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In this week's edition, we have a story about adult film actor Colton Ford and his efforts, at 50, to establish a music career. We say we really like the album. And actually, you can make a decision about it yourself. After the jump, watch the video. It's catchy and edgy and leather-daddyish … perfect for a Wednesday morning.
WATCH: Video of Colton Ford's single 'Let Me Live Again'
Porn actor Wilfred Knight kills self after screed on immigration inequality
Just last month, we reported that gay porn actor Arpad Miklos had died of an apparent suicide — the latest in a string of deaths to hit the adult film community. Then last week, we learned that another porn legend had killed himself.
Wilfred Knight, known for his videos for Lucas Entertainment and Colt Studio, took his own life just two weeks after the suicide of his partner. He had just turned 35. What makes Knight's death especially poignant were the reasons behind it.
See, Knight — a French citizen — had moved with his partner to Canada once his U.S. student visa expired, because even though the two were legally married in Canada in 2011, the U.S. government refused to acknowledge it, due to the Defense of Marriage Act. That meant they had to leave for the Great White North, where Knight's partner accepted a job that included same-sex partner benefits.
Knight's husband, however, lost his job about six months ago, and last month, took his own life. Knight found the body. The adult film actor then took his own life, angered by the unfair treatment of gay couples by the federal government.
How do we know all this? Because Knight said so. In a screed published on his blog, Knight railed against American immigration laws, blaming his partner's death on the lack of same-sex rights. It was practically a suicide note.
Because Knight was most famous for his involvement in the porn industry, it's unlikely the story will have much resonance outside the gay press. But isn't this exactly what should be pointed out the U.S. Supreme Court when deciding DOMA's constitutionality? How many couples like this much meet the tragic consequences of homophobic immigration policies?
Dave Wilson robo-calls Houstonians, warns of Annise Parker's 'alternative lifestyle'
Houston mayoral candidate Dave Wilson has stepped up his homophobic attacks against incumbent Mayor Annise Parker with a recent robo-call targeting Houston voters:
"Hello Houstonians, this is Dave Wilson, candidate for mayor. In 2009 I warned voters that Annise Parker would use her position to promote her alternative lifestyle, and she's done that. Her very first executive order was to allow men dressed as women to use the women's restroom. Her appointments have been based on sexual orientation, rather than ability. She appointed George Greanias, head of Metro, who was caught viewing porn sites such as rentaboy.com. Dave Wilson would have fired him on the spot. Join me in taking our city back, vote Dave Wilson, paid for by the Dave Wilson for Mayor."
Wilson's call contains several misleading, or outright false, claims, such as saying that Parker's first executive order was to allow "men dressed as women to use the women's restroom." The first executive order Parker signed after being sworn in (E.O. #1-50), clarified the process for filing sexual harassment claims for city employees. The second (E.O #1-25) dealt with city operations during a natural disaster, the third (E.O. #1-42) with city credit cards, and the fourth (E.O. 1-14) with the city's procurement procedure. The fifth and sixth executive orders signed by Parker (E.O. 1-8 and E.O. 1-20) dealt with discrimination on the basis of sexual orientation or gender identity and expression and the use of hate language by City of Houston employees while on the job. Both order were signed on March 25, 2011, 2 months and 23 days after Parker took office. These are is the ones that chafe Wilson. Under order 1-20 access to public accommodations in city buildings, including restrooms, cannot be denied to any member of the public because they are LGBT. While Wilson fears "men in dresses" discretely handling their business in the stall next to his wife, he seems to miss that it also allows burly, bearded men who happened to have been assigned a female identity at birth to use the men's room. One wonders if he's ever thought about that.
Executive Order 1-20 is about basic courtesy and access to public facilities that most of us take for granted. No one should be put in the position of risking arrest for using a public restroom (which happened shortly after E.O. 1-20 went into effect), and it is humiliating to expect trans Houstonians to have to ask "which bathroom do you expect me to use" every time they're in a city building.
The situation with George Greanias, CEO of Houston's public transit system Metro, is far more complicated than Wilson describes it. To hear the robo-call you'd think Greanias was simply caught looking at pornography, a constitutionally protected right. The issue is that Greanias was caught looking at porn on Metro's internet wi-fi, all be it accidentally. According to the Metro investigation Greanias accessed sites containing gay oriented adult material on 14 separate days between February 9, 2011 to July 1, 2011. The access was from Greanias' personal computer and he believed through his personal internet access. In a letter to Metro employees he explained that "the violation was unintentional. I thought I was using my own computer, but was in fact in Metro's system — but it was a violation all the same. The sites I accessed were of a sexual nature — to say the least, highly inappropriate, and embarrassing."
Typically a violation of this nature by a Metro employee would have resulted in a verbal warning. Because of the high profile nature of Greanias' job he received a much harsher punishment. According to Metro's official statement "Chairman Gilbert Garcia has concluded that, as president and CEO, Mr. Greanias must be held to a higher standard, and decided instead of a warning Mr. Greanias would receive a more stringent punishment of one week suspension, without pay."
None of that matters to Wilson. He "would have fired [Greanias] on the spot," bypassing the review process guaranteed to all Metro employees and likely subjecting the city to a very expensive lawsuit. More than his overt homophobia, it's Wilson's blind ignorance of the procedural facts of running a city that should frighten Houstonians.
Early voting in Houston municipal elections (including mayor) continues through Nov. 3 at all early voting locations. Election day is Nov. 8. Early voting turnout continues to lag; votes cast during the first four days of voting have trailed the 2009 municipal election turnout by 21%.


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My name is Gary and I'm a retired railroader. I have always enjoyed photography and now that I have the time I take lots of photos. My late wife of 40 years and I traveled from our home in Western North Carolina to her home in Ridgecrest Calif. one or more times a year. Our love is going to National Parks as we traveled this great land of ours. We have been blessed by seeing over 30 Parks showing Gods Wonders. WeatherUnderground allows me to visit across this country and around the world from my recliner.
WunderPhotos Upload
Frome the Dunes
Uploaded by: Railheel
Sunday December 23, 2012
Cape Hatteras
Caption: Worlds largest brick lighthouse. Cape Hatteras, landmark of the the Outer Banks
Manufacturer: Canon
Model: Canon EOS 40D
Orientation: top - left
x-Resolution: 72.00
y-Resolution: 72.00
Resolution Unit: Inch
Software: Adobe Photoshop Elements 6.0 Windows
Compression: JPEG compression
Exposure Time: 1/400 sec.
FNumber: f/7.1
Exposure Program: Landscape mode (for landscape photos with the background in focus)
ISO Speed Ratings: 100
Exif Version: Unknown Exif Version
Shutter speed: 8.64 EV (APEX: 19, 1/399 sec.)
Aperture: 5.66 EV (f/7.1)
Exposure Bias: 0.00 EV
MaxApertureValue: 3.00 EV (f/2.8)
Metering Mode: Pattern
Flash: Flash did not fire, compulsory flash mode.
Focal Length: 70.0 mm
SubSecTimeOriginal: 00
SubSecTimeDigitized: 00
Color Space: sRGB
PixelXDimension: 3888
PixelYDimension: 2592
Focal Plane x-Resolution: 4438.36
Focal Plane y-Resolution: 4445.97
Focal Plane Resolution Unit: Inch
Custom Rendered: Normal process
Exposure Mode: Auto exposure
White Balance: Auto white balance
Scene Capture Type: Standard
December 23, 2012 Photo Series
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subset: commoncrawl


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XL at Coachella 2013
Over the weekend, Vampire Weekend, Sigur Rós and The xx all played the Coachella festival in California. They'll all be back again next weekend, but in case you can't make it, here are some sights and sounds from their performances.
Vampire Weekend
Sigur Rós
[all photos via Pitchfork]


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Gear Photo
different angle
I have mine upside down, just change the setting in your camera to flip the image. You can install it the other way but I preferred this way because of how the video looks. You should try both ways to see which you prefer.
View More Details on K-Edge Pro Handlebar Mount for GoPro Hero


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News Section: Community
Sunday Favorites: Mary Jane Wyatt: a True Pioneer
|Mrs. William H. Whitaker (Mary Jane Wyatt) and grandchildren Karl E. and Sophie T. Children of Charles Clarence Whitaker.
Many locals might remember Mary Jane Wyatt Whittaker as a loving grandmother who sewed her grandchildren booties of raccoon hide, stuffed their mattresses with palm fronds and marked her place in her bible with a piece of seaweed. But as a young woman, Mary Jane Wyatt was one fearless woman. So much so, that this pioneer earned the respect of Billy Bowlegs, Chief of the Seminole Nation.
Wyatts father, Colonel William Wyatt, was originally from Indiana, but had ties in Tallahassee where the family first moved after the earliest Florida territories opened for settlement. William delivered mail from St. Augustine to Tallahassee but quickly moved up the political ranks. In 1838, he was one of 55 delegates who represented the Florida territory, which was then made up of 20 counties. William even ran for governor at one point, but was defeated by Robert Raymond Reid of St. Johns County by one vote, according to the Lures of Manatee by Lillie McDuffee.
Despite his success in the capitol, William had dreams of further settling Floridas frontier.
Florida is the hope of the emigrant, and the keystone of the South, he once said in a toast in Tallahassee.
He brought his family to Manatee in 1843, where he was one of the oldest pioneers, a man of 50 with a family of grown children, two of whom were married with children of their own.
Mary Jane remained single and is considered the first young lady to grace the wilderness of Manatee, according to McDuffee.
The familys life in rural Manatee was much different than the one they led in Tallahassee, where William had owned two hotels and consistently rubbed elbows with Florida bigwigs. William was quick to jump on board the cattle train and begin rounding up wild Florida piney wood cows to trade with Cuba. He moved his family temporarily to a ranch eight miles east of the Village of Manatee while Mary Jane recovered from malaria. While the family was not used to the isolation, Mary Jane thrived in the environment. Far from the social stigmas that surrounded young women during that era, she could ride horses with her brothers, herd cattle and shoot rifles. In the words of McDuffee, Mary Jane was as strong and brown-skinned as the Seminoles. She would often bring home a turkey she had killed for dinner. She could also swim and handle a boat better than her brothers could.
