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Getting it Right for Children when Parents Part
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Read about the latest research that suggests one in four parents secretly consider separating from their partner
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Star Tracks
The couple takes their dogs for a walk in a Los Angeles park. Plus: Miley & Justin, Beyoncé, Robert Pattinson and more
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Kendall Jenner's Makeup Secret & More - Orange Is the New Black Stars Win Big in Christian Siriano Gowns
- Screen Actors Glasses: Stylish Lady Frames Ruled the SAG Awards
- Birdman Wins the SAG Award for Outstanding Performance by a Cast in a Motion Picture

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Homestead Crafts
Our store is nestled in the beautiful rolling hills 3 miles west of Shell Lake, Wisconsin. It is a charming old dairy barn that we have renovated into a unique old fashioned and rustic store. We are proud to represent a number of local and non-local crafters and artisans in our store! Come and check out our Garden Decor room up in the hay loft and we also have a Fall, Halloween, and Christmas section year around. We have a beautiful selection of handmade rugs, handmade lamps, (they were made from old farm fence posts from Wisconsin), as well as handmade lamp shades! The beautiful hand painted windows are of different sizes, and themes. We have a nice selection of various bird houses including barn wood and beautifully painted gourd bird houses! Check out our handmade jewelry, candle mats, tote bags, metal art, beautiful handmade ceramics, little whimsical whitty signs, and various kinds of Home Decor. We also have adorable and beautifully handmade doll clothes that will fit the American Girl Doll or any 18 inch doll. Our primitive dolls are sooo cute and unique. There is something here for everyone! We are open seasonally from the first Saturday in May, ("Ladies Fishing Opener"), until mid December! We also have a Christmas Open House in November, which is always the Saturday just before Thanksgiving! We have drawings and refreshments and a lot of fun while the guys are out hunting! Stop out and see us! We are always happy to meet new people and look forward to seeing you!
Hours of Operation
WINTER HOURS- WE ARE CLOSED DEC 1-APRIL 30! We re-open the first Saturday in May! (MAY-LABOR DAY), Wednesday-Sunday 10am-4pm (AFTER LABOR DAY-DECEMBER), Saturday & Sunday 10am-4pm. Christmas Open House Hours: Saturday before Thanksgiving: 9am-5pm.
Leaving Spooner: Take Hwy 70 West 6 miles, turn left on Cty Rd O 4 1/2 miles. From Shell Lake: Go 5 miles west on Cty Rd B, turn right on Cty Rd O, 1/4 mile on left. From Siren: Take Hwy 70 East 18 miles, turn right on Cty Rd O 4 miles.
Shopping Type
- Antique
- Specialty Shop
Events: Near Homestead Crafts
Film Series: The Art of Film
1/31/2015 - Shell Lake - 2.2 miles away
Spooner-Trego Lions Club Ice Fishing Contest
2/7/2015 - Spooner - 5.98 miles away
Food and Wine Tasting
4/23/2015 - Spooner - 3.77 miles away
Mother's Day Brunch Train
5/10/2015 - Spooner - 3.54 miles away
Prairie Fling Festival
5/16/2015 - Sarona - 8.45 miles away
Wisconsin Canoe Heritage Day
5/23/2015 - Spooner - 3.7 miles away
Family Festival
6/6/2015 - Spooner - 2.99 miles away
Chuck Revak Memorial Kids Fishing Day
6/6/2015 - Spooner - 3.23 miles away
Badger Car Show
6/7/2015 - Spooner - 3.02 miles away
Tri County Dairy Breakfast
6/13/2015 - Spooner - 3.38 miles away


text:
The Algonquin Hotel
- Free High-Speed Internet
- Free High-Speed Internet
- Free parking
- Free parking
TripAdvisor Reviews The Algonquin Hotel Sault Ste. Marie
Travel Blogs from Sault Ste. Marie
Soo Locks
We continue on east and then just a little north to the city that shares it name with its sister city over the Canadian border, Sault Sainte Marie. Our plan was to see the Soo Locks and then take a quick day trip in the truck over the border.
The Soo Locks have been referred to as one of the great wonders of the world and are still the largest & one of the busiest waterway traffic systems on earth! Watching huge vessels pass through the Locks ...
Ontario, Cottage Country
Leaden grey skies and rain welcomed us to Ontario as we passed through Kenora, home of Husky the Muskie ( a sturgeon or Jackfish?). The scenic route wove a path around Lake of the Woods with over 17,000 islands that all seemed to have beautiful cottages, docks and every size and shape of water transport. Taking the northern trucker route to Thunder Bay was a little shorter but ...
A Tale of Two Gas Prices
... an interstate. Most of the TC is not limited access, which means a lot of traffic and stoplights north of Toronto. I thought at the time that the drive to Vancouver would be unbearable...imagine driving from Atlanta to Los Angeles on a federal highway instead of interstates. Thing is, Canada is sparsely populated outside of major cities, so you could drive for 100 miles and not see civilization.
That means the drive is full of ...
Raining shorter drive going to Sault Ste Marie
... Rain stopped for a while enough time for stretch and walk so lovely and peaceful at the cove but very cool. Reminds us for Vancouver Island with Terry and Diana plus we passed a car with two canoes on car roof. Took a few bumpy videos of Montreal River Harbor even with the rain the scenery is beautiful pity we can't pull off the highway to see them no slipways or you have to drive down side roads to see ...
June 22, 2011
... customs...the questions all make the girls feel very uncomfortable, and 2) buying milk in Canada, which comes in plastic bags rather than cartons. I have never seen this before, and it had us all laughing for a good 15 minutes!
Okay, will depart for Munising, Michigan in the morning and hope for dryer days to come!!


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22 results for "california golden bears"
Cal Neeman
MLB - Our favorite up close and personal All-Star Game memories
Brad Penner/USA TODAY SportsESPNKeepsake All-Star Game moments, collected by ESPN's own all-star eyewitness team of baseball analysts and writers.
Eticket | Conversation | July 12, 2014 -
2012 Rangers timeline: June-July
Richard DurrettWe've now hit the middle of the summer in the 2012 season in our Texas Rangers timeline. Here's a look at some of the highlights from those two months: June 2: After the Rangers' sloppy 3-2 loss to the Angels in Anaheim, manager Ron Washington cal...
Blog | October 12, 2012 -
Five rookies with best long-term futures
Jim BowdenYou know them, though you might not remember them. We're talking about rookie flashes in the pan -- Joe Charboneau, Bob Hamelin and Bobby Crosby, to name a few. However, you remember the rookies who go on to Hall of Fame careers, guys like Cal Ripken...
Blog | May 30, 2012 -
Domonic Brown could find a permanent spot in Philadelphia, or he ...
Kevin GoldsteinKevin Goldstein of Baseball Prospectus writes about 10 MLB prospects who failed to meet expectations this season and need a strong 2012 season to reclaim some lost value.
Story | Conversation | December 28, 2011 -
Cal Ripken heading to Japan as U.S. sports diplomat
Cal Ripken Jr. aspires to become president and CEO of a major league baseball team.
Story | Conversation | November 03, 2011 -
College Baseball: UConn against South Carolina is the most exciti...
Ryan McGeeRyan McGee looks at all eight super regionals and ranks them based on quality and star power.
Story | Conversation | June 10, 2011 -
MLB: After Cliff Lee signs, it'll be free-for-all; this is how it...
Buster OlneyIn Troy Tulowitzki, the Colorado Rockies saw a player who could be their Derek Jeter or Cal Ripken, which is precisely what the shortstop wanted. Plus, Buster's advice to Jeter, and a walk around free agency.
Blog | Conversation | December 02, 2010 -
MLB: In Troy Tulowitzki, Colorado saw a player who could be their...
Buster OlneyIn Troy Tulowitzki, Colorado saw a player who could be their Derek Jeter or Cal Ripken, which is precisely what the shortstop wanted. Plus, Buster's advice to Jeter, and a walk around free agency.
Blog | Conversation | December 01, 2010 -
Hunter five-hits fading Rays as Hamilton stays hot
Tommy Hunter pitched a five-hitter in his season debut, Josh Hamilton homered and the Texas Rangers beat the Tampa Bay Rays 6-1 on Saturday.
Recap | Box Score | Conversation | June 05, 2010 -
MLB - Buster Olney - Carlos Zambrano move is classic Lou Piniella...
Buster OlneyAfter moving starting pitcher Carlos Zambrano to the bullpen, Cubs manager Lou Piniella again proved that he is not the sort of manager who will sit on his hands while his team struggles.
Blog | Conversation | April 22, 2010 -
Colorado Rockies' Ubaldo Jimenez's no-hitter mirrors his career a...
Buster OlneyIn throwing the first no-hitter in Rockies team history Saturday, Ubaldo Jimenez demonstrated how he's grown as a player. Plus, a few notes on Cal Ripken's job prospects with the Orioles and a recap of the 20-inning Mets-Cardinals marathon.
Blog | Conversation | April 18, 2010 -
MLB Draft 2010 - Jason Churchill: A college shortstop that could ...
Jason A. ChurchillJason Churchill has updates on a lot of college talent that took to the field this weekend, kicking it off with a Cal State-Fullerton SS that could move up through the minors quickly.
Blog | Conversation | February 22, 2010 -
Buster Olney Blog -- MLB -- Milwaukee Brewers' Trevor Hoffman and...
Buster OlneyFor an idea of why Trevor Hoffman garners the kind of respect he does, a tale from the road might help, writes Buster Olney. Plus, some speculation from execs on what a deal for Prince Fielder might take, and the surprising team that could do it.
Blog | Conversation | September 15, 2009 -
Cal Ripken Jr. seeks answers from Alex Rodriguez regarding admitt...
Cal Ripken Jr. wonders what Alex Rodriguez's motives were for using performance-enhancing drugs and plans to ask the Yankees third baseman himself.
Story | Conversation | May 15, 2009 -
MLB - Baseball Prospectus - Derek Jeter should be Yankees' center...
Christina KahrlBy moving their captain to CF, the Yankees can solve two problems: Their hole in center and Jeter's subpar defense at shortstop.
Story | Conversation | February 04, 2009 -
Those crazy, nutty injuries
Jayson StarkFrom blown out knees to sneezing attacks, the 2004 season had its share of ridiculous injuries.
Story | Conversation | November 05, 2004


