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The present invention is directed to an improved hydrocarbon adsorbent slurry washcoat formulation, which can be used for controlling evaporative hydrocarbon emissions from a motor vehicle. More specifically, the present invention is directed to an improved slurry composition of the present invention comprises one or more hydrocarbon adsorbent materials, and an organic polymer binder containing an anionic dispersant and/or stabilizing pH. The binder is used to improve the adhesion of the hydrocarbon adsorbent to the surface of the fuel storage, fuel delivery, or air intake system component.
1. An improved hydrocarbon adsorbent washcoat slurry formulation comprising:
a) one or more molecular sieves for the adsorption of evaporative hydrocarbons;
b) an organic polymer binder to improve the adhesion of the hydrocarbon adsorbent to a surface; and
c) an anionic dispersant selected from the group consisting of sodium dodecylbenzene sulfonate and sodium dioctyl sulfosuccinate to stabilize said slurry formulation.
2. The improved hydrocarbon adsorbent washcoat slurry formulation of
3. The improved hydrocarbon adsorbent washcoat slurry formulation of
4. The improved hydrocarbon adsorbent washcoat slurry formulation of
5. The improved hydrocarbon adsorbent washcoat slurry formulation of
6. The improved hydrocarbon adsorbent washcoat slurry formulation of
7. The improved hydrocarbon adsorbent washcoat slurry formulation of
8. The improved hydrocarbon adsorbent washcoat slurry formulation of
9. The improved hydrocarbon adsorbent washcoat slurry formulation of
10. A substrate selected from the group consisting of the surface of a fuel storage, fuel delivery, or air intake system component of a motor vehicle to which is coated said hydrocarbon adsorbent washcoat slurry of
11. An improved hydrocarbon adsorbent washcoat slurry formulation comprising:
a) one or more molecular sieves for the adsorption of evaporative hydrocarbons;
b) an organic polymer binder to improve the adhesion of the hydrocarbon adsorbent to the surface; and
c) said slurry having a pH from about 4 to about 10 to stabilize said slurry formulation.
12. The improved hydrocarbon adsorbent washcoat slurry formulation of
13. The improved hydrocarbon adsorbent washcoat slurry formulation of
14. The improved hydrocarbon adsorbent washcoat slurry formulation of
15. The improved hydrocarbon adsorbent washcoat slurry formulation of
16. The improved hydrocarbon adsorbent washcoat slurry formulation of
17. The improved hydrocarbon adsorbent washcoat slurry formulation of
18. The improved zeolite washcoat formulation of
19. The improved zeolite washcoat formulation of
20. A substrate selected from the group consisting of the surface of a fuel storage, fuel delivery, or air intake system component of a motor vehicle to which is coated said hydrocarbon adsorbent washcoat slurry of
This invention is directed to the use of an improved hydrocarbon adsorbent washcoat formulation for use at low temperatures. In particular, this invention relates to the use of an improved hydrocarbon adsorbent washcoat formulation for controlling evaporative hydrocarbon emissions from motor vehicles.
Evaporative emission regulations for vehicles require the control of polluting substances (primarily hydrocarbons) from the vehicle as it sits unused. These emissions are leaked out of the vehicle from many sources including the air intake system. In the past, only emissions from the fuel tank were captured, with carbon-filled canisters, but this has now been expanded to other vehicle components such as the air intake system. These harmful substances need to be retained within the air inlet system until the powertrain is again used. At such time, the retention system will give up the harmful substances to be consumed and controlled through the normal exhaust emission control systems.
There are several ways to control the outward flow of pollutants from the air intake system of an automobile. One such technique is the careful shaping of the ducting and filter box. However, this method is often not sufficient to meet the regulatory requirements. Accordingly, other methods must be used such as the incorporation of systems in the air intake system that use some form of carbon or other material to adsorb the pollutants during the rest cycle. When the vehicle is next started, the in-rushing air will draw the pollutants from the adsorbent and direct the pollutants through the normal exhaust system pollution controls. This inward air rush also regenerates the adsorption systems so that such systems may be reused. Unfortunately, these extra adsorption systems add cost, weight and complexity to a vehicle and often restrict the air flow.
There continues to be a push to reduce emissions from internal combustion engines. One manner in which emissions are generated from an internal combustion engine is when the engine is shut off. Fuel which has been released from fuel injectors, but has not been consumed prior to engine shut down, may evaporate outwardly through the intake manifold, the intake air ducts and air filter to eventually escape into the atmosphere and contribute to air pollution.
In additional efforts to reduce these types of inadvertent evaporative emissions, many types of filters have been developed. Examples of filters for use in the intake system of a vehicle are found in U.S. Pat. No. 6,432,179 to Lobovsky et al. and U.S. Patent Application Publication No. U.S. 2002/0029693 to Sakakibara et al., both of which are incorporated herein by reference. The publication of Sakakibara et al. discloses several embodiments of hydrocarbon adsorbing devices having a case surrounding an inner cylinder portion. A hydrocarbon adsorbent material is provided in a chamber defined by the case and the inner cylinder portion. The inner cylinder portion has a central bore that extends through its length to permit induction air to pass therethrough, and also has windows that allow any hydrocarbons in the induction system to pass through a filter surrounding the inner cylinder portion to the hydrocarbon adsorbent material in the chamber to be adsorbed thereby.
As previously mentioned, adsorption systems and methods for trapping volatile hydrocarbon fuel vapors, from the fuel tank of an automobile are also well known. Such systems are typically referred to as evaporative loss control systems and rely on a canister containing a regenerable adsorbent such as activated charcoal. The adsorbent adsorbs the volatile hydrocarbons and when engine operating conditions are appropriate for combusting the trapped hydrocarbons, a stream of air is passed through the adsorbent to desorb the adsorbent and the hydrocarbon-laden air stream is passed into the engine where the desorbed hydrocarbons are combusted. Exemplary U.S. patents disclosing evaporative loss control systems include the following: U.S. Pat. Nos. 4,877,001; 4,750,465; and 4,308,841.
Furthermore, systems and methods for adsorbing uncombusted hydrocarbons in the exhaust gas stream of an automobile are also well known. These systems and methods are particularly useful for adsorbing uncombusted hydrocarbons emitted during the cold start of the automobile engine.
For example, U.S. Pat. No. 4,985,210 is directed to an exhaust gas purifying apparatus for an automobile employing a three-way catalyst with either a Y-type zeolite or a mordenite used in a hydrocarbon trap upstream of the three-way catalyst. In the embodiment of FIG. 2 of U.S. Pat. No. 4,985,210, a bed of activated carbon is disposed upstream of an adsorbent zone. A solenoid-operated valve mechanism serves to direct the exhaust gas stream either through or around the activated carbon bed, depending on the temperature of the exhaust gas stream, and then through the adsorbent zone and the three-way catalyst.
U.S. Pat. No. 5,051,244 is directed to a process for treating an engine exhaust gas stream in which the gas stream is directed through a molecular sieve in an adsorbent zone during the cold-start phase of engine operation. When the hydrocarbons begin to desorb, the adsorbent zone is by-passed until the catalyst is at its operating temperature, at which point the gas stream is again flowed through the adsorbent zone to desorb hydrocarbons and carry them to the catalyst zone. A paper by M. Heimrich, L. Smith and J. Kotowski entitled Cold-Start Hydrocarbon Collection for Advanced Exhaust Emission Control, SAE Publication Number 920847, discloses an apparatus which functions in a manner similar to that of U.S. Pat. No. 5,051,244.
U.S. Pat. No. 5,125,231 discloses an engine exhaust system for reducing hydrocarbon emissions, including the use of beta zeolites as hydrocarbon adsorbents. Zeolites having a silica/alumina ratio in the range of 70/1 to 200/1 are preferred adsorbents. The apparatus includes by-pass lines and valves to direct exhaust gases from a first converter directly to a second converter during cold-start operation and when the first converter reaches its light-off temperature, to either by-pass the second converter or recycle effluent from it to the first converter.
U.S. Pat. No. 5,158,753 discloses an exhaust gas purifying device comprising: a catalyst device installed in the exhaust gas path of an internal combustion engine for treating the exhaust gas of the engine; an adsorbing device installed in the exhaust gas path between the catalyst device and the internal combustion engine, for treating the exhaust gas of the engine. One embodiment includes a heat exchanger for performing heat transfer between the exhaust gas flowing from the internal combustion engine to the adsorbing device and the exhaust gas flowing from the adsorbing device to the catalyst device. Alternatively, the catalyst device includes a catalyst secured in the low-temperature-side gas flow path of a heat exchanger, and the exhaust gas flowing from the internal combustion engine to the adsorbing device is allowed to flow to the high-temperature-side gas flow path of the heat exchanger.
U.S. Pat. No. 6,171,556 discloses a method and apparatus for treating an exhaust gas stream containing hydrocarbons and other pollutants. The method comprises the steps of flowing the exhaust gas stream through a catalytic member comprising a monolith body having a first catalyst zone and a second catalyst zone therein to contact a catalyst in a first catalyst zone to convert at least some of the pollutants in the exhaust gas stream into innocuous products. The exhaust gas stream is then discharged from the catalytic member and flowed through an adsorbent zone to adsorb at least some of the hydrocarbon pollutants with an adsorbent composition. The exhaust gas stream is discharged from the adsorbent zone and flowed to the second catalyst zone to convert at least some of the pollutants into innocuous products. The exhaust gas stream, so treated, is then discharged to the atmosphere through suitable discharge means. A preferred adsorbent is a zeolite, having a relatively high silica to alumina ratio and a low relative Bronsted acidity. The preferred adsorbent compositions comprise beta zeolites.
As discussed above, zeolites are often used as coatings on monolithic substrates for various high temperature adsorption and catalytic applications. In these cases, inorganic binder systems are used that survive exposure to high temperatures (e.g., >500� C.) and provide good coating adhesion. However, for low temperature application (e.g., <500� C.), inorganic type binders are often not suitable since their binding characteristics are severely diminished. In these low temperature applications, organic polymer binders are ideal since they are structurally stable and provide excellent coating adhesion. This is accomplished by the addition of suitable stabilizing agents to the slurry formulation.
For example, commonly assigned U.S. Patent Publication No. 2004/0226440, incorporated herein by reference, discloses a hydrocarbon adsorption unit. The unit is positioned in the air intake system of an automobile engine and has an air intake and air outlet. According to the application the adsorber material may be silica gel, a molecular sieve and/or activated carbon and contains an organic polymer binder, as well as an anionic, nonionic or cationic dispersant, that will cause the material, preferably as an aqueous slurry, to adhere to the surface of a substrate.
However, without proper choice of these stabilizing agents, interparticle agglomeration of zeolite particles or coagulation of zeolite and binder particles will occur, thus rendering the slurry unstable for coating application. As a result, a zeolite-based coating formulation must be developed that not only has good adhesion (particularly to metal substrates) at low temperature and excellent adsorption characteristics, but also is stable with adequate shelf-life.
The present invention is directed to an improved hydrocarbon adsorbent slurry washcoat formulation, which can be used for controlling evaporative hydrocarbon emissions from a motor vehicle. More specifically, the improved slurry composition of the present invention comprises one or more hydrocarbon adsorbent materials, e.g., a molecular sieve, and an organic polymer binder. The binder is used to improve the adhesion of the hydrocarbon adsorbent to the surface of the fuel storage, fuel delivery, or air intake system component. Stabilization of the slurry formulation is achieved by addition of an appropriate anionic dispersant and/or by increasing the slurry pH.
In another embodiment of the present invention the improved hydrocarbon adsorbent slurry washcoat is a zeolite-based slurry washcoat formulation.
In another embodiment of the present invention an undercoat layer can be used to further improved the adhesion of the zeolite slurry washcoat to a substrate surface. In particular, a refractory oxide support can be used to further improve the adhesion of the hydrocarbon adsorbent to the surface of a fuel storage, fuel delivery, or air intake system component.
The present invention is directed to a hydrocarbon adsorption material for reduction of evaporative hydrocarbon emissions in a motor vehicle. In general, any known substrate surface, which may come in contact with evaporative hydrocarbons, may be coated with the hydrocarbon adsorbent and binder of the present invention. For example, the hydrocarbon adsorbent can be deposited on one or more surfaces of a fuel storage, fuel delivery, or air intake systems component using a binder, and preferably on the inner surface of such components. Preferably, the substrate surface comprises a polymer or a metal such as aluminum, titanium, stainless steel, a Fe—Cr. alloy or a Cr—Al—Fe alloy in the form of a sheet, mesh, foil, etc. In order to increase the surface area of the adsorbent, it is desirable that the metal substrate be present in a corrugated mode. Typically, the hydrocarbon adsorbent will be deposited on the substrate in a loading of about 0.2 to about 3 g/in3, e.g., 1.25 g/in3.
The adsorbent material may include any known hydrocarbon adsorbent such as activated alumina, porous glass, silica gel, molecular sieve, activated carbon and combinations thereof. Natural and synthetic molecular sieves are particularly effective. Preferably, the molecular sieve will be a natural or synthetic zeolite such as faujasite, chabazite, clinoptilolite, mordenite, silicalite, zeolite X, zeolite Y, ultrastable zeolite Y, ZSM zeolite, offretite, or a beta zeolite. Preferred zeolites include ZSM, Y and beta zeolites. The particularly preferred adsorbent comprises a beta zeolite of the type disclosed in U.S. Pat. No. 6,171,556 incorporated herein by reference in its entirety.
A preferred zeolite-based adsorbent material is a zeolite having a high silica to alumina ratio. Generally, sieve materials having so-called three dimensional pore configurations are preferred over sieve materials having one- or two-dimensional pore configurations, although some of the latter function acceptably well. Acceptable materials typically have a micropore diameter of from about 3 to 8 angstroms. The zeolites, preferably beta zeolites may have a silica/alumina molar ratio of from at least about 25/1, preferably at least about 50/1, with useful ranges of from about 25/1 to 1000/1, 50/1 to 500/1 as well as about 25/1 to 300/1, from about 100/1 to 250/1, or alternatively from about 35/1 to 180/1 is also exemplified. The preferred beta zeolites are ion-exchanged beta zeolites, such as H/beta zeolite and Fe/beta zeolite.
Preferred zeolites may include ZSM, Y and beta zeolites, with beta zeolites particularly preferred. The preferred zeolites can be treated to reduce the number of acid sites. This can be accomplished by leaching the zeolite with an organic or inorganic acid. Preferred acids include strong inorganic acids, such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and the like, and carboxylic acids such as trifluoro acetic acid, and dicarboxylic acids such as oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric, phthalic and the like. Useful acids preferably include polyacids, preferably difunctional acids, more preferably dicarboxylic acids with oxalic acid most preferred. The acid use is at a concentration of 0.02 to 12N, preferably 0.1 to 10N, and a solid zeolite concentration of 0.01 to 1.0 g/ml and preferably 0.05 to 0.5 g/ml. The leaching is conducted at a suitable temperature range, typically of from 10 to 100� C.; for example, preferably at 70 to 100� C. when using sulfuric acid and from 10 to 50� C. when using oxalic acid. The leaching is conducted for a sufficient time to achieve the desired silica to alumina ratio attainable at the leach conditions and concentrations, and is typically from about 0.5 to 5 hours, and preferably 0.5 to 3 hours.
The zeolite can be steam treated with steam at from 350 to 900� C. Preferably, the stream treatment is conducted at from 400 to 800� C., and more preferably 500 to 750� C. with a most preferred range being from 550 to 750� C. The steam temperature can be increased at a suitable rate such as from 100 to 600� C. per hour. A useful steam concentration is from 10 to 100% and preferably 30 to 100% with a preferred concentration at from about 50 to 100% with the balance being air. The steaming is preferably conducted at atmospheric pressure. The duration of the steam treatment is sufficient to treat the zeolite and is typically from 0.5 to 48 hours, preferably 0.5 to 24 hours, more preferably from 0.5 to 8 hours and most preferably 0.5 to 5 hours. The steam treatment is believed to reduce the acidity of the zeolite by removing at least some of the aluminum from the framework of the zeolite. Steam treated zeolites have been found to have an increased durability when used to adsorb hydrocarbons in gaseous streams and to resist coke formation. Preferably, the zeolite can be treated with both leaching and steam treatment. In a particularly preferred process, the zeolite is first acid leached followed by steam treatment. Optionally, the steps of steam treatment and steaming can be repeated in any desired order. For example, leached and steamed zeolite can be repeatedly leached followed by steaming. In a specific embodiment the zeolite can be leached, steamed and leached again.