Since the deportation of the Seminoles after the Second Seminole War, scarcely 100 men, women and children remained in the Manatee section. Billy Bowlegs, or Assinna Othulkeethloko as he was known to his people, was their leader and chief. He was a nephew of Chief Micanopy and son of another famous Seminole, Se Coffee, thus earning his position through hereditary channels. Under his rule the Seminoles led a peaceful existence and soon unease among pioneers faded. In fact, many of the pioneer families were visited by Bowlegs on a regular basis; he was usually accompanied by his brother-in-law No-Kush Adjo.
Both natives had a creative sense of humor. Their homemade moccasins allowed them to approach a homestead almost silently. Settlers passing the time by cross stitching or reading on their porch would almost fall from their rocking chairs in freight after looking up and seeing the Bowlegs and Adjo watching them in silence. The two Seminoles thought this was hilarious of course and bent over with laughter at the reaction.
But the Wyatt family, completely isolated from the rest of the community, were oblivious to these customs by Billy Bowlegs and his crew. One day, while Mary Jane and her mother were traveling along the river they heard voices from the other side. Thinking it was friends who wished to cross for a friendly visit, Mary Jane readied the canoe, but when she called out to the visitors, she heard no reply. Only then did she see Bowlegs and a few others peeking out from the underbrush. She gasped in surprise, which excited Bowlegs. He instructed her to bring the canoe across. At first she hesitated. McDuffee goes on to explain the rest of the episode.
Her father and brothers were away herding cattle. Mary Jane realized that her mother and herself were at the mercy of these Indians and that their safety depended largely on the amount of courage she would be able to display.
Bowlegs was reportedly impressed by her brazenness. He and his cohorts stayed near the Wyatt home for several days. They were recuperating from an illness and bleeding themselves and using various herbs to heal the wounds. One of the members of the family asked the natives, If there was an uprising, would you kill our family? Bowlegs replied, Yes, but we would kill you easy. Bowlegs meant this as a compliment.
Eventually Mary Jane would go from Manatees first single woman to Manatees first bride when she married William Whittaker, the founder of Sarasota. During the Seminole uprising the couple gave birth to their first son, Furman Whittaker, while at Fort Branch, a fortified encampment where the majority of the community was holed up for nine months.
The Whitakers settled Yellow Bluffs in Sarasota. While the location was breathtakingly scenic, it was also landmark visible from offshore, making it an easy target for the Union Blockade at the end of the Civil War. Mary Jane, who had braved both Seminole Wars, now had to face raids from hungry armed Union soldiers while her husband was off fighting for the Confederacy.
On one occasion soldiers searched the Whittaker place gathering chickens, hogs and citrus. One soldier confiscated seven-year-old Furmans gun. Mary Jane would not have it. She sent Furman to tell a commanding officer and the gun was returned.
On another occasion, an officer demanded Mary Jane fetch matches so he could burn down her house. She brought the matches but said to him, Sir, I want to look into the eyes of a man who can stoop so low as to burn the home of a helpless woman and her family.
The house was saved.
Mary Jane never lost her spunk, and women and men across the region remember her bravery to this day.
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BURLINGTON, Vt. – Matt Di Girolamo (Ambler, Pa.) stopped 40 shots including 18 in the third period and overtime to guide the eighth-ranked University of New Hampshire men's hockey team to Saturday night's 2-2 tie with the University of Vermont in the Hockey East action at Gutterson Fieldhouse.
UNH increases its lead in Hockey East to two points by virtue of a BC loss and moves to 18-7-5, 16-4-3 in Hockey East. Vermont is now 7-17-6, 5-13-5 HE.
In a scoreless overtime both teams had chances none greater than Vermont's opportunity in the final 25 seconds that was blocked by a sprawling out Mike Borisenok (Watervliet, N.Y.). The Catamounts held a 5-3 shot edge in overtime.
Vermont broke the scoreless deadlock as Tobias Nilsson-Roos scored a short-handed goal at 5:58 of the second period with assists from Josh Burrows. Nilsson-Roos won a battle for a loose puck at center ice that opened the one-on-none opportunity. New Hampshire responded just 30 seconds later as Mike Beck (Long Beach, Calif.) scored on the rebound of a Stevie Moses (Leominster, Mass.) shot at 6:28 of the frame. Kevin Goumas (Lake Worth, Fla.) also assisted on the power play goal. The play was setup by a fast transition pass from Goumas to Moses. UNH took its first lead of the night as Phil DeSimone (East Amherst, N.Y.) scored on the rebound of a Blake Kessel (Verona, Wis.) one-timer from the right point that deflected to an open DeSimone on the left slot. Paul Thompson (Derry, N.H.) was credited with an assist on the goal, which gave the 'Cats a 2-1 edge heading into the second intermission. UVM held a 13-12 shot advantage in a three-goal second period.
The Catamounts netted the equalizer at 9:05 of the third as Matt White scored from the center slot with assists from Connor Brickley and H.T. Lenz. The score remained tied thanks to a pair of sprawling saves by Di Girolamo in the 11th minute. Vermont outshot UNH 14-9 in the period.
In a scoreless first period, both teams had chances. Vermont's best chances came during its three power play opportunities including close to a minute of 5-on-3 play. New Hampshire challenged UVM netminder Rob Madore with a series of shots in the 11th minute, but neither team cracked the scoreboard. Vermont held a slim 10-8 shot edge in the stanza.
Di Girolamo turned away double-figures in all three periods to move to 18-7-5, while Madore stopped 30 shots and is now 7-17-6.
Vermont held a 42-32 shot advantage for the game, but was 0-6 on the power play. UNH went 1-3 in its extra-skater opportunities.
New Hampshire returns to action for a home-and-home series with Northeastern University (Feb. 25-26). The teams play in Durham on Friday (7 p.m.) at the Whittemore Center. Tickets to the Northeastern game are available online at www.UNHWildcats.com.
#8 Men's Hockey Skates to 2-2 Draw With Vermont
|New Hampshire (18-7-5, 16-4-3 HEA)
|Vermont (7-17-6, 5-13-5 HEA)
BURLINGTON, Vt. – Matt Di Girolamo (Ambler, Pa.) stopped 40 shots including 18 in the third period and overtime to guide the eighth-ranked University of New Hampshire men's hockey team to Saturday night's 2-2 tie with the University of Vermont in the Hockey East action at Gutterson Fieldhouse.


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Mason Dixon Council
Boy Scouts of America
First Christian Church
Hagerstown, Maryland
Hagerstown, Maryland
Den Meetings held at the House A Cross the Way
Tuesday, September 16 will be our Recruitment night at Potomac Heights Elementary School.
6:00 PM in the School Cafeteria.
Those interested in Scouting, come on out. Those already in the Pack, come on out too and bring a friend. There will be lots of fun and games and even a climbing wall. Hope to see you there!
Hello Everyone,
Friday (Oct 10) is our Pack camp-out in Leitersburg. This is a family event sponsored by the local Council.
Also. Saturday (Oct 11) is the Cub Scout Extravaganza. For those that are new, this is your one and only chance for your Scout to do archery and BB gun shooting until next summer. The boys can earn belt loop awards that they can wear on their uniform belt.
Brad Neisser
What to bring
Friday night Camp-out:
Saturday Extravaganza Event:
Check-in begins at 8am on Saturday at Camp Sinquipie with activities beginning with an opening ceremony at 9:30 am. Webelos Woods wraps up Sunday after Chapel Services at 10:00am. Webelos Woods is a Rain or Shine Event.
Meet at the church house at 9AM on Saturday, Nov 8. We will give you a map and a packet of flyers to distribute through the neighborhood.
Food Pick-up, Nov 15, 2014
Meet at the church house at 10AM on Saturday, Nov 15. We will group up to go through the neighborhood to collect bags of food.


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Stir-Fried Pork in Garlic Sauce
- 2 tablespoons peanut or vegetable oil
- 2 tablespoons chopped garlic
- 2 small dried chiles
- 1 1/2 pounds boneless pork, preferably from the shoulder (Boston butt or picnic), cut into thin shreds and thoroughly dried
- 1 bunch of scallions, trimmed and cut into 2-inch lengths, white and green parts separated
- 3 tablespoons soy sauce
1. Put the oil in a large nonstick skillet (12-inch is best) and turn the heat to high; a minute later, add the garlic and chiles and cook, stirring occasionally, until the garlic begins to color, just a minute or so.
2. Add the pork and stir once or twice. Cook until it begins to brown, about a minute. Add the white parts of the scallions and stir; cook for another minute, stirring occasionally.
3. Add the green parts of the scallions and stir; cook for 30 seconds, then turn off the heat and add the soy sauce. Serve immediately.
Stir-Fried Pork in Garlic Sauce, Thai Style.
In step 3, add 1 tablespoon sugar with the green parts of the scallions and substitute nam pla for the soy sauce.
Source Information
The Best Recipes in the World
Mark Bittman
Epicurious.com © Condé Nast Digital, Inc. All rights reserved.


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Hyland's, Leg Cramps, 100 Tablets
By Hyland's136 Reviews
Shipping Weight:?0.12 lbs (0.05 kg)
Shipping Weight
The Shipping Weight includes the product, protective packaging material and the actual shipping box. In addition, the Shipping Weight may be adjusted for the Dimensional Weight (e.g. length, width & height) of a package. It is important to note that certain types of products (e.g. glass containers, liquids, fragile, refrigerated or ice packed) will often require protective packaging material. As such, these products will reflect a higher Shipping Weight compared to the unprotected product.
- Product Code: HYL-29562
- UPC Code: 354973295629
- Package Quantity: 100 Tablets
- Dimensions: 1.1 x 1.6 x 3.4 in, 0.1 lbs (0.05 kg)
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Product Overview
- Homeopathic Since 1903
- 100% Natural
- Stop the Pain!
- Relax Calf & Foot Cramps
- Quick-Dissolving Tablets
Temporarily relieves the symptoms of cramps and pains in lower back and legs.
Hyland's Leg Cramps Or Hyland's Restful Legs?
