text:
|Publication number
|Publication type
|Application number
|Publication date
|Aug 22, 2006
|Filing date
|Dec 10, 2004
|Priority date
|Jan 13, 1997
|Fee status
|Also published as
|Publication number
|Steven J. Lentsch, Keith E. Olson, G. Jason Wei
|Original Assignee
|Ecolab Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (103), Non-Patent Citations (1), Referenced by (36), Classifications (38), Legal Events (2)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation of U.S. patent application Ser. No. 10/431,665, filed on May 8, 2003, now U.S. Pat. No. 6,831,054, which is a continuation of Ser. No. 09/708,903, filed on November 8, 2000, now U.S. Pat. No. 6,583,094, which is a continuation of Ser. No. 08/781,493, filed on Jan. 13, 1997, now U.S. Pat. No. 6,177,392 which applications are incorporated herein by reference.
The invention relates to substantially inorganic mild alkaline detergent materials that can be manufactured in the form of a solid block and packaged for sale. In the manufacture of the solid detergent a detergent mixture is extruded to form the solid. The solid water soluble or dispersible detergent is typically uniformly dispensed, without undershoot or overshoot of detergent concentration, from a spray-on type dispenser which creates an aqueous concentrate by spraying water onto the soluble solid product. The aqueous concentrate is directed to a use locus such as a warewashing machine.
The use of solid block detergents in institutional and industrial cleaning operations was pioneered in technology claimed in the Fernholz et al. U.S. Reissue Pat. Nos. 32,762 and 32,818. Further, pelletized materials are shown in Gladfelter et al., U.S. Pat. Nos. 5,078,301, 5,198,198 and 5,234,615. Extruded materials are disclosed in Gladfelter et al., U.S. Pat. No. 5,316,688. The solid block format is a safe, convenient and efficient product format.
In the pioneering technology, substantial attention was focused on how the highly alkaline material, based on a substantial proportion of sodium hydroxide, was cast and solidified. Initial solid block products (and predecessor powder products) used a substantial proportion of a solidifying agent, sodium hydroxide hydrate, to solidify the cast material in a freezing process using the low melting point of sodium hydroxide monohydrate (about 50� C.–65� C.). The active components of the detergent were mixed with the molten sodium hydroxide and cooled to solidify. The resulting solid was a matrix of hydrated solid sodium hydroxide with the detergent ingredients dissolved or suspended in the hydrated matrix. In this prior art cast solid and other prior art hydrated solids, the hydrated chemicals are reacted with water and the hydration reaction is run to substantial completion. The sodium hydroxide also provided substantial cleaning in warewashing systems and in other use loci that require rapid and complete soil removal. In these early products sodium hydroxide was an ideal candidate because of the highly alkaline nature of the caustic material provided excellent cleaning. Another sodium hydroxide and sodium carbonate cast solid process using substantially hydrated sodium materials was disclosed in Heile et al. U.S. Pat Nos. 4,595,520 and 4,680,134.
Similarly, pioneering technology relating to the use of solid pelleted alkaline detergent compositions in the form of a water soluble bag assembly and an extruded alkaline solid material wrapped in a water soluble film has also been pioneered by Ecolab Inc. These products within the water soluble bag can be directly inserted into a spray on dispenser wherein water dissolves the bag and contacts the soluble pellet or extruded solid, dissolves the effective detergent ingredients, creates an effective washing solution which is directed to a use locus.
In recent years, attention has been directed to producing a highly effective detergent material from less caustic materials such as soda ash, also known as sodium carbonate, because of manufacturing, processing, etc. advantages. Sodium carbonate is a mild base, and is substantially less strong (has a smaller Kb) than sodium hydroxide. Further on an equivalent molar basis, the pH of the sodium carbonate solution is one unit less than an equivalent solution of sodium hydroxide (an order of magnitude reduction in strength of alkalinity). Sodium carbonate formulations were not given serious consideration in the industry for use in heavy duty cleaning operations because of this difference in alkalinity. The industry believed carbonate could not adequately clean under the demanding conditions of time, soil load and type and temperature found in the institutional and industrial cleaning market. A few sodium carbonate based formulations have been manufactured and solid in areas where cleaning efficiency is not paramount. Further solid detergents made of substantially hydrated, the carbonate content contained at least about seven moles of water of hydration per mole of carbonate, sodium carbonate were not dimensionally stable. The substantially hydrated block detergent tended to swell and crack upon aging. This swelling and cracking was attributed to changing of the sodium carbonate hydration states within the block. Lastly, molten hydrate processing can cause stability problems in manufacturing the materials. Certain materials at high melting temperatures in the presence of water can decompose or revert to less active or inactive materials.
Accordingly, a substantial need for mechanically stable solid carbonate detergent products, having equivalent cleaning performance when compared to caustic based detergents, has arisen. Further, a substantial need has arisen for successful non-molten processes for manufacturing sodium carbonate based detergents that form a solid with minimal amounts of water of hydration associated with the sodium base. These products and processes must combine ingredients and successfully produce a stable solid product that can be packaged, stored, distributed and used in a variety of use locations.
The invention involves a solid block detergent based on a combination of a carbonate hydrate and a non-hydrated carbonate species solidified by a novel hydrated species we call the E-form hydrate composition. The solid can contain other cleaning ingredients and a controlled amount of water. The solid carbonate based detergent is solidified by the E-form hydrate which acts as a binder material or binding agent dispersed throughout the solid. The E-form binding agent comprises at a minimum an organic phosphonate and water and can also have associated carbonate. The solid block detergent uses a substantial proportion, sufficient to obtain cleaning properties, of hydrated carbonate and non-hydrated carbonate formed into solid in a novel structure using a novel E-form binder material in a novel manufacturing process. The solid integrity of the detergent, comprising anhydrous carbonate and other cleaning compositions, is maintained by the presence of the E-form binding component comprising an organic phosphonate, substantially all water added to the detergent system and an associated fraction of the carbonate. This E-form hydrate binding component is distributed throughout the solid and binds hydrated carbonate and non-hydrated carbonate and other detergent components into a stable solid block detergent.
The alkali metal carbonate is used in a formulation that additionally includes an effective amount of a hardness sequestering agent that both sequesters hardness ions such as calcium, magnesium and manganese but also provides soil removal and suspension properties. The formulations can also contain a surfactant system that, in combination with the sodium carbonate and other components, effectively removes soils at typical use temperatures and concentrations. The block detergent can also contain other common additives such as surfactants, builders, thickeners, soil anti-redeposition agents, enzymes, chlorine sources, oxidizing or reducing bleaches, defoamers, rinse aids, dyes, perfumes, etc.
Such block detergent materials are preferably substantially free of a component that can compete with the alkali metal carbonate for water of hydration and interfere with solidification. The most common interfering material comprises a second source of alkalinity. The detergent preferably contains less than a solidification interfering amount of the second alkaline source, and can contain less than 5 wt %, preferably less than 4 wt %, of common alkalinity sources including either sodium hydroxide or an alkaline sodium silicate wherein the ratio Na2O:SiO2 is greater than or equal to about 1. While some small proportion sodium hydroxide can be present in the formulation to aid in performance, the presence of a substantial amount of sodium hydroxide can interfere with solidification. Sodium hydroxide preferentially binds water in these formulations and in effect prevents water from participating in the E-form hydrate binding agent and in solidification of the carbonate. On mole for mole basis, the solid detergent material contains greater than 5 moles of sodium carbonate for each total mole of both sodium hydroxide and sodium silicate.
We have found that a highly effective detergent material can be made with little water (i.e. less than 11.5 wt %, preferably less than 10 wt % water) based on the block. The solid detergent compositions of Fernholz et al. required depending on composition, a minimum of about 12–15 wt % of water of hydration for successful processing. The Fernholz solidification process requires water to permit the materials to fluid flow or melt flow sufficiently when processed or heated such that they can be poured into a mold such as a plastic bottle or capsule for solidification. At lesser amounts of water, the material would be too viscous to flow substantially for effective product manufacture. However, the carbonate based materials can be made in extrusion methods with little water. We have found that as the materials are extruded, the water of hydration tends to associate with the phosphonate component and, depending on conditions, a fraction of the anhydrous sodium carbonate used in the manufacture of the materials. If added water associates with other materials such as sodium hydroxide or sodium silicates, insufficient solidification occurs leaving a product resembling slush, paste or mush like a wet concrete. We have found that the total amount of water present in the solid block detergents of the invention is less than about 11 to 12 wt % water based on the total chemical composition (not including the weight of the container). The preferred solid detergent comprises less than about 1.3, more preferably about 0.9 to 1.3 moles of water per each mole of carbonate. With this in mind for the purpose of this patent application, water of hydration recited in these claims relates primarily to water added to the composition that primarily hydrates and associates with the binder comprising a fraction of the sodium carbonate, the phosphonate and water of hydration. A chemical with water of hydration that is added into the process or products of this invention wherein the hydration remains associated with that chemical (does not dissociate from the chemical and associate with another) is not counted in this description of added water of hydration. Preferred hard dimensionally stable solid detergents will comprise about 5 to 20 wt %, preferably 10 to 15 wt % anhydrous carbonate. The balance of the carbonate comprises carbonate monohydrate. Further, some small amount of sodium carbonate monohydrate can be used in the manufacture of the detergent, however, such water of hydration is used in this calculation.
For the purpose of this application the term "solid block" includes extruded pellet materials having a weight of 50 grams up through 250 grams, an extruded solid with a weight of about 100 grams or greater or a solid block detergent having a mass between about 1 and 10 kilograms.
The solid block detergents of the invention can comprise a source of alkalinity, a sequestrant and an E-form hydrate binding agent.
The present method is suitable for preparing a variety of solid cleaning compositions, as for example, extruded pellet, extruded block, etc., detergent compositions. The cleaning compositions of the invention comprise conventional alkaline carbonate cleaning agent and other active ingredients that will vary according to the type of composition being manufactured.
The essential ingredients are as follows:
Solid Matrix Composition Chemical Percent Range Organo- 1–30 wt %; Phosphonate preferably 3–15 wt % Water 5–15 wt %; preferably 5–12 wt % Alkali Metal 25–80 wt %; Carbonate preferably 30–55 wt %
As this material solidifies, a single E-form hydrate binder composition forms. This hydrate binder is not a simple hydrate of the carbonate component. We believe the solid detergent comprises a major proportion of carbonate monohydrate, a portion of non-hydrated (substantially anhydrous) alkali metal carbonate and the E-form binder composition comprising a fraction of the carbonate material, an amount of the organophosphonate and water of hydration. The alkaline detergent composition can include an amount of a source of alkalinity that does not interfere with solidification and minor but effective amounts of other ingredients such as surfactant(s), a chelating agent/sequestrant including a phosphonate, polyphosphate, a bleaching agent such as an encapsulated bleach, sodium hypochlorite or hydrogen peroxide, an enzyme such as a lipase, a protease or an amylase, and the like.
The cleaning composition produced according to the invention may include minor but effective amounts of one or more alkaline sources to enhance cleaning of a substrate and improve soil removal performance of the composition. The alkaline matrix is bound into a solid due to the presence of the binder hydrate composition including its water of hydration. The composition comprises about 10–80 wt %, preferably about 15–70 wt % of an alkali metal carbonate source, most preferably about 20–60 wt %. The total alkalinity source can comprise about 5 wt % or less of an alkali metal hydroxide or silicate. A metal carbonate such as sodium or potassium carbonate, bicarbonate, sesquicarbonate, mixtures thereof and the like can be used. Suitable alkali metal hydroxides include, for example, sodium or potassium hydroxide. An alkali metal hydroxide may be added to the composition in the form of solid beads, dissolved in an aqueous solution, or a combination thereof. Alkali metal hydroxides are commercially available as a solid in the form of prilled solids or beads having a mix of particle sizes ranging from about 12–100 U.S. mesh, or as an aqueous solution, as for example, as a 50 wt % and a 73 wt % solution. Examples of useful alkaline sources include a metal silicate such as sodium or potassium silicate (with a M2O:SiO2 ratio of 1:2.4 to 5:1, M representing an alkali metal) or metasilicate; a metal borate such as sodium or potassium borate, and the like; ethanolamines and amines; and other like alkaline sources.
