it is. There's a few greens out there, even 18, that's getting a little bit too crusty, so they've got to watch it. They always turn up on Wednesday and say what a great setup, Thursday is the same, and then it starts getting a little bit over the edge. So far it's pretty nice.
Q. One of the members here said that they think 16, 17 and 18 are going to be the pivotal holes come Sunday. What do you think?
VIJAY SINGH: If the wind changes direction, it will be. Right now the wind is blowing in our favor. 17 you can get away with just hitting an iron off the tee. 18, as well. It's not playing as long as the card holes. If the wind changes direction like 9th hole, that's probably the hardest hole on the golf course, and I hit a driver, 9 iron today, and I hit driver, 5 iron in the practice round. That tells you the difference in the conditions.
VIJAY SINGH: You know, it's difficult when it's the first tee ball of the tournament. You're a little nervous and you don't want to make a mistake, but it wasn't that bad.
Q. What did you hit there?
VIJAY SINGH: I hit driver, 7 iron.
Q. Tell us about the emotion on Sunday. Relief?
VIJAY SINGH: Yeah, I think so, just the satisfaction of practicing so hard and pulling it off. The whole team, Paul, myself and Joey, we worked pretty hard in getting yeah, back to where I should be, really.
Q. You talked about the greens being more crusty and the winds picking up. Any putts or shots that you thought might break different than you thought they would?
VIJAY SINGH: Yeah, I think 18 is a lot different. I hit a really full sand wedge from 131 and spun it actually. But if you lay back where you can hit irons off the tee, it's very hard to stop the ball. I think if it gets crusty, I think three yards short of the pin you'll be down below. There's one of the hard ones, and there's a few other holes that's getting really hard.