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Latest PROBA Stories
Space-based cameras originally designed to combat famine in Africa by monitoring vegetation are being adapted to help detect diseases such as skin cancer, the ESA announced on Friday.
A pair of satellites flying in close formation to cast an artificial eclipse is now being turned into space-ready reality by ESA's industrial partners.
More than 5000 images, 65 daily global maps and six 10-day global syntheses, plus a quick peek at the Olympics: in its first two months of work, the vegetation-monitoring Proba-V minisatellite has yielded a valuable harvest for around a hundred scientific teams around the globe.
Less than seven months after launch, Earth-watcher Proba-V is ready to provide global vegetation data for operational and scientific use.
The first global map of vegetation from the recently launched Proba-V has been unveiled, demonstrating that the minisatellite is on track to continue a 15-year legacy of global vegetation monitoring from space.
The European Space Agency's (ESA) Proba-V has become the first satellite to pick up aircraft tracking signals.
ESA's Proba-V, a next-generation earth watcher designed to image the planet's vegetation, is now showing signs of life. More than a week after being set into a polar orbit roughly 510 miles over Earth, the mini satellite was switched on just in time to grab an image of the land cover over western France.
After a delayed launch due to strong wind conditions on Saturday May 4, ESA's Vega rocket lifted off early Tuesday (02:06 GMT May 7) on a complex mission to set three payloads into two different orbits.
The European Space Agency is set to launch the first of four missions as it starts an ambitious transition to commercial exploitation. The first launch, scheduled for May 3, will actually be the second launch for Vega, a rocket that has shown increased capabilities and flexibility to meet various demands in the launcher market.
ESA's Proba-V vegetation-mapping minisatellite has been fitted to the payload adapter and met its fellow passengers for its 2 May flight to orbit on a Vega launcher.
- The analysis of literature, focusing on the words and grammar to the exclusion of context or literary merit.


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Martin students awarded Nina Haven Scholarships Sunday
MARTIN COUNTY — On the cusp of graduating from high school, 27 Martin County students were awarded Nina Haven Scholarships Sunday to help them pursue their dreams of higher education.
Named after educator and part-time Martin County resident Nina Haven, the scholarships provide up to $10,000 over four years, with some targeted sectors receiving more. More than $5 million has been awarded since 1961.
Judith Weber, president, spoke of partnering with other organizations and businesses to increase available funds and identify specific sectors offering job opportunities along the Treasure Coast.
"It takes a community commitment for education to work," Weber said.
Keynote speaker John Textor, CEO of Digital Domain, recalled his gratitude in receiving financial assistance for college.
"What you're getting is a great gift," he said.
He shared details about films Digital Domain has produced, including "Transformers" and "The Curious Case of Benjamin Button." Textor also showed footage of a hologram of deceased rapper Tupac Shakur created by Digital Domain that debuted recently at the Coachella music festival.
Pointing out that this growing industry requires people with expertise in many different fields, Textor said the company hopes to fill those jobs locally.
Three students — Cullen Cormier, Ralph Rivera and Joseph Smith — received matching funds from the Martin County Community Foundation to bring their four-year total to $20,000.
James and Gretchen Cormier, parents of Cullen Cormier, said they are grateful their son, who attends Martin County High, will receive financial assistance to study chemical engineering.
"This organization is amazing. We're just very, very thankful," James Cormier said.
Joseph Smith of The Pine School plans to attend St. John's College in Annapolis and pursue a bachelor's degree in liberal arts.
"It will help prepare me for law school," he said, adding the scholarship money is essential to bridging the gap between loans and college tuition.
Zachary Bacak from Jensen Beach High received an additional $2,500 per year through the Marjorie S. Peters education sector award and Zac Ross from Clark Advanced Learning Center earned the Helen and Presley Blake Entrepreneur award, an additional one-time $2,500 award, for running a business while in school.
Additional funding from the Frances Langford Arts Sector award will help Reva Satchell from Jensen Beach High realize her dream of becoming a high school choir director.
Still waiting to finalize her school of choice, Satchell said this financial assistance "means everything. Without it, I wouldn't be in school. I'm very thankful for the Nina Haven scholarships."
2012 Nina Haven Circle of Scholars
Zachary Bacak, Jensen Beach High School
Cullen Cormier, Martin County High School
Kimberly Crandle, Jensen Beach High School
Alberto Cruz, South Fork High School
Carys Davies, Martin County High School
Kyle Gorman, South Fork High School
Anthony Hernandez, South Fork High School
Jenna Kingsley, Martin County High School
Kayla Kistler, Jensen Beach High School
Casey Levy, Jensen Beach High School
Stephanie Melchionna, Jensen Beach High School
Carissa Nichols, Clark Advanced Learning Center
Kristina Rich, South Fork High School
Ralph Rivera, Jensen Beach High School
Evan Rosato, Martin County High School
Zac Ross, Clark Advanced Learning Center
Reva Satchell, Jensen Beach High School
Joseph Smith, The Pine School
Maria Suito, Martin County High School
Courtland Thomas, South Fork High School
Preston Tirrell, Clark Advanced Learning Center
Tyler Trobert, South Fork High School
Ryan Uhazie, Martin County High School
Vladimir Villa-Vergara, Martin County High School
Orane Walters, Jensen Beach High School
Brandon Wilson, Martin County High School
Jia Ying Zhai, South Fork High School
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subset: commoncrawl


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As is the case with movies of the same vein, horror games employ a limited array of cliched scare-o-tactics. Resident Evil, as such, indulged in capers first introduced by Alone in the Dark. In this franchise, players were often -get this!- alone. IN THE DARK. Beset by ghastly (and blur-tastic, this being a wrinkly-titted ancient game and all) underworld entities, granted, but 'alone' nonetheless. The notion of stealthing through corridors apparently bereft of light switches has been regurgitated ad nauseam. So, too, have THERE'S SHIT IN MY PANTS! I HAVE MIXED FEELINGS ABOUT THIS WHOLE SITUATION jump scares, creep-tacular ambient sounds and other such horror stalwarts. Resident Evil, Silent Hill, Dead Space, Dementium et al all plunder each others' repertoires in this regard.
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An improved process for the preparation of thermoplastic elastomers by hydrosilylation crosslinking of a butyl rubber component, in which a platinum containing hydrosilylation catalyst is used. The butyl rubber component includes a copolymer of at least isobutylene and an aromatic divinyl compound such as divinylbenzene. The copolymer of at least isobutylene and divinylbenzene is significantly easier to crosslink into a substantially insoluble rubber in a thermoplastic vulcanizate than isobutylene copolymers with only unsaturated repeating units from conjugated dienes. A crosslinked rubber component is obtained in the thermoplastic elastomer composition.
1. A thermoplastic vulcanizate comprising
a) a thermoplastic resin
b) a crosslinked butyl rubber containing repeating units derived from copolymerizing an aromatic divinyl compound and including a hydrosilylation crosslinking agent chemically crosslinking said butyl rubber by forming bonds between said repeating units.
2. A thermoplastic vulcanizate according to claim 1, wherein said thermoplastic resin is a thermoplastic polyolefin resin.
3. A thermoplastic vulcanizate according to claim 2, wherein said repeating units derived from copolymerizing an aromatic divinyl compound are present in amounts from about 0.2 to about 5 weight percent based upon said butyl rubber.
4. A thermoplastic vulcanizate according to claim 3, wherein said repeating units are derived from copolymerizing divinylbenzene and are present from about 0.2 to about 4 weight percent and said butyl rubber further including from about 1 to about 5 weight percent repeating units derived from copolymerizing a polyene having from 4 to 14 carbon atoms.
5. A thermoplastic vulcanizate according to claim 1, wherein said thermoplastic resin comprises at least 85 weight percent repeating units from propylene.
6. A molded or extruded article comprising the thermoplastic vulcanizate of claim 3.
7. A molded or extruded article according to claim 6, in the form of a translucent or transparent component to a medical device or food processing equipment.
8. A molded or extruded article according to claim 6 having a halogen content of less than 200 ppm.
9. A molded or extruded article according to claim 8 used in an electrical condenser pack.
This is a continuation-in-part of U.S. patent application Ser. No. 08/749,756, now U.S. Pat. No. 5,936,028, filed Nov. 1, 1996 which is a continuation-in-part of U.S. patent application Ser. No. 08/566,380 filed Dec. 1, 1995 now U.S. Pat. No. 5,672,660, both of said prior references are hereby incorporated by reference.
This invention relates to thermoplastic elastomer compositions prepared using hydrosilylation crosslinking of a butyl rubber elastomer component of the composition. The butyl rubber is a copolymer of at least isobutylene and an aromatic divinyl monomer. A thermoplastic elastomer is generally defined as a polymer or blend of polymers that can be processed and recycled in the same way as a conventional thermoplastic material, yet has properties and functional performance similar to that of vulcanized rubber at a desired service temperature. High performance thermoplastic elastomers in which a highly vulcanized rubbery polymer (elastomer) is intimately dispersed in a thermoplastic matrix are generally known as thermoplastic vulcanizates.
Polymer blends which have a combination of both thermoplastic and elastic properties are generally obtained by combining a thermoplastic resin with an elastomeric composition in a way such that the elastomer component is intimately and uniformly dispersed as a discrete particulate phase within a continuous phase of the thermoplastic. Early work with vulcanized rubber components is found in U.S. Pat. No. 3,037,954 which discloses both static vulcanization of the rubber, as well as the technique of dynamic vulcanization wherein a vulcanizable elastomer is dispersed into a molten resinous thermoplastic polymer and the elastomer is cured while continuously mixing and shearing the blend. The resulting composition is a micro-gel dispersion of cured elastomer in an uncured matrix of thermoplastic polymer.
In U.S. Pat. No. Re. 32,028 polymer blends comprising an olefin thermoplastic resin and an olefin copolymer are described, wherein the rubber is dynamically vulcanized to a state of partial cure. The resulting compositions are reprocessible. U.S. Pat. Nos. 4,130,534 and 4,130,535 further disclose thermoplastic vulcanizates comprising butyl rubber and polyolefin resin, and olefin rubber and polyolefin resin, respectively. The compositions are prepared by dynamic vulcanization and the rubber component is cured to the extent that it is essentially insoluble in conventional solvents. A range of crosslinking, or curing, agents for the vulcanization of the rubber are described in the early art, including peroxides, sulfurs, phenolic resins, radiation, and the like.