The composition can comprises at least one cleaning agent which is preferably a surfactant or surfactant system. A variety of surfactants can be used in a cleaning composition, including anionic, nonionic, cationic, and zwitterionic surfactants, which are commercially available from a number of sources. Anionic and nonionic agents are preferred. For a discussion of surfactants, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 8, pages 900–912. Preferably, the cleaning composition comprises a cleaning agent in an amount effective to provide a desired level of cleaning, preferably about 0–20 wt %, more preferably about 1.5–15 wt %.
Anionic surfactants useful in the present cleaning compositions, include, for example, carboxylates such as alkylcarboxylates (carboxylic acid salts) and polyalkoxycarboxylates, alcohol ethoxylate carboxylates, nonylphenol ethoxylate carboxylates, and the like; sulfonates such as alkylsulfonates, alkylbenzenesulfonates, alkylarylsulfonates, sulfonated fatty acid esters, and the like; sulfates such as sulfated alcohols, sulfated alcohol ethoxylates, sulfated alkylphenols, alkylsulfates, sulfosuccinates, alkylether sulfates, and the like; and phosphate esters such as alkylphosphate esters, and the like. Preferred anionics are sodium alkylarylsulfonate, alpha-olefinsulfonate, and fatty alcohol sulfates.
Nonionic surfactants useful in cleaning compositions, include those having a polyalkylene oxide polymer as a portion of the surfactant molecule. Such nonionic surfactants include, for example, chlorine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and other like alkyl-capped polyethylene glycol ethers of fatty alcohols; polyalkylene oxide free nonionics such as alkyl polyglycosides; sorbitan and sucrose esters and their ethoxylates; alkoxylated ethylene diamine; alcohol alkoxylates such as alcohol ethoxylate propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate propoxylates, alcohol ethoxylate butoxylates, and the like; nonylphenol ethoxylate, polyoxyethylene glycol ethers and the like; carboxylic acid esters such as glycerol esters, polyoxyethylene esters, ethoxylated and glycol esters of fatty acids, and the like; carboxylic amides such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides, and the like; and polyalkylene oxide block copolymers including an ethylene oxide/propylene oxide block copolymer such as those commercially available under the trademark PLURONIC™ (BASF-Wyandotte), and the like; and other like nonionic compounds. Silicone surfactants such as the ABIL B8852 can also be used.
Cationic surfactants useful for inclusion in a cleaning composition for sanitizing or fabric softening, include amines such as primary, secondary and tertiary monoamines with C18 alkyl or alkenyl chains, ethoxylated alkylamines, alkoxylates of ethylenediamine, imidazoles such as a 1-(2-hydroxyethyl)-2-imidazoline, a 2-alkyl-1-(2-hydroxyethyl)-2-imidazoline, and the like; and quaternary ammonium salts, as for example, alkylquaternary ammonium chloride surfactants such as n-alkyl(C12–C18)dimethylbenzyl ammonium chloride, n-tetradecyldimethylbenzylammonium chloride monohydrate, a naphthylene-substituted quaternary ammonium chloride such as dimethyl-1-naphthylmethylammonium chloride, and the like; and other like cationic surfactants.
Solid cleaning compositions made according to the invention may further include conventional additives such as a chelating/sequestering agent, bleaching agent, alkaline source, secondary hardening agent or solubility modifier, detergent filler, defoamer, anti-redeposition agent, a threshold agent or system, aesthetic enhancing agent (i.e., dye, perfume), and the like. Adjuvants and other additive ingredients will vary according to the type of composition being manufactured. The composition may include a chelating/sequestering agent such as an aminocarboxylic acid, a condensed phosphate, a phosphonate, a polyacrylate, and the like. In general, a chelating agent is a molecule capable of coordinating (i.e., binding) the metal ions commonly found in natural water to prevent the metal ions from interfering with the action of the other detersive ingredients of a cleaning composition. The chelating/sequestering agent may also function as a threshold agent when included in an effective amount. Preferably, a cleaning composition includes about 0.1–70 wt %, preferably from about 5–60 wt %, of a chelating/sequestering agent.
Useful aminocarboxylic acids include, for example, N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), and the like.
Examples of condensed phosphates useful in the present composition include sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and the like. A condensed phosphate may also assist, to a limited extent, in solidification of the composition by fixing the free water present in the composition as water of hydration.
The composition may include a phosphonate such as 1-hydroxyethane-1,1-diphosphonic acid CH3C(OH)[PO(OH)2]2; aminotri(methylenephosphonic acid) N[CH2PO(OH)2]3; aminotri(methylenephosphonate), sodium salt
2-hydroxyethyliminobis(methylenephosphonic acid) HOCH2CH2N[CH2PO(OH)2]2; diethylenetriaminepenta(methylenephosphonic acid) (HO)2POCH2N[CH2CH2N[CH2PO(OH)2]2]2; diethylenetriaminepenta(methylenephosphonate), sodium salt C9H( 28−x)N3NaxO15P5 (x=7); hexamethylenediamine(tetramethylenephosphonate), potassium salt C10H(28−x)N2KxO12P4 (x=6); bis(hexamethylene)triamine(pentamethylenephosphonic acid) (HO2)POCH2N[(CH2)6N[CH2PO(OH)2]2]2; and phosphorus acid H3PO3. A preferred phosphonate combination is ATMP and DTPMP. A neutralized or alkaline phosphonate, or a combination of the phosphonate with an alkali source prior to being added into the mixture such that there is little or no heat or gas generated by a neutralization reaction when the phosphonate is added is preferred.
Polymeric polycarboxylates suitable for use as cleaning agents have pendant carboxylate (—CO2 −) groups and include, for example, polyacrylic acid, maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, and the like. For a further discussion of chelating agents/sequestrants, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 5, pages 339–366 and volume 23, pages 319–320, the disclosure of which is incorporated by reference herein.
Bleaching agents for use in a cleaning compositions for lightening or whitening a substrate, include bleaching compounds capable of liberating an active halogen species, such as Cl2, Br2, —OCl− and/or —OBr−, under conditions typically encountered during the cleansing process. Suitable bleaching agents for use in the present cleaning compositions include, for example, chlorine-containing compounds such as a chlorine, a hypochlorite, chloramine. Preferred halogen-releasing compounds include the alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, the alkali metal hypochlorites, monochloramine and dichloramine, and the like. Encapsulated chlorine sources may also be used to enhance the stability of the chlorine source in the composition (see, for example, U.S. Pat. Nos. 4,618,914 and 4,830,773, the disclosure of which is incorporated by reference herein). A bleaching agent may also be a peroxygen or active oxygen source such as hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrates, potassium permonosulfate, and sodium perborate mono and tetrahydrate, with and without activators such as tetraacetylethylene diamine, and the like. A cleaning composition may include a minor but effective amount of a bleaching agent, preferably about 0.1–10 wt %, preferably about 1–6 wt %.
A cleaning composition may include a minor but effective amount of one or more of a detergent filler which does not perform as a cleaning agent per se, but cooperates with the cleaning agent to enhance the overall cleaning capacity of the composition. Examples of fillers suitable for use in the present cleaning compositions include sodium sulfate, sodium chloride, starch, sugars, C1–C10 alkylene glycols such as propylene glycol, and the like. Preferably, a detergent filler is included in an amount of about 1–20 wt %, preferably about 3–15 wt %.
A minor but effective amount of a defoaming agent for reducing the stability of foam may also be included in the present cleaning compositions. Preferably, the cleaning composition includes about 0.0001–5 wt % of a defoaming agent, preferably about 0.01–3 wt %.
Examples of defoaming agents suitable for use in the present compositions include silicone compounds such as silica dispersed in polydimethylsiloxane, fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters, alkyl phosphate esters such as monostearyl phosphate, and the like. A discussion of defoaming agents may be found, for example, in U.S. Pat. No. 3,048,548 to Martin et al., U.S. Pat. No. 3,334,147 to Brunelle et al., and U.S. Pat. No. 3,442,242 to Rue et al., the disclosures of which are incorporated by reference herein.
A cleaning composition may also include an anti-redeposition agent capable of facilitating sustained suspension of soils in a cleaning solution and preventing the removed soils from being redeposited onto the substrate being cleaned. Examples of suitable anti-redeposition agents include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, styrene maleic anhydride copolymers, and cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and the like. A cleaning composition may include about 0.5–10 wt %, preferably about 1–5 wt %, of an anti-redeposition agent.
Various dyes, odorants including perfumes, and other aesthetic enhancing agents may also be included in the composition. Dyes may be included to alter the appearance of the composition, as for example, Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine and Chemical), Metanil Yellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis), Sandolan Blue/Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), and the like.
Fragrances or perfumes that may be included in the compositions include, for example, terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such as C1S-jasmine or jasmal, vanillin, and the like.
The ingredients may optionally be processed in a minor but effective amount of an aqueous medium such as water to achieve a homogenous mixture, to aid in the solidification, to provide an effective level of viscosity for processing the mixture, and to provide the processed composition with the desired amount of firmness and cohesion during discharge and upon hardening. The mixture during processing typically comprises about 0.2–12 wt % of an aqueous medium, preferably about 0.5–10 wt %.
The invention provides a method of processing a solid cleaning composition. According to the invention, a cleaning agent and optional other ingredients are mixed with an effective solidifying amount of ingredients in an aqueous medium. A minimal amount of heat may be applied from an external source to facilitate processing of the mixture.
A mixing system provides for continuous mixing of the ingredients at high shear to form a substantially homogeneous liquid or semi-solid mixture in which the ingredients are distributed throughout its mass. Preferably, the mixing system includes means for mixing the ingredients to provide shear effective for maintaining the mixture at a flowable consistency, with a viscosity during processing of about 1,000–1,000,000 cP, preferably about 50,000–200,000 cP. The mixing system is preferably a continuous flow mixer or more preferably, a single or twin screw extruder apparatus, with a twin-screw extruder being highly preferred.
The mixture is typically processed at a temperature to maintain the physical and chemical stability of the ingredients, preferably at ambient temperatures of about 20–80� C., more preferably about 25–55� C. Although limited external heat may be applied to the mixture, the temperature achieved by the mixture may become elevated during processing due to friction, variances in ambient conditions, and/or by an exothermic reaction between ingredients. Optionally, the temperature of the mixture may be increased, for example, at the inlets or outlets of the mixing system.
An ingredient may be in the form of a liquid or a solid such as a dry particulate, and may be added to the mixture separately or as part of a premix with another ingredient, as for example, the cleaning agent, the aqueous medium, and additional ingredients such as a second cleaning agent, a detergent adjuvant or other additive, a secondary hardening agent, and the like. One or more premixes may be added to the mixture.
The ingredients are mixed to form a substantially homogeneous consistency wherein the ingredients are distributed substantially evenly throughout the mass. The mixture is then discharged from the mixing system through a die or other shaping means. The profiled extrudate then can be divided into useful sizes with a controlled mass. Preferably, the extruded solid is packaged in film. The temperature of the mixture when discharged from the mixing system is preferably sufficiently low to enable the mixture to be cast or extruded directly into a packaging system without first cooling the mixture. The time between extrusion discharge and packaging may be adjusted to allow the hardening of the detergent block for better handling during further processing and packaging. Preferably, the mixture at the point of discharge is about 20–90� C., preferably about 25–55� C. The composition is then allowed to harden to a solid form that may range from a low density, sponge-like, malleable, caulky consistency to a high density, fused solid, concrete-like block.