text:
Koiranen GP's Dean Stoneman records fifth win of the season
ART Grand Prix's Marvin Kirchhöfer fastest, Alex Lynn takes title
Status Grand Prix's Richie Stanaway leads the way in opening session in Russia
A brand new venue for the GP3 drivers to contest.
Marussia Manor Racing's Dean Stoneman victorious in thrilling race in Italy
Koiranen GP's Jimmy Eriksson holds off Dino Zamparelli for victory.
Koiranen GP's Jimmy Eriksson fastest in GP3 qualifying in Italy.
Jenzer Motorsport driver fastest on home soil in Italy
Carlin continues to head the Teams' Standings.
Trident's Luca Ghiotto storms to first pole position in debut GP3 weekend
The summer break is officially over and the Series is ready to rock and roll for the final four events of the 2014 GP3 season.
ART Grand Prix trio on top in Hungary Free Practice
ART Grand Prix's Marvin Kirchhöfer fastest in qualifying on home soil
ART Grand Prix's Marvin Kirchhöfer victorious at the Hockenheimring


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text:
Patent application title: Polymer Brushes
Gary Stevens (Surrey, GB)
James D.b. Smith (Monroeville, PA, US)
John W. Wood (Winter Springs, FL, US)
IPC8 Class: AC08L6300FI
USPC Class:
Class name: Synthetic resins (class 520, subclass 1) processes of preparing a desired or intentional composition of at least one nonreactant material and at least one solid polymer or specified intermediate condensation product, or product thereof process of forming a composition containing a nonreactive material (nrm) and a polymer containing more than one 1,2-epoxy group, or a preformed polymer derived from or admixed with a reactant containing more than one 1,2-epoxy group, or with a polymer derived from an epihalohydrin and a polyhydric phenol or polyol; or composition or product thereof
Publication date: 2008-10-23
Patent application number: 20080262128
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Polymer brushes (50) in a resin that create phonon pathways therein The
polymer brushes themselves comprise structured polymer hairs having a
density of 0.8 to 1.0 g/cc, a chain length of 1 to 1000 nm, and a thermal
conductivity of 0.5 to 5.0 W/mK. The polymer brushes are 10-25% by volume
of the resin, and the polymer hairs can orient surrounding resin
molecules to the polymer hairs alignment (55).Claims:
1. A resin comprising:polymer brushes comprising structured polymer hairs
having a density of 0.8 to 1.0 g/cc and a chain length of 1 to 1000 nm,
and a thermal conductivity of 0.5 to 5.0 W/mK;wherein said polymer hairs
are configured to be sufficiently rigid for ordering said polymer hairs
at the density and the chain length effective to reduce entanglements;
andwherein an alignment of said polymer hairs orients surrounding resin
molecules effective to form phonon channels within said resin.
2. The resin on claim 1, wherein said polymer brushes are created on the surface of a substrate.
3. The resin on claim 2, wherein said polymer brushes are formed from vinyl monomers.
4. The resin on claim 1, wherein said polymer brushes are formed from a liquid crystal thermoset epoxy.
5. The resin on claim 1, wherein filler materials are added to said resin, and wherein said filler materials comprise 5-40% by volume of said highly structured resin and wherein said filler materials have aspect ratios of 3-100.
6. The resin on claim 1, wherein said polymer brushes are formed after said resin is impregnated into a porous media.
7. The resin on claim 6, wherein said porous media is a paper matrix.
8. The resin on claim 7, wherein said paper matrix is a mica-glass insulating paper.
9. The resin on claim 1, wherein the polymer hairs have a chain length of 2 to 100 nm.
10. The resin on claim 1, wherein said resin is an epoxy resin.
11. The resin on claim 1, wherein said resin is a hydrocarbon.
12. The resin on claim 11, wherein said hydrocarbon is polybutadiene and other resins may include, polysiloxanes, aromatic polyesters and aromatic polyamides.
13. The resin of claim 1, wherein said polymer brushes comprise 10-25% by volume of said resin.
14. An insulating tape comprising the resin of claim 1.
15. An epoxy resin comprising:filler materials that comprises 5-40% by volume of said highly structured resin and wherein said filler materials have aspect ratios of 3-100; andpolymer brushes, wherein said polymer brushes bridge said filler materials within said epoxy resin;wherein said filler materials form a continuous organic-inorganic composite with said epoxy resin and said polymer brushes;wherein said polymer brushes comprise 10-25% by volume of said epoxy resin;wherein said bridged filler materials create phonon channels within said epoxy resin.
16. The epoxy resin of claim 15, wherein said epoxy resin is selected from at least one of liquid crystal thremoset polymers, interpenetrating networks, polymer brush type matrices, expanding polymers, ladder polymers, star polymers and structured organic-inorganic hybrids.
17. The epoxy resin of claim 16, wherein said filler materials comprise one or more of Al2O3, AlN, MgO, ZnO, BeO, BN, Si3N4, SiC and SiO2.
18. The epoxy resin of claim 15, wherein the polymer brushes comprise structured polymer hairs having a density of 0.8 to 1.0 g/cc and a chain length of 1 to 1000 nm, and a thermal conductivity of 0.5 to 5.0 W/mK, wherein said polymer hairs are configured to be sufficiently rigid for ordering the polymer hairs at the density and the chain length effective to reduce entanglements.
19. An insulating tape comprising the epoxy resin of claim 15.
[0001]This invention is a Continuation in Part of U.S. application Ser. No. 11/152,983 "HTC Materials Incorporated into Resins," by Smith, et al., which is incorporated herein by reference.
[0002]The field of the invention relates to high thermal conductivity materials impregnated into highly structured resins.
[0003]With the use of any form of electrical appliance, there is a need to electrically insulate conductors. With the push to continuously reduce the size and to streamline all electrical and electronic systems there is a corresponding need to find better and more compact insulators and insulation systems.
[0004]Various epoxy resin materials have been used extensively in electrical insulation systems due to their practical benefit of being tough and flexible electrical insulation materials that can be easily adhered to surfaces. Traditional electrical insulation materials, such as mica flake and glass fiber, can be surface coated and bonded with these epoxy resins, to produce composite materials with increased mechanical strength, chemical resistance and electrical insulating properties. In many cases epoxy resins have replaced traditional varnishes despite such materials having continued use in some high voltage electrical equipment.
[0005]Good electrical insulators, by their very nature, also tend to be good thermal insulators, which is undesirable. Thermal insulating behavior, particularly for air-cooled electrical equipment and components, reduces the efficiency and durability of the components as well as the equipment as a whole. It is desirable to produce electrical insulation systems having maximum electrical insulation and minimal thermal insulation characteristics.
[0006]Electrical insulation often appears in the form of insulating tapes, which themselves have various layers. Common to these types of tapes is a paper layer that is bonded at an interface to a fiber layer, both layers tending to be impregnated with a resin. A favored type of insulation material is a mica-tape. Improvements to mica tapes include catalyzed mica tapes as taught in U.S. Pat. No. 6,103,882. The mica-tape may be wound around conductors to provide extremely good electrical insulation. An example of this is shown in FIG. 1. Illustrated here is a coil 13, comprising a plurality of turns of conductors 14, which in the example illustrated here are assembled into a bakelized coil. The turn insulation 15 is prepared from a fibrous material, for example glass or glass and Dacron which is heat treated. Ground insulation for the coil is provided by wrapping one or more layers of composite mica tape 16 about the bakelized coil 14. Such composite tape may be a paper or felt of small mica flakes combined with a pliable backing sheet 18 of, for example, glass fiber cloth or polyethylene glycol terephthalate mat, the layer of mica 20 being bonded thereto by a liquid resinous binder. Generally, a plurality of layers of the composite tape 16 are wrapped about the coil depending upon voltage requirements. A wrapping of an outer tape 21 of a tough fibrous material, for example, glass fiber, may be applied to the coil,
[0007]Generally, multiple layers of the mica tape 16 are wrapped about the coil with sixteen or more layers generally being used for high voltage coils. Resins are then impregnated into the tape layers. Resins can even be used as insulation independently from the insulating tape. Unfortunately this amount of insulation only further adds to the complications of dissipating heat. What is needed is electrical insulation that can conduct heat higher than that of conventional methods, but that does not compromise the electrical insulation and other performance factors including thermal and mechanical capabilities.
[0008]Other difficulties with the prior art also exist, some of which will be apparent upon further reading.
[0009]With the foregoing in mind, methods and apparatuses consistent with the present invention, facilitate the transport of phonons through a high thermal conductivity (HTC) impregnated medium to reduce the mean distances between the HTC materials below that of the phonon mean free path length This reduces the phonon scattering and produces a greater net flow or flux of phonons away from the heat source. The resins may then be impregnated into a host matrix medium, such as a multi-layered insulating tape.
[0010]These and other objects, features, and advantages in accordance with the present invention are provided particular embodiments by a resin that comprises polymer brushes. The polymer brushes themselves comprise structured polymer chains forming hair-like structures having a density of 0.8 to 1.0 g/cc, a chain length of 1 to 1000 nm, and in particular 2 to 100 nm, and a thermal conductivity of 0.5 to 5.0 W/mK. In an aspect of the invention, the polymer hairs are configured to be sufficiently rigid for ordering the polymer hairs at these densities and chain lengths effective to reduce entanglements. The polymer brushes may be 10-25% by volume of the resin, and the polymer hairs orient surrounding resin molecules to the polymer hairs alignment. This arrangement creates phonon pathways within the resin. In some embodiments the polymer brushes are formed after the resin is, impregnated into a porous media, which may be a paper matrix such as a mica-glass insulating paper
[0011]In an embodiment the polymer brushes are created an on the surface of a substrate, and may be formed from vinyl or vinyl-epoxy monomers. The polymer brushes may also be formed from liquid crystal epoxy.
[0012]In another embodiment filler materials are added to the resin, and the filler materials comprise 5-40% by volume of the highly structured resin and the filler materials have aspect ratios of 3-100.
[0013]In another embodiment the resin is an epoxy resin. In yet another embodiment, the resin may be a hydrocarbon, such as polybutadiene, polysiloxanes, aromatic polyesters and/or aromatic polyamides.
[0014]In another embodiment, the present invention provides for an epoxy resin that comprises filler materials and polymer brushes, where the polymer bushes brushes bridge the filler materials within the epoxy resin. The filler materials themselves comprises 5-40% by volume of the highly structured resin and have aspect ratios of 3-100. The filler materials also form a continuous organic-inorganic composite with the epoxy resin and the polymer brushes. The polymer brushes comprise 10-25% by volume of the epoxy resin, and the bridged filler materials create phonon channels within the epoxy resin.
[0015]In particular embodiments, the epoxy resin is selected from at least one of liquid crystal polymers, interpenetrating networks, polymer brush type matrices, expanding polymers, ladder polymers, star polymers and structured organic-inorganic hybrids. In other particular embodiments the filler materials comprise one or more of Al2O3, AlN, MgO, ZnO, BeO, BN, Si3N4, SiC and SiO2.
[0016]Other embodiments of the present invention also exist, which will be apparent upon further reading of the detailed description.
[0017]The invention is explained in more detail by way of example with reference to the following drawings:
[0018]FIG. 1 shows the use of an insulating tape being lapped around a stator coil.
[0019]FIG. 2 illustrates phonons traveling through a loaded resin of the present invention.
[0020]FIG. 3 illustrates the relationship between increasing polymer chain length and increased substrate attachment density for a conventional polymer brush with variable thermal conductivity.
[0021]FIG. 4 illustrates the relationship between increasing polymer chain length and increased substrate attachment density to achieve an increasing thermal conductivity of polymer brushes.
[0022]FIG. 5 illustrates one example of a reaction forming a high thermal conductivity polymer brushes on a substrate
[0023]FIG. 6 illustrates structural ordering around a high thermal conductivity polymer brush with an effect on surrounding resin molecules.
[0024]FIG. 7 illustrates a bridging of particles by high thermal conductivity polymer brushes.
[0025]High thermal conductivity (HTC) composites comprise a resinous host network combined with fillers that are two phase organic-inorganic hybrid materials. The organic-inorganic hybrid materials are formed from two phase organic-inorganic composites, from organic-inorganic continuous phase materials that are based on molecular alloys, and from discrete organic-polymer brush composites in which the organic-inorganic interface is non-discrete with the polymer brush branched brush structure. Phonon transport is enhanced and phonon scattering is reduced by ensuring the length scales of the structural elements are shorter than or commensurate with the phonon distribution responsible for thermal transport.
[0026]Two phase organic-inorganic hybrids may be formed by incorporating inorganic micro, meso or nano-particles in linear or cross linked polymers (thermoplastics) and thermosetting resins. Host networks include polymers and other types of resins, definitions of which are given below. In general, the resin that acts as a host network may be any resin that is compatible with the particles and, if required, is able to react with the groups introduced at the surface of the filler. Nano-particle dimensions are typically of the order of or less than the polymer network segmental length. For example 1-30 nm. The inorganic particles contain reactive surfaces to form covalently bonded hybrid organic-inorganic homogeneous materials. The particles may be oxides, nitrides, carbides and hybrid stoichiometric and non-stoichiometric mixes of the oxides, nitrides and carbides, more examples of which are given below.
[0027]The inorganic particles are surface treated to introduce a variety of surface functional groups which are capable of participating in reactions with the host network. The surface functional groups include but are not limited to hydroxyl, carboxylic, amine, epoxide, silane and vinyl groups. The groups may be applied using wet chemical methods, non-equilibrium plasma methods, chemical vapor and physical vapor deposition, laser beams, sputter ion plating and electron and ion beam evaporation methods.
[0028]The discrete organic-polymer brush composites may be reacted together or with the resin matrix to form a single material. The surface of the polymer brush can contain reactive groups similar to those mentioned above, which will either allow polymer brush-polymer brush or polymer brush-organic matrix reactions to occur. The polymer brush will have an inorganic handle and an organic hair containing the reactive groups of interest. It may also be possible to have an organic handle with an inorganic hair which also contains reactive groups such as hydroxyl or amino, carboxyl thiol, amide, cyanate, thiocyanate, isocyanate and isothio cyanate groups, silane, or a combination thereof groupings which can participate in inorganic reactions similar to those involved in common sol-gel chemistries. A third possibility is polymer brush with both an organic handle and organic hair.