U.S. Pat. No. 4,803,244 generally discusses the use of multifunctional organosilicon compounds in conjunction with a catalyst as an agent for crosslinking the rubber component of a thermoplastic elastomer by hydrosilylation. Hydrosilylation involves the addition of a silicon hydride across a multiple bond, often with a transition metal catalyst. This patent describes a rhodium catalyzed hydrosilylation of EPDM rubber in a blend with polypropylene to produce thermoplastic elastomers having a gel content of up to 34% (after correction for the plastic phase). This degree of vulcanization was achieved only with a high level of catalyst.
A further modification of hydrosilylation crosslinking of the rubber in a thermoplastic elastomer composition is disclosed in European Patent Application No. 651,009. A compatibilizing agent containing in the same molecule a component having an affinity for the rubber and a component having an affinity for the thermoplastic resin is incorporated into the composition, and is said to improve adhesion between the rubber and resin in order to prevent agglomeration.
U.S. Pat. No. 3,584,080 teaches how to prepare copolymers of an isoolefin (e.g. isobutylene) and an aromatic divinyl compound (e.g. divinylbenzene). U.S. Pat. No. 4,916,180 teaches peroxide curing of terpolymers of isobuylene and an divinyl aromatic monomer in the presence of polypropylene.
The present invention is based on 1) the discovery that the process for hydrosilylation crosslinking of the rubber in a thermoplastic elastomer can be improved by employing a platinum-containing catalyst in combination with an elastomer having predominately sterically unhindered carbon-carbon double bonds and 2) the discovery of specific copolymers of at least isoolefin (e.g. isobutylene) and aromatic divinyl monomers (e.g. divinylbenzene) that are capable of being effectively crosslinked with hydrosilylation crosslinking. This combination provides rapid crosslinking of the elastomer to a fully vulcanized state, yet requires an unexpectedly low concentration of the catalyst in order to achieve the cure. In the instant invention no compatibilizer is required in order to produce compositions with excellent mechanical properties, no bubble formation and very good colorability, due to the extremely low levels of catalyst concentration. Surprisingly, lower catalyst concentrations also produce compositions with much improved heat aging characteristics, resistance to degradation by ultraviolet light and having a non-hygroscopic character.
In a preferred embodiment, the butyl rubber includes a copolymer of isobutylene and divinylbenzene.
In a further embodiment of the invention, additives which react with residual silicon hydride functionality in the thermoplastic elastomer are incorporated into the process. This results in a composition which has further improved long term heat aging characteristics.
The compositions produced by the improved process have utility as replacements for thermoset rubber compounds in a variety of applications, particularly where molding or extrusion is involved and the combination of thermoplastic and elastomeric properties provides an advantage. The particular thermoplastic elastomers of this disclosure using a copolymer of at least an isoolefin and an aromatic divinyl monomer can be transparent or translucent when the refractive indexes of the rubber and thermoplastic are matched or nearly matched. Typical uses include molded articles for automobile underhood parts, engineering and construction materials, mechanical rubber goods, industrial parts such as hose, tubing and gaskets, electrical applications and household goods. Particularly preferred uses as translucent or transparent component in a medical device or food processing equipment. Another use is as a component in electrical devices such as condenser packs. For those uses, the halogen content of the TPV is desirably below 200 ppm.
Thermoplastic elastomer compositions may generally be prepared by blending a thermoplastic resin and a rubber, then melting the thermoplastic component and mixing the melt until the blend is homogeneous. If a composition of vulcanized rubber in a thermoplastic matrix is desired, crosslinking agents (also referred to as curatives or vulcanizing agents) are added to the blend and crosslinking occurs during the mixing. This latter process is described as dynamic vulcanization.
A wide range of thermoplastic resins and rubbers and/or their mixtures have been used in the preparation of thermoplastic elastomers, including polypropylene, HDPE, LDPE, VLDPE, LLDPE, cyclic olefin homopolymers or copolymers as well as olefinic block copolymers, polystyrene, polyphenylene sulfide, polyphenylene oxide and ethylene propylene copolymer (EP) thermoplastics, with ethylene propylene diene rubber (EPDM), butyl rubber, acrylonitrile butadiene rubber (NBR) and natural rubber (NR) as the elastomers. When the elastomer component is crosslinked, agents such as sulfur, peroxide, phenolics and ionic compounds are often used.
Hydrosilylation Agents
Hydrosilylation has also been disclosed as a crosslinking method. In this method a silicon hydride having at least two SiH groups in the molecule is reacted with the carbon-carbon multiple bonds of the unsaturated (i.e. containing at least one carbon-carbon double bond) rubber component of the thermoplastic elastomer, in the presence of the thermoplastic resin and a hydrosilylation catalyst. Silicon hydride compounds useful in the process of the invention include methylhydrogen polysiloxanes, methylhydrogen dimethyl-siloxane copolymers, alkyl methyl polysiloxanes, bis(dimethylsilyl)alkanes and bis(dimethylsilyl)benzene.
Preferred silicon hydride compounds may be described by the formula ##STR1## where each R is independently selected from the group consisting of alkyls comprising 1 to 20 carbon atoms, cycloalkyls comprising 4 to 12 carbon atoms and aryls. In formula (1) it is preferred that each R be independently selected from a group consisting of alkyls comprising 1 to 6 carbon atoms. Even more preferred is R=methyl, R' represents a hydrogen atom, an alkyl or alkoxy group having from 1 to about 24 carbon atoms, R" represents R or a hydrogen atom, D represents the group ##STR2## D' represents the group ##STR3## T represents the group ##STR4## m is an integer having a value ranging from 1 to 50, n is an integer having a value ranging from 1 to 50, and
p is an integer having a value ranging from 0 to 6.
Particularly preferred polyorganosiloxanes are those in which the silicon atom of the silicon hydride functionality is bound by heteroatoms/atoms having lone pairs of electrons. The preferred polyorganosiloxanes may also be substituted with appropriate functionality permitting solubility in the reaction media. A type of this functionalization is described in U.S. Pat. No. 4,046,930 which teaches alkylation of polyorganosiloxanes. Weight percent of alkylation should not exceed a level that does not permit adequate reaction rates due to steric constraints.
The amount of silicon hydride compound useful in the process of the present invention desirably can range from about 0.1 to about 10.0 mole equivalents of SiH per carbon-carbon double bond in the rubber, and preferably is in the range of about 0.5 to about 5.0 mole equivalents of SiH per carbon-carbon double bond in the rubber component of the thermoplastic elastomer. Lower molecular weight (and equivalent weight) silicon hydride compounds (e.g. lower degrees of polymerization) are generally more effective on a weight basis than higher equivalent weight silicon hydride compounds.
Thermoplastic Resins
Thermoplastic resins useful in the compositions produced by the invention include crystalline polyolefin homopolymers and copolymers. They are desirably prepared from monoolefin monomers having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene and the like, as well as copolymers derived from linear and cyclic olefins, with propylene being preferred. Desirably said thermoplastic resin comprises at least 80, 85, 90 or 95 wt % repeat units from a monoolefin monomer having either 2 or 3 carbon atoms. As used in the specification and claims the term polypropylene includes homopolymers of propylene as well as reactor copolymers of polypropylene which can contain about 1 to about 15 or 20 wt % of ethylene or an -olefin comonomer of 4 to 20 carbon atoms, and mixtures thereof. The polypropylene can be crystalline, isotactic or syndiotactic polypropylene. Commercially available polyolefins may be used in the practice of the invention. Other thennoplastic resins which are substantially inert to the rubber, the silicon hydride and the hydrosilylation catalyst would also be suitable. Blends of thermoplastic resins may also be used.
The amount of thermoplastic resin found to provide useful compositions is generally from about 5 to about 90 weight percent, based on the weight of the rubber and resin. Preferably, the thermoplastic resin content will range from about 20 to about 80 percent by weight of the total polymer.
Unsaturated rubbers useful to prepare thermoplastic elastomers according to the invention include monoolefin copolymer rubbers comprising non-polar, rubbery copolymers of two or more -monoolefins, preferably copolymerized with at least one polyene, usually a diene. In an embodiment a copolymer of at least an isoolefin e.g. isobutylene and an aromatic divinyl monomer is preferred as at least part of the rubber component of the thermoplastic vulcanizate. An unsaturated monoolefin rubber such as EPDM rubber is more suitable in some alternate embodiments. EPDM is a polymer of ethylene, propylene and one or more non-conjugated diene or non-conjugated dienes, and the monomer components may be polymerized using Ziegler-Natta or metallocene catalyzed reactions, among others. Satisfactory non-conjugated dienes include 5-ethylidene-2-norbornene (ENB); 1,4-hexadiene (HD); 5-methylene-2-norbornene (MNB); 1,6-octadiene; 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene; dicyclopentadiene (DCPD); 5-vinyl-2-norbornene (VNB) and the like, or a combination thereof. Decyclopentadiene (DCPD) is generally more hindered than the other dienes and consequently crosslinks slower, as shown in Table II.
In one embodiment of the invention, it has been found that rubber having a structure in which the diene monomer has carbon-carbon multiple bonds which are predominately unencumbered, i.e. bonds which are sterically unhindered such as terminal or pendant double bonds with respect to the polymer chain, provide a greatly improved rate of cure in the hydrosilylation curing process of the invention. Included in this embodiment are structures in which the bonds either normally are unencumbered or are easily isomerized to form a sterically unencumbered double bond, which is then rapidly hydrosilated, e.g. 1,4-hexadiene or ENB. This improvement is particularly significant where a fully cured rubber component is desired. The use of rubber in which the diene component is selected from the group consisting of 5-ethylidene-2-norbornene, 5-methyl-1,4-hexadiene, 1,4-hexadiene and 5-vinyl-2-norbornene is preferred 5-vinyl-2-norbornene is particularly preferred as a diene component of such rubber.