Optionally, heating and cooling devices may be mounted adjacent to mixing apparatus to apply or remove heat in order to obtain a desired temperature profile in the mixer. For example, an external source of heat may be applied to one or more barrel sections of the mixer, such as the ingredient inlet section, the final outlet section, and the like, to increase fluidity of the mixture during processing. Preferably, the temperature of the mixture during processing, including at the discharge port, is maintained preferably at about 20–90� C.
When processing of the ingredients is completed, the mixture may be discharged from the mixer through a discharge die. The composition eventually hardens due to the chemical reaction of the ingredients forming the E-form hydrate binder. The solidification process may last from a few minutes to about six hours, depending, for example, on the size of the cast or extruded composition, the ingredients of the composition, the temperature of the composition, and other like factors. Preferably, the cast or extruded composition "sets up" or begins to hardens to a solid form within about 1 minute to about 3 hours, preferably about 1 minute to about 2 hours, preferably about 1 minute to about 20 minutes.
The packaging receptacle or container may be rigid or flexible, and composed of any material suitable for containing the compositions produced according to the invention, as for example glass, metal, plastic film or sheet, cardboard, cardboard composites, paper, and the like.
Advantageously, since the composition is processed at or near ambient temperatures, the temperature of the processed mixture is low enough so that the mixture may be cast or extruded directly into the container or other packaging system without structurally damaging the material. As a result, a wider variety of materials may be used to manufacture the container than those used for compositions that processed and dispensed under molten conditions.
Preferred packaging used to contain the compositions is manufactured from a flexible, easy opening film material.
The cleaning composition made according to the present invention is dispensed from a spray-type dispenser such as that disclosed in U.S. Pat. Nos. 4,826,661, 4,690,305, 4,687,121, 4,426,362 and in U.S. Pat. Nos. Re 32,763 and 32,818, the disclosures of which are incorporated by reference herein. Briefly, a spray-type dispenser functions by impinging a water spray upon an exposed surface of the solid composition to dissolve a portion of the composition, and then immediately directing the concentrate solution comprising the composition out of the dispenser to a storage reservoir or directly to a point of use. The preferred product shape is shown in
Raw Material Description
Percent (%)
Soft Water
Nonionic Surfactant premix
Amino trimethylene phosphonate
Low Density Na2CO3
STPP, large granular
The product was formulated as follows: 2% of the nonionic was premixed with the large granular sodium triolyphosphate (STPP), the surfactant premix D and the aminotri(methylene phosphonate) (ATMP) in a first powder feeder. The purpose of this premix was to hold a fine, spray-dried ATMP NSD together with the large granular STPP to prevent segregation during processing. The anhydrous sodium carbonate (ash) is fed with a second powder feeder and the water and remaining surfactant were both pumped by separate pumps to a Teledyne processor equipped with an extrusion screw sections. The production rate for this experiment was 30 lbs/minute and a 1200 lb. batch of product was produced. In the DSC curve in
We have also conducted dispensing experiments with formulas substantially similar to those in formulas 1 and 2. We have surprisingly found that in conductivity based dispenser operation that control over dispensing of sodium carbonate based detergents can be significantly better than control over caustic based detergents. We have found in typical dispensing conditions, that caustic based detergents can often overshoot targeted levels to a degree greater than ash based detergents. We have also found that in sodium carbonate based detergents, after a first or second cycle, the amount of detergent dispensed in each cycle does not vary from a target concentration, e.g. about 800–1200 ppm active ingredient by more than about 2%. These data are shown in
In sharp contrast, using caustic based alkaline detergents, even in initial cycles, overshoot of the amount of caustic desired can often be as much as 100% or more. Even during typical use cycles, overshoot can vary between less than about 0.1% to about 20%. While these overshoot values typically do not harm cleaning capacity, such an overshoot can under certain circumstances be somewhat wasteful detergent material.
The above specification provides a basis for understanding the broad meets and bounds of the invention. The following examples and test data provide an understanding of certain specific embodiments of the invention and contain a best mode. The invention will be further described by reference to the following detailed examples. These examples are not meant to limit the scope of the invention that has been set forth in the foregoing description. Variation within the concepts of the invention are apparent to those skilled in the art.
The experiment was run to determine the level of water needed to extrude a sodium carbonate product. The product of this example is a presoak but applies equally to a warewash detergent product. A liquid premix was made using water, nonyl phenol ethoxylate with 9.5 moles EO (NPE 9.5), a Direct Blue 86 dye, a fragrance and a Silicone Antifoam 544. These were mixed in a jacketed mix vessel equipped with a marine prop agitator. The temperature of this premix was held between 85–90� F. to prevent gelling. The rest of the ingredients for this experiment were sodium tripolyphosphate, sodium carbonate, and LAS 90% flake which were all fed by separate powder feeders. These materials were all fed into a Teledyne 2″ paste processor at the percentages shown in Table 2. Production rates for this experiment varied between 20 and 18 lbs/minute. The experiment was divided into five different sections, each section had a different liquid premix feed rate, which reduced the amount of water in the formula. The percent of these reductions can be seen on Table 2. Product discharged the Teledyne through an elbow and a 1�″ diameter sanitary pipe. Included in Table 2 are the ratios of water to ash for each of the experiments. Also on this table are the results of the experiment, the higher levels of water to ash molar ratios (about 1.8–1.5) produced severe cracking and swelling. Only when levels of water approached 1.3 or less did we see no cracking or swelling of the blocks. Best results were seen at a 1.25 water to ash molar ratio. This shows an example that an extruded ash based product can be made but the water level has to be maintained at lower levels in order to prevent severe cracking or swelling.
The next example is an example of a warewashing detergent produced in a 5″ Teledyne paste processor. The premix was made of Surfactant Premix 3 (which is 84% nonionic a pluronic type nonionic and 16% of a mixed mono- and di (about C16) alkyl phosphate ester with large granular sodium tripolyphosphate and spray dried ATMP (aminotri(methylene phosphonic acid). The ATMP sprayed dried was neutralized prior to spray drying to a pH of 12–13. The purpose of this premix is to make a uniform material to be fed to the Teledyne without segregation occurring. The formula for this experiment is as follows:
Raw Material Description
Percent (%)
Soft Water
Dense Ash, Na2CO3
Tripoly, large granular
Amino tris(methylene
phosphonic acid)
The dye, which is Direct Blue 86 was premixed in the mix tank with the soft water. Production rate for this experiment was 30 lbs/minute and a 350 lb. batch was made. The molar ratio of water to ash was 1.3 for this experiment. The Teledyne process extruder was equipped with a 5�″ round elbow and straight sanitary pipe fitting at the discharge. Blocks were cut into approximately 3 lb. blocks. The Teledyne was run at approximately 300 rpm and the discharge pressure was about 20 psi. Water temperature for this experiment was held at 15� C. (59� F.), surfactant temperature was 26� C. (80� F.), and the average block discharge temperature was 46� C. (114� F.). Production ran well with blocks hardening up 15–20 minutes after discharging out of the Teledyne, no cracking or swelling was noted for this experiment.
Laboratory samples were made up to determine the phase diagram of ATMP, sodium carbonate and water. The spray dried neutralized version of ATMP used in Example 2 is the same material that is used in this experiment. Anhydrous light density carbonate (FMC grade 100) and water were used for the other ingredients. These mixtures were allowed to react and equilibrate in a 38� C. (100� F.) oven overnight. The samples were then analyzed by DSC to determine the onset of the hydration decomposition spike for each sample. The results of these experiments was a phase diagram which can be seen in
For this experiment we ran the same experiment as Example 3 except that Bayhibit AM (which is 2-phosphonobutane-1,2,4-tricarboxylic acid) was substituted for the ATMP. The material used was neutralized to a pH of 12–13 and dried. Mixtures of this material, ash and water, were then prepared and allowed to be equilibrated overnight in a 100� F. oven. Samples were then analyzed by DSE for the onset of hydration decomposition temperature. This system gave comparable results with a higher onset of hydration decomposition.
At this time we believe that an improved extruded ash based solid can be obtained by adding a phosphonate to the formula. We believe that the phosphonates, ash, water E-form complex is the main method of solidification for these systems. This is a superior solidification system to extant monohydrate of ash since it provides a much harder, stronger solid and less prone to cracking and swelling.
(9.5 mole)
A sodium carbonate based detergent (formula 1) was tested vs. a NaOH based detergent (formula 2). The compositions of these two formulas are listed in Table 3.
TABLE 3 Formula 1 Formula 2 Alkalinity NaOH — 45.6 sources NaCO3 50.5 6.1 Chelating Sodium 30 30 (water Tripolyphosphate conditioning) Sodium 6.7 — agents Aminotri(methylene phosphonate) Polyacrylic Acid — 1.6 Nonionic/ (EO) (PO) 1.5 1.4 Defoamers materials Detergency Nonionic 1.8 — enhancing surfactants (Others) Ash - 11% water Inerts Inerts S.P. >>[water] to 100 to 100
(II) Test Procedures
A 10-cycle spot, film, protein, and lipstick removal test was used to compare formulas 1 and 2 under different test conditions. In this test procedure, clean and milk-coated Libbey glasses were washed in an institutional dish machine (a Hobart C-44) together with a lab soil and the test detergent formula. The concentrations of each were maintained constant throughout the 10-cycle test.
The lab soil used is a 50/50 combination of beef stew and hot point soil. The hot point soil is a greasy, hydrophobic soil made of 4 parts Blue Bonnet all vegetable margarine and 1 part Carnation Instant Non-Fat milk powder.
In the test, the milk-coated glasses are used to test the soil removal ability of the detergent formula, while the initially clean glasses are used to test the anti-redeposition ability of the detergent formula. At the end of the test, the glasses are rated for spots, film, protein, and lipstick removal. The rating scale is from 1 to 5 with 1 being the best and 5 being the worst results.
(III) Test Results
In example 1, formula 1 was compared with formula 2 in the 10-cycle spot, film, protein, and lipstick removal test under 1000 ppm detergent, 500 ppm food soil, and 5.5 grains city water conditions (moderate hardness). The test results are listed in Table 4.
Formula 1 (Ash)
Not Done
Formula 2 (Caustic)
Not Done
These results show that under low water hardness and normal soil conditions, the ash-based formula 1 performs as well as the caustic-based formula 2.
In example 6, formula 1 was compared with formula 2 in the 10-cycle spot, film, protein, and lipstick removal test under 1500 ppm detergent, 2000 ppm food soil, and 5.5 grains city water conditions. The test results are listed in Table 5.
Formula 1
Formula 2
These test results show that under low water hardness and heavy soil conditions, higher detergent concentrations can be used to get good spot, film, and protein results that are comparable to those obtained in Example 5. Surprisingly, formula 1 outperformed formula 2 in lipstick removal by a large margin.
In example 7, formula 1 was compared with formula 2 in the 10-cycle spot, film, protein, and lipstick removal test under 1500 ppm detergent, 2000 ppm food soil, and 18 grains hard water conditions. The test results are listed in Table 6.
Formula 1
Formula 2
These test results show that under high water hardness and heavy soil conditions, cleaning results generally suffer, even with higher detergent concentrations. However, formula 1 outperformed formula 2, especially in lipstick removal.
In order to evaluate the relative importance of the detergency enhancing surfactant (LF-428, a benzyl capped linear C12-14 alcohol 12 mole ethoxylate), and the strong chelating agent (sodium aminotri(methylene phosphonate), in the ash-based detergent, four variations of formula 1 were compared vs. each other under 1000 ppm detergent, 500 ppm food soil, and 5.5 grain city water conditions. The test results are listed in Table 7.
Formula 1
Formula 1A
Formula 1B
Formula 1C
Formula 1A is Formula 1 without nonionic
Formula 1B is Formula 1 without nonionic and sodium aminotri(methylene phosphonate)
Formula 1C is Formula 1 without sodium aminotri(methylene phosphonate)
These test results show that surprisingly the chelating agents cooperate with the alkalinity sources to remove soil such as in lipstick removal.
The foregoing specification, examples and data provide a sound basis for understanding the technical advantages of the invention. However, since the invention can comprise a variety of embodiments, the invention resides in the claims hereinafter appended.
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|U.S. Classification
|510/445, 510/510, 510/446, 510/224, 510/451, 510/469, 510/228, 510/231, 510/509
|International Classification
|Cooperative Classification
|European Classification
|Jan 22, 2010
|Fee payment
Year of fee payment: 4
|Jan 22, 2014
|Fee payment
Year of fee payment: 8


