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Multi-layer nano-particle preparation and applications
A multi-layer nano-particle composition including a polymer core and at least two additional layers is provided. The nano-particles have a mean average diameter less than about 100 nm. The nano-particles can be modified via, for example, hydrogenation or functionalization. The nano-particles can be advantageously incorporated into rubbers, elastomers, and thermoplastics.
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This application is a continuation application U.S. Ser. No. 11/058,156 filed Feb. 15, 2005, which is a divisional application of U.S. Ser. No. 10/331,841 filed Dec. 30, 2002 (now U.S. Pat. No. 6,872,785), which is a continuation-in-part of U.S. Ser. No. 10/223,393 filed Aug. 19, 2002 (now U.S. Pat. No. 6,956,084), which is a continuation-in-part of U.S. Ser. No. 09/970,830 filed Oct. 4, 2001 (now U.S. Pat. No. 6,437,050) and U.S. Ser. No. 10/038,748 filed Dec. 31, 2001 (now U.S. Pat. No. 6,689,469).BACKGROUND OF THE INVENTION
The present invention relates to polymer nano-particles, methods for their preparation, and their use as, for example, additives for rubber, including natural and synthetic elastomers. The invention advantageously provides several mechanisms for surface modification, functionalization, and general characteristic tailoring to improve performance in rubbers, elastomers, and thermoplastics.
Polymer nano-particles have attracted increased attention over the past several years in a variety of fields including catalysis, combinatorial chemistry, protein supports, magnets, and photonic crystals. Similarly, vinyl aromatic (e.g. polystyrene) microparticles have been prepared for uses as a reference standard in the calibration of various instruments, in medical research and in medical diagnostic tests. Such polystyrene microparticles have been prepared by anionic dispersion polymerization and emulsion polymerization.
One benefit of using nano-particles as an additive in other materials is that they can be discrete particles uniformly dispersed throughout a host composition. Nano-particles preferably are monodisperse in size and uniform in shape. However, controlling the size of nano-particles during polymerization and/or the surface characteristics of such nano-particles can be difficult. Accordingly, achieving better control over the surface composition of such polymer nano-particles also is desirable.
Rubbers may be advantageously modified by the addition of various polymer compositions. The physical properties of rubber moldability and tenacity are often improved through such modifications. Of course, however, the indiscriminate addition of nano-particles to rubber may cause degradation of the matrix material, i.e., the rubber, characteristics. Moreover, it is expected that primarily through the selection of nano-particles having suitable size, material composition, and surface chemistry, etc., will improve the matrix characteristics.
In this regard, development of nano-particles having a surface layer which would be compatible with a wide variety of matrix materials is desirable because discrete particles could likely disperse more evenly throughout the host to provide a uniform matrix composition. However, the development of a process capable of reliably producing acceptable nano-particles has been a challenging endeavor. For example, the solubility of various monomers in traditional alkane solvents has made solution polymerization a difficult process by which to achieve nano-particles having tailored variety of surface layers. Moreover, the development of a solution polymerization process which produces reliable nano-particles, particularly nano-particles advantageously employed in rubber compositions, has been elusive.SUMMARY OF THE INVENTION
A multi-layer nano-particle composition including a poly (alkenylbenzene) core and at least two additional layers is provided. The nano-particles have a mean average diameter less than about 100 nm. As used herein, the use of the phrase "additional layers" reflects, for example, layers formed of divergent monomers or of the same monomers but having differing characteristics including molecular weight, vinyl modification, functionalization, etc. As one effective usual characteristic of the present nano-particles, they can be described as onion-like in view of their multiple layers.
A process for forming a multi-layer nano-particle is also provided. The process includes initiating the block copolymerization of a first monomer in a hydrocarbon solvent to form a living polymerization mixture. At least a second monomer is then added to the polymerization mixture and polymerized to form a living polymer chain. An alkenylbenzene monomer is also added to the polymerization mixture and allowed to polymerize onto the living polymer chain. The living polymer chains are made to aggregate to form micelles and at least one crosslinking agent is added to the polymerization mixture to form crosslinked nano-particles having a poly(alkenylbenzene) core and at least two additional layers.
A rubber composition including an elastomer, nano-particles, carbon black, silica and a curing agent having low shrinkage properties is also provided. A process for preparing the rubber compound is similarly provided. Such compound shows its relatively high hysterisis, good tensile strength, good tear strength, strong resistance to creep, high temperature resistance, and good aging properties. A process of making the rubber compound for engine mount applications is similarly provided.
Herein throughout, unless specifically stated otherwise:
"vinyl-substituted aromatic hydrocarbon" and "alkenylbenzene" are used interchangeably; and
"rubber" refers to rubber compounds, including natural rubber, and synthetic elastomers including styrene-butadiene rubber, ethylene propylene rubber, etc., which are known in the art.
This application incorporates by reference U.S. Ser. No. 09/970,830 filed Oct. 4, 2001 (now U.S. Pat. No. 6,437,050), 10/038,748 filed Dec. 31, 2001 (now U.S. Pat. No. 6,689,469), and Ser. No. 10/223,393 filed Aug. 19, 2002 (now U.S. Pat. No. 6,956,084).
One exemplary polymer nano-particle of the present invention is formed from multiblock polymer chains having at least three blocks selected primarily from poly(conjugated diene) block and poly(alkenylbenzene) blocks. Of course, the various monomer constituents may be present to a limited extent in the blocks of another selected monomer. In addition, the present invention anticipates nano-particles wherein one or more layers are formed of a random copolymer of two or more monomer units.
The poly(alkenylbenzene) blocks may be crosslinked to form the desired nanoparticles. The nano-particles have diameters—expressed as a mean average diameter—that are preferably less than about 100 nm, more preferably less than about 75 nm, and most preferably less than about 50 nm. The nano-particles preferably are substantially monodisperse and uniform in shape. The dispersity is represented by the ratio of Mw to Mn, with a ratio of 1 being substantially monodisperse. The polymer nano-particles of the present invention preferably have a dispersity less than about 1.3, more preferably less than about 1.2, and most preferably less than about 1.1. Moreover, the nano-particles are preferably spherical, though shape defects are acceptable, provided the nano-particles generally retain their discrete nature with little or no polymerization between particles.
The nano-particles are preferably formed via dispersion polymerization, although emulsion polymerization is also contemplated. Hydrocarbons are preferably used as the dispersion solvent. Suitable solvents include aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, nonane, decane, and the like, as well as alicyclic hydrocarbons, such as cyclohexane, methyl cyclopentane, cyclooctane, cyclopentane, cycloheptane, cyclononane, cyclodecane and the like. These hydrocarbons may be used individually or in combination. However, as more fully described herein below, selection of a solvent in which one polymer forming the nano-particles is more soluble than another polymer forming the nano-particles is important in micelle formation.
With respect to the monomers and solvents identified herein, nano-particles are formed by maintaining a temperature that is favorable to polymerization of the selected monomers in the selected solvent(s). Preferred temperatures are in the range of about
−40 to 250° C., with a temperature in the range of about 0 to 150° C. being particularly preferred. As described in more detail below, the interaction of monomer selection, temperature and solvent, facilitates the formation of block polymers which form micelles and ultimately the desired nano-particles.
According to one embodiment of the invention, a first multiblock polymer is formed of at least vinyl aromatic hydrocarbon monomers and conjugated diene monomers in the hydrocarbon solvent. The multiblock polymer contains at least one block that is soluble in the dispersion solvent, preferably a conjugated diene monomer, and at least an end block which is less soluble in the dispersion solvent, preferably a vinyl-substituted aromatic hydrocarbon monomer. Moreover, in one embodiment, a vinyl-substituted aromatic hydrocarbon monomer is chosen the polymer of which is generally insoluble in the dispersion solvent.
As is known in the art, such a multiblock copolymer may be formed by living anionic polymerization, in which each block is formed by adding a new monomer charge to a living polymerization mixture in which polymerization is substantially complete.
Additionally, other blocks are incorporated into the block copolymer, including additional poly(conjugated diene) blocks or poly(alkenylbenzene) blocks, as well as other blocks such as poly(alkylene) blocks. Other suitable monomer units include ethylene oxide, methyl methacrylate, nitrites, acrylates, and mixtures thereof.
Another method of forming substantially multiblock polymers is the living anionic copolymerization of a mixture of monomers, such as a conjugated diene monomer and a vinyl-substituted aromatic hydrocarbon monomer in a hydrocarbon solvent, particularly, in the absence of certain polar additives, such as ethers, tertiary amines, or metal alkoxides which could otherwise effect the polymerization of the separately constituted polymer blocks. Of course, certain advantages may be achieved via a random polymerization of at least one block of the polymer.
However, since more than one additional polymer block is to be incorporated into the nano-particle, it may be preferred to utilize the first-described polymerization technique, wherein subsequent monomer units are added after substantially complete polymerization of each previous block.
Such multi-block polymers, are believed to aggregate to form micelle-like structures, with for example, vinyl-substituted aromatic blocks directed toward the centers of the micelles and all other blocks as tails extending therefrom. It is noted that a further hydrocarbon solvent charge or a decrease in polymerization mixture temperature may also be used, and may in fact be required, to obtain formation of the micelles. Moreover, these steps may be used to take advantage of the general insolubility of the vinyl-aromatic blocks. An exemplary temperature range for micelle formation is between about 0 and 100° C., more preferably between about 20 and 80° C.
Although the above describes formation of multi-block polymers prior to micelle formation, it is noted that after the micelles have formed, additional monomer charge(s), such as conjugated diene monomer and/or vinyl-substituted aromatic hydrocarbon monomer, can be added to the polymerization mixture as desired. In this manner, multi-block polymers may again be formed when only diblock polymers form the micelles. Moreover, it is feasible to form the micelles of the block co-polymers with a further monomer(s) charge thereafter.
After formation of the micelles, a cross-linking agent is added to the polymerization mixture. Preferably a crosslinking agent is selected which has an affinity to the vinyl-substituted aromatic hydrocarbon monomer blocks and migrates to the center of the micelles due to its compatibility with the monomer units and initiator residues present in the center of the micelle and its relative incompatibility with the dispersion solvent and monomer units present in the outer layer of the micelle. The crosslinking agent crosslinks the center core of the micelle (i.e. alkenylbenzene) to form the desired nano-particle. Consequently, nano-particles are formed from the micelles with a core including, for example, styrene monomer units and a surface layer including, for example, butadiene monomer units. Reference to
The conjugated diene monomers contemplated for the block polymer are those soluble in non-aromatic hydrocarbon solvents. C4-C8 conjugated diene monomers are the most preferred. Exemplary conjugated diene monomers include 1,3-butadiene, isoprene, and 1,3-pentadiene.
Vinyl-substituted aromatic hydrocarbon monomers include styrene, α-methylstyrene, 1-vinyl naphthalene, 2-vinyl naphthalene, 1-α-methyl vinyl naphthalene, 2-α-methyl vinyl naphthalene, vinyl toluene, methoxystyrene, t-butoxystyrene, and the like, as well as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl derivatives thereof, in which the total number of carbon atoms in the combined hydrocarbon is generally not greater than 18, as well as any di- or tri-vinyl substituted aromatic hydrocarbons, and mixtures thereof.
The multiblock polymer, preferably has Mw of about 5,000 to 1,000,000, more preferably between about 10,000 and 100,000. A typical multiblock polymer will be comprised of 5 to 8% by weight conjugated diene and 95 to 5% by weight vinyl-substituted aromatic hydrocarbon, more preferably 30 to 70% by weight, and most preferably 40 to 60% by weight of each contributed monomer type, with the weight being distributed among multiple blocks if more than one block of each contributed monomer type is present.
The micelle formed by the above described polymerization is preferably crosslinked to enhance the uniformity and permanence of shape and size of the resultant nano-particle. Preferred crosslinking agents are di- or tri-vinyl-substituted aromatic hydrocarbons. However, crosslinking agents which are at least bifunctional, wherein the two functional groups are capable of reacting with vinyl-substituted aromatic hydrocarbon monomers are acceptable. A preferred crosslinking agent is divinylbenzene (DVB).
A 1,2-microstructure controlling agent or randomizing modifier is optionally used to control the 1,2-microstructure in the conjugated diene contributed monomer units, such as 1,3-butadiene, of the nano-particle. Suitable modifiers include hexamethylphosphoric acid triamide, N,N,N′,N′-tetramethylethylene diamine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1,4-diazabicyclo [2.2.2] octane, diethyl ether, triethylamine, tri-n-butylamine, tri-n-butylphosphine, p-dioxane, 1,2-dimethoxy ethane, dimethyl ether, methyl ethyl ether, ethyl propyl ether, di-n-propyl ether, di-n-octyl ether, anisole, dibenzyl ether, diphenyl ether, dimethylethylamine, bis-oxalanyl propane, tri-n-propyl amine, trimethyl amine, triethyl amine, N,N-dimethyl aniline, N-ethylpiperidine, N-methyl-N-ethyl aniline, N-methylmorpholine, tetramethylenediamine, oligomeric oxolanyl propanes (OOPs), 2,2-bis-(4-methyl dioxane), and bistetrahydrofuryl propane. A mixture of one or more randomizing modifiers also can be used. The ratio of the modifier to the monomers can vary from a minimum as low as 0 to a maximum as great as about 4000 millimoles, preferably about 0.01 to 3000 millimoles, of modifier per hundred grams of monomer currently being charged into the reactor. As the modifier charge increases, the percentage of 1,2-microstructure (vinyl content) increases in the conjugated diene contributed monomer units in the surface layer of the polymer nano-particle. The 1,2-microstructure content of the conjugated diene units is preferably between about 5% and 95%, and preferably less than about 35%.
