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US 5432245 A Abstract The invention provides acrylamide polymers that, when mixed with water solvent, provide thermoreversible solutions that form low viscosity melts at temperatures separated by a third region of maximum viscosity.
Claims(12) 1. A method of casting a layer comprising providing a solution comprising water and a polymer represented by the general Formula 1:
--(A).sub.x '--(B).sub.y '-- (1) wherein A and B are randomly distributed in the polymer chain and wherein A represents recurring hydrophobic units, and B represents recurring hydrophilic units "wherein x' is 40 to 99.9 mole %, y' is 60 to 0.1 mole %". casting a layer of said solution, and heating to thicken and gel said layer with the proviso that said hydrophobic units are selected from at least one member of the group consisting of ##STR15## and said hydrophilic units are selected from at least one member of the group consisting of ##STR16## 2. The method of claim 1 wherein said solution further comprises at least one of acetone, methanol, ethanol, tetrahydrofuran, and isopropanol.
3. The method of claim 1 wherein said layer comprises a layer of a photographic film.
4. The method of claim 3 wherein said layer comprises the antihalation layer.
5. The method of claim 1 wherein said solution has a viscosity of less than 10 cps.
6. The method of claim 1 wherein said layer is dried after said heating to thicken.
7. The method of claim 1 wherein said polymer comprises ##STR17##
8. The method of claim 1 wherein said solution is cooled to below the gel region prior to coating and then said heating after coating is to the gel point of said solution.
9. The method of claim 1 wherein in said polymer the hydrophobic unit comprises at least about 30 mole percent of said polymer.
10. The method of claim 1 wherein said polymer comprises ##STR18##
11. The method of claim 1 wherein after said heating, the layer is dried by removal of the aqueous solvent.
12. The method of claim 1 wherein after gelling, said layer is dried to remove said aqueous solvent.
Description To our knowledge there are no prior reported examples of synthetic heat-thickening polyamides, nor are there synthetic polyamides which have peak viscosities in water between two temperature regions in which they form low viscosity melts, as shown in FIG. 2. The invention polymers are highly desirable compositions as their peak viscosities in water could be varied over the entire liquid temperature range of water (0 boiling point of water, only the left half of the viscosity curve will be measurable (FIG. 3). Similarly, for those near freezing point, only the right half of the curve will be measurable (FIG. 4). A further advantage of the invention polymers is that heat-thickening is not accompanied by large changes in free volume of the polymer solution (syneresis), precipitation of the polymer, or significant changes in the optical transmission properties of the polymer solutions. A particular advantage over gelatin is realized in that invention polymers are soluble in common organic solvents such as methanol, ethanol, acetone, isopropyl alcohol, and tetrahydrofuran. These and other advantages are accomplished by providing a polymer that is comprised of a hydrophilic portion and a hydrophobic portion. The hydrophilic portion of the polymer comprises a polymerizable water soluble ionic vinyl monomer. The hydrophobic portion comprises an acrylamide or methacrylamide monomer that can undergo free radical polymerization, which is insoluble in water or forms homopolymers that are insoluble in water, or which forms polymers that exhibit LCST (lower critical solution temperature) properties. In addition, as long as at least 1 mole percent polymerizable water soluble ionic vinyl monomers is present, the polymerizable water soluble ionic vinyl monomer may be substituted by a nonionic hydrophilic vinyl monomer. The hydrophilic ionic portion is rendered ionic by charged functional groups, preferably NH.sub.3.sup.+, NH.sub.2 R.sup.+, NHR.sub.2.sup.+, and NR.sub.3.sup.+, CO.sub.2.sup.-, SO.sub.3.sup.-, O.sup.-, --SR.sub.2.sup.+, OPO.sub.2.sup.-, SO.sub.2.sup.-, or mixtures thereof. R is defined as lower alkyl of between 1 and 10 carbons. It is believed that in Formula 2, some of the hydrogen may be substituted with one or more fluorine, chlorine, bromine, iodine, alkoxy, acyloxy, sulfoxyalkyl, sulfoalkyl, nitro, thio, keto, or nitrile groups and retain the invention properties. It should be understood from the general description that the ionic hydrophilic portion can be selected from any class of vinyl monomer having an ionic group that can undergo free radical polymerization. Other vinyl monomers having either hydrophobic or hydrophilic properties may be incorporated as well, as long as one maintains the proper overall hydrophobic-hydrophilic balance required for heat-thickening behavior. Cationic, anionic, and mixed anionic/cationic heat-thickening polymers are prepared by combination of monomers from the above general classes of materials. For a given polymer in water, the position and magnitude of the peak viscosity will depend on molecular weight, concentration, presence of added salts, hydrophobic-hydrophilic balance of comonomers, polymerization solvent, pH, rate of heating or cooling, the presence of organic cosolvents and their concentration, compositional heterogeneity (monomer distribution), and shear rate. All of these factors effect the shape of the viscosity/temperature curve. The most preferred embodiments of the invention are those in which in Formula 2, the Z equals isopropyl, n-butyl, sec-butyl, iso-butyl, t-butyl, or 1,1-dimethylpropyl. Also, most preferred embodiments are those in which in Formula 3, the L equals ##STR4## or arylene. Further, most preferred embodiments are those where Y in formula B is an amine having NH.sub.3.sup.+, NH.sub.2 R.sup.+, NHR.sub.2.sup.+, NR.sub.3.sup.+ wherein R equals lower alkyl having 1-10 carbons, CO.sub.2.sup.- and SO.sub.3.sup.-. As observed in FIG. 5, the viscosity vs. temperature curve for a heated sample can appear quite different from the curve obtained by cooling the sample through the same temperature region (hysteresis). Curve A was observed by heating the polymer obtained in Example 1, concentration 3.2% weight percent polymer in water, at a rate of 1 5 and at an oscillating frequency of 10 rad/sec. Curve B was obtained by cooling the same sample under identical conditions from 75 5 is cycled back to the starting temperature. Unlike gelatin and other materials described in the section on prior art, the polymers described here are generally soluble in acetone, methanol, ethanol, tetrahydrofuran, isopropanol and mixtures of these solvents and water. However, the invention polymers show heat-thickening properties only in a predominantly aqueous solvent system. Solution properties of the polymers in organic solvents are typical, e.g., their viscosities decrease with increasing temperature between 0 organic solvents can be used to modulate the peak viscosity of the polymers in water if they are restricted to less than 50 weight percent of the total solvent, preferably less than 20%. Generally, for the polymers of this invention, peak viscosities in water shift to higher temperatures with increasing hydrophilicity of the polymer, and to lower temperatures with the addition of small amounts of organic cosolvent (<20% by weight of total solution). A smaller hysteresis has been seen for the more hydrophilic polymers. Added salts, such as potassium chloride, sodium sulfate, sodium chloride, lithium chloride, and calcium chloride, cause a shift in the peak viscosity toward lower temperatures and an increase in the magnitude of the peak until at very high concentrations the polymers precipitate or show a cloud point on heating. Higher molecular weights also cause an increase in the magnitude of the peak. High concentrations of urea (�4M) result in a total loss of heat-thickening properties. The appearance of the polymers in water can range from clear to milky white. Generally, the optical transmission properties do not significantly change upon heating the samples through a complete temperature cycle. Very slight haziness has been observed, however, when heating samples that contain more than 95% m/m hydrophobic monomer, particularly 97% or greater.. Generally, however, there is no observable change in the clarity of the polymer solutions as they are heated through their viscosity maxima, e.g., a clear melt at low temperature will remain clear as it is heated through its gel peak. Likewise, in those samples that are milky when dispersed in pure water, the presence of a dispersed phase does not appear to inhibit the heat-thickening properties of the sample. The polymers of the invention are clear when dried even if milky white when in water solution. The gelation properties of these polymers are particularly beneficial in coating applications where a low viscosity solution (<10 cps) is applied to non-absorbent supports, such as cellulose triacetate or polyethylene terephthalate. Such layers may function as subbing layers, antihalation layers, antistatic and lubricating layers, particularly when applied to the opposite side from the light sensitive layers. In a typical coating operation in which a solution is applied from a hopper to a moving support, there is a critical period before the solvent is fully evaporated when the coated layer has no rigidity, and may be disturbed by several causes, including vibrations from the machine, a possible vertical rise of the moving web, or impinging air currents from the drying section. The latter type of disturbance, referred to simply as "blowing", is particularly prevalent when the initial viscosity is low, (<10 cps) and the amount of water to be removed is great, resulting in extreme coating non-uniformities such as waves and lines. Another typical defect associated with low viscosity coating solutions is a heavy "edge bead", caused by the high accumulation of coated material at the very edge of the coating. Eventually, solvent evaporation results in a high enough viscosity so that adequate rigidity is obtained, but often this occurs after the aforementioned defects have set in. Gelatin solutions offer rapid rigidity and hence better coating uniformity prior to the evaporation of water by the chill setting property, whereby gelation occurs when a warm solution is cooled below the gel point upon application to the support. The polymers of this invention can also be chill set to offer solution rigidity prior to water evaporation, but also have the added flexibility to be "heat set" when the situation demands it by cooling the solution below the gel region and immediately warming it to the gel point upon coating. The advantage of heat setting, particularly when coating on bare supports, is that the layer is set and evaporated in one rapid step, rather than in a gradual process as with gelatin solutions where the coated layer is first chilled and then gently heated to drive off the water without remelting the layer before dryness is achieved. Heat setting would allow for faster drying and hence faster coating speeds on smaller coating machines with less drying capacity. Another advantage of the polymers of this invention for high speed machine coatings is the ability to vary the temperature of gelation and liquid by slight alterations in the polymer composition, so that desired coating temperatures can be matched. In addition, the ability to vary the ionic portion of the polymer and to include some functional monomers enables these polymers to be tailored for specific chemical and physical properties. The polymers of the invention generally are formed using about 30 to about 99.9 mole percent of a hydrophobic monomer of the general Formula 1 and about 70 to about 0.1 mole percent of a hydrophilic monomer having an ionic group selected from materials having the general Formula 2 or the general Formula 3. The hydrophilic monomer of Formula 1 bearing an ionic group represented by Formula 3 may be partially substituted with other hydrophilic ionic monomers having the same or opposite charge as represented by Formula 3. The substitute ionic or nonionic hydrophilic monomer may comprise up to 69 mole percent, as long as the ionic content represented by B is present in at least 0.1 mole percent. The substitute ionic or nonionic hydrophilic monomer can be selected from virtually any class of vinyl monomer capable of undergoing free radical polymerization. Representative nonionic monomers preferred are acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and 2-hydroxyethylacrylate. Other suitable nonionic monomers are allyl alcohol N-methylolacrylamide N-(3- or 5-hydroxymethyl-2-methyl-4-oxo-2-pentyl)acrylamide bis(1-dimethylaminoethyl)methyl methacrylate N-(isobutoxymethyl)acrylamide N-(isobutoxymethyl)methacrylamide N-(m- and p-vinylbenzyl)-N,N-dimethylamine m- and p-vinylbenzyl alcohol cyanomethyl methacrylate 2-poly(ethyleneoxy)ethyl acrylate 2-cyanoethyl methacrylate ethyl acrylamidoacetate methacryloyloxypolyglycerol glyceryl methacrylate N-(m-hydroxyphenyl)methacrylamide 2-hydroxyethyl acrylate 2-hydroxypropyl acrylate N-(1,1-dimethyl-3-dimethylaminopropyl)acrylamide 2-methyl-1-vinylimidazole 1-vinylimidazole N-vinyl-e-caprolactam p-methanesulsonamidostyrene N-methylmethacrylamide N,N-di(cyanomethyl)acrylamide methacrylamide maleic anhydride 2-hydroxyethyl methacrylate N-methylolmaleimide methacryloylurea acrylonitrile 2-chloroacrylonitrile methacrylonitrile N-(2-hydroxypropyl)methacrylamide N-acryloylpiperidine N-vinylsuccinimide 2-hydroxypropyl methacrylate 2-(5-ethyl-2-pyridyl)ethyl acrylate N-(3-methacryloyloxypropyl)thiourea N-vinyl-2-pyrrolidone p-aminostyrene N,N-dicyanomethylmethacrylamide 2-methyl-5-vinylpyridine N-vinylcarbazole 2-vinylpyridine 4-vinylpyridine N,N-dimethylacrylamide 2-(diethylamino)ethyl acrylate 2-(dimethylamino(ethyl acrylate 2-(dimethylamino)ethyl methacrylate 2-(diethylamino)ethyl methacrylate 3-{3-(dimethylamino)propyl}acrylamide 3-{-2-(dimethylamino)ethyl}acrylamide 3-{-2-(dimethylamino)ethyl}methacrylamide 3-(diethylamino)propyl acrylate 4-(diethylamino)-1-methylbutyl acrylate The substitute ionic or nonionic monomer may also be derived from any other monomer used to make the polymer, which can include hydrophilic monomer B of Formula 1 or hydrophobic monomer A of Formula 1, either by subsequent pH induced changed in ionization or chemical modification of the polymer after polymerization. In addition, the hydrophobic monomer A of Formula 1 may be partially substituted with other hydrophobic monomers represented by general Formula 2 or by other hydrophobic monomers not represented by Formula 2, to an extent generally less than 60 mole percent and preferably less than 20 mole percent. These can be selected from any class of vinyl monomer capable of undergoing free radical polymerization. They may also be derived from any other monomer used to make the polymer either by subsequent chemical modification of the polymer or by pH induced change in ionization to give an uncharged rather than ionic form. The substitute hydrophobic monomer may be one that is either insoluble in water, or form homopolymers that are insoluble in water, or form homopolymers that exhibit LCST properties. The polymers are formed in an organic solvent/water mixture, preferably methanol/water 1:1 volume ratio and most preferably methanol/water 2:1 volume ratio. Other solvents such as acetone, ethanol, dimethylformamide, dimethylsulfoxide, and dimethylacetamide may be substituted or added as necessary to control molecular weight, or to maintain solution. A preferred solvent will not cause precipitation of the polymer during the course of the reaction. In a preferred embodiment, monomers are combined in a solvent that dissolves all reactants completely at 60 at 25 initiators known in the art, potassium persulfate, or azoisobutyronitrile and other related materials. The concentration of monomers ranges from 10-40% weight monomer in water (w/w), preferably 15% weight monomer in water, and the initiator concentration ranges from 0.25 mole percent to 5 mole percent, preferably 1.0 mole percent relative to the combined moles of all monomers. Weight in water w/w means the percent of monomer, by weight, as a percentage of total solution weight, i.e., a 20% (w/w) solution is 20% polymer and 80% water. The preferred reaction temperature is 60 The polymers are typically prepared in batch mode, e.g., all monomers are combined before initiation. Changes in mode of addition, or solvents results in a variation in the heating and cooling profiles of the product polymers. There is no preferred mode of addition because this depends on the desired heat-thickening properties; however, modes of addition that cause block monomer distributions are not preferred. Generally, heat-thickening properties are favored by random incorporation of the monomers during chain growth. The molecular weight range for polymers of the invention extends from 20K to 1000K, most preferably 100-350K and determined by the GPC (polyvinyl pyrolidine equivalent) method. Polymers within the scope of this invention will heat-thicken at concentrations of 1-20% weight monomer in water (w/w), and preferably 1-10%, in a predominantly aqueous solvent system (>50% percent by total volume (v/v) water). Measurements were made using either a Brookfield viscometer at constant shear or an oscillating plate rheometer (Rheometrics) with a frequency (ω) range of 0.01 to 100 radians/sec and a percent strain (γ) of 1-25%. Typically, the strain was 1-10%, the frequency was 10 radians/sec, the heating rate was 1 and the concentration was 2-10% w/w. The shear rate for the Brookfield measurement typically was between about 0.4 and 80 sec.sup.-1. Repeat units and parent monomer names referenced in specific thermoreversible polymers of this invention are listed below: ##STR5## Specific examples of thermoreversible polymers of this invention are listed in Table 1. TABLE 1______________________________________COMPOSITION MOLE RATIO (%)______________________________________TBA:APM 80:20TBA:APM 85:15TBA:APM 75:25TBA:SSA 80:20TBA:SSA 85:15TBA:A:SSA 75:20:05TBA:A:SSA:APM 65:20:05:10TBA:A:SSA:APM 60:25:10:05TBA:A:SSA:APM 65:20:10:05TBA:A:CEA:APM 60:30:05:05TBA:A:CEA:APM 65:25:05:05TBA:A:APM 75:05:20TBA:A:APM 70:10:20TBA:A:APM 65:15:20TBA:A:APM 60:20:20TBA:A:APM 55:25:20TBA:A:APM 50:30:20TBA:CEA:APM 70:10:20TBA:CEA:APM 60:20:20TBA:CEA:APM 50:30:20TBA:DOA:APM 60:20:20TBA:IPA:APM 45:45:10TBA:IPA:APM 50:30:20IPA:APM 97:03DOA:APM 90:10NBA:APM 80:20TBA:SA 50:50IBA:APM 85:15IBA:APM 90:10SBA:APM 80:20SBA:APM 85:15TPA:APM 80:20TBA:IPA:SSA:APM 45:35:15:5TBA:IPA:SSA:APM 40:40:15:5SBA:IPA:SSA:APM 60:20:15:5______________________________________ The following examples illustrate the preparation of polymers within the scope of this invention: t-Butylacrylamide (101.6 g, 0.80 moles) and 3-aminopropylmethacrylamide hydrochloride (35.6 g, 0.20 moles) were combined at ambient temperature with methanol (350 ml) and water (350 ml). The mixture was purged 15 minutes with nitrogen and was then heated to 60 materials dissolved within 10 min. at which time AIBN (1.6 g, 0.01 moles in 60 ml methanol) was added in one portion. The solution became slightly hazy over an 18-hour period. The solution was diluted with 700 ml water and was concentrated in an open beaker with a nitrogen inlet at 60 C. until about 300 ml had been removed. ______________________________________wt 1255 g 10.23% solids______________________________________ theory C 61.15 H 9.82 N 12.22 Cl 5.15 found C 59.93 H 9.71 N 11.95 Cl 5.19 ______________________________________iv (.25% in .1N LiCl/methanol) 1.06wt % APM 25.4, 26.3 (reethanol, titrated with hexadecyl trimethylammonium hydroxide (HDTMAH))wt % HCl .74, .55w % MEOH 9.1______________________________________ The heating and cooling viscosity curves for this sample at 3.7% solids are shown in FIG. 5. Approximately half of the polymer was hot diafiltered (50 cutoff, 20 liters effluent) and was then concentrated in an open beaker at 60 ______________________________________wt 577 g, 7.2% solidsiv 1.09 dL/g (.25% in .1N LiCl/MeOH)wt % APM 23.7wt % HCl <0.1GC < 1% methanol, acetone, ethanol.______________________________________ found C 60.46 H 9.80 N 12.06 Cl 5.0 N-3-aminopropylmethacrylamide hydrochloride (17.8 g, 0.10 moles) were combined at 20 minutes and was then warmed to 60 additional 10 minutes, after which AIBN (1.6 g) in 20 ml acetone was added in one portion. The solution was maintained under positive nitrogen pressure with a slow bleed for the entire reaction time (18 hours). The resulting viscous solution was diluted with water (approximately 1 liter) to give a latex-like suspension that was concentrated at 70 an open beaker using a nitrogen sweep. ______________________________________wt. 1011 g 14.8% solidswt % APM 10.4wt % HCl .14iv .980 dL/g (.25% in .1N LiCl/MeOH)______________________________________ theory C 62.11 H 8.88 N 9.05 Cl 2.08 found C 61.22 H 8.68 N 9.02 Cl 2.23 The heating curves after equilibrating this sample for 4 hours and 6 days at 6 DMSO (500 ml), EtOH (60 ml), t-butylacrylamide (101.6 g, 0.80 moles ), and N-2-sulfo-1,1-dimethylethyl acrylamide sodium salt (46 g, 0.20 moles) were combined at ambient temperature to give a pale yellow solution that was purged with nitrogen for 15 min. The solution was heated to 60 followed by the addition of AIBN (1.6 g) in acetone (20 ml). The reaction mixture remained clear while heating for 48 hours. The product was diafiltered (20K cutoff, 20 liters effluent) against water. ______________________________________wt. 1563 g 7.6% solidsiv .554 dL/g (.25% in .1N LiCl/MeOH)wt % SSA 28.5______________________________________ theory C 56.87 H8.86 N 9.48 found C 56.10 H8.77 N 9.27 The heating and cooling viscosity curves for this sample at 7.6% solids are shown in FIG. 7. Methanol (350 ml), water (100 ml), t-butylacrylamide (95.3 g, 0.75 moles), acrylamide (14.2 g, 0.20 moles), and N-2-sulfo-1,1-dimethylethylacrylamide sodium salt (11.5 g, 0.05 moles) were combined at 20 mixture was purged with nitrogen for 15 minutes and was then warmed to 60 which AIBN (1.6 g) in 20 ml acetone was added in one portion. The solution was maintained under positive nitrogen pressure with a slow bleed for the entire reaction time (18 hours). The reaction remained clear in the methanol but turned white upon addition of water (1 liter). No particulates could be seen. The product was stripped at 70 a nitrogen sweep in an open beaker to give a white gel. ______________________________________wt. 536 g 19.4% solidsiv .927 (.25% in .1N LiCl/MeOH)______________________________________ theory C 61.48 H 9.49 N 11.56 S 1.32 found C 57.69 H 9.35 N 10.99 S 1.01 ______________________________________wt % SSA 8.95, theory 9.5______________________________________ The cooling viscosity curve for this sample at 6.0% solids is shown in FIG. 8. The reaction conditions were identical to those described in Example 4. Monomer feeds were t-butylacrylamide (82.5 g, 0.65 moles), acrylamide (14.2 g, 0.20 moles), N-(2-sulfo-1,1,-dimethylethyl) acrylamide sodium salt (11.5 g, 0.05 moles), and N-3-aminopropylmethacrylamide hydrochloride (17.8 g, 0.10 moles). ______________________________________wt. 1073 g 10.7% solidsiv 1.01 dl/gm (.25% in .1N MeOH/LiCl)wt % APM 15.4wt % HCl .072wt % SSA 11.4______________________________________ theory C 58.97 H 9.26 N 12.20 Cl 2.81 S 1.27 found C 57.16 H 9.88 N 11.85 Cl 2.42 S 1.24 The heating viscosity curve for this sample at 5.8% solids is shown in FIG. 9. The procedure was identical to the procedure in Example 4. Monomer feed ratios were t-butylacrylamide (82.5 g, 0.65 moles), acrylamide (14.2 g, 0.20 moles), N-carboxyethylacrylamide (7.15 g, 0.05 moles), and N-3-aminopropylmethacrylamide hydrochloride (17.8 g, 0.10 moles). The product solution was clear after 18 hours at 60 was poured into a 4-liter beaker, diluted with 1 liter water (it became milky white but no particulates could be seen), and was stripped at 70 ______________________________________wt. 979 g 11.5% solidsiv 1.05 dL/g (.25% in .1N LiCl/MeOH)wt % CEA 3.60wt % APM 15.6wt % HCl 0.15______________________________________ theory C 60.59 H 9.41 N 12.64 Cl 2.91 found C 59.14 H 9.80 N 12.45 Cl 3.24 The heating and cooling viscosity curves for this sample at 3.0% solids are shown in FIG. 10. Acetone (250 ml), ethanol (60 ml), water (350 ml), t-butylacrylamide (60 g, 0.47 moles), diacetoneacrylamide (20 g, 0.12 moles), and N-aminopropylmethacrylamide hydrochloride (20 g, 0.11 moles) were combined at 20 was then warmed at 60 minutes, after which AIBN (1.0 g) in 20 ml acetone was added in one portion. The solution was maintained under positive nitrogen pressure with a slow bleed for the entire reaction time (18 hours). The solution remained clear throughout the reaction time (18 hr). The product was diluted with water (1 liter) and was concentrated in an open beaker at 70 ______________________________________wt. 885 g, 11.1%iv .71 (dL/g) (.25% in .1N LiCl/MeOH)wt % APM 18.6______________________________________ theory C 62.17 H 9.78 N 11.58 Cl 3.82 found C 59.93 H 9.28 N 11.2 Cl 4.02 The heating and cooling viscosity curves for this sample at 3.0% solids are shown in FIG. 11. MeOH (50 ml), water (50 ml), N-sec-butylacrylamide (10.17 g, 0.08 moles), N-3-aminopropylmethacrylamide hydrochloride (3.57 g, 0.02 moles) were combined in solvents at 20 minutes, and heated to 60 (0.16 g) in acetone (5 ml) was added in one portion. The reaction was stirred 4 hours at 60 that time. After standing overnight at room temperature, the sample was dialyzed against water (10K cutoff) for 24 hours. ______________________________________wt. 105 g% solids 8.37iv .958 dL/g (.25% in .1N LiCl/MeOH)wt % APM 26.8______________________________________ Theory: C 61.15 Cl 5.16 H 9.82 N 12.23 Found: C 59.79 Cl 