A useful method to treat beta zeolite is disclosed, for example in CN 1059701A, published Mar. 25, 1992 and herein incorporated by reference. This reference discloses a high Si beta zeolite produced by calcining to remove nitrogen compounds from a beta zeolite made through an organo-amine template process. Leaching the beta zeolite is accomplished with an organic or inorganic acid solution having a concentration of 0.02 to 12N, preferably 0.1 to 10N, and a solid zeolite concentration of 0.01 to 1.0 g/ml and preferably 0.05 to 0.5 g/ml at from 10 to 100� C. for 0.5 to 5 hours, and preferably 1 to 3 hours. The leaching is followed by treating the zeolite with steam at from 400 to 900� C. with the steam temperature increasing at from 100 to 600� C. per hour. A useful steam concentration is 100% at a system pressure of 50 to 500 KPa. The duration of the steam treatment is from 0.5 to 5 hours.
Of particular interest with regard to the present invention is the acidity which is imparted by the alumina in the zeolite framework. It is believed that the high silica to alumina ratio attained by leaching is related to the acidity of the zeolite. The acidity of the zeolite is believed to affect the durability of the zeolite when used to adsorb hydrocarbons from exhaust streams such as automotive and industrial exhaust steams which are typically at temperatures in the range of from 300 to 800� C. and more typically from 350 to 600� C. The zeolite, when used in such environments tends to lose adsorption efficiency due primarily to clogging of the pores and/or collapse of the zeolite framework. Maintenance of the stable zeolite framework can be attained by controlling the conditions under which the zeolite is treated. Such conditions include acid concentrations, steam temperatures and the like. Milder conditions reduce the tendency for the zeolite framework to deteriorate during treatment and permit the framework to be stabilized at the location where the alumina was removed.
Additionally, it is believed that steam treatment removes aluminum from the zeolite framework. The affected aluminum continues to reside in the zeolite, probably in the pores. The zeolite framework is believed to stabilize without the aluminum and the aluminum ions in the pores becomes alumina. The remaining alumina in the pores is believed not contribute to the acidity of the zeolite which is reduced. The alumina in the pores can remain or be washed or leached out in a subsequent leaching step.
The zeolite, non-steamed or steamed, has been found to have improved coking resistance, i.e., the formation of coke during engine testing has been significantly reduced. While acid leaching methods to increase the silica to alumina ratio of a zeolite are known to decrease acidity, such methods are believed to remove aluminum atoms from zeolite particles indiscriminately. Methods such as steaming remove the aluminum from the framework of the zeolite preferentially at the Bronsted acid sites. The importance of this can be recognized by both more effective resistance to coking and by the knowledge of how to treat a zeolite to attain such performance with minimizing deterioration of the framework. In essence, leaching a zeolite to death will result in reduced Bronsted acidity; but using a method such as steam treatment alone, or more preferably balanced with leaching results in a more durable zeolite for use as a hydrocarbon adsorber in accordance with the present invention.
In one embodiment, the substrate surface can be initially coated with a slurry of a high surface area refractory metal oxide, dried for about 0.5 to about 2 hours at about 90 to about 120� C. and thereafter calcined at about 450 to about 650� C. for 0.5 to about 2 hours. High surface area refractory metal oxides are well known in the prior art. Typically, the refractory metal oxide will have a specific surface area of about 60 to about 300 m2/g. Useful refractory metal oxides include alumina, titania, zirconia and mixtures of alumina with one or more of titania, zirconia, ceria, baria and a silicate. Preferably, the refractory metal oxide comprises gamma-alumina.
Thereafter, the refractory metal oxide-coated substrate surface is coated with a slurry of the desired adsorbent and dried (e.g., at about 105� C.). Alternatively, the refractory metal oxide-coated substrate may be coated with separate slurries of the hydrocarbon adsorbent, such as silica gel, molecular sieve and/or activated carbon to create layers, with drying between each layer occurring as described above.
If desired, a further top coat layer of the high surface area refractory metal oxide may be applied on top of the adsorbent, thereafter drying as described above after the application of each layer.
The hydrocarbon adsorbent material will also include a binder that will cause the material to adhere to the surface of the substrate. Such a binder is also referred to as a washcoat binder. Washcoat binders typical for use in the formulation of slurries include, but are not restricted to, the following: organic polymers; sols of alumina, silica or zirconia; inorganic salts, organic salts and/or hydrolysis products of aluminum, silica or zirconium; hydroxides of aluminum, silica or zirconium; organic silicates that are hydrolyzable to silica; and mixtures thereof.
The preferred binder is an organic polymer used in amounts of from 0.5 to 20, preferably 2 to 10, percent by weight of binder based on the weight of the material. The organic polymer may be a thermosetting or thermoplastic polymer and may be plastic or elastomeric. The polymeric binder may contain suitable stabilizers and age resistors known in the polymeric art. Most preferred are thermosetting, elastomeric polymers introduced as a latex into the adsorbent composition, preferably as an aqueous slurry. Upon application of the composition and drying, the binder material fixes the hydrocarbon adsorbent particles to themselves and the substrate surface, and in some cases, can crosslink with itself to provide improved adhesion. This enhances the integrity of the coating, its adhesion to the substrate and provides structural stability under vibrations encountered in motor vehicles. The use of a binder enables the material to adhere to the substrate without the necessity of an undercoat layer. The binder may also comprise additives to improve water resistance and improve adhesion.
Useful organic polymer binder compositions include polyethylene, polypropylene, polyolefin copolymers, polyisoprene, polybutadiene, polybutadiene copolymers, chlorinated rubber, nitrile rubber, polychloroprene, ethylene-propylene-diene elastomers, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, poly(vinyl esters), poly(vinyl halides), polyamides, cellulosic polymers, polyimides, acrylics, vinyl acrylics and styrene acrylics, polyvinyl alcohol, thermoplastic polyesters, thermosetting polyesters, poly(phenylene oxide), poly(phenylene sulfide), fluorinated polymers such as poly(tetrafluoroethylene) polyvinylidene fluoride, poly(vinylfluoride) and chloro/fluoro copolymers such as ethylene chlorotrifluoro-ethylene copolymer, polyamide, phenolic resins and epoxy resins, polyurethane, acrylic/styrene acrylic copolymer latex and silicone polymers. A particularly preferred polymeric binder is an acrylic/styrene acrylic copolymer latex.
It has been found that compatibility of the components of a slurry comprising an adsorbent material and a polymeric binder, such as a latex emulsion, is important for maintaining slurry stability and uniformity. For the purpose of the present invention compatibility means that the binder and the adsorbent material remain as a mixture of separate particles in the slurry. It is believed that when the polymeric binder is a latex emulsion and the emulsion and hydrocarbon adsorbent material have electrical charges which cause the emulsion and hydrocarbon adsorbent material to repel each other, the emulsion and hydrocarbon adsorbent material are compatible and the slurry is stable and has a uniform distribution of the hydrocarbon adsorbent material and the polymer latex in the liquid vehicle, e.g. aqueous fluid such as water. If the adsorbent material and latex emulsion particles do not mutually repel each other, irreversible agglomeration of the latex on the adsorbent material will occur. These materials are therefore incompatible and the latex comes out of the emulsion.
For those zeolites that generate a low pH mixture when dispersed in water, additional stabilization can be achieved by increasing the pH. This is important since organic latex binder emulsions commonly used in the art are anionically charged and therefore, typically have a pH greater than 7. Combining a high pH binder emulsion with a low pH zeolite slurry creates instability that often results in slurry coagulation. The pH of the slurry can be controlled depending on the acidity of the adsorbent material, with pH levels being from about 4 to about 10. A preferred range is from about 5 to about 8, more preferably from about 6 to about 7.5.
In another embodiment, it is preferred to use a dispersant in conjunction with the binder. The dispersant may be anionic, non-ionic or cationic and is typically utilized in an amount of about 0.1 to about 10 weight percent, based on the weight of the material. Not surprisingly, the specific choice of dispersant is important. Suitable dispersants may include polyacrylates, alkoxylates, carboxylates, phosphate esters, sulfonates, taurates, sulfosuccinates, stearates, laureates, amines, amides, imidazolines, sodium dodecylbenzene sulfonate, sodium dioctyl sulfosuccinate and mixtures thereof. In one embodiment, a preferred dispersant is a low molecular weight polyacrylic acid in which many of the protons on the acid are replaced with sodium. In a particularly preferred embodiment, low molecular weight anionic dispersants such as sodium dodecylbenzene sulfonate and sodium dioctyl sulfosuccinate have been found to provide excellent zeolite dispersion and zeolite-binder stability. For example, in the case of slurry formulated with high Si/Al ratio SAL-beta zeolite (i.e., sulfuric acid leached beta zeolite) and styrene-acrylic latex binder emulsion, low molecular weight anionic dispersants have been found to provide excellent zeolite dispersion and zeolite-binder stability. A preferred composite comprising about 90 weight percent beta zeolite, about 9 weight percent acrylic polymer latex and about 1 weight percent sodium dodecylbenzene sulfonate or sodium dioctyl sulfosuccinate.
While increasing the slurry pH or adding anionic dispersant alone may provide enough stabilization for the slurry mixture, best results may be obtained when both an increased pH and anionic dispersant are used. For example, for zeolite-based slurries that generate a low pH when dispersed in water and/or a dispersant, additional stabilization can be achieved by increasing the pH, as described above.
The hydrocarbon adsorbent slurries of the present invention, particularly slurries containing polymer latexes, can contain conventional additives such as thickeners, biocides, antioxidants and the like. In one embodiment, a thickener such as a xanthan gum thickener or a carboxymethylcellulose thickener can be used. The thickener makes it possible to achieve a sufficient amount of coating (and hence sufficient hydrocarbon adsorption capacity) on relatively low surface area substrates. The thickener may also serve in a secondary role by increasing slurry stability by steric hinderence of the dispersed particles. It may also aid in the binding of the coating surface.
The improved zeolite binding slurry of the present invention can be applied to, for example, a fuel storage, fuel delivery, or air intake system component of a motor vehicle by any known means in the art. For example, the formulation can be applied by spray coating, powder coating, or brushing or dipping a surface into the zeolite slurry.
2000 g of SAL-beta zeolite were combined with 1618 g of DI water and subjected to high shear mixing for 10 minutes. The resulting mixture was then milled to a particle size 90%<25 um using a continuous type mill. 150 g of the milled zeolite slurry was placed in a separate container, and the pH was increased to 6 by addition of 10% potassium hydroxide solution in DI water. The slurry was mixed for 2 hours by rolling on a roll mill, and the pH was readjusted to 6, if necessary. Subsequently, 3.19 g of commercially available sodium dodecylbenzene sulfonate was added, and the resulting slurry was mixed on a roll mill for 5 minutes. Similarly, 13.99 g of a commercially available styrene-acrylic latex binder latex binder, and 7.98 g of a commercially available thickener were added with mixing after each addition. The resulting slurry was coated onto a 25 cpsi metallic substrate at a loading of 1.45 g/in3 (dry basis) and dried at 100� C. Coating adhesion and butane adsorption capacity were evaluated and found to be excellent.
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Barta Tournament Dates 2015 July 16th – 18th
Live Auction for a Yamaha 2014
benefiting the Boys & Girls Clubs of Coastal Carolina
2014 Youth of the Year Hunter LopezAfter a grueling few hours and 5 interviews from some fantastic BGCCC Club Members, Morehead City "Sunshine Lady" Club member Hunter Lopez was named the 2015 Youth of the Year. Hunter is in the 10th grade at West Carteret and has been attending the MHC Club since he was 6 years old. He has logged in 1,452 days attending the club and is currently co-president of the clubs "Keystone Club". During his interview Hunter said many times, "I am extremely proud to wear the Boys & Girls Club logo on my chest every day". When asked what he feels our American youth need at this time Hunter replied "Graduation rate is disheartening for me. Everyone attending High School should graduate and stay focused. If I had an opportunity to encourage youth in America it would be to "Be smart and stay in school and graduate". Hunter's goal is to attend the Naval Academy and serve his country, but if he is not able to get in he has a back-up plan of attending college and going into sports medicine and becoming a Doctor. Hunter stated that his mother, grandmother and BGCCC have made a tremendous impact in his life. "Growing up without a dad was hard but at BGCCC I have everything I want and need in a family". Hunter said the staff at BGCCC are his family, mentors and father figure. His closing remarks during the interview were "The club has made me the man I am today and I will embrace it for many years to come".
Resilient Releasing Barta Tournament
Resilient Releasing Barta Tournament hit $800,000 Donation
By Jason Hawkins
"Our goal is to raise over one-million dollars for the Boys & Girls Club right here in Beaufort, NC. They need it and we have the ability to do it and we are going to raise this money in a very special way," said Tred Barta in July of 2004 from downtown Beaufort. It was the week of the inaugural tournament and the fishing tournament that is really a charity event and celebration of philanthropy for the Boys & Girls Clubs of Coastal Carolina. In the eleven years since that statement, the tournament, the founder, and the economy underwent change and withstood dark moments and the wind and yet, the focus remained the same: To raise money for the youth of today that need it for tomorrow. Since those early moments in Beaufort the efforts of this tournament and charity have stood on the supportive wave of volunteers that donate countless hours and time and monies and effort to the cause. Combined with the generous and warm hearted donations from sponsors, participant sponsor, participants and local businesses the tournament has pushed the bow forward into sometimes rough seas and to date $800,000 has been raised and given to the Boys & Girls Clubs of Coastal Carolina. For a tournament that has a minimal entry fee and has no pay-out to winners and that relies on a tournament director to orchestrate volunteers to be accountable for every detail and moment during tournament week, this is nothing less than phenomenal. "Our sponsors are fantastic," says Cynthia Barber. She doesn't say this with just a smile; sometimes the emotion of knowing how people give to this special event moistens her eyes, too. "We have over one-hundred volunteers and they each give up days and hours of their own work and school and vacation to come here and serve; and they come here without having to be asked twice," Barber says. Throughout the tournament event, there are auction items donated by artists and local businesses and at least one fishing excursion, valued at over $7000.00 is up for bidding. "This past tournament, there were over 150 auction items alone," says Barber. In addition to the donations for auction items, two of the three meals fed to anglers and participants are donated and there are many in-kind donations from graphics design to the design of programs. Volunteers that help set-up, sell merchandise, tend bar, clean-up and pass out awards to participants are priceless in effort and good-will. Eleven years later and despite the challenges with economy and weather and the tasks of pleading to sponsors and encouraging philanthropy, the Barta tournament is ever so close to its goal. With one employee and no formal offices and supported by volunteers and donors, the tournament presented a check for $40,733 to the Boys & Girls Clubs of Coastal Carolina this year. The money raised over eleven years and this year are being raised on a promise and raised for the reason's that Barta spoke of, when this event was in its infancy. "Through this tournament, we have the ability to raise these monies, we have the desire to raise these monies, and thankfully, we have the sponsors, participants, donors, and volunteers that afford us to raise these monies in a specal manner".
For information on North Carolina Governor's Cup Billfishing Conservation Series Click the Governor's Cup logo.
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"Great jerseys, my team loves them! Will be ordering more soon!" (E8648)
"i bought these as a team gift embroidered for all the girls. They loved them! Great quality!" (E6212)
"Nice Socks.They look sharp, stay up, and are a good weight for long soccer games.
Ship from NC. American made-- I think. Apple Pie and home made socks. Delightful.
Adams Womens Naturexx Sliding Shorts - Closeout [E8905]


