|Publication number||US6136882 A|
|Application number||US 09/349,074|
|Publication date||Oct 24, 2000|
|Filing date||Jul 8, 1999|
|Priority date||Aug 19, 1998|
|Also published as||CA2279164A1, CA2279164C, DE69921747D1, DE69921747T2, EP0980901A2, EP0980901A3, EP0980901B1|
|Publication number||09349074, 349074, US 6136882 A, US 6136882A, US-A-6136882, US6136882 A, US6136882A|
|Inventors||Andrew T. Daly, Jeno Muthiah, Richard P. Haley, Owen H. Decker, Eugene P. Reinheimer, Matthew B. Snyder|
|Original Assignee||Morton International Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (21), Referenced by (17), Classifications (15), Legal Events (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a CONTINUATION-IN-PART, of copending application Ser. No. 09/136,184filed on Aug. 19, 1998 U.S. Pat. No. 6,011,080.
This invention relates to ultraviolet (UV) radiation curable powder coating compositions. More particularly, this invention relates to UV curable powder coating compositions containing crystalline resins adapted to prevent hazing in the coating formed therefrom when cured at low temperatures.
Powder coatings have gained considerable popularity in recent years over liquid coatings for a number of reasons. Powder coatings are virtually free of harmful fugitive organic solvents and, therefore, give off little, if any, volatiles during curing. This eliminates solvent emission problems and creates a healthier environment for workers employed in the coating operations. Powder coatings also improve working hygiene, as they are in dry solid form and have no messy liquids associated with them which adhere to workers' clothes and coating equipment. They are relatively non-toxic as well and can easily be swept up in the event of a spill without requiring special cleaning and spill containment supplies. Another benefit is that they are virtually 100% recyclable. The oversprayed powders are normally reclaimed and fed back into the original powder feed during the coating operation, leading to high coating efficiencies and minimal waste. Yet, despite such advantages, traditional thermosetting powder coatings have not been suited for coating heat sensitive substrates, since the temperatures at which these powders must be cured are usually higher than the heat sensitive substrate can withstand.
With the increased desire to coat heat sensitive parts with powder coatings and realize the foregoing benefits, recent emphasis has been placed on developing powders that permit polymerization or curing at lower temperatures. One class of low temperature-cure powder coatings recently developed for heat sensitive substrates are UV curable powder coatings. Such UV curable powders can be formulated to melt-flow and cure and produce desired smooth glossy coatings at much lower temperatures than had ever been possible with traditional thermosetting chemistry, which is primarily due to the curing reaction being initiated solely by ultraviolet radiation rather than heat. The UV curing mechanism also enables production of the powders in traditional melt-blending equipment and storage at room temperature without triggering unwanted prereaction.
UV curable powders are typically prepared from solid unsaturated non-crystalline base resins, solid unsaturated non-crystalline crosslinker resins, solid photoinitiators, flow additives, other performance-enhancing additives, and optional pigments and inert fillers. It is also common to replace some or all of either the base or crosslinker resin with a crystalline material, as taught, for example, in EP 0 636 669 to DSM. One UV powder coating promoted by DSM that is presently preferred employs a blend of a non-crystalline base resin and a co-reactive crystalline crosslinker resin. Specifically, it comprises a stoichiometric blend of a solid, relatively polar, unsaturated amorphous (non-crystalline) polyester base resin with fumarate or maleate unsaturations and a glass transition temperature (Tg) of about 125° F. (the Tg of the base resin being sufficiently high for desired blocking resistance but still low enough for desired low temperature melt-flow behavior), and a solid, somewhat incompatible, relatively non-polar, crystalline divinyl ether urethane crosslinker resin with a melting point (Tm) of about 195-230° F. (the Tm of the crystalline resin being above the Tg of the base resin and also above traditional melt-processing temperatures to avoid destruction of intact crystal structures during processing and attendant loss in melt-processing efficiency and blocking resistance), together with a solid photoinitiator, flow control agent, and optional pigments. The presence of crystalline ingredients, in particular, has been found highly desired because the powders will exhibit low melt viscosity and excellent flow out behavior during the initial melting stage of the coating process, allowing the powders to readily coalesce into smooth molten coating films which upon subsequent UV curing and develop into exceptionally smooth coatings with desired glossy appearance.
However, one drawback with the use of crystalline materials, particularly crystalline crosslinker resins, having such high melting points (Tm) is that in order to obtain cured coatings with desired smooth glossy appearances, the coating must be UV cured at temperatures above the melting point of the crystalline component. If the temperature of the molten coating after flow out is allowed to drop below the melting point to the point at which the crystalline component visually appears to recrystallize in the coating prior to UV curing, which can happen during transfer of the coated part from the melting to UV curing operation and/or as a result of the coated part having a variable mass, the cured coating will have an undesirable haze or blush on the surface with attendant loss in gloss and smoothness. The haze is believed to result as the crystalline resin component separates out and migrates to the surface of the coating whereupon it is believed to recrystallize back into intact crystal structures. This imparts to the coating a cloudy, rough, matte appearance characteristic of crystalline resins. While this is desirable when making low gloss coatings, it becomes troublesome when trying to control hazing and obtain higher gloss films at low temperatures. Moreover, with increased demand to coat heat sensitive parts that can only withstand temperatures near the melting point of the crystalline ingredient, there is a need to provide a non-hazing UV curable powder coating that can be cured at such low temperatures and still produce a uniform haze-free smooth glossy finish over the part.
The limitations of traditional UV curable powders containing a crystalline resin can be best seen when trying to coat assembled electric motor casings which house a number of heat sensitive components, including working parts and electric circuitry associated therewith. To avoid damaging such components, the melt-flow and curing temperatures must be kept at levels that are only slightly above the recrystallization point. To further complicate the matter, these motor casings tend to have a variable mass. During coating, as the powder is melted at the desired conditions for curing, the heavier mass sections create heat sinks and cause the temperature of the molten coating in these sections to drop below the point at which the crystalline ingredient recrystallizes, while in other sections the coating temperature is kept above the recrystallization point. As a result, the cured coatings produced therefrom have an unacceptable mottled appearance due to the haze appearing around the heavier mass sections, rather than having a consistent smooth glossy coating across the part.
To overcome the hazing and mottling problem, it is possible to use non-crystalline resins alone which do not recrystallize. However, in order to achieve adequate flow out at the low temperatures suited for heat sensitive substrates, the Tg of the non-crystalline resins must be lowered considerably, which would render the powders physically unstable and susceptible to blocking or sintering during storage at room temperature. Powders that block are extremely difficult to meter and spray during the coating operations and lead to inconsistent spray patterns and defects in the coatings. Reducing the amount of crystalline resin, particularly the crystalline crosslinker resin, to levels at which recrystallization does not occur (i.e., below 10 wt. % of the resin system) has also been tried, but at such low levels the powders exhibit poor flow out at low temperatures and produce incompletely cured coatings with severely textured appearances.
It would be desirable to provide an improved UV curable powder coating composition containing crystalline resins adapted to prevent hazing in the coating formed therefrom when cured at low temperatures.
It is, therefore, a primary object of this invention to provide a UV curable powder coating composition containing crystalline resins that do not suffer from the forgoing drawbacks.
It is another object of this invention to provide a UV curable powder coating composition containing crystalline resins adapted to prevent hazing in the coating formed therefrom when cured at low temperatures.
It is related object of this invention to provide a UV curable powder coating composition containing crystalline resins adapted to prevent mottling and impart visually consistent gloss and smoothness in the coating formed therefrom when cured over a broad range of high and low temperatures.
It is a further object of this invention to provide a UV curable powder coating composition of the aforesaid character that is melt-processable, storage stable chemically as well as physically, exhibits a low flow viscosity when melted for curing, and possess the ability to be melt-flowed and cured at low temperatures suited for heat sensitive substrates, all without detracting from the smoothness, gloss, and overall quality of the coating film produced therewith.
In accordance with a broad aspect of this invention, there is provided a melt-processable, storage-stable, low temperature flowable, UV curable powder coating composition containing crystalline resins that exhibits reduced or no hazing in the coating formed therefrom when cured at low temperatures, which comprises a film-forming particulate blend of: A) an unsaturated base resin; B) an unsaturated crosslinker resin co-polymerizable with the base resin; and, C) a photoinitiator, wherein the combination of components A) plus B) comprises a blend of at least one crystalline resin and at least one non-crystalline resin, and the improvement wherein the powder coating composition comprises D) a recrystallization or haze inhibitor for the crystalline component that visually appears to inhibits its recrystallization in the coating after the powder composition is melted for curing and foremost reduces or eliminates hazing in the coating formed therefrom when cured at low temperatures that normally give rise to such hazing.
In accordance with a preferred aspect of this invention, there is provided a melt-processable, storage stable, UV curable powder coating composition containing crystalline resins that is melt-flowable at low temperatures suited for preservation of heat sensitive substrates, e.g., 170° F.-300° F., and exhibits reduced or no hazing in the coating formed therefrom when cured at low temperatures, e.g., about 170° F. or lower, which comprises a film-forming particulate blend of: A) a non-crystalline unsaturated polyester base resin having a Tg above 90° F., preferably a non-crystalline unsaturated polyester having maleate or fumarate unsaturations; B) a crystalline vinyl ether functionalized crosslinker resin co-polymerizable with the base resin having a Tm above 180° F., preferably a crystalline vinyl ether terminated urethane oligomer; C) a photoinitiator; and the improvement wherein the composition contains D) a crystalline epoxy resin which serves as a recrystallization or haze inhibitor having a Tm above 180° F., preferably a crystalline epoxy oligomer compatible with both A) and B), wherein incorporation of component D) reduces or eliminates hazing in the cured coating formed therefrom.