5.27 H 9.62 N 11.95 The heating viscosity curve for this sample at 8.37% solids is shown in FIG. 12. MeOh (100 ml), N-t-Pentylacrylamide (22.6 g, 0.16 moles), N-3-aminopropylmethacrylamide hydrochloride (7.14 g, 0.04 moles) were combined at 20 minutes. The solution was heated to 60 ml acetone was added in one portion. The reaction was stirred overnight and was dialyzed (10K cutoff) against water for 24 hours. The dialysis bag was allowed to stand 3 days in a hood to allow evaporation of water. Gel formed on the inside of the membrane during that time. The product was heated unsuccessfully at 60 the consistency of a thick paste. The temperature was increased at 80 at this temperature and the polymer appeared homogeneous although not optically clear (slightly yellow, hazy). The melt was cooled to room temperature and allowed to stand 24 hours. A reversible gel was obtained by cooling the melt to 5 at room temperature. ______________________________________wt. 148 gsolids 15.6%iv .625 dL/g (.1N LiCl/MeOH, .25%)wt % APM 23.3______________________________________ Theory: C 63.00 Cl 4.77 H 10.17 N 11.30 O 10.76 Found: C 62.49 Cl 4.89 H 10.25 N 11.20 The heating viscosity curve for this sample at 10% solids is shown in FIG. 13. This Example serves to demonstrate the advantage of these polymers for coating uniformity when applied in a heat setting operation. A water-soluble polymer of this invention, TBA:APM-80/20, was compared with another water-soluble polymer, A:APM-80/20, which contains the identical ionic monomer (APM) and acrylamide (A) monomer in place of the N-alkyl substituted acrylamide and does not exhibit the heat thickening behavior. The coating solutions were chilled to 10 range for TBA:APM-80/20) and were applied by a coating hopper to a moving polyethylene terephthalate support which immediately entered a drying chamber whose air temperature was 32 26%, resulting in a web bulb temperature of 19 temperature is a reasonable estimate of the actual temperature of the coated solution during the evaporation of the water, and corresponds to the minimum gel temperature of the polymer TBA:APM-80/20. Table 2 lists the solutions coated and the uniformity observed. The coating solutions were applied at the wet volume laydowns (cc/ft..sup.2) indicated, and were comprised of water, polymer, and surfactants as spreading agents, at concentrations required to yield the following dry laydowns: 100 mg/ft.sup.2 polymer, 3 mg/ft.sup.2 surfactant Olin 10G, and 1 mg/ft.sup.2 surfactant Zonyl FSN (non-ionic fluorocarbon). The coating uniformity was visualized by dipping the dry coatings into a solution of aniline blue dye which absorbed onto the polymers, followed by washing in distilled water. The visualizations clearly indicate improved coating uniformity for the gelling polymer, TBA:APM 80/20 over the non-gelling polymer, A:APM 80/20, at volume laydowns over 4cc/ft.sup.2. There is also a noticeable reduction in edge bead tendency for the TBA:APM over the A:APM. It should not be inferred from this data that the improvements are limited to the wet laydowns and viscosity range cited (<10 cps) in this example, as the specific conditions depend on the particular coating machine used. The data demonstrate that at any given range of viscosity, wet laydown, and drying rate, the polymers of this invention yield greater flexibility in chosing the specific coating conditions to obtain uniform coatings. TABLE 2______________________________________Coating Wet Coating Defects/Solution Polymer Laydown Severity______________________________________A TBA:APM-80/20 4 cc/ft.sup.2 NoneB TBA:APM-80/20 6 cc/ft.sup.2 NoneC TBA:APM-80/20 8 cc/ft.sup.2 NoneD TBA:APM-80/20 10 cc/ft.sup.2 NoneE TBA:APM-80/20 12 cc/ft.sup.2 Blowing/ModerateF A:APM-80/20 4 cc/ft.sup.2 NoneG A:APM-80/20 6 cc/ft.sup.2 Edge Bead/ModerateH A:APM-80/20 8 cc/ft.sup.2 Blowing/HeavyI A:APM-80/20 10 cc/ft.sup.2 Blowing/HeavyJ A:APM-80/20 12 cc/ft.sup.2 Blowing/Heavy______________________________________ ANTIHALATION BACK COAT Several polymers of this invention were used as binders for photographic antihalation coatings to serve as examples of the utility of such polymers for photographic film back coat applications. Antihalation back coats on transparent supports are well known in the art of photography to serve as absorbers of light that might otherwise be reflected back towards the light sensitive emulsions causing the appearance of halos around bright objects in the developed image. Antihalation layers commonly used in the trade today may employ carbon with a polymeric binder of cellulose acetate hexahydrogen phthalate (hereafter to be referred to as CAP-6) and a wax overcoat to impart greater scratch resistance. The layer is removed from the film after exposure but prior to development of the latent image by first immersing the film in a "pre-bath" of sodium borate and sodium sulfate, followed by water bath and a vigorous spray of water as the film exits the water bath. The final portions of coating are removed by soft mechanical action both prior to development and at the very end of the normal image processing to remove the last traces of polymer-carbon matrix. The polymers of this invention may offer several features that are desired improvements over the currently used CAP-6 polymeric binder. First, there is the potential for improved coating uniformity. It is desired that the antihalation layer be uniform so as to provide a consistent light absorption element. Second, the ability to be coated from water, as are the invention polymers, afford improved compliance with ever more stringent environmental impact regulations. The CAP-6 polymer suffers in this respect as it must be coated from solvents, such as combinations of alcohols and acetone. Third, it would be advantageous to provide a layer that was easier and simpler to remove and represented a reduced potential for soiling the emulsion side of the coating during the removal process. As presently practiced, the CAP-6 polymer is softened by the borate, but is prevented from spontaneous removal by the high ionic strength provided by the sodium sulfate. If some coating were to be removed in this pre-bath, it could attach itself to the emulsion side and remain there as a black spot, completely ruining the developed image. It would, therefore, be desirous to provide for a stronger coating in the pre-bath, or preferably, eliminate the pre-bath altogether. The polymers of this invention cited here all offer the final advantage of being easily removed by just the action of a strong stream of tap water, followed by a minimal amount of wiping with a soft surface, i.e., sponge. In some cases, no mechanical wiping is required whatsoever when water only is used to remove the coating. The polymers in this example were all coated at a dry laydown of 50 mg/ft.sup.2, 20 or 30 mg/ft.sup.2 carbon from commercial aqueous carbon dispersion, "Aqua Black", 3 mg/ft.sup.2 Olin 10G, and 1 mg/ft.sup.2 Zonyl FSN. The wet laydown was 4 or 5 cc/ft.sup.2, and a heat setting mode of machine coating was employed as in the previous example. All the coatings were coated on bare cellulose triacetate support without a subbing layer. For the purpose of this demonstration, a wax overcoat was not placed over this layer as is commonly done in the trade, although such a layer may be employed, as well as lubricants and aqueous wax dispersions coated as an integral part of these layers. Table 3 lists the observations made during the two separate processes used to evaluate removability of the coatings. Process 1 was designed to approximate the process as it is practiced in the trade. It was executed by immersing the film strips for 15 seconds in a "pre-bath" at 106 F. that consisted of 20 g sodium borate hexahydrate and 100 g sodium sulfate in 1 liter of water, without agitation, followed by 15 seconds in a tap water bath at 106 were withdrawn from the water bath, they were placed under a vigorous stream of tap water at 105 the last traces of polymer-carbon matrix. The latter operations represent the water spray and mechanical wiping common to many machine processor. The term "stays on" in the pre-bath means that no coating was removed spontaneously, where "stays on" in the water bath means no coating was seen to come off under the flow of tap water. The term "comes off" in the pre-bath means that even a small portion of the coating was removed (an undesirable trait), and in the water bath it means that some began coming off without agitation, and the remainder came off under the water flow and gentle wiping (a desirable trait). The terms have the same meaning for process 2 (water only) which consisted of 15 seconds immersion followed by the strong water stream and gentle wiping. In both processes, there were instances where the flow of water alone completely cleaned the film, and these cases are indicated with an asterisk. All of the polymers cited here can be removed with water alone, as opposed to the check, which must be treated in the pre-bath. Polymer C is particularly interesting because it is compatible with both processes, and washes clean without additional wiping. Even the control (J) must be wiped for complete cleanliness in process 1. For initial acceptability in the marketplace, it may be advantageous for the coating to be compatible with either process. TABLE 3______________________________________Removal of Antihalation Back Coat Process 1 Process 2Polymer Pre-Bath Water Wash Water Only______________________________________A Stays on Comes off Comes offB Stays on Comes off Comes offC Stays on Comes off* Comes off*D Stays on Comes off Comes offE Stays on Comes off Comes offF Comes off -- Comes off*G Stays on -- Comes offH Stays on -- Comes off*I Stays on Stays on Comes offJ Stays on Comes off Stays on______________________________________ *Indicates complete cleaning by water flow only A = TBA:SSA70:30 B = TBA:SSA80:20 C = TBA:SSA90:10 D = TBA:IPA:SSA70:20:10 E = TBA:IPA:SSA45:45:10 F = TBA:CDAS60:40 (CDAS = 2carboxy-1,1-dimethyl-ethyl-acrylamide, sodium salt) G = TBA:CDAS70:30 H = TBAA:APM65:15:20 I = TBA:APM80:20 J = CAP6 (control) The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. FIG. 1 illustrates the heating and cooling viscosity curves for a prior gelatin and water solution. FIGS. 2, 3, and 4 illustrate the heating curves for materials of the invention. FIG. 5 is a heating and cooling viscosity curve of a material of the invention. FIGS. 6-13 illustrate heating and cooling viscosity curves of materials of the invention. This invention relates to polymer compositions that, in water, reversibly gel or thicken in the temperature range of about 0 In particular, the invention relates to polyacrylamides. There exist today many examples of polymers derived from natural, as well as synthetic sources, that exhibit thermoreversible gelation. By this term we mean a temperature-induced change in the viscous flow properties of a polymer in a solvent which results in the reversible formation of a rigid solution, or gel. The most notable of the naturally derived polymers having this property is gelatin which has been used as a protective colloid for light sensitive silver halides and other components of photographic films. Aqueous solutions of gelatin when cooled below about 38 upon heating. FIG. 1 shows this behavior viscosity plotted against temperature ( A limiting property of gelatin in the photographic industry is its relative insolubility in common organic solvents (e.g., acetone, methanol, ethanol). This restricts the components that film builders can use in photographic products. Another limiting property is the narrow temperature range in which gelatin forms a gel in water (0 Successful photographic film-making currently requires cooling the gelatin coating layers in order to retain their integrity while water and other volatile materials are removed in the drying stages. This increases the drying time and cost of the film manufacturing process. The following articles describe polymer compositions showing reversible heat-thickening properties in water: In J. Am. Oil Chem. Soc. 1977, 54, 110--Schmolka, I. R. and J. of Molecular Liquids 1984, 27, 165--Rassing, J. et al, the gelation of polyoxyethylenepolyoxypropylene, ABA block copolymers when 20-30% w/w aqueous solutions are heated from a cold melt at 5 20 In Macromolecules 1989, 22(3), 1397--Tanigami, T. et al, a poly(organophosphazene) gelled in water when a 5.4% solution was heated from a cold melt at 0 was accompanied by a cloud point (the gel was opaque and the cold melt was clear). In Macromolecules 1989, 22(1), 367--Westra, J. G., the heat-thickening properties of a polysaccharide, xanthan, are described. In J. Applied Polymer Science 1961, 5(17), 519--Jeanes, A. et al, polysaccharide B-1459 showed heat-thickening properties in water in the absence of added salts at a concentration of 1% w/w. Although heat-thickening in water has not been observed in prior art of synthetic polyacrylamides made by vinyl polymerization, some polymers derived from acrylamides and methacrylamides are known that mimic gelatin (form gels on cooling which melt on heating). U.S. Pat. No. 3,396,030--Haas, H. C. et al discloses acylglycinamides with these properties and U.S. Pat. No. 2,486,192--Minsk, et al describes imidized polyacrylamides that gel on cooling. It has been proposed that polymers be utilized as additions to gelatin or as a substitute for gelatin in photographic film formation. In U.S. Pat. No. 2,533,166--Jones, it was proposed that polyacrylamides be utilized as substitutes for gelatin in silver halide emulsions. These materials were not reported to gel or heat-thicken. In U.S. Pat. No. 2,968,558--Clavier et al, a thermoreversible gel formed by copolymerization of acrylic acid and acrylonitrile was claimed for use as a total or partial substitute for gelatin in photographic systems. In U.S. Pat. No. 2,486,192--Minsk et al, an imidized polyacrylamide was suggested as a synthetic reversible gel for use in photographic materials. In U.S. Pat. No. 2,522,771--Barnes, polyvinyl alcohol, in combination with other substrates such as amino acids, diketopiperazines, proteins, gelatin, casein, and albumin is reported to form thermoreversible gels. It would be desirable in manufacturing photographic film to accelerate the drying time by having polymers that when coated from water, either alone or in combination with gelatin, could be dried at a higher temperature. This would require polymers whose aqueous solutions (1-20% weight percent polymer in water) heat-thicken, i.e., show increasing viscosities with increasing temperature. By "increasing viscosity" we mean both moderate increases in which flow can still be observed or large increases resulting in the formation of gels. Polymers that heat-thicken in water may find utility as partial or complete substitutes for gelatin in other areas of photographic film manufacture as well, e.g., interlayers, overcoats, subbing layers, and in silver halide emulsion preparation. In the manufacture of photographic films, it would be desirable to have polymers that in one temperature range heat-thicken in water and in another temperature range, like gelatin, lose their viscosity with increasing temperature (FIG. 2). Polymers having this type of viscosity-temperature profile would allow the film builder to select different coating temperatures depending on whether chill-setting or heat-setting was preferred before drying. An object of this invention is to provide novel thermoreversible gels. It is another object of this invention to provide methods of forming aqueous heat-thickening thermoreversible polyacrylamides having varied peak viscosities between 0 It is a further object of this invention to provide polymers whose aqueous solutions form low viscosity melts in two temperature regions separated by a third region of maximum viscosity. It is another object of this invention to provide thermoreversible polyacrylamides derived from predominantly hydrophobic monomers whose peak viscosities in water occur at or below 20 heating and which chill-set on cooling. It is another object of this invention to provide novel polymers for coating photographic film layers. These and other objects of the invention are generally accomplished by providing a polymer that has a hydrophilic group and a hydrophobic group. The hydrophilic group is a polymerizable water soluble ionic vinyl monomer, and the hydrophobic group comprises an acrylamide or methacrylamide monomer that can undergo free radical polymerization, which is insoluble in water, or forms homopolymers that are insoluble in water or which form polymers that exhibit LCST (lower critical solution temperature) properties. Many polymers upon heating precipitate from solution causing a sharp drop in both viscosity and light transmittance. The temperature at which this occurs is called the lower critical solution temperature (LCST). The preferred polymers of the invention are those represented by the general Formula 1: --(A).sub.x '--(B).sub.y '-- (1) wherein A represents recurring units derived from one or more hydrophobic N-substituted acrylamide or methacrylamide monomers of the general Formula 2: ##STR1## wherein: X=H, CH.sub.3 Y=H, n-propyl (optional when Z=n-propyl) Z=alkyl substituents having 3 to 6 carbons including: (a) 3-carbon saturated substituents: isopropyl, n-propyl, cyclopropyl (b) 4-carbon saturated alkyl substituents: n-butyl, sec-butyl, iso-butyl, t-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl (c) 5-carbon substituents: n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,2-dimethylpropyl, cyclopentyl, 2,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1,3-dimethylcyclopropyl, 2-methylcyclopropylmethylene, 1-methylcyclopropylmethylene, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl cyclobutylmethylene (d) 6-carbon saturated alkyl substituents: n-hexyl, cyclohexyl, all branched saturated isomers of hexyl, all branched saturated isomers of substituted cyclohexyl, cyclobutyl, and cyclopropyl having a total of 6 carbons, (e) stereoisometric and optically active forms of the above groups (a-d) (f) phenyl or 1,1-dimethyl-3-oxo-butyl (g) combinations of the above groups, (h) heteroatoms on the hydrophobic fragment. When (A) in general Formula 1 represents a single hydrophobic N-substituted acrylamide (rather than a combination), and Y of general Formula 2 is H, then x' has the following restrictions: (a) 3-carbon substituents x'=96 to 99.9 mole % (b) 4-carbon substituents x'=50 to 95 mole % (c) 5-carbon substituents x'=40 to 95 mole % (d) 6-carbon substituents x'=40 to 95 mole % When (A) represents a single hydrophobic N-substituted acrylamide and Y=Z=n-propyl, x'=50-99.9 mole %. When (A) represents combinations of the groups designated by Z, x' (the total mole % of the combination) ranges from 50 to 99.9 mole %. y' in general Formula 1 ranges from 60 to 0.1 mole %. B in general Formula 1 represents recurring units of one or more ionic hydrophilic vinyl monomers of the general Formula 3: ##STR2## wherein: ##STR3## arylene, alkylene, combinations of alkylene and arylene --CO--, --C═N--, --S--, nitrilo, and heterocyclyl containing one or more N, O, S; and combinations of the above groups with alkylene chains Y=an ionic group including heterocyclic ionic groups such as imidazolium, thiazolium, pyridinium, as well as ionic groups such as --NH.sub.3.sup.+, --NH.sub.2 R.sup.+, --NHR.sub.2.sup.+, --NR.sub.3.sup.+, =NR.sub.2.sup.+, CO.sub.2.sup.-, SO.sub.2.sup.-, --SO.sub.3.sup.-, --O.sup.-, --OPO.sub.3, and --SR.sub.2.sup.+, wherein R=lower alkyl of 1 to 10 carbons, and associated counterions of these ionic groups, e.g., halide, alkali metal, ammonium, etc. It should be understood from the general description that the hydrophilic (B) portion can be selected from any class of vinyl monomer having an ionic group that can undergo free radical polymerization, including vinyl ketones, N-vinyl amides, N-vinyl lactams, vinyl imidazoles, vinyl pyridines, vinyl sulfones, vinyl ethers, vinyl esters, vinyl urylenes, vinyl urethanes, vinyl nitriles, vinyl anhydrides, vinyl imines, vinyl imides, vinyl halides, vinyl aldehydes, styrenes and substituted styrenes, vinyl naphthalenes, vinyl heterocycles containing oxygen, nitrogen, or sulfur and combinations of these heteroatoms, acrylamides, methacrylamides, acrylates, and methacrylates. Representative monomers include sodium acrylate, N-3-aminopropylmethacrylamide hydrochloride, p-styrenesulfonic acid sodium salt, N-3-dimethylaminopropylmethacrylamide hydrochloride, N-vinylimidazole hydrochloride, vinyl pyridine hydrochloride, N-2-sulfo-1,1-dimethylethylacrylamide sodium salt, and 2-aminoethylmethacrylate hydrochloride. In addition, (B) in Formula 1 can be derived from vinyl monomers known to undergo free radical polymerization which can undergo a subsequent reaction resulting in the formation of an ionic group, e.g., by hydrolysis, or by pH induced protonation or deprotonation. An example would be maleic anhydride which can be hydrolyzed by standard hydroxide base to give a carboxylate salt. It should also be understood that Y in general Fromula 3 can contain one or more ionic groups of similar or opposite charge. Other examples of anionic and cationic monomers are listed in Research Disclosure 19551, July 1980. The hydrophilic monomer B of Formula 1 bearing an ionic group represented by Formula 3 may be partially substituted with other hydrophilic ionic monomers having the same or opposite charge as represented by Formula 3, or by hydrophilic nonionic monomers not represented by Formula 3. The substitute ionic or nonionic hydrophilic monomer may comprise up to 59.9 mole percent, as long as the ionic content represented by B is present in at least 0.1 mole percent. The substitute ionic or nonionic hydrophilic monomer can be selected from virtually any class of vinyl monomer capable of undergoing free radical polymerization. Representative monomers include but are not limited to acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and 2-hydroxyethylacrylate. See Research Disclosure 19551 for other examples. The substitute ionic or nonionic monomer may also be derived from any other monomer used to make the polymer, which can include hydrophilic monomer B of Formula 1 or hydrophobic monomer A of Formula 1, either by subsequent pH induced change in ionization or chemical modification of the polymer after polymerization. In addition, the hydrophobic monomer A of Formula 1 may be partially substituted with other hydrophobic monomers represented by general Formula 2 or by other hydrophobic monomers not represented by Formula 2, to an extent generally less than 40 mole percent and most preferably less than 20 mole percent. These can be selected from any class of vinyl monomer capable of undergoing free radical polymerization. They may also be derived from any other monomer used to make the polymer either by subsequent chemical modification of the polymer or by pH induced change in ionization to give an uncharged rather than ionic form. The substitute hydrophobic monomer may be one that is either insoluble in water, or form homopolymers that are insoluble in water, or form homopolymers that exhibit LCST properties. Other vinyl monomers having either hydrophobic or hydrophilic properties may be incorporated as well, as long as one maintains the proper overall hydrophobic-hydrophilic balance according to the designations for x' and y' in Formula 1 above. Cationic, anionic, and mixed anionic/cationic heat-thickening polymers are prepared by combination of monomers from the above general classes of materials. For a given polymer in water, the position and magnitude of the peak viscosity will depend on molecular weight, concentration, presence of added salts, hydrophobic-hydrophilic balance of comonomers, polymerization solvent, pH, rate of heating or cooling, the presence of organic cosolvents and their concentration, compositional heterogeneity (monomer distribution), and shear rate. All of these factors effect the shape of the viscosity/temperature curve. As observed in FIG. 5, the viscosity vs. temperature curve for a heated sample can appear quite different from the curve obtained by cooling the sample through the same temperature region (hysteresis). Curve A was observed by heating the polymer obtained in Example 1, concentration 3.2% w/w in water, at a rate of 1 from 5 strain and at an oscillating frequency of 10 rad/sec. Curve B was obtained by cooling the same sample under identical conditions from 75 to 5 solution has been cycled back to the starting temperature. This is a Continuation of application Ser. No. 742,784 filed Aug. 8, 1991, now abandoned, which is a continuation-in-part of our earlier filed application U.S. Ser. No. 502,726, filed on Apr. 2, 1990 now abandoned. Patent Citations
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Regional News: Gulf of Mexico
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Petrobras Touts Record Production at GOM Cascade, Chinook Fields
Thursday, March 06, 2014 Petrobras announces record-levels of production at Cascade and Chinook fields.
BP Questions US Court's Decision on Oil Spill Payments
Tuesday, March 04, 2014 BP disputes decision made in a US appeal court to reject the company's move to halt payments under 2012's Economic and Property Damages Settlement relating to the Macondo oil spill.
InterMoor Wraps Up Decommissioning Ops in GOM Gomez Field
Monday, March 03, 2014 InterMoor successfully completes decommissioning operations of the Innovator platform in Gomez field, Mississippi Canyon Block 711, Gulf of Mexico.
Oil Flows from Third Phase of Na Kika
Monday, February 24, 2014 Production from the third phase of BP's Na Kika project comes online in the deepwater Gulf of Mexico.
Gulf of Mexico Lease Sales 231, 225 to Offer 40 Million Acres
Thursday, February 13, 2014 Bureau of Ocean Energy Management is set to hold two consecutive lease sales in March.