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Fires of Yavimaya is a bad idea. How many times will people be attacked on turn 3 by a hasty Polukranos, World Eater and a hasty 8/8 trampling Kalonian Hydra on turn 4?
Come join me at No Goblins Allowed
Because frankly, being here depresses me these days.
Because frankly, being here depresses me these days.
"Akros's greatest heroes are also its royalty."
Theros flavor aside, these are interesting looking decklists. I like the mix of old and new, and a little bit of aura vs counter synergy isn't a bad idea. But my instinct really feels like "Monsters" is stronger, and there are certain things like Gustcloak Sentinel whose inclusion really doesn't make sense to me.
If you're on MTGO check out the Free Events via PDCMagic and Gatherling.
Other games you should try:DC Universe Online - action-based MMO. Free to play. Surprisingly well-designed combat and classes.
Planetside 2 - Free to play MMO-meets-FPS and the first shooter I've liked in ages.Simunomics - Free-to-play economy simulation game.
192884403 wrote:surely one can't say complex conditional passive language is bad grammar ?
"Akros's greatest heroes are also its royalty."
That's pretty bad flavor text. If this set also features "awesome" names like Battleflight Eagle, it might start feeling like an episode of Axe Cop.
Trample seems very strange for the red-white Anax and Cymede.
No longer a commander as of 7/29/13.
I really like the idea of these decks but I would like to stay completely in the Theros set. Does anybody know if someone already has tried to rebuild these that way?