Butyl rubbers are also generally useful in the compositions of the invention. A preferred subset of butyl rubbers that result in low amounts of extractable rubber and good tension set is described in a subsequent paragraph. As used in the specification and claims, the term "butyl rubber" includes copolymers of an isoolefin and a conjugated multi-olefin, copolymer of an isoolefin and an aromatic divinyl compound, terpolymers of an isooolefin, a conjugated multi-olefin and aromatic divinyl monomers, and the halogenated derivatives of such copolymers and terpolymers. The useful butyl rubber copolymers comprise a major portion of isoolefin and a minor amount, usually less than 30 wt %, of a conjugated multiolefin. The copolymers may comprise about 85-99.5 wt % of a C4-7 isoolefin such as isobutylene and about 15-0.5 wt % of a multiolefin of 4-14 carbon atoms, such as isoprene, butadiene, dimethyl butadiene, 4-methyl-1,4-pentadiene and piperylene. Commercial butyl rubber, useful in the invention, is a copolymer of isobutylene and minor amounts of isoprene. Other butyl co- and terpolymer rubbers are illustrated by the description in U.S. Pat. No. 4,916,180 hereby incorporated by reference. Copolymer and terpolymers including repeating units from isobutylene and aromatic divinyl monomers are particularly preferred as an elastomer suitable for hydrosilylation crosslinking. A highly preferred subset of butyl rubbers are those having carbon to carbon double bonds with greater reactivity towards crosslinking reactions than is typically achieved with residual double bonds derived from conjugated dienes. Examples of these double bonds are the residual double bond in aromatic divinyl compounds such as divinylbenzene monomers after copolymerization with isobutylene.
The copolymer of at least an isoolefin and an aromatic divinyl monomer desirably comprises from about 80 to about 99.8 weight percent repeating units from an isoolefin (e.g. isomonoolefin) of 4 to 7 carbon atoms, from about 0 to about 19.8 weight percent repeating units from an aliphatic polyene (e.g. diene) of 4 to 14 carbon atoms and from about 0.2 to about 5 weight percent repeating units from an aromatic divinyl compound of the formula ##STR5##
Where the symbol X represents an aromatic nucleus and the symbols R which may be the same or different represent hydrogen atoms or alkyl groups of 1 to 5 carbon atoms. X, the aromatic nucleus, can be any aromatic group including those represented by the benzene ring, the naphthalene rings, pyridine ring, and mono or poly alkyl substituted versions thereof. The preferred isoolefin is isobutylene, the preferred polyene is isoprene, and the preferred aromatic divinyl compound is divinylbenzene. U.S. Pat. No. 3,584,080 is incorporated by reference for a more detailed description of the copolymer. Preferably the repeating units from the polyene is from about 0.1 to about 5 weight percent of the copolymer. Preferably the repeating units from aromatic divinyl compound is from about 0.2 to 4 weight percent (2000 to 40,000 ppm) and more preferably from about 0.5 to about 3 weight percent (5000 to 30,000 ppm) of the copolymer. It is noted that a large portion of the unsaturated repeat units from the aromatic divinyl compound are consumed in crosslinking reactions during polymerization and are not available as unsaturated units (i.e. they are converted to saturated crosslinks) for further hydrosilylation crosslinking.
Preferred butyl rubbers thus comprise copolymers of at least an isoolefin and an aromatic divinyl compound. The repeat units therein with unsaturation from an aromatic divinyl compound are desirably present from about 50 to about 5000 ppm (0.005 to about 0.5 wt % based on the total amount of butyl rubber) and more desirably from about 200 to about 2500 ppm. The repeat units from an isoolefin desirably are from about 85 to 99.5 wt % and repeat units from a multiolefin (polyene) of 4-14 carbon atoms can be absent or present in an amount from about 0.5 to about 15 wt % based on the total amount of butyl rubber copolymer. A percentage of the repeat units from divinylbenzene may be present as repeat units without residual unsaturation. As the repeat units from aromatic divinyl compounds (e.g. divinylbenzene) are very reactive to crosslinking, it is sometimes desirable to dilute the copolymers of isobutylene and aromatic divinyl compounds with more conventional butyl rubbers described in the previous paragraph. A commercial example of a copolymer of isobutylene and divinylbenzene is Polysar Butyl XL 10000 available from Bayer Corporation. Said Polysar Butyl XL 10000 has a Mooney viscosity 1+8 @ 125� C. of 60-75 and has 20-30 wt % of the polymer soluble in cyclohexane. XL 10000 starts with about 2000 ppm unsaturated repeat units from divinylbenzene. Butyl rubbers are also available from Bayer as XL 68102 having at 1500 ppm unsaturated repeat units from divinylbenzene and Mooney viscosity of 59-75 and XL 30102 having about 600 ppm unsaturated repeat units from divinylbenzene and a Mooney viscosity from about 67-83. The products with designations XL 68102 and XL 30102 are believed to be blends of two different butyl rubbers, one with repeat units from divinylbenzene and one without such repeat units (e.g. a butyl rubber of isobutylene and a conjugated diene).
An unsaturated repeat unit from an aromatic divinyl compound will desirably have the structure: ##STR6## Where X and R are as previously defined.
A close examination of this repeat units reveals that the carbon to carbon double bond has little steric hindrance and some mobility with respect to the polymer backbone which may facilitate its reaction with hydrosilylation crosslinking agents.
A further rubber suitable in the invention is natural rubber. The main constituent of natural rubber is the linear polymer cis-1,4-polyisoprene. It is normally commercially available in the form of smoked sheets and crepe. Synthetic polyisoprene can also be used with the particularly preferred synthetic polyisoprene elastomers being those that contain vinyl functionality pendant to the main polymer chain, i.e. 1,2-enchainments.
Polybutadiene is also a suitable elastomer for hydrosilylation curing, with polybutadienes that contain vinyl functionality being the most preferred.
Blends of any of the above rubbers may also be employed, rather than a single unsaturated rubber.
In preparing the compositions of the invention, the amount of rubber generally ranges from about 95 to about 10 weight percent, based on the weight of the rubber and thermoplastic resin. Preferably, the rubber content will be in the range of from about 80 to about 20 weight percent of total polymer of the thermoplastic vulcanizate (e.g. the total of the thermoplastic and the rubber).
Hydrosilylation Catalysts
It has previously been understood that any catalyst, or catalyst precursor capable of generating a catalyst in situ, which will catalyze the hydrosilylation reaction with the carbon-carbon bonds of the rubber can be used. Such catalysts have included transition metals of Group VIII such as palladium, rhodium, platinum and the like, including complexes of these metals. Chloroplatinic acid has been disclosed as a useful catalyst in U.S. Pat. No. 4,803,244 and European Application No. 651,009, which further disclose that the catalyst may be used at concentrations of 5 to 10,000 parts per million by weight and 100 to 200,000 parts per million by weight based on the weight of rubber, respectively.
It has been found in the process of the present invention that significantly lower concentrations of platinum-containing catalyst can be used, while obtaining improvement in both the speed of the reaction and the efficiency of the crosslinking. Concentrations of catalyst in the range of about 0.1 to about 10, 20 or 40 expressed as parts by weight of platinum metal per one million parts by weight of rubber, are effective in rapidly and completely curing the rubber from isobutylene and aromatic divinyl monomers in the process of dynamically vulcanizing blends of thermoplastic resin and rubber. These low catalyst concentrations are particularly effective in combination with a diene-containing rubber having carbon-carbon multiple bonds which are predominately sterically unhindered Catalyst concentrations of about 1 to about 25 parts per million by weight based on the weight of rubber, expressed as platinum metal, are particularly preferred.
Platinum-containing catalysts which are useful in the process of the invention are described, for example, in U.S. Pat. No. 4,578,497; U.S. Pat. No. 3,220,972; and U.S. Pat. No. 2,823,218 all of which are incorporated herein by this reference. These catalysts include chloroplatinic acid, chloroplatinic acid hexahydrate, complexes of chloroplatinic acid with sym-divinyltetramethyldisiloxane, dichloro-bis(triphenylphosphine) platinum (II), cis-dichloro-bis(acetonitrile) platinum (II), dicarbonyldichloroplatinum (II), platinum chloride and platinum oxide. Zero valent platinum metal complexes such as Karstedt's catalyst are particularly preferred, as described in U.S. Pat. No. 3,775,452; U.S. Pat. No. 3,814,730; and U.S. Pat. No. 4,288,345 all of which are incorporated herein by this reference.
In order for the catalyst to function most efficiently in the dynamic vulcanization environment, it is important that it is inherently thermally stable, or that its activity is inhibited to prevent too rapid a reaction or catalyst decomposition. Appropriate catalyst inhibitors that are suitable to stabilize the platinum catalyst at high temperatures include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxanc and its higher analogs such as vinyl cyclic pentamer. However, other olefins that are stable above 165� C. are also useful. These include maleates, fumarates and the cyclic pentamer. It is also particularly preferred in the invention to use a catalyst that remains soluble in the reaction medium.
The thermoplastic elastomer may contain conventional additives, which can be introduced into the composition in the thermoplastic resin, the rubber, or in the blend either before, during or after the hydrosilylation and curing. Examples of such additives are antioxidants, processing aids, reinforcing and nonreinforcing fillers, pigments, waxes, rubber processing oil, extender oils, antiblocking agents, antistatic agents, ultraviolet stabilizers, plasticizers (including esters), foaming agents, flame retardants and other processing aids known to the rubber compounding art. Such additives may comprise from about 0.1 to about 300 percent by weight based on the weight of the final thermoplastic elastomer (vulcanizate) product. Fillers and extenders which can be utilized include conventional inorganics such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black and the like. Additives, fillers or other compounds which may interfere with the hydrosilylation should be added after curing reaches the desired level (e.g. the desired extent of crosslinking of the rubber).
In another embodiment, it has been found that the heat aging properties of compositions prepared according to the invention can be greatly improved by the addition of a metal chelating agent to the blend. This effect is believed to be due to the fact that the hydrosilylation catalyst is in an active valence state. This form of the platinum metal accelerates degradation of the thermoplastic elastomer, particularly under conditions of elevated temperature over an extended time. Chelation prevents the metal from causing degradation.
Typical chelating agents useful for this purpose include materials such as 1,2-bis(3,5-di-ter-butyl-4-hydroxyhydrocinnamoyl)hydrazine and the like. Surprisingly, these agents may be incorporated into the composition prior to or after the hydrosilylation curing. Amounts of chelating agent ranging from about 0.025 parts per hundred parts of rubber (phr) to about 10 phr have been found to be useful, and amounts in the range of about 0.1 phr to 2 phr are preferred.