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Front End Web Developer jobs - West Seattle, WA
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Mar 08 | Front- End Web Tester - Temp | Nordstrom | Seattle, WA |
be responsible for testing complex front-end interactive web applications and ... on web-based production applications* Front-end testing across multiple platforms,... more |
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motivated Senior Front End Web Application Developer.Job Responsibilities/Duties:* ... companies.Job RequirementsSenior Front End Web Application Developer... more |
Mar 07 | Front-End Web Developer | Rylem | Seattle, WA |
position for a Front-End Web Developer at Pulitzer Prize-winning ... years of experience in a front-end engineer, web developer, UI developer, or... more |
Mar 06 | Junior Front End (web) Developer | Efinancial | Bellevue, WA |
The Front End Developer is responsible for implementing and maintaining the front-end ... are provided by the marketing team, the front end developers role is to bring life to... more |
Mar 05 | Front End Web Developer | Temporary Contract | Seattle, WA |
is looking for a self-motivated front end Web Developer to join their team. At ... Editing Tools (Illustrator, Photoshop), Web Font Embedding, · SEO Basics, Responsive Web... more |
Mar 05 | Sr Front End Web Developer | CompuCom | Seattle, WA |
DayOne Benefits(SM)! As a Sr. Front End Web Developer with the Pacific ... Knowledge of Sr. Front End Web Developer—Seattle, WA—1 Year Contract Did... more |
Feb 21 | Immediate Req:: Front End Web Developer | Rgen Solutions | Redmond, WA |
and skills 3+ years of web front end development experiences Solid software ... web applications In-depth understanding of web fundamentals C#,ASP.NET,MVC, HTML, CSS,... more |
Feb 20 | Front End Web Developer | Volt Workforce Solutions | Seattle, WA |
Front End Web Developer If you enjoy playing video games, our client has the perfect Web ... discuss this job with you: 300249GWDJ - Front End Web Developer and include the web... more |
Feb 19 | Front End Web developer (JavaScript development - Need Locals) | Venturesoft Global | Bellevue, WA |
Feb 05 | Web Developer II | Big Fish Games | Seattle, WA |
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Calipers, Digital
Digitally precise calipers makes reading easy and accurate. Ideal for those new to reading calipers and drafting classes.
MAIL: KELVIN®, 280 Adams Blvd., Farmingdale, NY 11735 USA PHONE: 1-800-535-8469 or 1-631-756-1750 FAX: 1-800-756-1025 or 1-631-756-1763 EMAIL: email@example.com• Request A Catalog
Copyright ® 2013 • KELVIN L.P. Registered trademarks of KELVIN L.P include, but are not limited to: KELVIN®, Kelvin Electronics®, Kelvin Technology™, Hands-On Science®, Build A Better Mousetrap Racer®, Join the Rat Racer®, And the Winner Is…®, New Standards® Modular Labs, and SUMO® Car.


