text:
US 5441718 A Abstract A process for making inorganic gels by reaction of tetraalkoxy orthosilicates, tetraalkoxy titanates and tetraalkoxy zirconates with strong carboxylic acids. Water need not be present initially as a reactant. Optically clear, very small pore size, narrow pore size distribution, and high specific area inorganic gels useful for abrasion-resistant coatings, optical applications, catalyst or enzyme support, gas separation, or chromatography packing are thus produced.
Claims(9) 1. A process for making open pore, inorganic gel, comprising:
(1) intimately mixing together the following components (A) and (B), either in a liquid state or in solution in an organic liquid: (A) at least one compound selected from the group consisting of Si(OR1 )4, Ti(OR2)4, Zr(OR3)4, Tia (OR4)n Xd p, and Zrb (OR5)n Xd p wherein each one of R1, R2, R3, R4, and R5 independently is a C1 -C8 alkyl; X is a chelating ligand; a and b is a coordination number having an integer value of 4-6; d is a number corresponding to the chelating ability of ligand X, being 2 for bidentate chelating ligands and 3 for tridentate chelating ligands; p is either 1 or 2, with the proviso that p is 1 for tridentate chelating ligands; n=a-d�p; and (B) a strong carboxylic acid, having a pKa value not higher than about 4.0, and containing from 0 to 40 mole % water, the amount of carboxylic acid being at least 1.5 moles of --COOH groups per mole of compound (A), and the total amount of water from any source initially present in the reaction medium being less than 5 moles per mole of Component (A); (2) agitating the above mixture while maintaining the mixture at a temperature within the range of about 0� to 100� C.; and (3) isolating the inorganic gel. 2. A process of claim 1 wherein (A) and (B) are mixed in a mole ratio of (B):(A) from 2: 1-40:1.
3. A process of claim 1 wherein the strong carboxylic acid contains at most 20 mole % water.
4. A process of claim 1 wherein temperature is maintained within the range from 0� to 60� C.
5. A process of claim 1 wherein the amount of carboxylic acid is at least 2 moles of --COOH groups per mole of compound (A).
6. A process of claim 1 wherein the total amount of water initially present in the reaction medium is less than 1 mole per mole of compound (A).
7. A process of claim 1 wherein R1 is a C1 -C4 alkyl.
8. A process of any one of claims 1 through 7 wherein the strong carboxylic acid is selected from the group consisting of formic acid, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid and hydroxyacetic acid
9. A process of claim 8 wherein the strong carboxylic acid is formic acid.
Description This is a continuation-in-part of my application Ser. No. 7/885,793 filed May 20, 1992, now abandoned. This invention relates to a rapid, nonaqueous process for producing optically clear, inorganic gels of silicon, titanium and zirconium. The above-described inorganic gels can be dried to form strong, hard, optically clear compositions that are useful as abrasion-resistant and controlled refractive index coatings in optical applications such as, for example, lenses and windows. They may be used as dielectric coatings and anti-corrosive coatings. Additionally, the gels have a pore structure of extremely small size, high specific surface area and narrow pore size distribution which makes them useful for catalyst or enzyme support, gas separation and in chromatography as column packing. Inorganic gels of silicon, titanium and zirconium are typically created by hydrolysis of organo-silicon, -titanium and -zirconium compounds, and subsequent condensation of the hydrolysis products. For silica gels, hydrolysis, (I), and condensation, (II) and (III), are represented by the following equations: --SiOR+H2 O←→--SiOH+ROH (I) 2(-SiOH)←→--SiOSi--+H2 O (II) --SiOH+--SiOR→--SiOSi--+ROH (III) where R is an alkyl group. Hydrolysis and condensation reactions are normally catalyzed by acids or bases. Existing methods of producing small pore size, high specific surface area, inorganic gels suffer from a number of problems. As discussed by C. Plank et al. in J. Colloid Sci., 2, 399 (1947) small pore, high surface area gel is ideally produced near the isoelectric point which for silica is about pH of 2. However, acid-catalyzed condensation reaction is so slow that several weeks or longer may be required for gelation to occur at about 25� C. at this pH. If condensation is conducted at elevated temperature, complete gelation can occur in less time; however, pore size will increase and surface area will decrease. In general, alkaline or fluoride ion catalyzed gelation is faster but produces larger pore size gels than acid catalyzed gelation and may lead to opaque gels. Another problem is that many conventional processes use alcohol as solvent for reactants. Presence of alcohol enhances the reverse of reactions (I) and (III) which hinders production of gel. U.S. Pat. No. 4,950,779 (Wengrovius, et al.) discloses a process for making organosilicon oligomers by reacting polyalkoxysilanes or polyaminosilanes with formic acid without addition of water. Wengrovius' products are organosilicon oligomers of low molecular weight, in contrast to gels of silicon dioxide which are completely crosslinked networks of unlimited molecular weight. Wengrovius' silicone oligomers contain at least one non-hydrolyzable organic substituent on each silicon atom which limits the ability of the oligomers to form gel. Coltrain et al. demonstrate in a paper presented at a 1989 conference and published in Ultrastruct. Process. Adv. Mater., Wiley, N.Y., N.Y., 1992, pp.69-76, that the rate of acid-catalyzed hydrolysis of tetraalkoxysilanes and formation of gels depends on the pH of the medium. For a strong organic acid such as trifluoroacetic acid, the rate of reaction in an aqueous medium slows down as the concentration of the acid increases. It is desirable to provide a rapid process requiring only as much water as necessary to propagate reaction, for the synthesis of open pore, inorganic gels having fine pore structure. According to the present invention, there is now provided a process for making open pore, inorganic gel, comprising: (1) intimately mixing together the following components (A) and (B), either in a liquid state or in solution in an organic liquid: (A) at least one compound selected from the group consisting of Si(OR1)4, Ti(OR2)4, Zr(OR3)4, Tia (OR4)n Xd p, and Zrb (OR5)n Xd p wherein each one of R1, R2, R3, R4, and R5 independently is a C1 -C8 alkyl; X is a chelating ligand; each one of a and b is independently a coordination number having an integer value of 4-6; d is a number corresponding to the chelating ability of ligand X, being 2 for bidentate chelating ligands and 3 for tridentate chelating ligands; p is either 1 or 2, with the proviso that p is 1 for tridentate chelating ligands; n=a-d�p; and (B) a strong carboxylic acid, having a pKa value not higher than about 4.0, and containing from 0 to 40 mole % water, the amount of carboxylic acid being at least 1.5 moles of --COOH groups per mole of compound (A), and the total amount of water from any source initially present in the reaction medium being less than 5 moles, and preferably less than 1 mole, per mole of Component (A); (2) agitating the above mixture while maintaining the mixture at a temperature within the range of about 0� to 100� C.; and (3) isolating the inorganic gel. There is also provided a process for synthesis of inorganic gel having extremely fine pore structure. FIG. 1 is a combination plot of gel time vs. hydrolytic agent:tetraethyl orthosilicate mole ratio for two series of experiments at 20� C., one in which the hydrolytic agent was water and reaction was catalyzed by hydrochloric acid, and the other in which the hydrolytic agent was 96 wt % formic acid. FIG. 2 is a plot of percent pore volume vs. pore size measured by nitrogen adsorption analysis at -196� C. of a gel produced by reaction of formic acid with tetraethyl orthosilicate. The process of this invention can produce an open pore, very small pore size, inorganic gel structure, occasionally hereinafter referred to as "ultrafine pore structure". The term "open pore" means a structure having voids which are interconnected and are accessible by an unobstructed path to the surface. Pore size of ultrafine pore structure has not been measured directly but is believed to be smaller than about 2 nm. Ultrafine pore structure is identified by specific surface area and density measurements. More specifically, ultrafine pore structure is detected by subjecting a gel to adsorption analysis by ASTM standard C1069-86 which measures nitrogen adsorption at -196� C. in four hours. This method, sometimes hereinafter referred to as "low-temperature nitrogen analysis", is suitable for determining the specific surface area of gel having open pores into which nitrogen readily diffuses at -196� C. Such pores are usually larger than about 1.5 nm. An open pore gel which indicates less than 10 m2 /g specific surface area by low-temperature nitrogen analysis has ultrafine pore structure. To determine that a gel which indicates less than 10 m2 /g has open porosity, it should be tested by both low pressure mercury porosimetry bulk density analysis according to ASTM standard C493(15.01 ), and helium pycnometry skeletal density analysis as described by T. Woigner et al. in J. Non-cryst. Solids 93, 17 (1987). Bulk density analysis provides the mass per unit volume of gel including the volume of void space of open pores. Skeletal density analysis provides the density of solid gel excluding open pore volume. If skeletal density of a given gel is higher than its bulk density, then the gel has open porosity. However, if skeletal density is equal to bulk density, the gel may either be nonporous or have closed pores. Gel made by the process of this invention which indicates greater than 10 m2 /g specific surface area by low-temperature nitrogen analysis may have a pore size distribution which includes ultrafine pore structure as well as pores larger than about 1.5 nm. A high diffusion rate adsorption analysis can sometimes be used to identify ultrafine pore structure in such gel. A suitable high diffusion rate adsorption analysis is provided by modifying the ASTM C 1069-86 test procedure, for example, by conducting the procedure at temperature higher than -196� C., (hereinafter, "high-temperature nitrogen analysis") or by substituting carbon dioxide for nitrogen and conducting the procedure at -78� C. or higher (hereinafter, "CO2 analysis"). Under such conditions, diffusion of adsorbate into ultrafine pores occurs more rapidly than during low-temperature nitrogen analysis. The BET method described in the Journal of the American Chemical Society, S. Brunauer et al., 60, page 309 (1938), can be used to calculate specific surface area of gel tested by adsorption analyses. Because the BET method relies on certain assumptions about pore geometry which may not be true for ultrafine pore structure, it may not accurately calculate pore sizes and specific surface area of gel containing such structure. Nevertheless a gel is believed to have ultrafine pore structure when CO2 or high-temperature nitrogen analysis indicates specific surface area more than that indicated by low-temperature nitrogen analysis. If CO2 or high-temperature nitrogen analysis does not exceed specific surface area indicated by low-temperature nitrogen analysis, no conclusion can be drawn that the gel possesses ultrafine pore structure. Compounds (A) are tetraalkyl orthosilicates Si(OR1)4, tetraalkyl titanates Ti(OR2)4, tetraalkyl zirconates Zr(OR3)4, chelated titanates Tia (OR4)n Xd p, and chelated zirconates Zrb (OR5)n Xd p, sometimes hereinafter collectively referred to as "tetraalkoxy compounds". The present invention is based on the discovery that tetraalkoxy compounds, which either are soluble in strong carboxylic acids or are soluble in nonaqueous solvents for strong carboxylic acids, readily react in the presence of significantly less than stoichiometric amounts of water or initially without any water to produce inorganic gels. R1, R2, R3, R4 and R5 are linear, branched, acyclic or alicyclic groups. Illustrative of such acyclic groups are ethyl, propyl, butyl, hexyl, 1-methylethyl, 2-methylpropyl, 1-methylpropyl, 1,1-dimethylethyl and 2,2-dimethylpropyl groups. Illustrative of such alicyclic groups are cyclobutyl, cyclopentyl and cyclohexyl