text:
Global stock markets plunged into the red yesterday amid fears of a new emerging markets crisis after Argentina's currency suffered its steepest fall for 12 years.
Investors headed for the exit as concerns grew of a repeat of last June's emerging markets rout following Thursday's plunge in the value of the Argentinian peso as the country's central bank gave up on its battle to prop up the currency through intervention in financial markets.
The FTSE-100 Index suffered its worst week of the year so far as investors made a flight to safety, falling 109.5 points to 6663.7 yesterday - a drop of 1.6%.
Loading article content
London's top tier has shed 2.4% this week after falls in the previous sessions after Wednesday's bigger-than-expected fall in UK unemployment reinforced speculation of an interest rate hike.
There were similar falls across European indices yesterday, with France's Cac 40 and the Dax in Germany down 2.8% and 2.5% respectively.
Nervous investors fretted that the emerging market woes would spread, with political turbulence also seeing the Turkish lira tumble to a record low against the US dollar and the South African rand dropping sharply.
After being buoyed in recent sessions by speculation over interest rate rises, the pound fell a cent to 1.65 US dollars and by a similar level to 1.21 euros.
Among stocks, those with exposure to emerging markets were hardest hit in the sell-off, with Aberdeen Asset Management the biggest casualty after a decline of 6% or 24.1p to 397.3p.
Other stocks on the back foot were International Airlines Group as the British Airways and Iberia owner is heavily focused on Latin America for growth. Shares fell 21.1p to 406.3p, while global brewing giant SABMiller fell 89p to 2889p and Asian-focused insurer Prudential sunk 48p to 1262p.
Lloyds Banking Group fell 1.7p, or 2%, to 81.4p, after Investec Securities removed its buy rating on the stock, citing a potential further hit from payment protection insurance repayments.
Royal Mail shares were 15.5p lower at 572.5p after a trading update in which it highlighted an 8% rise in parcels revenues for the first nine months of the year.
The company, whose shares have shot up from 330p since its flotation in October, said it was trading in line with expectations, helped by a busy December for parcels and Christmas cards.
There was no festive bounce for train set firm Hornby as it warned it will make a loss this year due to supply chain issues in China. Shares in the Scalextric maker fell by 4%, or 3p to 77.5p.
The biggest FTSE-100 risers were RSA Insurance up 2p to 101.7p, Fresnillo ahead 12p at 792p, Randgold Resources 45p stronger at 4233p and Sainsbury's 3.3p higher at 362.1p. The biggest FTSE-100 fallers were Aberdeen Asset Management down 24.1p at 397.3p, International Airlines Group off 21.1p at 406.3p, Experian down 52p to 1072p and Mondi 43p weaker at 936p.