Use Hyland's Leg Cramps if you have:
- Leg cramp pain
- Pain in limbs & joints
- Cramps and pain in lower back
- Cramps in calves & feet
- Pain and cramps in legs & calves
- Joint stiffness
Use Hyland's Restful Legs if you have:
- Agitated legs, especially when lying down
- Creepy, crawly itch in legs
- Leg agitation improved by activity
- Itching, tingling urge to move legs
- Twitching and jerking of legs
- Constant urge to move legs
Suggested Use
Adults and children ages 12 and over: Dissolve 2-3 tablets under tongue every 4 hours or as needed.
As with any drug, ask a doctor before use if:
- You are pregnant or nursing a baby
- Sensitive to quinine
- Under 12 years of age
Keep this and all medications out of the reach of children. Do not use if imprinted tamper band is broken or missing. In case of accidental overdose, contact a poison control center immediately. If symptoms persist for more than 7 days or worsen, discontinue use and seek the advice of a licensed healthcare professional.
|Drug Facts
|Active Ingredients
|Cinchona Off. 3X, HPUS
|Pains in limbs & joints
|Aconitum Nap. 6X HPUS
|Pains in joints, legs
|Gnaphalium Poly. 3X HPUS
|Cramps in calves & feet
|Ledum Pal. 6X HPUS
|Pain and cramps in legs
|Magnesia Phos. 6X HPUS
|Cramps in calves
|Rhus Tox. 6X HPUS
|Pain and stiffness
|Viscum Alb. 3X HPUS
|Pain in joints
|Inactive Ingredients: Lactose N.F.
iHerb Customer Reviews
Finally an effective treatment for leg cramps. Nothing else has worked as well. CO-Q 10 helped, but this STOPPED THEM COMPLETELY. PLEASE keep making and selling this product. Tell everyone. I have told several friends about this too.
This homeopathic remedy from ikronozhny spasms and spasms. During an attack helps well. I accept also for prevention by a course month. Tablets small. By-effects I do not observe. The homeopathy should be accepted in 15 minutes prior to food or in an hour after food. Это гомеопатическое средство от икроножных судорог и спазмов. Во время приступа помогает хорошо. Принимаю также для профилактики курсом месяц. Таблетки маленькие. Побочных явлений не наблюдаю. Гомеопатию следует принимать за 15 минут до еды или через час после еды.


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Sister Mary Joseph
Cunningham Library
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Fax: 732.987.2017
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|« Back to Article
O, so many Christmas trees
Holiday spirit is abundant in Mondin home
Cheryl Van Tuyl Jividen, For the Express-News : December 19, 2013 : Updated: December 21, 2013 1:11pm
Photo By Photos by Darren Abate / For the Express-NewsJack Mondin decorates throughout his Elm Creek house. He begins putting up his 11 trees in October to be ready for Thanksgiving entertaining.
Photo By For the Express-NewsA forest of miniature crystal trees in the Mondin home.
Photo By For the Express-NewsJack Mondin's home sparkles with Christmas decorations.
Photo By For the Express-NewsChristmas is the most wonderful time of the year for Jack Mondin.
Mondin drapes garland over an Asian screen in the master bed-room.
One of the trees is decked out in Christopher Radko glass ornaments.
A Boehm porcelain Nativity set was bequeathed from a friend.
Photo By Darren Abate/For the Express-NewsAngels have a tree of their own in Mondin's home.
Photo By Darren Abate/For the Express-NewsChristmas engulfs a jade dragon in Mondin's home.
Photo By Darren Abate/For the Express-NewsA lavish taxidermy white peacock adorns one tree.
More Information
House rules
Jack Mondin shares ideas for creating a special holiday look.
Showtime: When a collection grows too large to display all at once, rotate the pieces or use them in multiple locations, such as tabletops and the bar.
Packing instructions: Make decorating easier by packing everything for one room together. "It's all stowed away into tubs for each room, right down to the extension cord, remote control for the lights and the ornaments," he said.
Handle with care: Using a tip he learned from an antiques dealer, Mondin wraps fragile Radko ornaments individually in disposable absorbent bed liners he purchases from a medical supply store. He cuts the sheets into quarters to create ornament wrappers.
Fluff and stuff: Mondin has kept bows looking fresh for more than 20 years by stuffing individual loops with wadded paper towels before packing. He slips wreaths into plastic bags and hangs them in the garage.
SAN ANTONIO — The Christmas spirit sparkles brightly for Jack Mondin, a real estate agent who puts a bit of his favorite holiday in every room of his Elm Creek home.
Putting up 11 trees and fully decking the halls in time for Thanksgiving entertaining requires Mondin to start setting up in October. Guests who enter the double doors for parties throughout the holidays find Christmas is tucked into every corner, top to bottom. A slender 91/2-foot-tall tree in the foyer displays about 30 delicate angels and sets the tone for his holiday home.
Snowflake ornaments, saved from holiday packages, serve as filler between the branches, which are draped with sparkling silver mesh.
A peacock tree in the living room is the tree most guests consider the showstopper. Resplendent with rhinestone bracelets and antique baubles — including costume jewelry and pearls that belonged to his mother and grandmother — the tree is topped with a jewel-encrusted scepter.
The centerpiece is a taxidermy white peacock with a rhinestone choker, her tail plumage sweeping 4 feet down the tree.
Between the branches are white peacock ornaments, tiaras nestled in white hydrangeas and glittering twigs.
In the same room, another tree is filled with Christopher Radko ornaments. It is the one that takes the longest to assemble as each of the 400 ornaments must be unwrapped and wired onto a branch.
Mondin's Radko ornament collection began in 1987 with only Santa face ornaments, but over the years has grown to encompass all Christmas themes. Several of the pieces are signed by the artist. He added as many as a dozen each year, receiving many as gifts, picking them up on travels and purchasing at local boutiques. The collection includes limited editions, an Elegant Evergreens ornament featured in Radko's book and Mondin's favorite, a three-piece hot air balloon.
Because Mondin wanted a tree visible from the street, he designed one for the master suite, incorporating plum poinsettias, hearts and feathers to complement the color palette of the room. Lighted swags of evergreens and large grape clusters accent a vintage Oriental screen that serves as a headboard.
One tree, deemed the "Fun" tree, stays up year-round. Mondin changes out the décor to celebrate Mardi Gras, Fiesta, Fourth of July and Halloween.
One of the treasures of his holiday collections is a Boehm porcelain Nativity set, collected in the 1950s and '60s. The serene white scene was bequeathed to Mondin by a friend.
An avid entertainer, Mondin's wonderland is busy through the holidays. He's hosted seasonal parties for his garden club, a wedding reception and a get-together for members of his church. Family and friends will gather to celebrate Christmas.
Mondin is thankful for the season. "While there is all this (décor) it's about the birth of the Christ child. I hope guests have a feeling of 'tis the of season, peace, hope and togetherness."
Cheryl Van Tuyl Jividen is a San Antonio freelance writer.
Cheryl Van Tuyl Jividen is a San Antonio freelance writer.
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A clay-resin composition of a cured epoxy resin and a layered clay with the cured epoxy resin in the galleries of the clay by intercalation or exfoliation. The preferred epoxy resins are flexible and usually elastic because of the epoxy resin and/or curing agent which is used. The result is a composite which can have superior tensile strength and/or solvent resistance as compared to the cured epoxy resin without the clay or with the clay but without the intercalation or exfoliation. The flexible composites are particularly useful for seals and other thin layer applications.
1. In a method for providing a flexible sealant in an apparatus the improvement which comprises: providing as the sealant a resin-clay composite composition which comprises:
(a) a cured epoxy resin; and
(b) a smectite clay having layers with the cured epoxy resin separating the layers, the galleries containing the cured epoxy resin and organic onium cations wherein the onium cations are protonated unsubstituted alkyl ammonium cations containing 3 to 22 carbon atoms in the alkyl ammonium cations, wherein the composition contains between about 5 and 50 weight percent of the clay, and wherein the average separation between the clay layers corresponds to a gallery height of 7 Å to 300 Å.
2. The composition of claim 1 wherein an epoxy resin precursor is cured with a diamine as the curing agent to provide the cured epoxy resin.
3. The method claim 1 wherein a diglycidyl ether of bisphenol A monomer is cured with a polyoxypropylene diamine as the curing agent to provide the cured epoxy resin.
4. The method of claim 1 wherein a Novolac epoxy prepolymer is cured with a polyoxypropylene diamine to provide the cured epoxy resin.
5. The method of claim 1 wherein a diglycidyl ether of bisphenol F monomer is cured with a polyoxypropylene diamine to provide the cured epoxy resin.
6. The method of claim 1 wherein a diglycidyl polyalkylene ether epoxy prepolymer is cured with a polyoxypropylene diamine to provide the cured epoxy resin.
7. The method of claim 1 wherein an epoxy monomer or prepolymer is cured with a polyoxypropylene diamine having a formula: ##STR13## wherein x is between about 4 and 40 as the curing agent to provide the cured epoxy resin.
8. The method of claim 1 wherein the epoxy resin is a diglycidyl ether of bisphenol A monomer cured with a polyoxypropylene diamine having a formula: ##STR14## wherein x is between about 4 and 40 as the curing agent to provide the cured epoxy resin.
9. The method of claim 1 wherein the epoxy resin is derived from a diglycidyl ether of bisphenol F monomer cured with a polyoxypropylene diamine having a formula: ##STR15## wherein x is between about 4 and 40.
10. The method of claim 1 wherein the epoxy resin is derived from a Novolac polymer cured with a polyoxypropylene diamine having a formula: ##STR16## wherein x is between about 4 and 40.
11. The method of claim 1 wherein the epoxy resin is a diglycidyl polyalkylene ether epoxy resin cured with a polyoxypropylene diamine having a formula: ##STR17## wherein x is between about 4 and 40.
12. The method of claim 1 wherein the clay is selected from the group consisting of smectite clay minerals, montmorillonite, hectorite, saponite, nontronite or beidellite, and synthetic derivatives, fluorohectorite, laponite, taeniolite or tetrasilicic mica.
13. The method of claim 1 wherein the clay is a synthetic mixed layer clay mica-montmorillonite.
The invention described in this application was sponsored by the National Science Foundation Contract CHE-92241023. The U.S. Government has certain rights to this invention.