In a further embodiment of the invention, it has been demonstrated that reducing residual or unreacted silicon hydride functionality in the thermoplastic elastomer products results in compositions which have improved heat stability. Unreacted silicon hydride may be reduced or eliminated by reacting the silicon hydride with compounds containing active hydrogen, carbon-carbon multiple bonds, carbon-oxygen double bonds or carbon-nitrogen double bonds and the like. The residual silicon hydride reacts with these compounds to eliminate silicon hydride functionality and form silicon-oxygen or carbon-silicon bonds.
Typical compounds useful for this purpose are silica and water. These agents are incorporated into the composition after the hydrosilylation cure is complete. Water may be introduced as steam anytime after cure in a single or two pass operation. Amounts of such compounds may be estimated by measuring residual silicon hydride and adding a stoichiometric amount of the compound. One may also desire adding a stoichiometric excess if necessary to eliminate a sufficient amount of the residual silicon hydride in order to realize the desired improvement in heat aging properties. Amounts of such compounds ranging from about one mole equivalent to about 10 mole equivalents have been found to be useful, and amounts in the range of about 1 to 3 mole equivalents are preferred.
Extender Oil
The rubber processing or extender oils used in thermoplastic elastomers generally are paraffinic, naphthenic or aromatic oils derived from petroleum fractions. Polybutene oils are useful when the elastomer portion of the termoplastic elastomer are butyl rubbers. The type will be that ordinarily used in conjunction with the specific rubber or rubbers present in the composition, and the quantity based on the total rubber content of the thermoplastic elastomer may range from zero to several hundred parts per hundred rubber. Important to the efficiency of the catalyst is that the oils and other additives contain no or very low concentrations of compounds that are catalyst inhibitors or that interfere with the activity of the catalyst. These compounds include phosphines, amines, sulfides, thiols or other compounds that may be classified as Lewis bases. Lewis bases, or other compounds that have a pair of electrons available for donation, will react with the platinum catalyst, effectively neutralizing its activity. It has been discovered that the presence of such compounds has a surprisingly detrimental impact on hydrosilylation curing in the process of dynamic vulcanization of the rubber component of the thermoplastic elastomer compositions. If the concentration of compounds which have the chemical reactivity of Lewis bases, such as compounds containing sulfur or nitrogen, is maintained at or below a level which provides less than about 1000 ppm and 300 ppm of sulfur and nitrogen respectively, then the amount of platinum catalyst required to promote efficient hydrosilylation curing in dynamic vulcanization can be substantially reduced, usually to the range of about 4 ppm or less, without impact on the cure state of the rubber or the tensile properties of the thermoplastic elastomer product. Concentrations of sulfur and nitrogen below about 500 and 200 ppm respectively are more preferred, and concentrations of less than about 30 ppm sulfur and less than about 100 ppm nitrogen are most preferred. It has been discovered that, even at catalyst concentrations as low as 0.25 ppm, full cure of the elastomer can be achieved if the concentration of sulfur and nitrogen is within the most preferred ranges.
Most paraffinic petroleum oils for the rubber industry are derived from a crude oil distillation stream. A typical refining history would include some type of dewaxing to reduce the pour point, a solvent extraction to physically remove aromatic compounds and a hydrotreating process to chemically modify aromatic structures. Both extraction and hydrotreating result in a net increase in the total concentration of saturated hydrocarbon structures and a net decrease in the total aromatic, sulfur and nitrogen-containing compound concentration. The degree of reduction in concentration of these compounds in the oil is dependent upon the type and severity of the refining employed, and the nature of the crude oil. White and paraffinic oils have been treated more extensively than aromatic and napthenic oils and would contain a smaller concentration of aromatic, sulfur and/or nitrogen compounds. It is difficult to elucidate the exact chemical structure of these compounds due to their complexity. The tendency of an oil to interfere with platinum catalyzed hydrosilylation is directly related to the concentration of sulfur and nitrogen containing compounds, as well as compounds which contain phosphorus, tin, arsenic, aluminum and iron.
The rubber component of the thermoplastic elastomer is generally present as small, i.e. micro-size, particles within a continuous thermoplastic resin matrix, although a co-continuous morphology or a phase inversion is also possible depending upon the amount of rubber relative to plastic and the degree of cure of the rubber. The rubber is desirably at least partially crosslinked, and preferably is completely or fully crosslinked. It is preferred that the rubber be crosslinked by the process of dynamic vulcanization. As used in the specification and claims, the term "dynamic vulcanization" means a vulcanization or curing process for a rubber blended with a thermoplastic resin, wherein the rubber is vulcanized under conditions of shear at a temperature at which the mixture will flow. The rubber is thus simultaneously crosslinked and dispersed as fine particles within the thermoplastic resin matrix, although as noted above other morphologies may exist. Dynamic vulcanization is effected by mixing the thermoplastic elastomer components at elevated temperatures in conventional mixing equipment such as multiple roll mills, Banbury mixers, Brabender mixers, continuous mixers, mixing extruders and the like. The unique characteristic of dynamically cured compositions is that, notwithstanding the fact that the rubber component is partially or fully cured, the compositions can be processed and reprocessed by conventional plastic processing techniques such as extrusion, injection molding and compression molding. Scrap or flashing can be salvaged and reprocessed.
The terms "fully vulcanized" and "fully cured" or "fully crosslinked" as used in the specification and claims means that the rubber component to be vulcanized has been cured or crosslinked to a state in which the elastomeric properties of the crosslinked rubber are similar to those of the rubber in its conventional vulcanized state, apart from the thermoplastic elastomer composition. The degree of cure can be described in terms of gel content, or conversely, extractable components. Gel content reported as percent gel (based on the weight of crosslinkable rubber) is determined by a procedure which comprises determining the amount of insoluble polymer by soaking the specimen for 48 hours in organic solvent at room temperature, weighing the dried residue and making suitable corrections based upon knowledge of the composition. Thus, corrected initial and final weights are obtained by subtracting from the initial weight the weight of soluble components, other than rubber to be vulcanized, such as extender oils, plasticizers and components of the composition soluble in organic solvent, as well as that rubber component of the product which is not intended to be cured. Any insoluble polyolefins, pigments, fillers, and the like are subtracted from both the initial and final weights. The rubber component can be described as fully cured when less than about 20, less than about 5%, and preferably less than 3%, of the rubber which is capable of being cured by hydrosilylation is extractable from the thermoplastic elastomer product by a solvent for that rubber. Alternatively the degree of cure may be expressed in terms of crosslink density. All of these descriptions are well known in the art, for example in U.S. Pat. Nos. 4,593,062, 5,100,947 and 5,157,081, all of which are fully incorporated herein by this reference.
The following general procedure was used in the preparation of thermoplastic elastomers by the process of the invention, as set forth in the examples. The thermoplastic resin and oil extended rubber were placed in a heated internal mixer, with the hydrosilylation agent and hydrosilylation catalyst. The hydrosilylation agent and catalyst can be incorporated into the composition by any suitable technique, for example by injection as solutions in oil or as neat components, although a dilute catalyst solution is preferred. Additives such as antioxidants, ultraviolet stabilizers and fillers may also be added as a slurry in oil. Masterbatches of the components may also be prepared to facilitate the blending process. The mixture was heated to a temperature sufficient to melt the thermoplastic component, and the mixture was masticated, with added processing oil if desired, until a maximum of mixing torque indicated that vulcanization had occurred. Mixing was continued until the desired degree of vulcanization was achieved.
The order of addition of the hydrosilylation agent and hydrosilylation catalyst was found to be important. Maximum catalyst efficiency was obtained when the hydrosilylation agent was added first to the blend, followed by the hydrosilylation catalyst. The mechanical properties of the thermoplastic elastomer products, as well as the degree of cure, were improved when this order of addition was followed.
The invention will be better understood by reference to the following examples which serve to illustrate but not limit the present process. In the examples, the following test methods were used to determine the properties of the thermoplastic elastomer products.
Hardness (Shore A/D)--ASTM D 2240
Ultimate tensile strength (UTS-psi)--ASTM D 412
Ultimate elongation (UE-%)--ASTM D 412
Modulus at 100% elongation (M1 or M-100-psi)--ASTM D412
Gel content (%)--ASTM D2765
Tension set (TS-%)--ASTM D 412
Oil swell (OS-%)--ASTM D 471
Heat aging--ASTM D 573
The rubber component used in the compositions prepared according to the examples are further identified as follows.
EPDM Rubber "A"--EPDM-2.1% ENB; 52% ethylene
EPDM Rubber "B"--EPDM-5% HD; 55% ethylene
EPDM Rubber "F"--EPDM-3% VNB; 55% ethylene
EPDM Rubber "G"--EPDM-5.5% ENB; 60% ethylene
Butyl Rubber "A"--Butyl XL 10,000 from Polysar
Butyl Rubber "B"--Butyl XL30102 from Polysar
Butyl Rubber "C"--Butyl XL 68102 from Polysar
Butyl Rubber "D"--Butyl 268 rubber from Exxon
Polypropylene "A"--Homopolypropylene MFI=0.7
Polypropylene "B"--Low molecular weight Homopolypropylene MFI=2600
Polypropylene "C"--Copolymer of propylene and ethylene MFI=4
Polypropylene "D"--Homopolypropylene MFI=14
Polypropylene "E"--Homo-polypropylene MFI=20
Polypropylene "F"--Syndiotactic polypropylene MFI=10
Si--H "A"--2-2822 from Dow Corning, Hydrosilylation agent
Catalyst "A"--PC-085 1.0 wt % in paraffinic oil from Dow Coming (Platinum)
Oil (Polybutene) "A"--Exxon Parapol 950
Oil (Polybutene) "B"--Exxon Parapol 450
Oil (Paraffinic) "C"--Britol 20T mineral oil from Witco
Compositions were prepared by the method of the invention as generally described above, using polypropylene resin and EPDM rubber containing ENB, HD and VNB as the diene component. Compositions were also prepared using polypropylene and various butyl rubbers. Control samples used Butyl 268 which included repeating units from conventional dienes for crosslinking purposes. Examples of the invention used butyl rubber or mixtures of butyl rubbers that have repeat units from divinyl benzene. The plastic and rubber components were melt mixed in a Brabender mixer at 180C until the polypropylene was melted. Silicone hydride (alkylated methyl hydrogen polysiloxane) was added dropwise to the melt mix, followed by addition of an oil solution containing platinum [platinate (II) hexachloro, dihydrogen reaction product with 2,4,6,8-tetraethenyl-2,4,6,8-tetramethyl cyclotetrasiloxane]. The rubber was dynamically vulcanized by mixing the blend until the maximum torque was reached. The product was removed from the mixer, then returned to the mixer and masticated at 180C for an additional minute. Plaques were prepared by compression molding the products of the dynamic vulcanization at 200C to a thickness of 60 mil and cooling under pressure, and the physical properties were determined using these plaques. All of the products were elastomeric, as defined by ASTM D1566, i.e. all had tension set values of less than 50%. The compositions and their properties are set forth in Tables I through V.