Throughout this specification, all parts and percentages specified herein are by weight unless otherwise stated. Herein, the base resin A) plus crosslinker resin B) plus recrystallization or haze inhibitor D) are considered to be the "resin system" and equal to 100 parts. Levels of other components are calculated as parts relative to 100 parts of the resin system ("phr"). Also herein, "glossy" or "high gloss" means gloss levels of 50 or above on a 60° Gardner Gloss scale. Further herein, "non-crystalline" (otherwise referred to as "amorphous") broadly defines resins which show no or trace crystallization or melting point as determined by differential scanning calorimetry (DSC). While the term "crystalline" includes crystalline as well as semi-crystalline materials and broadly defines resins with a discernable crystallization or melting point by DSC. Lastly, "recrystallization temperature" or "recrystallization point" refers to the temperature at which the crystalline resin component visually appears to separate and recrystallize out of the powder composition after being melted for curing, as evidenced by the visual development of a haze in the coating.
The base resin A) is preferably comprised of at least one unsaturated polyester resin having at least one ethylenic unsaturation site per molecule. The unsaturated polyester resins can be prepared conventionally by condensation of one or more ethylenically unsaturated polyfunctional carboxylic acids (or their anhydrides) having carboxyl functionalities of 2 or greater with one or more polyhydric alcohols having hydroxyl functionalities of 2 or greater. While the unsaturation is typically supplied by the carboxylic acid, it is also possible to supply it through the alcohol. Moreover, the ethylenic unsaturation may be provided in the polymer backbone or at the end of the chain. If it is supplied at the chain end, ethylenically unsaturated monocarboxylic acids (or their esters) are employed in the condensation reaction. Also, whether the unsaturated polyester is carboxyl- or hydroxy-terminated will depend upon the --OH/--COOH ratio employed the monomer mixture. While these saturated reactivities generally do not participate in the curing reaction which proceeds through the unsaturated groups, they are often used to achieve desired chemical and mechanical properties.
Examples of suitable ethylenically unsaturated polyfunctional carboxylic acids (or their anhydrides) include maleic anhydride, fumaric acid, itaconic anhydride, citraconic anhydride, mesaconic anhydride, aconitic acid, tetrahydrophthalic anhydride, nadic anhydride, dimeric methacrylic acid, etc. Maleic anhydride, fumaric acid, or their mixtures are generally preferred because of economic considerations. Examples of suitable monofunctional acids employed for chain end unsaturation include acrylic acid, methacrylic acid, etc.
Often, polyfunctional saturated and aromatic acids are employed in conjunction with the polyfunctional unsaturated acids to reduce the density of the ethylenic unsaturation and provide the desired chemical and mechanical properties to the coating. Examples of suitable saturated and aromatic polycarboxylic acids (or their anhydrides) include adipic acid, succinic acid, sebacic acid, malonic acid, glutaric acid, cyclohexane dicarboxylic acid, dodecane dicarboxylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, pyromellitic anhydride, etc.
Examples of suitable polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propanediol, butanediol, neopentyl glycol, cyclohexanedimethanol, hexanediol, 2-n-butyl-2-ethyl-1,3-propanediol, MP Diol, dodecanediol, bisphenol A, hydrogenated bisphenol A, trimethylol propane, pentaerythritol, etc.
The unsaturated polyester resins can be formulated to have either a crystalline or amorphous microstructure. According to this invention, it is preferable that the resin system of the UV curable powders contain at least about 10 wt. % reactive crystalline material to impart desired low flow viscosity when melted for curing. It is well known in the art that certain alcohol and acid monomers can impart crystallinity to the unsaturated polyesters. For example, symmetrically substituted linear monomers or cyclic monomers or their mixtures are generally used to form crystalline polyesters. Examples of typical dihydric alcohols that are known to promote crystallinity include ethylene glycol, butanediol, hexanediol, and cyclohexane dimethanol. Examples of typical dicarboxylic acids that are known to do the same include terephthalic acid, adipic acid, dodecane dicarboxylic acid, and cyclohexane dicarboxylic acid.
Typically, only solid unsaturated base resins A) are of interest in powder coatings. Solid unsaturated polyester resins typically have a weight average (Mw) molecular weight ranging between about 400 and 10,000, and preferably between about 1,000 and 4,500.
The unsaturated polyesters typically have a degree of unsaturation, preferably fumarate or maleate unsaturation, between about 2 and 20 wt. %, and preferably between about 4 and 10 wt. %.
If the unsaturated polyesters are hydroxyl-functionalized, then the hydroxyl number is usually from about 5 to 100 mg of KOH/gram of resin. If the unsaturated polyester is acid-functionalized, then the acid number is usually from about 1 to 80 mg of KOH/gram of resin.
In a preferred embodiment, the base resin A) comprises a solid, relatively polar, non-crystalline unsaturated polyester resin with maleate or fumarate unsaturations. Accordingly, the reactive crystalline material is preferably supplied by the crosslinker resin B).
Generally, all of the non-crystalline resins useful herein should have a glass transition temperature (Tg) higher than 90° F., preferably in the range of about 110 to 150° F., which is sufficiently high for conventional melt-processing and for the powders to remain solid and not block or sinter during storage at room temperature. Yet, the Tg is still low enough so that the powders pass their softening point and flow freely at temperatures needed to preserve heat sensitive substrates, usually between about 170° F. and 300° F., and preferably between about 170° F. and 250° F.
The unsaturated base resins A) work best in combination with co-polymerizable crosslinker resins B) (otherwise known as curing agents) having ethylenic unsaturation, and preferably having two sites of unsaturation per molecule. Examples of such crosslinker resins include oligomers having ethylenically unsaturated vinyl ether, vinyl ester, allyl ether, allyl ester, acrylate or methacrylate groups, although the vinyl ether groups are generally preferred. These materials are usually available as crystalline resins.
Examples of suitable vinyl ether crosslinker resins include crystalline divinyl ether terminated urethane oligomers. This crystalline oligomer can be prepared by well known techniques, such as by reacting hydroxyl-functional vinyl ethers, such as hydroxybutyl vinyl ether, with crystalline diisocyanates, such as hexamethylene diisocyanate, hydrogenated methylene bis (cyclohexyl) diisocyanate, or biurets or uretdiones thereof. Another suitable vinyl ether crosslinker is a crystalline vinyl ether terminated ester oligomer. This crystalline material can be prepared by conventional methods as well, such as by the condensation of hydroxyl-functional vinyl ethers, such as hydroxybutyl vinyl ether, with crystalline carboxylic acids (or their anhydrides), such as phthalic anhydride.
Other suitable crosslinkers include resins having acrylate or methacrylate groups, such as dimethacrylate terminated urethanes. Again, these materials are usually crystalline resins which can be formed conventionally by reacting hydroxyl-functional (meth)acrylates, such as hydroxyethyl methacrylate and hydroxypropyl methacrylate, with crystalline isocyanates. Allyl ester crosslinkers are also commonly employed, such as the reaction product of allyl alcohol and crystalline carboxylic acids (or their anhydrides), typically phthalic anhydride. Standard crystalline allyl ether crosslinkers include the reaction product of an allyl ether, such as allyl propoxylate, and a crystallizing hydrogenated methylene diisocyanate.
The crosslinker resins B) of particular interest herein are solid materials as well because good powder stability and melt-processability is more easily achieved. The solid crosslinker resins typically have a weight average (Mw) molecular weight ranging between about 200 and 1,000, and preferably between about 300 and 800.
Of course, if these resins are liquids, as with any of the other materials employed in the UV curable powder other than the base resin, they can be converted to solid by absorption onto inert silica-type filler, such as fumed silica, before use, as is well known in the art.
In a preferred embodiment, the crosslinker resin B) comprises a solid, relatively non-polar, crystalline vinyl ether terminated urethane resin. As described above, the reactive crystalline ingredient is preferably supplied by the crosslinker resin B), with the base resin A) preferably supplying the reactive non-crystalline material.
Generally, all of the crystalline resins useful herein should have a melting point (Tm) higher than the Tg of the non-crystalline resins, and preferably higher than 180° F. up to about 300° F. This allows for efficient melt-processing of the powders using conventional equipment and at the same time ensures that the crystalline structures remain intact after melt-processing, which gives the powders the desired powder stability and blocking resistance. Moreover, the Tm is still below the flow temperature required for preservation of heat sensitive substrates.
It will be appreciated by a person of ordinary skill in the art that the relative amounts of unsaturated base resin to unsaturated co-polymerizable crosslinker resin in the UV curable powder coatings will depend on the choice of materials employed. Usually, such materials are employed in stoichiometric equivalent amounts to allow crosslinking to proceed to substantial completion, although excess of either can be used if desired. In general, if the crosslinker is a vinyl ether terminated urethane oligomer and the base resin is an unsaturated polyester with maleate or fumarate unsaturations, as preferred, the crosslinker is used in an amount ranging from 0.5-1.5 equivalents of the vinyl ether unsaturation to 1.0 equivalent of polyester unsaturation, preferably 1.0 to 1.0 equivalents.
To obtain the desired low viscosity melt-flow behavior at temperatures between 170° F. and 300° F., preferably between 170° F. and 250° F., the amount of crystalline resin, whether supplied by the base resin A) or crosslinker resin B), present in the UV curable powders generally ranges between about 10 and 50 wt. % of the total amount of A) plus B), and preferably between about 15 and 25 wt. %, with the balance being non-crystalline resin. Below about 10 wt. %, desired flow behavior at the lower melt temperatures generally cannot be attained. Above about 50 wt. %, recrystallization rates generally cannot be controlled effectively.
Standard free-radical photoinitiators C) are also incorporated in the UV curable powders to initiate photopolymerization of the ethylenically unsaturated compounds. Examples of suitable alpha cleavage photoinitiators include benzoin, benzoin ethers, benzyl ketals, such as benzyl dimethyl ketal, acyl phosphines, such as diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide, aryl ketones, such as 1-hydroxy cyclohexyl phenyl ketone, etc. Examples of suitable hydrogen abstraction photoinitiators include Michler's ketone, etc. Examples of suitable cationic photoinitiators include diaryliodonium salts and copper synergists, etc. Usually the amount of photoinitiator present ranges between about 0.1 and 10 phr, and preferably between about 1 and 5 phr.
In accordance with this invention, in order to reduce or eliminate hazing and maintain a consistent smooth glossy appearance when the powder coating, after having been melted and flowed out for curing, is cured in the molten state at temperatures below the normal recrystallization point of the crystalline resin component supplied by A) or B), preferably supplied by B), a recrystallization or haze inhibitor D) is employed in the resin system of the powder composition. In general, the recrystallization inhibitor D) comprises another crystalline resin that is mutually compatible with the co-reactive generally incompatible crystalline and non-crystalline resins supplied by A) and B). When incorporated in the powder composition, the recrystallization inhibitor visually appears to disrupt recrystallization of the crystalline resin species supplied by A) or B) in the coating and foremost prevents a haze from visibly developing in the coating formed therefrom when cured at temperatures that normally gives rise to such hazing.