Without being bound by theory, it is believed that an exemplary micelle will be comprised of ten to five hundred multiblock polymers yielding, after crosslinking, a nano-particle having a Mw of between about 5,000 and 10,000,000, preferably between about 5,000 and 4,500,000.Structural Modifications
In an alternative embodiment, at least one layer of the polymer nano-particle includes a copolymer including at least one alkenylbenzene monomer unit and at least one conjugated diene monomer unit. The copolymer may be random or ordered. In one such embodiment the copolymer layer includes a SBR rubber. Herein throughout, references to a poly (conjugated diene) layer are understood to include copolymers of the type described here.
Similarly, the density of the nanoparticle may be controlled by including monoblock, diblock, and/or multiblock polymer chains in the micelles. One method for forming such polymer chains includes forming a first polymer in the hydrocarbon solvent. After formation of the first polymer, a second monomer is added to the polymerization, along with additional initiator. The second monomer polymerizes onto the first polymer to form a living diblock polymer as well as forming a separate second polymer which is a living mono-block polymer. A third polymer may then be added along with additional initiator. The third polymer would polymerize onto the diblock polymer to form a multi-block onto the monoblock polymer to form a diblock, as well as forming a third polymer which is a living monoblock polymer. The multiblock polymer contains at least a first end block that is soluble in the dispersion solvent, and a second end block which is less soluble in the dispersion solvent, preferably the vinyl-substituted aromatic hydrocarbon monomer.
Without being bound by theory, it is believed that a large number of mono-block polymer chains in the core of the nano-particle results in and less entanglement of the tails of the diblock and multiblock chains. The resultant surface layer thus may have a brush-like structure.
The mono-block polymer preferably has Mw between about 1,000 and 1,000,000, more preferably between about 5,000 and 100,000. The multi-block polymer preferably has Mw of about 1,000 to 1,000,000 more preferably between about 5,000 and 100,000. The di-block polymer preferably has a Mw of about 1,000 to 1,000,000, more preferably between about 5,000 and 100,000.
The density of the surface layers of the nano-particles may be controlled by manipulating the ratio of multiblock to diblock to mono-block polymer chains. This ratio may be manipulated by altering the amount of initiator added during each step of the polymerization process. For example, a greater amount of initiator added during the first polymerization step than added during subsequent polymerization steps would favor multiblock formation over mono-block formation, resulting in a high density surface layer. Conversely, a greater amount of initiator added during the subsequent polymerization steps than added during the first polymerization step would favor mono-block or diblock formation over multi-block formation, resulting in a low-density surface layer. The ratio of the initiator added during the subsequent polymerization steps to that added during the first polymerization step can range from about 0 to 10.Hydrogenation of a Nano-Particle Surface Layer
After micelle formation, or alternatively, after crosslinking, polydiene blocks, for example, may be hydrogenated to form a desired surface layer. Furthermore, one or more poly (conjugated diene) blocks can be selectively hydrogenated while leaving additional poly (conjugated diene) blocks non-hydrogenated. A hydrogenation step may be carried out by methods known in the art for hydrogenating polymers, particularly polydienes. A preferred hydrogenation method includes placing the crosslinked nano-particles in a hydrogenation reactor in the presence of a catalyst. After the catalyst has been added to the reactor, hydrogen gas (H2) is charged to the reactor to begin the hydrogenation reaction. The pressure is adjusted to a desired range via addition of H2, preferably between about 10 and 3000 kPa, more preferably between about 50 and 2600 kPa. H2 may be charged continuously or in individual charges until the desired conversion is achieved. Preferably, the hydrogenation reaction will reach at least about 20% conversion, more preferably greater than about 85% conversion. The conversion reaction may be monitored by H1 NMR.
Preferred catalysts include known hydrogenation catalysts such as Pt, Pd, Rh, Ru, Ni, and mixtures thereof. The catalysts may be finely dispersed solids or absorbed on inert supports such as carbon, silica, or alumina. Especially preferred catalysts are prepared from nickel octolate, nickel ethylhexanoate, and mixtures thereof.
The layers formed by an optional hydrogenation step will vary depending on the identity of the monomer units utilized in the formation of poly (conjugated diene) blocks. For example, if a poly(conjugated diene) block contains 1,3-butadiene monomer units, the resultant nano-particle layer after hydrogenation will be a crystalline poly(ethylene) layer. In another embodiment, a layer may include both ethylene and propylene units after hydrogenation if the non-hydrogenated poly (conjugated diene) block contains isoprene monomer units. It should be noted that the non-hydrogenated poly (conjugated diene) block may contain a mixture of conjugated diene monomer units, resulting in a mixture of monomer units after hydrogenation.
Initiators and Functionalized Nano-Particles
The present inventive process is preferably initiated via addition of anionic initiators that are known in the art as useful in the copolymerization of diene monomers and vinyl aromatic hydrocarbons. Exemplary organo-lithium catalysts include lithium compounds having the formula R(Li)x, wherein R represents a C1-C20 hydrocarbyl radical, preferably a C2-C8 hydrocarbyl radical and x is an integer from 1 to 4. Typical R groups include aliphatic radicals and cycloaliphatic radicals. Specific examples of R groups include primary, secondary, and tertiary groups, such as n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.
Specific examples of exemplary initiators include ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and the like; aryllithiums, such as phenyllithium, tolyllithium, and the like; alkenyllithiums such as vinyllithium, propenyllithium, and the like; alkylene lithium such as tetramethylene lithium, pentamethylene lithium, and the like. Among these, n-butyllithium, sec-butyllithium, tert-butyllithium, tetramethylene lithium, and mixtures thereof are preferred. Other suitable lithium inititators include one or more of: p-tolyllithium, 4-phenylbutyl lithium, 4-butylcyclohexyl lithium, 4-cyclohexylbutyl lithium, lithium dialkyl amines, lithium dialkyl phosphines, lithium alkyl aryl phosphine, and lithium diaryl phosphines.
Functionalized lithium initiators are also contemplated as useful in the present copolymerization. Preferred functional groups include amines, formyl, carboxylic acids, alcohols, tin, silica, and mixtures thereof.
Especially preferred initiators are amine-functionalized initiators, such as those that are the reaction product of an amine, an organo lithium and a solubilizing component. The initiator has the general formula:
where y is from about 1 to about 3; SOL is a solubilizing component selected from the group consisting of hydrocarbons, ethers, amines or mixtures thereof; and, A is selected from the group consisting of alkyl, dialkyl and cycloalkyl amine radicals having the general formula:
and cyclic amines having the general formula:
where R1 is selected from the group consisting of alkyls, cycloalkyls or aralkyls having from 1 to about 12 carbon atoms, and R2 is selected from the group consisting of an alkylene, substituted alkylene, oxy- or N-alkylamino-alkylene group having from about 3 to about 16 methylene groups. An especially preferred functionalized lithium initiator is hexamethylene imine propyllithium.
Tin functionalized lithium initiators may also be preferred as useful in the present invention. Suitable tin functionalized lithium initiators include tributyl tin lithium, trioctyl tin lithium, and mixtures thereof.
Anionic initiators generally are useful in amounts ranging from about 0.01 to 60 millimoles per hundred grams of monomer charge.
A nano-particle including multiblock polymers initiated with a functionalized initiator may include functional groups on the surface of the nano-particle. For example, when block polymers are initiated by hexamethylene imine propyllithium, the initiator residue remaining at the beginning of the polymer chain will contain an amine group. Once the polymer chains have aggregated and have been crosslinked, the resultant nano-particles will contain amine groups on or near the nano-particle surface.
An exemplary nano-particle formed from copolymers initiated by a functionalized tin lithium initiator may have a crosslinked alkenylbenzene core, for example polystyrene, and a surface layer including at least a poly(conjugated diene), for example 1,3-butadiene. The surface layer will also include a functionalized initiator residue at the individual chain ends (i.e., tin).Polymer Nano-Particle Applications
A variety of applications are contemplated for use in conjunction with the nano-particles of the present invention. Furthermore, the several mechanisms described herein for modifying the nano-particles render them more suitable for different applications. All forms of the present inventive nano-particles are, of course, contemplated for use in each of the exemplary applications and all other applications envisioned by the skilled artisan.General Rubber
After the polymer nano-particles have been formed, they may be blended with a rubber to improve the physical characteristics of the rubber composition. Nano-particles are useful modifying agents for rubbers because they are discrete particles which are capable of dispersing uniformly throughout the rubber composition, resulting in uniformity of physical characteristics. Furthermore, certain of the present polymer nano-particles are advantageous because various layers including poly(conjugated diene), especially vinyl-modified poly(conjugated diene), are capable of bonding with a rubber matrix due to the accessibility of the double bonds in the poly(conjugated diene).
The present polymer nano-particles are suitable for modifying a variety of rubbers including, but not limited to, random styrene/butadiene copolymers, butadiene rubber, poly(isoprene), nitrile rubber, polyurethane, butyl rubber, EPDM, and the like. Advantageously, the inclusion of the present nano-particles have demonstrated rubbers having improved tensile and tear strength of at least about 30% over a rubber modified with non-spherical copolymers.
Furthermore, nano-particles with hydrogenated layers may demonstrate improved compatibility with specific rubbers. For example, nano-particles including a hydrogenated polyisoprene layer may demonstrate superior bonding with and improved dispersion in an EPDM rubber matrix due to the compatibility of hydrogenated isoprene with EPDM rubber.
Additionally, nano-particles with copolymer layers may demonstrate improved compatibility with rubbers. The copolymer tails within a layer of the nano-particles may form a brush-like surface. The host composition is then able to diffuse between the tails allowing improved interaction between the host and the nano-particles.Hard Disk Technology
Hydrogenated nano-particles prepared in accordance with the present invention may also find application in hard disk technology.
Disk drive assemblies for computers traditionally include a magnetic storage disk coaxially mounted about a spindle apparatus that rotates at speeds in excess of several thousand revolutions per minute (RPM). The disk drive assemblies also include a magnetic head that writes and reads information to and from the magnetic storage disk while the magnetic disk is rotating. The magnetic head is usually disposed at the end of an actuator arm and is positioned in a space above the magnetic disk. The actuator arm can move relative to the magnetic disk. The disk drive assembly is mounted on a disk base (support) plate and sealed with a cover plate to form a housing that protects the disk drive assembly from the environmental contaminant outside of the housing.
Serious damage to the magnetic disks, including loss of valuable information, can result by introducing gaseous and particulate contaminates into the disk drive assembly housing. To substantially prevent or reduce the introduction of gaseous and particulate contaminants into the disk drive housing, a flexible sealing gasket is disposed between the disk drive mounting base (support) plate and the disk drive assembly housing or cover plate. A sealing gasket is usually prepared by punching out a ring-shaped gasket from a sheet of cured elastomer. The elastomeric gasket obtained is usually attached to the base plate of the disk drive assembly mechanically, such as affixing the gasket with screws, or adhesives. The hydrogenated nano-particles, when compounded with a polyalkylene and a rubber, demonstrate a tensile strength comparable to that necessary in hard disk drive compositions.Thermoplastic Gels
Nano-particles prepared in accord with the present invention, whether hydrogenated or non-hydrogenated may also be blended with a variety of thermoplastic elastomers, such as SEPS, SEBS, EEBS, EEPE, polypropylene, polyethylene, polystyrene, and mixtures thereof. For example, nano-particles with hydrogenated isoprene layers may be blended with a SEPS thermoplastic to improve tensile strength and thermostability. These blends of thermoplastic elastomer and nano-particles would typically be extended as known in the art. For example, suitable extenders include extender oils and low molecular weight compounds or components. Suitable extender oils include those well known in the art such as naphthenic, aromatic and paraffinic petroleum oils and silicone oils.
Examples of low molecular weight organic compounds or components useful as extenders in compositions of the present invention are low molecular weight organic materials having a number-average molecular weight of less than 20,000, preferably less than 10,000, and most preferably less than 5000. Although there is no limitation to the material which may be employed, the following is a list of examples of appropriate materials:
Softening agents, namely aromatic naphthenic and □araffinic softening agents for rubbers or resins;
Plasticizers, namely plasticizers composed of esters including phthalic, mixed pthalic, aliphatic dibasic acid, glycol, fatty acid, phosphoric and stearic esters, epoxy plasticizers, other plasticizers for plastics, and phthalate, adipate, scbacate, phosphate, polyether and polyester plasticizers for NBR;
Tackifiers, namely coumarone resins, coumaroneindene resins, terpene phenol resins, petroleum hydrocarbons and rosin derivative;
Oligomers, namely crown ether, fluorine-containing oligomers, polybutenes, xylene resins, chlorinated rubber, polyethylene wax, petroleum resins, rosin ester rubber, polyalkylene glycol diacrylate, liquid rubber (polybutadiene, styrene/butadiene rubber, butadiene-acrylonitrile rubber, polychloroprene, etc.), silicone oligomers, and poly-a-olefins;
Lubricants, namely hydrocarbon lubricants such as paraffin and wax, fatty acid lubricants such as higher fatty acid and □ydroxyl-fatty acid, fatty acid amide lubricants such as fatty acid amide and alkylene-bisfatty acid amide, ester lubricants such as fatty acid-lower alcohol ester, fatty acid-polyhydrie alcohol ester and fatty acid-polyglycol ester, alcoholic lubricants such as fatty alcohol, polyhydric alcohol, polyglycol and polyglycerol, metallic soaps, and mixed lubricants; and,
Petroleum hydrocarbons, namely synthetic terpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic or alicyclic petroleum resins, polymers of unsaturated hydrocarbons, and hydrogenated hydrocarbon resins.
Other appropriate low-molecular weight organic materials include latexes, emulsions, liquid crystals, bituminous compositions, and phosphazenes. One or more of these materials may be used in as extenders.