Example 1 of U.S. Pat. No. 4,803,244 is also set forth in comparison to several EPDM rubbers crosslinked with a platinum catalyst. In this comparative example, similar resin and rubber components were dynamically vulcanized by hydrosilylation, but the equivalent of 35 ppm of rhodium metal was used as the catalyst.
TABLE I______________________________________ Patent Ex. 1 of U.S. Pat. No. Composition I 4,803,244 II III IV______________________________________Polypropylene A (parts) 67 50 67 41 41 EPDM Rubber "A" (parts) 100 100 -- -- -- EPDM Rubber "B" (parts) -- -- 100 -- -- EPDM Rubber "F" (parts) -- -- -- 100 -- EPDM Rubber "G" (parts) -- -- -- -- 100 Si-H A (phr) 2.5 6.7 3 2.2 3 Rhodium (ppm) -- 35 -- -- -- Platinum (ppm) 15 -- 7.6 4 13 Hardness (A/D) 93/40 88/26 39 D 69 A 63 A UTS (psi) 2500 769 2210 1080 905 UE (%) 405 240 330 211 406 M1 1750 305 1510 636 408 TS (%) 22 43 24 -- -- Gel (%) (corrected for 95 15 92 99 90 plastic phase)______________________________________ The composition III and IV also contained 130 phr paraffin oil, 42 phr clay, 5 phr wax, 2 phr ZnO
It can be seen that the use of much lower levels of platinum catalyst in the hydrosilylation crosslinking of Rubbers A, B, F and G (EPDM rubbers containing 2.1% ENB, 5% HD, 3% VNB, and 5.5% ENB) results in a marked increase in the level of crosslinking (as reflected by gel content) and improved tensile properties in the thermoplastic elastomer, as compared to the use of rhodium as the catalyst.
Three different butyl rubber copolymers including at least repeat units from isobutylene and divinylbenzene were formulated into thermoplastic vulcanizates crosslinked by hydrosilylation. The butyl rubbers (A, B and C) represent three different concentrations of residual unsaturation from divinylbenzene (2000, 600, and 1500 ppm) respectively. The fact that all three compositions Va, VIa, and VIIa all have comparable physical properties and no trends exist, as the amount of residual unsaturation from divinylbenzene decreases, is indicative of sufficient active unsaturation in all the butyl rubbers. Butyl rubbers A-C are all believed to include terpolymers of isobutylene, a conjugated diene, and divinylbenzene. Butyl rubbers B-C are believed to be blends of a copolymer of isobutylene, divinylbenzene, and a conjugated diene with a copolymer of isobutylene and a conjugated diene.
TABLE II______________________________________ Va VIa VIIa COMPOSITION Wt % Wt % Wt %______________________________________Ingredients Butyl Rubber A 47.39 Butyl Rubber B 47.39 Butyl Rubber C 47.39 Polypropylene B 2.37 2.37 2.37 Polypropylene C 9.48 9.48 9.48 Polypropylene D 9.48 9.48 9.48 Si-H A 2.84 2.84 2.84 Catalyst A 4.74 4.74 4.74 Oil (paraffinic) C 23.70 23.70 23.70 Total 100.00 100.00 100.00 ROOM TEMPERATURE PROPERTY Hardness A, 5 sec 57 53 56 UE, % 215 230 235 UTS, psi 669 527 528 M-100, psi 351 370 293 Tear Strength, pli 84 114 97 Tension Set, % 6 15 11 Comp, Set, 22 hrs, 70 C. 24 31 31______________________________________
This example is similar to Example 2 and Table II except the extender oil used is Oil (polybutene) "A" or Oil (polybutene) "B" rather than Oil (paraffinic) "C". The compositions have a suffix b or c indicating variations of the prior examples which had a suffix "a". The samples with the suffix "b" use polybutene oil "A" while the samples with the suffix "c" use polybutene oil "B" instead of paraffinic oil "C". Composition VIIc (a control) does not include a copolymer of at least isobutylene and divinylbenzene. The physical properties of Composition VIIIc are dramatically inferior which is interpreted to be caused by a lower level of crosslinking due to a lack of unsaturation from divinylbenzene in the butyl rubber. Composition VIIIc can be used as a control for any of the other compositions which include a copolymer of at least isobutylene and divinylbenzene.
TABLE III______________________________________ Vb VIb VIIb Vc VIIIc COMPOSITION Wt % Wt % Wt % Wt % Wt %______________________________________Ingredients Butyl Rubber "A" 47.39 47.39 Butyl Rubber "B" 47.39 Butyl Rubber "C" 47.39 Butyl Rubber "D" (Cntrl) 47.39 Polypropylene "B" 2.37 2.37 2.37 Polypropylene "C" 9.48 9.48 9.48 11.85 11.85 Polypropylene "D" 9.48 9.48 9.48 9.48 9.48 Si-H "A" 2.84 2.84 2.84 2.84 2.84 Catalyst "A" 4.74 4.74 4.74 4.74 4.74 Oil (polybutene) "A" 23.70 23.70 23.70 Oil (polybutene) "B" 23.70 23.70 Total 100.00 100.00 100.00 100.00 100.00 ROOM TEMPERA- TURE PROPERTY Hardness A, 5 sec 60 52 59 53 30 UE, % 256 319 285 237 124 UTS, psi 660 422 644 796 112 M-100, psi 326 302 322 360 112 Tear Strength, pli 128 143 131 78 39 Tension Set, % 10 26 15 6 55 Comp, Set, 22 hrs, 70 C. 27 46 38 24 100______________________________________
This example is similar to Example 3, Table III and varies from that Example by using less of Catalyst A (2.46 wt % of a 1 wt % solution in paraffinic vs 4.74 wt %), less Si--H "A" (1.48wt % versus 2.84 wt %) and the addition of a more flexible polypropylene (Polypropylene D) into the compositions. The physical properties of the resulting vulcanizates were not appreciably affected by the reduction in the amount of Si--H and catalyst.
TABLE IV______________________________________ Vd VId VIId VIIId COMPOSITION Wt % Wt % Wt % Wt %______________________________________Ingredients Butyl Rubber "A" 49.26 Butyl Rubber "B" 49.26 Butyl Rubber "C" 49.26 Butyl Rubber "D" (Cntrl) 49.26 Polypropylene "C" 12.32 12.32 12.32 12.32 Polypropylene "D" 9.85 9.85 9.85 9.85 Si-H "A" 1.48 1.48 1.48 1.48 Catalyst "A" 2.46 2.46 2.46 2.46 Oil (polybutene) "A" 24.63 24.63 24.63 24.63 Total 100.00 100.00 100.00 100.00 ROOM TEMPERATURE PROPERTY Hardness A, 5 sec 56 50 54 36 UE, % 286 343 338 737 UTS, psi 907 428 682 128 M-100, psi 353 268 310 122 Tear Strength, pli 87 109 108 50 Tension Set, % 6 18 13 35 Comp, Set, 22 hrs, 70 C. 25 50 39 81______________________________________
The first three compositions (Ve-VIIe) of this example are similar to Example 4 except for the substitution of Oil (polybutene) "B" for Oil (polybutene) "A". Compositions Vf and Vg vary from composition Ve in that they have lower amounts of Catalyst "A" (1.49 and 1.00 wt % respectively versus 2.46 wt %). This further reduction in the amount of catalyst (further with respect to Table III where it was 4.74 wt %) did not significantly affect the physical properties.
TABLE V______________________________________ Ve VIe VIIe Vf Vg COMPOSITION Wt % Wt % Wt % Wt % Wt %______________________________________Ingredients Butyl Rubber A 49.26 49.75 50.00 Butyl Rubber B 49.26 Butyl Rubber C 49.26 Polypropylene C 12.32 12.32 12.32 12.44 12.50 Polypropylene D 9.85 9.85 9.85 9.95 10.00 Si-H "A" 1.48 1.48 1.48 1.49 1.50 Catalyst "A" 2.46 2.46 2.46 1.49 1.00 Oil (polybutene) B 24.63 24.63 24.63 24.88 25.00 Total 100.00 100.00 100.00 100.00 100.00 ROOM TEMPERA- TURE PROPERTY Hardness A, 5 sec 53 47 47 53 57 UE, % 342 284 300 314 327 UTS, psi 831 350 632 959 879 M-100, psi 301 240 307 340 320 Tear Strength, pli 83 86 86 87 83 Tension Set, % 6 15 10 8 5 Comp, Set, 22 hrs, 26 51 38 27 24 70 C.______________________________________
While the best mode and preferred embodiment of the invention have been set forth in accord with the Patent Statutes, the scope of the invention is not limited thereto, but rather is defined by the attached claims.
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2 Texans to Alaska (and back)...
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Two wheeled traveler
Joined: Dec 2008
Location: Lowry Crossing, TX
Oddometer: 393
Cody, WY to Great Falls, MT
Fri. June 4, 2010 Day 5
Total Mileage Today: 372
Total Trip Mileage: 2,325
Got a late start out of Cody. We hung around the camp park sucking up wifi and what not. Today we were headed up to Montana via Yellowstone National Park and the Chief Joseph Scenic Byway. The day started out well enough.
I would totally live in that outhouse if that was my backyard
But soon there were some not so happy looking clouds coming in off the mountains.
Not long after, it started to rain. We went higher, and it continued to rain. It turned to a bit of snow flurry around the turn off to go to Red Lodge. I assumed Nikki's vest was keeping her comfortable, as I felt her head bounce off my back a few times because she was dozing off... Anyhow, we entered Yellowstone NP from the Northeast corner, right at rush hour.
But the weather was so damp and dreary that we just motored on through and out the North Entrance.
This was probably the day that I realized that my new Gaerne Balance Oiled Boots (advertised waterproof) were not waterproof
. Not too much I could do about it now.
We stopped for some Pizza right outside of Yellowstone. Talked about stopping for the day (even though it was early) or maybe pushing ahead till we hit some dry weather, and set-up camp. We decided to push on a bit as we felt better after lunch.