This is a divisional of copending application Ser. No. 08/498,350 filed on Jul. 5, 1995.
(1) Field of the Invention
The present invention relates to novel flexible clay-resin composite compositions containing a cured epoxy resin and to a method for their preparation. In particular, the present invention relates to the cured epoxy resin and clay composite containing the cured epoxy resin in the galleries of the clay, such that the clay is intercalated or exfoliated. The composites are flexible and usually elastic.
(2) Description of Related Art
Layered or smectite clays are natural or synthetic layered oxides such as bentonite, montmorillonite, hectorite, fluorohectorite, saponite, beidellite, nontronite, and related analogs. The layers are made up of a central octahedral sheet, usually occupied by aluminum or magnesium, sandwiched between two sheets of tetrahedral silicon sites. These negatively charged layers are approximately 10 Å thick, and are separated by hydrated cations such as alkali or alkaline earth metal ions.
Hybrid organic-inorganic composites can exhibit mechanical properties superior to those of their separate components. To optimize the performance properties of these materials, it is usually desirable to disperse the inorganic components in the organic matrix on a nanometer length scale (Giannelis, E. P. JOM 44 28 (1992); Gleiter, H. Adv. Mater. 4 474 (1992); and Novak, B. M., Adv. Mater. 5 422 (1993)). Smectite clays and other layered inorganic materials that can be broken down into nanoscale building blocks (Pinnavaia, T. J., Science 220 365 (1983)) are useful for the preparation of organic-inorganic nanocomposites.
In general, the polymer-clay composites can be divided into three categories: conventional composites, intercalated nanocomposites, and exfoliated nanocomposites. In a conventional composite, the clay tactoids exist in their original state of aggregated layers with no intercalation of the polymer matrix between the layers of the clay. In an intercalated nanocomposite the insertion of polymer into the clay layer structure occurs in a crystallographically regular fashion, regardless of the clay-to-polymer ratio. An intercalated nanocomposite normally is interlayered by only a few molecular layers of polymer and the properties of the composite typically resemble those of the ceramic host (Kato, C., et al., Clays Clay Miner, 27 129 (1979); Sugahara, Y., et al., J. Ceram. Soc. Jpn. 100 413 (1992); Vaia, R. A., et al., Chem. Mater. 5 1694 (1993); and Messersmith, P. B., et al., Chem. Mater. 5 1064 (1993)). In contrast, in an exfoliated nanocomposite, the individual 10-Å-thick clay layers are separated in a continuous polymer matrix by average distances that depend on loading. Usually, the clay content of an exfoliated clay composite is much lower than that of an intercalated nanocomposite. Consequently, an exfoliated nanocomposite has a monolithic structure with properties related primarily to those of the starting polymer.
The exfoliation of smectite clays provides 10- Å-thick silicate layers with high in-plane bond strength and aspect ratios comparable to those found for fiber-reinforced polymer composites. Exfoliated clay nanocomposites formed between organocation exchanged montmorillonites and thermoplastic nylon-6 have recently been described (Fukushima, Y., et al., J. Inclusion Phenom. 5 473 (1987); Fukushima, Y., et al., Clay Miner 23 27 (1988); and Usuki, A., et al., J. Mater. Res. 8 1174 (1993); and WO 93/04117 and 93/04118 describing thermoplastic polymers). Clay exfoliation in the nylon-6 matrix gave rise to greatly improved mechanical, thermal, and rheological properties, making possible new materials applications of this polymer (Usuki, A., et al., J. Mater. Res. 8 1179 (1993); and Kojima, Y., et al., J. Mater. Res. 8 1185 (1993)).
The clays used for nanocomposite formation are ion-exchanged forms of smectite clays in which the Na+ and/or Ca2+ gallery cations of the pristine mineral have been replaced by organic onium ions. The onium ions may be protonated primary amines (RNH3 +), secondary amines (R2 NH2 +), or they may be tertiary amines (R3 NH+) or quaternary ammonium ions (R4 N)+. The alkyl groups attached to nitrogen may be the same or different, and the alkyl groups may be replaced in part by a benzyl group (--CH2 --C6 H5), a phenyl group (--C6 H5) or by benzyl and phenyl groups. The alkyl groups may also be functionalized, as protonated α, ω-amino acid with the general formula (H3 N--(CH2)--COOH)+. Phosphonium ions may be used in place of ammonium ions for the formation of clay polymer nanocomposites.
In some polymer-clay composite systems it is possible to continuously vary the amount of intercalated polymer between the clay layers from one or a few monolayers of polymer chains to multiple layers of polymer. In such cases it is possible to prepare composites with properties that vary from those typical of an "intercalated clay" nanocomposite to those typical of an "exfoliated clay" nanocomposite. The intercalated and exfoliated states of the clay may be distinguished based on the ratio of the observed gallery height (ho) to the gallery height expected for a lipid-like bilayer of onium ions in the gallery (he) The value of he can be easily computer based on the van der Waals length of the onium ion (l). Thus, he =2l. The observed gallery height (ho) can be determined by subtracting the thickness of a smectite clay (9.6 Å) from the basal spacing obtained by X-ray diffraction measurement (d001). As illustrated in FIGS. 1A to 1D, if ho ≦he, then the spacing between the clay layers allows for van der Waals interactions between the onium ions on adjacent layers. These van der Waals interactions between onium ion chains link adjacent clay layers. Under these conditions, the intercalated polymer (polym.) resides in the gallery space between the associated onium ions. The polymer-clay composites in these cases can be regarded as an intercalated clay composite. However, if ho >he, as in FIG. 1E, then the adjacent layers of the clay are no longer linked through the onium ion interactions. However, the onium ion chains can reorient in the gallery to accommodate interaction of the polymer. Thus, as illustrated in the example in FIGS. 1A to 1E as the amount of intercalated polymer is increased the initial lateral bilayer structure of the organoclay in FIG. 1A has re-oriented to a paraffin structure in FIG. 1B and to a perpendicular bilayer in FIG. 1C, a lipid-like structure in FIG. 1D, and finally to an exfoliated structure in FIG. 1E. Consequently, the resulting state of the clay is best described as being exfoliated and the composite is an exfoliated polymer-clay composite. FIG. 1 illustrates these differences between intercalated and exfoliated polymer-clay composites in a system where the amount of interlayer polymer is varied continuously from one to multiple layers of polymer chains.
According to the teachings of Lagaly, the onium ions in an organo clay can adopt various orientations depending on the clay layer charge density and the chain length of the onium ions. The observed orientation of onium ions in smectite clays include lateral monolayers, lateral bilayers, pseudotrimolecular layers, paraffin-like layers and lipid-like bilayers.
U.S. Pat. No. 4,889,885 to Usuki et al shows thermoplastic vinyl polymer composites containing clay.
U.S. Pat. Nos. 3,432,370 to Bash et al; 3,511,725 to Stevens et al, 3,847,726 to Becker et al and Canadian Patent No. 1,004,859 to Nelson show various compositions incorporating flexible epoxy resins. There are numerous uses for these polymer matrices.
The problem has been to provide intercalated or exfoliated clay cured thermoset epoxy-resin composites. In general, it is difficult to obtain epoxy resins which are between the layers of the clay on a nanometer scale.
Epoxy resins tend to swell in the presence of organic solvents. This problem is not corrected by merely mixing a clay into the epoxy resin.
It is therefore an object of the present invention to provide a cured resin composition of a clay intercalated or exfoliated with a cured thermoset epoxy resin. Further, it is an object of the present invention to provide preferred flexible and elastic cured thermoset epoxy resin-clay compositions with unique strength and solvent resistance properties. Further, it is an object of the present invention to provide composites which are relatively easy and economical to prepare. These and other objects will become increasingly apparent by reference to the following description and the drawings.
FIGS. 1A to 1D illustrate intercalated claypolymer nanocomposites in which the gallery onium ion on adjacent clay layers link the layers through van der Waals interaction. The polymer in these examples occupy space between the associated onium ions. FIG. 1E illustrates an exfoliated clay-polymer nanocomposite in which the onium ions on adjacent layers are separated by the guest polymer chains and the clay layers are no longer linked through van der Waals interactions between the onium ions.
FIGS. 2A and 2B are graphs showing X-ray diffraction patterns of CH3 (CH2)7 NH3 + -montmorillonite (FIG. 2A) and CH3 (CH2)17 NH3 + -montmorillonite (FIG. 2B) in stoichiometric mixtures of epoxide resin and polyetheramine curing agent after reaction under the following conditions: (a) 75� C., 10 min; (b) 75� C., 1 h; (c) 75� C., 3 h; (d) 75� C., 3 h and 125� C., 1 h; (e) 75� C., 3 h and 125� C., 3 h. The clay loading in each case was 10 wt %. Samples a, b and c in both figures contain intercalated clay particles as indicated by the d001 diffraction lines, whereas samples d and e in both figures contain largely exfoliated clay layers.
FIG. 3 is a TEM image of an exfoliated epoxy-clay composite containing 20 wt % CH3 (CH2)17 NH3 + -montmorillonite showing the epoxy resin in the layers of the clay.
FIGS. 4A and 4B are graphs showing dependence of tensile strength (FIG. 4A) and modulus (FIG. 4B) of epoxy-organo clay composites on the chain length of the clay-intercalated alkylammonium ions. The clay loading in each case was 10 wt %. The dashed lines indicate the tensile strength and modulus of the polymer in the absence of any clay.
FIGS. 5A and 5B are graphs showing dependence of tensile strength (FIG. 5A) and modulus (FIG. 5B) on clay loading for exfoliated epoxy-CH3 (CH2)17 NH3 + -montmorillonite nanocomposites.
FIGS. 6A and 6B are models for the fracture of a glassy (FIG. 6A) and a rubbery polymer-clay (FIG. 6B) exfoliated nanocomposite with increasing strains.
FIG. 7 is a graph showing the effect of alkylammonium ion chain length on the mechanical properties of epoxy-montmorillonite composites (2 wt %) using metaphenylene diamine as a curing agent to form a rigid polymer-clay composite.