Surface functionalized nano-particles prepared in accordance with the present invention, whether hydrogenated or non-hydrogenated, may also be compounded with silica containing rubber compositions. Including surface functionalized nano-particles in silica containing rubber compositions has been shown to decrease the shrinkage rates of such silica containing rubber compositions. Functionalized nano-particles may be compounded in silica compositions in concentrations up to about 50 wt % of the total composition, more preferably up to about 40 wt % most preferably up to about 30 wt %.Tire Rubber
One application for such rubber compounds is in tire rubber formulations.
Vulcanizable elastomeric compositions of the invention are prepared by mixing a rubber, a nanoparticle composition, with a reinforcing filler comprising silica, or a carbon black, or a mixture of the two, a processing aid and/or a coupling agent, a cure agent and an effective amount of sulfur to achieve a satisfactory cure of the composition.
The preferred rubbers are conjugated diene polymers, copolymers or terpolymers of conjugated diene monomers and monovinyl aromatic monomers. These can be utilized as 100 parts of the rubber in the tread stock compound, or they can be blended with any conventionally employed treadstock rubber which includes natural rubber, synthetic rubber and blends thereof. Such rubbers are well known to those skilled in the art and include synthetic polyisoprene rubber, styrene-butadiene rubber (SBR), styrene-isoprene rubber, styrene-isoprene-butadiene rubber, butadiene-isoprene rubber, polybutadiene, butyl rubber, neoprene, acrylonitrile-butadiene rubber (NBR), silicone rubber, the fluoroelastomers, ethylene acrylic rubber, ethylene-propylene rubber, ethylene-propylene terpolymer (EPDM), ethylene vinyl acetate copolymer, epicholrohydrin rubber, chlorinated polyethylene-propylene rubbers, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, terafluoroethylene-propylene rubber, and the like.
Examples of reinforcing silica fillers which can be used in the vulcanizable elastomeric composition include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and the like. Other suitable fillers include aluminum silicate, magnesium silicate, and the like. Among these, precipitated amorphous wet-process, hydrated silicas are preferred. Silica can be employed in the amount of about one to about 100 parts per hundred parts of the elastomer (phr), preferably in an amount of about 5 to 80 phr and, more preferably, in an amount of about 30 to about 80 phrs. The useful upper range is limited by the high viscosity imparted by fillers of this type. Some of the commercially available silica which can be used include, but are not limited to, HiSil® 190, HiSil® 210, HiSil® 215, HiSil® 233, HiSil® 243, and the like, produced by PPG Industries (Pittsburgh, Pa.). A number of useful commercial grades of different silicas are also available from DeGussa Corporation (e.g., VN2, VN3), Rhone Poulenc (e.g., Zeosil® 1165MP0, and J. M. Huber Corporation.
Including surface functionalized nano-particles in silica containing rubber compositions has been shown to decrease the shrinkage rates of such silica containing rubber compositions. Functionalized nano-particles may be compounded in silica compositions in concentrations up to about 30 wt % of the total composition, more preferably up to about 40 wt %, most preferably up to about 50 wt %.
The rubber can be compounded with all forms of carbon black, optionally additionally with silica. The carbon black can be present in amounts ranging from about one to about 100 phr. The carbon black can include any of the commonly available, commercially-produced carbon blacks, but those having a surface are of at least 20 m2/g and, or preferably, at least 35 m2/g up to 200 m2/g or higher are preferred. Among useful carbon blacks are furnace black, channel blacks, and lamp blacks. A mixture of two or more of the above blacks can be used in preparing the carbon black products of the invention. Typical suitable carbon black are N-110, N-220, N-339, N-330, N-352, N-550, N-660, as designated by ASTM D-1765-82a.
Certain additional fillers can be utilized including mineral fillers, such as clay, talc, aluminum hydrate, aluminum hydroxide and mica. The foregoing additional fillers are optional and can be utilized in the amount of about 0.5 phr to about 100.
Numerous coupling agent and compatibilizing agent are know for use in combining silica and rubber. Among the silica-based coupling and compatibilizing agents include silane coupling agents containing polysulfide components, or structures such as, for example, trialkoxyorganosilane polysulfides, containing from about 2 to about 8 sulfur atoms in a polysulfide bridge such as, for example, bis-(3-triethoxysilylpropyl)tetrasulfide(Si69), bis-(3-triethoxysilylpropyl)disulfide(Si75), and those alkyl alkoxysilanes of the such as octyltriethoxy silane, and hexyltrimethoxy silane.
It is readily understood by those having skill in the art that the rubber composition would be compounded by methods generally known in the rubber compounding art, such as mixing the various vulcanizable polymer(s) with various commonly used additive materials such as, for example, curing agents, activators, retarders and accelerators processing additives, such as oils, resins, including tackifying resins, plasticizers, pigments, additional filers, fatty acid, zinc oxide, waxes, antioxidants, anti-ozonants, and peptizing agents. As known to those skilled in the art, depending on the intended use of the sulfur vulcanizable and sulfur vulcanized material (rubbers), the additives mentioned above are selected and commonly used in the conventional amounts.
Specifically, the above-described nano-particle containing rubber compounds are contemplated for use in rubber compounds used to make tire treads and side walls due to the enhanced reinforcement capabilities of the present nano-particles. The higher dynamic modulus (G′) and its lower temperature dependence along with the lower hystersis values at high temperatures leads to improved cornering, handling, dry, snow, and wet traction, rolling resistance, dispersion, and aging properties of the resultant tire compositions. Tin-functionalized nano-particles are especially suited for use in tire compositions. Improved aging properties, thermal aging (high temperature), or mechanical aging (static or dynamic deformation cycles), include retention of the G′ modulus, hysteresis, mechanical strengths, etc. Tin-functionalized nano-particles are especially suited for use in tire compositions. Nano-particles including a copolymer layer are also suitable for use in such tire compositions, because the longer copolymer chains in the layer lead to greater diffusion of the host rubber composition into the surface layer of the nano-particle. Of course, a functionalized nano-particle having at least one copolymer layer, i.e., the combination of the two alternatives may be most beneficial.Engineering Plastic and Others
Similarly, the nano-particles can be added into typical plastic materials, including polyethylene, polypropylene, polystyrene, polycarbonate, nylon, polyimides, etc. to for example, enhance impact strength, tensile strength and damping properties.
Of course, the present inventive nano-particles are also suited to other presently existing applications for nano-particles, including the medical field, e.g. drug delivery and blood applications, information technology, e.g. quantum computers and dots, aeronautical and space research, energy, e.g., oil refining, and lubricants.Engine Mount, Etc.
Another application for such rubbers is in situations requiring superior damping properties, such as engine mounts and hoses (e.g. air conditioning hoses). Rubber compounds of high mechanical strength, super damping properties, and strong resistance to creep are demanded in engine mount manufacturers. In engine mounts, a rubber, because it sits most of its life in a packed and hot position, requires very good characteristics. Utilizing the nano-particles within selected rubber formulations can improve the characteristics of the rubber compounds.
The present invention now will be described with reference to non-limiting examples. The following examples and tables are presented for purposes of illustration only and are not to be construed in a limiting sense.EXAMPLES
Preparation of Multi-Layer Nano-Particles
An 8 L reactor equipped with external jacket heating and internal agitation was used for all polymerizations. 1,3-Butadiene was used as a 22.0 or 21.1 wt % solution in hexane (Bridgestone/Firestone Polymer Co., Akron, Ohio). Styrene was used as a 33.0 wt. % solution in hexane (Bridgestone/Firestone Polymer Co., Akron, Ohio), and
n-butyllithium was used as a 15 wt % solution in hexane (Bridgestone/Firestone Polymer Co., Akron, Ohio). An antioxidant butylated hydroxytoluene (BHT), (Aldrich Chem. Co., Milwaukee, Wis.) was used as an approximately 17 wt % solution in hexane. Technical grade divinylbenzene (DVB), (80% as a mixture of isomers, Aldrich) was passed through a column of inhibitor remover under N2 before use. Neat bis-oxalanyl propane (OOPs), (Aldrich) was similarly treated and used as a 1.6 M solution in hexane, stored over calcium hydride.Example 1
The reactor was first charged with 2.3 kg of hexane. The reactor was then charged with 517 g butadiene/hexane blend that contained 22 wt % butadiene, and the batch was heated to 57° C. After the temperature stabilized, polymerization was initiated with 5.4 mL of a 1.5 M solution of n-butyl lithium in hexane. The reactor batch temperature was maintained at 57° C. for the duration of the polymerization. After 2 hours, (when the reaction was finished) the reactor was charged with 4.5 kg of isoprene/hexane blend that contained 15% isoprene. After 1.5 hours, the reactor was charged with 453 g of a styrene/hexane blend that contained 33 wt % styrene. After an additional 1.5 hours, the reactor was charged with 50 mL of divinyl benzene. The reactor was maintained at 57° C. for a 2-hour period and then discharged. The product was dropped into an acetone/isopropanol (˜95/5) blend, and dried. GPC analysis of the product showed that the molecular weight (Mw) of the particle polymer is 954,390. The polydispersity of the product is 1.10. TEM analysis showed that the average particle size was ˜30 nm, and the dispersity of the particle size was about 1.1 (see
A 4 L polymerization reactor was used for the preparation. The reactor was first charged with 3 L of a nano-particle/hexane solution, containing 10 wt % of example 1. The reactor was then charged with 75 mL of a Ni catalyst solution, which was made according to the following procedure.
111 m/L of nickel octolate (8 wt % in hexane), 37 mL hexane, and 06 mL of cyclohexene were charged to a 1 liter N2 purged bottle. Then, the bottle was placed into a dry ice bath. A charge of 266.4 mL of tributyl aluminum (0.68 M in hexane) was slowly added into the bottle while kept cool.
The hydrogenation reactor, containing polymer product and catalyst was then heated to 120° C. After the temperature stabilized, the hydrogenation was initialized by charging high pressure H2 gas into the reactor to about 792 kPa. After about 15 minutes, the pressure dropped as the H2 began to react. The reactor was again recharged to about 792 kPa. The procedure was then repeated until the butadiene hydrogenation conversion reached about 95%, based on H1 NMR analysis. The reactor was then cooled and the product dropped into isopropanol solvent. The obtained polymer particles were dried in vacuum for 2 days at 23° C.
The procedure was repeated until the isoprene hydrogenation conversion reached 100% based on H1 NMR analysis. TEM analysis showed that the average particle size was ˜35 nm, and the dispersity was about 1.1 (see
The reactor was first charged with 517 g of hexane. The reactor was charged with 340 g styrene/hexane blend containing 33 wt % styrene, and the batch was heated to 57° C. After the temperature had stabilized, polymerization was initiated with 5.4 mL of a 1.5 M solution of n-butyllithium in hexane. The reactor batch temperature was maintained at 57° C. for the duration of the polymerization. After 1.5 hours, (when the reaction was finished), the reactor was charged with 1.0 kg of butadiene/hexane blend that contained 22 wt % butadiene. After another 1.5 hours, the reactor was charged with 340 g of styrene/hexane blend that contained 33 wt % styrene. After an additional 1.5 hour reaction, the reactor was charged with 1.8 kg hexane. After 20 minutes, the reactor was charged with 50 mL of DVB for the crosslinking reaction. The reactor was maintained at 57° C. for another 1.5 hour period, then discharged. The product was dropped into acetone/isopropanol (˜95/5) blend, and dried. GPC analysis of the product showed that the molecular weight (Mw) of the particle polymer was 3,271,180. The polydispersity was 1.08. TEM analysis showed that the average particle size was ˜35 nm, and the dispersity of the particle size was about 1.1 (see
Three kinds of rubber compositions were prepared according to the formulation shown in Tables 1 and 2 by selectively using the synthesized onion like polymer particles (i.e., example 1) to replace 10 parts of butadiene rubber in the compound formulation. In each sample, a blend of the ingredients was kneaded by a method listed in Table 3. The final stock was sheeted and molded at 160° C. for about 30 minutes.
As shown in Table 4, the test compounds exhibited well balanced physical properties. At least, the tensile strength, dynamic modulus and damping properties were improved over that of the comparative compounds.
The invention has been described with reference to the exemplary embodiments. Modifications and alterations will occur to others upon reading and understanding the specification. The invention is intended to include such modifications and alterations insofar as they come within the scope of the disclosure and claims.
1. A polymeric nanoparticle comprising at least two multiblock polymers, the polymers comprising: wherein the first blocks of the at least two multiblock polymers are crosslinked by a crosslinking agent and wherein the nanoparticle has a mean average diameter of less than about 100 nm.
- a first block consisting essentially of poly(alkenylbenzene); and,
- a second block and a third block independently comprising at least one first monomer chosen from conjugated dienes, alkenylbenzenes, alkylenes, ethylene oxide, methyl methacrylate, nitriles, and acrylates;
2. The nanoparticle of claim 1, wherein the first block consists essentially of polystyrene.
3. The nanoparticle of claim 1, wherein at least one of the second block and the third block comprises at least one second monomer different from the at least one first monomer.
4. The nanoparticle of claim 3, wherein the block comprising at least one second monomer different from the at least one first monomer is randomized.
5. The nanoparticle of claim 4, wherein the block comprises conjugated diene and alkenylbenzene monomers.
6. The nanoparticle of claim 5, wherein the conjugated diene monomer is 1,3-butadiene and the alkenylbenzene monomer is styrene.
7. The nanoparticle of claim 1, wherein the crosslinking agent is divinylbenzene.
8. The nanoparticle of claim 1, wherein the nanoparticle has a mean average diameter of less than about 75 nm.
9. The nanoparticle of claim 8, wherein the nanoparticle has a mean average diameter of less than about 50 nm.
10. The nanoparticle of claim 1, wherein the nanoparticle has a Mw of about 5,000 to about 4,500,000.
11. The nanoparticle of claim 1, wherein at least one of the second block and the third block comprises conjugated diene monomers.
12. The nanoparticle of claim 11, wherein the conjugated diene monomers are hydrogenated.
13. The nanoparticle of claim 1, wherein the third block is functionalized.
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Type: Grant
Filed: Jun 29, 2005
Date of Patent: Jul 3, 2007
Patent Publication Number: 20070027264
Assignee: Bridgestone Americas Holding, Inc. (Akron, OH)
Inventors: Xiaorong Wang (Hudson, OH), Victor J. Foltz (Akron, OH)
Primary Examiner: Bernard Lipman
Attorney: Finnegan, Henderson, Farabow, Garrett, and Dunner, L.L.P.
Application Number: 11/168,297
International Classification: C08F 279/00 (20060101);