The recrystallization inhibitors D) of particular interest herein are solid materials as well. More particularly, this material is a solid crystalline oligomer having moieties that are compatible with both the co-reactive non-crystalline and crystalline materials supplied by A) and B). The crystalline oligomer typically has a weight average (Mw) molecular weight ranging between about 200 and 1,000, and preferably between about 300 and 800. The melting point (Tm) should also fall within the range described above for crystalline materials, i.e., a Tm higher than the Tg of the non-crystalline resins, and preferably higher than 180° F. up to about 300° F. It may also contain unsaturated groups which participate in UV curing, although it typically does not. This component can further be characterized by not being able to recrystallize from a neat melt as shown by DSC in contrast to the crystalline component supplied by A) or B) that is susceptible to hazing.
In a preferred embodiment, where the non-crystalline resin is an unsaturated polyester base resin A) and the crystalline resin is a vinyl ether terminated urethane crosslinker resin B), the recrystallization inhibitor D) is preferably a crystalline oligomer that contains one or more moieties compatible with the relatively polar non-crystalline unsaturated polyester, such as an aryl, e.g., benzyl, substituted aryl, sulfone, ether, glycidyl ether, hydroxyl, ester, and the like which render component D) compatible with the base resin A), and an aliphatic crystalline backbone and a molecular weight (Mw) close to that of the crystalline crosslinker resin B) which render component D) compatible with the crystalline crosslinker resin B).
Most preferably, the recrystallization inhibitor D) is comprised of a crystalline epoxy oligomer that has by definition a glycidyl ether moiety and may contain other moieties listed above as well. It may further contain unsaturated functionalities, although typically only saturated functionalities are present. Preferably, the molecular weight (Mw) of these crystalline epoxy oligomers is less than 800. Crystalline epoxy resins of the aforesaid character can be prepared by well known techniques, such as by the glycidylation of an alcohol containing the aforesaid functional groups and known to have limited rotation with epichlorohydrin. Examples of suitable crystalline epoxy resins useful in the practice of this invention include, but are not limited to, tetramethylbisphenol diglycidyl ether, triglycidyl isocyanurate, dihydroxydiphenyl sulfone diglycidyl ether (bisphenol S diglycidyl ether), 2,5-di-t-butylbenzene-1,4-diglycidyl ether, diglycidyl isophthalate, epoxypropoxydimethylbenzylacrylamide, hydroquinone digylcidyl ether, 2,5-di-t-butylhydroquinone diglycidyl ether, and terephthalic acid diglycidyl ester, etc.
As discussed above, it is also possible to supply the recrystallization inhibitor D) with unsaturated groups which will participate in the UV curing reaction which proceeds primarily through the unsaturated groups. An example of a suitable co-reactive recrystallization inhibitor includes a crystalline vinyl ether containing one or more of the aforesaid moieties such as butanol-4-ethylenyl-oxy-benzoate.
While not wishing to be bound by any particular theory, it is believed that the recrystallization inhibitor inhibits the recrystallization of the other crystalline component by making the other crystalline component more compatible with the non-crystalline resin. In this more compatible blend, the other crystalline resin component visually appears to separate and recrystallize out of the molten coating powder less completely than it does in the absence of the recrystallization inhibitor.
The amount of recrystallization inhibitor D) employed will, of course, depend on the amount of reactive crystalline resin contained in the UV curable powder composition. The amount generally ranges between about 0.1 and 100 wt. % of the total amount of crystalline resin supplied from A) or B), and preferably between about 1 and 50 wt. %.
Other ingredients such as standard catalysts may also be employed to increase the crosslinking rate, such as transition metal compounds based on a fatty acid or oil, or tertiary amines. Cobalt soaps, such as cobalt octoate, cobalt neodecanoate, cobalt naphthenate, and cobalt octadecanoate, are especially preferred. If employed, the amount of catalyst present is typically less than about 1.0 phr, and preferably ranges between about 0.1 and 0.5 phr.
In addition, thermal free-radical initiators, such as organic peroxide and azo compounds, in conjunction with the photoinitiators can also be employed. The presence of thermal initiators alongside photoinitiators has been found to assist in curing down near the substrate, particularly when pigmented, opaque, or thicker film coatings are desired. Examples of suitable peroxide and azo initiators include diacyl peroxides, such as benzoyl peroxide, azobis (alkyl nitrile) peroxy compounds, peroxy ketals, such as 1,1-bis(t-butyl peroxy)-3,3,5-trimethylcyclohexane, peroxy esters, dialkylperoxides, hydroperoxides, ketone peroxides, etc. If employed, the amount of thermal initiator present usually ranges between about 0.1 and about 10 phr, and preferably between about 1 and 5 phr.
Common additives such as pigments and fillers, flow control agents, dry flow additives, anticratering agents, surfactants, texturing agents, light stabilizers, etc., can be used as well. For instance, the UV curable powders made in accordance with this invention can be clear coats (i.e., unpigmented and unfilled) or contain up to about 200 phr, usually up to about 120 phr, of traditional fillers and/or pigments for desired opacity and/or coloration. Examples of suitable fillers include calcium carbonate, barium sulfate, wollastonite, mica, china clay, diatomaceous earth, benzoic acid, low molecular weight nylon, etc. Examples of suitable pigments include inorganic pigments, such as titanium dioxide, and organic pigments, such as carbon black, etc. The other common additives mentioned above are typically present in a total amount up to about 15 phr. Examples of typical flow control agents include acrylic resins, silicone resins, etc. Examples of typical dry flow additives include fumed silica, alumina oxide, etc. Examples of typical anticratering agents include benzoin, benzoin derivatives, low molecular weight phenoxy and phthalate plasticizers, etc. Examples of typical surfactants include acetylenic diol, etc. Examples of typical texturing agents include organophilic clays, crosslinked rubber particles, multiple crosslinkers, etc. Examples of typical light stabilizers include hindered amines, hindered phenols, etc.
The UV curable coating powders employed in this invention are produced by conventional melt-blending techniques. The components are dry blended together, and then melt blended in a single screw or twin screw extruder with heating above the melting of the resin system. The extruded composition is rapidly cooled and broken into chips, ground in a mill with cooling, and, as necessary, the particulates are sorted according to size. Average particle size is typically between about 20-60 microns. Gaseous or supercritical carbon dioxide may be charged to the extruder to lower extrusion temperatures. This is particularly desirable with powders containing crystalline resins. These powders tend to experience drastic reductions in viscosity above the melting point (Tm) of the crystalline materials, which, in turn, undesirably reduces the amount of shearing and mixing action occurring in the extruder, leads to longer processing time while waiting for the crystalline materials to recrystallize and the powder to harden, and also reduces the shelf stability of the powder produced due to destruction of crystal. Thus, extrusion is preferably carried out at temperatures above the Tg of the non-crystalline resins but below the Tm of the crystalline components for efficient melt-processing and desired storage stability.
Once the dry, free-flowing, UV curable powders containing the crystalline resins are produced, they are ready for application onto a substrate to be coated.
The UV curable powders are applied in the usual fashion, e.g., electrostatically, to the substrate. Usually electrostatic spray booths are employed which house banks of corona discharge or triboelectric spray guns and a reclaim system for recycling the overspray powders into the powder feed. The applied powders are next exposed to sufficient amount of heat to melt and flow out into a continuous, smooth, molten film over the substrate. The substrate may be heated at the time of application (pre-heated) and/or subsequently (post-heated) to effect melting and flow out. Heating can be performed in infrared, convection ovens, or a combination of both, although infrared ovens are preferred.
In the initial melting stage, the UV curable powders employed in this invention have the ability to melt and flow out into exceptionally smooth films very rapidly (e.g., in about 5-190 seconds) at very low melting temperatures (e.g., between 170-300° F.), making these powders suited for coating a plurality of heat sensitive substrates. Usually, the flow viscosity is also very low (e.g., around 100-4,000 cone and plate) which helps to produce extraordinarily smooth coatings at the desired flow temperatures.
Immediately following melting and flow out of the powders, the molten powder coating is exposed to UV light, which, in an almost instant, cures and hardens the film into an attractive, durable, haze-free, uniformly smooth and glossy coating across the entire substrate. Standard UV light sources are suitable for curing the coating, such as standard medium pressure mercury-, iron doped mercury-, and/or gallium doped mercury-vapor lamps, e.g., 600-watt Fusion H-, D- and/or V-lamps. Electron beam radiation may be used instead of UV radiation, if desired. Hardening of the coating takes between about 1 millisecond and 10 seconds, and typically less than about 3 seconds. The coating thickness that can be obtained is typically between about 0.5 and 25 mils, and more commonly between about 1 and 10 mils.
The glossiness of the cured coating (measured on a 60° Gardner Gloss scale) is desirably about 50 or above, preferably about 70 or above, with no visually significant drop off in the level of gloss and smoothness across the film when cured at temperatures which the crystalline ingredient supplied by A) or B) would normally separate and recrystallize out in the absence of the recrystallization inhibitor D).
The UV curable powder coatings employed in this invention are particularly suited for heat sensitive substrates. They are also suited for traditional heat resistant substrates. Examples of typical heat sensitive substrates include wood, such as hardwood, hard board, laminated bamboo, wood composites, such as particle board, electrically conductive particle board, high, medium or low density fiber board, masonite board, laminated bamboo, and other substrates that contain a significant amount of wood. These substrates may be filled or primed with UV liquids, powder primers, or solvent- or waterborne coatings to improve smoothness and reduce the required film builds. Other heat sensitive substrates include plastics, such as ABS, PPO, SMC, polyolefins, polycarbonates, acrylics, nylons and other copolymers which usually will warp or outgas when coated and heated with traditional heat curable powders, along with paper, cardboard, and heat resistant composites and components having a heat sensitive aspect, and especially those which have a variable mass, etc. Examples of typical heat resistant substrates, include metal, steel, other alloys, glass, ceramic, carbon and graphite.
This invention will now be described in greater detail by way of specific examples.
