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US 6043177 A Abstract A process for modifying surfaces of zeolites and molecular sieve membranes to decrease effective pore size for separation of materials includes atomic layer controlled vapor or liquid deposition. The atomic layer controlled deposition process steps include (i) exposing the surface to a metal atom coordinated with ligand groups having bonds that are hydrolyzable to form molecular bonded structures on the surface, which structures comprise the metal atoms coordinated with the ligand group or a modified ligand group and then (ii) hydrolyzing the bonds and possibly, but not necessarily, cross-linking the bonds in the ligand or modified ligand group.
Claims(8) 1. A process for modifying selective permeance of a crystalline membrane with hydroxyl groups (OH) on its surface, comprising:
exposing the membrane to a reaction gas molecule having the formula M(Z.sub.m L.sub.n), where M is a metal atom coordinated to ligand group Z.sub.m L.sub.n, wherein said membrane has the formula Y-OII*, wherein Y is a substrate atom and OH* is a surface hydroxyl group, and wherein said reaction gas molecule M(Z.sub.m L.sub.n) has sufficient volatility and reactivity to react with said membrane surface hydroxyl group, and allowing a solid/vapor phase chemical reaction to proceed generally as follows: Y--OH*+M(Z.sub.m L.sub.n)→Y--O--M(Z.sub.m L.sub.n)+ZH↑(1) where Y--O--M(Z.sub.m-1 L.sub.n)is a bonded coordinated group that results from reaction (1), M(Z.sub.m-1 L.sub.n) coordinated is a resulting group comprising the metal atom (M) and ligand group Z.sub.m-1 L.sub.n, wherein Z.sub.m-1 L.sub.n is capable of being hydrolyzed by water, and ZH↑ is a gaseous by-product of the reaction (1); and exposing the surface of the membrane and the bonded Y--O--M(Z.sub.m-1 L.sub.n) coordinated group that results from reaction (1) to water (H.sub.2 O) molecules to hydrolyze M(L) bonds according to a hydrolyzing reaction generally as follows: M(Z.sub.m-1 L.sub.n)*+H.sub.2 O→M--OH*+Z.sub.m-1 L.sub.n H↑(3) where M(Z.sub.m-1 L.sub.n)* is the group on the membrane surface comprising the coordinated metal atom (M) and ligand group (Z.sub.m-1 L.sub.n), M--OH* is a resulting group comprising the metal atom M coordinated with a hydroxyl group (OH) formed on the surface of the membrane, and Z.sub.m-1 L.sub.n H↑ is a gaseous by-product of the hydrolyzing reaction (3), wherein a monomolecular layer of said M--OH* is deposited on the surface of said membrane. 2. The process of claim 1, including continuing the step of exposing the membrane to the metal atoms M coordinated with the ligand Z.sub.m L.sub.n until substantially all available OH* is reacted according to reaction (1) and the reaction (1) substantially stops.
3. The process of claim 2, including continuing the step of exposing the surface of the membrane and the bonded Y--O--M(Z.sub.m-1 L.sub.n) coordinated group of water (H.sub.2 O) molecules to hydrolyze M(Z.sub.m-1 L.sub.n) bonds until substantially all available M(Z.sub.m-1 L.sub.n) bonds are hydrolyzed.
4. The process of claim 3, including the step of condensing OH groups of adjacently deposited molecules from reaction (3) to form a cross-linked monomolecular layer of coordinated groups comprising at least two metal atoms M bonded with a common oxygen O atom and coordinated with at least two other oxygen O atoms that are bonded with substrate atoms Y.
5. The process of claim 1, wherein said membrane is zeolite, said Y atoms are silicon Si, said M(Z.sub.m L.sub.n) is trimethylaluminum Al(CH.sub.3).sub.3, and said reaction (1) proceeds generally as:
Si--OH*+Al(CH.sub.3).sub.3 →Si--O--Al(CH.sub.3)+CH.sub.4 ↑,(2) and said reaction (3) proceeds generally as: Al(CH.sub.3)*+H.sub.2 O→Al--OH*+CH.sub.4 ↑ (4). 6. 6. The process of claim 5, including continuing the step of exposing the membrane to the Al(CH.sub.3).sub.3 until substantially all available OH* is reacted according to reaction (2) and the reaction (2) substantially stops.
7. The process of claim 6, including continuing the step of exposing the surface of the membrane and the bonded Si--O--Al(CH.sub.3) coordinated group to water (H.sub.2 O) molecules to hydrolyze Al--CH.sub.3 bonds in the Al(CH.sub.3) groups until substantially all available Al--CH.sub.3 bonds are hydrolyzed.
8. The process of claim 7, including the step of condensing the OH groups of adjacently deposited molecules from reaction (4) to form a cross-linked monomolecular layer of coordinated groups comprising at least two Al atoms bonded with a common oxygen O atom and coordinated with at least two other oxygen O atoms that are bonded with silicon Si substrate atoms.
Description 1. Field of the Invention This invention relates to membrane structures for separation of materials on a molecular scale, such as selective sorption, molecular sieving, and the like, and more particularly to modification of such membranes by atomic layer controlled chemical vapor deposition to increase effectiveness of the membrane for materials separation, or other purposes. 2. Description of the Prior Art Materials, such as gases or liquids, can be separated from other different materials on the molecular level by a number of techniques. Some well-known examples include evaporation and condensation, which is used to distill alcohol, electrolysis, which is used to remove chromium from solution and plate it onto parts, and crystallization, which is used to purify salts, drugs, or other substances from contaminated mixtures or solutions. More relevant to this invention, thin membranes of some solid materials that have very small pores are permeable to certain gases or liquids comprising small molecules, and impermeable to other gases or liquids that may comprise larger molecules, different shaped molecules, molecules with different polarizability, different absorption properties, or combinations of any of these factors. In industrial applications, organic polymer membranes are used, for example, to separate substances such as ethanol from water. Also of interest, some solid materials are adsorbents for certain gases or liquids. Some zeolites, such as 4A, are more adsorbent of molecular nitrogen (N.sub.2) than of molecular oxygen (O.sub.2) at increasing pressures and desorb the nitrogen when pressure is decreased. This adsorption/desorption cycle is used in combination with reversing flow directions to separate nitrogen gas (N.sub.2) from oxygen (O.sub.2) in air. Recognizing how such molecular separation materials and mechanisms work, it is, of course, desirable to improve them to make them more effective and more efficient for their material separation functions. For example, in the U.S. Pat. No. 3,837,500, issued to Nichols et al., a process is described for reticulating or cross-linking an organic porous polymer membrane comprising ultrathin layers of polyvinyl alcohol and polyvinyl pyrrolidone with diisocynate reticulation agent to decrease and control the pore size of the membrane for more effective water/salt separation. Zeolites are microporous crystalline alumina silicates with a narrow distribution of pore sizes on a molecular scale, and they have high thermal, chemical, and mechanical stabilities. Molecular sieves can be, for example, alumina phosphates (ALPO) or silicaaluminaphosphates (SAPO), which are also microporous, crystalline materials with a narrow distribution of pore sizes and also have high thermal, chemical, and mechanical stabilities. Therefore, zeolites and molecular sieves can be used not only for gas separations in adsorption/desorption processes, as mentioned above, but also as diffusion membranes when prepared in thin film form. The size and adsorption properties of the zeolite pores, however, limit what can be separated with a particular type of zeolite membrane, even if the crystalline structure is perfect and defect free. However, perfect and defect free zeolite crystalline structures are not readily available or easy to prepare, so most zeolite materials have defects and separations or spaces between crystals, which can be larger than the pore sizes in the crystalline structures. Therefore, transport of molecules by diffusion can take place both within the zeolite crystals and between adjacent crystal faces. Since the spaces between adjacent crystal faces can be larger than the pores in the zeolite crystals themselves, it is very difficult to produce zeolite membrane types with good separation capabilities, and only a few have been prepared prior to this invention. There is a substantial need for better and different zeolite membranes. For example, the sequential adsorption/desorption pressure swing cycles mentioned above for separating gases require a high capital investment for any significant volume production in industrial plants, and such systems have high maintenance costs. A gas separation system that takes advantage of both the adsorption and diffusion properties of zeolites, but operates at steady state rather than pressure cycling would be much more efficient, but such a system would require good, effective, and efficient continuous zeolite membranes. In recent years, thin, dense layers of zeolites have been prepared both in self-supporting thin film membrane structures and on macroporous substrates or supports. See, for example: W. J. W. Bakker et al., "Single and Multi-Component Transport Through Metal Supported MFI Zeolite Membranes," Precision Process Technology, Eds. M. P. C. Weiznen and A. A. H. Drinkenburg, Lluwer Academic Publishers, 1993, page 425; W. J. F. Bakker et al., "Doorbreak in Ontwikkeling Zeolietmembranen, in Dutch (English translation of title: Break-Through in Development of Zeolite Membranes," Proces Technologies, Vol. 3, December 1993, page 7; M. Jia et al., "Ceramic-Zeolite Composite Membranes and Their Application for Separation of Vapor/Gas Mixtures," J. Membr. Sci., Vol. 90, 1994, page 1; Y. Yan et al., "Zeolite ZSM-5 membranes grown on porous α-Al.sub.2 O.sub.3," J. Chem Soc. Chem. Commun., 1995, page 227; T. Sano et al., "Potentials of Silicalite Membranes for Separation of Alcohol/Water Mixtures," Studies in Surface Science and Catalysis, 1994, vol. 84, page 1175; J. Tsikoyiannis et al., "Synthesis and characterization of a pure