text:
Let $(X, x_0)$ be a pointed space. Then we can define the homotopy groups $\pi_i(X, x_0)$ for $i \geq 1$. They are abelian groups for $i \geq 2$. It is well-known that the fundamental group $\pi_1(X, x_0)$ acts on each of the higher groups $\pi_i(X, x_0)$, and that this action generalizes to the Whitehead Products which are maps
$$ \pi_p(X, x_0) \times \pi_q(X, x_0) \to \pi_{p+q -1}(X, x_0).$$
The details are given in the wikipedia article I linked to above. Together the Whitehead products turn the graded group $\pi_*(X, x_0)$ (for $* > 0$) into a graded (quasi-) Lie algebra over $\mathbb{Z}$, where the grading is shifted so that $\pi_i(X, x_0)$ is in degree $(i-1)$. Well, it is a little funny since the bottom group is not necessarily abelian.
This is all well and good, but what if we don't want to pick base points? Is there a similar algebraic gadget in that situation?
If we don't pick base points, then it seems natural to consider the fundamental groupoid $\Pi_1(X)$. Then the different homotopy groups of $X$ at different base points can be assembled into local systems on $X$. That is for each $i \geq 2$ we have a functor,
$$\pi_i: \Pi_1 X \to AB$$
where $AB$ is the category of abelian groups. This already incorporates the action of $\pi_1$ on the higher homotopy groups but does it in a way which doesn't depend on the choice of base point.
Question: Can we enhance these local systems with a structure which generalizes the Whitehead product, and if so what precisely is this extra structure?