[0029]In regards to the use of non-discrete organic-inorganic hybrids it is possible to use sol-gel chemistry to form a continuous molecular alloy. Gel sol-chemistries involving aqueous and non-aqueous reactions may be used. Other compounds for the formation of organic-inorganic hybrids include the polyhedral oligomeric silsesquioxanes (POSS), tetraethyl orthosilicate (TEOS) and tetrabutyl orthotitanate (TBOT) and related monomeric and oligomeric hybrid compounds which are organic functionalized inorganic compounds. In the example of POSS, molecules are built around a building block of R--SiO1.5 in which the R group is chosen to compatibilize with and/or react with other organic compounds and the host network. The base compounds may be combined to yield larger molecules commensurate with the size of polymer segment and coil structures. POSS may be used to create organic-inorganic hybrids and may be grafted into existing polymers and networks to control properties, including thermal conductivity. The materials may be obtained from suppliers such as Aldrich® Chemical Co., Hybrid Plastics® Inc. and Gelest® Inc..
[0030]As mentioned, it is important to control the structural form of the materials to reduce phonon scattering. This can be further assisted by using nano-particles whose matrices are known to exhibit high thermal conductivity and to ensure that the particles size and its interfacial characteristics with the resin are sufficient to sustain this effect, and also to satisfy the length scale requirement to reduce phonon scattering. A choice of structures that are more highly ordered will also benefit this, including reacted polymer brush lattices having both short and longer range periodicity and ladder or ordered network structures that may be formed from a host resin, such as liquid crystal epoxies and polybutadienes.
[0031]The filled resins may be used as bonding resins in a variety of industries such as circuit boards and insulating tapes. A particular kind of insulating tape is the mica-glass tape used in the electrical generator fields. Resins with these types of tapes can be used as bonding resins, or as impregnating resins as is known in the art. The filled resin may also be used in the electrical generator field without the tapes to fulfill electrical insulation applications in the rotating and static electrical equipment components.
[0032]The tapes may be impregnated with resin before or after being applied to electrical objects. Resin impregnation techniques include VPI and GVPI, discussed more below. In VPI, once a tape is lapped and impregnated it is compressed. Once in position, the resin in the compressed tape is cured, which effectively locks the position of the HTC materials. In some embodiments the resin is cured in a two stage process, as will be apparent to one of ordinary skill in the art. However, optimal compression of the loaded HTC materials favors a completely uncured resin during the compression stage.
[0033]FIG. 2 shows one embodiment of the present invention. Illustrated here are HTC materials 30 loaded into a resinous matrix 32. Phonons 34 traveling through the matrix have a mean path length n, this is the phonon mean free path. This path length can vary depending on the exact composition of the resin matrix, but is generally from 2 to 100 nm, and more typically 5-50 nm, for resins such as epoxy resins. Therefore the mean distance between the loaded HTC materials should be on average less than this distance. Note that the distance between the HTC materials can vary in the thickness versus transverse direction of the tape, and it is generally the thickness direction where the spacing needs to be optimized.
[0034]As phonons 34 travel through the resin 32 they will tend to pass along the embedded HTC materials 30. This will increase the local phonon flux since the raw HTC materials will have a thermal conductivity of between 10-1000 W/mK, as opposed to the resin which is about 0.1-0.5 W/mK. As phonons pass along a loaded HTC material the phonons 36 pass to the next HTC material if the distance between the materials is less than n, therefore the HTC materials form an interconnecting network. FIG. 2 illustrates an idealized path. In practice there will be phonon scattering as the phonons pass between the resin and HTC materials, although the shorter the distance between the materials, and the better the match of phonon propagation characteristics between the HTC materials and the resin, the less the scattering.
[0035]The amount of HTC materials loaded in the resin could actually be quite low, for example about 10% as illustrated in FIG. 2. The average distances, or length scales, between loaded HTC materials therefore may be slightly greater than n, however, a large percentage will still be less than n and therefore fall within embodiments of the present invention. In particular embodiment, the percentage materials that are less than n distance from the next HTC material is over 50%, with particular embodiment being over 75%. In particular embodiment the average length of the HTC materials is greater than n, which further aids in phonon transport.
[0036]The shorter n the greater the concentration of loaded HTC materials, and conversely, the greater the particle size, the less HTC materials needed. Particular embodiment use 5-60% loaded HTC materials by total volume of the resins and fillers, with more particular embodiments at 5-40%. When the resin is impregnated into the tape, it will fill up the spaces between the tape fibers and substrates. The HTC distribution within the tape at this point, however, is often not optimized, and can even have the mean distance between HTC materials greater than n. Practice of the present invention then compresses the resin impregnated tapes and reduces the distances between the loaded HTC materials.
[0037]When a loaded resin is being impregnated into a tape, the fibers or particles of the tape act to block some of the HTC materials, particularly if the resin is 30% or more filler. However, by compressing the tapes, the reverse happens, and more fillers are trapped within the tape as the HTC materials attach themselves to non-mobile parts of the overall structure. The HTC fillers even get pinned to one another. In the embodiments given, it has been implied that the fillers do not react with the resin matrix, however, in some embodiments the fillers do form covalent bonds with the resin and form more homogeneous matrixes. In a homogenous matrix, the resin molecules that are bound to fillers will be retained better than the unbound resin molecules during compression.
[0038]Resins are used in a plurality of industries, and have a large number of uses. Different properties of the resins affect not only their uses, but also the quality and efficiency of the products that they are used with. For example, when resins are used in electrical insulation applications, their characteristics of dielectric strength and voltage endurance needs to be high, as does the thermal stability and thermal endurance. However, often contrary to these objectives, resins usually will also have a low thermal conductivity. The present invention balances the various physical properties of resins and the insulation system they are introduced into to produce a system that has a higher thermal conductivity than conventional electrically insulating materials while maintaining adequate, and even enhancing, key physical properties such as dielectric strength, voltage endurance, thermal stability and thermal endurance, mechanical strength and viscoelastic response.
[0039]As used herein, the term resin refers to all resins and epoxy resins, including modified epoxies, polyesters, polyurethanes, polyimides, polyesterimides, polyetherimides, bismaleimides, silicones, polysiloxanes, polybutadienes, cyanate esters, hydrocarbons etc. as well as homogeneous blends of these resins. This definition of resins includes additives such as cross-linking agents, accelerators and other catalysts and processing aids. Certain resins, such as liquid crystal thermosets (LCT) and 1,2 vinyl polybutadiene combine low molecular weights characteristics with good crosslinking properties. The resins can be of an organic matrix, such as hydrocarbons with and without hetero atoms, an inorganic matrix, containing silicate and/or alumino silicate components, and a mixture of an organic and inorganic matrix. Examples of an organic matrix include polymers or reactive thermosetting resins, which if required can react with the reactive groups introduced on inorganic particle surfaces. Cross-linking agents can also be added to the resins to manipulate the structure and segmental length distribution of the final crosslinked network, which can have a positive effect on thermal conductivity.
[0040]The present invention uses polymer brushes as part of the resin composition. Polymer brush ordinarily refers to molecular array assemblies with chemical structures similar to that of host resins (see above) comprising chains of polymers that are attached to the surface of a substrate, particle surface, or in some cases, polymers that are attached to other polymers. A plurality of the polymers form the hairs, or the brush part of the polymer brush, while a substrate or a single, but usually longer, polymer of a different type will form the handle. The brush contains functional groups such as hydroxyl, amino, carboxyl, thiol, amide, cyanate, thiocyanate, isocyanate and isothio cyanate groups, silane, or a combination thereof. A polymer brush is capable of supporting macromolecular array synthesis comprising covalently linked monomers having, with chemistries similar to those mentioned above, for example hydroxyl, amino, sulfydryl or carboxyl groups or any combination thereof may be formed, and provide attachment points.
[0041]Depending on use, the brushes may start as a whole brush ready for reaction, as individual polymers that are assembled during a process, or combinations thereof. If a resin is being impregnated, the polymerization, ie brush formation, can be done after impregnation, and initiated from the surface. In particular embodiments, the polymer brushes are synthesized first and then added to the rest of the resin, such as a micabond and/or VPI resin used during the manufacture of generator coils discussed above. In such a case the various polymer hairs find reactive sites on a substrate and form the brush. In other embodiments, the polymer brushes are made directly onto a substrate, such as the mica particles in an insulation tape.
[0042]In order to increase the thermal conductivity, the present invention increases the order and density of the polymer brushes. This runs contrary to conventional polymer brushes in which increasing polymer density on a substrate increases the disorder of the hairs due to the Gaussian entanglements of the molecular segments. This is seen if FIG. 3, where when the polymer hairs 50 are attached to a substrate 52, the Gaussian entanglements increase as the chain length increases 51. This type of polymer brush, shown in FIG. 3 , would not be expected to exhibit high thermal conductivity because of the Gaussian entanglements
[0043]Generally in the prior art, as the number of polymer hairs in a given area increase the chain entanglements even more severely as the hair lengths become longer. However, referring to FIG. 3 and FIG. 4, the present invention increases the polymer brush ordering as the polymer hair 50 density increases. Even the longer hairs maintain a rigid order as the density is increased 51. In fact, the longer chains 53 can create areas of higher density than the shorter chains, which will result in better matching of interfaces and reduce phonon scattering. In order to prevent Gaussian entanglements, the present invention uses hairs that are of a more rigid structure. Particular types of polymer hairs that are more rigid are LCT epoxies such as, for example, Diglycidylether of 4,4'-Biphenol, and 1.2 vinyl polybutadienes.
[0044]Referring more specifically to FIG. 4 the present invention increases the polymer brush ordering as the polymer hair 50 density increases. Even the longer hairs maintain a rigid order as the density is increased 51. In fact, the longer chains can create areas of higher density than the shorter chains, which will result in better matching of interfaces and reduce phonon scattering. In order to prevent Gaussian entanglements, the present invention uses hairs that are of a more rigid structure
[0045]Referring to FIG. 5, an example of how polymer brushes of the present invention are formed is shown. A base layer 70, such as a substrate, has an initiator layer 72 thereupon. An energy source 71, such as heat or light, creates surface bound free radicals 74 on the initiator layer 72. An epoxy-vinyl monomer is then added 76, creating an epoxy-vinyl monomer polymer layer 77. To this is added 75 an epoxy resin, such as an LCT epoxy, creating epoxy brush hairs 78. Examples of substrates include alumina, silica, boron nitride , polymer (e.g., polycarbonate, polyimide), and mica or glass fibers. Examples of free radical initiators include (for substrate treatment) water soluble azonitrile compounds such as VA-044 available from Wako Chemicals and DuPont. Examples of monomer polymerization catalysts are benzoyl peroxide, t-butyl peroxide, MEK peroxide. Cumene hydroperoxide is available from Arkema Chemicals and the Chemtura Corporation. Examples of epoxy functionalized vinyl monomers are p-vinylphenyl glycidyl ether (VPGE) and p-isopropenylphenyl glycidyl ether (IPGE). Examples of epoxy curing catalyst include (B-staging) dicyandiamide, diaminodiphenyl sulfone (DOS), Benzyldimethylamine (BDMA). In the example given in FIG. 5, the prepared polymer brush may not be fully cured after preparation ( i.e., B-staged with residual unreacted epoxy and hydroxyl groups), so that it may be reacted at some later time with micabond resins and impregnating resins. The amount of B-staging catalyst and the optimum reaction temperature would be carefully selected to allow this B-stage condition to be achieved.
[0046]Unlike the disordered polymer brushes of the prior art that would not increase the thermal conductivity of the resin component, the ordered polymer brushes will significantly increase the thermal conductivity through and around the affixed substrates. In addition, as seen in FIG. 6, the ordered polymer brushes 50, can impart increased order on the resin around them 55. This has the effect of magnifying the ordered region and further increasing thermal conductivity around the substrate 52. As discussed below, the terminal ends of the hairs can have particular function groups that can react to the resin matrices to further lock in this ordering.
[0047]Polymer brush type resin matrices shown above are a fraction of the total resin used, and will typically be from 10-25% of the resin by volume. This lower percentage will allow the bulk of the resin to maintain its recognized properties, such as impregnability, wettablility, etc, while still allowing the polymer brushes to increase thermal conductivity around a substrate. However, in some embodiment the polymer brushes can make up the entire resin matrices. A resin matrix of the prior art will have a maximum thermal conductivity of about 0.15 W/mK. The present invention provides resins with a thermal conductivity of 0.5 to 5 W/mK and even greater.
[0048]The polymer brushes comprises a handle, which is often a substrate, and hairs or repeating units connected to the handle, which may have distinct terminal moieties. A polymer brush can be defined into a multitude of structures by fine tuning the architectural components. The ends of the polymer brush can be composed of a large number of functional groups which can be reacted with other polymer species to give unusual copolymer structures. These functional groups include amino, hydroxyl and carboxyl which would be reactive with resins such as the LCT epoxies. Specific types of polymer brushes include polypropylene-imine, polyamido-amine, and polyamido-amines with an organic silicon exterior These types of polymers can also form inorganic networks with the inclusion of inorganic fillers.
[0049]Although the polymer brushes may make up the entire host resin structure, it is more often the case that they are a part of the resin that comprises different types of molecules. Particular types of resin, such as Micalastic and Thermalastic resins, are particularly well suited for mixing with the polymer brushes. In addition more highly structured resins, such as liquid crystal thermosets (LCT) and 1,2 vinyl polybutadiene are also good since they combine low molecular weights characteristics with good crosslinking properties. Highly structured resins, form highly organised micro-structures both prior to and during crosslinking when cured. The structures include crystallinity, para-crystallinity and liquid crystalline structures, unique polymer architectures, controlled crosslinking and network expansion and contraction during cure. The use of highly structured resins enhances the HTC properties, particularly the heat conductivity, and can achieve significant enhancement to electrical and mechanical properties