The present invention relates to a flexible resin-clay composite composition which comprises: a flexible cured epoxy resin; and organo-clay particles having layers and galleries between the layers, the galleries containing the cured epoxy resin and organic onium cations, wherein the clay particles have a particle size about 0.02 and 2 μm, wherein the ratio by weight of epoxy resin to clay is between about approximately 200:1 and approximately 1:1, wherein the cured epoxy polymer composition has a glass transition temperature (Tg) between about -100� C. and 100� C., and wherein the average separation between the clay layers corresponds to a gallery height of 5 Å to 300 Å.
Further, the present invention relates to a method for the preparation of a flexible resin-clay composite composition which comprises: mixing particles of an organo-clay having layers with galleries between the layers which has been ion exchanged with organic onium cations with a flexible liquid epoxy resin and a curing agent which produces a cured epoxy resin; and curing the liquid epoxy resin with the curing agent to produce the polymer-clay composite composition, wherein the galleries contain the cured epoxy resin, wherein the cured epoxy polymer composition has a glass transition temperature (Tg) between about -100� C. and 100� C., and wherein the average separation between the clay layers corresponds to a gallery height of 5 Å to 300 Å.
Finally, the present invention relates to a method for providing a flexible sealant in an apparatus operated at a particular temperature (To) the improvement which comprises: providing as the sealant a resin-clay composite composition which comprises: a flexible cured epoxy resin; and clay particles having layers and galleries between the layers, the galleries containing the cured epoxy resin and organic onium cations, wherein the clay particles have a particle size about 0.02 and 2 μm, wherein the ratio by weight of epoxy resin to clay is between about approximately 200:1 and approximately 1:1, wherein the cured epoxy polymer composition has a glass transition temperature (Tg) between about -100� C. and 100� C., and wherein the average separation between the clay layers corresponds to a gallery height of 5 Å to 300 Å.
The clay particles are preferably smectite clays with galleries of about 3 to 30 Å in height before introduction of the epoxy resin. Suitable smectite mineral clays are montmorillonite, hectorite, saponite, nontronite, or beidellite. Suitable synthetic derivatives of smectite clays are fluorohectorite, laponite, taeniolite, tetrasilicic mica or a mixed layer clay mica-montmorillonite. The layers are preferably about 10 Å thick as discussed previously for smectite clays. The particles have a particle size between about 200 and 20,000 Å and a ratio of length to width in a range between about 2,000 to 1 and 20 to 1.
The clay is ion exchanged using ammonium salt, particularly an alkylammonium halide such as a chloride, so that the cation is in the gallery of the clay. The alkyl group preferably contains between 3 and 22 carbon atoms, which can be substituted with various non-carbon groups such as halogen (I, Cl, Br, F), nitrogen, oxygen, sulfur hydroxyl and the like and can be straight chain or branched. Ion exchange is performed as described in Pinnavaia, T. J., ACS Sym. Ser. 499 146 (1992).
The epoxy resins are well known to those skilled in the art and are described in Kirk-Othmer, John Wiley & Sons, 9 267-290 (1980). They are available from a variety of commercial sources including Shell Co., Ciba, and The Dow Chemical.
Bisphenol A type EPON-828 (Shell Co.), is an epoxy resin precursor with the bisphenol A structure and a molecular weight of 380, and has the formula: ##STR1## wherein n=0 (88%); n=1 (10%); n=2 (2%).
Bisphenol-A type, DER 331 (Dow Chemical Co., Midland, Mich.), is an epoxy polymer precursor and is an analog to Epon-828 having the formula: ##STR2##
Bisphenol-F type, DER 354 (Dow Chemical Co.) is an epoxy polymer precursor having the formula: ##STR3##
Novolac type, DER 43, DER 438 and DER 439 (Dow Chemical Co.) are epoxy polymer precursors having the formula: ##STR4## wherein n is between about 0.2 and 1.8.
Epoxy polymer, DER 732 (Dow Chemical Co.) is an epoxy resin precursor of the general formula: ##STR5## There are numerous other types of epoxy polymer precursors which are suitable and which are well known to those skilled in the art.
Amine curing agents are used to cure the epoxy resin precursors into an epoxy resin. The most preferred curing agents are polyoxypropylene di- or triamines which are sold as JEFFAMINES, Huntsman Chemical Company, Austin, Tex. Most preferred are the polyoxypropylene diamines (D-series) of the formula: ##STR6## wherein x is between about 4 and 40.
The preferred diamines when used as curing agents for the epoxy resin precursors produce a glass transition temperature of less than ambient temperatures (25� C.) and preferably less than 0� C. As a result, when cured to a pristine epoxy resin without any filler, the resins are flexible when x is between about 4 and 40 in the polyoxypropylene diamine, the cured epoxy resin is also elastic.
The T series JEFFAMINES can be used. These are ##STR7## wherein x+y+z between about 4 and 120.
Various other epoxy resin curing agents, such as anhydrides and amides, can be used, so long as they do not interfere with the curing action of the primary ammonium cations in the clay. The amide curing agents are for instance ##STR8## where X is between about 5 and 15.
The organic onium cations in the clay act to catalyze the epoxy resin in situ in the galleries. As a result the clay is intercalated or exfoliated with the cured epoxy resin. The ion-exchanged organic onium cation intercalated clay is mixed with the epoxy resin precursor preferably using shear mixing. Usually the mixture is degassed with a vacuum. The mixture is cured at between about 50� C. to 150� C. depending upon the epoxy resin precursor (monomer or prepolymer) and the curing agent.
When the resin-clay composites of the present invention are flexible, they are very strong in comparison to the pristine epoxy resin. The flexible composites of the present invention are particularly useful as sealants and flexible adhesives. They are strong, exhibiting a relatively high tensile strength. The compositions of the present invention can be used for: surface coatings, particularly decorative coatings; protective coatings; casting and encapsulation; construction, particularly seamless floors, sand-filled flooring, decorative aggregate, polymer concrete, trowel coatings, and wood consolidation; reinforced composites, particularly for propeller and impeller blades, boats, filament-wound tanks and piping; and adhesives. Other uses where a relatively thin flexible layer is needed are for instance in the dampening of interfaces between vibrating surfaces.
The following are illustrative Examples 3 to 28, 30 and 31 showing the use of various clay epoxy polymer precursors, amine and amide curing agents. Examples 1 and 2 are Comparative Examples. Example 29 shows absorption data. Example 32 shows a rigid epoxy-clay polymer composite prepared from meta phenylene diamine as a curing agent.
A pristine epoxy polymer with a sub-ambient glass transition temperature (-40� C.) was prepared by crosslinking Epon-828 epoxy resin (Shell) and JEFFAMINE D2000 (Huntsman Chemicals, Austin, Tex.) polyetheramine curing agent. Equivalent amounts of the epoxide resin (27.5 wt %) and the polyetheramine (72.5 wt %) were mixed at 75� C. for 30 minutes. The epoxide-amine complex was then outgassed in vacuum for 10 minutes and transferred into an aluminum mold for curing at 75� C. for 3 hours and then at 125� C. for an additional 3 hours. The pristine epoxy matrix was named Example 1 (E1). E1 has tensile strength of 0.6 MPa and tensile modulus 2.8 MPa. ##STR9##
A conventional clay-epoxy composite (E2) was prepared from naturally occurring Na-montmorillonite from Wyoming. The Na-montmorillonite was purified and the portion of 40˜50 μm was used to prepare the composite. Equivalent amounts of the epoxide resin (27.5 wt %) and the polyetheramine (72.5 wt %) were mixed at 75� C./ for 30 minutes. 10 wt % of the clay was added to the epoxide-amine mixture and stirred for another 30 minutes. The clay-epoxide-amine complex was then outgassed in vacuum for 10 minutes and transferred into an aluminum mold for curing at 75� C. for 3 hours and then at 125� C./ for an additional 3 hours. E2 is a phase-segregated composite. Tensile strength and modulus of the composite are 1.2 and 3.5 MPa, respectively. The phase segregation of the clay in the polymer matrix indicates little interaction between the inorganic clay and the polymer matrix. XRD analysis shows that the clay retains its basal spacing after composite formation.
An improvement of affinity between resin matrix and clay is essential to prepare useful polymer-clay composite. Akylammonium exchanged clays (organoclays) enhance phase affinity and nanocomposite formation. Examples 3-7 demonstrate the relationship between the chain length of the onium exchange ion and the extent of epoxy resin intercalation (XRD) and the tensile properties of the resin-clay composite. The organoclays were obtained by ion exchange reaction of Na-montmorillonite. The cation exchange reaction was carried out by mixing 500 ml of 0.05M alkylammonium chloride ethanol:water (1:1) solution and 2.0 g of clay at 70�˜75� C. for 24 hours. The exchanged clays were washed with ethanol:water (1:1) several times until no chloride was detected with 1.0M AgNO3 solution and then air dried. Finally, the clays were ground and the particle size fraction of 40˜50 μm was collected. The hydrophobicity of clay gallery surface of an organoclay is controlled by the chain length of the gallery alkylammonium cations. The extent of epoxy resin intercalation into the clay is dependent on the hydrophobicity of the interlayer gallery regions. Alkylammonium cations with different alkyl chain length (carbon number 4, 8, 10, 12, 16 and 18) were used to prepare organo montmorillonites. Epoxy resin was Epon-828 from Shell Co. Curing agent is JEFFAMINE D2000. Equivalent amounts of the epoxy resin (27.5 wt %) and the polyetheramine (72.5 wt %) were mixed at 75� C. for 30 minutes. 10 wt % of the organoclays was added to the epoxide-amine mixture and stirred for another 30 minutes. The clay-epoxide-amine complex was then outgassed in vacuum for 10 minutes and transferred into an aluminum mold for curing at 75� C. for 3 hours and then at 125� C. for an additional 3 hours. The composite samples were labeled Examples E3, E4, E5, E6, E7, and E8, representing alkylammonium chain length, C4, C8, C10, C12, C16, and C18 respectively. X-ray diffraction results for the epoxy resin-clay composites indicate that the clays with alkyl chain length ≧10 (E5, E6 and E7, and E8) the absence of a d001 diffraction. Therefore, C10-C18 chain alkylammonium exchanged montmorillonite clays were exfoliated in the cured epoxy resin matrix. Clay layer separation in sample E5, E6, E7 and E8 was observed from TEM images obtained from ultrathin sections. In comparison, the E3 (C4) and E4 (C8) alkylammonium exchanged montmorillonite clays, exhibited d001 X-ray diffraction in the cured composites. Tensile strengths, moduli and clay properties for examples E1, E2, E3, E4, E5, E6, E7 and E8 are listed in Table 1, indicating the mechanical performance was improved significantly with clay exfoliation in the matrix.