subset: commoncrawl


text:
Past Continuous
We use the past continuous to talk about past events which went on for a period of time.
We use it when we want to emphasize the continuing process of an activity or the period of that activity. (If we just want to talk about the past event as a simple fact, we use the past simple.)
We often use it to describe a "background action" when something else happened.


text:
Event box
Research 101 Certificate Class
The Kurt R. Schmeller Library is pleased to offer Research 101 Certificate Classes throughout the Fall 2018 semester.
All classes are held in either Library Classroom L302 or L311.
We cannot accommodate latecomers – please be on time.
You will learn how to:
* Distinguish between scholarly and non-scholarly resources
* Narrow and refine a topic
* Utilize OneSearch and subject-specific databases to find relevant books and articles
* Locate authoritative, credible information on the web
* Understand the basics of citation
Library faculty will present a certificate of completion at the end of the class.
Related LibGuide: Research 101 by Neera Mohess
- Date:
- Friday, November 30, 2018 Show more dates
- Time:
- 10:00am - 11:00am
- Location:
- Library Classroom - L302
- Campus:
- Queensborough Community College
- Categories:
- research workshop
Registration has closed.
Event Organizer
Christine Kim


text:
Donkeys Come Wi-Fi Equipped at Tourist Attraction in Israel
A tourist attraction in lower Galilee that seeks to recreate daily life as it was in ancient Israel recently got a technological upgrade when it began putting Wi-Fi hotspots around the necks of donkeys so tourists can have access to the Internet.
"We're the only place in the world that will give the opportunity to surf the Internet when riding a donkey," Menachem Goldberg of Kfar Kedem told The Christian Post from Israel on Thursday.
The Kfar Kedem park is located in the hills of Galilee in view of the city of Nazareth, and offers tourists the opportunity to wear the same clothes, make the same foods and ride the same animals as did those who lived in ancient times.
According to the attraction's website, "Kfar Kedem creates a holistic experience using all your senses ... connecting these tangible experiences with the values and spirit of the ages from the time of the Bible and the Mishnah, that are still part of our lives today."
Now, because the experience also includes an Internet connection, tourists can also share the experience with their friends and family at home.
If someone "wants to change his profile on Facebook, for example, in the middle of the riding, now we give the opportunity to do it," explained Goldberg.
Kfar Kedem currently has about 30 donkeys, although only a few are equipped with wireless routers. Goldberg says one wireless router is enough to serve between five and seven people with Internet access.
At its busiest, the park can host about 1,000 tourists per day. In addition to donkey rides, visitors can also learn ancient techniques for spinning wool, milking goats, making bread, pressing olives and making wine.
"I would ask more people to come and have the experience, because we believe that if you are doing something in your hands, you wouldn't forget it in your life," said Goldberg.
After serving in the Israel Defense Forces, Goldberg studied to become a licensed tour guide and traveled around the world, the website for Kfar Kedem explains. He later returned to Israel, got married, and settled with his family in Hoshaya, a community of Orthodox Jewish families, where the park is located today.


text:
This weeks The Genealogy Roadshow , at 7.30 on RTÉ ONE will feature a man from Mallow with one very dramatic story;
Granny kept her identity a Secret
Michael Kenning from Mallow knows his family are all from Belfast. Many of the men were in the Orange Order. When his grandmother died, they found information that suggested she was a Catholic from Cork, rather than the protestant from Liverpool they thought she was. We search for the truth. The original Irish programmeis returning to screens on May 11th with a brand new series full of amazing stories. Once again the people of Ireland are the stars of the show. The series will be presented again by Derek Mooney. The Roadshow's crack historical and genealogical team help people trace their family's roots and discover surprising stories from the past. People from all four provinces got to know the truth about tragic events, infamous ancestors and famous cousins. Thousands of people contacted the show with questions. Some wanted to know if they were related to someone famous. Others wanted to solve mysteries going back generations. Others had heart-breaking adoption stories and tales of families ravaged by war. Our team set out to help these people fill in the blanks. The mission is to answer the questions, solve the riddles and uncover the truth. Some people get the news they want but not every tale has a happy ending. In this series, there are tears of pride and joy, as well as fantastic surprises. The Genealogy Roadshow also sheds light on the people history has forgotten. We look at local and national events and ask who didn't get the credit they deserve? We also take a look at people and events you think you know, but tell the stories you haven't heard before. This year the show has added technology to the bag of tricks. Historians and witnesses from around the world are able to beam in directly to the roadshow to give expert testimony and corroborate evidence. RTE's The Genealogy Roadshow is now an international hit series. PBS in America has already broadcast a US version of the show shot in Detroit, San Francisco, Nashville and Austin, Texas. Season 2 of the US show is on the way. Some of the stories involve Irish people in far flung places:
- Irish immigrants starting a new life in Argentina were part of an international crisis as thousands were scammed out of their life savings and left stranded in a strange land;
- An innocent Irish girl was gunned down in a Canadian frontier town, caught up in a local blood feud;
- A Wexford man was spared a terrible fate at Custer's Last Stand, only to be forgotten by history, until now;
- A Longford woman went to America and became a notorious criminal in the era of Al Capone.
Some of the stories are closer to home:
- After years of listening to his father's stories, a Dundalk man finds out once and for all if he is related to St. Oliver Plunkett;
- A Cork man discovers that his relatives were saved from the gallows by none other than Daniel O'Connell in a famous trial;
- We hear the tale of an Orangeman's wife who kept her Catholic identity a secret, even from her family, for her whole life;
And there's even some myth-busting in this series as we delve into the mystery of 'The Lost Village of Audleystown' to see if there's any evidence to back up the story of a village full of families who were forcibly migrated to the USA by a wicked land owner who levelled their homes. This original Irish programme is back on your screens from Sunday 11th May at 7pm on RTE One.
Follow us on Facebook; https://www.facebook.com/thegenealogyroadshow
Follow us on Twitter: https://twitter.com/_BigMountain
Or visit our Website: http://bigmountainproductions.com/the-genealogy-roadshow/