[0050]The polymer brushes may also have mixed macromolecular arrays, which allows for switching and/or self-assembling properties such as wettability, porosity and adhesion.
[0051]When the high thermal conductivity fillers are homogeneously mixed with resins containing the polymer brushes (or brushes are formed after mixing) they form a continuous product, in that there is no interface between the resins and the fillers, and covalent bonds are formed between the fillers and the polymer brushes.
[0052]When the HTC materials form essentially homogenous mixtures with the resins, they are essentially free of undesired microscopic interfaces, variable particle wetting and micro void formation. These homogeneous materials form a continuous-phase material which are non-discrete at length scales shorter than either the phonon wavelength or phonon mean free path in conventional electrical insulating materials. In some embodiments, intentional interfaces can be placed in the resin structure so as to control dielectric breakdown. In insulating materials, dielectric breakdown will occur given the right conditions. By controlling the nature and spatial distribution of the interfaces in two-phase system, dielectric breakdown strength and long term electrical endurance can be enhanced. Increases in dielectric strength will take place in part because of increased densification, the removal of micro voids and a higher level of internal mechanical compression strength.
[0053]Generally, the larger the polymer brush, the greater its ability to function as a phonon transport element. However, its ability to permeate the material and its percolation potential can be adversely affected by its size so optimal sizes are sought to achieve the balance of structure and properties required. Like other HTC materials, solvents can be added to the polymer brushes so as to aid in their impregnation of a substrate, such as a mica or a glass tape.
[0054]In all cases phonon transport is enhanced and phonon scattering reduced by ensuring the length scales of the structural elements are shorter than or commensurate with the phonon distribution responsible for thermal transport. Larger HTC particulate materials can actually increase phonon transport in their own right, however, smaller HTC materials can alter the nature of the resin matrix, thereby affect a change on the phonon scattering. This may be further assisted by using nano-particles whose matrices are known to exhibit high thermal conductivity and to ensure that the particle size and interface characteristics are sufficient to sustain this effect and also to satisfy the length scale requirements for reduced phonon scattering.
[0055]Continuous organic-inorganic hybrids may be formed by incorporating inorganic nano-particles in linear or crosslinked polymers and thermosetting resins in which nano-particles dimensions are of the order of or less than the polymer or network segmental length (typically 1 to 50 nm). This would include, but is not exclusive to three routes or mechanisms by which this can occur (i) side chain grafting, (ii) inclusive grafting e.g. between two polymer chain ends, (iii) cross-link grafting involving at least two and typically several polymer molecules.
[0056]These inorganic nano-particles will contain reactive surfaces to form intimate covalently bonded hybrid organic-inorganic homogeneous materials. These nano-particles may be metal oxides, metal nitrides, and metal carbides, as well as some non-metal oxides, nitrides and carbides. For example, alumina, magnesium oxide and zinc oxide and other metal oxides, boron nitride and aluminum nitride and other metal nitrides, silicon carbide and other carbides, diamond of natural or synthetic origin, and any of the various physical forms of each type and other metal carbides and hybrid stoichiometric and non-stoichiometric mixed oxides, nitrides and carbides. More specific examples of these include Al2O3, AlN, MgO, ZnO, BeO, BN, Si3N4, SiC and SiO2 with mixed stoichiometric and non-stoichiometric combinations.
[0057]The volume percentage of the HTC materials in the resin may be up to approximately 60% or more by volume, and more particularly up to approximately 35% by volume. Higher volume filling tends to give higher structural stability to a matrix. However, with control of the size and shape distribution, degree of particle association and alignment the HTC materials can occupy as little as 1% by volume or less. Although, for structural stability reasons, it might be useful to add an amount greater than the minimum needed for percolation to occur. Therefore the resin can withstand physical strains and deformation without damaging the percolation structure and the HTC characteristics.
[0058]The addition of surface functional groups may include hydroxyl, carboxylic, amine, epoxide, silane or vinyl groups which will be available for chemical reaction with the host organic polymer or network forming resin system. These functional groups may be naturally present on the surface of inorganic fillers or they may be applied using wet chemical methods, non-equilibrium plasma deposition including plasma polymerization, chemical vapour and physical vapour deposition, laser beams, sputter ion plating and electron and ion beam evaporation methods. The matrix polymer or reactive resin may be any system which is compatible with the nano-particles and, if required, is able to react with the reactive groups introduced at the nano-particle surface. These may be epoxy, polyimide epoxy, liquid crystal epoxy, cyanate-ester and other low molecular weight polymers and resins with a variety of crosslinking agents.
[0059]In one embodiment the polymer brushes of the present invention are used to bridge filler particles, such that groups of fillers particles are joined to one another directly through polymer brushes. This may be done through single, double or multi stage brushes. Referring to FIG. 7, some these examples are shown. Polymer brush hairs 51 connect multiple substrates 52 either directly 60, through two brushes linking 62, or through multiple brushes linking 64. This is controlled through the end functional group selection on the hairs and well as the overall percentage of polymer brushes in the resin matrix. Note that the angles joining the various brushes are exaggerated for clarity, and the hairs may in fact be joined straight. or can be overlapped at the junction point (e.g., laddered polymers).
[0060]In one embodiment the present invention provides for an resin that comprises, polymer brushes. The polymer brushes themselves comprise structured polymer hairs having a density of 0.8 to 1.0 g/cc, a chain length of 1 to 1000 nm, and in particular 2 to 100 nm, and a thermal conductivity of 0.5 to 5.0 W/mK. The polymer brushes are 10-25% by volume of the resin, and the polymer hairs orient surrounding resin molecules to the polymer hairs alignment. This arrangement creates phonon channels within the resin. In some embodiments the polymer bushes are formed after the resin is impregnated into a porous media, which may be a paper matrix such as mica-glass insulating paper.
[0061]In particular embodiments the polymer brushes are created on the surface of a substrate, and may be formed from vinyl monomers. The polymer brushes may also be liquid crystal epoxy.
[0062]In other particular embodiments filler materials are added to the resin, and the filler materials comprise 5-40% by volume of the highly structured resin and the filler materials have aspect ratios of 3-100.
[0063]In other particular embodiments the resin is an epoxy resin. In converse embodiments, the resin is a hydrocarbon, such as polybutadiene. Other possible resins are polysiloxanes, aromatic polyesters and/or aromatic polyamides.
[0064]In another embodiment the present invention provides for an epoxy resin that comprises filler materials and polymer brushes, where the polymer bushes bridge the filler materials within the epoxy resin. The filler materials themselves comprises 5-40% by volume of the highly structured resin and have aspect ratios of 3-100. The filler materials also form a continuous organic-inorganic composite with the epoxy resin and the polymer brushes. The polymer brushes comprise 10-25% by volume of the epoxy resin, and the bridged filler materials create phonon channels within the epoxy resin.
[0065]In particular embodiments, the epoxy resin is selected from at least one of liquid crystal polymers, interpenetrating networks, polymer brush type matrices, expanding polymers, ladder polymers, star polymers and structured organic-inorganic hybrids. In other particular embodiments the filler materials comprise one or more of Al2O3, AlN, MgO, ZnO, BeO, BN, Si3N4, SiC and SiO2.
[0066]As mentioned, filled resin may be used in the electrical generator field without the tapes to fulfill electrical insulation applications in the rotating and static electrical equipment components. The use of high thermal conductivity materials in a generator is multiple. Within the stator coil there are component materials other than the groundwall which must have high thermal conductivity to optimize the design. Likewise other components associated with the coils to maximize heat removal. Improvements to stator design dictate that improvements be made to rotor design so that generator efficiency can by maximized.
[0067]One embodiment of the present invention adds high thermal conductivity (HTC) materials to resins to improve the thermal conductivity of the resins. In some embodiments the other physical properties of the resins are reduced in a trade-off with higher thermal conductivity, but in other embodiments, some of the other physical properties will not be significantly affected, and in some particular embodiments these other properties will be improved. In particular embodiments, the HTC materials are added to resins, such as LCT epoxy, that have ordered sub-structures. When added to these types of resins, the amount of HTC material used can be reduced versus use in resins without ordered sub-structures.
[0068]The HTC materials loaded into the resins are of a variety of substances that can be added so that they may physically and/or chemically interact with or react with the resins to improve thermal conductivity. In one embodiment, the HTC materials are polymer brushes, and in another embodiment they are nano or micro inorganic fillers having a defined size or shape including high aspect ratio particles with aspect ratios (ratio mean lateral dimension to mean longitudinal dimension) of 3 to 100 or more, with a more particular range of 10-50.
[0069]In a related embodiment, the HTC materials may have a defined size and shape distribution. In both cases the concentration and relative concentration of the filler particles is chosen to enable a bulk connecting (or so-called percolation) structure to be achieved which confers high thermal conductivity with and without volume filling to achieve a structurally stable discrete two phase composite with enhanced thermal conductivity. In another related embodiment, the orientation of the HTC materials increases thermal conductivity. In still another embodiment, the surface coating of the HTC materials enhances phonon transport. These embodiments may stand apart from other embodiments, or be integrally related. For example, polymer brushes are combined with other types of highly structured materials such as thermoset and thermoplastic materials. They are uniformly distributed through a resin matrix such that the HTC materials reduce phonon scattering and provide micro-scale bridges for phonons to produce good thermally conducting interfaces between the HTC materials.
[0070]Resins of the present invention may be used for impregnation of other composite constructions such as a mica tape and glass and polyester tape. In addition to the standard mica (Muscovite,Phlogopite) that is typically used for electrical insulation there is also Biotite mica as well as several other mica-like Alumino-Silicate materials such as Kaolinite, Halloysite, Montmorillonite and Chlorite. Montmorillonite has lattices in its structure which can be readily intercalated with polymer resins, metal cations and nano particles to give high dielectric strength composites.
[0071]In other embodiments, the present invention is used as a continuous coating on surfaces where insulation is desired; note that "continuous coating" is a description of a macro-scale application. In a continuous coating, the resin forms a coating on materials. When used with a substrate, the HTC materials can be combined with the resin by a variety of different methods. For example, they can be added prior to the resin being added to the substrate, or the resin can be added first, followed by the HTC material and then an additional impregnation of resin. Other fabrication and process methods will be apparent to one of ordinary skill in the art.
[0072]Insulating papers are just one type of porous media that may be impregnated with the resin of the present invention. Many other materials and components made therefrom, in many industries, some of which are mentioned below, can use different types of porous media to impregnate the resin into. By way of examples there are glass fiber matrix or fabric, and polymer matrix or fabric, where the fabric might typically be cloth, matt, or felt. Circuit boards, which are glass fabric laminate, with planar lamination, will be one product which will benefit from the use of resins of the present invention.
[0073]Although the present invention has been discussed primarily in use with electrical industries, the invention is equally applicable in other areas. Industries that need to increase heat transference would equally benefit from the present invention. For example, the energy, chemical, process and manufacturing industries, inclusive of oil and gas, and the automotive and aerospace industries. Other focuses of the present invention include power electronics, conventional electronics, and integrated circuits where the increasing requirement for enhanced density of components leads to the need to remove heat efficiently in local and large areas. Also, while specific embodiments of the invention have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the inventions which, is to be given the full breadth of the claims appended and any and all equivalents thereof.
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The 2010 Syrah Lot 354 Crozes Hermitage dishes out earthy, spice-laced aromas and flavors as well as a medium-bodied, straightforward profile on the palate. As with this estates other releases, its geared for near-term drinking. Drink now. (JD) (8/ 2013)
Gold Medal winner, 2013 San Diego International Wine Competition. Thanks to the sorcerer of sourcing, a Crozes-Hermitage under $25! This wine is a great, classic example of a Crozes-Hermitage, an exciting blend of dark berry fruit, dried meat, hints of earth and spices with a blast of black pepper at the end. The 2010 vintage is a great one in the Rhône Valley; that helps explain why this wine is hitting on all cylinders. Pair this wine with roast duck, lamb or a thick-cut pork chop and it will absolutely sing.
Below is a listing of the wine review scores we frequently reference in our notes. While these sources remain an excellent source of information, we always recommend that you trust your own palate. Scores in these publications often represent the personal taste of an individual critic, which may not always coincide with your own. We have a huge team of excellent wine professionals that can match wines you've had in the past with new arrivals that meet your flavor profile.
The item you have chosen is in stock, and has inventory in at least one of our retail stores. Below is the current quantity on hand information for this product within our database. It is never more than five minutes old. Additionally, our shopping cart looks at real time inventory so when you add an item to you cart we will do an immediate check of available inventory and alert you if there are any issues.
2010 E. Guigal Côtes du Rhône $12.99
2012 Château de Montfaucon Côtes du Rhône $11.99
2012 Domaine la Garrigue "Cuvée Romaine" Côtes du Rhône $13.99
2011 Moulin de la Gardette "Tradition" Gigondas $24.99
2011 Château de Montfaucon "Baron Louis" Lirac $18.99