groups. Chelating compounds suitable for use in the present invention are chemicals containing chelating ligands capable of bonding to titanium or zirconium through two or more oxygen atoms. Illustrative of compounds containing bidentate chelating ligands, X2, is acetylacetone. Illustrative of compounds containing tridentate chelating ligands, X3, is triethanolamine. Examples of tetraalkyl orthosilicates suitable for use in this invention include: tetramethyl orthosilicate, tetraethyl orthosilicate (TEOS), and tetra(n-propyl) orthosilicate. It is to be noted that the above organosilicon compounds can be named in two different ways, and both nomenclatures are generally accepted and understood by those skilled in the art. The alternative nomenclature is "tetraalkoxysilanes", for example, tetraethoxysilane and tetramethoxysilane. Examples of suitable tetraalkyl titanates include: tetraisopropyl titanate, tetra(n-butyl) titanate and tetra(2-ethylhexyl) titanate. Representative of bidentate chelated titanates is titanium triisopropoxide- 2,4-pentanedionate and representative of tridentate chelated titanates is isopropoxy(triethanolaminato-)titanium. An example of tetraalkyl zirconates is tetra(n-propyl) zirconate and an example of chelated zirconates is zirconium bis(acetoacetonate)diisopropylate. Inorganic gel of either exclusively one of silicon, titanium and zirconium or a mixture of them, can be produced by hydrolyzing and condensing the corresponding tetraalkoxy compound or appropriate mixture of tetraalkoxy compounds. In general, titanium- and zirconium-containing inorganic gel has higher refractive index than silicon gel. Gels can be made within broad ranges of silicon/titanium/zirconium compositions by controlling the reactant mixture ratios of silicon:titanium:zirconium tetraalkoxy compounds accordingly. Gels made by the process of this invention typically may have a small amount of unreacted alkoxy and hydroxy groups on the silicon, titanium and zirconium atoms. To obtain rapid gel formation, strong carboxylic acids suitable for use in the present invention should be capable of attaining homogeneous, liquid phase contact with tetraalkoxy compounds. Consequently, such strong carboxylic acids are either liquid and miscible with tetraalkoxy compounds under reaction conditions or soluble in solvents for tetraalkoxy compounds at reaction conditions. Either strong carboxylic acid or tetraalkoxy compound can be first dissolved in solvent and the other reactant added to the resulting solution. Alternatively, both reactants can be separately dissolved in either the same or different solvents and the two solutions combined. Suitable solvents for use in the present invention are nonaqueous, polar and aprotic. Illustrative of such solvents are tetrahydrofuran, acetone, acetonitrile and dichloromethane. Presence of solvent dilutes the concentrations of carboxylic acid, and tetraalkoxy compound, which generally slows gel formation, but gel formation rate can be increased by raising reaction temperature. Solvents capable of forming hydrogen bonds with silanol (Si--OH) groups, such as, for example, tetrahydrofuran and alcohols, also can slow the gelation rate by impeding the condensation reaction of the silanol groups Strong carboxylic acid which is solid at room temperature can be used without a solvent if heated above the melting point in order to mix it with tetraalkoxy compound in the liquid state. Such high temperatures can increase reaction rates dramatically but can inhibit formation of ultrafine pore structure. Therefore, to avoid using too high a temperature, it is preferred to dissolve solid acids in suitable solvents at about room temperature when production of ultrafine pore structure gel is desired. It is generally desirable to carry out hydrolysis and condensation at a temperature in the range of 0�-100� C., and preferably in the range of 0�-60� C. Reaction temperature in the range of 0�-30� C. is most favorable for the formation of ultrafine pore structure. Operation in the strong carboxylic acid to tetraalkoxy compound mole ratio range from 2:1 to 10: 1, and preferably from 3:1 to 5: 1, also favors production of ultrafine pore structure. The process of this invention therefore provides the advantage of producing gels having ultrafine pore structure that has not been reported for gels made by conventional processes. Most favored conditions for producing ultrafine pore structure are the combination of low mole ratio of 2:1 to 10:1 and low reaction temperature. Wet gel can be dried to produce coatings, monoliths and other shaped forms, such as optical lenses. By "dried"it is meant that the liquid residue of hydrolysis and condensation, including solvents, carboxylic acid, tetraalkoxy compound and byproducts of reaction, are removed. Volatile liquid residue can be removed by evaporation at elevated temperature and/or subatmospheric pressure. If the volatility of the liquid residue is low, high temperatures and vacuum conditions may be needed. Shaped articles can fracture if dried under such harsh conditions. To avoid the need for harsh drying conditions, volatile reactants, such as strong carboxylic acids having atmospheric boiling points below about 180� C., are preferred for use in this invention. If acids having atmospheric boiling points above 180� C. are used, they may be removed from the wet gel by alternative methods such as by extraction with a solvent boiling below 180� C. followed by evaporation of the low boiling solvent. Alternatively, mild drying conditions can be employed, but they usually must be maintained for long duration to accomplish drying. The process of this invention has the surprising, desirable feature that no water need be added to the reactants initially and that the steady state water concentration during reaction is quite small. One of the benefits of this feature is that clear gels can be made readily without a need to use a water-miscible solvent to obtain a homogeneous medium. While water is necessary for hydrolysis, a sufficient amount is formed by reaction of strong carboxylic acid with alcohol produced by hydrolysis and by metathesis reaction (IV): HCOOH+--SiOR←→--SiOOCH+ROH (IV) The process then continues as shown in equations (V) and (VI), below and then as shown above in equation (I). HCOOH+ROH→HCOOR+H2 O (V) --SiOOCH+SiOH→--SiOSi--+HCOOH (VI) Naturally, any water which may be present as diluent in strong carboxylic acid can contribute to hydrolysis. Strong carboxylic acid containing at most 20 mol % water is preferred for the process of this invention. The overall, idealized, stoichiometry of the reactions occurring in the process of the present invention requires at least two moles of organic acid per mole of compound (A), as shown below in equation (VII), but it has been found in practice that satisfactory results can be obtained when the amount of organic acid is less than required, but at least 1.5 moles per mole of compound (A). 2 HCOOH+Si(OR)4 →SiO2 +2ROH+2ROOCH (VII). Examples of strong carboxylic acids effective in this invention include formic acid, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid and hydroxyacetic acid. Neat formic acid is chemically unstable. Reagent grade formic acid, which is typically supplied commercially with about 4-20 wt % (9.6-38.9 mol %) water is stable, however. The process of this invention has been found particularly effective with 96 wt %, reagent grade formic acid, without further addition of water. Formic acid which has been dried to about 99.5 mol % purity is also highly effective. Other strong carboxylic acids, including dichloroacetic acid and trifluoroacetic acid, for example, can exist in essentially anhydrous form having less than about 0.1 mol % water. Weaker acids, such as acetic acid, and strong mineral acids such as hydrochloric and nitric acid, are not satisfactory for use according to this invention. FIG. 1 is a compound plot of gelation times vs. initial reactant compositions from two series of experiments, one series of which was run by V. Gottardi, et al., and reported in J. Non-cryst. Solids, 63, 71 (1984). TEOS was the tetraalkoxy compound used in both series. The abscissa is the mole ratio of hydrolytic agent to TEOS. The experiments in the series conducted according to the present invention are represented by square data points. This series was run at 20� C. and the strong carboxylic acid used was 96 wt % formic acid. In the acid-rich reactant mole ratio range of about 6-20, gelation occurs in from about 30-120 minutes. In the mole ratio range of 2-6, gelation time is found to increase to greater than about 100 hours. The Gottardi data, obtained at 60� C., are represented by the circular data points. The Gottardi experiments used water as the hydrolytic agent and the reaction system was catalyzed by hydrochloric acid. Gelation time at 20� C. was calculated for FIG. 1 by using 14 kcal/mol (58,700 J/mol) activation energy of gelation reported by M. W. Colby, et al., in J. Non-cryst. Solids 99, 129 (1988). FIG. 1 shows that gelation according to the present invention at each hydrolytic agent:TEOS mole ratio is several hundred times faster than accomplished by the conventional process. When very highly reactive tetraalkyl titanates, such as, for example, tetraisopropyl titanate, are used in the presence of water, titanium dioxide tends to precipitate. Clear, homogeneous gels suitable for optical applications cannot be made from such highly reactive tetraalkyl titanates and stoichiometric amounts of water, as reported in, for example, Sol-gel Science, C. J. Brinker et al., Academic Press, 1990, page 53. According to the present invention, titanium dioxide precipitate can be avoided by using essentially anhydrous, strong carboxylic acids, such as trifluoroacetic acid, rather than 96 wt % formic acid. Furthermore, even 96 wt % formic acid can be used to make clear gel from less reactive titanates such as tetrabutyl titanate. Therefore, the process of the present invention allows formation of gels not obtainable by conventional means. The high gelation rate of the process of the present invention is quite unexpected. In J. Non-cryst. Solids, 73,681 (1985), Schmidt reports that Is in the presence of 0.002M aqueous HCl, TEOS undergoes hydrolysis approximately fifty times more slowly than does an alkyltrialkoxysilane, (CH3)Si(OC2 H5)3. Wengrovius discloses that the reaction of alkyltrialkoxysilane with formic acid to form silicone oligomers is very slow, taking several hours or days. The combined disclosures of Schmidt and Wengrovius suggest that formation of gel by reaction of tetraalkyl orthosilicates with formic acid would be extremely slow since hydrolysis of the silicon-alkoxy bond is an essential step in the process. Surprisingly, it has been found that such gel formation occurs remarkably quickly. Inorganic gel produced according to the present invention can be dried slowly, under mild temperature and pressure conditions to a monolithic form. Alternatively, the gel can be rapidly dried at up to 300� C. and either under vacuum or in a stream of inert gas to make a powder. Prior to complete gelation, the solution can also be applied by conventional techniques such as dip coating, spray coating and knife coating, for example, to provide coatings on various substrates. Wet gels can also be dried to produce an aerogel by extraction with supercritical fluids such as, for example, CO2 and methanol, which preserves the original pore structure in the product. Such aerogels are useful as acoustic or thermal insulating materials, especially when the density of the aerogel is very low. Accordingly, it is desirable to generate wet gels of very low solids content which can serve as precursors to useful aerogels. This invention is now illustrated by representative examples of certain preferred embodiments thereof, where all parts, proportions, and percentages are by weight, unless otherwise indicated. All units of weight and measure other than SI units have been converted to SI units. Formic acid was commercially available acid solution containing 4% water and example quantities are given on the basis of formic acid actually present, unless otherwise stated. TEOS was added to formic acid in a 3.00:1 mole ratio of formic acid:TEOS at room temperature and stirred intermittently. A mildly exothermic reaction ensued during which the temperature rose to a maximum slightly above room