zeolite membrane," Zeolites, February 1992, vol. 12, page 126; E. Wu et al., "Hydrocarbon adsorption characterization of some high silica zeolites," Studies in Surface Science and Catalysis, 1986, vol. 28, page 547; and S. Xiang et al., "Formation and characterization of zeolite membranes from sols," 3rd International Conference on Inorganic Membranes, Worcester, Mass., Jul. 10-14, 1994. Hydrothermal synthesis with aqueous solutions of zeolite precursors is the most widely used method to form the membrane layer. See, for example: M. Jia et al., supra,; T. Sano, supra; E. Geus et al., "High temperature stainless steel supported zeolite (MFI) membranes: preparation, module construction, and permeation experiments," Microporous Materials, 1993, vol. 1, page 131; Y. Yan et al., "Preparation of zeolite ZSM-5 membranes by in-situ crystallization of porous α-Al.sub.2 O.sub.3, Ind. Eng. Chem. Res., 1995, vol. 34, pages 1652-1661; Y. Yan et al., "Zeolite ZSM-5 Membranes Grown on Porous α-Al.sub.2 O.sub.3," J. Chem. Soc., Chem. Commun., 1995, pages 227-228. Other techniques for forming zeolite membranes may include: (i) treating a dry layer of zeolite precursors in steam, N. Nishiyama et al., "A defect-free modernite membrane synthesized by vapor phase transport method," J. Chem Soc. Chem. Commun., 1995, page 1967; (ii) embedding zeolite crystal in a metal matrix, P. Kolsch et al., "Zeolite-in-metal membranes: Preparation and testing," J. Chem. Soc. Chem. Commun., 1994, vol. 21, page 2491; and (iii) sintering zeolite crystals to form a dense layer, C. Engelen et al., "Membrane for separation of small molecules and its manufacture," PCT Int. Appl. WO 93/19841, 1993, to ECN. Such zeolite membranes prepared by these processes have shown a good potential for the separation of molecules that have sufficient differences in their respective adsorption and diffusion behavior. Other commercially important separations, such as nitrogen from carbon dioxide (N.sub.2 /CO.sub.2) or nitrogen from methane (N.sub.2 /CH.sub.4) have not been obtained with these zeolite membranes, most likely because the CO.sub.2 and CH.sub.4 molecules are small and can easily enter and permeate through the regions between the zeolite crystals. It is noteworthy that polycrystalline silicalite membranes have been modified with silane coupling reagents to improve pervaporation performance with aqueous ethanol solutions. The modification was performed from the liquid phase with a large alkyltrichlorosilane molecule (alkyl=C.sub.8 H.sub.17 and C.sub.18 H.sub.37). The coupling agents were dissolved in an inert solvent. The authors concluded that the change in permeation properties was caused by an altered hydrophobicity of the external membrane surface. See T. Sano et al., "Improvement of the pervaporation performance of silicalite membranes by modification with a silane coupling reagent," Microporous Materials, 1995, vol. 5, pages 179-184. However, the coupling agents used were longer molecules that were not able to enter the zeolite pores and may be too large to enter gaps between crystals. Also, diffusion and transport in the fluid phase is different than in the gas or vapor phase, so different membrane regimes should be accessed at different rates. Accordingly, it is a general object of this invention to provide a process by which improved molecular sieves and altered membranes can be fabricated for separation of materials in a mixture that have different molecular properties, such as size, shape, or adsorption characteristics. It is another object of this invention to provide a method by which passages through zeolite or molecular sieve membranes can be reduced in a very controlled and effective manner for improved material separation effectiveness from mixtures. Still another object of the present invention is to decrease pore sizes in zeolite or molecular sieve membranes. A more specific object of this invention is to provide a method for blocking or partially blocking regions between crystals in crystalline membranes or molecular sieves to inhibit transfer of larger molecules through the membranes or molecular sieves, but without substantially inhibiting transfer of small molecules through pores in the crystalline structures. Another specific object of this invention is to improve zeolite or molecular sieve membranes to effectively separate materials with smaller molecules than has been feasible with some zeolites, such as 4A. Another specific object of this invention is to provide a process for changing adsorption characteristics of zeolite or molecular sieve membranes. Another more specific object of this invention is to block or partially block regions between zeolite crystals in zeolite membranes without blocking or substantially affecting or decreasing effective pore size and molecular transfer through the zeolite crystals. Additional objects, advantages, and novel features of the invention shall be set forth in part in the description that follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by the practice of the invention. The objects and the advantages may be realized and attained by means of the instrumentalities and in combinations particularly pointed out in the appended claims. To achieve the foregoing and other objects and in accordance with the purposes and objects of the present invention, as embodied and broadly described herein, the method of modifying membranes according to the present invention includes modifying a zeolite or other crystalline membrane that has surface hydroxyl groups with an atomic layer controlled chemical vapor deposition (ALC-CVD) process or atomic layer controlled chemical liquid deposition (ALC-CLD) process. Both the ALC-CVD process and the ALC-CLD process include (i) exposing the membrane to molecules comprising a metal atom coordinated with ligand groups having bonds that are hydrolyzable and allowing them to react with the surface hydroxyl groups on the zeolite membrane or substrate to form molecular bonded structures on the zeolite surface that comprise the metal atoms coordinated with the ligand group or with a modified ligand group that results from the reaction and bonded to oxygen atoms that are bonded to zeolite substrate atoms (e.g., silicon atoms) and then (ii) hydrolyzing and possibly, but not necessarily, cross-linking the bonds in the ligand or modified ligand group. The resulting monomolecular layer deposited on the zeolite surface has coordinated groups of atoms that include (i) the metal atom bonded to oxygen atoms that are bonded to the zeolite substrate atoms (e.g., silicon atoms) and (ii) either hydroxyl groups bonded to the metal atoms or additional oxygen atoms bonded to the metal atoms. These coordinated groups of atoms that comprise the deposited monomolecular layer modify the surface of the zeolite by reducing effective sizes of defects in substrate crystalline structures as well as of gaps or separations between adjacent crystalline structures that comprise the zeolite membrane while preferably, but not necessarily, modifying substantially the effective pore sizes in and through the zeolite crystals. However, if desired, one or more additional layers can be deposited substantially in the same manner as described above, which will substantially modify and possibly even partially or entirely block the pores in the zeolite crystals. The accompanying drawings, which are incorporated in and form a part of the specifications, illustrate the preferred embodiments of the present invention, and together with the descriptions serve to explain the principles of the invention. In the Drawings: FIG. 1 is an enlarged diagrammatic cross-section of a surface of a crystalline membrane illustrating separate crystal structures separated between juxtaposed faces or surfaces; FIG. 2 is a diagrammatic representation and illustration of the hydroxyl (OH) groups or sites on the surface of a material in a specific preferred reaction of the reaction gas Al (CH.sub.3).sub.3 to produce intermediate structures that comprise the reactive atom aluminum (Al) bonded to oxygen atoms remaining from the previous hydroxyl (OH) sites and also bonded to one or more ligand (CH.sub.3) groups; FIG. 3 is a diagrammatic representation and illustration of hydrolyzing the bond between the reactive atom (Al) and the ligand (CH.sub.3) to produce monomolecular surface structures as described for FIG. 2, but with each CH.sub.3 ligand replaced with a hydroxyl (OH) group; FIG. 4 is a diagrammatic representation and illustration of the monomolecular layer composition after condensing to replace some hydroxyl (OH) groups; FIG. 5 is an enlarged isometric view of portions of adjacent crystals illustrating diagrammatically in general terms the hydroxyl groups (OH) or sites on the surfaces of the crystals as volatile reaction gas molecules coordinated with ligands (M(L.sub.3)) are introduced; FIG. 6 is an enlarged isometric view of the adjacent crystals of FIG. 5 illustrating in general terms the intermediate molecular structures after reaction with the gas molecules; FIG. 7 is an enlarged isometric view of the adjacent crystals of FIG. 6 as the second step of exposing to molecular structures of FIG. 6 to water vapor (H.sub.2 O) begins; FIG. 8 is an enlarged isometric view of the adjacent crystals of FIG. 7 illustrating in general terms the new hydroxyl groups (OH) formed on the molecular structures of FIG. 7; and FIG. 9 is an enlarged isometric view of the adjacent crystals of FIG. 8 further modified by condensation to produce continuous, cross-linked monomolecular layers on the surfaces. An enlarged cross-sectional view of a portion of a crystalline membrane or molecular sieve 10 is illustrated diagrammatically in FIG. 1 with a monomolecular layer 20 deposited or grown on the top surfaces 14 and side surfaces 16, 18 of the crystals 12 to modify the permeability of the membrane or molecular sieve 10 for gases according to this invention in order to improve the capability of the membrane to separate mixtures. For purposes of facilitating the description and explanation of this invention, the illustrations in the drawings are diagrammatic representations of crystalline and molecular structures. They are conceptual representations based on the