We entered Montana.
And then ran head on into a storm. This one looked like the real deal. It was like one of those storms we get in Texas that spin up those things that are always pickin on trailer parks.
It's amazing how exposed you feel in a storm while on a bike
My dad would always tell us that the best thing to do while driving through a storm was to haul ass. He'd see all those people pulled off on the shoulder and exclaim "pussy's" as he hit the accelerator. I guess it mostly worked out ok for him - I am still here
. Anyhow, I guess I carried that little nugget of info with me and decided that was the method I would use. There wasn't really anybody else around that I could accuse of being a pussy, but non the less we hauled ass straight through the storm.
We made it though and stopped for a break.
Those eyes are telling, aren't they?
I liked this picture a whole lot, but it is a bummer about the orange construction fencing at the base.
Now, here I have 2 things to apologize to BigDog for. #1. Sorry about the small font, I hope this is better
#2. We camped this night at a KOA - as BigDog puts it (and rightfully so) "the death of camping"
We had come out of the forest and into the plains in Great Falls. We were pooped, and it was the first place we came to. But holey crap $43 bucks
! I guess it is still half of what the motels were wanting, but still, I wasn't even planning on using the water slide or the "Kountry Kitchen"
Well, at least we don't have to worry about bears... for tonight.
FWIW there was another camp park in town, but they had, umm... some "permanent residents"
2 Texans to Alaska (and back)...
2 Texans Ride The TAT...
Ultimate Utah Adventure Route - The UTBDR and a Whole Lot More!!
Utalorado 2014 - The Over-Ambitious Loop
-- RR In Progress now!
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About Schools in LaGrange, AR
Contact a Coldwell Banker® real estate agent to learn more about the schools and school districts in LaGrange, AR.FIND AN AGENT
LaGrange, Arkansas is located in Lee County. Nearby cities and towns include Lexa, Rondo, Marianna, Aubrey, Helena-West Helena, Marvell, Haynes, Lake View, Moro, Lula, Tunica, North Tunica, Friars Point, White Oak, Coahoma, Palestine, Forrest City, and Elaine. LaGrange is a rural community with a population of 82. The median household income is $15,832. In LaGrange, 60% of residents are married, and families with children reside in 32% of the households. Half the population of LaGrange commutes 17 minutes or less to work, with 75% of residents holding white collar jobs and 25% residents holding blue collar jobs. The median age of homes in LaGrange, AR is 25 years, with 63% of those homes owned, 26% rented, and 12% not occupied.
Contact a Coldwell Banker® real estate agent to learn more about the schools and school districts in LaGrange, AR.FIND AN AGENT
See if your personality and goals are right for real estate.SEE ALL REAL ESTATE CAREERS
Community information and market data Powered by Onboard Informatics. Copyright ©2015 Onboard Informatics. Information is deemed reliable but not guaranteed.
This information is provided for general informational purposes only and should not be relied on in making any home-buying decisions. School information does not guarantee enrollment. Contact a local real estate professional or the school district(s) for current information on schools. This information is not intended for use in determining a person's eligibility to attend a school or to use or benefit from other city, town or local services.


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The 2010 Inc. 5000: Top 10 Latino- and Hispanic Entrepreneurs
Mary Ellen Trevino, CEO
San Antonio
No. 135
2009 Revenue: $17.9 million
Three-Year Growth: 1,950.3%
Trevino's Mexican mother, who immigrated to the United States from Vera Cruz, and American father raised her in the border town of Port Isabel, Texas. After working in the Department of the Treasury for 12 years and gaining a perspective of what the government was looking for, Trevino (right) started her own company, P3S, to provide services to the federal government ranging from IT to program management. She took to her company the sense of compassion and hard work she learned from her parents, making it a priority to take care of her customers and her employees.


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Two national databases are available with which to assess the quality of cancer care, but each has limitations.
Existing data systems must be enhanced so that questions about quality of care can be answered comprehensively, on a national scale, without delays of many years between data collection and analysis. An effective system would capture information about:
It may be costly and difficult to obtain all of the desired data elements for all individuals with available sources, so sampling techniques could be used to make the task manageable for targeted studies. Alternatively, it may be feasible to link some databases (e.g., those describing structural aspects of care such as hospital characteristics) to other existing databases. It is unlikely that one single database can meet all of the various objectives of such systems, for example, cancer surveillance, research, and quality monitoring. Data systems need to be monitored to assure accuracy, and should be automated to improve the timeliness of quality data. Data gathered into national databases, in particular, should be made available quickly for analysis by investigators and evaluators.
RECOMMENDATION 8: Public and private sponsors of cancer care research should support national studies of recently diagnosed individuals with


text:
|Property type
|Minimum Stay
|5 - 12 nights
Our spectacular oceanfront, corner unit is directly on the beach and has spectacular, unobstructed panoramic views of the Pacific overlooking the islands of Lanai and Molokai from its wraparound windows and lanai! Being on the 11th floor (out of 12), and actually only few yards from the ocean, the condo has some of the very best views anywhere on the island! The Mahana Resort is a well known upscale resort located on world famous Kaanapali Beach. It is ranked #4 among resorts for west Maui.
The uncrowded, white, sandy beach is just footsteps from your door. The beautifully decorated, air conditioned unit is on the 11th floor and magnificent sunsets and whale watching can be experienced from its premier corner location. In the approximately 1400 square feet, the spacious master bedroom offers a king-size bed, cable LCD TV, and above all, an OCEANFRONT view, which is not found in many bedrooms on Maui. In the large guest bedroom there are two twin beds, cable LCD TV and DVD. In the living room, there is an LCD TV, too. There is free highspeed wireless internet access inside the unit, lobby, and around the pool and jacuzzi! Our kitchen is complete with all stainless steel appliances and ready for you!
The Mahana Resort is an upscale private resort located on the north end of Kaanapali Beach. The beautiful grounds include carefully manicured landscaping, tennis court, and newly remodeled swimming pool, jacuzzi, and barbecue area. You may stroll to a variety of nearby restaurants, as well as stores for groceries, souvenirs, diving, and swimming accessories, art, and videos. A short drive away is the town of Lahaina, golfing, an abundance of restaurants, and shopping.
We have been serving our guests on Maui since 1998 and look forward to serving you! Hawaii Tax ID WO197472-03. The Mahana Resort is a nonsmoking resort including inside units and lanais according to Hawaii State Law.
Keywords: Condominium, Condominium, Beachfront Maui Condo, Oceanfront Maui Condo, Maui Condo, Condo, Maui Vacation Rental condo, Mahana Resort, Aston Mahana
We have been in the hospitality and tourist industry for almost 30 years, having owned and operated two hotels in the tourist area and wine country of San Luis Obispo, California since 1983, which has provided us the background to offer our guests one of the finest lodging experiences on Maui. Our family began vacationing in the Kaanapali area over 20 years ago and loved it so much that we became owners at the Mahana in 2000. Hawaii Tax IDW01697472-03
Bill and Dondi's Mahana 1109 Condo purchased this condo in 2001
What attracted us to this particular area was the upscale resort and its peaceful setting, beautiful uncrowded beaches allowing long walks, water sports, and incredible views of the Pacific and the islands of Lanai and Molokai. Our family was also attracted to its proximity to many restaurants and shops, many within walking distance. Our children especially loved the beach and the many activities of the resort including the pool and jacuzzi. We were particularly attracted to this unit since it was one of the few one bedroom condos we found on the island with both the living room and bedroom being oceanfront with floor to ceiling windows providing the best of oceanfront views. It was also larger than average which was great for our entire family.
Our direct oceanfront, beachfront views are truly stunning from the 11th floor. Many of our guests describe the view as like 'being on a cruise ship' whether you are on the balcony or in the living room or master bedroom looking through the floor to ceiling windows. Being on a corner, the 270 degree panoramic views of the Pacific with Lanai to the south and Molokai to the north as well as whale watching and beautiful sunsets are unforgettable. Even the guest bedroom has wonderful views from its floor to ceiling windows of the verdant dormant volcanos of Maui. The resort amenities are for all ages, including the tennis courts, swimming pool, jacuzzi, and saunas. Kaanapali Beach is uncrowded and offers great water sports including snorkeling, swimming and even surfing. Sunning and strolling along the beach are popular along the beach or even along the new boardwalk that extends down towards Black Rock. The location of the resort is within walking distance to many restaurants and shopping, and is a short drive away to many more as well as world class snorkeling and golfing. The Mahana Resort is known for its superior quality of travel experience on Maui, being #4 on the main trip advising website. Our guests enjoy the beautiful tropical interior and excellent maintenance of our condo as seen in our online guestbook.
Bill and Dondi:
We had an absolutely wonderful visit to your condo. It was my sister and
brother-in-laws first visit to Hawaii and they were very impressed by the
accomodations. Saw numerous rainbows both to the east and west. Enjoyed
watching the turtles in the water from the lanai every day that we ate lunch
there. Loved having all of the windows available for viewing. Seeing the West
Maui mountains from the 2nd bedroom was impressive.
Hope to return in the next couple of years and stay again!
Our family of four (two college aged kids) recently stayed here for a week and had an amazing time. This is the very first time we have ever used VRBO and I was a bit skeptical of all the great reviews. Well, they were all true! The condo was large, comfortable, had absolutely everything you needed with a full setup in the kitchen, beach chairs, body boards, even some snorkeling equipment. Beds were comfortable, washing machine worked great, etc. etc. And the view was absolutely amazing. Although there were a set of binoculars already in the unit, I brought my own pair of 11x80 binoculars with a tripod and it was setup all week. Almost every daylight moment we were in the condo, somebody was looking through them and observing whales, dolphins, and turtles...almost nonstop. And the communication from the owners before the trip was terrific. Everything was clear, exactly as described, with no issues checking in. We would definitely stay there again! I simply could not have been more satisfied and impressed with the owners, the reservation process, and the condo. Very professional!
My wife, brother and I have just returned from a 2 week stay in unit 1109 at the Mahana. This whole experience could not have gone better. Bill and Dondi were a pleasure to work with, a great combination of professionalism and friendliness. The reservation process was completely painless and easy. The actual stay at the condo was just amazing. 1109 is very well maintained and cared for...it was spotless when we arrived. As for the view...the views from the Mahana are almost legendary, and they never disappoint. Staying on the eleventh floor was a bonus, making the views even more expansive. The whale watching was phenomenal. We saw many whales every day, from the comfort of the lanai. We can't recommend this unit, and the owners, highly enough. Thank you Bill and Dondi. This was truly an exceptional vacation.