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Syracuse Does It Again, Former Indiana-Signee Ron Patterson Pledges Commitment
Indiana's loss was Syracuse's gain on Saturday as heralded recruit Ron Patterson joined the Orange's 2013 recruiting class. Patterson becomes the fourth member of that group who have all come since July. He'll join five star Tyler Ennis as well as B.J. Johnson and Chinoso Obokoh. Ennis is the crown jewel of this group. The school was able to fortify both the front and backcourts.
Patterson signed with Indiana and was expected to be with them in 2012, but he didn't meet the school's academic standards. The Bloomington Herald-Times was reporting that Patterson's test scores and grades were good enough for him to get in, but a tough summer semester led IU's faculty council to decide that he wouldn't be admitted this year.
Xavier was in the mix as well as Michigan, Illinois, Cincinnati and Ohio State. The 6-foot-2 guard from Indiana has "an old school game" according to his scouting report on ESPN.com. It adds that "He is a good scorer that has very little wasted motion. He has solid form and a nice rotation on his shot."
The Orange are not done as they are rumored to be in the mix for Jermaine Lawrence, Tyler Roberson, Rysheed Jordan and Noah Vonleh. Roberson has the school in his final three while Jordan has the Orange in the mix as well. This young roster will lose Brandon Triche and James Southerland for sure at the end of the year so the new infusion of talent will be nice for them.
Kentucky Wildcats Face Tough Stretch of Games
John Calipari, head coach of the Kentucky Wildcats, is fond of many sayings, but one in particular seems pertinent this season. Read More
Virginia's Weaknesses Exposed in Loss to Duke
The Duke Blue Devils provided the blueprint for beating the Virginia Cavaliers in March with a 69-63 victory in Charlottesville. Read More
Texas' Weaknesses Exposed In Loss To Baylor
The Texas Longhorns showed their vulnerabilities in a blow-out loss to the Baylor Bears. Read More
Louisville Basketball Shaves Out Close Win
Find out how Louisville basketball took care of business in overtime and why Rick Pitino should shave his beard. Read More
5 Midseason Things About Pac-12 Basketball
Only one thing on this list isn't a surprise. It's been a pretty interesting year in the west so far. Read More
Kansas Jayhawks' Bill Self Underrated
There are a number of legendary coaches in college basketball today. One is rarely mentioned with the others. Read More
Pittsburgh Takes Major Step Forward vs. Notre Dame
Pittsburgh earned its biggest win of the season. What does this mean for the Panthers moving forward? Can this save their March Madness hopes? Read More
Pac 12 Schedule-Makers Messed Up This Week
There's no legitimate reason why Arizona and Arizona State had two home games during Super Bowl week. Honestly. What are they thinking? Read More
Wisconsin Benefits from Team Experience
In today's college basketball environment, there is one factor that is most commonly overlooked as it relates to great teams. Read More
Wake Forest Devin Thomas A Diamond In The Rough
The Wake Forest Demon Deacons are awful, but Devin Thomas is a star. Read More
5 Must-See Big Ten Games
Here are five of the most exciting Big Ten conference games remaining on the schedule in 2015. Read More
Alabama vs. Kentucky: Game Preview, Prediction
The Kentucky Wildcats return home on Saturday to host the Alabama Crimson Tide in an SEC clash. Read More