inventors' understandings and to some extent guesses about the chemical and physical structures, since there are no direct microscopy techniques to provide actual images of the structures involved. Consequently, these diagrammatic representations only facilitate explanations, but are not intended to provide accurate depictions, dimensions, or proportions and, more importantly, are not intended to limit the scope of the invention or of this patent in any way. At the same time, it is important to note that membranes can be and have been modified by the process of this invention, regardless of how the structure actually looks on the atomic scale. The membrane materials 10 of which this invention is particularly applicable are crystalline substances, such as zeolites, and molecular sieves, such as ALPO'S, SAPO's, and MCM41, that are characterized by pores of molecular dimensions and fairly uniform size that have the ability to adsorb and/or pass small molecules but not large ones. Zeolites are one type of such materials and will be used in the exemplary description of this invention, although this invention is not limited to zeolites. Zeolites are naturally occurring and synthetic crystalline substances, composed primarily of silicon, aluminum, and oxygen and often found in nature. They are naturally porous, very uniform crystals 12. Silicalite is a particularly useful zeolite that comprises very uniform, well defined crystal structures of silicon dioxide (SiO.sub.2), which can be fabricated into membrane structures. As illustrated in FIG. 1, the zeolite membrane structures usually comprise a plurality of crystals 12, which, as mentioned above, are porous in the crystal lattice. Small molecules, such as gaseous nitrogen (N.sub.2), can enter and pass through the porous crystal lattice, while larger molecules, such sulfur hexafluoride (SF.sub.6), can hardly enter or pass through the crystal lattice of the crystals 12. However, there are defects in individual crystals as well as microscopic gaps between individual crystals. For purposes of illustration, the gap or region 22 between the juxtaposed faces 16, 18 of adjacent crystals 12 in FIG. 1 represents diagrammatically such defects and gaps. Such regions 22 can and do provide conduits through which larger molecules can pass, thus inhibiting the effectiveness of the membrane 10 for separation of larger molecules from smaller molecules. On a smaller level, even though the size of pore openings 24 in zeolite and molecular sieve crystals 12 of, for example, (MFI) zeolites, such as silicalite or ZSM-5, is comparable in size (ovular 0.51.times57 nm) to small organic molecules and are interconnected by a zig-zag system of straight channels 26 with nearly circular cross-sections of about 0.54 nm diameter, membranes 10 made of such zeolite materials are not effective in such commercially important separations as nitrogen gas from carbon dioxide gas (N.sub.2 /CO.sub.2) or nitrogen gas from methane gas (N.sub.2 /CH.sub.4). Apparently, smaller molecules, CO.sub.2 and CH.sub.4, can enter easily and permeate through the pore channels 26 along with the nitrogen gas molecules. To alleviate these problems of larger molecules passing through the gaps 22 between crystals 12 and some significant smaller molecules from passing through pore channels 26 in the lattice of the crystals 12, according to this invention one or more layers 20 of additional structures are formed on one or more of the surfaces 14, 16, 18 of the crystals 12 (such layers 20 can also be formed on the bottom or other surfaces, which are not shown), which layers 20 are also porous enough to allow entry and passage of smaller molecules through the crystal lattice, but which otherwise substantially block or clog the gaps 22 between the crystals 12 enough to inhibit entry or diffusion of larger molecules into and through such gaps 22. Such layer(s) 20 can also decrease the effective size of the pore openings 24 or otherwise affect adsorbent properties of the crystal 12 surfaces to inhibit migration of some smaller or strongly adsorbing molecules through the pore channels 26 in the crystal 12 lattice. Therefore, while the layer(s) 20 cover the top surface 14 as well as other exposed surfaces 16, 18 sufficiently to block or inhibit larger molecules and even some smaller molecules from flowing through the membrane 10, such layer(s) do not substantially inhibit entry of the smallest molecules, such as nitrogen, helium, or hydrogen, into the pores in the crystals 12. To obtain this feature according to this invention, the lattice layer(s) 20 have to be kept very thin--on the order of only a few (1 to 10) angstroms. Even with such thin lattice layer(s) 20, the fluxes do decrease for all molecules, but for some more than others. One plausible explanation for this observation could be that some pores may become totally blocked, although this explanation is not essential to the invention or to the practice of this invention. Conventional thin film deposition processes, such as chemical vapor deposition (CVD) and chemical liquid deposition (CLD), are very difficult, if not impossible, to control sufficiently to achieve the surface modifications required for such separations as those discussed above, at least on a predictable and dependable basis. Therefore, according to this invention, atomic layer controlled chemical vapor depositions (ALC-CVD) can be used to modify the surfaces 14, 16, 18 of crystalline membranes 10, such as, for example, but not for limitation, the zeolite crystals 12 illustrated in FIG. 1. ALC-CVD as used in this invention is based on reaction of volatile molecules with hydroxyl (OH) groups 30 on the surfaces 14, 16, 18, which are illustrated in FIGS. 2 and 5, to form O--M bonds, where O is oxygen and M can be any one or more metal atoms, for example, aluminum (Al), silicon (Si), germanium, (Ge), indium, (In), cadmium (Cd), and the like, coordinated with ligands (L), such as a alkyl group (C.sub.n H.sub.2n+1), chlorine (Cl), alkoxy group (O--C.sub.n H.sub.2n+1), and the like. Any molecules (i) according to this specification, (ii) that are volatile and reactive enough to react from a gas phase with surface OH-groups, and (iii) that result in an attached layer that has remaining ligands that can be hydrolyzed with water to form new OH-groups are suitable for purposes of this invention. At least one ligand is necessary if it is desired to form one monomolecular layer and at least two ligands are necessary if it is desired to form two or more monomolecular layers. After completion of this first reaction, the resulting M--L bonds (chemical bonds between the reactive atoms M and the ligands L) are hydrolyzed with water (H.sub.2 O) vapor to form new hydroxyl (OH) groups. The new hydroxyl (OH) groups of adjacent molecular formations can condense to form a cross-linked monomolecular layer. These reaction steps are illustrated and described below in more detail. FIGS. 2-4 illustrate in a graphical manner some exemplary chemical reactions used according to this invention to modify zeolite membranes 10, while FIGS. 5-9 illustrate diagrammatically in more general or generic terms and in three-dimensional views surface molecular layer formation phases according to these atomic layer controlled chemical vapor deposition (ALC-CVD) chemical reactions. While surface modification of zeolite crystal surfaces based on the presence of hydroxyl (OH) groups on the crystal surfaces is illustrated in FIGS. 2-9, other crystalline membranes or molecular sieve materials having surface hydroxyl groups or other reactive groups, such as NH.sub.2 and SH, can also be accomplished according to this invention. Referring now primarily to FIGS. 2 and 5, the top and side surfaces 14, 16, 18, as well as the bottom surface (not shown), of the zeolite crystals 12 have a natural abundance of hydroxyl (OH) group sites 30. Some zeolites, such as those that contain some aluminum (Al) in the crystal 12 lattice, have a high density of surface hydroxyl (OH) groups 30, while others, especially silica-rich zeolites, such as, silicalite, have fewer surface OH-groups 30. Usually, however, even in silica-rich zeolites, there are enough crystal defects that have OH-groups in sufficient numbers and densities to accommodate the above-described chemical reactions required for atomic layer controlled chemical vapor deposition (ALC-CVD) for purposes of this invention. In the first step, the volatile, reactive, gaseous compound denoted generically as M(Z.sub.m L.sub.n) (more specifically for simplicity of illustration--M(L)--in FIG. 5) and with the exemplary compound trimethylaluminum Al(CH.sub.3).sub.3 in FIG. 2 is introduced into a vacuum chamber (not shown) containing the zeolite membrane 10. The volatile M(Z.sub.m L.sub.n) molecules 32 react with the hydroxyl (OH) sites 30 on the exposed surfaces 14, 16, 18 of the zeolite crystals 12 to form O--M bonds that are coordinated with ligands according to the reaction expressed in general terms as: Y--OH*+M(Z.sub.m L.sub.n)→Y--O--M(Z.sub.m-1 L.sub.n)+ZH↑(1) where Y is the substrate material, OH* is the surface hydroxyl site, M(Z.sub.m L.sub.n) is the reaction gas molecule, M(Z.sub.m-1 L.sub.n) is the resulting coordinated reactive atom and ligand group, and ZH↑ is the gaseous by-product of the reaction as illustrated in FIG. 6 at 38. In general, there can be any number of ligands and any combination of ligands for purposes of this invention. Also, L could be the same ligands as Z, and Z.sub.m L.sub.n can comprise one of a kind ligand or a combination of different ligand types in different numbers. The Z.sub.m ligand can be a combination of different ligands, and L.sub.n can also be a combination of different ligands. The resulting intermediate crystalline structure, as illustrated in FIG. 6, can be, for example, one metal atom (M) bonded to two oxygens (O) and a ligand (L) as illustrated at 34, or one metal atom (M) bonded to one oxygen (O) and two ligands (L) as illustrated at 36. Of course, instead of just one ligand (L), there could also be any combination of ligands Z.sub.m-1 L.sub.n as described above and as will be understood by persons skilled in the art. However, these alternatives are not illustrated in FIG. 6, because they would add