The following ingredients were blended and extruded together in the manner given to produce UV curable powder coatings according to this invention that are capable of forming a consistent haze-free smooth glossy finish when UV cured at variable high and low temperatures, along with a traditional UV curable powder coating that is not capable of such results which serves as the control.
__________________________________________________________________________ PHRINGREDIENTS CONTROL EXAMPLE 1 EXAMPLE 2__________________________________________________________________________DRY BLEND UNTIL HOMOGENEOUSUralac XP-31251 (Non-Crystalline) 80 80 80 Uralac ZW-3307P2 (Crystalline) 20 20 20 Epon RSS-14073 (Crystalline) -- 5 -- Ciba RD 97-2754 (Crystalline) -- -- 5 Lucerin TPO5 2 2 2 Resiflow p-676 2 2 2 Shepard Black7 6 6 6CHARGE TO EXTRUDER AND EXTRUDE AT MELT TEMPERATURE OF 180° F. AIR COOL EXTRUDATE AND BREAK INTO CHIPS AND THEN ADDAluminum Oxide C8 0.2% 0.2% 0.2%CHARGE TO MILL AND GRIND TO POWDER SCREEN TO -140 MESH__________________________________________________________________________ Table Footnootes 1 Uralac XP 3125 is a solid, amorphous, unsaturated polyester resin that is believed to be based on fumaric or maleic acid, terephthalic acid and 1,6hexanediol, sold by DSM Resins. The resin individually has a Tg of about 125° F. 2 Uralac ZW3307P is a solid, crystalline, divinyl ether urethane crosslinker resin that is believed to be based on hexamethylene diisocyanate and 4hydroxybutyl vinyl ether, sold by DSM Resins. The resin individually has a Tm of about 223° F. and a recrystallization point of about 176° F. 3 Epon RSS1407 is a crystalline epoxy resin composed of tetramethyl bisphenol diglycidyl ether, sold by Shell Chemical. The resin individuall has a Tm of about 221° F. 4 Ciba RD 97275 is a crystalline epoxy resin composed of bisphenol S diglycidyl ether, sold by Ciba Polymers. The resin individually has a Tm of about 257° F. 5 Lucerin TPO is a solid photoinitiator composed of diphenyl (2,4,6trimethyl-benzoyl) phosphine oxide, sold by BASF. 6 Resiflow P67 is a solid acrylic flow control agent, sold by Estron Chemical. 7 Shepard Black is a black spinel copper chromite pigment, sold by Shepard Color. 8 Aluminum Oxide C is a dry flow additive composed of aluminum oxide sold by Degussa.
Each powder formulation above was electrostatically applied by a corona discharge spray gun onto two separate steel panels that had been pre-heated to different temperatures, i.e., 70° F. and 250° F. The panels were coated at these two temperatures to simulate what happens on a heat sensitive part which has both thin and thick sections which heat up to different temperatures depending on the mass of the part. The applied powders were then allowed to fuse as a result of the residual heat given off by the pre-heated until a smooth continuous molten coating film had been formed. Immediately after fusion, while the film was still molten, the panels were cured by exposure to UV radiation. The cured coatings all had a film thickness of between 2.2-3.0 mils. The coating conditions and performance results are given in the Table below.
__________________________________________________________________________ CONTROL EXAMPLE 1 EXAMPLE 2__________________________________________________________________________Pre-heat (15 minutes) 175° F. 250° F. 175° F. 250° F. 175° F. 250° F.Powder Application 100 kV Corona Gun 100 kV Corona Gun 100 kV Corona Gun UV Cure (1 second) 600 Watt D-Lamp 600 Watt D-Lamp 600 Watt D-Lamp Substrate Q-Panel Q-Panel Q-PanelCoating Temperature 170° F. 242° F. 168° F. 241° F. 168° F. 242° F. at UV Cure Haziness Hazy No No No No No Mottled Haze Haze Haze Haze Haze Smoothness Textured No Heavy No Heavy Slight Orange Orange Orange Orange Orange Peel Peel Peel Peel Peel 60° Gloss 72 90 82 94 77 94 MEK Resistance Slight No No No No No (50 Double Rubs) Rub Off Rub Off Rub Off Rub Off Rub Off Rub Off__________________________________________________________________________
The above results confirm that incorporation of a more compatible crystalline resin into the powder composition alongside the crystalline crosslinker resin prevents a haze from visibly developing on the surface of the coating upon being cured at temperatures at which the crystalline crosslinker resin would normally recrystallize out in absence of the other crystalline ingredient. This enables production of cured coatings with a more consistent smooth glossy appearance especially over a variable mass, heat sensitive part despite having sections of the part cured at different temperatures above and below the usual recrystallization temperature.
The following ingredients were blended and extruded together in same manner as provided in Examples 1-2 to produce another UV curable powder coatings according to this invention that is capable of forming a consistent haze-free smooth glossy finish when UV cured at both high and low temperatures, along with a traditional UV curable powder coating that is not capable of such results which serves as the control.
______________________________________ PHRINGREDIENTS CONTROL EXAMPLE 3______________________________________Crylcoat E52521 (Non-Crystalline) 80 80 Uralac ZW-3307P (Crystalline) 20 20 Epon RSS-1407 (Crystalline) -- 5 Lucerin TPO 2 2 Resiflow P-67 2 2 Shepard Black 6 6 Aluminum Oxide C 0.2% 0.2%______________________________________ Table Footnote 1 Crylcoat E5252 is a solid, amorphous, unsaturated acrylated polyester resin. The resin individually has a Tg of about 140° F.
Each powder formulation was tested in the same manner as provided in Examples 1-2. The coating conditions and performance results are given in the Table below.
______________________________________ CONTROL EXAMPLE 3______________________________________Pre-heat (15 minutes) 175° F. 250° F. 175° F. 250° F.Powder Application 100 kV Corona Gun 100 kV Corona Gun UV Cure (1 second) 600 Watt D-Lamp 600 Watt D-Lamp Substrate Q-Panel Q-Panel Coating Temperature Generally Same As Generally Same As at UV Cure In Examples 1-2 In Examples 1-2Haziness Very Hazy Slight No No Very Haze Haze Haze Mottled Smoothness Slight No Moderate No Orange Orange Orange Orange Peel Peel Peel Peel 60° Gloss 24 86 66 86 MEK Resistance Slight No Slight No (50 Double Rubs) Rub Off Rub Off Rub Off Rub Off______________________________________
From the foregoing it will be seen that this invention is one well adapted to attain all ends and objects hereinabove set forth together with the other advantages which are apparent and inherent. Since many possible variations may be made of the invention without departing from the scope thereof, the invention is not intended to be limited to the embodiments and examples disclosed, which are considered to be purely exemplary. Accordingly, reference should be made to the appended claims to assess the true spirit and scope of the invention, in which exclusive rights are claimed.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3919352 *||May 29, 1973||Nov 11, 1975||Kansai Paint Co Ltd||Powder coating compositions|
|US3988288 *||Aug 21, 1974||Oct 26, 1976||Kawakami Paint Mfg. Co. Ltd.||Powder paint|
|US4859760 *||Dec 7, 1987||Aug 22, 1989||Eastman Kodak Company||Polyurethane powder coating compositions|
|US4973646 *||Apr 9, 1990||Nov 27, 1990||Eastman Kodak Company||Powder coating compositions|
|US4988793 *||May 23, 1989||Jan 29, 1991||Eastman Kodak Company||Powder coating compositions|
|US5019636 *||May 10, 1989||May 28, 1991||Allied-Signal Inc.||Polyester chain-extended vinyl ether urethane oligomers|
|US5160792 *||Feb 4, 1991||Nov 3, 1992||Eastman Kodak Company||Thermosetting powder coating compositions|
|US5168110 *||Feb 15, 1991||Dec 1, 1992||DSM N.V. of Het Overloon||Powder coating based on a carboxyl-functional polyester and an epoxy-functional cross-linking agent|
|US5321063 *||May 19, 1992||Jun 14, 1994||Nippon Oil And Fats Co., Ltd.||Powder coating materials for producing crepe-like coatings, preparation and use thereof|
|US5334455 *||May 26, 1992||Aug 2, 1994||Stamicarbon B.V.||Free-radical curable compositions|
|US5414058 *||Jul 15, 1993||May 9, 1995||Somar Corporation||Powder coating composition comprising conventional epoxides with crystalline epoxides and curing agents|
|US5439896 *||Sep 28, 1993||Aug 8, 1995||Nippon Oil And Fats Company, Limited||Thermosetting powdery coating composition|
|US5635548 *||Nov 5, 1993||Jun 3, 1997||Courtaulds Coatings (Holdings) Limited||Powder coating compositions and their use|
|US5639560 *||Apr 22, 1996||Jun 17, 1997||U C B S.A.||Powder composition of crystalline polyesters containing end methacrylyl groups|
|US5710214 *||Apr 30, 1996||Jan 20, 1998||Ppg Industries, Inc.||Thermosetting powder coating compositions|
|US5740893 *||Jun 3, 1996||Apr 21, 1998||Ntn Corporation||One-way clutch and method of making bearing ring|
|US5763099 *||May 7, 1996||Jun 9, 1998||Dsm N.V.||Binder composition for powder coatings|
|US5811198 *||Oct 27, 1997||Sep 22, 1998||Shell Oil Company||Acid functional and epoxy functional polyester resins|
|US5922473 *||Dec 26, 1996||Jul 13, 1999||Morton International, Inc.||Dual thermal and ultraviolet curable powder coatings|
|EP0636669A2 *||Jul 26, 1994||Feb 1, 1995||Dsm N.V.||Radiation curable binder composition for powder paint formulations|
|WO1996001283A1 *||Apr 28, 1995||Jan 18, 1996||Ppg Industries Inc||Polyester and vinyl ether radiation curable compositions with reactive diluent|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US6410147 *||Aug 24, 2000||Jun 25, 2002||E. I. Du Pont De Nemours And Company||Low gloss crosslinkable coating compositions|
|US6747070 *||Nov 26, 2001||Jun 8, 2004||Degussa Ag||UV curable powder coating compositions|
|US6777027||Oct 8, 2002||Aug 17, 2004||Rohm And Haas Company||Coating powders for smooth, low gloss finishes, and powder coatings formed therefrom|
|US6777089 *||Apr 11, 2000||Aug 17, 2004||Basf Aktiengesellschaft||Radiation-curable composite layered sheet or film|
|US6825240 *||Dec 18, 2002||Nov 30, 2004||Degussa Ag||Radiation curable powder coating compositions and their use|
|US6852765||Jun 7, 2002||Feb 8, 2005||E. I. Du Pont De Nemours And Company||Low gloss free radical powder coatings|
|US6890997||Dec 19, 2002||May 10, 2005||Rohm And Haas Company||Powder coating of free radical curable epoxy resin and another free radical curable resin|
|US6960620 *||Dec 23, 2002||Nov 1, 2005||Degussa Ag||Powder coating compositions comprising crystalline urethane acrylates and use thereof|
|US7241494||Jun 21, 2004||Jul 10, 2007||Basf Aktiengesellschaft||Radiation-curable composite layered sheet or film|
|US7381764 *||Oct 6, 2004||Jun 3, 2008||Bayer Materialscience Ag||Radiation-curing binders containing carboxylic acid esters|
|US7479322||Mar 26, 2007||Jan 20, 2009||Basf Aktiengesellschaft||Radiation-curable composite layered sheet or film|
|US20040068027 *||Dec 19, 2002||Apr 8, 2004||Daly Andrew T.||Free radical cured coating powders for smooth, low gloss powder coatings|
|US20040185259 *||Jan 30, 2004||Sep 23, 2004||Edward Nicholl||Coating powder composition, method of use thereof, and articles formed therefrom|
|US20040224162 *||Jun 21, 2004||Nov 11, 2004||Basf Aktiengesellschaft||Radiation-curable composite layered sheet or film|
|US20050080174 *||Oct 6, 2004||Apr 14, 2005||Thomas Facke||Radiation-curing binders containing carboxylic acid esters|
|US20050137279 *||Feb 4, 2005||Jun 23, 2005||E.I. Du Pont De Nemours And Company||Low gloss free radical powder coatings|
|US20050153070 *||Nov 29, 2004||Jul 14, 2005||Decker Owen H.||Low gloss free radical powder coatings|
|U.S. Classification||522/107, 427/180, 522/104, 428/480, 522/170, 522/108, 522/109, 522/179, 522/93, 522/174, 522/106|
|International Classification||C08F2/46, C09D167/06|
|Jul 8, 1999||AS||Assignment|
Owner name: MORTON INTERNATIONAL, INC., ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DALY, ANDREW T.;MUTHIAH, JENO;HALEY, RICHARD P.;AND OTHERS;REEL/FRAME:010109/0254;SIGNING DATES FROM 19990628 TO 19990707
|Apr 26, 2004||FPAY||Fee payment|
Year of fee payment: 4
|Aug 29, 2005||AS||Assignment|
Owner name: ROHM AND HAAS CHEMICALS LLC, PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MORTON INTERNATIONAL, INC.;REEL/FRAME:016480/0091
Effective date: 20050722
|May 5, 2008||REMI||Maintenance fee reminder mailed|
|Oct 24, 2008||LAPS||Lapse for failure to pay maintenance fees|
|Dec 16, 2008||FP||Expired due to failure to pay maintenance fee|
Effective date: 20081024