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Hi: 4° Lo:-2°
BROMSGROVE needs a depedestrianised High Street, cheaper parking and a better mix of shops - that's the view of directors from a town-based property consultant who have called for action to reverse the decline of the town centre.
John Truslove and Ian Parker from John Truslove chartered accountants said, in their opinion, those changes would entice shoppers back to Bromsgrove.
Mr Truslove said: "Parking is always the big issue, so let's address it.
"Lack of parking, and the expense of what parking there is, will often deter people from picking a particular town for their shopping expedition – hence the popularity of out-of-town shopping parks where the parking is free and you can drive virtually to the door to load your shopping if necessary."
Mr Parker said Bromsgrove did not feel like the market town it was and added there was not a varied mix of stores to entice people to shop there.
The pair called for both of those issues to be sorted out and added the final improvement they would like to see was depedestrianisation.
Mr Parker said: "At the moment, people drive along New Road and all they see is Poundland and empty shops.
"If they could drive down the High Street, they would see what Bromsgrove had to offer."
Mr Truslove added: "Pedestrianisation doesn't work - it leads to a major decline in footfall for those stores furthest from the available parking.
"A one-way system, with a maximum 20mph speed limit, and two hours of free parking provides the best of both worlds.
"Let's try it and see the difference it makes," he said.
The calls come as the High Street is being dug up so a new pedestrianised surface.
Mr Truslove said shopping was one of the most dynamic elements of the economy and added that, although an increasing amount of shopping was done online, consumers still liked to 'browse' and 'touch and feel the goods' - something Internet shopping could not offer.
Bromsgrove District Council's portfolio holder for the town centre, Coun Rita Dent, said the authority welcomed any views which added to the High Street debate and said she hoped Mr Truslove would engage with the ongoing process like so many residents and local businesses.
"There are always counterpoints in such discussions of course, including the ability to enjoy clear high streets without traffic and the associated safety and air quality issues in narrow enclosed areas.
"However it is a fact that Mr Truslove's comments come too late, for now.
"The town centre regeneration partnership is at this very moment delivering the kind of heritage-grade High Street that befits Bromsgrove's status as an historic market town.
"Designed from the ground up, this has come out of many years of consultation that demonstrated the value that traders, disability groups and other groups attach to having completely clear access to the main shopping area, which a good pedestrianised area provides.
"To support that, ample, safe, high quality parking alongside and at both ends of the High Street is still cheaper than many comparable towns – from 80p an hour or £3 all day."
* What do you think? What improvements do you think could make Bromsgrove Town Centre a more appealing place to shop? Email your views to email@example.com
1 Popular Bromsgrove pub set to be reopened
2 CCTV image released after Bromsgrove burglary
3 Bromsgrove town centre trees to be cut down to size
4 Bromsgrove couples invited to renew vows for Valentines Day
5 Temporary lights put on Lydiate Ash islands after complaints
RESIDENTS have been invited to vote for Sainsburys
A BROMSGROVE man has been charged with inflicting
DRIVERS across Bromsgrove have been warned to take
A MAN who is being hunted by police
LITTLE Freya Powell's mother is set to host a charity ...
AGE was certainly no barrier as young and old scooped ...
Visit the Worcester Observer website for the latest.
A RALLYING call has been made for residents and schools ...