unnecessarily to the complexity of the drawing without contributing substantially to clarity or the understanding of this invention. The more specific example of this reaction (i), where Al(CH.sub.3).sub.3 is used as the reaction gas to produce O--Al bonds at the hydroxyl (OH) sites is: Si--OH*+Al(CH.sub.3).sub.3 →Si--O--Al(CH.sub.3).sub.2 +CH.sub.4 ↑ (2) which produces the coordinated group comprising one aluminum (Al) atom bonded with two oxygen (O) atoms and one CH.sub.3 ligand as illustrated at 34' in FIG. 2 or the alternative group comprising one aluminum (Al) atom bonded with one oxygen (O) atom and two CH.sub.3 ligands as illustrated at 36' in FIG. 2. The gaseous by-product of this reaction (2) is methane gas (CH.sub.4). When all of the hydroxyl (OH) sites are filled, the reaction stops automatically, so it is self-limiting, which makes this process very conducive to use in industrial applications. After the initial reaction (1) or (2) described above, the M--L bonds can be hydrolyzed with water (H.sub.2 O) vapor, as indicated by FIG. 7, to form hydroxyl (OH) groups in place of the ligands according to the reaction generally expressed as: M(L)*+H.sub.2 O→M--OH*+LH↑ (3) The more specific exemplary hydrolyzing reaction is: Al(CH.sub.3)*+H.sub.2 O→Al--OH*+CH.sub.4 ↑ (4) This reaction is also self-limiting. When all of the sites are hydrolyzed and ligands replaced with hydroxyl (OH) groups, as indicated generally in FIG. 8 and for the exemplary reaction in FIG. 3, this reaction also stops. The resulting bonded O--M--OH groups of either one reactive atom M grouped with two oxygen (O) atoms and one hydroxyl (OH) as illustrated at 38 in FIG. 8 or one reactive atom M grouped with one oxygen (O) atom and two hydroxyls (OH) as illustrated at 40 in FIG. 8 form a monomolecular layer 20 on the surfaces 14, 16, 18 of the zeolite crystals 12 as also illustrated in FIG. 1. In the exemplary reaction (4), the resulting bonded groups of one aluminum (Al) atom grouped with two oxygen (O) atoms and one hydroxyl (OH) as illustrated at 38' in FIG. 3 or one aluminum (Al) atom grouped with one oxygen (O) atom and two hydroxyls (OH) as illustrated at 40' in FIG. 3 form the monomolecular layer 20 on the zeolite crystals 12 in FIG. 1. The gaseous by-product of the exemplary reaction (4) described above is also methane (CH.sub.4) as illustrated in FIG. 3. The hydroxyl (OH) groups of adjacently deposited molecules, such as those illustrated at 38 and 40 in FIG. 8, can also condense to form a continuous, cross-linked monomolecular layer as illustrated at 42 in FIG. 9. It is possible, although not necessary to this invention, for molecules deposited on very closely spaced juxtaposed surfaces 16, 18 of adjacent crystals 12 or in defects to also cross-link, as illustrated at 44 in FIG. 9. The cross-linked molecular groups of bonded O--Al--O--Al atoms resulting from condensed adjacently deposited molecules in the exemplary reaction is illustrated in FIG. 4. The by-product of such condensation is water (H.sub.2 O) vapor. Regardless of whether or how much such condensation actually occurs, however, the resulting O--M--OH or O--M--O groups that form the monomolecular layer 20 on the surfaces 14, 16, 18 of the zeolite crystals 12, especially those formed on and over juxtaposed surfaces 16, 18 of adjacent zeolite crystals 12 or defects in crystals 12 reduce the effective sizes of the separations or gaps 22 between crystals 12 or defects in crystals 12 to an extent that improves very substantially selectivity between species and the ability of the zeolite crystals to block transport of larger molecules, thus improving molecular separation or sieving capabilities of the zeolite crystals 12 and of membranes made of such zeolite crystals 12. One monomolecular layer deposited as described above may also have some of the resulting O--M--OH or O--M--O groups formed around and over pore openings 24 in the crystals 12. In general, as described above, one such monomolecular layer will not substantially inhibit entry or transport of the smallest gas molecules, such as nitrogen, helium, or hydrogen into the pore openings 24 and through the pores 26, although larger gas molecules could be inhibited by such structures. Since the resulting monomolecular layer 20 after the sequence of reaction (1) or (2) followed by reaction (3) or (4), as described above, leave hydroxyl (OH) sites 46, as illustrated in FIGS. 4, 8 and 9 the same sequence of reaction (1) or (2) followed by reaction (3) or (4) can be repeated to deposit an additional atomic level layer (not shown) of the same resulting material, which will reduce even further the effective pore openings 24 and separation or gap 22 between juxtaposed surfaces 16,18. This sequence of reactions can be repeated as often as desired to obtain the zeolite adsorption and sieving characteristics desired. However, it has been found that one of such sequences to produce one monomolecular layer 20 as described above is sufficient and preferred for general gas separation purposes and that an additional sequence of these reactions to deposit another layer can block the effective pore openings 24 too much for practical usage, even for small gas molecules. It is emphasized again that while the above description and associated illustrations are explained mostly in terms of relative sizes of pores, defects, and molecules, which is useful for visualization and could even be quite accurate, it is not really known for sure whether size, shape, polarizibility, adsorption properties, or some combination of these or other characteristics are really affecting the selective permeability of the membranes. Therefore, the process of this invention, which does modify the permeability of the membranes, might be causing modifications in any one or combination of these factors. Silicalite (zeolite) layers were synthesized hydrothermally from a gel in much the same manner as described by Flanigen et al., "Silicalite, a new hydrophobic crystalline silica molecular sieve," Nature, 1978 271, 512, on the inside of commercially-available porous γ-Al.sub.2 O.sub.3 tubes (US Filters, 5-nm pores). After two synthesis steps, the membranes were washed, dried, and calcined at 733 K. The detailed synthesis procedure for the silicalite is described by Funke et al. 1995, Ind. Eng. Chem. Res. 1996, Vol. 35, page 1575, and Jia et al. 1994, supra. The membranes were characterized by pure gas permeation at room temperature and 150 kPa pressure difference between feed and permeate side. Gases with different molecular sizes were used as probes. Sulfur hexafluoride (SF.sub.6) has a kinetic diameter of 0.55 nm, which is close to the pore size of silicalite and hardly passes the zeolite pores, whereas small molecules such as He, N.sub.2, H.sub.2, or CH.sub.4 readily permeate through silicalite pores. The pure gas permeance for N.sub.2 (kinetic diameter of 0.36 nm) and SF.sub.6 and the pure gas permeance ratios of the unmodified membranes are listed as the first row in Tables 1 and 2 below. The ALC-CVD depositions were performed in a standard high vacuum setup with a dosing device to adjust the partial pressure of precursors in the system. The modification of the zeolite membranes required four treatment steps. First, an effort was made to remove surface water from the membrane layer so that the Al(CH.sub.3).sub.3 would only react with surface OH-groups. Heating to 523 K at 10.sup.-4 torr for several hours was thought to be sufficient for silicalite membranes, but it was not possible to know for sure that all of the surface water was actually removed. Because the deposition reaction is sensitive to adsorbed organic compounds a cleaning step removed adsorbed hydrocarbons. Treatment for 2 min. with H.sub.2 O plasma at 0.20 torr at room temperature prior to each deposition was sufficient to remove adsorbed molecules and allow the deposition. The plasma was created by an electrical discharge in the system. The dried and pretreated membranes were exposed to Al(CH.sub.3).sub.3 for 10 min. at 5 torr and 500 K. The progress of the reaction can be monitored by analyzing the gas composition. At least one molecule of CH.sub.4 is formed for each reacted Al(CH.sub.3).sub.3. If the surface OH-density is high, one Al(CH.sub.3).sub.3 molecule can react with more than one OH group, and more than one CH.sub.4 molecule forms, as illustrated in FIG. 2, which effect was also shown by Dillon et al., "Surface chemistry of Al.sub.2 O.sub.3 deposition using Al(CH.sub.3).sub.3 and H.sub.2 O in a binary reaction sequence," Surface Science, 1995, 211, 2330. The membranes were exposed to 5 torr of water vapor at 500 K to hydrolyze the unreacted Al--CH.sub.3 bonds of the surface and form hydroxyl groups as shown in FIG. 3. The hydrolysis step can also be accomplished by exposing the membrane to ambient air that has some moisture content. The hydroxyl groups of adjacently deposited compounds in close proximity can cross-link by condensation to form a continuous, monomolecular Al.sub.2 O.sub.3 layer as illustrated in FIG. 4. The influence of the water plasma treatment on the permeation properties of a zeolite membrane (HSil54) was determined by measuring N.sub.2 and SF.sub.6 permeances of membrane HSil54 before and after a plasma treatment. The pure gas permeances of N.sub.2 and SF.sub.6 at room temperature was 640 10.5.times.10.sup.