text:
The selected performance is NOT available for sale.
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Nolte Academy: 2019 Vocal & Acting Showcase
Tuesday, May 28, 2019 at 7:00PM
The Coralville Center for the Performing Arts
1301 5th St
Located inside Plaza on 5th, at the corner of 5th St & 12th Ave
An end-of-the-year theatrical extravaganza featuring Nolte Academy’s Voice, Acting and Musical Theatre students. This evening of repertoire will feature senior solos, senior intensives and plenty of crowd-pleasing songs and vignettes to delight.

domain: entertainment


Abacus Consultants understands the importance of keeping our clients and stakeholders informed about our latest news and developments. We regularly update our Media page with the latest news and insights, We value transparency and believe in fostering open communication, and our Media page is one of the ways we achieve this.
Browse through the archives of press releases to stay up-to-date with the latest developments at Abacus Consultants. You can also read what the print and electronic media has to say about us, which offers valuable insights into our reputation and standing in the industry. Visit Achievements and recognition by ABACUS Consultants
We would like to pay our sincerest gratitude to all the family, friends, and especially our team for being a constant source of encouragement and support for our journey.
Abacus Consultants added another feather in its cap with the announcement of the opening of its new office at Ajmer Road, Jaipur.
The inauguration of the office was a mega event and the presence of Mr. Pratap Singh Khachariyawas, the Transport Minister of Rajasthan, graced the occasion as he attended the event being our respected chief guest.The special media coverage made it quite an exceptional occasion for all of us. We take great pride in sharing that our inauguration event was super successful and was also featured in multiple leading publications like Dainik Bhaskar, Rajasthan Patrika, Daily News, Dainik Jagaran, etc.


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Horoscope for today
Going on a short trip for pleasure is strongly advised. Take this opportunity to enjoy a gourmet meal or an expensive outing. You're long overdue for a treat. Ask a luxury loving friend along for the ride; they'll be a great travel companion. If you're looking for romance, you'll find it with a sophisticated admirer. You'll learn a lot from your partner about art, music and literature. Are you already in a relationship? Arrange a romantic outing that is catered to your amour's taste.Obey your conscience at a glamorous event. If someone makes offensive remarks, don't just stand there and smile. Simply state your displeasure and walk away. People who admire your courage will sing your praises. You'll gain a reputation for being a decent, trustworthy person. Your relatives have tremendous respect for you. They always come to you for advice and moral support. Take this opportunity to encourage a loved one to pursue a career in the arts. Your encouragement will work wonders on their confidence.

domain: artistic


text:
Nurses say they have to work off the clock at MethodistMay 19, 2014 Updated: May 19, 2014 10:11pm
Houston Methodist Hospital has been sued for allegedly requiring its nursing staff to work off the clock through its practice of automatically deducting a 30-minute lunch break.
One of its former nurses, Joy Corcione, is seeking permission from a local federal court for collective action on behalf of more than 5,000 co-workers. Her lawsuit alleges the giant hospital system owes back wages to the nurses, nursing assistants, patient-care assistants and associates because they're required to respond to patient calls, meet with physicians and perform other work duties during their lunch breaks.
Sometimes nurses and other patient-care workers don't get to eat lunch because they are too busy, the lawsuit claims.
The hospital system responded in a written statement that it makes sure to pay employees "appropriately even if their lunch is interrupted to care for patients" and that Methodist officials "take great strides to ensure a fair compensation process and a fair work environment."
"We will address any claims during the litigation process," the statement read.
Under federal labor law, employers do not have to pay for lunch breaks when employees are not working. But it's considered work time when employees are still on duty answering calls, checking email and doing other work-related activities even through they're also eating a sandwich or sending personal text messages.
The lawsuit, which covers seven Methodist locations in the Houston area, alleges that nurses do not clock in or out from their lunch breaks but that the payroll system automatically deducts the 30-minute break.
Galvin Kennedy, an employment lawyer with Kennedy Hodges in Houston who is representing Corcione, said his initial research found many large hospitals use a similar time-tracking system that automatically deducts time for meal breaks.
Kennedy said he also found from talking to nurses at Methodist that they routinely work through lunch. It's rare when they have an uninterrupted 30-minute lunch break, he said.
While the nurses and other patient-care employees can file a form indicating they worked through lunch on a particular day, Corcione's lawsuit says they are discouraged from correcting the hours on their time sheets.
But nurses are committed to their patients, and when a patient calls for help or family members or the attending physician stops by, the nurse is still on duty, he said.
The case has been assigned to U.S. District Judge Gregg Costa, who will decide whether to certify it as a collective action. Nurses and others patient-care employees will then receive notices asking if they'd like to opt in. Only employees who do so can share in any settlement.
It could be a significant amount of back wages, Kennedy said, estimating that a couple of hours of overtime each week for a nurse earning $40 an hour could work out to about $6,000 a year.
To read this article in one of Houston's most-spoken languages, click on the button below.
Kennedy is seeking three years of back wages and damages that would double the back-pay award.

domain: law


text:
NEWS: Facebook - K-OTIC Reaches 5000 Likes
5000 LIKES and growing. Thank you to everybody who has LIKED my Facebook page. A lot of you guys show me love and support and it never goes unappreciated. Within the next month or so expect the release of a few tracks I produced, some more news and updates, and more.
Visit K-OTIC's Facebook page and support me by clicking the LIKE button.


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The U.S. Supreme Court denied the Georgia attorney general’s request to lift a stay of execution a federal appeals court issued less than an hour before Warren Hill was to have been executed Tuesday evening for a 1990 murder.
The justices in Washington offered no reason, simply writing Thursday that the application to vacate the stay was denied.
A panel of the 11th U.S. Circuit Court of Appeals voted 2-1 Tuesday to stop Hill’s execution to consider his appeal based on “new evidence” that the experts who testified in 2000 that he was not mentally retarded and was eligible for the death penalty had now changed their opinions. A psychiatrist and two psychologists who worked for the state recently told Hill’s lawyer that they had been rushed to make an evaluation 13 years ago, that they are now more experienced than they were then and there had been advances made in the profession’s understanding of mental retardation.
Hill was been sentenced to die for beating to death his cellmate at a prison where Hill was already serving a life sentence for murdering his 18-year-old girlfriend in 1986.
Enjoy expanded coverage of college football for UGa, Tech and the SEC, with our SEC Insider, covering all Southeastern Conference matchups and articles by AJC staff and regional newspapers that cover the SEC.