subset: commoncrawl


text:
Database Snapshots in SQL Server 2005
November 29, 2006[From SQL Server Central]
Database snapshots is a new feature added in SQL Server 2005.Database Snapshot can be used to create a read-only copy of the database. Database snapshot consists of the read-only static view of the database without including the uncommitted transactions. The uncommitted transactions are rolled back to make the database snapshot transactionally consistent.
The article continues at http://www.sqlservercentral.com/columnists/akhosla/2733.asp


text: theme 3 level 2. you have a bomb bird, one 1 to 3 blue bird, and 2 red birds. bottom right has 2 pigs with glass over head. middle bottom and bottom left has pigs with helmets, and middle of screen has 2 pigs with 3 wooden blocks.. ive been stuck for DAYS....ive tried everything.


text:
MOVIE SYNOPSIS [ General Audiences ] Steve Jobs biopic focusing on the era that launched the three iconic Apple products. You can watch Steve Jobs online on TV cable or theaters with original audio in English at different dates. This film premiered in theaters in 2015.
Rating: 5 by 10 users./
Runtime: 100 minutes
Michael Fassbender, Kate Winslet, Sarah Snook, Seth Rogen, Jeff Daniels, Michael Stuhlbarg, Katherine Waterston, Perla Haney-Jardine, Adam Shapiro, Jackie Dallas, Makenzie Moss, Afsheen Olyaie, Tina Gilton, Jahmilla Jackson and Alex Bretow.
100-minute film (full movie) directed by Danny Boyle.
The original audio of Steve Jobs has dialogues in Dolby Digital, it was produced in USA.
It premiered in cinemas or television in 2015.
Screenplay written by Aaron Sorkin and Walter Isaacson.
Alwin H. Küchler.
Christian Colson, Guymon Casady, Mark Gordon and Scott Rudin.
This film was produced and / or financed by Cloud Eight Films, Mark Gordon Company, The, Decibel Films, Management 360 and Scott Rudin Productions.
Universal Pictures.
Without commercial breaks, the full movie Steve Jobs has a duration of 100 minutes; the official trailer can be watched in streaming on the Internet. You can watch this full movie free in EnglishDolby Digital in movie TV channels, renting the DVD or with VoD services (Video On Demand player, Hulu) and PPV (Pay Per View, Netflix).
See the page of this full movie, Steve Jobs in FULLTV Movies.


text:
Israel News
Middle East
American Politics
Edition française
Green Israel
The text of Prime Minister Binyamin Netanyahu's speech to a joint session of the US Congress on May 24, 2011, as provided by the Prime Minister's Office.I am deeply honored by your warm welcome. And I am deeply honored that you have given me the opportunity to address Congress a second time.
By Gil Stern Stern HOFFMAN
By Gil Stern Stern HOFFMAN
Sponsored Content
By YONAH JEREMY BOB
By HERB KEINON
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By Brian Livingston
Power users of Microsoft Windows found themselves with nothing to read but blogs when a disk crash took down the WindowsSecrets.com site Oct. 13–14, subjecting Web surfers to 48 hours of utter boredom.
Fortunately, all the site's information was soon back online, to the chagrin of some of our columnists, who'd hoped that a few poorly chosen sentences here and there would disappear forever.
Being the geeks that we are, the Windows Secrets server is crammed with hardware designed to keep things running 24/7. The box is packed with four separate hard disks, which we imaginatively call Drives 0, 1, 2, and 3.
Because hard disks can crash, our server uses RAID technology. RAID, as described by PCGuide.com, instantly switches from a failed hard drive to a second, identical drive. This is supposed to eliminate down time.
A built-in RAID controller on our server's motherboard mirrors Drives 0 and 1, which contain our operating system and thousands of lines of code. An independent RAID add-in card synchronizes Drives 2 and 3, which contain our database.


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: Education
Mitt Romney on Problems with Airplanes
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J Diddy
One Groovy Cat
Join Date: Aug 2001
Location: The Pitt State baby
Casino cash: $27292
Originally Posted by
Well technically it is the exact same thing. And in reality .. you'd have to be RIGHT next to the open hole or it would have to be below you for you to get "blown" out of a plane. The idea is mostly Hollywood nonsense. It's like the idea that if you were in space (or on mars) your body would explode or some craziness. No, you'd simply pass out from lack of air. Which would not take the standard few minutes by more like 10-20 seconds since the lack of pressure will cause the oxygen to start getting pulled out of the blood actively.
Dude, ya don't know shit. I once flew on a commercial airliner.
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Am in Fabulous Southern Destination City for big conference.
Look! There are palm trees out there!
And not only my sister met up with me here, but my father as well. So academic conference plus family reunion!
I still miss my husband and my girls, but this trip is now officially more than worthwhile!