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Murder suspect Drew Edward Planten is unresponsive at his first court appearance at the Wake County jail. Planten, 35, a chemist, was charged with first-degree murder in the May 2002 death of Stephanie Bennett. 1130279664168407
Join the Discussion
News & Observer is pleased to provide this opportunity to share information, experiences and observations about what's in the news. Some of the comments may be reprinted elsewhere on the site or in the newspaper. We encourage lively, open debate on the issues of the day, and ask that you refrain from profanity, hate speech, personal comments and remarks that are off point. Thank you for taking the time to offer your thoughts.


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Cardiac tamponade related to a coronary injury by a pericardial calcification: an unusual complication
1 Service de Réanimation Polyvalente, CHU Dupuytren, 2 avenue Martin Luther King, Limoges 87042, France
2 Service de Chirurgie Thoracique et Cardio-vasculaire, CHU Dupuytren, 2 avenue Martin Luther King, Limoges 87042, France
3 Service de Cardiologie, CHU Dupuytren, 2 avenue Martin Luther King, Limoges 87042, France
4 Service d'Anatomopathologie, CHU Dupuytren, 2 avenue Martin Luther King, Limoges 87042, France
BMC Cardiovascular Disorders 2012, 12:28 doi:10.1186/1471-2261-12-28Published: 25 April 2012
Cardiac tamponade is a rare but severe complication of pericardial effusion with a poor prognosis. Prompt diagnosis using transthoracic echocardiography allows guiding initial therapeutic management. Although etiologies are numerous, cardiac tamponade is more often due to a hemopericardium. Rarely, a coronary injury may result in such a hemopericardium with cardiac tamponade. Coronary artery aneurysm are the main etiologies but blunt, open chest trauma or complication of endovascular procedures have also been described.
Case presentation
A 83-year-old hypertensive man presented for dizziness and hypotension. The patient had oliguria and mottled skin. Transthoracic echocardiography disclosed a circumferential pericardial effusion with a compressed right atrium, confirmed by contrast-enhanced thoracic CT scan. A pig-tail catheter allowed to withdraw 500 mL of blood, resulting in a transient improvement of hemodynamics. Rapidly, recurrent hypotension prompted a reoperation. An active bleeding was identified at the level of the retroventricular coronary artery. The pericardium was thickened with several "sharping" calcified plaques in the vicinity of the bleeding areas. On day 2, vasopressors were stopped and the patient was successfully extubated. Final diagnosis was a spontaneous cardiac tamponade secondary to a coronary artery injury attributed to a "sharping"calcified pericardial plaque.
Cardiac tamponade secondary to the development of a hemopericardium may develop as the result of a myocardial and coronary artery injury induced by a calcified pericardial plaque.