domain: news


text:
The newly retrofitted pier is located at the existing ferry, Song Thuan linking Song Thuan Commune in Tien Giang Province’s Chau Thanh District and Phu Tuc Commune in Ben Tre Province’s Chau Thanh District, about 9 km from the current Rach Mieu Bridge. The ferry stop worth VND70 billion (US$3 million) includes items of a waiting room, a ticket box, the embankment, an access bridge, a floating pontoon bridge.
In addition, the construction of a path leading to Rach Mieu temporary ferry stop has been kicked off at a capital of VND41 billion (US$1.7 million). The street running from the National Road 57C to the ferry station is designed for vechicles that weigh about 10 tons and have a speed of 60km per hour.
There are around 18,000 vehicles per day and night across Rach Mieu Bridge on the National Road 60 connecting provinces of Tien Giang and Ben Tre. The operation of Rach Mieu temporary ferry stop before the lunar New Year helps ease Tet overload and aims to meet the increasing travel demand of people while waiting for the completion of the new Rach Mieu Bridge No.2.
Rach Mieu Bridge No.2 is a cable-stayed bridge connecting Tien Giang and Ben Tre provinces. The bridge is designed with four lanes and will have a total length of 17.5 kilometers and be 17.5 meters in width with a total investment capital of more than VND5,000 billion (US$221 million). The project’s construction will be kicked off in 2021 and completed by 2025. It is expected to help reduce the traffic overloading on the current Rach Mieu Bridge.
At the opening ceremony

domain: geography


CMMG AR-9 Bolt Rebuild Kit for 9mm Bolt
Manufactured by CMMG
The CMMG 9mm Bolt Rebuild kit contains the most commonly broken, lost, or worn parts for the AR-9 bolt including firing pin, firing pin spring, extractor, extractor roll pin, and firing pin retaining pin. All parts have been made to MIL-SPEC standards.
TypeSpare Parts Kit


text:
(Earlier news on this development here)
Bloomberg | December 18, 2007
U.S. Working on New Pacific Trade Accord, People Say
By Mark Drajem
Dec. 18 (Bloomberg) — The Bush administration is preparing to negotiate an agreement linking the U.S., Chile, Singapore, Brunei and New Zealand in a Pacific-region accord to reduce barriers to trade and foreign investment, according to lobbyists briefed by the U.S. trade office.
Talks with the four nations will start as early as next month, the U.S. Trade Representative’s office has told lobbyists. The administration envisions the accord, which may be left to the next president to complete, as forming the core of a broader agreement among Pacific-rim nations, the lobbyists said.
``Senior officials are holding exploratory discussions,’’ said Stephen Norton, a spokesman for the trade office. ``We are consulting closely with many countries on possible paths toward Asia-Pacific regional integration.’’
While Congress earlier this month approved a trade agreement with Peru, lawmakers such as presidential candidate Senator Hillary Clinton are balking at similar accords with Colombia, Panama and South Korea. Clinton, former Senator John Edwards and Republican candidate Mike Huckabee all pledge to rework U.S. trade policy if elected president next year.
Even so, the administration is pushing ahead with the new plan. Officials say that otherwise the U.S. will be left behind as Asian nations, led by China, put together their own agreements, cutting out American companies and exports. New Zealand and China are set to complete a free-trade agreement before April of next year, the New Zealand Herald reported yesterday.
``If we go through a protracted period’’ without new trade agreements, ``others will move on without us,’’ said Monica Whaley, executive director of the National Center for APEC in Seattle, a group of companies that support trade with Asia and the Pacific region.
The new agreement would tap into an accord the four other nations completed in 2005 to eliminate tariffs and build upon free-trade agreements the U.S. previously worked out with Chile and Singapore.
Those four nations are already among the most open in the world and so are natural partners for the U.S., Whaley said.
The U.S. will initially try to negotiate rules governing foreign investment in areas such as express delivery, insurance and telecommunications, with the idea that the accord would expand and become a full regional free-trade agreement later, said two people familiar with the talks.
Once that deal is completed, other Asian or Pacific nations, such as Vietnam, Peru, Mexico or South Korea may be added, creating a larger trading bloc.
New Zealand Rebuffed
New Zealand tried to persuade the Bush administration to negotiate a free-trade agreement in 2003, when the U.S. was negotiating with Australia, New Zealand’s primary commercial partner. The U.S. rebuffed New Zealand as leaders of the two nations differed over the war in Iraq, and New Zealand refused to allow U.S. nuclear-powered ships to dock there. Diplomatic ties have improved recently.
``The last 18 months have shown a very strong upturn in the relationship,’’ said John Mullen, president of the United States- New Zealand Council in Washington. ``We hope the possibility of free-trade negotiations will be on the agenda for the near future.’’


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Friday 17th July
Date: 17th Jul 2020 @ 11:00am
Good Morning Everyone,
Sorry for the late blog but we're in school trying to sort through the classroom!
It's a bit sad today to think that if we were together in school we would be doing lots of fun activites together. Anyway today all four us in Reception have set you a task. We would like you to think about a memory from reception. The memory might be a book we did, experinece, topic that we did or an area that you have enjoyed playing in. We want you to share this memory as a picture, painting, model or just a video telling us.
Here are our memories...
Mrs Iqbal - I loved the story 'Ready Steady Mo.' I enjoyed the actions we did when retelling the story and when we learnt the Mobot!
Miss Wiliams - I enjoyed the story Chicken Licken. I loved it when we dressed up as farm animals for World Book Day and went into the hall and shared a story with our Year 4 buddies.
Mrs Cooper - I enjoyed World Book Day celebrations. I loved dressing up as Chickin Licken.
Miss Cogger - I enoyed it when we went to Blue Planet Aquariu and saw all the animals under the sea.
We can't wait to see your memories!
Love Mrs Iqbal, Miss Williams, Mrs Cooper and Miss Cogger.

domain: literature


text:
By Pina Peters
Could Trey Songz Possibly be dancing to Davido’s New Song? That’s the question anyone who’s watched the video is asking.
Davido has confirmed it though, but the Clarity of the 10 seconds video still remains in question.
The industry has experienced a new trend where footage of international stars bumping and grooving to the music hits of some of our home grown artistes surface online.
Started off with Swizz Beatz who was caught vibing hard to Wizkid’s Ojuelegba
Then his bae, Alicia Keys shared a video of her jamming to Wizkid’s Caro and Ojuelegba and later Skales’ Shake Body
Rihanna did same with Timaya’s Bum Bum while he performed at a fiesta in Barbados and Kylie Jenner topped it off with her waist grind to the now epic tune, Ojuelegba by our Starboy lord.
Following this trend; R’n’B music star, Trey Songz was caught goofing around to one of Davido‘s new materials suspected to be off his hotly anticipated sophomore album already titled ‘TheBaddest‘
The HKN management had previously confirmed a feature with Trey Songz on the album which is set to drop in September.


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Couple questions regarding AICAR:
Mostly see it in lyophilized form for reconstituting...Is the oral liquid form available through one reputable RC site good to go or is the oral bioavailability not good with this stuff?
Is it optimal to use this with GW-501516 or can the GW-501516 be effective solo sans AICAR?
Someone out there has to have some input..
Post in supp section for more responses

domain: medical


The University of Minnesota will lead a $12.8 million project, funded over the course of five years by the National Institute on Aging (NIA), to study how educational experiences in adolescence impact cognitive functioning and deter the development of dementia later in life. NIA is part of the National Institutes of Health (NIH).
The project, led by the University’s Minnesota Population Center (MPC), will bring together a group of sociologists, neuropsychologists, epidemiologists and survey researchers to understand the connection between education and cognitive function over the life course and to determine how racial, ethnic, and other social inequalities in education may lead to inequalities in rates of Alzheimer’s disease and other forms of cognitive impairment. In addition to the University of Minnesota, the team includes researchers from the University of Texas at Austin, the University of Wisconsin-Madison, and Columbia University.
“Cognitive impairments and dementias are a huge and increasing burden on people's lives, the healthcare system, and the economy,” said principal investigator, Dr. John Robert Warren, director of MPC and professor of sociology in the College of Liberal Arts. “Preventing cognitive impairment later in life by understanding – and potentially changing – the conditions of early life is a promising way to alleviate these burdens for future generations.”
Alzheimer’s is the sixth leading cause of death in the US, according to the Alzheimer’s Association. About 5.8 million Americans are currently living with the disease, and that number is projected to grow to nearly 14 million by 2050.
The research team will interview and collect genetic information from the 25,000 surviving members of the High School & Beyond (HS&B) cohort – a nationally representative group of people who have been interviewed on several occasions since they were high school students in 1980 – to assess their cognitive function. While HS&B panelists will be in their late 50s during the interviews and Alzheimer's disease is rare at this age, milder forms of cognitive impairment are likely to be more common among the cohort and may foreshadow the later development of more serious impairments.
Using these data, the team will examine how social and educational disparities in adolescence lead to racial or ethnic differences in cognitive impairment at midlife, how these effects manifest over the course of a person’s life, and how educational and social advantages may help people genetically predisposed toward dementia delay or avoid its onset. Ultimately, the researchers aim to inform efforts to develop strategies that reduce cognitive impairments among older people.


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The 13 best Amazon Prime Day toy deals for kids in 2021
Get $100 off GE’s Nugget ice maker this Amazon Prime Day
The best Amazon Echo deals for Prime Day 2021
The 10 Best Adidas deals of Prime Day 2021: Slides, sneakers and more
Amazon Prime Day is rockin’ and rollin’ and the deals just keep getting better! Big sale events are the most ideal time to buy tech items and entertainment products like streaming devices.
While the percentage of cable users is inevitably getting smaller by the year, if you haven’t cut the cord yet and are in the market for a streaming device, consider one of the following that are all currently on sale for Prime Day.
Streaming devices are ideal for those who love to watch the latest and greatest shows and movies on apps like Amazon Prime Video, Hulu, Netflix, Disney+, HBO Max and more.
Ahead find three great deals on the Amazon Fire TV Stick 4K, the Apple TV 4K and the Roku Express 4K+ that are well-loved and come at a variety of different price points.
1. Amazon Fire TV Stick 4K, $25; original price: $50
The Fire TV Stick has more than 600,000 raving reviews on Amazon — and for good reason. It features picture quality with access to 4K Ultra HD, Dolby Vision, HDR and HDR10+ — all for the market price of just $50 (on sale for half the price!). The Alexa Voice remote lets you use your voice to search and launch shows across apps and more than 500,000 movies and TV episodes included in your Prime membership.
2. Apple TV 4K, $150; original price: $199
If you’re already tied to the Apple “ecosystem” you’ll definitely find the Apple TV to be super user-friendly — if not, it may take you a minute to get used to. If you’re an iPhone user, you can easily use AirPlay, which will mirror anything on your phone to your TV. You can download just about any streaming app on Apple TV and even play your iTunes music and Apple music directly on your TV.
For a limited time you can snag the Apple TV 4K for $50 less than usual!
3. Roku Express 4K+ 2021, $30; original price: $40
The Roku Express 4K+ (released in 2021) allows you to upgrade your streaming experience with a large selection of free, live and premium TV options, including Roku Originals and more than 150 free Live TV channels on The Roku Channel.
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text: Discover Bruges – one of the most captivating cities in Belgium – on this day trip from Amsterdam. After traveling to Bruges by coach, you will receive a brief overview of city sights from your knowledgeable guide. Then, enjoy 5 full hours exploring the churches, canals and lace shops of Bruges on your own. See the Begijnhof, the city gates and the eye-catching windmills. And indulge in some delicious Belgian chocolates on your ride back to Amsterdam! In addition get a complimentary 1-hour canal cruise in Amsterdam to use at your leisure (worth €16).ItineraryThis is a typical itinerary for this productPass By: Begijnhof, Amsterdam, North Holland Province.Pass By: Burg Square, Bruges, West Flanders Province.Pass By: Historic Centre of Brugge, Bruges, West Flanders Province.Pass By: Lindbergh Day Tours, Amsterdam, North Holland Province.Pass By: Boottochten Brugge, Bruges, West Flanders Province.Pass By: Centraal Station, Amsterdam, North Holland Province.