Amazing unobstructed view and ease of access, parking great, location to everything, beaches, stores, restaurants, and shopping ideal! The condo had everything we needed and didn't think of.. Beach chairs and toys. We saw so much wildlife from the windows, 11 floors up! Every day was an adventure spotting and then swimming with them from the beach. The grounds and common area are well maintained.
Bill and Dondi's condo is perfect. Floor to ceiling windows overlooking the ocean and neighboring islands, ocean breeze flowing in to our bedrooms from the lanai, clean living space, comfortable beds, modern kitchen, refreshing pool and hot tub, quiet and private, close to good food and beaches, helpful concierge...I could go on and on. My only regret was that this was the first place we stayed—it made the other rentals we stayed at seem pale in comparison.
Thanks Bill and Dondi. What a wonderful place. Will be back as soon as we can. great location, then there is the view, amazing.
Beautiful, breath taking, magnificent views. Our vacation was sooo relax, we didn't want to leave. Coming back AGAIN !!!!
Direct Oceanfront, Beachfront. The beach is 30 feet in front of the building. Beautifully landscaped in a classic peaceful Hawaiian theme with tennis court. Free Hi-speed Internet Access and parking. Wworld famous Kaanapali Beach right out in front for swimming, surfing, snorkeling, whale and dolphin watching in season. Very convenient location to shopping, restaurants, and entertainment, golfing, historic Lahaina, and Whaler's Village.
|Rate Period
|Weekend Night
Spring 2015
May 5 2015 - Jun 14 2015
5 night minimum stay
Summer 2015
Jun 15 2015 - Aug 23 2015
5 night minimum stay
Aug 24 2015 - Dec 20 2015
5 night minimum stay
Christmas-Jan 3
Dec 21 2015 - Jan 3 2016
12 night minimum stay
January 2016
Jan 4 2016 - Jan 31 2016
5 night minimum stay
February 2016
Feb 1 2016 - Feb 29 2016
5 night minimum stay
Spring 2016
Mar 1 2016 - Apr 10 2016
5 night minimum stay
|Exit cleaning and linen
|$175.00 + Tax
|Tax Rate
On some dates, we are as low as 1/2 of ASTON'S or EXPEDIA'S RATES! LAST MINUTE SPECIALS!
Jan and Feb reservations due by November 1 of the prior year.
Cancellation Policy: Deposits refunded minus $300 if canceled 60 or more days before arrival. For cancellations less than 60 days before arrival, refunds will be amount it is re-rented for minus $300.
Payment is usually accepted in the quoted currency (USD) unless the currency and the amount is specifically agreed in advance with the owner / advertiser.


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Mo'Nique, Waltz win supporting-acting Oscars
LOS ANGELES Villainous roles snatched the supporting-acting prizes Sunday at the Academy Awards: "Precious" co-star Mo'Nique as a contemptible mother and "Inglourious Basterds" co-star Christoph Waltz as a sociable Nazi fiend.
Both performers capped remarkable years, Mo'Nique startling fans with dramatic depths previously unsuspected in the actress known for lowbrow comedy and the Austrian-born Waltz leaping to fame with his first big Hollywood role.
"I would like to thank the academy for showing that it can be about the performance and not the politics," said Mo'Nique, who plays the heartless, abusive welfare mother of an illiterate teen (Gabourey Sidibe, a best-actress nominee in her screen debut) in the Harlem drama "Precious: Based on the Novel `Push' by Sapphire."
Mo'Nique added her gratitude to the first black actress to win an Oscar, Hattie McDaniel, the 1939 supporting-actress winner for "Gone With the Wind."
"I want to thank Miss Hattie McDaniel for enduring all that she had to so that I would not have to," she said, adding thanks to Oprah Winfrey and Tyler Perry, who signed on as executive producers to spread the word on "Precious" after it premiered at last year's Sundance Film Festival.
"Precious" also won the adapted-screenplay Oscar for Geoffrey Fletcher.
"This is for everybody who works on a dream every day. Precious boys and girls everywhere," Fletcher said.
Waltz's award was presented by last season's supporting-actress winner, Penelope Cruz, who gave Waltz a kiss as he took the stage.
"Oscar and Penelope. That's an uber-bingo," Waltz said.
Though a veteran stage and TV actor in Europe, Waltz had been a virtual unknown in Hollywood before Quentin Tarantino cast him as the prattling, ruthless Jew-hunter Hans Landa in his World War II saga.
"Quentin with his unorthodox methods of navigation, this fearless explorer, took this ship across and brought it in with flying colors, and that's why I'm here," Waltz said. "This is your welcoming embrace, and there's no way I can ever thank you enough."
The Iraq War drama "The Hurt Locker" won four prizes, including original screenplay for Mark Boal, who spun a story about the perils and pressures of a U.S. bomb unit in Iraq.
The science-fiction blockbuster "Avatar" won three Oscars, for visual effects, art direction and cinematography, beating "The Hurt Locker" for the latter. "The Hurt Locker" won out over "Avatar" for film editing, sound editing and sound mixing.
With nine nominations each, "The Hurt Locker" and "Avatar" came in tied for the Oscar lead. The evening's last two categories, best director and picture, marked the two films' main rivalry, which is spiced up by a personal connection between "Hurt Locker" director Kathryn Bigelow and "Avatar" director James Cameron. They were married from 1989-91.
Cameron took the directing prize at the Golden Globes, but Bigelow earned the top honor from the Directors Guild of America, whose recipient almost always wins the same award at the Oscars.


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Rising sea levels to impact low areas
Scientists at a Denmark conference say rising sea levels will have a major negative impact on 1-in-10 humans living in the Earth's low-lying coastal areas.
Research presented during this week's International Scientific Congress on Climate Change in Copenhagen shows the upper range of sea level rise by 2100 could be in the range of about 1 meter (3 feet) or possibly more. At the lower end of the spectrum, studies show it is increasingly unlikely sea level rise will be much less than 50 centimeters (19 inches) by 2100.
That, the scientists said, means if emissions of greenhouse gases aren't reduced quickly and substantially even the best-case scenario will hit low-lying coastal areas housing 1-in-10 humans on the planet
Unless we undertake urgent and significant mitigation actions, the climate could cross a threshold during the 21st century committing the world to a sea level rise of meters, said John Church of the Center for Australian Weather and Climate Research.
Our study centered on Australia showed that coastal flooding events that today we expect only once every hundred years will happen several times a year by 2100.
The preliminary conclusions from the congress will be presented Thursday during the event's closing session and will be included in a synthesis report to be published in June.


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According to our research of Louisiana and other state lists there were 50 registered sex offenders living in Haughton, Louisiana as of May 28, 2015.The ratio of number of residents in Haughton to the number of sex offenders is 70 to 1.
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About Schools in Java, SD
Contact a Coldwell Banker® real estate agent to learn more about the schools and school districts in Java, SD.FIND AN AGENT
Java, South Dakota is located in Walworth County. Nearby cities and towns include Selby, Bowdle, Lowry, Akaska, Mound City, Hoven, Glenham, Hillsview, Hosmer, Eureka, Tolstoy, and Herreid. Java is a rural community with a population of 142. The median household income is $42,499. In Java, 67% of residents are married, and families with children reside in 23% of the households. Half the population of Java commutes 13 minutes or less to work, with 49% of residents holding white collar jobs and 51% residents holding blue collar jobs. The median age of homes in Java, SD is 40 years, with 48% of those homes owned, 11% rented, and 41% not occupied.
Contact a Coldwell Banker® real estate agent to learn more about the schools and school districts in Java, SD.FIND AN AGENT
See if your personality and goals are right for real estate.SEE ALL REAL ESTATE CAREERS
Community information and market data Powered by Onboard Informatics. Copyright ©2015 Onboard Informatics. Information is deemed reliable but not guaranteed.
This information is provided for general informational purposes only and should not be relied on in making any home-buying decisions. School information does not guarantee enrollment. Contact a local real estate professional or the school district(s) for current information on schools. This information is not intended for use in determining a person's eligibility to attend a school or to use or benefit from other city, town or local services.


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It was in Franklinton. Bought a truck there from Griffin Trucks (wouldnt ever do that again) in franklinton and needed a place to sleep close
Room smelled a little funny and there were plenty of open roms, but it seemed that all the occupants were placed next to each other. I would have preffred to have a room seperating to allow better parking and quiet.
The Motel was easily accessable.
I did not like the dirty towels that were left out, as if they had not been properly washed with detergent. The room was very dusty. The bed had hair in and on the sheets.
Hotel was clean. Staff was great! I forgot several items and they happily helped me out.
The hotel is a very good value. We had a king-size bed, which was great; and a bathroom equipped for a guest who might be physically handicapped or elderly. We liked the size of the bathroom - but them the rest of the room was small.
Room could have been cleaned better on 3 of the 5 night stay. Admittedly, the hotel was full and busy, but our room, after being cleaned, did not have everything even put back in place(lamp moved back in place, etc.) Had to request coffee at front desk
The staff was very friendly; the location was convenient for us; the bed/mattress was great; the breakfast re-introduced us to dry cereal which was a treat. Coffee was great.
The bed was hard, it took me about 3 hours to go to sleep
I like the overall look of the room. Very nice.
I didn't like the doors banging around at night. My door would rattle when other doors slammed closed. I had to put a chair against my door real tight to stop that nonsense.
Overall a good place to stay.
The parking lot was not well lighted and overgrown trees surrounding the parking areas blocking some of the light available.
Facility very old and poorly maintained. Bathroom light was flickering all the time. Exhaust fan was not running, pool was out of maintenance.
The people who cleans the room was very nice
The bradfest is over on the weekend at 900 am & not at 10.00 am
The people at the desk were very kind and very helpful. This was my first time to this hotel and due to me visiting someone in the prison I will b back often and I will be staying here in same room. Was told about discounts when staying again. ;0)
I didn't care for the ABC store being right next door but that us not their fault. Maybe some fencing or trees would help ;0)
The room was amazingly clean! I think it was one of the cleanest hotel rooms I have ever been in.
Not at all!
Great value and breakfast.