TABLE 1______________________________________Gallery Chain Length Effect on Nanocomposite Formation andProperties. Clay Initial Gallery Clay Height Length Onium Gallery in Com- of Mod- ion, Height posite Onium Strength ulusExample (n)a (Å) (Å) Ion (Å) (MPa) (MPa)______________________________________E1 na na na na 0.6 2.8E2 na na na na 1.2 3.5E3 4 3.6 ≧7b 10.0 1.3 8.1E4 8 4.2 ≧8b 15.1 2.9 9.0E5 10 4.2 80-110C 17.6 3.2 12.2E6 12 6.0 80-100C 20.2 3.5 13.8E7 16 8.0 100-130c 25.3 3.6 13.9E8 18 8.4 100-150c 27.8 3.6 14.5______________________________________ a: n of gallery ions (CH3 (CH2)n-1 NH3 + ; b: Obtained from XRD; c: Obtained from TEM. MPa = pascals � 1,000,000.
The tensile strengths and moduli of the epoxy resin-clay nanocomposites have been measured according to the ASTM method 3039 using a Universal Test System (UTS). The relationship between the alkylammonium cation chain length of the organoclay and the mechanical properties of the composites is illustrated in FIG. 4 for loadings of 10 wt % CH3 (CH2)n-1 NH3 + -montmorillonite. The presence of the organoclay substantially increases both the tensile strength and the modulus relative to the pristine polymer. The mechanical properties increase with increasing clay exfoliation in the order CH3 (CH2)7 - NH3 + -<CH3 (CH2)11 NH3 + -<CH3 (CH2)17 NH3 + - montmorillonite. It is noteworthy that the strain at break for all of the epoxy resin-clay composites is essentially the same as the pristine matrix, suggesting that the exfoliated clay particles do not disrupt matrix continuity.
The X-ray diffraction patterns of the epoxy resin-clay composites containing CH3 (CH2)7 NH3 + --and CH3 (CH2)17- NH3 30 -montmorillonite are shown in FIG. 1A. These diffraction patterns reveal the change in clay basal spacing that occurs in the epoxy curing process. It is noteworthy that CH3 (CH2)7 NH3 + - and CH3 (CH2)17 NH3 + -montmorillonites respond differently to the epoxide-poly(etheramine) reaction mixture. For CH3 (CH2)7 NH3 + -montmorillonite (cf. FIG. 2A), the initial basal spacing at 15.2 Å is retained throughout the curing process, but significant broadening and reduction of scattering intensity occur for this reflection at 125� C. For CH3 (CH2)17 NH3 + -montmorillonite (cf. FIG. 2B), the basal spacing increases with reaction time and temperature. A new diffraction line with basal spacing at 54 Å appears after curing at 75� C. for 3 hours, while the intensity of the original clay diffraction line decreases. With further curing at 125� C., the clay diffraction lines are too broad to be distinguishable. Therefore, for CH3 (CH2)17 NH3 + -montmorillonite, an exfoliated nanocomposite is achieved. In contrast, CH3 (CH2)7 NH3 + -montmorillonite is only partially exfoliated in the polymer matrix.
The formation of exfoliated clay nanocomposites is dependent on the nature of the alkylammonium-exchanged clays. Longer linear alkyl chains facilitate the formation of the nanocomposite. Heating the CH3 (CH2)17 NH3 + -montmorillonite system at 75� C. causes the epoxide and amine to migrate into the clay galleries and form an intermediate with a 54 Åbasal spacing. Upon additional heating, further polymerization is catalyzed by the acidic primary ammonium ion (Kamon, T., et al., In Epoxy Resins and Composites I.V; Dusek, K., Ed. Springer-Verlag: Berlin; Advances in Polymer Science, 80 177 (1986); Barton, J. M., Advances in Polymer Science, 72 120 (1985); and May, C. A., Ed. Epoxy Resins, 2nd ed; Marcel Dekker: New York (1988)) and more epoxide and amine enter the galleries, leading to the formation of an exfoliated nanocomposite. Thus, the exfoliation of the clay is caused by intragallery resin formation. In the case of CH3 (CH2)7 NH3 + -montmorillonite, the hydrophobicity of the galleries is relatively low, and the amount of intercalated epoxide and amine is insufficient to achieve exfoliation. Therefore, only a portion of the clay is delaminated, as evidenced by the broadening and decreased scattering intensity of the 15.2 Å reflection, and the remainder of the clay retains its original basal spacing. Consequently, the final product in the case of CH3 (CH2)7 NH3 + -montmorillonite is a mixture of exfoliated and conventional clay composites.
A typical TEM image of the epoxy-exfoliated clay nanocomposite containing CH3 (CH2)17 NH3 + -montmorillonite is shown in FIG. 3. The dark lines are the cross sections of the 10-Å-thick silicate layers. A face--face layer morphology is retained, but the layers are irregularly separated by ˜80-150 Å of resin. This clay particle morphology is correlated with the absence of Bragg X-ray scattering. The TEM images and XRD patterns of the epoxy composite formed with CH3 1 (CH2)11- NH3 + -montmorillonite were essentially the same as those for the CH3 (CH2)17 NH3 + -montmorillonite system.
Reinforcement of the epoxy-clay nanocomposites also is dependent on clay loading. As shown in FIG. 5A and 5B, the tensile strength and modulus for the CH3 (CH2)17 NH3 + -montmorillonite system increases nearly linearly with clay loading. More than a 10-fold increase in strength and modulus is realized by the addition of only 15 wt % (˜7.5 vol %) of the exfoliated organoclay.
For the low-Tg epoxide-amine system of the present invention, the reinforcement provided by the exfoliated clay is much more significant. Owing to the increased elasticity of the matrix above the Tg, the improvement in reinforcement may be due in large part to shear deformation and stress transfer to the platelet particles. In addition, platelet alignment under strain may also contribute to the improved performance of clays exfoliated in a rubbery matrix as compared to a glassy matrix. The most significant difference between glassy and rubbery resins is the elongation upon stress. The rubbery epoxy matrix used in these Examples exhibits 40-60% elongation at break, whereas for the glassy epoxy resin matrix it was reported previously that it was only 5-8%.
As illustrated in FIGS. 6A and 6B, the clay platelets in the cured resin are capable of being aligned in the direction of the matrix surface. When strain is applied in the direction parallel to the surface, the clay layers are aligned further. This strain-induced alignment of the layers enhance the ability of the particles to function as the fibers in fiber-reinforced plastics. Propagation of fracture across the resin matrix containing aligned silicate layers is energy consuming, and the tensile strength and modulus are reinforced. In a glassy matrix, clay particle alignment upon applied strain is minimal and blocking of the fracture by the exfoliated clay is less efficient.
Examples 9-13 illustrate the relationship between clay charge density, the degree of resin intercalation and tensile properties of composites formed from different 2:1 clays having the same gallery onium ions, namely CH3 (CH2)17 NH3 +. Clay layer charge density is an important factor in determining the clay exfoliation in the polymer matrix. Several smectite clays such as hectorite (Hect), montmorillonite (Wyoming and Arizona), and fluorohectorite (Fhect) were used to prepare epoxy-clay composites. For comparison, non-smectite 2:1 clays such as vermiculite (Verm) and rectorite (Rect) also were used to prepare epoxy resin-clay composites. The preparation method is essentially the same as described in Example E3-E8. C18 alkylammonium cation was used as gallery ions. The composite samples were labeled E9, E10, E11, E12, and E13 for composites containing hectorite, montmorillonite from Arizona, fluorohectorite, rectorite, and vermiculite, respectively. Clay gallery heights, clay layer density and tensile properties are listed in Table 2. The Example E12 contains rectorite, a regularly interstratified clay unlike normal smectite clays has a layer thickness of 20 Å rather than 10 521 . Thus, the exfoliation of rectorite in epoxy matrix provides 20 Å-thick silicate layers dispersed uniformly in the matrix. Natural rectorite was purified and ion-exchanged to CH3 (CH2)17 MH3 + -rectorite. Comparing E12 and E8, it was noticed that at the same clay loading, rectorite composite has a comparable strength and modulus as montmorillonite composite, even though the number of clay layers in the rectorite composite is nearly half of those montmorillonite composite. Therefore, the 20 Å-thick rectorite clay layers are more effective than the 10 Å-thick clay layer as reinforcement particle in a flexible matrix.
TABLE 2______________________________________Composite Formation and Properties with Different Layer ChargeDensity Clays (E8-E13), clay loading is 10 wt %. Clay Initial Gallery Layer Clay Height charge Gallery in Com- density (e- / Height posite Strength ModulusEx. Clay O20 (OH)4) (Å) (Å) (MPa) (MPa)______________________________________E8 Mont- 0.76 24.5a 80-110b 3.6 14.5WyE9 Hect 0.66 25.7a 80-110b 3.0 14.5E10 Mont- 1.2 25.0a 80-110b 3.7 14.0AzE11 Fhect 1.4 24.1a 95a,b 2.5 15.1E12 Rect 0.7 25.1a 80-120b 3.2 13.1E13 Verm 1.6 25.3a 45a 1.8 9.0______________________________________ a: Obtained from XRD; b: Obtained from TEM.
These examples show the dependence of clay reinforcement on clay loading. Epoxy resin-clay nanocomposites were prepared according to the preparation method described in the E3-E8 with different clay loadings prepared. The examples with clay contents of 2, 5, 15 and 23 wt % were labeled E14, E15, E16 and E17, respectively. X-ray diffraction results indicate that they are exfoliated clay nanocomposites. Tensile properties of the examples, along with the reference epoxy resin from Example 1 are given in FIG. 5A and 5B.