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Small-business owners find ways to buck financing trends
Andrew Bornand is no stranger to recessions. He founded Reflex Design and Technology in 2000, during a previous economic downturn, and managed to expand his staff from eight to 13 this year, during an environment that's much worse.
With eight workers, he considered his digital marketing business understaffed. He thought about asking his family for a loan, but decided against it because of tax concerns. He held discussions with community banks and ended up striking a deal with National City and Huntington banks.
"They were just a better fit," he said, because they were savvy about taking advantage of Small Business Administration-guaranteed loans.
The banks approved loans for $140,000, which Bornand used to hire staff. Nowadays, he's the exception, not the norm.
Studies abound that say credit cards have replaced bank loans as the No. 1 form of financing for small firms. And news reports say SBA funding is drying up.
The Federal Reserve's monthly survey of loan officers at 55 U.S. banks and 23 U.S. branches of foreign banks in August, according to Bloomberg.com, shows banks tightened standards on all types of loans in the second quarter and said they expect to maintain strict criteria on lending until at least the second half of 2010.
Finding a way
Small business owners are figuring things out, despite the tough conditions.
Stephanie Rucinski, "HeadJoe" for JoeMetric Inc., a six-employee firm that is developing applications for market researchers to gather information on customer habits via devices such as the iPhone, said the recession actually was a boon for her business. The company was envisioned during a TechColumbus start-up event in June 2008. The firm got a $50,000 TechGenesis grant from the technology advocacy organization to get off the ground.
JoeMetric then applied for a Wheeler Entrepreneurship Enterprise Program grant from Ohio State University's Fisher College of Business, which covers the costs of interns so they can gain experience at no charge to the host company.
The interns also brought their own equipment, such as laptops, sparing the cost to JoeMetric.
The company also saved on office space by setting up shop in German Village's Qwirk, a collaborative where independent professionals elect to work together for a low monthly membership.
Vitaliy Levit, a Qwirk tenant and co-founder of Recess Mobile, a text messaging paging system, said since the recession kicked in, it's been easier to find help. He said the tenants invest in each other's companies, not only financially but by trading services.
Patrick Murphy, CEO of Brand Thunder, a two-year-old company that creates custom browser designs for businesses, said there was no chance of getting a bank to loan the company money because the firm has no inventory or accounts receivable – clients pay for services up front.
"We never got a loan from a bank, ever," Murphy said.
In fact, Brand Thunder doesn't even have an office. Murphy said the five employees work from home and communicate virtually.
"We interact all day," he said. They meet in person once a week.
Murphy said Brand Thunder got started with $250,000 from TechColumbus' Regional Commercialization Fund and through angel funding.
He also said he's willing to barter for services with other businesses.
No slam dunk
Delinquency rates for commercial and industrial loans rose from 3.12 percent in the first quarter to 3.73 percent in the second quarter, according to the Federal Reserve.
Banks throughout the country made fewer business loans in the second quarter, largely because of weaker loan demand and deteriorating creditworthiness, according to a quarterly Federal Reserve report.
The good news: A smaller percentage of banks tightened loan standards for May through July, compared with the prior survey, released in April.
Susan Zazon, CEO of FirstMerit Bank's Columbus region, said loans are available, and down economies spur small business development because people who have lost their jobs are trying something new.
"Some are saying, 'Now it's time to give it a shot,' " she said.
FirstMerit loan officers look for management potential in clients and make sure the new business includes a leader with deep business experience.
"I don't think it's all that different than it used to be," Zazon said. "The same things are being asked as two years ago."
While banks rely on the SBA to guarantee small business loans, that partnership doesn't mean a slam dunk.
Jenny Morehead, vice president of Park National Bank's downtown Newark office, said even with the SBA involved, the bank would approve a deal only if a good business plan was in place.
Dana McDaniel, Dublin's economic development director, said small firms also can look to the community for help. The Dublin Entrepreneurial Center had its first open house March 19. The incubator can help a small business solidify its business plan and help navigate the variety of funds in Central Ohio, from angel funds to venture capital funds to the Third Frontier program.
"An incubator is a way for people to advance their ideas and to get into that funding stream," he said.
Scott Rawdon is a freelance writer.


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Fun ways to show your American pride on the Fourth
5 ways to get over your ex in a flash
USA wins Women's World Cup!
Exclusive: Teen Beach 2 stars tell all about their thoughts on the movie
July's Back-to-School Style Giveaway: week 1 winners (plus June's grand prize winner)
DIY jewelry storage for the traveling fashionista
Beauty Spy: GL reader Anna I. shares her pretty, natural makeup routine
The only workout you need this summer
Have you ever been bullied? Share your story to help other girls!
GL + Disney take a look at the Teen Beach 2 premiere
More Friends = More Fun
GL Tweets !
4 HOURS AGO #BeautySpy: GL reader Anna I. shares her pretty, natural makeup routine: http://t.co/P3yvII6nCn pic.twitter.com/V6ISX6wkEM
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Pictured above: The
U.S. men's and women's gymnastics teams at the Olympic Trials
These chicas cannot live without their iPods. From pop music
to inspirational gospel, they listen to it all. A few most-played picks for
Jordyn's iPod: "Wild Ones" by Flo Rida,
"What Makes Your Beautiful" by One Direction and "Boyfriend" by Justin
Pictured above: A meme
made by a fan
Beauty booty
World champ Jordyn Wieber is a beauty babe. She keeps her
gym bag stocked with CoverGirl favorites, like Wetslicks Fruit Spritzer
Lipgloss in Caramel Apple Splash (she loves the flavor), NatureLuxe Silk
Foundation (because it's super light) and LiquiLineBlast Eye Liner (because
it's a pencil that looks like a liquid liner).
And don't forget that flat iron! She absolutely cannot live without it.
Pictured above: Team
USA posing with the London 2012 official mascot
Drama, drama drama!
Just 'cause they clock a ton of time in the gym doesn't mean
they aren't totally plugged in. Their can't miss series? Gabby adores Vampire Diaries, while Aly is a major Pretty Little Liars addict. Talk about
good taste!
Pictured above: The
team looking totally fierce in the Olympic Village
Their besties
All teammates claim to be buds, but McKayla and Kyla really are super tight. They started training
together when they were tots, and now they've hit the big time as part of the
Fab Five.
Pictured above: Team
USA celebrating their gold medal victory in the women's all-around team
competition. Way to go, girls!
9 young Olympians you should be watching
Olympics, then and now: Vintage pics you've gotta see
POSTED IN athlete, gymnastics, olympics, London 2012
What your idea of a perfect date?
Weather can give you headaches.
Win it: Visit all your favorite villains in The Isle of the Lost!
Ever wonder what happened to all of your excellently evil Disney faves? Enter for a chance to check out the new generation of bad guys (and girls) in The Isle of the Lost, a prequel to Disney Channel's Descendants!
CLICK HERE for your chance to win.


text:
I have a table having hierarchical menus like
"id" "parent_id" "name"
1 0 menu
2 1 item1
3 2 item1_1
4 1 item2
5 4 item2_1
and I have 100s of menu items here. In order to get all items in an array I have to write a recursive function like this
getmenu function(parent_id = 1)
$items = mysql_query("SELECT id FROM table WHERE parent_id = " + parent_id);
while ($item = msyql_Fetch_assoc($items)) {
...here I put them in array and call recursive function again to get sub items...
but this executes 100s of queries. Is this the best way to do this, to get hierarchical menus from database? Does this way loads mysql much?


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Product Details
Would you like to update product info or give feedback on images?
This book is filled with useful information about body cycles and in particular what times you should eat. Very useful in dieting.Published on April 1, 2013 by V. Reck
I am gonna be forty years old this year and I wanna be prepare mentally and physically and this book its helping me a lot to be aware of my upcoming age its a very good book I... Read morePublished on January 13, 2009 by J. Gonzalez