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There is probably nothing worse than being either "over dressed" or "under dressed", so as you consider which Penguins Formalwear suit to select, there are several things to keep in mind:
- The time of year
- The time of the ceremony
- The formality of the event you intend to attend
- Has the invite stipulated a certain "dress code"
The following is a guide to dressing in the correct attire for the occasion
White Tie
This is the most formal dress code, often referred to as Ultra Formal. White tie means full dress, tail coat, white bow, vest, dress shirt, cummerbund and patent leather shoes.
Black Tie
This means formal. Normally either Tuxedo or Dinner Suit with a black bow, dress shirt, cummerbund and patent leather shoes. Vests are also commonly worn to add an individual touch.
Black Tie Optional or Black Tie Invited
This gives you the option of wearing either a Tuxedo or a Dinner Jacket, but it should clue you to the formality, meaning a dark suit and tie would be your other option.
Creative Black Tie
This leaves room for trendy interpretations of formalwear. The key dress here would be a dark coloured suit. You would normally also wear a dinner jacket with perhaps a shirt and no tie.
This usually means the same as black tie, but in most instances a dark suit with formal shirt and tie would be appropriate. You could also wear a dinner jacket with a shirt and no tie.
Semiformal is possibly the trickiest of all the dress codes. What you should consider is the formality of the event and also the time of day. This would usually mean that a dinner suit is not required. For an evening event - a dark suit with no tie. For a daytime event - any colour suit with no tie.
This means elegant. Wear a dark suit with a formal shirt and tie.
Dressy Casual
This usually means no jeans or shorts. Similar to semi-formal. Casual generally means anything goes.
This can mean the same as casual. However, when associated with a wedding or other special event, some form of decorum and good taste should prevail. A pair of trousers and shirt are informal, but respectful to the event.
Suit Sizes
If you would like to make a booking for a suit but cannot come in for a fitting, simply fill out this size chart to find out your measurement details and e-mail or phone them through to us.


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Ed "Too Tall" Jones Signed Dallas Cowboys Authentic Helmet
$479.98with case
$349.99without case
Cowboys' Great Ed Too Tall Jones has personally hand-signed this Dallas Cowboys Authentic Helmet-Ed Too Tall Jones was one of the most dominant defensive players of his era, playing in 16 playoff games and three Super Bowls. He was part of three NFC championship teams and the Super Bowl XII champion. His success batting down passes convinced the NFL to keep track of it as an official stat. This Ed Too Tall Jones autograph is guaranteed authentic by Steiner Sports and includes a Steiner Sports tamper evident hologram. The Steiner Seal Means It's Real.
**This Item May Not Be Eligible For Some Discounts Or Promotions**


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I have purchased Altaire Paris Skin Care from this store and it arrived ontime. They even offer Free Shipping if you qualify.
Take a look at the store at :
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Potatoes and cheese in Yangshuo
Yangshuo Travel Blog› entry 16 of 20 › view all entries
We spent three days in the potato-and-cheese-heaven that is Yangshuo. Two of my favourite foods, which weren't available anywhere else we went in China, were available in abundance in Yangshuo, due to the presence of a large number of western tourists. I even ordered a side portion of mashed potato with my lasagna for one meal!
We arrived into Guilin on a short flight from Chengdu. We immediately headed into town, and found a small bus heading to Yangshuo. We agreed a price and got on. When the lady conductor tried to charge us extra for our bags, I grabbed the money back from her and moved to get off the bus: we didn't have to pay extra for our bags after that!
One village before Yangshuo a very "friendly" character calling himself Larry got onto the bus.
Yangshuo is very much a traveller hangout, with loads of shops and cafes, but we really enjoyed it after a fairly hectic couple of weeks travelling down China. One day we hired bikes and headed out into the countryside, but I was having another bout of being ill (left over from Mongolia), plus we'd just started taking our malaria medication for India in a week's time, so I didn't have much energy to go too far.
The scenery around Yangshuo is very strange and beautiful, consisting of many tall limestone pinnacles. The town itself nestles between many of these, so that some of them seem to be almost up against the backs of buildings on the main street.
We stayed in a clean and cheap hotel called the Holiday Inn (not affiliated to the international chain; just borrowing the name), on the main street. We booked a bus ticket to Shenzhen through them, for which I suspect we paid over the odds, but otherwise the hotel was good.


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The country that gave birth to nuclear weapons is terrified of N Korean missile strikes
Caspian Report breaks down the recent missile tests that North Korea has been conducting for well over two weeks much to the chagrin of the U.S. Most Americans terrified of a possible nuclear showdown between the two countries, have shrugged off North Korea's lopsided missile launches and the N. Korean government's showing off its aerial defence muscle. Neighboring countries South Korea, Japan, Phillipines and China, North Korea's strongest and oldest ally, have condemned the missle launches. Given the history of nuclear weapons and destructive wars over military bases after World War II and civilian protests against numerous U.S. military bases in Okinawa, Philippines and South Korea, the parade of military weaponry in Pyongyang is not taken lightly.
Caspian Report breaks down the recent missile tests that North Korea has been conducting for well over two weeks much to the chagrin of the U.S. Most Americans terrified of a possible nuclear showdown between the two countries, have shrugged off North Korea's lopsided missile launches and the N. Korean government's showing off its aerial defence muscle. Neighboring countries South Korea, Japan, Phillipines and China, North Korea's strongest and oldest ally, have condemned the missle launches. Given the history of nuclear weapons and destructive wars over military bases after World War II and civilian protests against numerous U.S. military bases in Okinawa, Philippines and South Korea, the parade of military weaponry in Pyongyang is not taken lightly.
The Bomb: Nuclear Weapons PBS Documentary History of Weapons of Mass Destruction and Society
It has been close to 40 years since the Three Mile Island Nuclear power plant made front page news across the United States. On March 28, 1979, the Three Mile Island plant suffered a mini nuclear meltdown that reminds one of the worst nuclear meltdowns in American history. The town around the Three Mile Island was evacuated immediately and town residents weren't allowed to return. It was a small partial reactor meltdown compared to proceeding and later nuclear diasters, Three Mile Island accident still serves as a reminder on the dangerous of society leaning on nuclear power as a cure all for fossil fuel technology or the new popular but equally dangerous, fracking for shale. As an interesting note, Abdul Qadeer Khan, the founder of Pakistan's URanium Enrichment Program was born in Bhopal. Today, the city of Bhopal is well known for the 1984 Bhopal Gas tragedy that injured 500, 000 people and killed around 3000 when the pesticide factory leaked toxic gas across the city's shanty towns.
The 1970s gave birth to the environmental movement, Earth day and environmental rights fight. Nuclear disasters by 1979 were nothing new. The August 7th Hiroshima and NAgaski bombing carried out by the United States against civilians still reminds one of the most horrific bombings of any war. The name Hiroshima has become a universal synonym for massive infrastructure and human destruction either through man made and natural disasters. The destruction of both Japanese cities on the heel of the firing bombing of Tokyo and other cities that were equally destructive. This was an early American use of Shock and Awe even though the Japanese government and the Army had all but surrender by May 8, 1945.
The atomic bomb was the invention of J Oppenheimer most famous for the Manhattan Project that introduced the world to his team's earth shattering invention. The Hydrogen bomb which is both more dangerous and destructive than the Atomic bomb, was the brain child of Edward Teller (who built one of the first) and Richard Darwin who is still alive and was the designer of the H bomb. European born American scientists would contribute greatly to the American development of thermal nuclear weapons among them Edward Teller who worked in collaboration with Stanislaw Ulam on the Teller-Ulam theiry . John von Neumann, a polyglot scientist who worked in everything from cellular automata to game theory and on the Manhattan Project.
Flexing the nuclear muscles and defense weaponsIn the immediate aftermath of WWII in Japan and other parts of the Pacific Islands, the U.S. military and government alongside the UK and France, began an early race to develop new nuclear weapons and seismic bombs mostly to show off the power of Western nuclear power and military might to the wider world. People should remember that both the Atomic and hydrogen bombs are man made. Both wouldn't have existed without the push for experimenting on the limits of theoretical physics, nuclear radiation, rockets and nuclear fusion and fission. The U.S. Army Engineering Corps and particularly the CIA was interested in some of the early rocket experiments of Nazi Germany and Nazi sceientists' knowledge in physics, engineering, chemistry and technology. This is not conspiracy theory. The scientists were brought into the United States under the codename Operation Paperclip to aid the CIA, who had its own scientific development office in developing some of the U.S. well known engineering and technological programs among them stealth technology, guided missles and atomic research. Technology was widely used throughout Nazi Germany and occupied Europe as a means to test how to efficiently destroy and murder millions of people. Even after knowing of the horrors of holocaust and how technology was used, the U.S. turned its sight to developing defense weapons for the military industrial complex. The hydrogen bomb was soon developed and tested on the PAcific islands of Bikini atoll, Diego Garcia, and parts of the Marshall Islands.
People can't breathing: Suffocating health defects from U.S. Weapons of Mass Destruction
Ted Talks: Takashi Saito shares his memories of the A bomb dropped on Hiroshima
The indigenous Marshallese, Diego Garcians and the Bikini islanders were forcibly evacuated from their homelands and not allowed to ever return. Many Bikini Islanders and neighboring islands and residents of Hiroshima, Nagaski and now Fukushima, continue to suffer from throid, lung and all types of cancers, leukaemia, skin disease, radiation poisoning and birth defect to this day. The children and adults of Fukushima and nearby towns are also suffering the cancerous affects of the 2011 Fallout. To add to the disrespect and insult, Diego Garcia and Bikini were turned into military bases that exists to this day. Guam, Okinawa, South Korea and have been home to U.S. military bases since the end of World War II despite the protests of ordinary people each country and region, the local governments refuse to abide by the wishes of the Okinawans or Marshallese and order the U.S. military bases to be shut down permanently. As with most other foreign policy operations, the U.S. portrays itself as the justice and righteous super power inspite of the WMD destruction in the Pacific and throughout Asia. The Okinawans, Marshellese and Filipinos have not stopped their ongoing protests against military bases, violent foreign policy and no one has forgotten the nuclear destruction of the islands and mainlands. This is why the ordinary people are do not overlook or downplay the real threat of nuclear confrontation or even rising tensions. The Demilitarize Zone represents more than just a touristic Cold War relic and lesson in nuclear or global war. It represents the history of nuclear industrial complex and the physical, mental and lasting scars of U.S. WMD that were used and continue to be waved the face of the ordinary Marshallese, Japanese, Vietnamese (Agent Orange) who will continue to live with the fear and nightmare of such power.
It was also a show of muscle to the Soviet Union who had gone from being an ally of the West during World War II and World I to become an enemy of the United States. Americans have a long history of making their allies their enemies once a war is fought for American interest. It's from the early days of the Cold War, that the Unitd States became paranoid everyone and everything related to the Soviet Union. Josef Stalin went from being a trusted ally to a gulag boogeyman. For 50 years, the U.S. stockpiled its own nuclear weapons, assured the public that nuclear energy was clean and harmless as a energy source, downplayed nuclear and chemical disasters as small incidents and created hundreds of nuclear bunkers for government officials in the event of a Soviet nuclear attack that never came. The image of Russia as a boogey man has not changed even though the Soviet Union has been gone for nearly 30 years. Despite fears of Soviet nuclear destruction, the U.S. still holds first place as the only nation to purposely bomb large civilian areas that historians and even the generals at the time among them MacArthur and then future President Dwight Eisenhower regarded it as a war crime. Than try to justify the bombings by saying it was to protect the lives of soldiers. North Korea continues to test fire its ballistic missiles that has worried the U.S.