The results in FIG. 5A and 5B clearly show the reinforcing effect of the exfoliated clay layers in the resin matrix. Similar results also were observed for exfoliated clay nanocomposites containing other smectite clays.
These examples demonstrate the relationship between layer separation and tensile properties of resin-clay nanocomposites. Exfoliated epoxy-clay nanocomposites were prepared by using in situ gallery intragallery catalyzed polymerization. Intercalated nanocomposites were also prepared without intragallery catalyzed polymerization. The gallery cation acidity plays a very important role in determining the intragallery epoxy-amine polymerization rates and in controlling the clay exfoliation in the epoxy-amine thermosetting process. Quaternary alkylammonium ion such as CH3 (CH2)17 N(CH3)3 + (C 183M) was used to prepare organoclays. X-ray diffraction results indicated that the composites have distinct d001 diffraction at 42 Å, corresponding to a 32 Å gallery height. Therefore, they are typical intercalated nanocomposites. The examples are labeled E18, E19, E20, and E21 for the composites containing CH3 (CH2)17 N(CH3)3 + -montmorillonite at 2, 5, 10 and 15 wt % clay loading. Tensile properties of the intercalated nanocomposites are listed in Table 3. For comparison, the exfoliated nanocomposites prepared with similar chain length primary alkylammonium exchanged clays (E8, E14-16) are listed as well.
TABLE 3__________________________________________________________________________Comparison of Tensile Properties of Intercalated and ExfoliatedEpoxy-MontmorilloniteClay Nanocomposites. Initial Clay Clay Gallery Clay Tensile Tensile Gallery Gallery Height in Loading Strength ModulusSample Onium Ions Height (Å)a Composite(Å) Composite Type (wt %) (MPa) (MPa)__________________________________________________________________________E18 Q 12.5 32.0a intercalated 2 1.3 6.5E14 P 8.4 100-220b exfoliated 2 0.9 5.9E19 Q 12.5 32.0a intercalated 5 1.7 6.9E15 P 8.4 80-160b exfoliated 5 1.6 7.6E20 Q 12.5 32.0a intercalated 10 2.6 12.4E8 P 8.4 80-110b exfoliated 10 3.6 14.5E21 Q 12.5 32.0a intercalated 15 3.0 15.2E16 P 8.4 80-110b exfoliated 15 7.4 24.1__________________________________________________________________________ P: Primary ammonium ion CH3 (CH2)17 NH3 +; Q: Quaternary ammonium ion CH3 (CH2)17 N(CH3)3 +; a Obtained from XRD; b Obtained from TEM.
The mechanical property data in Table 3 demonstrate that the reinforcing effect for intercalated and exfoliated nanocomposites are comparable at low clay loading up to 5 wt % and similar in magnitude to the pristine resin. However, at higher clay loadings in the range 10 and 15 wt %, the reinforcing effect for the exfoliated nanocomposites is much larger than the intercalated nanocomposites. Thus, at clay loading above about 5 wt %, the extent of clay layer separation determines the performance properties of the epoxy resin-clay nanocomposites. Similar effects were observed for fluorohectorite and other 2:1 clay systems.
These examples demonstrate the relationships between reinforcement properties and the extent of clay layer exfoliation. CH3 (CH2)3 NH3 +, CH3 (CH2)7 NH3 +, and CH3 (CH2)17 NH3 + exchanged montmorillonites are used to prepare epoxy resin-clay nanocomposites. The epoxy resin and curing agent are identical to the composition described in Examples 3, 4 and 8. The curing condition is modified to hot-mold-casting, which means that transfer of the degassed epoxy-clay composition to a preheated- (125� C.) mold and continuance of the curing at 125� C. for 6h. The hot-mold-casting method promote the intercalation of the epoxy monomer to the clay galleries in the clay and clay exfoliation, especially for the shorter chain alkylammonium exchanged clays. In Table 4, epoxy-clay composites prepared by the hot-mold-casting method are compared with the ones with the same composition but prepared by the conventional casting method.
TABLE 4______________________________________Comparison of Tensile Properties of Epoxy-clay Composites ContainingAlkylammonium Exchanged Montmorillonite (10 wt %) Prepared underDifferent Curing Conditions. Clay Initial Gallery Clay Height Gallery in Com-Onium Curing Height posite Strength ModulusEx. ion, (n)a Condition (Å) (Å) (MPa) (MPa)______________________________________E1 None CC -- -- 0.6 2.8E3 4 CC 3.6 ≧7b 1.3 8.1E22 4 HMC 3.6 ≧10 2.1 12E4 8 CC 4.2 ≧8b 2.9 9.0E23 8 HMC 4.2 ≧100c 4.7 16E8 18 CC 8.4 100-150c 3.6 14.5E24 18 HMC 8.4 100-150c 3.8 14.6______________________________________ a: n of gallery ions CH3 (CH2)n-1 NH3 + ; b: Obtained from XRD; c: Obtained from TEM. CC: Conventional casting; HMC: hotmold-casting.
Tensile properties of these composites are compared in Table 4. For the composites containing CH3 (CH2)3 NH3 + -, as well as CH3 (CH2)7 NH3 + -montmorillonite, a great improvement in mechanical properties is achieved by using the hot-mold-casting method. However, for the composite containing CH3 (CH2)17 NH3 + -montmorillonite, which is easily exfoliated under both normal and hot-mold-casting conditions, no further mechanical improvement is observed.
Epoxy-clay nanocomposites were prepared by using other epoxy resins from DOW Chemical Co. and JEFFAMINE D2000 containing CH3 (CH2)17 NH3 + -montmorillonite. The basic structures of the DOW epoxy resin are given as follows: ##STR10##
The epoxy-clay nanocomposites prepared from above-mentioned epoxy resin with 10 wt % CH3 (CH2)17 NH3 + -montmorillonite have exfoliated structures. Their mechanical properties compared to those of the pristine resin matrices are superior and comparable to the results obtained from Epon 828-D2000 systems of Examples 1 to 24.
Solvent adsorption experiments for Examples E1, E2, E3 and E8.
Solvent absorption data were obtained using a mass differential technique. Samples of a known weight were immersed in toluene at room temperature and reweighed periodically after blotting to remove excess solvent. The difference between two weighings corresponded to toluene uptake. Samples were weighted until constant weight at which point it was assumed that they had reached equilibrium. The relative rate of toluene adsorption and total uptake at equilibrium of Examples E1, E2, E3 and E8 are listed in Table 5.
TABLE 5______________________________________Relative Toluene Adsorption Rate and Total Uptake of Epoxy-ClayNanocomposites. Relative InitialNanocomposites Type of Clay Adsorption Relative TotalExample Composite Rate (%) Uptake (%)______________________________________E1 na 100 100E2 conventional 95 100E3 intercalated 84 93E8 exfoliated 42 51______________________________________
The toluene adsorption results exhibit a substantial decrease in solvent uptake for the exfoliated epoxy-clay nanocomposite E8. The exfoliated 10 Å-thick clay layer in the matrix may contribute to the decrease of the rate and amount of the solvent uptake. Whereas, for the intercalated nanocomposite and the conventional composite, the clay exists as tactoids, the effect of clay in decreasing solvent adsorption is not significant. Similar experiments with hexane adsorption were carried out and comparable results were obtained.
The adsorbed organic molecules can be removed by air-drying or vacuum-drying. During the drying process, the pristine polymer matrix (E1), conventional composite (E2), and intercalated nanocomposite (E3) crack, whereas, the exfoliated nanocomposite (E8) retains its integrity. Therefore, for the exfoliated nanocomposite, the adsorption-desorption of organic molecules occurs with structural reversibility. The ability of the nanocomposite to return to its pristine structural state upon desorption of dissolved organic solvent greatly extends their use as sealants and gaskets which may contact organic substances frequently.
Exfoliated epoxy-clay nanocomposites can also be obtained by replacing the D2000 curing agent in Examples E8, E9, E10, E11, and E12 with glyceryl poly(oxypropylene)triamine curing agents of the type ##STR11## and x+y+z=4˜120. These curing agents are commercially available under the trademark JEFFAMINE 403, T703, T3000 and T5000.
The curing of epoxy resin is not limited to amine curing agent. Replacement of the amine curing agents in Examples E8, E9, E10, E11 and E12 with polyamide of the type ##STR12## and x=5˜15, also affords nanocomposite materials with greatly improved mechanical properties. These polyamide curing agents are commercially available under the tradename VERSAMID 140, 125 and 100, available from Henkel, Ambler, Pa.
Comparative epoxy resin-exfoliated clay nanocomposites formed from Epon-828 resin and m-phenylenediamine as the curing agent were prepared using long-chain alkylammonium-exchanged smectite clays. Due to the high glass transition temperature (˜150� C.) of the epoxy matrix, the composites were in a glassy state at room temperature. The results are shown in Table 6.
TABLE 6______________________________________Mechanical Properties of Epoxy-Clay Nanocomposites formed withCH3 (CH2)15 NH3 + ClaysClay Samples Failure Strength Tensile Modulus(1 wt %) (MPa) (GPa)______________________________________Laponite 83 � 2 1.59 � 0.04Hectorite 94 � 2 1.65 � 0.03Montmorillonite 92 � 5 1.49 � 0.03Fluorohectorite 73 � 3 1.55 � 0.06______________________________________
It was found that the improvement over the admixtures with the clay were not as pronounced as with the polyoxypropylene diamines. This can be seen from FIG. 7.
The inventors described this Example 32 in publications by Lan et al, Proceedings of the ACS, PMSE 71 527-528 (published August 1994) and Lan et al, Chemistry of Materials 6 2216-2219 (December 1994). A derivative work based on the inventors' work was published in Chemical Materials 6 1719-1725 (December 1994).
It is intended that the foregoing description be only illustrative of the present invention and that the present invention be limited only by the hereinafter appended claims.
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COLUMBIA CITY — Columbia City Mayor Jim Fleck is calling on his town's department heads to come up with ways to help reduce "pain at the pump."
The mayor said earlier this week at the regular meeting of the Columbia City Common Council, and reiterated on Friday to the Board of Works and Safety, there is seemingly no end in sight to elevating gas prices.
"We do have a need to create a plan within your department," Fleck told the town's department heads Friday morning.