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Home page > Support > Becoming a sponsor > Corporate subscriptions > Corporate
Purchasing this package entitles you to a subscription for 11 operas in the 2015/2016 Season, with a number of seats to be defined according to your needs (max. 6 stalls seats or one 4-,5- or 6-seater box). As an alternative to the Opera Season you may wish to purchase a mixed Opera and Ballet subscription.
Benefits include:
- Direct contact with La Scala's Marketing Department
- Visibility: publication of your company name in performance programmes for the season, season calendar (150,000 copies), direct link from our website to your company's site and many other communications benefits
- Flexible management of your subscription, with opportunities for personalisation by conversion into a book of tickets
- Opening night of the season, 7 December: priority booking for 2/4 box seats at one of the world's most exclusive cultural events (by 21 September 2015).
- Hire of spaces: discounted rates for the hire of the celebrated spaces of La Scala, the Theatre Museum and the Ansaldo Workshops
- Special ticketing arrangements: purchase up to 10 seats for all performances in the season (excluding opening nights and private evenings).
Subscription prices
Subscription fees:
Corporate Opera (11 Operas)
- 1 seat in stalls € 2,260
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- IV rank boxes: 4-seater box € 5,188; 5-seater box € 6,887; 6-seater box € 9,516; box 19 (6 seats) € 10,682
Corporate Mixed (6 Ballets and 5 Operas)
- 1 seat in stalls € 1,951
- I, II, III rank boxes: 4-seater box € 6,269; 5-seater box € 7,308; 6-seater box € 10,391
- IV rank boxes: 4-seater box € 4,577; 5-seater box € 6,045; 6-seater box € 8,322; box 19 (6 seats) € 9,285
Sponsorship fee:
Find out more about La Scala's corporate subscribers.
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text:
Allerdale council axes 10 staff
Published at 13:46, Thursday, 14 February 2013
Ten staff at Allerdale council have been made redundant today in the latest step of the council's bid to cut costs.
The employees were among 40 people who were told last month that their jobs were at risk of being scrapped under a council restructure.
They had been due to find out last Thursday whether they would be kept on but the consultation period was extended to allow further discussions.
Chief executive Harry Dyke confirmed this afternoon that five full-time and five part-time jobs had been lost.
He said: "Considerable effort has gone into seeking redeployment opportunities for staff and a small number of staff have also left through voluntary redundancy.
"Despite this, regrettably, 10 employees have been issued with notice of redundancy."
The jobs have gone in organisational development and transformation, finance, development services, community services, and business and property services.
Mr Dyke said there were still some vacancies in the restructuring programme and the council where possible would try to redeploy staff who had been made redundant.
Published by http://www.timesandstar.co.uk
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Blog your thoughts and opinions here.
Greetings Guys,
Sunday Night's Royal Rumble was a great show, and it was a great way to kick off "The Road To Wrestlemania XXVIII."
While we are on the road to South Beach, we still have a PPV in between, Elimination Chamber. How is WWE going to book this Pay-Per-View? This is how I would do it.
Ringside Commentators:
For those of you who read my last/first blog i mentioned that there would be a part two stemming from my initial predictions. After a bit of thought, i decided that i will try my hand at a semi regular blog with my own twist, or gimmick if you will. Il try and discuss a PPV or one of the weekly shows (RAW, Smackdown! and maybe even iMpact.. maybe), looking ahead at the possibilities that could come
So the dust has settled on the 2012 Royal rumble and before we see the fallout begin on Raw lets think about what we've see, what my humble thoughts are, and what it could mean going forward to Wrestlemania...
Bryan vs Henry vs Big Show
As is quite often the case these days a WWE PPV opens with the World Heavyweight Title match. I get why this is done, a good way to get the crowd
Hello Everybody, pay attention.
I've not been writing here for long but I've read shit loads of blogs, the majority of which are just recycled every week. Examples include "Who needs to get pushed","Why WWE has ruined X and Y's push","What I would have done about Raw/Smackdown/Previous PPV". It's a bit tiresome an unoriginal, much like this blog but what
Updated 01-30-2012 at 01:25 PM by Earthquake
I felt the Royal Rumble was a show of missed opportunities. The matches were good, and some aspects were entertaining, but I found something missing. Perhaps, the best way to describe the issue is that the matches at the RR don't seem to have a huge impact (if any at all) on the over-arching backdrop of the WWE Universe. It did not prove momentous, epic, historic, which I believe should be the goal
Hello, and welcome to my first ever blog! I've always enjoyed reading others work here on the site, and I finally decided I'd join in on the fun. I'm a long time fan of proffesional wrestling, and I love making match cards and seeing how they measure up to the final event. Please enjoy as I take a look at each of my predicted Wrestlemania matches.
1- John Cena Vs. The Rock
As Wrestlemania
Hey fans. DK Wrestling Savior, or DK Genius for short, is back with another post. I figure 75 people will post their Royal Rumble thougts on the blog board so, as always, I'm throwing a curve ball.
However, it's not much of a curveball is it? My title pretty much says what this blog is going to be. Because I'm officially done with the Chris Jericho saga. Let's look at a run-down of what
Updated 01-30-2012 at 10:05 AM by DK Wrestling Savior
Although I can expect a lot of other people blogging about this PPV, I thought i'd try to get in early about what I feel about everything that just happened. Maybe injecting a few lulz here and there along the way too...I know I waffle on about bullshit quite a bit but it is a never boring read.
After WWE waste about $10,000 of pyro and fireworks the card begins with the World Heavyweight
Updated 01-31-2012 at 05:32 AM by VanHooliganX
Whats up guys? I'm Taylor Westfall, been coming to this site for a long time now catching the news and reading the blogs, and this is my first blog so bear with me if my grammar is awful, if i go off topic or clash topics and what not. i'll try to make this less painful as possible
Now some of you guys yourselves may take offense to this, and if you do i send you my humblest of apologies.
What's poppin folks, RatedATB back at it again with my thoughts on this years Royal Rumble. I'm not gonna waste any time so without further ado...
Match #1 - Steel Cage World Heavyweight Championship - Daniel Bryan (c.) vs. Big Show vs. Mark Henry
Not the greatest match, but it was ok for what it was worth. You had two big men, one of which was injured, and little D-Bry so you can't
© 2011 eWrestlingNews, All Rights Reserved.


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Mercedes Silent On Ross Brawn Exit Rumors
Mercedes has remained silent in light of intensifying rumors that its technical director, Ross Brawn, is leaving the team at the end of the season. Brawn has been the central figure of the Mercedes ever since 2009 (when the team was called "Brawn GP" and won both world championships). After that championship year, the team has struggled to challenge the top teams on a consistent basis, except for this season.
Earlier this year, McLaren technical director Paddy Lowe left the team to head for Mercedes, prompting many to guess he was a potential successor to Brawn (even back then, rumors of Brawn's exit were strong). With Lowe now firmly a feature of the Mercedes team, it seems it is only a matter of time before Brawn makes his way out of Mercedes.
The question now is, where will Brawn go? Whisper in the F1 world suggest a move to Williams is on the cards, though, in what capacity we don't know yet. The role of technical director has been recently taken by Pat Symonds, formerly of Marussia, so technical options would be limited for Brawn, at least high-level positions.
Another option would be for Brawn to stay on at Mercedes in an ambassadorial role, promoting the brand through his vast experience and success at the team. Toto Wolff, a former shareholder at Williams who now is a sporting director at Mercedes, has a similar role, as does Formula One world champion Niki Lauda.
There are a plethora of options, all pretty similar, for Brawn to undertake should the rumors prove true at the end of the season. For now, Mercedes' tight battle for second in the championship hinges on Brawn's leadership. Mercedes may end up missing it in the future.
NASCAR Power Rankings, Week 9
NASCAR drivers at the top found a lot of trouble at Bristol while Matt Kenseth's win jumped him up a few spots in this week's rankings. Read More
5 NASCAR Drivers About To Pick Up First Win
Several drivers have been knocking on the door of a win and a berth into the Chase all season. Matt Kenseth broke through on Sunday at Bristol, and these five others should be next. Read More
Danica Patrick Quietly Improving This Season
It was a quiet, uneventful day/night at Bristol for Danica Patrick, which is exactly what she and her team needed. Read More
NASCAR Power Rankings For Week 8
After dropping last week, Jimmie Johnson shoots back up the power rankings with his second win of the season at Texas on Sunday. Read More
Week 7 NASCAR Power Rankings
Kurt Busch and Ryan Newman fell outside the top 10 this week, while Hendrick teammates Jimmie Johnson and Dale Earnhardt Jr. each fell back. However, the top three remain the same. Read More
NASCAR Should Have Half The Cars Go The Other Way
Can NASCAR regain lost fans by simply changing up their race format? Read More
Brad Keselowski Has Turned New Leaf This Season
Brad Keselowski had many opportunities to wreck Denny Hamlin in the closing laps at Martinsville on Sunday, but raced clean. It was just the latest example of Keselowski's maturity this season. Read More
Toyota Will Be A Force On Short Tracks
Denny Hamlin's victory at Martinsville on Sunday capped a huge day for Toyota, which should be a factor at short tracks throughout the rest of the year. Read More


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- Remember, fireworks are dangerous
- Wallace asks citizens to fight cuts
- Dispute over state payroll rolls on
- Why fight over free trade confounds partisan divide
- Still no state budget
- Crime control is not the responsibility of landlords
- Fly over to the Poplar Grove Wings and Wheels Museum benefit
- Local leaders warn of budget deadlock's impact
- SHUTDOWN: Illinois preps for the worst
- TRRT Online Edition | July 1-7
NT and JT Bocce Tournament set for June 25
Staff Report
Bocce players of all skill levels are encouraged to sign up for the seventh annual NT and JT Bocce Tournament, to be from 9 a.m. to 6 p.m., Saturday, June 25, at the St. Ambrogio Society, 802 Montague St., Rockford.
"There are so many families in need in our area, especially right now," said John Terranova, event founder. "Since its inception, our tournament has raised over $24,000, helping local organizations. We want to encourage folks to come out, join us and let's raise some money for families at the same time."
Each team consists of two men and two women, and participants can sign up together or individually to be assigned to a team. A team fee is $100 ($25 per person), and includes play, dinner and the admission to the evening's entertainment by Vito Zatto. The event also includes games, a 50/50 raffle and a prize raffle, as well as a silent auction.
Dinner and entertainment begin at 6 p.m., and those who wish to attend just this portion of the evening can do so for $25 per couple or singles for $15. Tickets can be purchased at the door.
Donations are being accepted for the prize raffle and silent auction. Cash donations will also be accepted.
The NT and JT Bocce Tournament is a 501 (c) 3 charitable foundation. For more information, contact John Terranova, (815) 282-6530, or visit helpingkidsandfamilies.org.
From the June 8-14, 2011 issue