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Cardinal Health Specialty Solutions on Monday announced the acquisition of privately held Sonexus Health, a Dallas-based company that offers a range of patient access and specialty commercialization services.
Procter & Gamble's Oral-B has announced the launch of an oral care app for children — the Disney Magic Timer App by Oral-B.
SodaStream, a manufacturer of home beverage carbonation systems, announced that it has entered into an agreement with Sunny Delight Beverages Co., a producer of juice-based drinks. The companies will co-develop flavors like SunnyD Tangy Original Orange and Orange-Strawberry exclusively for the SodaStream system.
The L'Oréal Foundation and UNESCO have announced that they will present the L'Oréal-UNESCO For Women in Science awards to five women scientists on March 19 in Paris.
Peapod last week announced the opening of a new fulfillment facility in Agawam, Mass., to better serve the needs of consumers from Hampshire and Hampden counties.
Pfizer is recruiting for a 1,200-patient actual use study to measure whether or not patients can appropriately self-select treating high cholesterol with the statin Lipitor, the Wall Street Journal reported on Sunday.
Skin care company derma e has introduced its first sun care products — Antioxidant Natural Sunscreen SPF 30 Oil-Free Face Lotion and Body Lotion.
Teva Pharmaceutical Industries announced the launch of Adasuve (loxapine) inhalation powder in a 10-mg dosage. The drug is the first and only orally inhaled medicine for the acute treatment of agitation associated with schizophrenia or bipolar disorder in adults.
The Food and Drug Administration last week ruled that generic equivalents to Teva Pharmaceutical's Plan B emergency contraceptive can be sold alongside Plan B without any behind-the-counter merchandising restrictions or a requirement to verify the age of the purchaser in a letter to the interested parties.
The Little Clinic, which operates 114 retail-based health clinics in seven states, has selected VisualDx, a mobile app and online resource used by doctors to diagnose and treat disease, to enhance the care its staff provides to patients, VisualDx maker Logical Images announced.