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Is there some sort of competition among Republicans to see who can stray farther from the truth and bend over backwards to turn the entire nation over to Wall Street and big corporations? It’s hard to know which one is leading this charge to come in second to Trump. John Faso is certainly in the running.
His latest obfuscation concerns the disastrous Republican (Destroy) Health Care Plan. He brags that they are preserving coverage for children under the age of 26, and mandating coverage for preexisting conditions. Here is just some of what he conveniently misses: cancelling the mandate for individuals to secure coverage and employers to provide it; cancelling the tax subsidies for low-income Americans to help pay for coverage; cancelling the expansion of Medicaid; cancelling national coverage standards for health plans; cancelling the federal health insurance exchange; and forcing those with pre-existing conditions into special high cost pools. Estimates are that insurance companies will reap a billion dollar windfall in the first year –and you can be sure that some of that will trickle down to the campaign coffers of John Faso.
No doubt he will change his public stand on some of these, but you can bet that in the end he will vote the way Paul Ryan tells him to.
WE WILL ALL BE HURT, TOGETHER WITH OUR ENTIRE ECONOMY, unless you are a billionaire or a member of Congress. Here is a link to the letter AARP sent to Congress opposing the bill.
One item that may be easy to overlook is how it will affect students over the age of 26, who do not make enough for the proposed tax breaks to help them.Higher education costs are already way too high and this is sure the drive students away, impacting those on whose future the nation’s technological future depends.
Here is a simple statistic that should convince you that a single payer system is the only way to go. Overhead and profit take at least 20% of the health care dollars spent on private insurance; Medicare’s overhead is below 2% (This number rises to around 6% if it includes the overhead of private insurers participating in Medicare Parts c & D). So if you spend $500 per month on private health insurance, over $100 is immediately withdrawn from what can be spent on actual care.

domain: finance


Lionel Messi, LeBron James, and Roger Federer feature prominently when it comes to earning power in sport.
Floyd Mayweather, Conor McGregor, and even KSI and Logan Paul have been smash-hit box office successes over the years.
2 of the world's best boxers are desperate to fight Conor McGregor, proving the balance of power has swung wildly towards UFC and Dana White
Manny Pacquiao and Terence Crawford join Justin Gaethje, Nate Diaz, Jorge Masvidal, and Khabib Nurmagomedov in a list of who could fight McGregor next.
From the fighting pride of Ireland to MMA's Jekyll and Hyde: Why Dublin started turning its back on Conor McGregor
Since earning $100 million from fighting Floyd Mayweather, Conor McGregor has shown the world the two sides of his personality.
Manny Pacquiao's manager says Conor McGregor knows where to go if he wants a 'proper fight' after UFC 246
Manny Pacquiao sent a good-luck message to Conor McGregor, who fights Donald Cerrone at UFC 246 on January 18, in a video posted on Twitter.
A fight against Conor McGregor could generate $250 million and be Manny Pacquiao's retirement party, according to an expert
One boxing expert describes Manny Pacquiao as "at the end" of his career and says a fight against Conor McGregor is "viable" for 2020.
Former heavyweight Wladimir Klitschko says UFC is far tougher than boxing and Conor McGregor deserves respect
Wladimir Klitschko also said Conor McGregor, who fights at UFC 246 on Saturday, was well-behaved and disciplined when he fought Floyd Mayweather.
Tyson Fury gave a bizarre interview ahead of his Deontay Wilder fight where he said he's masturbating 7 times a day to 'keep testosterone pumping'
The Gypsy King then followed the comment up with a brief rendition of Endor's dance hit "Pump It Up."
An American boxer danced to Beyonce, wore a crown to the ring, then dominated her opponent to become the fastest 3-weight champion in history
Claressa Shields said "Who run the world? Girls" on Twitter after storming to her 10th professional win and another championship.
Jake Paul says he and his brother Logan are the 'big bad wolves' of YouTube that everyone wants to see fail
Amid a whirlwind marriage and series of controversies, YouTube's Jake Paul will follow in the steps of his older brother and try his hand at boxing.
Bob Arum, a promoter for more than five decades, told Business Insider: "I would hate to be gone when that happens."
Boxer Tyson Fury posted a throwback photo showing him at 400 pounds to remind you that 'anything is possible'
"When someone says you can't do something, look at this and remember anything is possible," the boxer wrote.
YouTube star Logan Paul and NFL player Antonio Brown are trading insults online and hinting at a possible boxing match
Both Logan Paul and Antonio Brown have left paths of controversy in their respective careers in YouTube and the NFL.
Logan Paul has turned oddball boxing matches into big business, and a fight against Antonio Brown could be next on the docket.
Floyd Mayweather made $500,000 for every punch he landed in the last decade, and he landed a lot of punches
And he landed a lot of punches in the 10 fights he contested.
Israel Adesanya, Saul 'Canelo' Alvarez, and Jorge Masvidal raised their stock considerably in 2019, while Tyson Fury failed to take a challenge.
FightCamp turns your living room into a professional boxing gym — its full-body workouts are fun and get you results
FightCamp is a connected boxing system for at-home workouts. It's like having a professional gym in your home. We tried it to see if its jabs get results.
Saul "Canelo" Alvarez, Manny Pacquiao, and Deontay Wilder feature prominently in Business Insider's list of the best boxers in the world today.
Daniel Dubois knocks Kyotaro Fujimoto down with a jab, then out for good with a hard right hand to leave the Japanese heavyweight needing oxygen treatment in the ring
Daniel Dubois left the ring a matter of minutes after he entered it, finishing Kyotaro Fujimoto with ease in the second round in London.
Serena Williams has been taking boxing lessons from Mike Tyson, and the former heavyweight champion says he wouldn't 'want to get in the ring' with her
Tyson also said Williams has "got some power" as she shared a video of the tennis star delivering punches to a training bag.


The implementation of Group technology (GT) involves the use of a Classification and Coding (CC) system and/or a direct analysis of the production methods. Classification and Coding is a laborious and time-consuming activity, and has been one of the main impediments for the implementation of GT. A considerable time is also spent in the selection of a coding system and training. Thus the need for computer-assisted procedures in this area can be clearly understood. This paper first gives a review of the approaches that have been used for automation of the activity of classification and coding. Next it presents a part feature recognition system that eliminates the human effort of translating part definition data (from a CAD drawing), which is geometry based into a scaled bitmap pattern representation of part drawings which serves as input for a neural network GT code generator. The neural network, designed with back-propagation, is used to generate the part geometry related digits of the VUOSO code from the transformed bitmaps of the CAD drawings. This interface via a CAD primitives processor not only reduces time for classification and coding, but also eliminates any need to change the neural network because of design changes in CAD. In addition to making the system less error prone, further recoding of parts are also easier because of the adaptability of neural networks. The effort thus shows the feasibility of CAD to a CC system and automation of the process of GT code generation.


Where can you find instructions on how to replace the front window wiper motor on a 1999 Chevrolet Lumina 4 dr sedan?
Get a manual on your car to get it done right.
I had the same problem in my '97 Lumina. There is an actuator switch in the steering column that was bad. I was going to replace it myself but the covers for the steering column required that the steering wheel be removed and I didn't have the tools so I had to take it to the garage and have them replace the actuator. Hope this isn't too late to help
Instructions on how to replace the driver's side window motor and master switch and also the passenger window switch and motor on a 2000 Toyota Camry?
Here are complete step-by-step instructions (with photos) on how to remove a door panel: http://www.ricksfreeautorepairadvice.com/repair-topics/window-power-repair/remove-a-door-panel-from-any-vehicle-without-a-diagram Here are complete step-by-step instructions (with photos) on how to test a power window motor to determine whether the problem is in the motor/regulator or the switch/wiring http://www.ricksfreeautorepairadvice.com/repair-topics/window-power-repair/replace-a-power-window-regulator -cable
Purchase a Haynes Manual that is for your car. It will show illistrations as to what to take off and what not. To replace the drivers side window on a 1983 Z287 Camaro allow approximately six hours. Remove the inner door skin and remove the rivets that attach the motor to the door. Slide the window out of track and unbolt the vertical track. Unplug the harness and retrieve the assembly.