text:
Peter van Onselen
Professor Peter van Onselen (born 1976 in Sydney, New South Wales) is an Australian academic, author and political journalist. He was awarded a PhD in political science from the University of Western Australia, converting his dissertation into a book (published by Melbourne University Press). Van Onselen also holds a Bachelor of Arts with first-class honours in political science, majoring in philosophy, and a Masters in Policy Studies (with Distinction). Both degrees were obtained from the University of New South Wales. He has also completed a Master of Commerce (with Distinction) and was included in the Dean's honours list.
He is a presenter on Sky News Australia, and hosts Australian Agenda. Until 2014, he was the regular presenter of Friday afternoon program The Contrarians, but stepped down as permanent host to begin hosting his Monday to Thursday nightly PVO NewsHour.
Van Onselen grew up in the Eastern Suburbs of Sydney. He went to The Scots College in Bellevue Hill, University of New South Wales and University of Western Australia.[1]
He is the Contributing Editor at The Australian newspaper and Sky News. He also writes a column in the Sunday Times and is the paper's Political Analyst. Van Onselen hosts PVO News Hour 7-8pm AET Monday to Thursday on Sky News. He also hosts Australian Agenda on Sunday mornings, a joint production between Sky News and The Australian newspaper, interviewing politicians such as Julia Gillard, Kevin Rudd, Tony Abbott, John Howard, Barry O'Farrell and Malaysian opposition leader Anwar Ibrahim.
In early 2011 van Onselen became a Winthrop Professor and Foundation Chair of Journalism at the University of Western Australia. He was an associate professor in politics and government at Edith Cowan University where he worked from 2004-2011, having previously taught political science at the University of New South Wales. During his time at Edith Cowan University Professor van Onselen held various administrative positions, including chair of the politics and government discipline as well as post graduate coordinator for his school. He was on the faculties higher education research committee.
Prior to completing his PhD and commencing his academic career Professor van Onselen worked for Prime Minister Tony Abbott as an adviser when Mr Abbott was the Minister for Workplace Relations in the Howard government. Professor van Onselen also previously worked as a policy analyst in the non-government sector and as an intelligence analyst at the New South Wales Crime Commission.
Dr van Onselen has written or edited four books, including the best selling John Winston Howard (with Dr Wayne Errington), rated by the Wall Street Journal Asia as the best biography of 2007 and shortlisted in the Queensland Premiers literary awards. He also wrote (with Dr Phil Senior) Howard's End, which was short listed for the John Button prize for writings on public policy. Van Onselen has written numerous refereed journal articles and conference papers, including articles for the Australian Journal of Political Science, the British Journal of Legislative Studies, the Journal of Commonwealth and Comparative Politics and the Australian Journal of Communication. His teaching and research areas include Australian political institutions, political communications and public policy. More recently he has written book chapters on the role of the media for Palgrave and Oxford University Press publications.
Prior to joining News Corporation, Van Onselen wrote a column for The Bulletin magazine and before that wrote opinion columns across a range of newspapers, including the Sydney Morning Herald, The Age, The Australian Financial Review, the Canberra Times and The Courier-Mail. He worked for Channel Nine's current affairs program Sunday in 2007 and 2008, where he presented cover stories on Australian politics and provided commentary in the lead-up to the federal election.
Van Onselen has been a panelist for state, federal and United States election coverages for Channels Seven and Nine. He has also appeared on programs such as ABC 7:30 Report, Q&A, Lateline and Four Corners, as well as 60 Minutes on Channel Nine. For the 2010 federal election he was the host of Sky News' 2010 tally room panel and was satirized by the ABC comedy group The Chaser as part of its Yes We Canberra! coverage. Van Onselen debated at university World and Australasian championships with members of the Chaser during their studying days. He was a member of the combined Australian University Test Team at the 1998 Australasian Championships in Sydney, where he reached the semi-finals. He also reached the semi-finals of the 1999 World Debating Championships in Manila.
Personal life[edit]
Van Onselen is married to Ainslie and they have two daughters, Sasha and Chloe.[1]
Published works[edit]
- John Winston Howard: The Biography (with Wayne Errington, 2007) (Melbourne University Press) finalist for the Queensland Premier's Literary Award
- Howard's End: The Unravelling of a Government (with Philip Senior, 2008) (Melbourne University Press) finalist for the John Button Prize for public policy writing
- Liberals and Power: The Road Ahead (Editor, 2008) (Melbourne University Press) launched by radio presenter Alan Jones
- ^ a b O'Dwyer, Erin (29 July 2007). "'I'm as boring as John Howard. I like sport and politics'". The Sun-Herald (Fairfax Media). Retrieved 24 February 2012.
External links[edit]


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Holly Madison: When I Was With Hef, I 'Expected' Jokes About Age
'Holly's World' star Holly Madison wasn't ever bothered by the jabs about her dating a much older man.
"I expected those kind of jokes," she tells PopEater of dating Hugh Hefner. "Anyone who gets into that situation knows that jokes like that are going to happen." Watch Our Chat With Holly Inside!
Madison and Hefner, of course, are no longer dating. The Playboy mogul recently became engaged to Crystal Harris -- Madison's successor as number one girlfriend. And when Madison heard the news, she went to the mansion to confront the couple.
"It was definitely an awkward situation," Madison explains of the meeting, but she wanted to get her reaction on camera.
"I have a lot of different feelings about it," she adds. "I'm protective of Hef and I want him to make good decisions."
As if finding out that your ex is engaged wasn't enough, the former 'Girls Next Door' starlet had to endure being told to lose weight for her Las Vegas burlesque act, 'Peep Show,' -- but she let those criticisms go, too.
"I'm all for getting healthier," she says. "I don't think my body wants to lose a lot of weight."
The second season of 'Holly's World premieres on Sunday at 10:30PM on E!
- Filed under:
- TV News -
- Interviews -
- Holly Madison
- Thursday 20 JanuaryBy LIZHighest Rank Vote downVote upReport this
Shut up already!
She is just jealous because some other bimbo is getting the money! They are just as nasty & gross as he is!
- Thursday 20 JanuaryBy stu
such a doll! but honey ur not @ the mansion. ur legs r open in this video.
- Thursday 20 JanuaryLow Ranked Vote downVote upReport this
Holly, Holly, Holly ! You're a Cutie . I have had some interesting thoughts about you. I'll bring the Dom, You, just bring you. My Place 9 PM.
- Thursday 20 JanuaryBy LaBeKaHighest Rank Vote downVote upReport this
lol Holly is just mad 'cause Hef didn't marry her!
- Thursday 20 JanuaryBy porchprimate
Like the Wendy Williams vid, wanted to see the rearview..nice big Amazon Butt!!!!
- Thursday 20 JanuaryBy Shasta
Holly of course you did! You look OLDER than HEF!
Your one ugly dog!
- Thursday 20 JanuaryBy maryHigh Rank Vote downVote upReport this
She's amazingly gorgeous she doesn't need to lose a pound.
- Friday 21 JanuaryBy flamoon
Hef loves her as much as he loved you Holly. NOT.
She is much more attractive than you are. I think you remind
him of his sister.
- Friday 21 January
I am sure people were not making jokes, they were facts.
When a beautiful woman like this, is with a hundred year old man, there will always be talk. People will talk about how your are a gold digger. Hef may have loved her, but I cant believe any woman this young, could be in love with a man that age.
Money does the strangest things to people.
Love, and in love, are two different thing.
- Friday 21 January
I wonder how she feels to be married to the biggest PIMP in the world, and has screwed dozens of TRAMPS like you???? What are uou gettig out of this
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eli Kulp
GoFundMe Site Set Up For Acclaimed Philly Chef Injured In Amtrak Derailment
According to the GoFundMe account, Kulp was in the first row of the second car of the train and was thrown during the crash, resulting in a "severe spinal cord injury."
Old City Restaurant Named The Second Best In The Country By Bon Appetit Magazine
High Street on Market has been ranked the second best new restaurant in the country by Bon Appetit Magazine.
Chef at Old City Restaurant 'Fork' Gets National Magazine Honor
Eli Kulp of Fork restaurant, at Third and Market Streets, has been named one of the best chefs in the country by Food & Wine magazine.
Acclaimed Old City Restaurant Offering New Tasting Menu Celebrating Pennsylvania
Fork's Chef Eli Kulp is introducing a new chef's tasting menu that incorporates the traditions and culture of the area to tell a story.