temperature. A transparent, wet gel was produced after 23 hours at 20� C. The wet gel was dried within minutes of its formation in a rotary evaporator at 20 kPa for 30 min at 60� C. Thereafter, pressure was lowered to 15 Pa and drying was completed at 50� C. for 16 hours to produce granular, dry gel. The dry gel was pulverized and subjected to surface area measurement by low-temperature nitrogen analysis. The dry gel sample did not show appreciable nitrogen adsorption after 4 hours, which indicated that the specific surface area was less than 10 m2 /g. Dry gel was analyzed by low pressure mercury porosimetry which indicated the bulk density to be 1.64 g/cm3. Measurement by helium pycnometry revealed that skeletal density was 1.83 g/cm3. Experimental error of the density measurements was �0.02 g/cm3. Because skeletal density was greater than bulk density, the gel had open porosity. The findings of less than 10 m2 /g specific surface area and open porosity show that the gel contained ultrafine pore structure. The same sample was then subjected to CO2 analysis at 25� C. as well as at -78� C. Each CO2 analysis indicated appreciable adsorption of CO2, from which minimum specific surface area of 250 m2 /g was calculated. Results of CO2 analyses thus confirmed that the gel contained ultrafine pore structure. The procedure of Example 1, was repeated with formic acid and TEOS combined in a mole ratio of 7.74:1. A clear gel formed in 41 minutes at 23� C. The gel was dried as in Example 1 then subjected to low- temperature nitrogen analysis which indicated that nitrogen had not been adsorbed to significant extent. Bulk density and skeletal density of the gel were determined to be 1.21 and 1.89 g/cm3, respectively, showing that it had open porosity. Taken with the low nitrogen adsorption result, open porosity indicated that the gel had ultrafine pore structure. Pieces of dried gel were submerged in water. The gel fractured spontaneously and bubbles of air evolved. It was concluded that the air had been trapped within the pores and was liberated by gel fracture, additionally confirming that the gel had open porosity and ultrafine pore structure. The procedure of Example 2 was repeated with formic acid to TEOS mole ratio of 2.31: 1. A clear wet gel was formed in approximately 120 hours at 23� C. Again, insignificant nitrogen was adsorbed after 4 hours at -196� C. Bulk and skeletal densities were determined to be 1.41 and 1.64 g/cm3, respectively, indicating that the gel had open porosity. Pieces of dried gel fractured and liberated air bubbles when submerged in water. Examples 1-3 suggest that low to intermediate mole ratios of acid to tetraalkoxy compound favor production of gel having ultrafine pore structure. At room temperature, 4.54 g of TEOS was added to 31.39 g of formic acid and stirred intermittently to produce a 31.3:1 mole ratio acid:TEOS mixture. A mildly exothermic reaction ensued during which the temperature rose to a maximum of 34.8� C. A transparent, wet gel was produced after about 120 minutes. The flask was evacuated to a pressure of 13.33 Pa for 24 hours and a powdered, dry gel resulted. The pore size distribution of the dry gel was determined by low-temperature nitrogen analysis. The results are plotted in FIG. 2 as percent pore volume vs. pore size. FIG. 2 shows that 52% percent of total detected pore volume of the sample had pore size less than 2.0 nm. The fraction of pore volume drops dramatically as pore size increases above 2.0 nm. FIG. 2 also indicates that the pore size distribution produced by the process of this invention is narrow. Specific surface area of the powdered gel was also determined by nitrogen adsorption analysis to be 570 m2 /g. Formic acid and TEOS in initial mole ratio of 2.16 were placed in a flask. Heat was applied to control reaction temperature at 65� C. A transparent wet gel was produced after 21 hours. The gel was dried as in Example 4 for 3 hours at 70� C. but did not crumble into powder. As measured by low-temperature nitrogen analysis, average pore diameter of the dried gel was 1.9 nm and specific surface area was 577 m2 /g. Solids content of the gel was determined by calculation to be 19.4 percent. Liquids that were removed from the wet gel during drying were analyzed by gas chromatography which revealed the presence of ethyl formate, ethyl alcohol, and a small amount of water. No formic acid was detected because it had reacted with ethyl alcohol to form ethyl formate. As compared to Examples 1 and 2, this example suggests that higher reaction temperature produces larger pore size. At room temperature, TEOS was added to glacial acetic acid and stirred intermittently to produce a 9.66:1 mole ratio acid:TEOS mixture. No gel formation was detected after several weeks at room temperature. Into a vessel was placed formic acid and tetra(n-propyl) orthosilicate in a mole ratio of 19.8:1. Initially, reactants were only partially miscible but a homogeneous solution was obtained after 15 minutes of stirring. After standing without further agitation for 16 hours, a transparent wet gel was produced. The method of Example 4 was repeated, except that initial formic acid:TEOS mole ratio was 2.16:1. An clear gel was formed after 7 days at room temperature. Bulk density of the dried gel as determined by mercury porosimetry was 1.72 g/cm3 which is high compared to that of sol-derived gel made conventionally, in the presence of stoichiometric amounts of water. High bulk density gels usually have higher hardness than low density gels and are useful for example, for scratch- resistant coatings. Reagent grade, 97.7 % dichloroacetic acid was combined with TEOS in acid:TEOS mole ratio of 7.19:1 to form a solution. After standing overnight, at room temperature, a clear gel was formed. TEOS (7.52 g, 36.1 mmol) was allowed to react with 5.98 g of formic acid (125 mmol) for 10 minutes in a flask. Tetra(2-ethylhexyl) titanate (1.124 g, 1.99 mmol) was then added. A clear solution resulted which formed a gel in 90 minutes. The gel was dried for approximately 16 hours at 125� C. and at a pressure of 20 kPa, and then analyzed for titanium and silicon content by the inductively coupled plasma method of ASTM standard E1277-91. This analysis revealed that the weight ratio of titanium to silicon was 0.127 indicating that both elements had been incorporated in the gel network. Complete incorporation of titanium and silicon in reactants would have produced a titanium/silicon ratio of 0.094, which suggests that titanium somewhat more efficiently incorporates into the network than does silicon. The method of Example 4 was repeated, except that acid was diluted with water to 72 wt % formic acid (50 mol %). Acid to TEOS mole ratio was 8.15:1. The solution was initially clear and formed a translucent gel after 55 minutes at room temperature. After standing for several days, the gel became opaque. Opacity indicates the presence, due to the large amount of water used, of components having particles large enough to scatter visible light; nevertheless, this example demonstrates that strong carboxylic acid having as much as 50 mol % water can produce gel rapidly according to the present invention. By dropwise addition of 0.643 g trifluoroacetic anhydride to 6.416 g reagent grade trifluoroacetic acid, any water initially present was converted to the acid. The anhydride added was in excess of the amount needed to convert the small amount of water. To the anhydrous trifluoroacetic acid mixture was added 1.674 g of TEOS with stirring. Mole ratio of acid to TEOS was 7.00: 1. The reaction container was placed in a temperature controlled bath maintained at 26� C. A clear gel formed 97 minutes thereafter, demonstrating that the process of this invention can operate without any water initially present. Trifluoroacetic anhydride was not observed to react with TEOS in the absence of trifluoroacetic acid. Into a well thermally insulated vessel was placed formic acid and TEOS in initial mole ratio of 7.97:1. that of reaction raised internal temperature to a maximum of 53� C. After 26 minutes, a transparent wet gel was produced. Commercially available trifluoroacetic acid containing 0.4 wt % water as determined by Karl-Fischer analysis was reacted with TEOS at an acid to TEOS mole ratio of 5.88: 1. Gelation was observed after 38 minutes at 23� C. The gel was dried as in Example 4. Low-temperature nitrogen analysis indicated specific surface area of 510 m2 /g and average pore size of 2.4 nm. The method of Example 4 was repeated with formic acid to TEOS mole ratio of 16.4:1. Reactants were placed in a cylindrical vial and a few mg of rhodamine G dye was added. A bright orange solution was produced which gelled on standing overnight at room temperature. Drying at room temperature and atmospheric pressure for 24 days produced an orange cylinder approximately 6 mm in diameter and 12 mm high of gel of 1.52 g/cm3 bulk density. The color was uniform throughout except for a slightly darkened region at one end of the cylinder. This example suggests the compatibility of gel produced by the process of this invention with materials which may be employed in optical applications, such as dyes for lenses or filters. Formic acid and TEOS were each cooled to 2� C., then mixed in initial mole ratio of 7.69: 1. Throughout mixing and reaction, temperature was maintained at 2� C. After 5 hours, a clear gel was observed. A solution was prepared by dissolving 1.25 g monochloroacetic acid (13.2 mmol) in 0.73 g tetrahydrofuran (10 mmol) over a 5-minute period. While the acid solution was stirred, 0.61 g TEOS (2.9 mmol) was added and a clear solution resulted. The solution was allowed to stand at room temperature for 3 days, after which it had not gelled, illustrating that dilution by solvent can slow reaction rate. After heating to 60� C. for 22 hours the solution did form a clear gel. Thus the rate reduction was offset by increased reaction temperature. Tetrabutyl titanate was placed in a small flask under inert atmosphere. Over a two-minute period, 96% formic acid was added to the flask at room temperature to make a 4.89:1 mole ratio acid:titanate mixture. An exothermic reaction was apparent, but no precipitation of titanate was observed. After 15 minutes, a clear, pale yellow gel had formed. The gel was dried at atmospheric pressure and room temperature for several weeks, after which it was dried tinder vacuum at 100� C. for approximately 16 hours. Translucent pieces of gel several millimeters in size were produced. Low- temperature nitrogen analysis indicated specific surface area of 301 m2 /g and average pore size of 4.2 nm. Inside an inert atmosphere glove box 4.25 g tetraisopropyl titanate (19.3 mmol) was placed into a small flask. While contents of the flask were stirred at room temperature, 7.33 g anhydrous trifluoroacetic acid (64.3 mmol) was slowly added. An exothermic reaction was apparent, but no precipitation of titanium dioxide was observed. After 17 hours, a clear, pale yellow gel had formed. The gel remained clear after drying at room temperature and atmospheric pressure for several weeks. This example demonstrates that highly reactive tetraalkyl titanate, which typically precipitates titanium dioxide during hydrolysis in the presence of stoichiometric amounts of water used in conventional gel formation, was capable of producing a homogeneous gel by the process of this invention. Water, TEOS, and ethanol were combined in a 2:1:5 mole ratio. Ethanol was necesssary to maintain miscibility. The resulting solution was divided into several portions, to which varying amounts of 96% formic acid were added. Those samples were placed in sealed containers and thermostatted at 60� C. The gelation times of those samples are reported in the table below: ______________________________________Mole ratio Gel time,HCOOH/TEOS hrs.______________________________________0.010 310.056 1930.101 2140.201 173______________________________________ The above data confirm the observation made by Coltrain, loc. cit., that with an acid as a catalyst in an aqueous medium, gelation times increase with acid concentration. The process of the present invention, which requires larger amounts of acid and can operate in an initially nonaqueous medium or in the presence of a small amount of water, produces gelation in very short times, usually minutes, rather than hours. Patent Citations
Non-Patent Citations
Referenced by
Legal Events
Rotate |