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- Jun 25, 2012 | 6:55 PM EDT
Author Comments
Nothing special, i know, but i wanted to do this after i saw preatty funny gif.
Dont post its badly done and poor shaded >
Rated 1 / 5 stars June 27, 2012
The thing is, and I see you seem to have figured this out, this shouldn't be a movie. It should be an animated gif. I think the idea is funny, but as a movie, I can't justify giving it a good rating, sorry.
Rated 3 / 5 stars June 26, 2012
good concept and decent crack at it but you need sound and bullet casings. perhaps add a few bits of sweat on the brow and some face animation too
Rated 1.5 / 5 stars June 25, 2012
It's really just a simple animation. Some sort of sound would of atleast kept this out of blam territory with me (I'm not that hard to impress. xD) but this really has nothing to redeem beyond the fact that it's not the ugliest thing I've ever seen. I can tell that's Pinkie... in fact I don't think it's poorly shaded, it's just there is nothing really to the animation.
how i was thinking, i should post it as 100x100 gif... Its made for gif, not for swf in this quality.


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I would guarantee that SEC would gladly take A&M independent of OU and Texas. By just adding A&M, the SEC would gain the Dallas-Fort Worth (#5 TV market in US), Houston (#10), and San Antonio (#37) tv markets. It would be easy for them to find another school from the east to match A&M. The SEC's total population of states they have schools in is just over 57,000,000. There are over 24,000,000 people in Texas alone, and the SEC would love to branch into Texas.
Originally Posted by Matador96 5. Just because you want the Big 12 (Temp 10) to stay together, doesn't mean it will. The Big 12 (Temp 10) will break up--it's simply a matter of time. It may be 10 years down the road, but this conference just screams "One Night Stand". If the conference makes it two years, it will be around a long, long time. If recent TV deals are any indications, the Big 12 will be signing 25-year deals and the buyout clauses will be heavy.
"Don't worry Boss...they can't do nothin' 'til they're through sparklin'..." Avatar - America's new superhero...Cenex Guy
Anybody notice ATM = automatic teller machine $$$$$$$
Originally Posted by woodie tell the aggies to go **** themselves and get houston, memphis, and either bring in nevada,and one of the new mexico schools. a and m has always been a pain the arse.they they stole the biotech research firms from iowa state that iowa state should have had.. i worked for an aggie once.he was one of the most pompus(sp) b******ds i ever worked for.they aggies think they are something if they have been in the corp.i know i once worked for one and he always strutted like an ostrich.i put him in his place because i got promoted to his same level as a vice president and i did not work for him.that was sure a nice promotion. Do Vice Presidents ever use capitals?
Originally Posted by cykadelic2 Regarding #3, it was foolish/stupid for A&M to make a needless publicity stunt out of the penalty money until there was actually a meeting to iron out the details. That meeting had yet to take place. Regarding #4, you are insulting the intelligence of B12 ADs and Presidents by calling Beebe a snake oil salesman. Those ADs and Presidents were not going to buy into any type of flimsy numbers coming from Beebe as well as the TV networks. Regarding #6. no news there. The TX legislature had scheduled hearings before UT made their decision to stay with the B12. As Pac-10 Commish Larry Scott admitted, the political pressure in his opinion was the primary reason why UT stayed. I tend to disagree with that, UT was not sold on the Pac-10's TV numbers and UT wanted their own branded TV network while retaining their own video/media rights. You've missed your guess on a few things. 3. A&M made the release at the time it did to show that they are not a puppet to UT, which is what their fanbase not only wants, but demands. They could have done this privately, and it would have been given a private response. However, by going public, you are making Beebe go public as well. A&M, like many in the Temp 10 view Beebe as a whipping boy for DeLoss Dodds. And, as I pointed out, A&M is broke, and needs to show its fanbase it is trying to correct their financial issues. 4. No, Beebe is HORRIBLE. But to your point. 5 of the ADs/Presidents would do anything, and apparently give up money, just so they would have a conference to play in. 3 of the ADs/Presidents were about to get a hell of a payday. 2 were ******. Look, as a Tech fan, I get it. We didn't have a "stand alone" offer from the PAC 10. Fine. But that does not mitigate that Beebe sold the remaining 8 schools a bill of goods. All he did was take the already crappy TV deal, and let the remaining schools have more of it. He had "consultants" give "projections" on future TV revenues. No TV deal has been signed or has taken place, and yet he "guarantees" certain schools a minimum revenue stream if they would stay. He is promising future money on a deal that hasn't been negotiated. ENRON just called, they love that idea. And another sign of his weakness. When Tubs was critical of his "leadership" on a Tuesday morning, Beebe didn't issue a reprimand until literally 4:50 on a Friday before a 3 Day Holiday Weekend. That, if nothing else, says "I am really, really weak." It certainly not leadership. #6. Welcome to Election Season in Texas, of which I have managed more than my fair share of campaigns. The "hearing" you speak of was a regularly scheduled Higher Education Committee Hearing, and the agenda can be changed up to 24 hours before the hearing begins. The Hearing was political posturing, plain and simple, and it worked. UT and A&M cannot do anything to upset the Lege. With a mandatory 10% budget cut for FY '12 and '13, they simply cannot risk damaging any relationships with the Lege. Tech is in line to recieve Tier 1 status, and join A&M and UT as the only schools in Texas to earn that honor. It has already been suggested that the reason Tech didn't blow the whole thing up was that it has been promised Tier 1 status as a delayed quid pro quo--but I doubt that. IMO, UT views itself as equal to or greater than Notre Dame. It really does want to be an independent, but realizes that in a changing college athletic landscape, it cannot. So, it is in the next best position. It traded independent status for it's own conference. This will only hold water for so long. Hitching your wagon to Dan Beebe will not take you where you want to go. As some on this board has suggested, I would begin being proactive in making myself more attractive to other conferences. I'm not saying you are not, but like Tech, OSU, and the reamining North schools, sticking your head in the sand and hoping things work out is not the best strategy. And, as most of you know, everytime you hear someone say they are committed to the Big 12, or whatever it is going to be called, just think of this phrase: "I did not have sexual realations with that woman." It's the same line, just in different context.
Originally Posted by JonDMiller It bought ISU time, and hopefully it brought them closer with MU, KU, KSU, etc, to realize that they are in the same boat. If those schools stick together, they will have solid options in the future. Maybe not as much money as they would being in a league with Texas, but they will have time to plan for it. I think that ISU, Mizzou, KU, Baylor, and KSU realize from the last realignment fiasco, that as a package, they hold more value than as individual institutions. Conference realignment is all about football TV revenue, so KU's dominant MBB team doesn't add up to a hill of beans in this discussion. If the Big 12 blows up, I hope the "forgotten five" stay together and keep the Big 12 alive long enough to collect all the fees due from the schools leaving; which would add up to way more than $100 million in today's TV market. Enough money, I would say, to reform the Big 12. If super conferences start forming, I hope the penalty money would be enough to entice a school like Notre Dame to join a reformed Big 12. Just my opinion.
P.J. Farmer rocks!
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Alice Medrich's House Truffles
1 lb. semisweet chocolate, coarsely chopped10 tbsp. unsalted butter, cubed
⅛ tsp. salt
2 egg yolks, at room temperature
⅓ cup Dutch-process cocoa powder
1. Line an 8" x 8" baking pan with foil; set aside. Melt chocolate, butter, and salt in a 2-qt. saucepan over low heat, stirring frequently until smooth, 8 to 10 minutes; transfer to food processor and set aside. Place the yolks in a bowl, and whisking constantly, slowly pour in ½ cup boiling water. Strain and add to chocolate mixture; puree until smooth. Spread evenly into prepared pan; chill until firm, about 1 hour.2. Place cocoa powder in a bowl. Invert chocolate block onto cutting board; discard foil. Cut into 1" squares, toss with powder, and arrange in a single layer on a parchment paper-lined baking sheet; chill until set, 10 to 15 minutes.
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Ratings & Reviews (6)
I loved the idea of enriching with egg yolks. I tried 4 different versions of this recipe and prefer these changes:
instead of one pound semisweet chocolate I used a combination of 12 ounces semisweet chocolate and 4 ounces bittersweet chocolate.
Instead of 1/2 cup boiling water I used 6 T. water boiled with 2 T. Grand Marnier and then added 1 rounded T. instant espresso coffee.
My other suggestion is to let inverted chocolate block rest 1 minute before slicing, as it might crack.
Thank you Alice Medrich and Saveur!
for real 1/2 cup boiling water ?
easy recipe that will make tastier and better-quality chocolates than what you can pick up at the big name stores at least, and depending on the type of chocolate you use, compares nicely to some of the expensive boutique kinds. seems like there are a lot of ways to alter it too; i added a bit of natural sugar to the top before i chilled it and a tablespoon or two of confectioners' sugar to the cocoa for their coating. i would say that they need longer than one hour to chill initially however. i went ahead and made them as flimsy as the middle was, next time i'll let them sit longer.
Easy recipe! I let the truffles sit in the fridge over night,then on the counter for 10 minutes before cutting. I like that these truffles don't have to be made into balls, but rather just cut into squares. A lot less messy that way!
OMIKEO- the boiling water cooks the egg yolks - a really smart way to simplify the recipe.
These are fantastic. Must now give many away, or we'll eat them all...