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Hendrick drivers Gordon, Johnson running away with Chase
Several Chase drivers had good days at Talladega, at first glance. That they still lost ground to leaders Jeff Gordon and Jimmie Johnson tells them they're in trouble, writes David Newton.
Updated: October 8, 2007, 3:28 AM ETBy David Newton | ESPN.com


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vinila - gigi 'espresso cup'
2 Recommendations
shopmodi's recommendation
gigi is a super mommy. she sits on her nest and waits for her little babies to hatch. gigi is part of "pepe and friends" collection designed by camila prada at vinila, UK. there are 16 characters in this "gang". check them out! they will soon be your favorite tabletop friends.
Yournewbestfriend's recommendation
Gigi is a super bird. She holds your espresso and sits on her eggs to keep them warm pre-hatch. She's super cute, and this is such a nice gift for the espresso drinker in your life. Nothing makes coffee better than having a really nice cup and saucer to drink it out of.
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Shop now and get Free Value Shipping on most orders over $49 to the contiguous 48 states, DC and to all U.S. Military APO/FPO/DPO addresses.
We want to ensure that making a return is as easy and hassle-free as possible! If for any reason you decide that your purchase just isn't for you, simply return the item within 30 days of receipt and we'll cover the cost of return shipping. Learn more about our Return Policy.
Check out the Calligraphy Collections new products from Calligraphy Collections that we just got in inventory! There's an already large selection, but we're excited to provide you with much more. Calligraphy Collections strives for brilliance in their gear and present technological innovation that is constantly improving. Always in contact with their customers, Calligraphy Collections takes under consideration what their users require and want. New products from Calligraphy Collections always boost the extensive line presently available with improvements and new series. In case you have any queries about new Calligraphy Collections products, we've got a team of highly trained customer service experts ready to answer your questions. Visit regularly to see what Calligraphy Collections new products Calligraphy Collections has put out on the market!
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Robin Shreeves
Robin is a freelance writer who started blogging about the environment when she and her family began making many changes to their day-to-day lives. She's the founder of the South Jersey Locavore website and a frequent contributor to "Edible Jersey" magazine, a member of the James Beard Award-winning Edible Publications. Her first book, "The One Year Women in Christian History" (which has absolutely nothing to do with food), will be published in September 2014. A former high school English teacher, she left teaching to stay home with her two sons and turned her love for writing into a career. She lives in New Jersey with her family.
|"...Broga? Really? Are they targeting college frat boys as a demo? ..."
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- 12 plants that repel unwanted insects
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- Map points the way for the ultimate U.S. road trip
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Curtiss Hall 142
8 a.m.-4:30 p.m.
(Eastern Standard Time)
Course Outline
Course 1: Keys to Customer Service Learning to build your customer service skills will have a powerful impact on your career success as well as success in other areas of your life. Through this course, you will discover the direct relationship between service skills and career achievement. You will become skilled at being an exceptional service provider. You can help your organization and your career by translating your good service intentions into a workable plan and gain knowledge of ways to consistently deliver great service. The payoff is enormous. One-month online course, Nanette Sanders-Cobb, COI, instructor.
Unit 1
Unit 2
Unit 3
Unit 4
Course 2: Extraordinary Customer Service Transform your customer service into something extraordinary. As a result, more repeat business will improve your bottom line. Customer service separates you from your competition. Extraordinary customer service comes from focusing on the few essential elements that yield big results. Discover
how easy it is to tweak your customer service from the ordinary to the extraordinary. You'll take away a customer service plan that will help you focus on the key elements that will get you started on your pathway to success. Unit 1: Understanding Your Customer
Unit 2: Setting Customer Expectations
Unit 3: Developing Effective Processes
Unit 4: Marking Customer Service Extraordinary
Who Should Attend:
Those interested in retaining customers, serving your audience, or turning inquiries from potential customers into sales.
Customer Service is now essential for business and all work organizations. With the increase of technology, human interaction with customers becomes all the more important. Whether it relates to retaining customers, serving your audience, or turning inquiries from potential customers into sales, good customer service is now one of the central factors in organizational success.
Learn to improve your customer service skills to enhance your career skill set, improve productivity, and increase your organization's success. You will also take away some extraordinary customer service techniques you won't find anywhere else.
Two one-month courses, Nanette Sanders-Cobb and Fred Bayley, instructors.
About the Instructors
Nanette Sanders-Cobb, COI has been developing and teaching customer service classes for over ten years in addition to teaching online for fifteen years. She is a speaker and advisor, engages in marketing community festivals, and has trained and managed audit team members.
Having been in senior management and an audit team leader in the United States Air Force, she has trained staff in providing extraordinary service. She holds a Bachelor's Degree in Business Administration and a Master's Degree of Business and Public Administration. Nanette Sanders-Cobb has earned the distinction as a Certified Online Instructor.
Fred Bayley has extensive service working on non-profit boards from creation to re-organization. He was the founding chair of a group that helps business through technology. He has helped rejuvenate a number of non-profits through consulting and being on the board. All of his work with non-profits was to help find ways not only for them to become more self-sustaining but to also fulfill their mission and complete their vision. Fred is a past president of the local chamber of commerce, Habitat work crew member, volunteer middle school wrestling coach and one-fourth of a handbell quartet.
About online learning
Online learning is a fun, enjoyable and very productive way to learn. Millions of people are learning online each year. You will engage with the instructor and other participants. You will get to know your instructor and other participants. You may make friends. It's easy. It's fun.
How the Course Works
It is easy to participate in your online course. After you register, you will be given a web address to go to get into your online classroom. You will have a password and use your email address and password to gain access.
Once inside the online classroom, here's what you can expect.
Participate when you want
You can participate any time of day or evening. The online classroom is open 24 hours a day, 7 days a week.There are no live real-time requirements or meetings. You decide when you participate.For the best learning, participants should log into the course on 2-3 different days of the week.
What you will do
For each Unit, you will:
For best learning, you should make one or more comments at 2-3 different times each week.The content (readings, audio lectures, slides) and self quizzes are accessible for the entire course, so you can work ahead, or go back and review again, at your convenience.
The Discussion for each Unit lasts one week. All comments are made in writing and can be made at any time of the day or night.
Your instructor will log into the Discussion area at least once a day and answer questions, make comments, and respond to comments by you and the other participants.
We encourage you to make 2-3 comments each week to maximize your learning and enjoyment of the course.
Summer Session:
06-01-2015 - 07-31-2015
Register Here for Summer
Fall Session:
09-08-2015 - 11-27-2015
Register Here for Fall
Cancellation Policy:
Cancellation Policy (295kB)


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Hugo Bonded Leather Ottoman
Bring a sophisticated modern style to your living room.
Simply add comfort to your home.
The Hugo Bonded Leather Ottoman with Tufted Cushion by Coaster is the perfect choice for your living room or family room. The ottoman features a plush top cushion with modern tufting for comfort and style. Rich chocolate bonded leather and slim exposed wood feet complete this style. Sofa, loveseat, and ottoman sold separately.
Dimensions: 30" x 20" x 19"; Weight: 34 lbs.
Hugo Bonded Leather Ottoman
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Our Members Say
- smoeltje
- Reviews: 2
Vila Damjanovic: Warm welcome and enjoyable stay
Services were very good, rooms cleaned every day, good food - big portions, own beach, a lot of space on terrace and beach to enjoy your dinner.
friendly people, quick serving
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- Reviews: 239
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if you rent a room in private house, you can have much more space for yourself. it's much cheaper than hotel.
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A tree for your tree, this vibrant red ornament is completed by a striking gold hue and pearlized embellishments.
Luscious fabrics, robust colors, and sublime patterns are the hallmarks of Divine Design's offering. Classic Eastern textiles--kilims, paisleys, ikats--provide a clear inspiration, but these centuries-old themes have been reinvigorated so that they provide a superb complement to all manner of Western decor styles, from traditional to contemporary.


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Last week, we showed you guys some of the crazy prop bets Bovada is providing for tomorrow's (Sat., May 2, 2105) super fight between Floyd Mayweather and Manny Pacquiao. As it turns out, the online s read news >>
Light heavyweight champion Jon Jones was involved in a car accident and his UFC 187 title fight against Anthony Johnson is in jeopardy, MMAWeekly.com learned on Sunday. read news >>
UPDATE: Tuesday, April 21 at 7:00 p.m. ET Rampage is back. According to Nancy Gay of UFC.com, Quinton "Rampage" Jackson is officially back on the UFC 186 fight card against Fabio Maldonado in a catch read news >>
Rough weekend for "Killer" Cub. You likely won't be seeing Cub Swanson inside the Octagon anytime soon. The Ultimate Fighting Championship (UFC) featherweight contender was not only beatdown and subm read news >>
Hall of Famer Mark Coleman will stop by to update us on his current health situation. read news >>
A lack of ranked fighters meant a lack of movement in the UFC fighter rankings. The only ranked fighters from UFC Fight Night: Maia vs. LaFlare were Demian Maia, Ryan LaFlare, and Amanda Nunes. So un read news >>
UFC legend Rich Franklin stops by to update us on the latest going on his life. read news >>
See you this summer. Ultimate Fighting Championship (UFC) lightweight titleholder Rafael dos Anjos is headed under the knife following his five-round unanimous decision win over Anthony Pettis at the read news >>
The official UFC rankings are still terrible, and Tim B. is here to give you an update on this week's version of the hilarity. Hi, folks. Remember me? My name is Tim, and I used to be a part of the o read news >>
Paul Gift, John Nash and Jason Cruz debate issues with year-round drug testing, free boxing and if the UFC muscled back on antitrust. read news >>
UFC heavyweight veteran Pat Barry has been forced to withdraw from Glory 20, but a featherweight title fight between Gabriel Varga and Mosab Amrani has been added in replacement. Pat Barry has been f read news >>
Check out the full bout order and all the pre-fight hype, odds, predictions, and festivities for UFC 187: Jones vs. Johnson, which takes place at the MGM Grand Garden Arena on May 23rd in Las Vegas, read news >>
Full fight coverage here for the Floyd Mayweather vs. Manny Pacquiao PPV on Saturday, May 2. Check out video, previews, analysis and more on our live update stream. It's been brewing for weeks. No, m read news >>
It may be time to update that record… Following in Duane Ludwig's footsteps, "Judo" Gene LeBell is convinced Ronda Rousey's record-setting 14 second armbar victory over Cat Zingano in the main event read news >>