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|Artist: Beatles
Learn more about Magical Mystery Tour (Remastered):
Song Listing
Album Notes and Credits
Notes & Personnel Info
|The Beatles: John Lennon (vocals, acoustic & electric guitars, harmonica, piano, harpsichord, organ, clavioline, Mellotron, maracas, tambourine, tape loops); George Harrison (vocals, guitar, violin, harmonica, Hammond organ, timpani, congas, firebell, tambourine, tabla); Paul McCartney (vocals, guitar, flute, recorder, piano, acoustic & electric basses, bongos, congas); Ringo Starr (vocals, drums, maracas, tambourine, finger cymbals, tape loops).
|Additional personnel includes: Dave Mason (piccolo, trumpet); Philip Jones (trumpet); George Martin (piano); Mal Evans (tambourine); Mick Jagger, Gary Leeds, Keith Richards, Marianne Faithfull, Jane Asher, Patti Harrison, Keith Moon, Graham Nash (background vocals).
|Recorded at Abbey Road Studios, Olympic Sound Studios, De Lane Lea and Chappell Recording Studios, London, England between November 24, 1966 and November 7, 1967.
|This reissue of MAGICAL MYSTERY TOUR has been digitally re-mastered. It comes packaged with replicated original U.K. album art, an expanded booklet containing original and newly written liner notes, and rare photos. Limited quantities of the CD are embedded with a brief documentary film about the album.
|Audio Remasterers: Sean Magee; Sam O'Kell; Steve Rooke; Guy Massey; Paul Hicks.
|Liner Note Authors: Mike Heatley; Kevin Howlett.
|Recording information: 04/25/1967-11/07/1967.
|The first six songs on MAGICAL MYSTERY TOUR were the soundtrack to the Beatles' TV movie of the same name. The film was an experimental mess, but the experimental pop of the album included some of their most memorable productions. The soundtrack side was dominated by Paul McCartney pop tunes, including the bittersweet piano ballad "Fool On The Hill" and "Your Mother Should Know," an impossibly catchy bit of Vaudevillian pop. But it also featured George Harrison's mystical "Blue Jay Way" (about his house in Hollywood) and John Lennon's "I Am The Walrus," which wedded a stream-of-consciousness lyric to a fierce drum beat, layers of strings, odd voices and some dialogue from Shakespeare's "King Lear."
|McCartney's "Hello Goodbye," which led off the assorted singles, featured some neatly arranged contrapuntal vocals, and may well have been about the dissolving partnerships (songwriting and otherwise) between McCartney and Lennon. Lennon's strangely arranged "Strawberry Fields Forever," whose two halves blend different takes of the same song, one slowed down to match the pitch of the other, was a trippy reverie; its bridges, orchestrated with horns, cellos, and backward cymbals, are sheer brilliance. "Penny Lane," a wistful fantasy featuring a beautiful trumpet solo, was McCartney at his melodic best, the AM foil to Lennon's FM headiness.
Producer: George Martin
Engineer: Geoff Emerick; Ken Scott
Musical Guests
|Mick Jagger
|Keith Richards
|Keith Moon
|Graham Nash
|George Martin
|Marianne Faithfull
Compilation Appearances
Associated Artists and Works
Technical Info
|Release Date : 09/09/2009
|Original Release Date : 1967
|Catalog ID : 3824652
|Label : Apple Corps
|Number of Discs : 1
|Studio/Live : Studio
|Mono/Stereo : Stereo
|SPAR Code : n/a
Professional Reviews
- Included in Q Magazine's "Best Psychedelic Albums of All Time" issue.
- "...the weirdest beast in the entire Beatles catalogue....As good an indicator as any that all the madness was about to end. It had to."
- "With much better material and no forced concept to weigh down the proceedings, Martin's production work shines, particularly on the Lennon tracks."
BioThe Beatles
"I have never seen anything like it. Nor heard any noise to approximate the ceaseless, frantic, hysterical scream which met the Beatles when they took the stage after what seemed a hundred years of earlier acts. All very good, all marking time, because no one had come for anything other than the Beatles...
Then the theatre went wild. First aid men and police -- men in the stalls, women mainly in the balcony -- taut and anxious, patrolled the aisles, one to every three rows.
Many girls fainted. Thirty were gently carried out, protesting in their hysteria, forlorn and wretched in an unrequited love for four lads who might have lived next door.
The stalls were like a nightmare March Fair. No one could remain seated. Clutching each other, hurling jelly babies at the stage, beating their brows, the youth of Britain's second city surrendered themselves totally."
- Derek Taylor (From his book Fifty Years Adrift)
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Great Performances at The Met
LA DAMNATION DE FAUSTSeries Website »
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Director Robert Lepage applies stunning artistry to Berlioz's musical examination of good and evil.
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text:
LibreOffice 4.0 tested
The developers have also implemented a couple of functions, for example,
COUNTIF(), and
IFERROR() for the first time. The new XML Source dialog (Data | XML Source) lets you import arbitrary XML content into Calc.
The Gnumeric import filter is currently a work in progress. If you want to test this feature and provide feedback, you can enable the experimental function in the preferences below Tools | Options | LibreOffice | Advanced. Much work remains to be done (Figure 4); for example, the office suite repeatedly presented unusable data if a Calc sheet was not open when importing a Gnumeric file.
One of the highlights of the new LibreOffice version is remote control via an Android smartphone; the LibreOffice Impress Remote app is available from Google Play [5]. Cellphones can use Bluetooth to communication with the computer, switch Impress to full-screen mode for a presentation, and navigate the slides via swipes (Figure 5, right) or, optionally, using the volume keys on the phone (Figure 5, left). The app displays the time at the top edge of the screen to help the speaker keep track of time limits on the presentation.
Right now, only Android users can use the remote control software. According to the developers, plans exist for a BlackBerry app, but other platforms such as iOS, Tizen, Nokia, Windows Phone 8, and so on could also have a chance if they find a developer willing to tackle the project. Volunteers are welcome!
Happy Birthday!
The new version is a successful and mature product; LibreOffice has every right to celebrate the 4.0 in its name. I expect the developers will soon fix the minor niggles in one of the future point releases.
- LibreOffice: http://www.libreoffice.org
- Fosdem 2013, "The story of cleaning and re-factoring a giant code-base" by Michael Meeks: https://wiki.documentfoundation.org/Marketing/Events/Fosdem2013#Main-track_talk
- ICU Regexp module: http://userguide.icu-project.org/strings/regexp
- Firefox personas: https://addons.mozilla.org/en-US/firefox/themes/
- LibreOffice Impress Remote: https://play.google.com/store/apps/details?id=org.libreoffice.impressremote
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About 29 percent of people nationwide reported owning a gun.
The previous Cold War enemies agreed to reopen embassies in each other's capitals, with the Cubans saying that could happen as soon as July 20.


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Security News
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'Rednecks who like to have a good time': Hopedale holds July 4th parade
Yesterday | Burlington Times News | Comment?
What to do: Hometown fun, fireworks & festivals
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Yesterday | Santa Cruz Sentinel | Comment?
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Upcoming City Council Agenda For Tuesday
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Thursday | Cleveland.com | Comment?
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Thursday | The Miami Herald | Comment?
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text: After Superstorm Sandy, the Food Bank of Monmouth and Ocean Counties in Neptune, N.J., is filled with water bottles, canned food and other goods. But these supplies are going out almost as fast as they come in. Amy Walters/NPR hide caption itoggle caption Amy Walters/NPR The Salt Storm-Battered Food Banks Struggle To Help The Hungry November 13, 2012 Some charitable organizations that were in the path of Superstorm Sandy were left in as bad shape as their clients. With Thanksgiving around the corner, they wonder how they will feed the storm's victims and the poor. Listen Loading… 4:42 Playlist Download Embed Embed Close embed modal <iframe src="http://www.npr.org/player/embed/165046153/165057205" width="100%" height="290" frameborder="0" scrolling="no">


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MWC Daily: Rainy Days and Mondays
Rain boots, umbrellas and slickers. Your Monday wardrobe essentials.
Rain boots, umbrellas and slickers. Your Monday wardrobe essentials.
The Country Music Association (CMA) and the Academy of Country Music (ACM) might as well just deliver their 'Video of the Year' trophies to Brad Paisley now.
If you're a coffee drinker and you bring your own mug to work, you're probably not going to like what I'm about to write.
This week's 'Tweet of the Week,' belongs to Elizabeth Dinan and Seacoast Online. It's not everyday you hear about the possibility of a 'drunk raccoon.'
Country crooner, Brett Eldredge wins Twitter this week with his tweet about chewing gum.
We were having some fun with 'Fifty Shades of Grey' this morning. If you read the book(s), you know the movie hits theatres this Friday, just in time for Valentine's Day!
If you HAVE to be on the roads today, my best advice is to go slow and make sure you have enough gas in your vehicle.
Thank you so much to all our listeners who posted their suggestions on Facebook on how to stay healthy. Both Roy Sullivan and Tim Tern, the former intern are sick and I need ways to stay healthy and avoid going to the doctor's!
Brrr, it was one of those mornings where you just didn't want to get out of your warm bed.
We all have at least one of 'em! That person that is so difficult to buy a gift for.


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"'Gay Marriage': Logic, Rhetoric, and Reality," with Dr. Rollen Edward Houser
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Jerry Hall in 20 looks
Jerry Hall turns 59 today and we're celebrating with a throwback to the model's most stylish moments from the 1970s through to the 1990s.
30 Summer Sandals
A Summer must-have whatever the trends, we edit this seasons' sandals from feminine festival-style in natural leather, to touches of sunny gold, folk charm and tribal details. The 30 sandals you need to know about for Summer 2015.
Hubert de Givenchy celebrates Audrey Hepburn
Collector, aesthete, master of French elegance, and founder of the house that still bears his name, Hubert de Givenchy also wrote a book dedicated to his lifelong friend Audrey Hepburn that beautifully traced the years of friendship between the artist and his muse though more than 150 fashion sketches he made for her. As an exhibition dedicated to the style icon opens at London's National Portrait Gallery, rediscover the exclusive interview Hubert de Givenchy granted to Vogue.fr, in which he speaks tenderly of his dear friend.
Alberta Ferretti Demi-couture Spring/Summer 2016 unveiled in her new Paris showroom
Alberta Ferretti previewed her demi-couture Spring/Summer 2016 collection on Tuesday in her new Parisian showroom on Rue du Faubourg Saint-Honoré. Around 20 evening gowns were shown, in the designer's romantic signature style which aligned perfectly with the refined baroque boudoir setting. Explore the gold embroidery, floral prints, airy cuts and sensual drapery of the new collection.
Models in Swimwear
From Australia to the paradise islands of the Caribbean, the Vogue girls are already hitting some of the world's most spectacular beaches. Swimsuit or bikini, look to the biggest models in the business for a lesson in lengthening, sculpting for summer: see Gisele Bündchen, Gigi Hadid and Doutzen Kroes in our favorite swimsuit looks.
20 dresses for Summer
With bohemian trends, military influences, mismatched colors, transparent white and playful prints, this year's summer dress are influenced by a storm of runway trends that are shaping a seasonal staple. Look back at the star dresses from Spring/Summer 2015 Fashion Month and find your style