text:
Commercial Mixer?
- h
- hipkitchen1102 Jul 1, 2013 07:01 PM
- 7
- Follow
I hear Kitchenaid has a commercial mixer. Anyone know what makes it "commercial" - or know anything about it, or where to get one?
Here is KA's info on it:
They are available at a lot of places including Chef's Catalog, Williams-Sonoma, Sur La Table, webstaraunt.com, etc.
There have been some user reviews at www.thefreshloaf.com.
0 -
re: BIGGUNDOCTOR
Where the heck do you live? Out here, all the Chinese @#$& you want or broken worn out Hobarts for a $1,000+.
re: Sid Post
Found mine in Fabulous Las Vegas Nevada. Also picked up a 14" Hobart buffalo chopper with stainless rolling cart plus meat grinder for $100 at an estate sale. Hobart full auto meat slicer at a military auction for $360. Hobart power drive with VS9 slicer with 2 more meat grinders, and extras for $350 off Craigslist.
Deals are out there, be patient and you will find them.
When I was researching the last time, the only difference between the commercial and non-commercial versions of the KA top line mixers were minor alterations required for certification: a heavier duty power cord and cast aluminum attachments.
The KA Q&A section I think has these issues discussed, I think.

subset: commoncrawl


text:
Use code PPUYAP details >*To Receive Free Shipping on orders over $399, use promotion code PPUYAP during checkout. Discount applies to ground shipping orders being shipped within the contiguous United States only. Cannot be used on previous orders or combined with any other offer. Discount does not apply to customs, duties, or delivery surcharges. Offer expires on 3/7/15 at 11:59 PM EST.
details >Sign up for our FREE Party Newsletter to help you plan the best event ever! Also by signing up for the Stumps Party Newsletter today you will receive a coupon for 50% Ground Shipping on your next order! We'll help you make your event a night to remember.
details >Orders placed by midnight ET for most personalized and made-to-order items will ship the next business day. Excludes holidays and weekends. Some personalized and made-to-order items require a longer processing time and is noted as such on each product page. Credit card and billing information must be correct at time of order. Please note that shipping transit time still applies, look for the estimated delivery date during checkout. Processing time will apply to any in-stock items that are consolidated with items that are made-to-order. There is never an up charge for adding personalization to our products. In a very few cases, the retail price of a personalized item may be slightly more than that of a similar stock item, due to production processes.
details >
For a limited time, Save Big!
(based on 1 review)
Ratings Distribution
5 Stars
4 Stars
3 Stars
2 Stars
1 Stars
Reviewed by 1 customer
Displaying review 1
Back to top
By Donna
from New Jersey
This tiara was perfect for a sweet sixteen party! The stones are brilliant and their setting is strong. The combs were firmly attached.
Comment on this review(earn points)


text:
POLIÇA began as a collaboration between fellow Gayngs' members Channy Casselle and Ryan Olson in June of 2011. By July they had completed 11 songs, made the key additions of drummers Ben Ivascu and Drew Christopherson, bass player Chris Bierdan, and headed into the studio. After Mike Noyce (Bon Iver) lent his voice on Lay Your Cards Out and Wandering Star, the record was brought to Austin, TX to be mixed with Jim Eno (Spoon). In a few days, the LP was completed and the band Poliça was formed. On stage, the original beats composed by Olson play amongst Channy's passionate vocals & an intense rhythm section, that lead to a description somewhere in the area of electro-r&b goth-pop.
Marijuana Deathsquads is the ever-evolving, experimental project lead by Ryan Olson, (producer/writer of POLIÇA and GAYNGS), Isaac Gale, and Stefon Alexander (P.O.S). With multiple drummers, a slew of electronic instruments, and highly effected vocals, their live shows are a violent onslaught of improvised yet tightly woven, jagged, intricate experimental sound.
This marks the first official tour Marijuana Deathsquads have done, and the shows themselves will no doubt be special, as Polica and Marijuana Deathsquads have a affinity towards each other of uncanny proportions. The chemistry these to acts will provide for attendees will be epic, and we would not recommend missing it.
Who's Going
Upcoming Events
9:30 Club
Tue, March 3
Gang of Four
Wed, March 4
Josh Abbott Band (Cancelled)
Wed, March 4
Thu, March 5
Pat Green & Josh Abbott Band
Fri, March 6
The Travelin' McCourys featuring Billy Nershi and The Jeff Austin Band
Sat, March 7
of Montreal
Sun, March 8
RuPaul's Drag Race: Battle of the Seasons (NEW DATE)
Mon, March 9
The Church
Tue, March 10
Jukebox the Ghost
Wed, March 11
G. Love and Special Sauce


text:
- 162Promote
Art Print
Collect your choice of gallery quality Giclée, or fine art prints custom trimmed by hand in a variety of sizes with a white border for framing.
Thank you Ally, noblackcolor, Ann, filiskun, Michael, Biff, Lisa, Angela, Karin, Catherine, Daleeeeeeee, Chungkong and gwenola!!! You guys made my morning ♥♥♥
See More Comments


text:
recipe reviews for:
"Potatoes, onion, celery, and seasonings are cooked until soft. Creamy cheese soup and cream are stirred in, creating this smooth mellow soup."
My Profile | Cooks I Like Reviews | Photos | Recipes | Menus | Blog
Cooking Level: Expert
Cooking Level: Intermediate
Muffins are great for breakfast, with coffee, or just as a snack on the go.
Soup is what the doctor ordered to cure those winter blahs.
Delicious recipes, party ideas, and cooking tips! Get a year of Allrecipes magazine for $7.99!
This may be the simplest potato soup ever.
See how to make a creamy, green garlicky potato soup.
A rich, creamy potato with bacon soup you make in the slow cooker.


text:
One CEO's 13-year-old daughter garners more than $5,000 in letter-writing effort.
Jenny Serrambana is one of 11 U.S. credit union employees and the only one from Texas in World Council trip.
Credit union reps from U.S. made December trip to North African nation to explore industry development there.
IIFC Group now has 92,456 members and $4.5 million in savings shares.
Bicycle for loan officers, mobile phone airtime, water pumps, fencing for farm animals just part of the list for AIDS-afflicted rural community.
World Council and European Network of Credit Unions meet with policymakers to discuss regulatory proposals that would affect credit unions.
Wisconsin credit union hosts guests through World Council's international leadership program.
South American delegation visits Maryland, D.C. credit unions through World Council program.
Whether it's offering tea in England or coffee in the U.S., credit unions are celebrating International Credit Union Day by inviting their members in.
Just like the 14,000 member credit unions it supports, the World Council of Credit Unions in Madison, Wis., must intermittently reevaluate its structure and programs in order to best meet the needs of those it serves.


text:
New to Typophile? Accounts are free, and easy to set up.
I like this typeface that I found on the Vitra website. Anyone what know what it is? If you can suggest similar style fonts I would be interested in those too!
Thanks in advance.
Attachment | Size |
indent_type_please.gif | 3.25 KB |
I think it's a Bodoni Black italic, similar to this one from URW.
- Mike Yanega
Hi Mike.
Yeah that's close. The "u" is slightly different.


text:
Canvas Wall Art
Wall Decals
Wall Letters
Personalized Art
Hand Painted Art
Growth Charts
Framed Art
Wall Hangings
Wall Murals
Art Prints
Wall Plaques
Wooden Art Plaques
Prepasted Wall Murals
Baby Photo Art
Room Themes
Free Shipping
Disney Frozen Chair Rail Prepasted Wall Mural Turn your little girl's room into a magical place with the Disney Frozen Chair Rail Prepasted Wall Mural. Featuring a favorite scene from Disney's Frozen.
SIZE: Assembled Size: 10.5'W x 6'H
Category: Art, Prepasted Wall Murals
©2004-2015 Rosenberry Rooms, LLC. All Rights reserved. | 1003 Morrisville Parkway, Suite 180, Morrisville, NC 27560
ecommerce enabled by fastpivot | PRIVACY POLICY


text:
Follow Scrubs
My Kingdom Pic
Around the Web
- Photo Credit:
- Pending
- Show:
- Scrubs
- Episode:
- Scrubs Season 2 Episode 19: "My Kingdom"
- Characters:
- J.D., Turk
- Related Photos:
- Scrubs Photos, J.D. Photos, Turk Photos
- Uploaded by:
- Eric Hochberger
- Uploaded:
Scrubs Season 2 Episode 19 Quotes
Woman: Hi! Can I buy you a drink?
Turk: No, I'm good. Thank you.
J.D.: You see that? You see that right there? That has never happened to me - a hot girl has never asked to buy me a drink. Apple-tini please - easy on the tini.
Bartender: No problem, lady.
- Permalink: Hi! Can I buy you a drink? No, I'm good. Thank you. You see ...
- Added:
J.D.: Man! Ever since college, you always make everything seem so easy. No matter where you are, you always fit in. I dunno, I guess, I thought with this surgery elective, it might be nice not to feel like a total dork for once.
Turk: J.D., look at me. You are a dork.
J.D.: Not all the time!
Turk: Every second, since the moment I met you.
- Permalink: Man! Ever since college, you always make everything seem so easy...
- Added:


text:
- Your file is being downloaded. It will remain available for download from the "My Files" section of your member area for 72 hours.
superior gold agenda2020 3d
© XK - See portfolioPricing
Author | XKSee portfolio |
Image reference | 50401700 |
Country | Germany |
Descriptive Category | Abstract Sign/Symbol |
Conceptual | Business Business Concepts Business Vision/Perspective |
Keywords |
["agenda","alphabet","business","concept","extra","fashion","future","gold","intend","letter","logotype","planning","quality","square","star","super","superior","symbol","three-dimensional","to do","unique","vector",5,2020]
agenda alphabet business concept extra fashion future gold intend letter logotype planning quality square star super superior symbol three-dimensional to do unique vector 5 2020
The vector illustration "superior gold agenda2020 3d" from XK is available on Fotolia under a Royalty Free license from 1 credit (Credit from $0.74).
Available in AI/EPS and JPEG formats, this vector file may be downloaded for all kinds of professional uses. The V and XV files are delivered in AI/EPS. To modify this file, vector editing software such as Adobe Illustrator, Freehand, or CorelDRAW is required. JPEG files are available in different resolutions (up to 3,873 x 3,873 pixels in 300 DPI).
The author of this picture, XK also has 135 images in the same series.
To download this vector file, you can buy Fotolia credits or purchase a subscription plan and benefit from the amazing price of $0.19 per image.
The V and XV licenses are vector files (AI, EPS).
To modify this file, vector editing software such as Adobe Illustrator, Freehand, or CorelDRAW is required. All other licenses are JPEG files.


text: Beaches along the Atlantic coast and Florida Gulf coast need greater safeguards for nesting loggerhead sea turtles. The U.S. coast hosts most nesting sites for North Atlantic loggerhead sea turtles and is home to one of the most significant nesting aggregations of loggerheads in the world. The Center for Biological Diversity and allies have sought greater loggerhead protections, but the government is delaying and backpedaling from its proposal to extend "endangered" status to loggerheads in the Atlantic, at the same time postponing uplisting of loggerheads in the Pacific Ocean. This delay is inexcusable, especially in light of the oil spill disaster in the Gulf of Mexico last year. The future of Northwest Atlantic loggerheads is even more precarious now than when we petitioned for uplisting, and the need for urgent action is even greater. While the government postpones uplisting and critical habitat designation, loggerhead sea turtles continue to drown in fishing gear and lose nesting habitat to sea-level rise and development. Your comments are critical to enhancing protections for loggerhead sea turtles. We need your help voicing support for uplisting this population in spite of fishing-industry opposition to more stringent protections. Please act now.