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Bio: Age 32, Male, Amsterdam, Netherlands
Entrepreneur and networker with a passion for events and social media | Owner Vivo.nu | Co-Founder of Triqle Event Intelligence | Partner of How Can I Be Social (HCIBS) | Eventprof | Public speaker
Main strenghts: enthusiasm, execution power, analytics and communication.
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a place for zinesters - writers and readers
If there's a new zine by someone you haven't read before, what is it in a zine that might make you want to read it? Is it a the cover? the way the zine is presented? Personally, what draws me would be a catchy title, that will make me wonder what the zine is all about.
© 2014 Created by Krissy PonyBoy Press. Powered by


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You are currently not logged in, do so now to add comments, like articles as well as photos, submit to competitions, translate articles and gain access to unlimited photo upload! If you are not registered yet, go here to find out more about Lomography and join now! If you just want a limited account for now you can use Twitter or Facebook. We would love to have you as a member here!
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How to add the social networks to the sidebar
- go into the customization screen by clicking customize on the right hand side of your dashboard.
- Once on this page click the themes tab at the top of the page, then click "use custom html" at the bottom of the little window that opens.
- In the custom HTML pane scroll down until you find this
- Follow the instructions provided and uncomment whicever social networks you wish to use.
- Enjoy Ultralite.
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Stary Eyed


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How many episodes it takes to finish a fight. (It's like that joke: how many saiyans does it take to change a light bulb? One but it takes 12 episodes.)
The filler episodes.
The same old one liners that come up over and over again.
I don't particularly like how the show seems to mostly be about Naruto. Granted the show is named after him. But with so much focus predominantly on one character, it gets kinda difficult to see the character development of a lot of the other characters.
Lack of variety during his fights. The multi shadow clone jutsu I understand. Rasengan a little. But anytime you can predict what persons actions will be for any three fights in an episode you haven't seen before, and be right, something's wrong.