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Subscribe to our Newsroom RSS feed | What is RSS?
Follow Loyola University New Orleans on Twitter
School of Nursing director named to executive leadership program
Loyola press release - August 6, 2012
Ann Cary, Ph.D., M.P.H., R.N., director of the School of Nursing at Loyola University New Orleans, has been chosen by the American Association of Colleges of Nursing to participate in the new AACN-Wharton Executive Leadership Program. Scheduled for August 14-17, 2012 at the Wharton School of the University of Pennsylvania in Philadelphia, this world-class enrichment program is designed exclusively for top academic leaders in nursing. Cary is one of 37 nurse educators from 25 states participating this year in the leadership program.
"Though many executive leadership programs are available at top schools like Wharton, none focus exclusively on the needs of nursing deans. AACN is hopeful that this innovative program will help to amplify nursing's voice in national conversations about healthcare reform and enhancing patient care," said AACN President Jane Kirschling. "Fortified with a new layer of leadership expertise, those completing the program will be well-prepared to make a lasting impact on how nurses are educated and how they practice."
The American Association of Colleges of Nursing is the national voice for university and four-year college education programs in nursing and represents more than 700 member schools of nursing at public and private institutions nationwide. The Wharton School of the University of Pennsylvania, founded in 1881 as the first collegiate business school, is recognized globally for intellectual leadership and ongoing innovation across every major discipline of business education. Informed by in-depth academic research and extensive industry experience, Wharton Executive Education programs offer a supportive and challenging context from which participants gain the skills necessary for their next level of executive development.
About Loyola University New Orleans School of Nursing:
The Loyola University New Orleans School of Nursing offers online degrees for RN- B.S.N, R.N.-to-M.S.N., MSN in HCSM, and the Post B.S.-D.N.P. and Post Masters to D.N.P. Loyola's nursing program is based on Jesuit values and educates professional nurses to lead change and translate science into practice in a dynamic global health care environment. Loyola's School of Nursing is consistently ranked by both U.S. News and World Report and thebestcolleges.org as one of the premier nursing schools in the country. The online graduate nursing programs at Loyola—the Master of Science in Nursing and the Doctor of Nursing Practice—are ranked in the top five graduate nursing online programs in the U.S. by the U.S. News & World Report 2012 rankings. For more information about the nursing online programs, including application requirements, visit the Loyola School of Nursing website.


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Bring the Family / Friends
What to do with your friends, significant other, partner, spouse, kids or in-laws while attending conference?
Bring them!
Exhibits and Speaker Series Passes
You can purchase one of three types of passes for your people: Exhibits Only at $25.00, Exhibits Plus at $35.00, or Exhibits Supreme at $50.00.
Exhibits Only provides badge access to The Stacks, the world's largest trade show for the library community, with hundreds of publishers and suppliers with booth events every day of the conference. Be sure to visit the Live at Your Library stage for daily readings and author events.
Exhibits Plus provides full access to The Stacks, plus badge access to the Opening General Session (Saturday, June 23, 2007, 5:30 - 7:00 pm) and the Closing Session, featuring a special presentation by Garrison Keillor (Tuesday, June 26, 2007, 8:00 – 9:00 am).
Exhibits Supreme gives your guests all that, PLUS badge access to 9 featured speakers in the Auditorium Speakers Series. Confirmed Presenters Include:
- Khaled Hosseini
- Ken Burns
- David Baldacci
- Nancy Pearl
- Anthony Romero
- Marian Wright Edelman (presented by ALSC)
- Irshad Manji
- Julie Andrews (presented by American Libraries)
- Elizabeth Edwards (presented by PLA)
Visit http://www.ala.org/annual to purchase any of these Passes. You can also purchase the passes on-site. All passes are 4 day passes, but can be used on any single day or combination of days.
CAMP ALA welcomes children ages 6 months – 17 years. The cost for the camp is $80 per child per day. Optional field trips for children ages 6 and older are available, including: Smithsonian National Zoo, Smithsonian Air & Space Museum with IMAX, & National Aquarium and Picnic at the Monuments. Child Care services are provided by ACCENT, a nationally recognized professional childcare company organized to provide quality on-site children's activities in a nurturing, safe, educational environment. To ensure that your child has a place at Camp ALA, please pre-register by June 8, 2007 at http://www.accentoca.com/campala07 .


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Foodies Trip of Delhi, Agra & Jaipur
Foodies Trip of Delhi, Agra & Jaipur
Places covered: New Delhi, Agra & Jaipur.
Activities: Food tours, cooking classes, photo walks, camel rides, playtime with elephants, kitchen tours, introduction to spices, city walks.
Mode of transport: By road
Accommodation: A mix of best luxury and heritage hotels.
Transport: In comfortable air-conditioned vehicles.
Sightseeing: Major landmarks of all cities in addition to some hidden gems on the way
Duration: 6 days, 7 nights. ( Option to add more days)
UPDATE ITINERARY Link 1 and Link 2
Travel Itinerary
DAY 1, Delhi: Delhi Delights
First day in Delhi will be the time to begin the food tour of Delhi from Old Delhi. This tour which is the top ranked culinary tour service in Delhi will serve as a great introduction to Indian food and culture and will help set the tone for rest of your trip to India. There will be approximately 16-18 different Indian food dishes from different Indian cuisines and you'll visit up to 10 different food joints in Old Delhi, Central and South Delhi. All of the food joints that you'll visit have been in business for generations and are famous for their quality of food. The oldest place in the list is in business for 110 years and youngest for 40. You'll sample delicacies like samosa, lassi, butter chicken, kulfi (Indian ice creams), melt in mouth kebabs and much more. The Old Delhi part of the tour will take you through the old, narrow streets of medieval Delhi marked by old mansions, centuries old market and thousands of people milling about in their daily routine. Each lane in this area is a market for different commodity like invitation cards, spices, bicycles, cameras, utensils, vegetables, clothes , shoes, books and much more. The [...]