-9 moles/(m.sup.2 s Pa) respectively for the untreated membrane with a permeance ratio of 61. The pure gas permeances did not change within experimental errors after the treatment (650 moles/(m.sup.2 s pa) for N.sub.2 and 11 Pa) for SF.sub.6). The changes of the single gas N.sub.2 and SF.sub.6 permeances through silicalite zeolite membranes induced by depositing atomic layers of Al.sub.2 O.sub.3 are listed in Table 1 and 2. Six silicalite membranes with different initial permeation properties were characterized before and after the deposition of 1 and 2 layers of Al.sub.2 O.sub.3. The N.sub.2 permeances through membranes HSil50, HSil52, HSil54, and HSil56 decreased by 30-70% whereas the SF.sub.6 permeance decreased by factors up to 17. Therefore, the pure gas permeance ratio for N.sub.2 over SF.sub.6 increased for those four membranes. Membrane HSil50 showed the best results with an increase in permeance ratio by a factor of more than five to over 560. The permeance ratio in the other three membranes increased by factors of two to three. A second layer deposited on HSil52 and HSil54 further decreased the N.sub.2 -permeance by factors of 10 to 40 whereas the SF.sub.6 permeance only dropped a factor of 5 for HSil52 and slightly increased for HSil54. As a result permeance ratios dropped sharply for both membranes. For two membranes (HSil51N and HSil53 in Table 2), a single ALC-CVD layer apparently was sufficient to block a large fraction of the zeolite pores so that the permeances for N.sub.2 decreased by a factor of 6 and 20 respectively, but the SF.sub.6 permeances changed less dramatically. The single gas permeance ratios therefore decreased for both membranes by a factor of 6. Single compound permeances and selectivities of gases with different kinetic diameters through membrane HSil50 and some selected permeance ratios are listed in Table 3. The smallest molecules (He and H.sub.2) permeated �1500 and 2400 times faster than SF6, the slowest molecule. Gases with similar kinetic diameters, such as N.sub.2 and CO.sub.2, permeated at similar rates. The permeance of two fluorinated hydrocarbons (CHF.sub.2 --CH.sub.2 F, kinetic diameter �0.49 nm and CF.sub.3 --CH.sub.3, kinetic diameter --0.51 nm) through HSil56 were measured to determine if the Al.sub.2 O.sub.3 layer changed the size of the zeolite pore openings. These kinetic diameters are slightly smaller than the pore size silicalite. Table 4 indicates that both compounds permeated at similar rates and only a factor of 1.7 slower than N.sub.2. Apparently, a sharp size cutoff between 0.55 and 0.51 nm results in permeance ratios of more than 100 between CF.sub.3 --CH.sub.3 and SF.sub.6. Zeolite membranes 10 can have defects or other non-zeolitic pores such as grain boundaries 22 between the crystals that are significantly larger than the zeolite pore openings 24 as indicated by relatively large permeances of molecules that should not be able to enter the zeolite pores 24 based on their molecule size. For example isooctane (kinetic diameter 0.62 nm, see Funke et al. 1996, supra), or m-and o-xylene (kinetic diameters �0.68 nm, see C. D. Baertsch et al., Permeation of aromatic hydrocarbon vapor through silicalite-zeolite membranes," J. Phy. Chem., 1996, vol. 100, page 7676) should not be able to enter silicalite pores 24. Compounds with kinetic diameters close to the zeolite pore 24 size such as SF.sub.6 should be highly hindered to enter the small zeolite pores 24. The experimentally observed fluxes of SF.sub.6 therefore should be mainly attributed to grain boundaries 22 between the crystals or other non-zeolitic pores or defects. If the deposition closes or decreases the non-zeolite pores 22 that allow non-selective permeation, a strong decreases of the SF.sub.6 permeance is expected. The extent to which each pathway contributes to the total SF.sub.6 flux, however, is not known. The high N.sub.2 /SF.sub.6 selectivity of 560 obtained for membrane HSil50 after one deposition suggests that for an ideal membrane 10 only a small SF.sub.6 permeance is expected. It is noted that zeolites exhibit some flexibility in their pore structures, so molecules that are larger than the pore sizes determined by crystalography can be accommodated. See E. L. Wu, G. R. Landolt, and A. W. Chester, "Hydrocarbon adsorption characterization of high silica zeolites," Studies in Surface Science and Catalysis, 1986, vol. 28, page 547. Therefore, fraction of the permeance of the larger molecules can be due to diffusion through the zeolite pores. The permeance for N.sub.2 decreases more than expected if ALC-CVD only blocks the regions or gaps 22 between crystals 12 and N.sub.2 and SF.sub.6 have the same permeances in these pores. Apparently some Al.sub.2 O.sub.3 overgrows the zeolite pores 24 which are the main pathway for N.sub.2. For two membranes (HSil51N, HSil53), one Al.sub.2 O.sub.3 layer 20 was sufficient to block most of the zeolite pore openings 24, and both N.sub.2 and SF.sub.6 permeated at slow but similar rates. Apparently the deposited layer 20 did not seal all defects, which are not selective, but the layer 20 did seal zeolite pore openings 24. The density and location of hydroxyl groups on the zeolite surface may affect whether zeolite pore openings 24 are sealed. The properties of the initial membrane are not identical, as indicated in Table 1 and 2. Even membranes with similar separation properties do not necessarily have the same surface structures and density and location of surface OH-groups. Growth of the ALC-CVD layer close to the pore openings 24 should also alter the effective size of the zeolite pores 26. If some SF.sub.6 molecules permeate through silicalite pores 26, a small decrease in pore opening 24 size should be sufficient to totally exclude the SF.sub.6 molecules from entering the zeolite pores 26. The observed permeance decrease therefore could also be partially attributed to a decrease in pore opening 24 size caused by Al.sub.2 O.sub.3 close to the pore openings 24. The decrease cannot be too large, however, because the two CFC compounds, which are only slightly smaller than SF.sub.6, permeated at rates close to N.sub.2 as listed in Table 3. If the deposition decreased the zeolite pore openings 24 significantly, the CFC's should also be strongly excluded. The CVD layer can also change the adsorption properties of the zeolite surface. Barrer, "Porous crystal membranes," J. Chem. Soc. Faraday Trans., 1990, vol.86, 1123, suggests that the first step for the transport through zeolite membranes is adsorption on the external membrane surface. A change in external adsorption properties can therefore significantly alter the overall transport rates without decreasing the pore sizes. The surface properties of Al.sub.2 O.sub.3 are sufficiently different from those of the silica surface of silicalite to change adsorption behavior. Atomic layer controlled chemical vapor deposition (ALC-CVD) of Al(CH.sub.3).sub.3 was used to modify single gas permeances through silicalite zeolite membranes 10 by depositing layers 20 of Al.sub.2 O.sub.3 on the membrane surface. The deposited layers 20 alter the membrane 10 properties probably by either closing defects in the membrane structure or changing the surface adsorption properties. The best improvement was a more than fivefold increase in the N.sub.2 /SF6 pure compound permeance ratio to 550 with a three-fold decrease in N.sub.2 permeance. The deposition apparently did not change the zeolite pore size 24 significantly. The deposition of additional layers closed the zeolite pore openings 24 and the permeance ratio decreased. TABLE 1__________________________________________________________________________# of CVDHSil50 HSil52 HSil54 HSil56layersP[N.sub.2 ] P[SF.sub.6 ] α P[N.sub.2 ] P[SF.sub.6 ] α P[N.sub.2 ] P[SF.sub.6 ] α P[N.sub.2 ] P[SF.sub.6 ] α__________________________________________________________________________0 990 9.9 100 915 22 42 650 11 62 860 8.8 98 1 320 0.58 550 441 4.4 100 485 3.5 139 530 2.8 188 2 13 0.7 19 41 6.7 6.1__________________________________________________________________________ TABLE 2______________________________________# of CVD HSil51N HSil53layers P[N.sub.2 ] P[SF.sub.6 ] α P[N.sub.2 ] P[SF.sub.6 ] α______________________________________0 590 9.6 61 438 5.7 76 1 98 9.3 10.5 22 1.6 14______________________________________ TABLE 3__________________________________________________________________________molecule SF.sub.6 CH.sub.4 N.sub.2 CO.sub.2 H.sub.2 He kinetic diameter (nm) 0.55 0.38 0.36 0.33 0.29 0.26__________________________________________________________________________Permeance 0.58 440 320 280 1400 910 [moles/(m.sup.2 sPa)] selected permeance N.sub.2 /SF.sub.6 : CH.sub.4 /SF.sub.6 : H.sub.2 /N.sub.2 : N.sub.2 /CO.sub.2 : H.sub.2 /SF.sub.6 : He/SF.sub.6 : ratios 550 760 4.4 1.15 2420 1570__________________________________________________________________________ TABLE 4______________________________________compound N.sub.2 SF.sub.6 CHF.sub.2 --CH.sub.2 F CF.sub.3 --CH.sub.3 kinetic diameter (nm) 0.36 0.55 0.51 0.49______________________________________Permeance 530 2.8 300 320 [moles/(m.sup.2 sPa)]______________________________________ The foregoing description is considered as illustrative only of the principles of the invention. Furthermore, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and process shown and described above. Accordingly, all suitable modifications and equivalents may be resorted to falling within the scope of the invention as defined by the claims which follow. Patent Citations
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More quality games for Sky Sports customers
Ten races exclusively live on Sky Sports F1 in 2014
Marouane Fellaini finally showed what he could do in a Manchester United shirt, writes Adam Bate.
Watch the full-length version of Sky Sports News' exclusive chat with McLaren boss Ron Dennis.
Adam Bate addresses the main issues to emerge from England's game against Denmark at Wembley.
Listen to the latest news and views from the NFL with our very own Neil Reynolds and Jeff Reinebold.
Norwich could find themselves drifting towards relegation under Chris Hughton, writes Adam Bate.
team 1 | time | team 2 |
No scheduled matches |
Player details | |
Name | James Tredwell |
Dob | 27th February 1982 |
Club | Somerset |
Batting Style | Left-hand |
Bowling Style | Off break |
James Tredwell will welcome another Australian assault on his bowling in Saturday's must-win ODI in Cardiff.
James Tredwell will captain England in their second T20 international against New Zealand at The Oval after Eoin Morgan was ruled out with a hand injury.
England captain Alastair Cook paid tribute to James Anderson and James Tredwell for destroying South Africa's batting in a one-sided ICC Champions Trophy semi-final.
Spinner James Tredwell says England fancy their chances of claiming a first ever 50-over global tournament success in the Champions Trophy.
Graeme Swann will miss England's Test series in New Zealand in order to undergo surgery on his right elbow.
Kent spinner James Tredwell has been added to England's squad as cover for the final two Tests in India.