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Melt & pour method. Made loads & loads using essential oils, shimmer powders and occasionally some dried lavender or rose petals! They made great gifts!
Tags: crafts
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Jib City Nights at Mountain High
Posted 01/11/2011 04:09:25 by Kelly
Come out and enjoy a night of snowboarding the Mt. High park, bbq and some cool prizes starting tomorrow night, Wednesday, January 12th and happening twice a month until the end of April. We will pick several features in the park throughout the night for some jams and hand out prizes to riders at each feature. The party in the park starts at 5 pm.


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This page contains Jeanne D'Arc Unlockables for PSP called "Visit to the graveyard" and has been posted or updated on Aug 28, 2007 by Lonewolf1991. Let us know what you think of this Unlockable by thumbs voting.
- Developer: Level 5
- Publisher: SCEA
- Genre: Strategy Turn-Based Historic
- Release Date: Aug 21, 2007
- ESRB: Teen
Visit to the graveyard
Complete the game once, save your game and load your completed game save. A new map, The Graveyard, will appear. Now go to the colosseum and fight through 10 battles. You will receive a piece of equipment (a pendant) that nobody seems to be able to equip. Visit the Graveyard with the pendant, and a special event will occur.
Back to all Cheats
Stuck on this game? Set a specific, clearly defined question and let others answer your question or view answers to previously asked questions. If you think you are an Jeanne D'Arc expert then please try to help others with their questions.
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"This christmas card was just beautiful, the colors are so vibrant and festive and the paper quality is fantastic. I was really pleased with this product adn would reccomend it others looking for a holiday card that will stand out from teh rest."
"A nice layout to showcase a small collection of pictures. Used semi-glossy stock, and was really pleased with how the pictures "popped." Rounded corners completed the look."
"This card turned out so nice. I used a collage of family photos and used the "vintage" option to change the look of the photos a little. I love that Tiny Prints has that option. The neutral colors allow me to send these out for Chanukah, Christmas or New Years. I am extremely happy with my holidays cards."
"The quality was beautiful, the pictures were clear and the printing did not reduce the clarity of the picture at all. I paid for rush and got them 2 days later. Very, very happy. So happy in fact, I ordered more the same I got my cards int he mail."
"There was just enough space to fit our family's two last names legibly. Opted for rounded corners and used photos from a family photo shoot to create a cohesive look. Everyone loved the cards, and the colors and options were great."


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Package Delivery Services Key Terms
Pick up a bundle of package delivery services key terms
Key terms in the package delivery service industry discuss special charges, such as accessorials. They also name required documents, like a bill of lading and certificate of origin. New technological methods and software in the package delivery system have created a new vocabulary. Key package delivery terms describe new delivery methods, as with rate-shopping software. Some terms, such as LTL shipper, describe the actual package carrier. Make sure you understand the following terms to make the right choices for your business.Accessorials
Bill of lading
A bill of lading is a document used by package delivery carrier services. This document is the record of receipt from the carrier for the packages being shipped.Certificate of origin
A certificate of origin is a special document used by the package delivery service industry specifying where the product originated. This is a necessary document that some countries require in order for a package to clear the country's customs system.Less than truckload (LTL) shipper
A less than truckload (LTL) shipper, as opposed to a truckload (TL) shipper which only operates with full truckloads, is a package delivery carrier that combines small shipments from different shippers. These packages are collected at specially placed hubs.Rate-shopping software
Companies use rate-shopping software to find the least costly carrier for packages needing delivery. The software determines the carrier based on the package's weight and final destination.Tariff code
A tariff code is a set of numbers, consisting of a six to 10 digit number code, that is specific to certain types of products. The World Customs Organization determines the code and it is used for tax purposes on packages shipped internationally.Copyright © 2014 Business.com, Inc. All Rights Reserved.
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"Great Service, price and experience. THANKS KEVIN!"
Print your own elegant greeting cards, announcements and invitations with heavyweight quarter-fold greeting cards. Simply design on your computer and print with your inkjet printer. Cards are scored for easy folding and include matching envelopes. Made of high-quality, matte-coated stock for vivid color and photo printing. Great for party invitations, birthdays, holidays, announcements and much more.


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Empress Audio
Serving all your audio needs.
If you're looking for superior car and truck accessories in Gulfport, your search ends here: Empress Audio has all of the car accessories and mobile electronics you need under one roof! We specialize in providing local vehicle owners with an impressive selection of car audio equipment, remote starters, marine electronics, and more. Our sleek, aftermarket car stereo components will give your car, truck, or SUV the boost it needs. Offering impeccable installation services for all of our brand-name car accessories, we'll have you riding around town in style. Combined, we have over 30 years of experience selling and installing a full range of car GPS systems, car alarms, and more. We're committed to providing you with unbeatable quality in every way imaginable. So give your dowdy sedan or frumpy minivan the jump-start it needs—call or visit Empress Audio today!
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Founded in 1975, Empress Audio has been a family business for more than 36 years. Our talented installers and friendly staff are committed to delivering the very best when it comes to quality mobile electronics products and installation. From car alarm systems to marine electronics to remote starters, our varied selection suits a wide variety of customers. We're dedicated to treating our customers with the highest form of customer care, regardless of which services you require. You'll be able to count on us for the car GPS system, mobile video player, or window tinting you need to have your car looking and performing its best. And when it comes to installation, our experienced professionals simply can't be beat. To get your free estimate, call or e-mail us right away!
For your extra protection and peace of mind, Empress Audio is fully insured. We're also members of the Mobile Electronics Specialists of America (MESA), and we proudly support Brewers Little League.
Empress does it all // audio // video // tinting // accessories


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An online petition looking to grab the attention of the folks who hand out the Oscars hopes they can gather enough signatures to honor a 27-year-old former Columbia woman who was killed while filming a movie in Georgia.
Sarah Elizabeth Jones, a camera assistant, died when she was struck by a train last week while working on the Gregg Allman biopic, "Midnight Rider".
The petitioners are hoping they can get the Academy to add Jones to the annual Academy Awards Memoriam, a segment that honors former actors, actresses, directors, and film workers who died over the course of the previous year.
"Crew members are the unsung heroes of film and television production who work long hours and sometimes very dangerous conditions for the love of filmmaking," said the petition. "Sarah Elizabeth Jones was one of us."
The petition runs until Feb. 28 at 10 a.m. So far, it has garnered closed to 14,000 signatures and has already met several signature goals.
Mourners have also taken to Twitter to call for greater safety measures on film shoots through the hashtags #SlatesForSarah and #SafetyForSarah.
A memorial will be held for Jones on Wednesday at 4 p.m. at the Ashland United Methodist Church in Columbia. There will also be celebration of Sarah's life at 5 p.m. at Saluda River Club.
Copyright 2014 WIS. All rights reserved.
635 W. 7th Street Cincinnati, OH 45203 Switchboard: (513) 421-1919 Newsroom: (513) 421-0119 Press releases: firstname.lastname@example.com
FCC Public File firstname.lastname@example.com 513.421.1919 EEO Report Closed Captioning


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cycling is life, i love cycling, cycling, Radfahren, Radsport, cykling, pyöräily, cyclisme, rothaíocht, ciclismo, sykling, wielrennen, sykling, jazda na rowerze, tour spain, tour france, wielrenner, cycle racer, cyclist, coureur cycliste, Radsportler, ciclista
This great product in purple/white from our department Men and T-Shirt category can be printed just for you in the size and style you like. The design cycing is life - retro was created by Nowhereman78 and uploaded to Spreadshirt for you to have printed on a T-Shirt. Next to a host of other great designs, you can find this cycing is life - retro design in Spreadshirt's Cycling category. If you are interested in topics like CICLISTA or Radsport, then you'll love cycing is life - retro designs by Nowhereman78. Spreadshirt also offers a huge selection of t-shirts, jumpers and accessories for the category Cycling as well as top Radsportler clothing. Nowhereman78's designs have already impressed many of our customers, so we are sure that we've got right stuff for you! Spreadshirt is your address for great designs of all kinds – whether it's CICLISTA, Radsport or Radsportler. We are sure that you will find something nice in our shop, there are many amazing Cycling t-shirts, jumpers or accessories for you to find!Tags: Design ID: 14691876
Hi, if you like to contact me: jekanhetdakop at msn.com
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Sporty and feminine. Tailored in slightly body-huggging fashion and with shorter sleeves, our Contrast T-Shirt will help you cut a good figure when combined with skirts, hot pants or trousers alike. Contrasting skirtings on collar and sleeves lend a retro charme á la 1965 to this high-quality item. The fabrics are made of pre-shrinked single jersey, which gurantees both top comfort-wear and wash resistence. Double-stitched seams on the hems and a fabric weight of 175 g/m2 make sure this shirt will defy the perils of time. 100% cotton.