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By logging in as a member, you will be able to access content which has been provided exclusively for GIMA members only.
Member Testimonials
- "Winning the GIMA Innovators' Seed Corn Fund is our biggest achievement to date. It means a great deal to us to have our product recognized by such highly experienced people from within the gardening,
- Thank you for all your help throughout the year, we find our membership in GIMA to be very helpful in building our UK business. Have a Merry Christmas!,
- "We wanted to become part of an organisation and what a great organisation to be a member of. Good people to deal with, and some fantastic opportunities to meet like minded folks at organisedSteve Webb, Managing Director, Plant Magic Plus Ltd
- "Joining GIMA has helped us gain insight more quickly and reliably than we could otherwise have done, and in a very friendly and supportive environment too. GIMA membership offers the opportunity to make greatSusanne Pinnock, Sales & Marketing Manager, SteadyPost Ltd
- "We chose to become a member of GIMA because the association sits at the very centre of the garden industry. The Kärcher brand enjoys sales of over £100m in the UK, but as relativePhil Springall, Marketing Manager, Karcher UK
- "Through GIMA membership, Briers enjoys profitable relationships across the entire garden industry. These relationships – and the ever-expanding network of contacts – have helped Briers become the business it is today. A highlight ofJackie Eades, Managing Director, Briers Ltd
- Kelkay Ltd have now been a full member for over 6 years and [as much as we find the membership great value the financial benefits we gain are well worth the fee alone. AnotherAnthony Harker, Managing Director, Kelkay Ltd


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Prepare to enjoy every journey when you're driving a new 2017 Jeep Grand Cherokee. The latest iteration of this classic Jeep SUV brings you legendary Jeep performance combined with modern comfort and convenience options. And with more than 70 standard and available safety features, you get peace of mind whether you're cruising down the highway or tackling off-road trails. Come to our Jeep dealership near Tilton, NH, today and speak with our Jeep finance and sales teams about buying or leasing a 2017 Grand Cherokee SUV!
Performance & Capability
From top-of-the-line engine options to its innovative performance features, the 2017 Jeep Grand Cherokee will provide you with the power you crave. When properly equipped, this Trail Rated® Jeep SUV gives you premium capabilities, including the ability to tow up to 7,400 pounds. Enjoy outstanding horsepower with an optional HEMI® V8 engine, or opt for one of the other impressive powertrains to complement your style. Three available 4x4 systems each provide you with remarkable handling, and you can add the Selec-Terrain® Traction Control System that allows you to select from five modes that will enhance your experience. Your engine specs, along with other standard and available performance features, include:
- 6-liter Penstastar® V6 engine that generates 295 hp and 260 lb-ft of torque
- 0-liter EcoDiesel V6 engine that outputs 240 hp and 420 lb-ft of torque
- 7-liter HEMI® V8 engine that produces 360 hp and 390 lb-ft of torque
- Quadra-Trac I® 4x4 System
- Quadra-Drive® II 4x4 System
- Quadra-Trac II® 4x4 System
Interior & Technology
Open the door to your cabin and you'll find a litany of comfort and technology options at your disposal. You and your passengers will enjoy the standard Uconnect® infotainment system that provides you with features such as Integrated Voice Command and Bluetooth®. Opt to upgrade trims and you can enjoy a more advanced system: the Uconnect® 8.4 with premium Navigation system. You'll also discover other features to enhance your in-car experience, such as the available CommandView® dual-pane panoramic sunroof and power liftgate. Additional standard and available interior and tech options include:
- Harman Kardon® audio system with 19 GreenEdge® speakers and Logic 7® multichannel surround-sound processing
- SiriusXM® Traffic and SiriusXM Travel Link
- 9-speaker Alpine® Surround Sound audio system
- Siri® Eyes Free
Safety Features
Drive confidently when you take on your journeys behind the wheel of the 2017 Jeep Grand Cherokee. You'll have total awareness of what's around you with the standard ParkView™ rear back-up camera. Add the Parallel and Perpendicular Park Assist feature and your Grand Cherokee will help you as you park on busy streets. Add the Blind Spot Monitoring System and you'll receive notifications if there are vehicles in your hard-to-see-zones. More standard and available safety systems include:
- Adaptive Cruise Control with Stop technology
- LaneSense®Lane Departure Warning Plus
- Forward Collision Warning with Active Braking
- ParkSense® Front and Rear Park Assist System
- Electronic Stability Control
If you'd like to test-drive a new 2017 Jeep Grand Cherokee, head over to Bob Mariano Chrysler Jeep Dodge Ram today!


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Developing Public Health Capacity across Wigan Borough. Making Health Everyone's Business Andi Sizer, Health Improvement Service Co-ordinator Claire Roberts, Assistant Director, Health Improvement. Local Challenges.
Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.
Making Health Everyone's Business
Andi Sizer, Health Improvement Service Co-ordinator
Claire Roberts, Assistant Director, Health Improvement
Good partnerships but history of training that didn't translate to increase in referrals
Numerous topic based training programmes- competing demands/ unco-ordinated
Staff confidence in raising issues
Public health 'not our business'
Additional & time consuming- not seen as integral to existing role
Staff Health &
staff skills
& confidence
For Health
Health Gain
in health &
Public Health
RSPH training delivered to admin teams
Cascade training within workplaces
Workplace Health Champions
Primary care
Helping people to access the right support
Health Trainer service with capacity to work with over (3,500 capacity)
Industrial scale weight management programme (11,000 capacity)
Stop Smoking services
Find & Treat
'DIY Health Guides'
Least developed area
Starting to use competency framework within service specifications
RSPH training- voluntary sector leads, Youth Forum members, Teaching Assistants
Workplace Health Champions
Briefings/ training for elected members Foundation Trust members & governors (proposed)
Primary Care Staff
'Connecting Communities to Health' programme
RSPH delivered in community settings- support for NHS Lifecheck
Community Health Advocates
Use of Yorks & Humber Competency Framework
Essential Public Health programme
Topic based training where appropriate
City & Guild HT award
Health Trainer Qualification- Health Trainers & Health Trainer Champions
Level 3
Topic specific brief intervention
Advance behaviour change
Thematic training, e.g. smoking, alcohol, mental health.
Advanced behaviour change techniques. Target frontline staff
Level 2
Practical skills & tools to raise health issues. Delivered to all frontline staff who regularly work with patients/clients on a 1:1 basis
Level 1
Essential Public Health (EPH)
Develops knowledge & understanding of health improvement. Local health priorities covered. Covers aspects of self care/awareness of own health & well being. Delivered to support cultural change in organisations & as part of staff health & well being programmes. Developing health leadership
Level 1
RSPH Level 2 award
Self Care. Understanding impact of own behaviours/lifestyle on health & well being. Delivered to local community groups, local people. Supports community Health Advocates.
Connecting Communities to Health
Level 0
Developed by NHS Stockport
Evidence based content and approach
Reduces training time from 2 days to 2.5 hours (can be more flexible)
Improved knowledge & confidence by at least 30% in Stockport
Increased lifestyle service referrals
Winner of 2009 North West Public Health Award
Roll out of EPH in Wigan starting with ALW Community Healthcare
Programme to be rolled out to acute trust and non-NHS organisations e.g. adult social care staff, Wigan Leisure & Culture Trust and Housing staff
Increase frontline staff knowledge of local public health issues
Increase individuals understanding of role
Increase confidence in addressing lifestyle issues through conversations with clients- delivering 'health chats'
Increase referrals into lifestyle support services
Obesity (inc Breastfeeding)
Alcohol & Substance Misuse
Sexual Health
Ageing (falls & fuel poverty)
For both staff & patients
Very Brief Intervention!
Raise Issue
Assess Patient Motivation
Practical Not 'Fact Packed'
Aim to Signpost
Start Positive Change
Evidence Based (NICE etc)
ALW CH agreed to adopt EPH as part of mandatory training
Communication strategy
15 staff trained as trainers for EPH
Support and additional resources provided through the Health & Wellbeing Care Group
Performance metrics agreed using existing monitoring systems where possible
Implementation programme for roll out agreed
Collection of metrics to assess:
Delivery of RSPH level 2 award to promote staff health & wellbeing
Use of Yorks & Humber Competency Framework to inform staff learning & development plans
Secondment of Public Health Analyst to improve data collection and analysis which will support workforce and service planning