text:
Lyrics Depot | |
Lyrics » E-40 Lyrics » Bootsee Lyrics |
Lyrics Depot is your source of lyrics to Bootsee by E-40. Please check back for more E-40 lyrics. |
Bootsee LyricsArtist: E-40Album: In A Major Way Now I want you to tell me if you know somebody in yo town that fit the description A sucka, a ignorant mothafucka One of them show boatin' high sidin' want to get some attention type nagas Just as flashy but bitches be askin me If they can borrow a couple of bucks until tuesday Pleases that man go say no man be tryin to play Captain Save A Hoe Gettin marked by all them sneaky caniving ass set up hoes You see bootsee is that ol' nigga with that ol' gold around his neck Gold around his muthafuckin house, gold around his muthafuckin pet Got everybody in the town thinkin' he sittin' nice on at least 20 ki's But bootsee ain't movin nothin but half thangs Straight fuckin with some of y'all niggas domes Braggin and boastin, How can I make this shit look clean Y'all really want to know who the man behind the fat sack well lookie here Sho nuf ain't bootsee boss and thats for sure Cuz bootsee be frontin himself off y'all niggas just don't know The ones you least expect you know them square ass niggas in your city They be the ones who have a grip , they be the ones who be sittin pretty Instead of tryin to be super to start a fuckin track man What a nigga really need to do is sit back and straight stack man Cuz I've been on this Earth for 3 and some odd months man Trippin off how these niggas out here be straight transforming Laughing and smiling, loving and hugging a brother grinning Turn around and talk behind your back the next minute Bitch we call him bootsee Chorus Let me define it you can rewind it after I finish spittin But what about bootsee It be them bootsee muthafuckas in your town that's always game It be them bootsee muthafuckas in your town that's always game bootsee is that busta with in no gizame, with in no gizame, with in no gizame You's a loud talkin runnin off the mouth deeck Wishy washy be puttin yourself on front street Sloppy grindin, failizing, bitch buying pussy licka That's what hella heads be sayin about that bootsee nigga And ah In case some of y'all ain't knowin this Do to do almost anything to be noticed Like ah Pull out his whole bank account and dang near everything he owns And ah Tell everybody in the hood that he got a chip in his phone And how the fuck you gone be about you scratch when you gossip like a batch And all them fools know where your stash be at That ain't no sharp shit Nigga that's that hoe shit Potna just keep on doin what you do and watch your perv get peeled Ridin around here loose stickin out dumb like a soar thumb Nigga tell the truth Don't have a gun but I need one You want to come up quick in this old shit so you can get it But how the fuck you gone make your revees givin out credit To tweakers, droamers, drifters, leftovers, geekers, zombies Folks that steal from they mommies When I was doin my thang I had strategy main Sellin' that ˜hite girl?you should have seen me main You would have been proud of yo nigga cuz I was briliant wid it I snuck in and snuck out without slippin in it Get what you need out the game and sit your ass down Invest your money in some thangs and start clockin' pal Chorus
Related: |
All lyrics are the property of their respective authors, artists and labels. |


text:
Shyam Ranganathan
CHENNAI: Nearly 150 colleges in the State may be eligible for the unitary university status, the Committee appointed by the government to look into the issue has said in its report.
The five-member committee under V.C. Kulandai Swamy appointed last year to look into the issue of upgrading government and government-aided colleges to unitary universities submitted its report to Chief Minister M. Karunanidhi on Wednesday.
In the report, the Committee listed eight criteria, including the age of the institution, land area, number of faculty, number of undergraduate and postgraduate courses, ratio of PhDs, accreditation and potential for excellence.
It has provided marks for each criterion and a maximum of 75 marks may be obtained by any institution.
Of the 202 government and government-aided arts and science colleges in the State assessed by the Committee, it has found that 150 scored over 50 per cent (37.5 marks), and may be eligible for the unitary university status.
Speaking to The Hindu over telephone, Dr. Kulandai Swamy said the idea was to provide a benchmark for the status of unitary universities. "There are other considerations in policymaking, including distribution of universities, based on regional and other criteria. The final number of colleges upgraded depends on the government's policy requirements. We have kept 50 per cent as a minimum threshold," he added.
He said five government colleges suggested for upgrading last year – Presidency College, Queen Mary's College, Government Arts College, Coimbatore, and Government Arts and Science College (Men and Women), Kumbakonam – had all scored "extremely well."
The report suggests that expert teams be formed by the Tamil Nadu State Council for Higher Education to visit the respective colleges to assess them and that a Model Act be prepared based on which separate Acts may be passed by the Legislative Assembly to upgrade each college.
While the report describes the actions to be taken to address the concerns of various teachers' associations and other groups who made representations to the committee, the Association of University Teachers (AUT), which had boycotted the Committee, said the main concern had not been addressed.
"Once these colleges receive university status, they may function just like a deemed university with very few constraints," P. Jayagandhi, president, AUT said.
The report is available on the government's website.


text:
Today, Matthew Carter is overseeing the re-working and expansion of the Verdana and Georgia font families, with David Berlow of The Font Bureau leading the effort ... read more at macworld.com.
· Awards Contributors
· David Berlow Subscribe |
NEWS · January 19, 2010Verdana Pro: Not just another pretty faceToday, Matthew Carter is overseeing the re-working and expansion of the Verdana and Georgia font families, with David Berlow of The Font Bureau leading the effort ... read more at macworld.com. INTERVIEWS · January 12, 2010FontCast: Dyana Weissman on Kerning"At ATypI in Mexico City Stephen Coles broached the topic of kerning with Dyana Weissman of The Font Bureau, one of the few type designers who claims to actually enjoy the tedious task of assigning thousands of kern pairs to each font. She explains the difference between kerning and spacing, why it should be done by hand, and the mystical concept of flow." Watch it here on The FontFeed. NEWS · January 11, 2010Yah-hey!I will be in America's dairyland on the 14th to give a talk, sponsored by Design Madison. They suggested that I come in March when it's warmer but I said no way I grew up in Wisconsin, I am coming in January. Doncha know. SKETCHES · January 4, 20102010Happy New Year! SKETCHES · December 18, 2009happy new year'Ras as-Sana' drawn in Kufic style lettering. NEWS · December 15, 2009December Newsletter: Season's Greetings, Sloop WGL, Hutch, Web Fonts, and Scripty MastheadsOur December newsletter's holiday greeting of spreading hope in any language features Richard Lipton's Sloop WGL. Allan Haley writes about the story of David Berlow's Hutch for Rolling Stone. Adding to the buzz about fonts for the web is David Berlow's interview on FontFeed, and Cyrus Highsmith draws an original scripty masthead for Rhode Island Monthly. If you missed our November newsletter featuring decorated letters and more, view it here. SKETCHES · December 11, 2009happy hanukkahHebrew lettering, inspired by Ben Shahn. NEWS · November 23, 2009Communication Arts: David Berlow's Hutch for Rolling StonePARIS BEAUTY MEETS A ROLLING STONE Hutch, from Font Bureau, is a modern interpretation of Cochin, another French typeface. Cochin was first released in about 1915 by the Peignot type foundry in Paris and was based on the lettering of late eighteenth-century French copperplate engravers. Metal and phototype versions of Cochin were used in some of the first issues of Rolling Stone magazine. When Joe Hutchinson, the magazine's current art director, approached famed publication designer Roger Black about creating a display typeface for the publication, Black immediately suggested Cochin. David Berlow, Font Bureau founder, and Jim Parkinson, who drew ... More ...SEEN AND NOTED · November 13, 2009think löçãlDrawing a masthead is a nice change of pace. While a typeface contains hundreds of different glyphs, a masthead is usually just several letters long. You even know what order they go in. In contrast, the parts of a typeface can be assembled in almost any sequence and the letter drawer must plan for that. There are some folks who delight in obscure letter combinations, archaic diacritic marks, and other linguistic minutiae. And it is important to take care with such details. Sometimes, I also like to just draw though. I had a great time drawing this masthead for a ... More ...INTERVIEWS · November 12, 2009FontShop's Webfonts Week: An Interview with David Berlow"ATypI ambitiously billed this year's Typ09 conference as the discussion epicenter for the future of fonts on the Web... The loudest — and often the most interesting — of these voices was unarguably David Berlow's." Read more by Stephen Coles... More ... |