- Achieving Women's Equality: South Australia's Women's Policy
- Aboriginal women
- Economic status
- Leadership and Participation
- Safety and wellbeing
- Women in STEM
- Office for Women eNews
- Useful Links and Resources
- 125th Anniversary of Women's Suffrage
Achieving Women's Equality: South Australia's Women's Policy
Aboriginal and Torres Strait Islander people — please be aware this website may contain names, images and voices of deceased persons.
Women and girls in South Australia will be able to fully participate in and share the benefits of living in South Australia.
- All individuals, women or men, are equally entitled to participate in and benefit from living in South Australia.
- Equality, diversity and social inclusion are valued by all South Australians.
- Vulnerable groups of women need targeted support to access services and participate fully in our community.
- Strong partnerships with non-government organisations, business and community are critical to achieve gender equality.
- Measuring and reporting on progress is fundamental to achieving gender equality.
South Australia's Women's Policy: Achieving Women's Equality
The first biennial report under South Australia's women's policy Achieving Women's Equality: Status of Women in South Australia Report 2017
In 2015 the Office for Women released Achieving Women’s Equality: South Australia’s Women’s Policy. This document set out three priority pillars for Government actions:
In this policy it was stated that the Office for Women would release biennial reports against strategic priorities under these pillars. The first of these was released in 2017 and can be accessed below:
Additionally, all South Australian Government departments provided information on programs and initiatives that support women under the above three pillars. This report is also provided below:
For the purposes of this policy the terms Aboriginal community and Aboriginal people are inclusive of Aboriginal and Torres Strait Islander peoples.


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Sharp’s “Free-Form” Tech No Longer Limits Displays to Rectangular Shapes
June 19, 2014 2:37 PM
Say "goodbye" to rectangles and "hello" to more organic shapes
If you look at the display screens for nearly any type of consumer electronic device — be it a smartphone, tablet, computer, television, or GPS unit — they are all rectangular-shaped. The same goes for the screens that we find in our vehicles that display navigation/infotainment information.
Finding displays that buck this trend are few and far between, with most recent example being the
Motorola Moto 360
Nest Learning Thermostat’s
display screen “appears” to be round, but it’s actually a square display with “with only the visible portion populated with pixels”
Sharp is looking to think outside the box with its new Free-Form Display technology that allows displays to take on a more organic shape to better blend in with its surroundings. Traditional displays must maintain a sizeable bezel around the screen for the drive circuit or “gate driver.” Using IGZO technology and some of its own “secret sauce,” Sharp was able to commingle the gate driver with the pixels on the screen to drastically minimize the size of the bezel.
This allows the for a display screen that can be shaped in almost any design that you desire. The two prototypes that Sharp has on display are clearly geared towards the automotive sector, but the applications of this technology are endless.
Sharp is working to bring Free-Form Display technology to the market as soon as possible.
"I want people to see my movies in the best formats possible. For [Paramount] to deny people who have Blu-ray sucks!" -- Movie Director Michael Bay
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text:
THE World's most visited cities have been revealed and Bangkok has taken the top spot for the fourth consecutive year.
And for the first time, Paris has overtaken London in visitor numbers.
The 2019 index is based on visitor numbers from 2018, and included a total of 200 cities.
According to the index, Bangkok received 22.78million visitors last year, followed by Paris with 19.1million and London with 19.09million.
They're followed by Dubai at number four, Singapore at number five, Kuala Lumpur at number six and New York at number seven.
The top ten is rounded out by Istanbul at number eight, Tokyo at number nine and Antalya at number ten.
Over the last decade, London, Paris and Bangkok have consistently been in the top three destinations in terms of visitor numbers.
However, while London used to take the top spot, it was overtaken by Bangkok and now Paris.
And there's more bad news for London as visitor numbers have fallen by 3.47 per cent in 2018 compared to 2017, which equals around 800,000 visitors.
This echos an overall fall in the number of visitors to the UK last year according to the Office for National Statistics.
A number of major incidents that took place in London in 2017 may have impacted the popularity of the UK capital for tourists in 2018.
Among them was the high profile terror attack on Westminster Bridge.
It was followed by another terrifying attack, this time at London Bridge, months later.
However, Paris may have seen an extra boost to visitor numbers last year thanks to easier visa procedures for Chinese tourists.
Most read in travel
Sun Online Travel previously revealed that TripAdvisor's best tour in the UK is a £25 pub crawl of London.
There's a new hotel opening in the city that will feature free on-demand porn.
And there could be a direct flight from London to Sydney in the future.


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Avengers: Endgame hit theaters in April, and has since become the highest grossing movie of all time. The Russo Brothers made this happen by crafting a character-driven story that delivered countless cameos and surprising plot twists. But the narrative was also a bit complicated, especially regarding time travel, and the Time Heist to acquire the Infinity Stones. But with Endgame being released digitally and for physical copies, concerns and questions are being answered by the filmmakers.
One of the questions that has remained in the months since Endgame arrived in theaters is about Hawkeye and Black Widow's journey to Vormir for the Soul Stone. The idea is that Nebula knew what the price of the Stone was, and was therefore sending the pair of Avengers to their death. But the director/writer's commentary revealed the truth. As writer Stephen McFeely put it:
It should be noted, I've seen this on the Internet, that Nebula doesn't know about the exchange that's required at Vormir. No one knows other than anybody who was there. She just knows her sister didn't come back.
Well, that clears things up. Nebula has never actually been to Vormir, and doesn't know about Red Skull, and the Soul Stone's sacrifice. All she knows is that Gamora was taken there by her father, and the beloved Guardian perished in the process.
Nebula had a small role in Avengers: Infinity War, especially compared to Endgame. After being tortured by her father, she pops up in the epic battle on Titan. But she quickly puts the pieces together, realizing Thanos got the stone and Gamora was MIA. It's this realization that seems to make the fandom think that she knew what happened on Vormir. But according to the writers and directors, she did not.
Later in the digital copy's commentary Joe Russo also clarified Nebula's assessment of the Soul Stone, saying:
She knows her sister went there with her father and her sister didn't come back, and he left with the stone. So only assumptions can be made about what happens on that planet, but who knows? She could have tried to stop him and he murdered her. We have no idea.
This is another great point, and helps to show exactly where Thanos' emotionally damaged daughter's head was at while the Time Heist was being thought out. While she gave her limited intel about Vormir and the Soul Stone, she was in the dark about exactly how her sister died.
These comments strip Nebula from any guilt or association with Black Widow's heroic sacrifice on Vormir. Although one has to wonder: wouldn't Nebula want to travel to the planet during the Time Heist and find out what might have happened to her sister? It was in the past, so Red Skull wouldn't have knowledge of the actual events. But he would have revealed the sacrificial nature of the Soul Stone.


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JUMEIRAH LIVING KUALA LUMPUR RESIDENCES
The global home of Effortless Living
Over the past two decades, Jumeirah Hotels & Resorts has captured the imaginations of the most discerning global travellers with the brand promise of STAY DIFFERENT™. These two words encapsulate the multitude of personalised experiences offered at iconic properties including the Burj Al Arab Jumeirah in Dubai, Grosvenor House Suites By Jumeirah Living in London and Jumeirah Himalayas Hotel in Shanghai.
At the heart of Malaysia’s vibrant capital, an elegant new icon of modern luxury living is on its way. A place where every moment inspires and enlivens – a place you can truly call home. Welcome to Jumeirah Living Kuala Lumpur Residences. Together with Jumeirah Kuala Lumpur, a five star luxury hotel, it will grace the new Oxley Towers development – a landmark destination due to transform Kuala Lumpur’s skyline by 2021.
The very best amenities and personal service, along with cool contemporary styling, are the hallmarks of Jumeirah Livingª. With world-class dining and entertainment, spectacular city views and spacious open air pool decks, luxurious Talise Spa and state-of-the-art Fitness Club, Jumeirah Living Kuala Lumpur Residences is set to offer Kuala Lumpur’s finest lifestyle.
Warm, welcoming and serene, the lobby area is the consummate expression of the urban oasis. Its ambience is striking yet soothing with artisan curiosities, rich vegetarian and spiced aromas to intrigue the sense.
Staying at Jumeirah Living Kuala Lumpur Residences is about a sense of identity as much as a sense of place. Each Residences is a unique environment with bespoke design that adapts to you individual lifestyle where the authenticity of the experience and quality of craftsmanship is enshrined in each fixture, fitting and flawless finish
At your new residence in Kuala Lumpur, the very essence of the Jumeirah Living concept will be exemplified through a collection of Signature Standards, exceeding your expectations and fulfilling your desires with bespoke local touches. Cutting-edge technology and distinctive design, in addition to the exemplary service and luxury standards for which Jumeirah is renowned, will finesse a modern urban life with uniquely Malaysian flavour

domain: travel


If ceramic fiber blanket manufacturers want to get better competitiveness and can take advantage of better development in the whole industry, manufacturers need to continuously improve production and processing technology, and need to introduce more high-end production equipment to improve production process, so that Better meet the needs of customers, and there will be better development in the entire industry.
Throughout the entire production industry, if you want to get better development, and can have a better advantage in the industry competition, it is recommended that the manufacturers need to pay attention to these details, and can be measured from the customer’s point of view, in production Processing can find a better direction.
As the technical level is gradually increasing, the standard requirements for production and processing are getting higher and higher, and the mass customer’s requirements for the use of this product are improved.
Therefore, it is necessary to be able to meet the development needs of the industry for production, and it is necessary to better determine the customer’s needs. Demand for production, naturally, can get a better advantage in sales.


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Trip Planner: Europe / Poland / Western Poland / Western Pomerania Province / Kolobrzeg / Kolobrzeg Lighthouse
Kołobrzeg Lighthouse (Polish: Latarnia morska Kołobrzeg) is a lighthouse in Kołobrzeg on the Polish coast of the Baltic Sea. The lighthouse in located in Kołobrzeg, West Pomeranian Voivodeship; in Poland.Put Kolobrzeg Lighthouse and other Kolobrzeg attractions into our Kolobrzeg online trip itinerary maker, and watch your holiday take shape.
The lighthouse is located in between the lighthouse in Niechorze (about 34 km to the west) and the lighthouse in Gąski (22 km to the east).
Kolobrzeg Lighthouse reviews
The lighthouse is located at the entrance to the port of and its history dates back to 1666. In World War II the lighthouse was blown up by German engineers and after that time was built at a... more »
...lighthouse with a beautiful view over the beaches, in fact over long stretches of coastline. Not bad. more »
As we found ourselves in the vicinity of the lighthouse, my mother and I felt that going up would be fairly interesting. So we did, and it definitely wasn't a waste of money. The entrance fee was merely 8 złoty for a adults, and makes for a great experience. Beatiful view over the pier, beach, and city.
Quite crowdy place during the season, and honestly I think there are better lighthouses at the seaside
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