subset: commoncrawl


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Best Celeb Pics of the Week: March 25, 2013
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American Idol: Greatest Moments
American Idol: Greatest Moments
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American Idol: Greatest Moments
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American Idol Greatest Moments
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American Idol
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Justin Guarini
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American Idol Greatest Moments
The album debuted at number four on the album chart for the week ended October 6, 2002 and sold 146,000 the first week. It was certified gold on November 26, 2002, and has sold a total of 643,000 by May 31, 2006.
Track listing
(You Make Me Feel Like) A Natural Woman -
Kelly Clarkson
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United States Border Patrol agents from the Calexico station apprehended another dangerous gang member attempting an illegal entry into the United States, two gang members in just the last three days. Border Patrol agents earlier this week observed a 34 year old male and Mexican national identified as Jessie Ruelas-Ruiz, cross into the United States illegally from Mexico. Agents arrested Ruelas without incident.
Ruelas was transported to the Calexico Border Patrol station, where it was revealed he was an active member of the "18th Street" criminal street gang out of Los Angeles and has immigration and a criminal record.
He is in Border Patrol custody and will be presented for prosecution for re-entry after being previously removed from the United States.


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Excellent films, exquisite art, fashion shows, spoken word fest, special events, stand up comedy, and much more at the Pan African Film Festival! February 10 - 21, 2005
The Pan African Film Festival is better than ever this year -- film screenings of notable movies like George C. Wolfe's Lackawanna Blues, Spike Lee's Sucka Free City, Tyler Perry's Diary of a Mad Black Woman, and Queen Latifah's Beauty Shop, brilliant documentaries, fascinating short works -- it's a film lover's delight!
For complete schedule, list of all events, and more information, please visit www.paff.org
Date: Thursday, February 10, 2005
Time: 1:00 PM - 1:00 PM
Magic Johnson Theatres and
Baldwin Hills Crenshaw Plaza
3650 Martin Luther King, Jr. Blvd.
Los Angeles, CA United States
Cost: Film screenings: $9.25 general admission (4 PM and after); $7.25 adult matinee (before 4 PM); $6.50 Seniors (62 and over); $6.50 Children (11 and under); $7.50 students (with ID) - for other event prices, please visit the website at www.paff.org
To purchase tickets and passes: All screening and SpokenwordFest tickets on sale at Magic Johnson Theatre Box Office. Opening night tickets, Night of Tribute and Passes on sale online at www.paff.org or at the Manager's Desk in Magic Johnson Theatre Lobby.
Pan African Film Festival
Tel: 323-295-1706
Sponsor(s): Multiple sponsors; please check the PAFF website for a complete list.
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Nominated for: BEST Seafood BEST Breakfast
You guys are awesome. The ONLY way you could be even MORE awesome is if returned the favor and voted for Artistic Edge for Best Custom Framing. Then you'd just be like "whaT? omg! AMAZING!" Thanks you guys and keep up the great work you all do! :)
Vote: BEST Seafood
Let's just be honest here - the Virgin Sturgeon is an odd, odd place and it isn't going to appeal to everybody. One look at their Yelp reviews and you'll see everything from it's disgusting, dirty, weird and smells like pee, with bad food to boot, to it's cozy, charming, unique and the food is delicious. The truth is somewhere in the middle. It IS unique AND it's old, worn and a tad sticky with a tiny bit of a smell that testifies to that fact, but I am one of those people who find it charming. From the oddball entrance down an old airliner jetway, to sitting on a barge on the Sacramento River, to the absolutely delicious seafood coquille they served me, I enjoyed it all, to the extent that I didn't mind the slightly musty smell. It's a must try, at least once, even if just for the experience!
Vote: BEST Seafood
People who voted Joe's Crab Shack clearly have no idea what good seafood is!!!
Vote: BEST Seafood
prettynpetite on March 22, 2012
best catfish & eggs! also chorizo n egg plate is delish!
Vote: BEST Breakfast
The best mushroom cheeseburger in Town. And a gorgeous bartender on Saturdays with you Burger!!!!
Vote: BEST Burger


text:
Juvenile Collection
The USC Upstate Library's Juvenile Collection is located near the center of the library, past the Oversize Collection. These books are organized by the Library of Congress Classification System. They are identified by the location "Juvenile" in the Library's system. The Juvenile Collection contains: non-fiction, fiction, easy books and many of the Newbery & Caldecott Award winning titles.


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LATHAM - Major General Patrick A. Murphy, The Adjutant General for the State of New York, announces the promotion of members of the New York Army National Guard in recognition of their capabilities for additional responsibility and leadership.
Bradley Rhoades of Cassadaga, serving with the Company D (Forward Support Company Reconnaissance, Surveillance and Target Acquisition), 427th Brigade Support Battalion is promoted to the rank of private first class.
Army National Guard promotions are based on overall performance, attitude, leadership ability, and development potential. These promotions additionally recognize the best qualified soldiers and attract and retain the highest caliber citizen soldiers for a career in the New York Army National Guard.


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Photo by Kathy Browning
The Elks are here
The Downtown Improvement Committee placed one of its planters in front of the Hotchkiss Elks Lodge recently. Elk members ooked through the Elks' catalog and found this metal emblem. They ordered it and bolted it to the planter. It makes for a striking sight on Bridge Street. The Downtown Improvement Committee would like all the planters to be decorated. Contact Mary Hockenbery, president of the Hotchkiss Planning Commission, with your ideas.
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August 2001, Vol. 13, No. 8
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The Affiliate Support Council met on July 19 in Las Vegas to elect its chair and to review its roles. The council is made up of one member from each region, four at-large members, and the NAPM chief executive officer. The chair is chosen by the Affiliate Support Council members and will be announced in September.
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Liner Notes
NAPM annually honors an outstanding individual in the purchasing profession with the J. Shipman Gold Medal Award. The Shipman Medal was established in 1931 to commemorate the contributions of Johnson Shipman, a purchasing agent for Neptune Meter Company in New York and a pioneer in the purchasing profession.
NAPM Headquarters will be closed on Monday, September 3, 2001, in observance of Labor Day. Offices will reopen Tuesday, September 4.


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Stranger Joined: May 19, 2011 Post Count: 3 Status: Offline |
I upload module Thai bible (tbs1971-commercial, I used sword for PC) to pocketsword it pass but when I open bible or commentary program show message "This Chapter is empty for this module" |
Veteran Australia Joined: Dec 17, 2009 Post Count: 212 Status: Offline |
Hi there, can you let me know where you got this Bible from? I have not heard of it, and so are you sure that the module is properly working in any of our other front-ends? If it appears empty in PocketSword that could either be because the module hasn't been created or because PocketSword has a bug in it. I may have some time to look into this for you, if you would like, but you would need to email me the module - to niccarter [AT] mac [DOT] com Thanks, ybic nic... :) ---------------------------------------- PocketSword Developer http://twitter.com/PocketSword |
Stranger Joined: May 19, 2011 Post Count: 3 Status: Offline |
Thk for answer, I try to many way and i found way to add bible to pocketsword. I used config file from sword program for pc, in config file contain password. But have some problems... have 2 bibles and 1 commentary....i can add 1 bible and commentary but another one can not..... I will sent to you for suggestion... Thk And one question thai bible that i add to pocketsword can not search. went i search it had a screen download modules search index. I try to downdload but not have. How make a seach index? Thk very much for help. God bless! |
Veteran Australia Joined: Dec 17, 2009 Post Count: 212 Status: Offline |
Hi there, To create a search index, you can use MacSword/Eloquent, which you can download from http://www.macsword.com/ -- although it is only available for the Mac. Then you need to package up the module as a ZIP file again and reinstall the module into PocketSword. I hope that helps! :) ---------------------------------------- PocketSword Developer http://twitter.com/PocketSword |
Current timezone is GMT Mar 14, 2014 12:51:58 PM |


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The head of Europol's cyber crime division, Troels Oerting, has warned against using public Wi-Fi hotspots, after the law enforcement agency has seen an increase in the misuse of public Wi-Fi for identity theft and financial attacks.
Logging into public Wi-Fi hotspots can be risky, particularly for business users with sensitive data on their devices – but a new breed of hi-tech hotspots may make things safer, the Wi-Fi Alliance claims.
When we relayed the FBI/IC3 warning to travelers about a threat involving hotel Internet service overseas last week it produced a lot of requests for advice on how to respond to the threat. So a few of us researchers at ESET came up with a list of data security tips for travelers. These tips will
You just got a new wireless router for Christmas, but when you set it up it asks about wireless security. Do you want WEP, WPA, WPA2 or any of the other alphabet soup options they give? While it's easiest to just pick the default setting, are you setting yourself up for trouble from aspiring hackers?
An aspect of mobile computing that affects generations unborn…
With fantastic teeny model helicopters sporting mini hacked Linux platforms that long to take over your wireless network and wreak havoc, or so recent headlines would suggest. Now, we're big fans of innovation, and technology on the go, but these pseudo-drones (built on the cheap, for the under-budgeted aspirer of wireless world domination) lack the
Sitting in an airport you rarely frequent, you grab your laptop and snap out a couple e-mails to send, and look, there's a free WiFi hotspot. Bang, you connect and send, and are off on your way. What you don't know is the free WiFi may come with a price: your login credentials and network
There are reports coming out today about Google Android and how approximately 99.7% of its users are potentially open to compromise. This news cycle started by the Ulm University publishing some information on the 13th of May showing some results. I'm sure this story will develop and CTAC may follow-up to my blog with more details;
An article came out yesterday from Clement Genzmer who is a security engineer at Facebook. His tagline is "searching and destroying malicious links". Those of us in the business of digital security and safety can certainly identify with that, especially the part where we aim to identify the criminals and work with law enforcement to
[C. Nicholas Burnett, the manager for ESET LLC's tier three technical support, contributed the following guest blog article on the FireSheep plugin for Firefox. Thank you very much, Carl! Aryeh Goretsky] The past several days have seen the security community abuzz about a program presented in San Diego at ToorCon 12 this last weekend called
[Part 9 of an occasional series, updating a blog series I ran in early 2009 to reflect changes in the threat landscape. This series is now available as a white paper at http://www.eset.com/download/whitepapers.php.] Be Wireless, not Careless Don't connect to just any "free Wi-Fi" access point: it might alter your DNS queries or be the "evil twin" of


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Welcome to the JHUF Jamia Hafsa Forum جامعہ حفصہ فورم.
In this section Admin and Moderators will be making Announcements.
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Let's Talk: Terror in Newtown
Join Loop 21 on Twitter tonight at 8 to talk about the rampage at Sandy Hook Elementary
The massacre of 20 first-graders and six educators at a small elementary school in Newtown, Conn., Friday has led to some of even the staunchest gun-owners advocates questioning the unfettered right to bear arms in this nation.
The rampage at Sandy Hook Elementary School is hardly the first mass shooting this nation has faced, nor is the country immune to the deadly gun violence that takes place in homes and on street corners almost daily in cities big and small. But the murders in the bucolic New York suburb of Newtown seem to have struck the largest nerve in the country, with stoic journalists and the president of the United States alike finding it difficult to remain composed.
Why? What is it about the Newtown massacre that makes it stand out from the movie theater massacre in Aurora, Colo., or the rampage on the campus of Virginia Tech, or the hundreds of people, most of them young black men and boys, killed in gun violence on the streets of Chicago this year? What could be/should be the outcome when it comes to the regulation of guns in the United States?
Let's talk about it! Follow Loop 21 on Twitter to join a TweetUp tonight at 8 p.m. EST when we'll talk about the Sandy Hook Elementary School massacre in Newtown, Conn. The hashtag is #L21Newtown.
Join us for our live TweetUp!