text:
New gold CD-Rs and DVDs that are said to extend the storage life of data, music and images for many decades are being introduced by KMP Media, LLC of Rochester, NY. Operating under trademark license from Eastman Kodak Company, KMP Media is marketing them as the KODAK Preservation CD-R and the KODAK Preservation DVD (-R).
Phase One is hosting the "See The Difference" road show seminar series tailored for professional photographers in the US between March and October 2006. Attendees will experience Phase One's medium format digital backs and learn how to streamline their workflow using Capture One RAW Workflow. Those wishing to attend "See The Difference" can find more information about the show and its sponsors and register online at: www.phaseone.com/roadshow.aspx....
Phase One has updated Capture One RAW Workflow to support more cameras, more RAW file formats and Intel-based Macs. Capture One 3.7.4 is a Universal Mac application designed to run natively on both Intel and PowerPC-based Mac computers. Initial tests by the company show that the capture rate has increased by up to 40 per cent when version 3.7.4 is run on an Intel-based Mac. Processing RAW files with Capture One 3.7.4 is now 15 per cent faster on both Intel-based and PowerPC based Macs. Windows users will also enjoy enhanced capture rate and RAW processing speed with Capture One 3.7.4. Initial tests show performance gains of up to 200 per cent in capture rate made possible by an improved high-speed capture option in the Capture One software. Tests also show a 10 per cent increase in the processing speed of RAW files.
Based on early commitments by North American exhibitors, photokina 2006 holds a lot of promise for photo and imaging companies from the United States and Canada. photokina will take place from Sept. 26 -- Oct. 1, 2006 in Cologne, Germany.
X-Rite Inc. has introduced the the OPTIX XR2 display calibration and profiling solution. Combining a state-of-the-art colorimeter with enriched software, the OPTIX XR2 is said to deliver an unparalleled color management solution for displays; including LCD, CRT and newly developed wide gamut technologies. Easy to use, the OPTIX XR2 is X-Rite's most recent upgrade of MonacoOPTIX XR, which joined X-Rite's product line after X-Rite acquired Monaco in 2003. This latest iteration completes the integration of the product into the X-Rite family of color measurement solutions. The first and most fundamental step to ensure consistent and accurate color is a properly calibrated monitor. The OPTIX XR2 allows users to adjust color at the touch of a button. Plus, a new help system puts easy to find answers at the user's fingertips. OPTIX XR2 also has the ability to automatically recognize and take control of your color display, with Automatic Display Control (ADC). Using one touch, ADC will optimize your display's color temperature, contrast and brightness settings to ensure you build the highest quality ICC profile and obtain the best color results from your monitor. In addition, an ambient diffuser attaches to the bottom of the OPTIX XR2 hardware, allowing for more exact characterization of the user's environment, thus improving the accuracy of profiles. Designed to advance with users as they upgrade their display types, the OPTIX XR2 builds the highest quality profile for today's as well as tomorrow's advanced display technologies. Additionally, it recognizes when an upgrade is necessary and prompts users to download the correct information required to properly profile their monitor. The OPTIX XR2 will be available to the market in late May, as will the OPTIX XR2PRO, a network version for multi-workstation environments. www.xrite.com...
Combining a leading medium-format single reflex camera and a 22-megapixel high-performance digital back is the idea behind the "Super Bundle" now available in the U.S. from Digital Marketing Services.
Having logged more airline miles recently than I'd care to admit, with cameras and lenses and laptop to boot, I welcome any products that can make the trip, and transition between connections easier. The "post-9/11 world", as it sadly has come to be known, has not made it easier on photographers to get where they need to go with the gear they must trudge along with them. With that in mind, we recently had a close look at the Airport Security Roller/Backpack from ThinkTank Photo, which combines carry-on capability with security and gear --protecting features.
There are many options for traveling photographers these days, including on-the-go download devices, portable CD and DVD burners and of course the venerable laptop computer. But a new breed of storage devices, USB Flash Drives, is also making a big for the store and show photographer who doesn't want to lug along anything more than a drive the size of a pack of gum. Memorex has come up with a twist on all this with their TravelDrive ID USB Flash Drive. This is the first USB flash drive with a built-in, customizable LCD screen. The clever iLCD screen not only shows the remaining memory but also lets you display a descriptive name for the drive or its contents. This sure helps me sort out the bunch of Flash Drives I have rattling around my backpack, and now I can assign one to teaching, one to word docs and one to storing images for show, all activities I might engage in over the course of a week. What Memorex calls the "advanced Surface Stabilized Cholesterin (SSC) LCD" can display up to 11 characters, so you can ID it even when it's not plugged into a computer's USB port. TravelDrive ID conforms to the USB 2.0 standard and comes in 512MB, 1GB and 2GB of portable storage. It's also Mac or PC compatible. The Memorex TravelDrive ID has a suggested retail price of $79.99 for 512MB of capacity, $119.99 for 1GB of capacity, and $199.99 for 2GB of capacity. It just shows you that there can be something new under the sun in something as "generic" as USB drives.www.memorex.com
Brandess-Kalt-Atena Group, Inc. has announced the introduction of the first two models in their new Pelican RSV line. RSV stands for Rugged, Strong, and Versatile which are terms used to describe this series of cases designed for professional digital photographers on the move. The PCS247 model is an upright camera/computer case on wheels that measures, outer dimensions are 18x14x10". The inner dimensions are 16x12 1/2x7". The PCS2552 is a large camera/computer case that can be hand or shoulder carried and can fit into the Pelican 1550 shell for added security. It measures 17 1/2x12 1/2x7" and features an expandable computer pocket on the outside. Both are constructed from water resistant 1680D ballistic nylon and feature leather grain trim, moveable dividers, a padded computer compartment, and PVC lined inner mesh pockets. Available in black or green. Contact: Brandess-Kalt-Aetna Group, Inc., 701 Corporate Woods Parkway, Vernon Hills, IL 60061, (800) 621-5488.
Datacolor has introduced ColorVision PrintFIX PRO, a new spectro precision profiling hardware and software package. The PrintFIX PRO's handheld Spectrocolorimeter is designed to meet the needs of discerning photographic professionals as well as graphic designers and digital imaging specialists for quality output with an RGB workflow. A key offering in the ColorVision by Datacolor portfolio of products, ColorVision PrintFIX PRO represents the next generation of the world's most recognizable and honored brand in color calibration, the Spyder2.
The Zeiss Ikon--hereafter ZI--has all the features you might hope for, plus optional autoexposure. At $1617, the body lists between Leica and Voigtländer. In features, it goes head-to-head with the Leica M7. Because we received the camera and no fewer than six lenses--15mm f/2.8, 21mm f/2.8, 25mm f/2.8, 28mm f/2.8, 35mm f/2, and 50mm f/2--we have split...
Just when you thought the R2 was the pinnacle of Voigtländer Bessa design, along came the R2A and R3A. They differ from the R2 in several ways, most notably the adoption of an electronic shutter allowing Aperture Priority automation; this is combined with a new meter. Other significant differences are a revised (and easier-to-use) rewind crank; the addition of a back lock...
Wi-Pics is designed for anyone who shoots large volumes of images and needs to easily find them. The DICE AMERICA Wi-Pics with a USB port allows Wi-Pics users to work with hand held barcode scanners, magnetic strip readers, and later this year RFID. What makes Wi-Pics unique from other wireless cameras is its data association. Data association is the ability to rename files as they are captured and place data into the EXIF header of a JPEG file. Wi-Pics can work with virtually any digital camera with a type 2 compact flash port.
Based on their highly successful Goombah, the new mini-Goombah has all the same features, in a smaller, lighter package. It's both a rolling case and a backpack. The wide-set oversize wheels provide a stable platform for rolling the case through airports, or down city streets. The thickly padded concealable shoulder straps, adjustable lumbar pad and waist belt transforms the mini-Goombah into a backpack.
Sigma Corporation has announced the launch of the new 17-70mm F2.8-4.5 DC MACRO lens, an ideal large aperture standard zoom lens for digital SLR cameras featuring an APS-C size image sensor. The lens has a minimum focusing distance of 20cm (7.9") throughout the entire zoom range. Maximum magnification of 1:2.3 enables close-up photography like a macro lens. The new lens design and multi layer lens coating reduces flare and ghosting. A Special Low Dispersion (SLD) lens and two aspherical lens elements provide excellent correction for all types of aberrations and produce a high level of optical performance throughout the entire zoom range.


text:
SKY – Rodgers sets sights on title
Brendan Rodgers says Liverpool can challenge for the Premier League title next season.
DetailsBrendan Rodgers says Liverpool can challenge for the Premier League title next season.
DetailsLiverpool forward Raheem Sterling admits he still has plenty of room for improvement in his new central role for the Reds.
DetailsSky Sports has announced its latest live Premier League fixtures, with Liverpool's clash with Manchester United part of a bumper schedule.
DetailsChelsea had Thibaut Courtois to thank for keeping a relentless Liverpool side at bay, writes Matt Stanger…
DetailsRaheem Sterling's superb second-half goal means Liverpool go into their Capital One Cup semi-final second leg with Chelsea with the scores level at 1-1, despite dominating at Anfield.
DetailsLiverpool boss Brendan Rodgers insists he is not driven by a personal desire to beat opposing managers – only to win football matches.
DetailsJordan Henderson saluted Liverpool's defiance at the back in shutting out Aston Villa in Saturday's 2-0 win.
DetailsLiverpool saw off a spirited second-half display from Aston Villa to record a 2-0 win at Villa Park and move to within four points of the top four.
DetailsWith another huge round of Premier League contests ahead of us, we ponder 10 questions that will be answered by the end of Monday….


text:
View Your Earnings
| ||||||||||||
View Your Earnings
| ||||
Handling Fee Reminding: $2.50 handling fee will be charged for ALL items from the same series, product code beginning with AZU- if you order less than $60.00.
SweetLeaf liquid stevia is a natural, convenient and healthy sweetener. It contains no calories or carbohydrates and may be used in tea, coffee, smoothies, protein shakes or any recipe. SweetLeaf liquid stevia is delicious, has no aftertaste, and is diabetic friendly.
From drinks to desserts, appetizers to entrees and so much more, the options are endless.
With just a few drops, SweetLear liquid stevia can turn a boring bottle of water or virtually any other food or beverage into a flavorful, healthier experience.
Ingredients: Purified water, Organic Stevia, Natural Flavors, Vanilla Extract, Natural Aromatics.
Supplement Facts
Serving Size: 5 drops to 8 ozs. of liquid or to taste.
Servings per Container: 288
Calories 0
Calories from Fat 0
Total Fat 0g 0%
Saturated Fat 0g
Trans Fat 0g
Cholesterol 0mg 0%
Sodium 0mg 0%
Total Carbohydrate 0g 0%
Dietary Fiber 0g
Sugars 0g
Protein 0g
Vitamin A 0%
Vitamin C 0%
Calcium 0%
Iron 0%
Condition | New |
If you want to: - Make product changes;- Create something not in stock6,000 + (and growing) factories in our existing network are eager to make it for you. When it comes to selling in stock products, we are no difference from many other Internet retailers, but we take pride in going extra miles to do something special for you: Have some products custom made for you. We cannot do everything, but we usually can accommodate a certain changes in product options such as color, size, material, or minor design twist. We primarily work with vendors or factories, not individual artist or craftsman. For custom made products, we usually only cater to bulk size order that meets the minimum quantity requirement of a single factory run. Don't be shy. Ask. What we can accomplish may surprise you! Read this first: Copyrights & Trademarks | ||
Thank You for Your Request!If we can meet your requirements, we'll contact you within 1 business day. | ||
View Your Earnings
| ||||||||||||
View Your Earnings
| ||||
Didn't find the right price? Put it here.
Login with your Opentip.com account to continue.
View Our Privacy Policy
| ||||||||||
Didn't find the right price? Put it here.
We'll email you when we can offer a lower price on this product.
View Our Privacy Policy
| ||||


text:
Top Definition
a really gay music teacher
reify looks around in remorse, watching for kids walking on the left side of the hall.
by jamisonfool1
April 05, 2009
Type your email address below to get our free Urban Word of the Day every morning!
Emails are sent from firstname.lastname@example.com. We'll never spam you.


text:
Lincoln will for the first time advertise at the Super Bowl 2013. Lincoln is relaunching its branding with The Lincoln Motor Company name. This is the original name from the 1920s.
"The new Lincoln brand will be defined by great new luxury vehicles, such as the new MKZ, that feature quality, unique style with substance and innovative technology. These elements, coupled with a new level of warm, personal and surprising experiences, will enable Lincoln to appeal to today's new luxury customer." said Ford Motor Company CEO Alan Mulally.
Lincoln will advertise during the broadcast of the upcoming Super Bowl 2013. Lincoln has signed comedian Jimmy Fallon to lead the first-ever Super Bowl commercial written entirely by social media, with consumers participating through Twitter.
Consumers will provide their best 140 character thoughts to a script, and Fallon will then lead the curation of the best contributions that will create the ad to run during the broadcast of the big game.
Can the crowd come up with a great Super Bowl commercial? I get the crowd sourced Super Bowl ads like Doritos is doing since years. This works great. But having everybody work on a single ad seems difficult.
The Lincoln Super Bowl 2013 Ad will definitely be an ad to look out for on Super Bowl Sunday.
The Super Bowl 2013 will take place on Sunday, February 3, 2013 in New
Orleans. Super Bowl Ads for Geeks will again offer full coverage about
the Super Bowl Ads ahead and during the Super Bowl XLVII. The first big
news is that Kate Upton will star in the Mercedes Super Bowl 2013 Ad.
Until Game day, which will bring the new 2013 Super Bowl Ads you can check out the Super Bowl 2012 Ads.
Subscribe to:
Post Comments (Atom)
Hot Super Bowl News
Coca-Cola is bringing back the animated Polar Bears to the Super Bowl 2012. The Coca-Cola Super Bowl 2012 Ads will feature the two cute be...
Several Super Bowl 2012 ads are using the old marketing concept of sex sells. The Go Daddy Super Bowl ads have always been sexy and th...
This just in. Kate Upton will star in the upcoming Mercedes-Benz Super Bowl 2013 Commercial. Kate Upton has dominated the model headline...
The first Go Daddy Super Bowl 2012 Ad is here. Go Daddy released the 30 second Go Daddy .co Super Bowl 2012 commercial featuring sexy mode...
Go Daddy has jumped the gun and released the full Internet Only version of the Go Daddy Super Bowl 2012 Ad Body Paint with Natalia Velez ...
Blog Archive
- Super Bowl 2013 Live Online Stream to be Available...
- Go Daddy Super Bowl 2013 Ad for .co Has Danica Pat...
- MillerCoors Redd's Super Bowl 2013 Ad run on Local...
- Volkswagen Super Bowl 2013 Ad Has its Work Cut Out...
- Oreo Super Bowl 2013 Ad has Kate Upton too?
- Axe Super Bowl 2013 Ad is titled Lifeguard
- Fast & Furious 6 Super Bowl 2013 Ad Trailer Coming...
- Doritos Super Bowl 2013 A Entries are Up for Votin...
- Gildan Super Bowl 2013 Ad Coming
- Super Bowl 2013 Advertiser Listed
- Pepsi Super Bowl 2013 Ad will Star Beyonce
- SodaStream Super Bowl 2013 Commercial is already i...
- Lincoln Motor Company Super Bowl 2013 Ad Coming
- USA Today Super Bowl 2013 Ad Meter will include On...