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Symposium: Complex Issues in Glenohumeral Instability 10 articles
Arthroscopic Bristow-Latarjet Combined With Bankart Repair Restores Shoulder Stability in Patients With Glenoid Bone Loss
Arthroscopic Bankart repair alone cannot restore shoulder stability in patients with glenoid bone loss involving more than 20% of the glenoid surface. Coracoid transposition to prevent recurrent shoulder dislocation according to Bristow-Latarjet is an efficient but controversial procedure.
Shoulder Instability in the Setting of Bipolar (Glenoid and Humeral Head) Bone Loss: The Glenoid Track Concept
An assortment of variables has been used in predicting anterior shoulder instability resulting from pathologic engagement of Hill-Sachs lesions on the glenoid. The glenoid track is a unique biomechanical model that relates both Hill–Sachs and bony Bankart lesions to predict shoulder engagement. We examined the glenoid track concept to determine if it provides a model that unifies glenoid rim and humeral head bone loss in predicting engagement.
The Open Latarjet Procedure Is More Reliable in Terms of Shoulder Stability Than Arthroscopic Bankart Repair
Arthroscopic Bankart repair and open Latarjet bone block procedure are widely considered mainstays for surgical treatment of recurrent anterior shoulder instability. The choice between these procedures depends mainly on surgeon preference or training rather than published evidence.
A Large Humeral Avulsion of the Glenohumeral Ligaments Decreases Stability That Can Be Restored With Repair
Humeral avulsion of the glenohumeral ligaments (HAGL) has become a recognized cause of recurrent shoulder instability; however, it is unknown whether small and large HAGL lesions have similarly destabilizing effects and if large lesion repair results in restoration of stability.
Remplissage Versus Latarjet for Engaging Hill-Sachs Defects Without Substantial Glenoid Bone Loss: A Biomechanical Comparison
Recurrent shoulder instability is commonly associated with Hill-Sachs defects. These defects may engage the glenoid rim, contributing to glenohumeral dislocation. Two treatment options to manage engaging Hill-Sachs defects are the remplissage procedure, which fills the defect with soft tissue, and the Latarjet procedure, which increases glenoid arc length. Little evidence exists to support one over the other.
External Rotation Immobilization for Primary Shoulder Dislocation: A Randomized Controlled Trial
The traditional treatment for primary anterior shoulder dislocations has been immobilization in a sling with the arm in a position of adduction and internal rotation. However, recent basic science and clinical data have suggested recurrent instability may be reduced with immobilization in external rotation after primary shoulder dislocation.
Biceps Detachment Decreases Joint Damage in a Rotator Cuff Tear Rat Model
Pathology in the long head of the biceps tendon often occurs in patients with rotator cuff tears. Arthroscopic tenotomy is the most common treatment. However, the role of the long head of the biceps at the shoulder and the consequences of surgical detachment on the remaining shoulder structures remain unknown.
Effects of External Rotation on Anteroposterior Translations in the Shoulder: A Pilot Study
Using physical examination to make the diagnosis of shoulder instability can be difficult, because typical examination maneuvers are qualitative, difficult to standardize, and not reproducible. Measuring shoulder translation is especially difficult, which is a particular problem, because measuring it inaccurately may result in improper treatment of instability.
How Does External Rotation Bracing Influence Motion and Functional Scores After Arthroscopic Shoulder Stabilization?
After arthroscopic shoulder stabilization, the loss of motion or delayed recovery of motion remains a clinical problem and may lead to poor patient satisfaction. There remains no consensus regarding the optimal position for postoperative immobilization and it is not known whether the position for shoulder immobilization has an effect on motion and functional recovery.


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Dutchess Auto Body & Service
Review for Dutchess Auto Body & Service
Jerry W. on 04/04/2012
Jerry said they picked up his vehicle on a Sunday because it was an emergency. They are very good and very professional.
Category: Service
Service Date: 04/02/2012
Review Created: 04/04/2012
This review was collected via phone interview by Customer Research Inc.


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Here is a favorite recipe I love to make. It is so healthful and it is impressive to serve. It makes me feel good to know I am feeding my family this healthy and oh so delicious, hearty soup. It is filled with fresh vegetables and the wonder vegetable: Kale.
Kale: a highly nutritious vegetable with powerful antioxidant properties; considered to be anti-inflammatory. Contains sulforaphane, a chemical believed to have potent anti-cancer properties.
I love the colors and textures. Just look at the kale, beans, squash. Yum!
My youngest daughter loves to help me in the kitchen making anything healthy! She likes to pull the stems off the kale!
This Soup will give you Super Hero Powers!
thanks for the recipe i will have to try this soon
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$150.00 5 months ago
Diesel programmer - $150 (Cambridge)
Diesel programmer for a 1997 and up ford. Call or textDo not need help selling this.
5 months ago
Tuscarawas, OH
$500.00 7 months ago
Diesel edge cts2 programmer - $500 (google map)
It's been very great 5 to 7 mpg extra tons of more power. I'm hitting my 100k miles and I'm ready to do full deletes. I'm fully satisfied with what it's done for me. I have the original box and papers. Ill help you install it too. If there's any questions just text me
7 months ago
Victoria, TX
$32,000.00 9 months ago
White Diesel 2013 4x4 Laramie Dodge Cummins 3500 programmer Deleted! - $32000 (Cushing ok)
2013 dodge Cummings Full delete with smarty 5 inch exhaust heated cooled seats heated steering wheel heated backseats 4x4 bulk tank running board Electric start. Tinted windows Drop star rims Cooper s/t tires
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2005 Ford F-250 SD XLT FX-4 OFF ROAD PKG EDGE PROGRAMMER DIESEL - $19988 (GRETNA AUTO OUTLET HUGE INDOOR SHOWROOM!)
2005 Ford F-250 SD XLT FX-4 OFF ROAD PKG EDGE PROGRAMMER DIESEL - $19,988http://www.gretnaauto.com/Year: 2005Make:FordModel:F-250 SDTrim:XLT FX-4 OFF ROAD PKG EDGE PROGRAMMER DIESELMileage:115,501Stock #:11666VIN:1FTSW21P65ED39385Trans:AutomaticColor:RedVehicle Type:State:NEDrive Train:4WDEngine:8 CylinderNotes* 6 LITER 8 Cylinder engine * * GREAT DEAL AT $19,988 ** ONLY ONE PREVIOUS OWNER * * 200
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2005 Ford F-250 SD XLT FX-4 OFF ROAD PKG EDGE PROGRAMMER DIESEL - $19988 (▆▆1800BUYACAR TEXT ?S 24/7 402-669-5961▆)
2005 Ford F-250 Super Duty , 115,501Address: 11808 Standing Stone Drive GRETNA, NE 68028View our website: gretnaauto.com Notes: * 6 LITER 8 Cylinder engine * * GREAT DEAL AT $19,988 ** ONLY ONE PREVIOUS OWNER * * Check out this 2005 Ford F-250 Super Duty XLT * * 2005 ** Ford * * F-250 Super Duty * * XLT * This Red Clearcoat 2005 Ford F-250 Super Duty XLT might be just the crew cab 4x4 for you. Get
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Lincoln, NE
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2002 Ford F350 F-350 Crew cab 4dr 4x4 7.3 Turbo Diesel PROGRAMMER nice - $8995 (Ride Auto sales of Burnsville)
Low interest rates******Low down payment******Low monthly payments******Fast credit approvals******Apply now at RideAutoSale.comLariat, Crew cab with 4 doors, long box bed, 4x4, 1 ton super duty, legendary and powerful 7.3 liter power stroke turbo diesel V8, tuned and programmed, Automatic transmission, Air conditioning, fully loaded with power options, power heated leather seats, CD player, chrom
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Minneapolis, MN
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