text: People from Tennessee Create Classic editor Talk0 Category page This page needs content. You can help by adding a sentence or a photo. Add to this page!orSearch for "People from Tennessee" "Calpernia Sarah Addams (born 20 February 1971) is an American transgendered author, actress, and... Calpernia Addams Pages in category "People from Tennessee" This category contains only the following page. C Calpernia Addams


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Rubber of Whist(A). A game of cards called "whilst." "Rubber" is transferred from bowls, in which the collision of two balls is a rubber, because they rub against each other. Source: Dictionary of Phrase and Fable, E. Cobham Brewer, 1894
24 X 7Private Tutor
Explore Math Answer , Algebra 2


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- Shopping Bag ( 0 items )
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Assessment of Couples and Families considers the impact of recent changes on the assessment process and provide practitioners with a review of contemporary techniques and the means by which they can be implemented into practice in conjunction with new reporting inventories and observational methods. These new assessment strategies will be presented collaterally with case material that addresses a specific problem, such as family violence or marital suitability. This unique problem focus will provide practitioners with a handy point of reference to acquaint themselves with modern practice techniques that address issues new to the therapy session while providing a supplement to coursework on assessment.
Contributors. Series Foreword. Foreword. Preface. Acknowledgements. Part I: Basic Considerations and Models. Sperry, Assessment of Couples and Families: An Introduction and Overview. Bray , Models and Issues in Couple and Family Assessment. Part II: General Strategies. Duffy, Chenail, Qualitative Strategies in Couple and Family Assessment. Nurse, Sperry, Effective Use of Psychological Tests with Couples and Families. Hampson, Beavers, Observational Assessment of Couples and Families. Sperry, Clinical Outcomes Assessment of Couples and Families. Part III: Specific Applications. Bagarozzi, Sperry, Couples Assessment: Strategies and Inventories. Yingling, Child and Family Assessment: Strategies and Inventories. Fernandez, Veshinski, Child Custody and Divorce Assessment: Strategies and Inventories.Friedrich, Olafson, Connelly, Child Abuse and Family Assessment: Strategies and Inventories . Part IV: Postscript and Future Prospects. L'Abate, Couple and Family Assessment: Postscript and Future Prospects. Index.


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Book your room at Best Western Marina Del Rey
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Max Occupancy: 2 guests (up to 1 child, 1 infant)Family-friendly Vina del Mar hotel near Quinta Vergara Amphitheatre
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Simply enter your Nectar card number when prompted. Your points will be credited 30 days after you return from your trip.*Offers may apply
This family-friendly hotel is located in the city center, close to Palacio Presidencial de Cerro Castillo, Caleta Abarca Beach, and Parque Potrerillos. Also nearby are Teatro Municipal and Quinta Vergara Amphitheatre.
Hotel Features
In addition to a restaurant, Best Western Marina Del Rey features a bar/lounge. Other amenities include a coffee shop/café and conference space.
Air conditioning
Guestrooms have air conditioning, safes, and minibars; rooms also include coffee/tea makers and hair dryers.
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Kelly Osbourne's New Haircut: Elton John AIDS Foundation Party
Love It or Hate It? Kelly Osbourne's Dramatic Do
Last night Kelly Osbourne stepped out at the Grey Goose and Elton John AIDS Foundation party in London revealing a decidedly dramatic new do. The last time we met up with Kelly she was rocking a much more subdued chin bob and she left the drama to her mod smoky eye. Here she went a little more natural with the eye makeup, matched her lips to her red-ribbon pin, and created a stir with this severe, cascading bob. As I've recommended before, long, side-swept bangs are much more flattering on round faces, as it draws attention away from the face. Here, Kelly's blunt bangs and short layers are adding volume. So, now that you know my opinion, what do you think? Do you love it or hate it?
Kelly Osbourne
Love It or Hate It
7 years
Oh No! It's Too Robert Smith/Cure. I expected to see her in a cave with Spiders and runny eyeliner! Afraid..
7 years
Nuh-uh, she needs a cut that stops well under her jawbone, a little fuller on the top, and NO STRAIGHT BANGS! Her new look makes her face look even rounder than it is. For the coloring, she looks like one of those pictures where there's only black/grey/white and one single fresh color (her lips). A bit odd, and as Dollylo said: Very Morticia..
7 years
She looks too severe for my tastes. And it seems sort of obvious that her hair is styled to mask her round face. Wouldn't it make more sense simply to have your hair longer? It's kind of like the hair version of using contour powder to create cheekbones you don't have. Draws more attention to the problem than if you'd left well enough alone...
7 years
Well it's very much her and I guess she loves it but I personally think it's too over the top.
7 years
I don't like this cut at all especially not with her full face. I love her and I think she'd look amazing with an inverted bob that brushes her collarbone.
7 years
I didn't like this at all. I also don't like it when she makes her hair bright red or bright pink. The rest of her (how she dresses and how she carries herself) is so outrageous that she really doesn't need to do all that extra stuff to make her point. We get it Kelly!
7 years
I think it suits her beautifully. Good for her for having such a strong sense of personal style at her age!
7 years
I love it because Kelly doesn't care if you hate it... she does what she wants and what she likes and if you don't like it, don't look at her sorta deal... Love her attitude, love her creative look
7 years
This girl has to do the best with what she has to work with. I think she will be criticized for anything she wears. She's a non traditional looking girl that's for sure. She'd never look right in the California blonde look.
I don't love her look and I could never pull that off, but she's working the whole look and she is pulled together. It's very CZJ in Chicago.
Link Love
- The more you wash your hair, the worse it'll look — SheFinds
- Nourishing lip oils to replace that old melted balm in your pocket — InStyle
- The benefits of getting Botox before you hit your 30s — Byrdie
- Tricks to pick the best hair color for your skin tone — The Fashion Spot
- Horse oil is the new skin care trend to try — The Cut
- Hydrating, affordable hand cream for dry Winter hands — The Gloss
- How to remove any kind of nail polish (even glitter) — Beauty High
- Survival strategies for growing out your bangs — xoVain


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Okay so this has been a huge issue with me, and is one of the things that I would have to say utterly pisses me. I have always had problems with people that stare. There have been some instances when I didn't really care because for one I dress weird and everyone knows that if you wear something that is considered different you are going to get some looks, so when I am wearing something that I know is going to attract attention it doesn't really bother me. Yet for some reason I can walk into a store in a plain gray hoodie, jeans, and my converse and I still get stared at relentlessly.
Another reason I have problems with people who stare is because I have a handicapped sister who also has Cerebal Palsy which resulted from a car crash my mother was in awhile back when she was pregnant with my sister. My sister cannot walk very well and tires very easily, so naturally when we go to wal-mart she has to use a wheelchair. Everytime we are in wal-mart people just stare at her, I've even seen them double around isles to take second looks like she is some kind of circus animal. It makes me want to rip their face off! For goodness sakes she is a child who is handicapped and had her whole life altered because some idiot ran into my mother because he wasn't watching where the hell he was going! It infuriates me so much that people can be so closeminded and heartless it seems like! I mean I don't want them to come up to us and hand us money or their sympathy for what happened...I just want them to keep their eyes to themselves for once in their life!
So you've heard my piece now I want to hear from you all, here are my questions: Why do you think people stare at others? Do you think it is right for people to stare?
Questions or comments anyone? ^-^