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Sunday, 4 January 2015
First Card Of the New Year!
First things first....HAPPY NEW YEAR!
I do hope that you have all had a good Christmas, having visited many of you over the last couple of days, it seems you have, been trying to catch up with comments and get back to some sort of normality.
Our Christmas was, well lets say, different. Remember my grandchildren having Chicken-pox? well one of them still did, so Christmas at our house was cancelled.
Christmas Day is always just me and DH anyway, but on Boxing Day we have our son's and the grandchildren, that's when they have their gifts from us and each other.
Unfortunately we had to cancel, our little grandson was covered from head to toe in spots, poor little might.
He had spots just about everywhere, he was not too bad in himself, a bit grumpy, and who can blame him, and not sleeping too well, (unfortunately for his Mum & Dad) he certainly had it worse than his sister had.
Also my son was poorly too, some sort of virus had got him and he was really not up to Christmas festivities, they have to travel to get to us so it wasn't wise.
So, we had our 'Boxing Day' on Tuesday, a little late but still enjoyable, the children were back on form, more or less, and they loved the new toys we had got them, we had our buffet and did everything as we normally would, so not too bad really, we got there in the end.
Last Christmas they were all full of colds but they did still manage to come on Boxing Day, so I'm hoping, and keeping everything crossed, that next Christmas... will be a bit more successful!
So onto crafting.....
As usual, challenges and card recipe below, hope you like it and thanks for dropping by.
Craftycatz...Anything Goes
Crafty Hazelnuts Patterned Paper... Use Patterned Papers
ABC Challenge....A Is For Anything Goes
Crafts Galore Encore....Anything Goes
Imagination Crafts...Anything Goes
Sisters Of Craft...Anything Goes
Your Scrapbook Place...Anything Goes
613 Avenue Create...Anything Goes/Matching Envelope
Polkadoodles...Tic Tac Toe. (Sentiment, Ribbon, Polka Dots)
Crafty Calender...What's New (ribbon)
Card Recipe....
Pre-coloured Image...By Digital
Papers...Black Cat
Card Stock, Ribbon, Brads....From Stash
53 comments:
- Tracy W said...
Stunning card. Thanks for joining in with the Sisters of Craft Blog Challenge. Creative Blessings, Tracy SOC DT
- 4 January 2015 at 17:18
- chrissy xx said...
Oh My! Glad things turned out alright in the end Jacee..Such a shame that your Christmas was late.
A FABulous card..LOving your image, colours and design.
Happy New Year xx
- 4 January 2015 at 19:15
- Just Me said...
Love your card. Just gorgeous. Thanks for joining us at SBP
- 4 January 2015 at 19:28
- Andree said...
A gorgeous card. The papers and image are wonderful and make me hanker for Springtime.
Thank you for joining in with the Crafts Galore Encore January Challenge, "Anything Goes" and good luck x
- 4 January 2015 at 19:42
- Holley (Tondre) Barnhart said...
oh WOW!! Your details, layering, inside and out gorgeous. Awesome work. Thanks so much for sharing with us at the Your Scrapbook Place Challenge blog. Cheers, Holley
- 4 January 2015 at 19:58
- Diane said...
Happy New Year Jacee !! Shame about all you christmas plans, but you got there in the end !!
Love your fresh bright birthday card !!
hugs Diane xx
- 4 January 2015 at 20:41
- Sheila H said...
I love the tea cup full of beautiful flowers. The matching envelope is so pretty, too! Thanks for playing along with our challenge at 613 Avenue Create.
- 4 January 2015 at 20:59
- Donna said...
Beautiful card Jacee, I love the cheerful colours and design and the polka dot papers are lush! So sorry to hear your family were unwell over Christmas, hope they're on the mend now! :) Donna ♥ x
- 4 January 2015 at 21:02
- Jan Ltc said...
I love this Jacee. Great layering xx Jan
- 4 January 2015 at 21:23
- Sandra H said...
Absolutely fabulous is your card!
- 4 January 2015 at 21:47
- Beth Brovold said...
Hi Jacee!!! Happy New Year to you...wishing you and yours all the best!! So glad that you finally got to celebrate with the family! Your card is like a glimpse of Spring and a breath of fresh air!!!! A gorgeous image and beautiful design...so nice to look at flowers!!!
Take care,
- 4 January 2015 at 21:49
- Carol S. said...
Gorgeous card Jacee. Shame about Christmas. There was a lot of illnesses around this Christmas. We were going to friends for Christmas day but 2 were un well so we had the day on our own but made up for it on Boxing day. We had a lovely family day and the grandchildren loved their presents. Hugs, Carol S.xx
- 4 January 2015 at 22:08
- Gram's Treasures said...
Beautiful card, Jacee. So glad everyone is on the mend!
Joyce xx
- 4 January 2015 at 22:12
- KT Fit Kitty said...
Gorgeous card! Love the image! Glad you had your family holiday get-together after all! Happy New Year!
- 4 January 2015 at 22:22
- Juls said...
Beautiful, love the bright colours :-) xx
- 4 January 2015 at 23:08
- jimlynn said...
You always know just the right patterned paper to mix with each other. A stunning card!
Glad you finally got to celebrate Christmas with the family even if it was a little late. Hope you have a wonderful 2015!
- 4 January 2015 at 23:09
- Elizabeth Hart said...
Your first card of the year is awesome = awesome colors and layout!!
- 5 January 2015 at 03:43
- Chana said...
Beautifully composed card! The colors are vibrant and visually stimulating. Very well conceive and executed! Thanks for slipping this under our door here at 613 Avenue Create!
Chana Malkah, Owner
- 5 January 2015 at 04:43
- Jackie said...
What a gorgeous card. Lots of peeps have been ill over the Christmas period, good to hear your family is much better now :o)
Jackie xx
- 5 January 2015 at 07:28
- Craftin Suzie (Susan Flynn) said...
Happy New Year Jacee, so pleased you managed to get your celebrations in with your grandchildren eventually! Fabulous card love the image and papers! Susan x
- 5 January 2015 at 07:38
- Shirley said...
Gorgeous card Jacee and all the best to you for 2015.
- 5 January 2015 at 07:50
- brenda said...
Oh dear Jacee, not the Christmas as planned, so sorry.
But you have bounced back with a gorgeous creation, full of summertime.
B x
- 5 January 2015 at 08:01
- Pop's Cards said...
Good morning sweetie, this is simply stunning, I love the colours too, hugs Pops x
- 5 January 2015 at 09:48
- meg said...
Beautiful card Jacee, it's great to see the lovely bright summery colours. Hope the grandchildren are better now and that you managed to have a good day with them in the end.
- 5 January 2015 at 10:39
- Veerle said...
Very beautiful Jacee.
Gr Veerle
- 5 January 2015 at 13:16
- Pamellia Johnson said...
I am loving the bright cheery colours here Jacee, it's such a refreshing switch from the bleak weather up here in Canada! Gorgeous flower image! hugs :)
- 5 January 2015 at 13:45
- Irene said...
Hello jacee
I'm just loving the bright colours
and stunning image. Hope all the grandchildren are improved.
- 5 January 2015 at 15:32
- coldwaters2 said...
Happy New Year Jacee, I am glad that your family finally got to have a Christmas with you albeit a tad late. Jacee your card is so beautiful the image is full of so much delight the papers are so vibrant and fresh a truly wonderful creation to start the New Off with.
lorraine x
- 5 January 2015 at 18:01
- Stamps and Paper said...
Stunning card Jacee ..hope your grandchildren are feeling better
- 5 January 2015 at 18:01
- Christine L said...
Your floral card is fabulous Jacee... lovely colours and a gorgeous image!
I'm glad you managed to have a 'late Christmas' - I'm sure you enjoyed it just as much!
Christine x
- 5 January 2015 at 18:04
- Pia S said...
Sorry to hear about your Christmas not going according to plan, but it sounds like the postponed version was a success anyway,,,
It's a lovely birthday card you've made, the colors make me think of, and long for, spring.
Question - do you make your own envelopes? Do you decorate blank ones? Or do you use some sort of kits? I love how you made both the front, inside and envelope match...
- 5 January 2015 at 18:18
- Chrissy said...
Beautiful bright sunny colours Jacee..the flowers are gorgeous.Fabulous papers and design too.Glad you finally had your Christmas together..hope everyone is feeling better by now.
Happy New Year 2015..
luv CHRISSYxx
- 5 January 2015 at 18:39
- Sue B said...
Happy New Year Jacee!! Aww so many people have been poorly over Christmas… what a shame your family were so unwell. I'm glad you managed to have a nice day on Tuesday though :-) I really hope next Christmas is much better for you all !!
I love your card… the image and papers are SO pretty! fab layout too!
I can't seem to get back into my normal routine… hopefully as the week goes on I will !! ;-)
Hope you have a good week!
Big hugs, Sue B xx
- 5 January 2015 at 21:18
- Patty Sue 2 said...
It is no fun when sickness occurs this time of year. My goodness you have had your share. Your bright cheery card certainly brightened my day. Love it! Thank you for joining us at ABC CHALLENGE! Good luck and please join us again for our next challenge!
- 6 January 2015 at 02:55
- Pollard Carole said...
An absolutely stunning card I love the gorgeous flowers and beautiful vibrant colours so pretty. so glad you got your family Christmas eventually and they have all recovered. Best wishes to you and your family for 2015 Love and hugs Carole x
- 6 January 2015 at 08:39
- aussie aNNie said...
Fabulous card, lovely added goodies and design. I'm glad things turned out well in the end,....xxx{The Journey is the Start – my personal blog}
- 6 January 2015 at 09:37
- Carolina Girl (Cely) said...
So gorgeous...as always! You never let me down on putting a smile on my face and beauty in my eyes.
- 6 January 2015 at 16:46
- Rainey's Craft Room said...
I'm a little late catching up with everyone, been a bit poorly myself. Sorry to hear that Christmas had to be delayed and that your family were ill, someone always seems to get something for Christmas Day.
A great card here, love the colours and your cards are always so beautifully finished off.
- 6 January 2015 at 22:03
- Heather said...
Hi Jacee, I hope the New Year is more successful than your Christmas. Mine could have been better with a broken arm for the last 4 weeks (2 more to go!!)
Your card is gorgeous, a beautiful design with fabulous colours and papers.......your image is beautiful!!
Heather xx
- 6 January 2015 at 22:26
- Rebecca Bradshaw said...
Happy New Year Jacee! I'm so sorry to hear about your family being ill over Christmas, that's such a shame.
Your card is so beautiful and bright - it's definitely getting me in the mood for Spring! Such lovely papers.
- 7 January 2015 at 19:08
- Anna Jasiolek said...
What a sunny and elegant card for our first challenge this year! Love it! Thank you for joining our 'anything goes' challenge at Crafty Catz and please come back on Friday to find out who is the winner. Good luck!
Anna xxx
- 7 January 2015 at 20:11
- Christine's Craftyart Blog said...
A fabulous colourful card. x
- 8 January 2015 at 11:55
- Anita Byrne said...
Stunning creation thanks for joining the fun over at Polkadoodles and good luck.
Anita (DT)
- 8 January 2015 at 20:24
- Pat K said...
Happy New Year Jacee. I look forward to more of your beautiful creations. This card is stunning..love the yellows with this gorgeous bouquet. hugs, Pat K x
- 9 January 2015 at 12:40
- Chana said...
Great project, Jacee!
I stopped by to let you know that you have been selected as our FB Designer of The Day for January 10, 2015. Pease stop by our page www.facebook.com/avenue613 to say hello and to grab your Designer of The Day badge.
Your project will be posted at 10:00AM EST.
Congratulations and Welcome to The Front Porch Gang
Chana Malkah Harris, Owner
613 Avenue Create Challenge Blog
- 10 January 2015 at 14:15
- JD/ Jill said...
Your card is so beautiful...bright and cheery!
Sorry to hear that your family was sick over Christmas.
Our Christmas wasn't quite what we planned either. Christmas is usually just hubby and myself...but we usually go to visit our daughter the day before to celebrate Christmas...We're getting ready to leave to go to her house, and hubby hears water running in the basement...a leaky pipe on Christmas eve! He wanted to cancer our visit...I said no way! smile. So he shut off the water and we went to her house...(poor hubby had to deal with it on Christmas eve after we got home...Glad I married a plumber's son...or we would have been without water for days over the holidays.
- 10 January 2015 at 19:49
- Louise said...
Gorgeous card! So pretty and cheery for dull January days! x
- 10 January 2015 at 21:39
- Pat said...
This is really pretty Jacee and a lovely bright way to start the new cardmaking year. x
- 12 January 2015 at 14:23
- Melanie Joyce said...
A simply beautiful card, gorgeous colours! Thanks for joining in with our Tic Tac Toe challenge on the Polka Doodles blog http://polkadoodle.blogspot.co.uk/2015/01/week-1-tic-tac-toe-polkadoodles.html x
- 13 January 2015 at 22:49
- Hazel said...
Beautiful card. Thank you so much for sharing your delightful crafting for my Craftyhazelnut's Patterned Paper Challenge for January - hope to see you again soon. x
- 24 January 2015 at 17:13
- caroline said...
beautiful card, so pretty, thanks for joining us at soc, good luck
caroline dt
- 26 January 2015 at 15:57
- rachel said...
A lovely card and so very colourful. Thanks for joining us at Imagination Crafts this month. Hugs rachel x
- 26 January 2015 at 22:09
- Beverley said...
Gorgeous card. I love the colours. Thanks for joining in our 'What's New" challenge at Crafty Calendar this month.
Bev x
- 6 February 2015 at 22:07