text:
Yes, it's a summer league highlight from a D2 athlete, but this dunk by Elizabeth City State University's senior guard Angelo Sharpless is ridiculous. It'd be good enough for a midnight madness dunk tourney, let alone with a defender in his face Also, warning on the volume level. Starts quiet and cell phone quality blows it up in a hurry. [ame=http://www.youtube.com/watch?v=h60pSZyaJBo]D2 Player Angelo Sharpless with Dunk of the Summer! At Ben Wallace Pro Am - YouTube[/ame]
Ri Dunk u lous
Wow! That defender had to feel just worthless after that. The most painful 2 points ever scored on him I think.
Oh my god that was sick
While on live TV, Ford used a vulgar term to describe a private part of the female anatomy, adding that he was happily married and got more than enough to eat at home.
holy smokes!! epic.. thx for the link!
Originally Posted by State43 Wow! That defender had to feel just worthless after that. The most painful 2 points ever scored on him I think. only positive for him is that the only evidence is on a crappy cell phone and not high def.
To give proper credit, it looks like this is the original video. The first video is just a cropped and blown up version of it that the other site threw their watermark on. Smaller and bizarre dimesions, but not as grainy. [ame=http://www.youtube.com/watch?v=26EJuw6IhAQ]Dunk Of The Week: Angelo Sharpless At Ben Wallace Pro-Am! - YouTube[/ame]
Holy ****! I would quit the game of basketball if I was that defender.
Has Fred been notified??
Time to turn off the lights in the gym, its closing time.
I bet he can't make a shot outside the paint.
It's Levi-O-sa, not LeviosAR
Forum Rules


text:
| |
RATINGS: 193 WEIGHTED AVG: 3.84 SEASONAL: Special IBU: 83 EST. CALORIES: 270 ABV: 9%
COMMERCIAL DESCRIPTION Black as night and every bit Imperial, this RIS was originally launched to tremendous accolades. Going further, this Stranahans Whiskey barrel aged version meshes the rich chocolates, the coffee-like aromatics with the sweet whiskey nose and drying character of the oak. Slightly behind on the palette are the hops held in restraint by the wonderfully full mouthfeel and broad flavors brought on by the perfect blend of so many malted barley varieties. 2013 United States Open Beer Championship Bronze Medal Wood / Barrel Aged Strong Beer 2013 Los Angeles International Commercial Beer Competition Gold Medal Wood / Barrel Aged Strong Stout 2012 United States Open Beer Championship Bronze Medal Wood/Barrel Imperial Stout 2012 Los Angeles International Commercial Beer Competition Gold Medal Wood / Barrel Aged Strong Stout 2012 United States Beer Tasting Championship Regional Champion Imperial Stout
We Want To Hear From YouJoin us! RateBeer is made by beer enthusiasts for the craft beer community. Your basic membership is free and allows you to read all beer ratings. Click here to create your account... and give your opinion! Join Us » Page 1 2 3 4 5 6 7 » 20 |
More Imperial Stouts By Style
Lagunitas Cappuccino Stout (Bourbon Barrel) 63 Pizza Port Order In The Port 79 Monks Café Blend no.1 Uniqum 77 Pink Elephant Imperious Rushin Stowt 70 Block 15 Imagine 79 Emelisse White Label Imperial Russian Stout (Makers Mark BA) 96 Mikkeller Black Hole Barrel Aged Edition White Wine 85 Bluegrass Cherry Inyouendo 62 |
about us About RateBeer FAQ Contact/Feedback New Beers |
add Advanced Search Add A Beer Add A Brewer Add A Place Events |
membership Log In Edit Personal Info Buy Premium Membership Your Messages |
the best RateBeer Best 100 Beer Club The Top 50 |


text:
Martha Stewart Clears the Air Mike Jubinville November 25, 2009 Martha Stewart Show, News, Talk Shows TVGuide.com is reporting Martha Stewart has no ill will toward fellow talk show host Rachael Ray. Stewart commented on a recent Nightline episode that Ray was "not good enough for me" regarding her kitchen skills. On Monday's Martha Stewart Show she stated, Just for the record, there are no bad feelings between us nor have there ever been, Stewart said apologetically. I truly believe that Rachael has done a terrific job bringing people, many people who would of never of even stepped into the kitchen or made a dish to cook. I applaud Rachael for her enthusiastic approach to cooking. Ray has an open invitation to return to Stewart's show.
Olbermann and Martha Discuss Pumpkin Pie and Ben Affleck on SNL Luke Kerr November 26, 2008 Martha Stewart Show, Talk Shows 2 Comments Bill O'Reilly's nemesis Keith Olbermann dropped by the Martha Stewart Show to help Martha make a chocolate pumpkin pie. In addition to discussing the pie, Olbermann's girlfriend and Thanksgiving plans they talked about Ben Affleck's impression of Ketih on SNL.
Martha Stewart and Snoop Dogg "Ball Til Ya Fall" Luke Kerr November 20, 2008 Martha Stewart Show 4 Comments Could you have put as two opposite of people in one segment as Martha Stewart and Snoop Dogg? Check out Snoop Dogg as he teaches Martha the meaning of his vocabulary. Turns out they have "ball til ya fall" in common.


text:
recipe reviews for:
"A chocolaty take on the classic Italian cream cake."
Cooking Level: Intermediate
My Profile | Cooks I Like Reviews | Photos | Recipes | Menus | Blog
Cooking Level: Expert
Muffins are great for breakfast, with coffee, or just as a snack on the go.
Soup is what the doctor ordered to cure those winter blahs.
Delicious recipes, party ideas, and cooking tips! Get a year of Allrecipes magazine for $7.99!
This authentic Italian cream cake is rich and coconutty.
Ice cream on a cookie crust topped with whipped cream, fudge, and cherries!
See how to make moist, rich chocolate cake.


text:
Lea Michele Pays Tribute To Cory Monteith At The TCAs
Video: Via Digital Spy.
Please upgrade your browser for the best Refinery29 experience. Read more.
Once upon a time, Taylor Swift formed a circle of best friends. Her posse is ever-growing. But, at its core, it includes Selena Gomez, Hailee Steinfeld, Jaime King, and anyone who gets Swift to appear at a birthday party. Today, Fifth Harmony's Camila Cabello became the newest member of the girl-power group. Swift and read
Ah, to be a fly on the wall in a room Sofia Vergara and Reese Witherspoon occupy. It's possible — digitally, of course, but definitely possible. Just look at today's cute back-and-forth between the two girlfriends. Witherspoon tweeted some Bob Marley lyrics at her Hot Pursuit costar, along with a photo of her in read


text:
"Breast surgery will save my life"
Miss District of Columbia, Allyn Rose is in a fight for her life, and it's not just for the title of Miss America. She tells the AP why she's planning to get a preemptive double mastectomy after her pageant season ends. AP video.(Jan. 11)
advertisement | advertise on newsday
Snow tapering off, more snow possible Thursday
Laurel Hollow home a sports fanatic's dream
IHOP celebrates National Pancake Day
Maia, LaFlare ready for UFC fight in Brazil
Slippery Monday morning rush
Islip: Roads to be clear by morning rush
LI company's ATM reader helps prevent skimming
Animals at JFK airport
Slippery roads in forecast for your Monday morning commute
Paraglider crash injures Shirley man
Snow falling across LI
Cops, firefighters play hockey for charity