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Archived Story
Thanks for helping Hormel retirees
Published 3:25am Thursday, May 16, 2013Letter to the Editor
The Hormel Foods retirees group wishes to thank the following merchants for their generous donations for our drawings at our May 14 breakfast: Berg's Nursery, Dolan's Landscaping and Nursery, Hy-Vee Garden Shop, Jim's Marketplace, Jim's Super Fresh, Johnson Floral, Shopko Garden Shop, Sterling Main Street Garden Shop, Walgreen Drug and Walmart Garden Shop.
All of the recipients appreciate your gifts and thank you very much.
Charlie Valdahl and Duane Olson,


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iSedora is designed to easily play your digital media — movies, broadcast recordings, music albums, photos, podcasts, audiobooks and the others — on TV or any DLNA compatible device. Using iSedora is simple: just install it, point out where you store the media and forget about it. No more effort is required to access the media from anywhere in your house: simply turn a TV on and select what you want to play by a remote control.
Keeping iSedora easy to use means getting it more powerful inside. Whenever you are playing any piece of media, iSedora does the best to bring you extra quality of content rendering. Playing Full HD movies with 5.1 digital sound or viewing hundreds of photos seems a trivial task for your TV or other DLNA compatible device when communicating with iSedora. Moreover, iSedora is able to render media to multiple devices simultaneously, revealing all its inner power to keep your home smarter.
iSedora comprehends your media files, no matter which of dozens of existing formats you choose to store your collection. iSedora follows up your DLNA devices and performs intelligent transcoding of media files if these are not playable by a device natively. While fine-tuned to work best with Sony Bravia TV, PlayStation 3 and Microsoft Xbox 360, iSedora makes all its efforts to harmonize with any DLNA-compliant gadget.
With iSedora being constantly tested upon clouds of media types, formats and codecs there is just a small chance of some file being not playable. In case it actually happens — or any other trouble occurs — feel free to report a problem to iSedora Development Team. We'll trace your issue asap and release a new iSedora version fixing the point or introducing a new feature. Greater part of latest public updates was inspired by iSedora users' requirements. Read their feedback below or leave your own.
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Native support for Sony Bravia TV | Yes | Yes | Yes |
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August 17, 2005
Moultrie - Two six year old boys made the frightening discovery. Underneath the house at 404 East Central Avenue, lies a 6 year old boys dream of a playground. There are places to crawl in the dirt, toys to play with, and the unknown to explore, but on Tuesday, that exploration revealed a human skull.
Linda Turner, who lives in the house, says, "It's like living on a graveyard, and you don't even know it. (Is it scary?) Yes, it's scary."
She said she looked out the window and made a frightening discovery of her own. "All kind of police and investigators. A crowd, people come from all around when something's going on, and I'm in the house and didn't know what was going on, and when I looked out, that's when I saw everybody out here," says Linda.
That's when investigators removed the skull. Police say it appears the skull has been there for a while, but no other body parts were found. Linda says, "Had to of happened years ago."
It's unknown who's skull it was, how it got there, or if foul play was a factor in the person's death, but neighbors hope the mystery will soon be solved.
The skull has been sent to the GBI crime lab for testing to determine the sex, race, and age, and ultimately who the person was.
comments: email@example.com


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Seagulls Resort on the Seafront
Travel Blogs from Townsville
Bowen and Townsville
... and Torre Straight people known as the aboriginals in Australia. It was noticeable that there was a big community of aboriginal descendants living in Townsville. The centre was really interesting, learning about the tribes and what happrned after white folk settled in oz. there was some beautiful art work up in the gallery too. We took a trip up Denham street, which just had to be done! Scott was in his element we took lots of photos for the ...
Townsville - exploring
... tin roof. A much tougher life for sure. They were masters of recycling though and making do with what they had. The crates stacked together and dressed simply with fabric to form Dad's armchair. Crates stacked to make kitchen cupboards; even inserting the kero boxes with rudimentary handle for drawers. It was a reminder of the basic lifestyle they would have lived. A simpler existence. We were too busy talking with and listening to Roy to think about photos, so none for ...
Magnetic Island
When we were staying at Townsville we went to Magnetic Island. We had to catch a boat to the Island, the boat ride to Magnetic Island took about twenty minutes to get there. We left the pier at 9.00, the boat was pretty slow at the start, it got a little faster once we came out of what was a bit like a sea channel. On the boat ride to ...
Time in Townsville
... the city and is giant 286 metres red rock. You get terrific views of the city, Cleveland Bay and Magnetic Island.
We also managed to get a walk in along The Strand which stretches about 2.5 Kms along Cleveland Bay. Great views of Magnetic Island. The Strand is looking much better than it did when we were last here two years ago. They were doing major works on the beach and The Strand. These works are all completed and The Strand and the beach look great.
Magnetic Island
... I really liked it. It's long but I think it's worth the watch, even if you just pay attention long enough to check out Hugh Jackman dumping water all over his body ;). The first night we got here there were bar wars at the bar, so we made a team and competed in little competitions like dizzy bat, blowing up a balloon til it popped while its between someone's legs, putting a bucket on a persons head with anything but hands, and ...
- Swimming pool
- Restaurant
- Wheelchair accessibility
- Business Services
- Free parking
- Kitchenette


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MLB Trade Rumours: 5 Moves Yankees Could Make Not Involving Ubaldo Jimenez
By Jordan Lewis ,
Ubaldo Jimenez has been among the top tier players on the trading block in the last couple of weeks, and as the days remaining to the trade deadline get fewer and fewer, and the Rockies' asking price for their ace evades a markdown of any sort, I feel very confident in saying that the Yankees will not have Ubaldo Jimenez on the roster on August 1.
These are the same Yankees who are considered the front runners for the hurler by many highly acclaimed sports writers across the nation.
Oddly enough, many of these same writers have noted that Yankees GM Brian Cashman has noted that top prospects Dellin Betances, Manny Banuelos, Austin Romine, and Jesus Montero are going nowhere.
Even more oddly enough, the Rockies have requested three of the four untouchables in return for Jimenez, and have also publicly noted, according to ESPN's Jayson Stark, that they would need "three sure-thing young players, including one pitcher who goes into their rotation immediately". The starter to be immediately put into their rotation would likely be Ivan Nova.
Seeing this indicates that although the Yankees may be the number one contenders for Jimenez at this time, there is an obvious wall that both teams will eventually run into. Hopefully the Yankees don't value Jimenez so highly that they be inclined to break through this wall, conceding to the Rockies' outrageous demands for their overrated starter.
This all being said, I firmly believe that Cashman is a wise GM and, if nothing else, understands the value that his top prospects offer to the welfare of the Yankees' lineup, or to future trade possibilities that wouldn't be as lopsided.
Here are five acquisitions Cashman could make to the Bombers instead.
Although Kuroda has stated that he doesn't particularly want to leave the West coast, and he has a full no trade clause to veto any trade offer that he sees, the Dodgers believe, according to Danny Knobler of CBSsports, that Kuroda could be persuaded to waive his no trade clause.
What is the best tool for persuasion I wonder?
Enter Brian Cashman.
Knobler maintains that an incentive of $1-2M to waive the no trade clause could be in order, and with $6M of his $12M contract being owed to him after the deadline, the price of Kuroda steadily rises.
However, the Yankees print money, and with a 3.19 ERA, 6.9 K/9, 2.3 BB/9, 0.99 HR/9, and 43.2% groundball rate in 127 innings its a small price to pay.
Especially when you consider Jimenez stats in 2011. A 4.20 ERA, 8.6K/9, 3.5 BB/9, .70 HR/9 line is far too similar to Kuroda's, with significantly higher walks per nine innings, and ERA, to yield New York's most coveted prospects.
Assuming Kuroda is like most other human beings, and can be squired by money incentives, I expect that New York could make an offer to LA (one that would likely require none of their top prospects) and Kuroda could be in pinstripes before August 1.
The Yankees have been subtly searching for a lefty reliever in hopes to land a cheap hurler who can take some of the pressure off of Boone Logan, as well as provide a strong solution for left handed hitters.
According to the New York Post, Chicago had scouts at the Yankees' game last night, which makes the acquisition of the 33 year old reliever a bit more realistic.
Grabow has allowed only 15 hits, 1 HR, 8 RBI, a .238 BA, and .314 OBP to left handed hitters in 2011, making him a very attractive, cheap left handed relief option for the Yankees.
New York will be certainly making a move for a lefty relief pitcher or two, and Grabow is one of the best available options and would cost very little to acquire.
Gio Gonzalez has looked like an ace this year in Oakland's rotation, posting a 9-7 record, with a 2.67 ERA, and 124 K's in 124 innings of work.
He is among one of the up and coming top tier starting pitchers in the league, and although Oakland hasn't opened up talks for their ace yet, there is still a great deal of hope that the Yankees would be able to sway Billy Beane into favour of trading him.
Gonzalez is at the end of his contract, which pays him $420,000 this year.
If Beane wants to keep him, its going to cost him a great deal more that that, and he can expect Gonzalez would be looking for at least 3-4 years in a new contract, giving him anywhere from $8-12M per year.
The father of the Moneyball strategy isn't characteristically a man who would offer a contract of this nature, and an offer including one of New York's coveted starters in Manny Banuelos, or Dellin Betances is a reasonable trade that would benefit both organizations.
The Yankees wouldn't have to part ways with the kind of prospects that Colorado is looking for, but could send one away and get a young, lights out starter to follow up CC Sabathia in the rotation.
Look for talks of this trade to surface any time between now and Sunday.
Tyler Clippard is an ex Yankee, and as New York looks to bolster their bullpen up a little bit for the final stretch, the righty with a 1.73 ERA, and 72 K's through 57.1 innings could share innings with Rafael Soriano upon his return, and provide security in the late relief innings while Soriano eases his way back into the bullpen, or even be shifted to a middle relief position to setup for Soriano, who could enter games in the 7th or 8th innings.
Clippard's 57.1 innings is the most of any pitcher in the Yankees' bullpen, and his 1.73 ERA is within 20 points of David Roberton - New York's most effective relief pitcher - with almost 20 more innings of work.
The Nationals have made it public that Clippard is on the block according to Ken Rosenthal of Fox Sports, and with the recent struggles the Yankees' bullpen have been having you can bet New York will have their eyes on Washington's setup man.
With Edwin Jackson's recent relocation to Toronto, the White Sox starter has officially been put on the trading block, according to Fox Sports' Ken Rosenthal.
The Yankees haven't opened discussions with the Chicago club yet, but in their search for an adequate starting pitcher and with a deal for Ubaldo Jimenez seeming more and more unrealistic, you can be certain Danks will be on New York's radar.
Danks is a point under a 4.00 ERA, posting 3.99 in 101 innings with 71 K's and only three wins, but Danks has posted three straight seasons prior to 2011 with a sub 4.00 ERA and is coming off of a 15-win season.
With the way that the Yankees' bats have been performing in 2011, Danks will have a lot of support and would look to greatly increase his win percentage.
Although Gio Gonzalez would be a better option for New York, Oakland has yet to open talks about him, and he would come at a much higher price than Danks, who could be a suitable starter in the third spot in the rotation for the Yankees for a cheaper price.
Expect the Sox and Yankees to open discussions on Danks in the next couple days, and if the price is right for Brian Cashman, don't be surprised to see a deal for the young starter be completed.