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Boys Basketball: Black Knights take care of OneidaROME, N.Y. (WKTV) - The RFA boys basketball team won another Tri-Valley League game Friday, beating Oneida 74-46 at Strough Middle School. Jon Griggs led the Black Knights with 18 points, while Lloyd Parkmond added 14. RFA took a 16-12 lead at the end of the first quarter and slowly extended that lead throughout the rest of the game. The Black Knights led the Indians 32-21 at halftime and 51-35 after three quarters, then used a 23-11 fourth quarter to put the game away. Chris Morehouse led Oneida (1-3, 0-3 TVL) with 17 points. RFA (4-1, 3-0 TVL) will next travel to Whitesboro on Monday. |
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Sorry this item is currently sold out. Please use this discount coupon for an additional 5% off during checkout:
Sessions Achilles Snowboard Pants are lightweight pants that are sure to keep you comfortable in the elements of cold, rain or snow, without feeling heavy and bogged down. The pants are manufactured using DWR treated nylon for strength and comfort. Another benefit the Achilles Snowboard pants offer is inseam venting. This is a critical feature that helps to prevent overheating. Waterproof fabric will keep cold liquid from getting wet while out on the slopes. There are dual cargo, and butt pockets, along with lined hand warmer pockets, and even a lower leg cargo pocket. These are all around solid snowboard pants which are up for the challenge.
I go boarding 2-3 times a week. These pants have kept me warm and dry every single time. Very flashy pants, and stylish too!
Love these pants! Super cool look. Not too baggy and still look very awesome. Awesome bright blue color. Does not get in way in bindings or tripping. The perfect pants for an even more perfect price
I was told by staff that the blue was supposed to be darker than the picture shows. But the colour is exactly dead on. I like that its a baggy so it doesn't restrict movements. Overall, solid pants from Sessions!
Picked up these pants because they were reasonably priced and had great reviews. They definitely met my expectations. Kept me warm in 20 degree days on the mountain. Kept me dry in the slush. Overall great pants.
My boyfriend bought these pants as he needed news one (cos I stole his old ones) and they are great. Baggy and comfortable and he LOVES them. Great buy!!!!
My boyfriend bought these pants as he needed news one (cause I stole his old ones) and they are great. Baggy and comfortable and he LOVES them. Great buy!!!!
Bought a pair of these this year - I was looking for a cheaper pair of baggy pants and these fit the description perfectly!
These pants are a pretty good buy, they have good specs as far as water proofing goes. Great that they have RECCO Very wide leg fit (not good for short or thin legs) I advise that if you are a 32 in jeans do not buy big...
The velcro strap doesn't really work as it keeps getting loose by itself. There is enough room for extra layers as it is on the baggy side. Other than that it's good for it's price.
the best snowpants i have owned i use them to ride my snowcat and to snowboard. i go about ever weekend and they have not let me down yet. try them out.....
the best snowpants I have owned I use them to ride my snowcat and to snowboard. I go about every weekend and they have not let me down yet. try them out.....
these snowpants are sick, they are comfortable and have this cool zipper vent that you can open on a chairlift ride. i reccomend getting these pants
These snowpants are sick, they are comfortable and have this cool zipper vent that you can open on a chairlift ride. I recommend getting these pants
These are my favorite pants, they breath awesome, they are extremely warm, and they are nice and light. Not too bad for your wallet either.
I got these pants just this summer. Even though I haven't got to wear them while I was riding, I have tried them on and they fee great. They are a baggier fit but I think that they feel great. They feel nice and warm inside. Great buy.
I got these pants just this summer. Even though i haven't got to wear them while i was riding, i have tried them on and they fee great. They are a baggier fit but i think that they feel great. They feel nice and warm inside. Great Buy
I bought this according to the sizing chart and it fits perfectly. I was worried the legs weren't going to be long enough but it wasn't too much of an issue. The pants fit well, so follow the sizing chart! The pants are pretty warm. I tried them on without my cold gear underarmour and 1 minute later my legs were super toasty. Lots of pockets for storing all types of things. I was impressed to find the draw-strings on there to help pull your pant legs up (my previous pair didnt have that). The pants are a more of a loose fit/baggy style. Which is perfect since it keeps your legs loose and agile for mobility on the slopes. I've yet to hit the slopes with this pair but from what I see and feel, this is a winner.
I bought these pants over the summer for $40. Talk about the deal of the year. I would easily pay $150 for these pants, and not feel bad about it. They are very warm and water resistant. They have all the pockets, zippers and other features you'd want in some snowboarding pants without looking like 007. I was surprised how often I use the straps on the sides so they don't drag on the muddy parking lot as I'm changing or walking to the ski lodge. If your looking for some solid pants these will definitely meet your expectations.
Very nice pants; sick colors that pop. These pants will keep you dry and comfy even in deep pow or extreme cold. Wore these in below zero temps (wind chill) and they were great. I really like that it has this feature that allows you to pull your hems up when you're walking thru the parking lot so they don't get all muddy and stepped on. plenty of pockets.
This are an amazing pair of pants for this price. This is probably the best deal on pants. The pockets are in great locations. The pants hold up very well.The fleece lining is really nice in them. I usually am not to pleased with stuff from sessions but I was pleased with this pair of pants.
I bought this pant after my DC pair got a hole in it and no longer kept me dry. I was hoping that this pant would keep my butt dry, but I am disappointed. I fall a lot, and I also often sit in the snow to rest or catch my breath. This results in water leaking through my pants and I was hoping that the Achilles 10K waterproofing would be enough - It was not. Water still got through my pants, which sucks. Granted though, I am in California where the snow is much more wet. I am 5'7, bout 150, have a 31 waist, but this pant (size small) was just a little too baggy for me. After wearing it just 2 times, the bottom of my pants are already completely frayed because I stepped on it too much. I don't plan on wearing this pant anymore, and will be upgrading to gore tex soon.
i looked at about 6 pairs of pants before deciding on getting one of these. they have the string so you can pull up the pant legs when walking with out walking on them but they dont seem to stay up but im ok with that. i have been out in all weather. in slush i stayed dry. and then in negative wind chill i only had a pair of under armor cold gear long johns on and was fine. if your looking to get a pair, get these ASPA! the price is just right!
These are great pants that look great.Lots of pockets, and there is even a little hole where you can put your earphones through if you want to listen to music. However, the pants don't button up with my '06 Sessions jacket. The pants have a plastic button while my jackets has metal ones :( It works with newer jackets
These pants are sick. I have the blue ones in XL. i had to get the XL because they were sold out of everything else, but i am glad that i did. the variety of colors is sick and these pants go well with my sessions revolution jacket. the pants have a ton of pockets. they are functional and fashionable at the same time. in addition they have a nice lining. these pants are great for spring conditions and moderate temp days. however they do allow room for thermals underneath so if it is a cold day these pants would also suffice. Overall, these pants are a great value and would recommend purchasing them before they are sold out.
I bought these to go with my green and black sessions jacket and i absolutely loved them! They fit good, look good, and best snowpants i worn. I like how it dont have too many pockets but just enough. The price is remarkably cheap. You cant pass these up.
Sessions pants are sick! I have never had a problem with any of their products. These pants fit well, loose but nothing crazy. The Medium length is perfect for me when I wear them low. I'm 5'11 175 lbs. Plenty of pockets and adjustable leg openings. The vents are placed in the right spots! Keeps you warm, but not hot. Great Pant
This is my second pair, First pair is great, except brown with brown jacket and nobody could see me in flat light or far away. Picked royal blue this time around and they can be seen from the moon. Very light weight, fit loose without being baggy and great feature list. The downside is they are not very warm compared to some of my other pants, and most likely will not be my pick for those really cold high mountain days. Also I have not ever had a super wet day in these to find out how good the waterproofing is. pockets everywhere, even by your foot? drawstrings to pull up legs, snaps at ankles to provide extra boot room. the crotch venting, is not as well constructed as some other brands, I am aware the zips are there, and I should not be. They dont keep the correct shape. overall, you can get warmer , tougher gear, but if you are looking for an early season, sunny day pair of pants that will keep you warm but let you breath and will not overheat the goods then these are a good choice. I picked these 2011s on sale for 62!
I bought these pants because they were the cheapest insulated pants I could find in my size and I am very happy with my purchase. I am 5'8 with a 36-38 waist, and the waist on these fit perfect, but the legs are quite long. Not to much of an issue while riding, but when walking, I ended up pulling the bottoms up so they would not drag. One issue I had was the split at the bottom has a button closure, so if they popped up on the hill, they would fill with snow and then no longer snap closed. I have the same issue when snow gets onto velcro, so I think a zipper would work better down there. Some features I like about these pants are: Really good elastic gaiters Zippered hand pockets are warm and lined, and include headphone holes zippered thigh vents work very well draw string waist adjustment belt loop snaps to work with some jackets. They were perfectly warm, but the coldest it got here was 25degrees My local mountain has the Recco system which these pants are equipped with. The legs are big enough to wear over my bindings, so my bindings do not pull on my pant legs. Some things I did not like about these pants: The 2 back pockets, 2 cargo pockets and little ankle pocket all close with only one snap. No velcro and no zipper so I did not feel secure putting anything in them. The snaps won't stay closed once they get snow in them. They were longer then I expected. I read some of the other reviews, and I guess they must have removed some of the features. The 2011 model does not have snaps and velcro for the pockets, and there is no strap to pull up the pant legs. I would reccomend these pants to anyone looking for an inexpensive pair of pants for nice spring snow days. One last thing...I got stuck a couple times in knee deep pow but no snow ever got in my boots.
These pants are great! I'm a snowboard instructor and I go through a pair of pants almost once a season. I'm on my second year of owning these pants and I couldn't be happier with them. They fit nice and baggy so you can get low without feeling restricted and for the price you can't beat it!
Used these pants over the past two weeks in AZ. The first week at Sunrise the temps were in the high 50s the snow was packed powder and ice in spots. In warmer temp these pants are great. The vents work great but the netting in the crotch zipper catches and tears.The second week was at Snowbowl in Flagstaff more packed powder and ice. The temps were much colder 20's and 30's. These pants were a little too thin for my liking even with a base layer. The fit of the pants is great and the tabs on the legs to pull the cuffs up is a awesome innovation which makes going through a muddy parking lot no big deal. My only gripe with these pants is the bottom of the leg tore up. The thin material got chewed up by the edge of my board while riding the lifts. Overall good pants better suited for warmer days.
this is a no frills pant that has tons of pockets to store all that precious cargo of yours. the pants are extremely light compared to the burton cargos i used to wear. it's like you're not even wearing pants. but they run a little baggy, which was expected. with it being lightweight, sitting on the snow for more than a few minutes doesn't feel comfortable. they have these straps for the legs that button in as you pull them up. they're supposed to keep you from dragging your heals. but they're more gimmicky than useful.