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How to Design Memorable Outdoor Advertising
The number of options for your outdoor ads may seem overwhelming, but the processes for designing them are identical in most cases. Exactly what makes a great outdoor ad campaign? A dozen advertising experts will give you two dozen answers, but you do need to know two primary measuring factors for outdoor advertising:
Impact: The ability to grab a viewer's attention in a matter of seconds.
Appeal: Persuasiveness and positive response by the viewer to the creative content.
This figure shows a sign used inside a bus terminal. The ad immediately catches viewer attention with its simple message, bold color, four-word header, and colorful product images.
Designing your ad
Here's how to make your outdoor ad outstanding:
Pursue potential customers. Before you can come up with an award-winning slogan, you must know who your target audience is. Who's most likely to buy your product or use your service?
Make your ad readable. If customers can't read your outdoor ad, then what's the point? Your design should be connected with a simple, clean text in a very readable typeface. Prioritize the keywords of your copy and keep your copy short and full of punch.
If you're using a graphic element — a picture, drawing, or logo — make it big and keep it simple. Don't force your viewers to search for the message. They won't bother.
Keep your ad clear. Viewers don't want to be teased; they want to be informed. And with a billboard, they need to be informed in a split second, so don't get too cute. Be clear, concise, and direct.
Six words is the most favorable number for billboard readability, but keeping your message that short is often impossible. Try eight words if you must, but any more than eight could be dangerous to the health of your ad budget.
Make it worth remembering. Imagery is often more important than words. The use of a hard-hitting visual element can generate more memorability for the viewer. Possibly your best solution is a bold display of your slogan, package, storefront, or logo.
Above all, make your outdoor ad's message simple and easy to recall. Use bright, eye-catching color and brief, well-written copy. You only have a few seconds to make an impact on someone who's probably already preoccupied.
Getting help
To find help with your business's outdoor advertising, check out the Outdoor Advertising Association of America (OAAA). Your business can find help from this trade organization for the industry, which has reams of information about who, what, when, and where.
You can also call outdoor advertising companies operating in your area, accessible through another great source: SRDS Media Solutions's Out-of-Home Advertising Source. This book can both steer you to the right outdoor company and give you a list of the company's rates. You can find the book for sale in print or electronically on SRDS's Web site; or you may find it at your local business library.


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The Dow Jones industrial average moved more than 400 points in five out of the last six trading days through Thursday as investors reacted to news from the debt ceiling debacle, the Fed and interest rates, fiscal troubles in the United States and Europe, and the Standard & Poor's downgrade of U.S. debt.
Experts, like Bill Gross and Jeremy Grantham, of course, have been weighing in on what's behind such swings and how to view the underlying issues in the longer term. Here are the five best quotes from a wild ride in the markets so far this month.
'Debt Men Walking'
Future liabilities facing the U.S. government are staggering, said Bill Gross, PIMCO managing director, in his early August outlook "Kings of the Wild Frontier."
"In addition to an existing nearly $10 trillion of outstanding Treasury debt, the U.S. has a near-unfathomable $66 trillion of future liabilities at 'net present cost' … I call these liabilities 'debt men walking,' because as long as 330 million living Americans require promised entitlements, the $66 trillion that wear shoes are as much of a liability as the $10 trillion on paper."
'The U.S. Is Bankrupt'
The country can't kid itself about its debt anymore, investor Jim Rogers said on CNBC on Tuesday, after expressing similar comments to the Economic Times of India a day earlier.
"It seems to me it's physically, humanly impossible for the U.S. to ever pay off its debt. They can roll it over and continue to play the charade, but the U.S. is bankrupt."
U.S. 'Looking Like a Banana Republic'
Due to its own misbehavior, Congress had to act, said investment guru Jeremy Grantham (below right) in GMO's quarterly newsletter released Aug. 1.
"So now [July 30], the U.S.—with a dysfunctional Congress—[had] to decide between two of the ugliest choices seen in a long time. Should they cut government expenditures and therefore cut aggregate demand at a time of a critically weak economy on the cusp, perhaps, of a double dip? Or should they do nothing and allow a technical default … Come to think of it, the choice was between technical default and looking like a Banana Republic, and technical blackmail and looking like a Banana Republic! Just different bananas perhaps?" 'Debt Dramas and Crises Will Not Go Away Any Time Soon'
Thanks to over-spending by governments, things will not be 'normal' for a while, PIMCO CEO and co-CIO Mohamed El-Erian said in an Aug. 1 commentary.
"We should all accept that Europe and America—the former for fundamental reasons and the latter for self-inflicted ones—are now in a de-levering cycle whose consequences will be with us for many years … and governments will mix and match from the menu of options … Accordingly, periodic debt dramas and crises will not go away any time soon … Unfortunately, none of us have the ability to fully insulate ourselves from the collateral damage and unintended consequences. The best we can do is to understand the process …"
Two More Years of Interest Rate Heaven
The typically bland Federal Open Market Committee (FOMC) announcement on Tuesday was exciting to the markets, which surged, but stocks flopped Wednesday.
"The Committee currently anticipates that economic conditions — including low rates of resource utilization and a subdued outlook for inflation over the medium run — are likely to warrant exceptionally low levels for the federal funds rate at least through mid-2013."
(Photos on Pages 1 and 3-6 are by The Associated Press.)


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Baltimore is a city of contradictions. Located south of the Mason-Dixon line, it lies in a state that never seceded from the Union. Essentially southern in temperament, pace and quality of life, it is one of the great industrial port cities of the nation. Despite a population of less than one million in Baltimore proper, it is served by three daily newspapers, the same number published in New York City. Like most metropolitan areas today, Baltimore is plagued by financial problems. Yet it ended fiscal 1975 with a surplus of $52 million. Perhaps most important, it is a city that has not lost its will to live, that has taken a hard look at its economic and social ills and is taking realistic steps to find remedies. It is a city where picturesque historic neighborhoods contrast with new construction—a Baltimore outer harbor bridge to be opened later this year that will improve the traffic flow on 1-95, the major interstate highway running from Maine to Florida; an extensive redevelopment of the Inner Harbor area that will turn it into an attractive and versatile business, cultural and recreational center. Baltimore is a city where the residents voted approval of a $10 million bond issue to finance a complete renovation of the historic, century-old City Hall, while in Annapolis the State General Assembly recently voted approval for a new underground rapid transit system and a convention center for Baltimore. It is a municipality that takes pride in being home to both the Peabody Institute, the oldest privately endowed music school in the country, and the ultramodern Maryland Science Center, built by the 179-year-old Maryland Academy of Sciences and opened just this June as part of the Inner Harbor Redevelopment Area. Like the original colony of Maryland, established early in the seventeenth century, Baltimore was founded on the tobacco trade. Named after the English Barons Baltimore, the city was chartered as a "tobacco port" in 1729. It was not long before Baltimore's harbor facilities and strong merchant community transformed it into one of the busiest port cities in the New World. By the time of the American Revolution, Baltimore had established itself as a key center of shipping to northern Europe, the Mediterranean and the Caribbean. (It's a little-known fact that Congress held sessions BAMMORE Just about everything one could want! An Office Profile


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OAKLAND, Calif. -- The Athletics have bought outfielder Casper Wells from the Toronto Blue Jays.
The A's transferred infielder Scott Sizemore to the 60-day disabled list Monday to clear a spot on the 40-man roster. Oakland will make a move to put Wells on the 25-man roster once he joins the team in Boston.
Wells spent spring training with Seattle but did not make the team. The Blue Jays claimed him off waivers April 10 and he did not play a game before being designated for assignment.
The 28-year-old Wells hit .228 with 10 homers and 36 RBIs in 93 games with the Mariners last season.
Sizemore is out for the season with a left knee injury.


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Things to do...
9:00 AM- Declare myself a candidate for President of the United States.
9:01 AM- Call Barak Obama the first mainstream African-American who is articulate, bright and clean and a nice looking guy".
9:02 AM- Begin apologizing for Obama comment.
Worse start to a campaign since William Jennings Bryan started off a speech in South Carolina by saying..."Helloooooooooo Cousin Kissers!"
Never recovered from "Cousin Kisser-Gate".


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PinkFloyd22 wrote:I know there are alot of people here from the USA and before you start flaming and arguing with me I ask you think about the situation you are in and how your goverment acted few years ago(especialy Bush) and reconsider believing in all they say.
Yes you are right,maybe I expressed myself badly,trust me I don't believe Obama is better than Bush I just gave him as an exemple.thetan wrote:PinkFloyd22 wrote:I know there are alot of people here from the USA and before you start flaming and arguing with me I ask you think about the situation you are in and how your goverment acted few years ago(especialy Bush) and reconsider believing in all they say.
This is indicative of the fact that you too are a media slave. Nothing has changed with the context switch from the bush administration to the Obama administration.
The only thing that's changed is Obama is cooler because he's black and he uses FB and twitter, so "he must be hip y0!"
The fact of the matter is the nation is in no better condition or even path towards a better condition then when bush was calling shots.
If you truly understood how the US and the world as a whole in it's current state works, you'd realize governance is for the most part nothing more then globally distributed shadow puppet theater. The world is governed by a small amount of geographically explicit plutocracies (governments ruled by the rich, for all the kids around here). Democratic republics and parliamentary only create an illusion that people have a say when really at the end of the day the only votes that count are those that are pledged as dollars and the ones with the cash pull the strings.
When you see such a campaign being pushed around the media like the one in this topic it typically only means one thing. This is a hugely sponsored PR stunt. May it be what i call distractovision or NLP (neuro linguistic programming) priming and association ore some other new corporately sponsored mind manipulation gimmick.
Theres always an agenda and some one is always trying to gain something. Business is never ending war and the battlefield is for your and on your minds.
thetan wrote:It's actually part of their culture to burn Qurans. They believe that the Quran should only exist in a "beautiful" condition and Qurans that don't live up to that standard should most definitely be burned.
Vulpine wrote:Language barrier aside, yes, I think I see the point that you're making.
However, when learning about a religion, I feel that it's equally important to consider historical research just as much as, if not more than, religious doctrine. I won't blame a modern community for it's long past actions, but I like knowing where they came from and what they did to get to where they are now. A broader picture, instead of a narrower one, so to speak.
Very off topic though, so I'll leave it at that.
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