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Most of the overripe bananas in my kitchen are destined to go into a batch of banana bread or banana cake. There are occasions when I don't have quite enough bananas to make a whole loaf – such as the mornings when I decide to add half of one of those bananas to a bowl of cereal, leaving half to languish in the fruit bowl. ... Read More »
Category Archives: Recipes
Strawberry, Mint and Lime Shortcakes
As soon as strawberries come into season, I start making strawberry shortcakes for dessert. I love the combination of cake or biscuits, whipped cream and strawberries – especially when the strawberries are perfectly ripe and sweet – and it is so easy to make that it is always one of my go-to summertime desserts. Thees Strawberry, Mint and Lime Shortcakes put just a little twist ... Read More »
S'mores Scones
As soon as it gets warm enough to enjoy dinner outdoors, I count that as the start of s'mores season. The combination of toasted marshmallows, melted chocolate and crispy graham crackers is one of my favorites, and once my pantry is stocked up for the season, those ingredients seem to find their way into all kinds of baked goods. These S'mores Scones are a way to ... Read More »
Mint Julep Pie
Mint Juleps are a cocktail that is a tradition at the Kentucky Derby, which is run at Churchill Downs on the first Saturday in May every year. The drink is made with bourbon, sugar and mint, and served over ice. It's strong, yet refreshing – and both of those qualities are what make this drink such a hit at a big, festive springtime event like ... Read More »
Vanilla Crumb Cake
A coffee cake with a buttery crumb topping is hard to resist. Most crumb toppings include cinnamon or other spices, both because spices add a great aroma to a cake while it is baking and because darker spices give a crumb topping a darker color to contrast with the rest of the cake. This Vanilla Crumb Cake is for vanilla lovers and you won't find ... Read More »
Lemon and Lavender Shortbread
You can never go wrong with a buttery batch of shortbread cookies. They're delicious plain, where you get a generous dose of butter flavor, and they can also be a blank canvas for other flavors. This Lemon and Lavender Shortbread is a great example of how a few simple additions can take a shortbread recipe from something good to something special without even trying. It ... Read More »
Blood Orange Margarita
Blood orange season typically runs from December through March, but this year I had a few oranges that tenaciously hung onto the tree branches until late spring and I could only think of one way to celebrate the last oranges of the season: Blood Orange Margaritas. These drinks get their vivid red color from fresh blood orange juice, which makes them really stand out if ... Read More »
PB&J Whoopie Pies
Soft, cake-like whoopie pies are so much fun to eat that they make me feel like a kid again – even though I didn't really eat whoopie pies as a kid. That sense comes from the fact that whoopie pies are finger food and are often a bit mess to eat, as filling ineviatably squishes out from one side or the other and gets onto ... Read More »


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Black teen executed in 1944 may get new trial
George Stinney was just 14-years-old when he was convicted for the murders of two white girls ages 11 and 7. The confession was shaky, and Stinney did not have proper representation. The young child didn't stand a chance against the South Carolina jury.
Although it has been almost 70 years since the boy's execution, supporters of Stinney asked a judge to grant him a new trial in hopes of clearing his name.
The request for a new trial is largely symbolic, but Stinney's supporters say they would prefer exoneration to a pardon.


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Jake Arrieta surrendered just one (unearned) run over seven innings Wednesday as the Cubs played the role of spoiler with a 3-1 victory over the Cardinals.
Jake Arrieta flirted with a no-hitter, losing it with one out in the eighth, but still finished off a one-hit, 13-strikeout shutout of the Reds on Tuesday.
Jake Arrieta limited the Blue Jays to two runs over 6 1/3 innings but took a no-decision as the Cubs' bullpen was trampled late in a loss on Tuesday.
Jake Arrieta held the Brewers to one run over six innings in a win on Tuesday.
Jake Arrieta was tagged for six runs in four innings by the Reds on Thursday.
Jake Arrieta held his former team to one run across seven innings in Friday's 4-1 victory over the Orioles.
Cubs manager Rick Renteria said Monday that the club has no plans to shut down Jake Arrieta.
Jake Arrieta fired seven shutout innings Sunday as the Cubs beat the Mets 2-1 at Citi Field.
Jake Arrieta said Tuesday that he's open to a contract extension with the Cubs.
Jake Arrieta was hammered for nine earned runs in five innings Wednesday in a loss to the Rockies.
Jake Arrieta shut down the Rockies on Thursday, allowing just one run and three hits over seven innings to improve to 6-2.
Jake Arrieta held the Cardinals to two runs in six innings Saturday but the Cubs lost.
Jake Arrieta took his second loss of the season after allowing three runs in 6 2/3 innings to the D'Backs on Sunday.
Jake Arrieta delivered another strong outing against the Braves on Friday, allowing three runs on four hits over 7 2/3 innings, but was denied his sixth victory of the season after Hector Rondon blew his lead in the ninth inning.


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5:15 AM: My alarm clock goes off and I get up, eat a slice of cinnamon raisin ezekial bread with some almond or peanut butter and pour a cup of coffee (and then another cup). B's diapers might need a few more minutes in the dryer, if not I stuff them and pack her diaper bag and prep her bottles for the day. Throw on some work clothes and minimal makeup.
6:30 AM: Tate wakes B up, changes her and plays with her for a while while I load up the car. I am a legitimate bag lady. Diaper bag, bottle bag, pump bag, work bag, lunch bag, gym bag...
6:40- 7:05 AM: Feed B.
7:10 AM out the door to daycare and arrive around 7:25.
7:45 AM: I'm supposed to be at work. (I won't be there for another 5 minutes).
8:30-9:00 Pump
9:00-9:30 Fourth grade group. This week's theme is Halloween, so I am incorporating several books, games, worksheets, apps, and activities to target my student's communication goals. Some students are seen individually, but most are seen in pairs or groups of three at the most.
9:30- 10:00 Second grade group
10:00-10:30 paperwork such as writing evaluation reports, IEPs, meeting notices, etc.
10:30-11:00 Third grade group
11:00-11:30 Time to eat lunch and pump again.
11:30-12:00 Kindergarten group
12:00-12:30 Fifth grade group
12:30-1:00 Evaluations, collaboration with teachers, meetings
1:00-1:30 First grade group #1
1:30-2:00 First grade group #2
2:30-3:00: Help with dismissal.
3:00 PM-4:30 PM Hop in the car and drive to an early intervention visit. Early intervention services are part of a state program for children from Birth-three years of age. I'm glad that my second job is in the same field as my full-time job, but I get to help families facilitate the development of their children's communication skills.
4:30 PM- 5 PM Pick up B at daycare, chat with the teachers, "Oh she didn't nap again?! I'm so (not) surprised". Swing by practice, since the stadium isn't far out of the way to get home, so B and Tate can have a few minutes of time together today.
5:00 PM- 6:00 Feed B and she falls asleep. Time to cook dinner, throw in a load of laundry and check the mail...and email
6:00-6:30 PM Take a walk. I haven't been getting in many workouts since B was screaming her head off at Crossfit and I hate to leave her in child care for more time each day, so I make sure we get a walk each day that I don't get a real workout. I love the Ergo carrier and B does too. She usually dozes off while we are walking.
6:30-7:30 PM B plays on the floor or exersaucer for a little bit, then it is bathtime, diaper change and time for jammies.
7:30 PM Bedtime. We send pictures to Tate, who is still at work and then read a few stories. Currently in rotation are "Counting Kisses" and "That's Not My Puppy". Finally I nurse her again and she falls asleep, so I gently rouse her and bring her to her crib to fall asleep We have been working on letting her fall asleep on her own.
8:30 PM Pack leftovers for lunch tomorrow...and snacks, lots of snacks. breastfeeding STILL makes me ravenous.
8:45 PM Check on B, sit and check my email, Facebook, ok...and Pinterest, then do my billing for my home visit.
9:30 Take a shower. Think about drying my hair, then throw it up in a bun.
10:00 Tate gets home and we recap our days and watch The Sopranos on Netflix and I fall asleep.
What are your tips for making "getting out the door" easier in the mornings?


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recipe reviews for:
"Toss hot pasta with chopped walnuts sauteed with garlic and a handful of crumbled blue cheese for a rich and pungent dish with a very interesting crunch."
Cooking Level: Intermediate
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Ladies black leather look running trainers. Featuring DMXRide technology for lightweight cushioning, a contrasting black and pink design and a padded inner for a more comfortable fit. Read more ...


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Ms. Toni Smith-Whiteeagle
Family Medicine, Rushing Family Practice
- 5005 Live Oak St
Greenville, TX 75402 - 1 Office Location
- (903) 455-3500
Ms. Smith-Whiteeagle works in Greenville, TX and specializes in Family Medicine. Ms. Smith-Whiteeagle is affiliated with Hunt Regional Medical Center. Ms. Smith-Whiteeagle speaks English and Spanish.
Gender: Not Available
Years in Practice: Not Available
Languages Spoken: English, Spanish
Medical School: Not Available
Graduation Date: Not Available
Hospital Affiliations: Hunt Regional Medical Center
Specialties: Family Medicine