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Originally posted by: olman on 10/29/2005 10:30:18 PM
life member looking forfor someone to fish with in the billings area. in the area till mid dec.from ill doing work for power company & can only go out on sundays
Sorry it took so long to get back to you! I've been avoiding the forum for awhile. Just thought I would check-in.
I live in Columbia Falls, also! If it has fins, I enjoy catching!!
I guess you're right tanda1.
At least at, www.ultralitefishing.com there is some great stuff happening. I can't wait to see some fish this coming April 1st - Aug. for the Multi-species Tournament. It's free and most of the prizes are donated from other members of ULF. A great family of fisherman with kids, grand kids, brothers, sisters, mom, dad, grandpa and grandmas. 1st class fisherman the enjoy the love the fishing and teaching fishing.
And I know there are some great fish that are going to be caught this 2008 season. Do you have it in you, camera, card, tape measure, and picture of you and fish. Are You in. Show us your different fisheries.
See ya there or back here???


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Albuquerque Homeschool Forum / Swap meet / ISO Decent working piano
Posted by:
514 (Guest), November 2, 2011, 9:03pm
We are looking for a decent working piano for our daughter who wants to learn to play. We'd prefer to pay $250 or less and would be willing to pick up anywhere in the Albuquerque/Rio Rancho area.
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Developed by Carey R. Dayrit, listed in Data Type
Stack provides API to manipulate a stack using two dimensional arrays.
Functions of Stack:
- Push an element
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- Retrieve the element at the top of the stack without removing it
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If you want to read more about the makeup in this photo, check out the blog: Fall 2012 Makeup Trends: Geometric Makeup. As for the hairdo, dust off those crimping irons because frizzy, funky hair is hot right now!
When it comes to crimped hair, the shorter the hair, the more wild the style will turn out. Our model here has long hair with grown out bangs, which works well with crimping. She also has minimal layers in her hair, which keeps it looking semi-smooth. Hair that is very layered can look a bit odd when it's crimped because all of the ends are accentuated and they do not blend together—just keep this in mind if you have your heart set on crimping your short 'do.
Another thing to consider is your fringe. What if you have a blunt Jessie J style fringe- do you crimp it or leave it straight? It's up to you and how retro you want to look, but it may be best to pin them back when you crimp your hair to eliminate face-framing frizz.
Now that we've covered the crimping basics, the only question left is: can you pull it off?
To see how you'd look with the hairstyle pictured in this blog, click on the above image to try the virtual hairstyle with your own photo!


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Students participating in the London Program pay regular St. Lawrence University comprehensive fees. The comprehensive fee covers tuition, room and board with the homestay families, theatre tickets for students in the theatre course, and program-integrated field components.
If you receive financial aid, your normal financial aid is applied. Contact the Financial Aid Office if you would like information about additional loans for extra costs associated with studying on this program.
The fee does not cover:
Breakfasts and two evening meals per week are provided by host families. Students will be given funds from the board fee every week to cover the cost of additional meals. Students are encouraged to make use of the University of London Student Union cafeteria.
Please note that London is a very expensive city, as is all of Europe today. See Money Matters for more details.
A non-refundable first payment of $500 is to be made upon acceptance. The remaining sum must be paid upon receipt of bills from St. Lawrence University. Participants in a program will have incurred responsibility for the full cost once they have formally accepted enrollment. Refunds will be made in accordance with the policy outlined in the St. Lawrence catalog, minus any money that has been paid out on behalf of the student.


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Winter Adventure
Rates from $79 per night
Valid: 1/12/2014 to 3/31/2014
As a Callaway Gardens Winter Adventure guest, you'll enjoy the splendor and serenity of our renowned woodland Gardens, plus a wide array of recreational, educational and social opportunities – and in a mild Southern climate that allows you to get out and comfortably enjoy it all. Spend one, two or three months – January through March – with us and you'll leave with memories of the most satisfying Winter ever!
*Rate is per night in a one-bedroom Cottage. Minimum one-month stay. Valid January through February, 2014. March rate also available. Some restrictions may apply. Golf cart rentals available for additional fee.
Summer Family Adventure
Packages starting at $2163 per 5 people
Valid: 5/31/2014 to 8/2/2014
Summer Family Adventure is a four- to seven-day summer vacation that connects your loved ones and offers countless options for fun in a beautiful natural environment. Callaway Gardens partners with the Florida State University Flying High Circus, whose members lead guests ages 3-17 in a variety of exciting day camp activities. Adults have their own eclectic lineup of offerings, and late afternoons and evenings reunite families to enjoy beach parties and competitions, bingo and trivia games, educational shows and outings, and much more. Summer Family Adventure runs for nine weeks between May 31 and August 2, 2014, with options for four, five, six and seven nights. Regardless of how long you stay, you're sure to make memories for a lifetime.
*Rate is per week in a two-bedroom Cottage or Villa. Valid May 31 through August 2, 2014. Tax and gratuity not included.


text: WASHINGTON, Monday—We came down to Washington yesterday evening to find the trees in bud, the fountains playing outside the White House and the daffodils all in bloom along Pennsylvania Avenue and in the little garden on which my window looks down. One magnolia tree is completely out and everything looks as though spring has arrived. Yet, in Hyde Park, we had snow Sunday morning, and they tell me they even had a flurry of it here. I had everything tidied up and put to rights in my room before I went to bed last night and found it quite exciting to look into the few pacakages containing things which I had bought in San Francisco. It was like discovering something entirely new. This morning dawned clear and sunny, much to my joy, for it means a much happier time for the children and their parents who are on the South Lawn for the egg rolling. At 9:15 the Easter lilies flown from Bermuda, as a gift from the Governor of Bermuda, were presented to me and they are now making the West Hall on the second floor beautiful.


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The Internet and information and communications technologies (ICT) are powerful tools for expression and political participation. Increasingly, however, repressive countries (and even some democratic ones) are harnessing the power of the Internet and ICTs in ways that violate basic human rights such as freedom of expression and privacy. Authoritarian regimes censor web content, encourage self-censorship, demand real-name registration, actively surveil and block online communications, and even limit Internet access altogether. They also punish activists who attempt to use the Internet as a medium to dissent or challenge state authority. Governments also often seek to enlist technology companies and other intermediaries in these efforts.
CDT's fast-growing work in promoting global Internet freedom focuses on developing best practices for industry for advancing freedom of expression and privacy, promoting governmental policies that advance and protect human rights, and supporting the efforts of other global Internet freedom advocates all over the world by providing policy advice and technical assistance.
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I hate Fantastical. And I hate Fantastical 2 even more. Except I kinda love them. And I hate that most of all. Thing is, I don't like calendars. They remind me of everything I have to do, and I have far too many of those things, and I don't want to do most of them. I don't even want to enter them into my calendar. I want them to leave me alone. But I don't have that option. So, since I have to do them, and I need a way to remember to do them, I also need a way to make that as quick and painless as possible. And that brings me right back to Fantastical, the one calendar app that's actually quick and painless enough that I have no excuse not to use it. More precisely, Fantastical 2, and even quicker, more painless, flat out better way than even the original. With an iOS 7 redesign. And Reminders integration. And a landscape week view. Dammit.
More →
The popular and totally awesome calendar app Fantastical for iPhone has been updated with a new setting that allows you to display only one day at a time in the event list. The default setting is an infinite list that shows all future events. A few bugs in Fantastical have also been addressed.
Fantastical, the fantastically functional calendar app by Flexibits, has just been updated to version 1.1. I've been beta testing it for a while, and as clichéd as it sounds, it really does make the already great app even better.
Flexibits didn't have a booth at this year's Macworld|iWorld, but what they lacked in structured location they made up for in the big personality of designer Michael Simmons, the ninjary of coder Kent Sutherland, and pure event-based awesomeness that is Fantastical.
While the default Calendar app for iPhone can get the job done, the interface leaves a lot to be desired. At the end of the day, a calendar app should be powerful, but still allow you to enter and find appointments as quickly and easily as possible. It's a balancing act. But which one is the best balance?
We've taken a look at a lot of the most popular alternative calendar apps for iPhone including, Week Cal, Calvetica, and many more. After testing all of them out, we believe Fantastical by Flexibits is the best choice for most iPhone users. Here's why...
I have a love/hate relationship with Flexibits' Fantastical. There is absolutely no faster, easier, more human way to enter appointments into your calendar. And because of that, my calendar -- previously a wasteland -- is now bristling with appointments. My only saving grace was that Fantastical was bound to my Mac, and I couldn't use it when I was out and about, with only an iPhone in my pocket. But with Fantastical's terrible awesomeness coming to the iPhone, I can now fill up my calendar faster, easier, and more humanly than ever before on the go, and no matter where I am. I'm organized now. I have no excuse left not to be. Dagnabit.
Marc, Rene, and Seth iterate through Android 4.1 Jelly Bean, the Nexus 7, and Windows Phone 8, and interrogate Michael Simmons of Flexibits and Fantastical. This is Iterate!
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