text:
This property is unavailable.
This is the fee charged by Airbnb
This is the fee charged by Airbnb and includes VAT
Edit Summary
Contact Host
Space where guests can cook their own meals
Central heating or a heater in the listing
Towels, bed sheets, soap, and toilet paper
In the building, free or for a fee
Continuous access in the listing
Breakfast is provided.
The listing can accommodate a gathering of 25 or more attendees
Easy access to the building and listing for guests in wheelchairs
Private or Shared
Free, in the building or nearby
Posted emergency information and resources
The Space
A furnished apartment located on historic via Giulia in the heart of Rome. This intimate, romantic, comfortable and quiet space has been recently restored and renovated, revealing the original wooden beamed ceiling and an old brick arch.
The apartment consists of an air conditioned studio bedroom with double bed, furnishings, linens, TV and dining area with charming table and chairs; a separate kitchenette (refrigerator, stove, utensils and accessories); and a full bathroom (shower, hair-dryer). Free Internet wifi connection!!!
The flat is situated on the ground floor facing a characteristic courtyard where you can see an ancient stone wash-tub.
The silence and history surrounding via Giulia seem surreal as you walk to the nearby colourful market of Campo de' Fiori, or cross into the old neighborhood of Trastevere. Within five or ten minutes of easy walking you can reach many of the famous sights that are described in the guidebooks: Piazza Navona, Pantheon, Fori Imperiali, San Pietro, Piazza di Spagna, Ghetto, Castel Sant'Angelo, Colosseo and so on. Via Giulia is also close to a network of city buses that will link you to the farther areas of the city, including a direct route to the train station.
Via Giulia itself is one thousand meters long and is considered one of the oldest street of Rome, commissioned by Pope Giulio II more than five hundred years ago. A charming and elegant cobblestone route, it runs parallel to the Tiber river from the Ponte Sisto bridge up to the Chiesa dei Fio(website hidden) church. Walking down via Giulia (crossed by twenty-seven lanes!) you can visit eight churches and two beautiful fountains. Each corner or old mansion has an unbelievable story. For example, you can linger at the corner of via Giulia and via dei Cimatori: here, the painter Raffael purchased the site of the current building where, just before his death in 1520, he began construction on his new house and work shop. Or, if you like, you can sit and relax for ten minutes on "the sofas in via Giulia" just opposite your apartment. These benches are none other than the remains of the foundation of the Court of Justice that Pope Giulio II commissioned of Bramante.
With so much history right outside your door, a stay in via Giulia is sure to be a memorable visit.
Queste non vogliono assolutamente essere regole di comportamento, sono semplici consigli di buon senso ed educazione. These are not behaviour rules, but just some advice of good sense and education.
Cerca di rispettare il silenzio di via Giulia e di questo condominio, i "tuoi" vicini lo apprezzeranno molto. Try to respect Via Giulia silence and the quiet of this condominium, your neighbours will appreciate it very much.
Usa la cucina a tuo piacimento e cerca di lasciarla in ordine per chi verrà dopo di te. You can use the kitchen as you want but please leave it in order for the next guests.
Ricordati di spegnere sempre le luci ed il condizionatore d'aria quando esci dall'appartamento: il risparmio energetico è un problema che riguarda tutti. Please remember to turn the lights and the air conditioned off when you leave the flat: saving energy is a problem which regards everybody.
Evita di fumare nell'appartamento, proteggerai i soffitti in legno, la tappezzeria e rispetterai chi, magari non fumatore, lo abiterà dopo di te. Try not to smoke in the flat. In this way you will protect the wooden ceiling and tapestry too. You will also respect people, perhaps not smokers, who will live the flat after you.
Nell'armadio troverai una tovaglia per il tavolo, usala se devi mangiare, ci aiuterai a conservare intatto il mosaico. In the wardrobe you will find a tablecloth for the table, please use it if you have your meals at home. You will help us to preserve intact the mosaic.
Grazie e buon soggiorno Thank you and have a nice holiday
Alessandro's appartment is exactly as on the pictures: very charming ! The location is great - you can do evrything by foot - and Alessandro and his family are very kind and helpful We will come back to this place next time we come !
L'appartement d'Alessandro était parfait pour passer quelques jours à Rome. Il est exactement comme décrit sur les photos et très propre. Nous avons été reçu par la femme d'Alessandro et elle nous a renseigné sur tout ce que l'on désirait savoir, nous a indiqué le supermarché le plus proche, les monuments à visiter, etc... L'appartement est situé dans un très bon quartier, proche de Campo de Fiori avec son marché et ses restaurants traditionnels. Pendant 4 jours, nous n'avons jamais pris le bus, ni le métro, nous avons tout fait à pied, c'était l'idéal. Je te recommande très vivement cet appartement.
We had a great experience with this flat. The location was perfect and the hosts did a great job. They met us at the flat and gave us a rundown of the apartment and the neighborhood. The flat was cozy and charming and had everything that we needed. Highly recommended for a great value visit to Rome.
Staying in Allesandro's place was a great experience, the flat is even more beautiful than in pictures, the neighbourhood is wonderful, very quiet, safe, and typically Roman. We were able to cook our meals easily, walk to every attraction in the city and rest at night. We had a little problem with our luggage before arriving and Allesandro was very helpful and easy to contact, he is very nice and professional. We will certainly stay here again if we have the chance!
Alessandro's flat on Via Giulia is a perfect base for a visit to Rome. The neighborhood is safe and the flat itself is adorable and conveniently located within walking distance of all the incredible sites as well as delicious restaurants. Alessandro himself greeted us warmly and made us feel welcome. Highly recommended for travelers.
We just loved staying in this wonderful little flat. You are so close to all Rome's major sights, and there are loads of great bars and restaurants to explore nearby, yet the flat itself is tucked away from the main street and so is really quiet and peaceful. The bed is really comfortable too, so we slept very well each night after busy days of walking, sightseeing and eating! There is air-con/heating, a little kitchen, and bathroom with great shower and everything you need. The wifi internet was fast and reliable - so useful for looking up sights you might have seen in Rome that day, to give some historical background. Kana came to meet us and was very friendly and helpful, even showing us some nice places nearby on a map. I wholeheartedly recommend this place!! Thanks Kana and Alessandro!
Great location on the Via Giulia, very quiet. Large and beautiful room with it's own archeaological excavation! Clean and comfortable, though I personally prefer softer pillows. Thanks for a great stay Allesandro and especially for allowing me to check in so late in the evening.
This host has 245 reviews for other properties.
I am Alessandro, born in Rome and in love with my city... I am on call 24/7 and do my best to help people have the best experience possible during their stay. Archeology is my first passion, then food and good wine (my wife is a sommelier). I think that living in Rome means… walking through the streets of history, where around every corner you come upon an architectural wonder, written about in history books, or a museum rich with original and important works of art – all objects of beauty that were created for your enjoyment by artists throughout more than two thousand years of history... discovering that, even during winter – when the entire peninsula is under snow, from the Alps to Sicily – you can enjoy sun-drenched spring-like days, guaranteed from the affectionate and protective embrace of the Abruzzo Apenines. Rome is the only city in Italy where the sun is always brilliant and the moderate temperatures never end....To experience the constant struggle between christianity and paganism; to worship the beauty of the eighteenth century churches while bowing to the graces of the ancient temples. ... To stop in at the local shops and chat for a while with real Romans who can be sceptical, are often impatient, but underneath it all they're big-hearted. What I wanna say is that no one of my guest should come away from a visit to Rome, eternal city of history and art, without having relished the experience completely, in the best way possible, and with a full understanding of her finest characteristics…
Are you or your friends connected with this host?
You and Alessandro Learn More!
Every Superhost has their own style, but they've all reached key hospitality goals.
See What Makes a Superhost
Congratulations, you're a Superhost! We'll reward you with priority support, product previews and more.
Review Your Rewards
Alessandro has completed online and offline ID verification.
Learn more »
Thanks for taking the time to report this listing. Your participation helps keep Airbnb a safe and trusted community, and it doesn't go unnoticed!


text:
Overview | Experience | Hospital Quality | Appointments & Offices |
Key things you need to know aboutDr. Husain:
Dr. Husain's Experience
Research training, expertise and qualifications
Dr. Husain's Specialties
- Nephrology
- View 1 specialty and 2 board certifications
Procedures Dr. Husain Performs
- Arteriovenostomy for Renal Dialysis
- End-Stage Renal Disease Related Services
- See all 3 procedures
Conditions Dr. Husain Treats
- Acidosis
- Acute Kidney Failure
- See all 29 conditions
More About Dr. Husain's Background
Hospital Quality
The right hospital is as important as the right doctor
- North Shore University Hospital
- 300 Community Drive
- Manhasset, NY 11030
- Saint Francis Hospital Roslyn
- 100 Port Washington Boulevard
- Roslyn, NY 11576
9 Facts About Hospital Quality
Patients' risk of dying during a hospital stay for heart bypass surgery could be 85.2% lower, on average, at a hospital rated 5 stars compared to a hospital rated 1 star for that procedure. Choosing the right hospital is critical to your health. View Slideshow
Appointments & Offices
Check insurance plans, locations and make an appointment
Accepting new patients?
- Yes
- Long Island Kidney & Hypertens
- Long Island Kidney & Hypertension
- 891 Northern Blvd Ste 203
- Great Neck, NY 11021
7 Tips to Prepare for Your Appointment
The key to a successful appointment is communication. To get the most out of your visit, prepare ahead of time so you can lead the conversation with your doctor. These 7 tips will get you ready


text:
- 492Promote
Tote Bag
Our quality crafted Tote Bags are hand sewn in America using durable, yet lightweight, poly poplin fabric. All seams and stress points are double stitched for durability. Available in 13" x 13", 16" x 16" and 18" x 18" variations, the tote bags are washable, feature original artwork on both sides and a sturdy 1" wide cotton webbing strap for comfortably carrying over your shoulder.
thanks Maite :D Peter thanks you too^^ thanks Calvin :D Hugo gracias de corazon :D Basilique kouklamou euxaristo poli !! ^^
i love the pattern in the weater and the colors and the whole composition how the wolf comes in the back in her but seems like its 2 personalities amazing Kris
thanks :D Margarite yep the wofl and her its kind of 2 personalities as you can see the sweater its a attached with the wolf too^^ so yeah its kind of that interpretation like her soul basically :) thank for your kind coment fills me a lot
Kris esto si esta demasiado grande, cada vez me impresionas deverdad sos una artista Kris me encanta todo , quiero la T-shirt :)
Hola Mariela vi que sos de Argentina gusto conocerte gracias por pareciar mi arte linda, thanks Holly apreciate ^^
Hi Kris i am Matt i found you in tumblr you work its amazing here its good to follow your work your new piece its shocking very well complete piece of art :)
hey thanks Eleanorrigby yes people like in the top look very cool! , thanks monography :D apreciate both
yes Polkip actually i want to give that shape of the wolf like the soul of the girls basically i unite the jumper of her with the wolf like it is her soul her mind , her thoughts but giving that line with the wolf :) thanks you so much ^^
thanks spectral and Kristy ^^ yes Krysty basically got the idea to unite both like in one soul :D give that shape the girl its a She Wolf i love wolves so cute animals ^^
I love the colors that you use in your work! The balance of colored pattern, sketch and negative space is well done!
See More Comments


text:
Product Description
Available while supplies last.
This Amanti Art Don Li-Leger Spring Chorus framed art is offered in a 22.21-in x 22.21-in size. Part of the Abstract collection.
Born & raised in British Columbia, Li-Leger early on demonstrated a keen interest in art and an affinity for the natural world around him. This symbiosis of art & nature has been an instrumental force in Li-Leger's life & in his decision to become an artist. His work has been featured in exhibitions throughout North America.
- Artist: Don Li-Leger
- Title: Spring Chorus Framed Art Print
- Frame: Dark Espresso Finish with Raised Lip
- Mat: Pure White/Seafoam
- Ready to hang -- comes with a hanging wire for easy installation
- Gallery-quality acrylic glazing and premium-quality frame assembled in the U.S.A.
- Long-lasting, fade-resistant ink on high quality lithographic paper
- Paper is dry-mounted to prevent rippling
Size: | 22.21-in x 22.21-in | |
Materials: | Wood and Gallery Quality Acrylic | |
Listing: | Made in USA | |
Application | Indoor, Residential | |
Framed Art Subject | Abstract | |
Number of Pieces | 1 |
Coordinating Items
Related Items
Items in this collection
$90.00Your total:
Add to Cart
Questions & Answers
There are no questions from the community yet
Customer Reviews
This product has no customer reviews yet
Write an online review and be the first to share your thoughts with other customers
Write an online review and be the first to share your thoughts with other customers
Tag This Product
A tag is a keyword assigned to a product which helps describe the item and allows it to be found by other customers
Add a new tag:
Separate multiple tags with commas
What's this?Additional Details
Mfr Part # | |
Sku | |
Group # | 964110 |
Category | Framed Art - 757 |
Style | Modern - 3 |
Sales Rank | 110 |
Your Recently Viewed Items
You have no recently viewed items. After viewing product detail pages or search results, look here to find an easy way to navigate back to products you are interested in.
Your Recommended Items
You currently have no recommended items. Browse a few more items to give us an idea of what you like.
©1999 - 2015
Copyright notice | Site Map | By using this site you agree to our Terms & Conditions of Use and Privacy Statement