Fleck said he realizes a "one size fits all" approach will not work.
"Every department has different gas consumption needs, we realize that," he said.
"But we need to get a strategy around."
Fleck said he has talked to other communities about their ideas for reducing gasoline consumption and also commented that New Haven is starting a vehicle take-home program.
"As we see gas prices continue to rise, approaching four dollars a gallon, and certainly $3.60, I would like your suggestions by next week, so we can make sure that we manage as gas prices go up."
Gas prices are in the stratosphere, which means more individuals than ever are looking into option gasoline choices. For diesel automobile owners, biodiesel is an environmentally conscious option that costs less than $1 per gallon. Biodiesel gasoline can even be made at home. While there are pros and cons to the process, it's hard to deny that running a diesel automobile on biofuel is cheaper in the long run than gasoline. I read this here: Make your own biodiesel fuel and save big money
It is indeed a better idea to reduce gasoline use and start electric cars that runs with a battery or solar power. Using this can also help to reduce the pollution also saving energy and money. These days we can see electric cars being popular because it doesn't require a gasoline at all. Many underdeveloped countries are also using this type of vehicle to minimize the pollution and save energy. Recently U.S. president Barrack Obama has announced a major step regarding fuel efficiency policy which will not only reduce the dependency of US on oil but also will be in the line of mitigating ongoing climate crisis. So, now the time has come to adopt holistic approach in whatever way, be it biogas or any fuel efficient mechanism like diesel exhaust fluid will be highly sustainable for all-from individual to global from economical to environmental.
Maybe they should use their own car in going to Fort Wayne. I have seen them roaming the town on many occasions with family in the car, so we know it is not "official business"
How about having city police and other officials use their own vehicles for personal use. I see them driving with their families in city vehicles to schools, to stores etc.


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This week we launched a major initiative to help educate people about safer tattooing practices to prevent transmission of hepatitis B, hepatitis C, bacterial infections and other pathogens—Hepatitis & Tattoos. The heptitistattoos.org website will feature regular articles on tattooing and pictures, but the main message is that getting a tattoo is safe – as long as safety precautions are closely followed.
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text: MANKATO (TEC News) -- While Sunday's KEYC newscast is being watch worldwide for the anchor's unusual behavior, the anchorwoman should take note it may not be the strangest thing ever seen on local TV news. And we are not talking about former weatherman "Too Tall" Tom Szymanki. Remember former KEYC Chief Meterologist Bob Conzemius? He's now Dr. Bob Conzemius, having received his PhD. from the University of Oklahoma. An online bio also say he's a part-time storm chaser and serves as a Senior Atmospheric Scientist at Minnesota-based Wind Logics. We can't confirm the date of this infamous KEYC weathercast or the name of the anchorman who plays it straight for Conzemius during this Halloween weathercast.


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Museo de Arte de Ponce
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Following an extensive renovation, Museo de Arte de Ponce reopened in 2010 boasting a bigger space and a larger art collection. Today, the museum houses more than 4,500 works from Europe, Africa and the Americas dating back to as early as the 14th century. During its brief hiatus, the museum lent 125 items from its permanent collection to 15 museums across nine countries, where it was admired by countless visitors. At home in the Puerto Rican city of Ponce — along the island's southern coast — the collection is particularly beloved for its blend of European baroque works, Victorian paintings and Puerto Rican folk art.
Recent travelers loved the variety within the collection and raved about the museum's intuitive, easy-to-follow organization. Others found the museum's setting perfect for a bit of R&R: "On the third floor there is a private nook with 2 chairs overlooking the grounds and garden which is a nice spot to take a load off," one TripAdvisor reviewer wrote.
The museum is open Wednesday to Monday from 10 a.m. to 6 p.m., and closed on Tuesdays; last admission is at 5:15 p.m. Adult admission costs $6 USD, while seniors and children 12 and younger can get in for $3 USD. Museum de Arte de Ponce offers daily guided tours (included in the admission price) in both English and Spanish at 11 a.m. and 2 p.m.; audio guides are also available for $2 USD. Visit the museum's website for more information.
Nearby Things To Do
Parque de las Cavernas del Río Camuy36.0 miles away
Calle del Cristo45.8 miles away
El Morro (Fuerte San Felipe del Morro)46.0 miles away
Nearby Hotels
Dorado Beach, A Ritz-Carlton Reserve38.6 miles away
Horned Dorset Primavera45.2 miles away
Hilton Ponce Golf & Casino Resort2.4 miles away


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We know you've already ordered several dozen copies of Division 18 #1 (due to stores in October), but are you as excited as we are for Division 18 #2? We won't even talk about the awesomeness that is going to be Division 18 #3 yet…
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text: Healthy Recipes Spicy Fish Stew Recipe E-mail recipe Print recipe To save this recipe, register now! Quick Info: Servings Nutritional Info (Per serving): Calories: 115, Saturated Fat: 1g, Sodium: 480mg, Dietary Fiber: 2g, Total Fat: 4g, Carbs: 11g, Sugars: 7g, Cholesterol: 33mg, Protein: 11g Exchanges: Vegetable: 2, Lean Meat: 1 Carb Choices: 0.5 Recipe Source: Reproduced with permission from "ADA Cookbooks"© American Diabetes Association ® Ingredients 2 cup(s) mushrooms, sliced 1 cup(s) onion(s), chopped 2 clove(s) garlic, minced 1 tablespoon oil, olive 1 tablespoon thyme 1 quart(s) juice, tomato, or vegegtable cocktail 2 teaspoon sugar 1 bay leaf 1/2 teaspoon hot sauce 1/2 teaspoon pepper, black ground 1 pounds fish, catfish, or cod or perch or white fish 1/4 cup(s) parsley, fresh 1 cup(s) celery, chopped Preparation 1. In a large saucepan, sauté the mushrooms, celery, onion, and garlic in oil over medium heat about 5 minutes. Add the thyme and sugar; sauté 1 minute. Add the tomato juice, bay leaf, pepper sauce, and pepper. Bring to a boil. 2. Reduce the heat. Add the fish and simmer, uncovered, about 10 minutes. 3. Discard the bay leaf. Stir in the parsley and serve hot. E-mail recipe Print recipe To save this recipe, register now!


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Alesis DM8 Studio - Don't bother. Alesis DM10 - Better but noisy.
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Dr Crinkle
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Alesis DM8 Studio - Don't bother. Alesis DM10 - Better but noisy.
I got an Alesis DM8 just before Christmas and the trigger in the bell on the ride cymbal packed up within a month. By the end of January the whole ride was dead and the hi-hat controller pedal starting getting temperamental. Sometimes it didn't work at all.
I suspected it was a problem with the leads - the DM8 has all the leads from the triggers going into one DB25 connector that goes into the brain. I sent the broken parts back (including the brain and loom) to Andertons and after 6 week they said that they couldn't get a replacement ride but I could have one from a DM10 kit instead.
I was so frustrated I told them I wanted to send the whole thing back which I did. I spent another £170 to upgrade to an Alesis DM10 instead.
The DM10 is much sturdier looking and feeling and the triggers all have their own inputs which inspires confidence. The trouble with the DM10 is that the pads don't half make a racket when you hit 'em - they are way louder than the DM8. It's like beating on icecream tubs!
I'm gonna try some mesh heads on the DM10 to make it quieter. Hopefully it'll last longer than the DM8.
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Ellie Goulding at the Pageant, 1/30/13: Photos
England's ever-talented songstress Ellie Goulding played to a capacity crowd at the Pageant last night. Goulding's debut studio album Lights catapulted the singer to dizzying heights of success in 2010. The October 2012 release of follow-up Halcyon made sure that she stayed there.
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Be sure to check out our full slideshow here: Ellie Goulding at the Pageant.
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Updated: 12/19/2012 6:47 PM KSTP.com By: Amanda Theisen
When you see someone in trouble, your first instinct is often to race in and help. The instincts of a group of students from Oak-Land Junior High School in Lake Elmo proved to be all the difference for their school bus driver from Stillwater.
On December 11, school bus driver Duane Burmeister went to pick up nine 7th and 8th graders at Oak-Land for nordic ski team practice. The next thing he knew, he was waking up in a hospital bed.
Students say Burmeister blacked out behind the wheel as the bus started to roll across four lanes of Manning Avenue. One student, Rana Kraftson, saw Burmeister faint and screamed. She ran to the front of the bus, pulled the emergency brake and got on the bus radio to alert other drivers.
While some students stayed with Burmeister, others ran back into the school and alerted teachers to what happened. Ambulances soon arrived and rushed Burmeister to the hospital. He suffered a mild stroke and a broken arm. However, he is otherwise okay.
None of the students on board the bus was hurt. They credit their quick actions to instincts and bus safety training they go through at the start of every school year.
The Washington County Sheriff plans to nominate the students for a lifesaving award.


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August 2, 2015
On January 29, Montgomery County police investigated a suspected methamphetamine laboratory in Willis.
Investigators served a search warrant and recovered items used in the manufacture of methamphetamine.
Tony Lynn Gray was arrested for possession of a controlled substance.
No children were present during time of investigation but Child Protective Services will be notified due to children living at the home. This investigation is on-going.
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Daze, he says, is based on a character's base defense rating as compared to a mob's base attack skill. The standard Daze rating is 20% (so if you're facing a mob of equal level and your defense rating hasn't been increased, then a hit from behind should daze you 1/5 of the time), and it goes up or down from there from 0 to 40%. Characters below level 30, interestingly enough, have a much reduced chance to be dazed (it's almost impossible for a level 1 character to be dazed by an equal level mob), in order to make the game easier when players first begin playing.
The reason Drysc gives for us seeing it more in Outland is a little shaky-- he says there weren't many actual level 60 mobs in Azeroth, and there are now quite a few level 70 (and higher) mobs in Outland, which means a fully leveled character will be dazed more. Finally, the reason, he says, for Daze in the first place is that they don't want to make it "safe" to randomly run through a group of mobs. "A cautious and alert player," he says, "is less likely to be dazed than one who is haphazard and careless."
My only problem with that is that I get dazed more not when I'm trying to run away from characters (I understand I'm going to be penalized when I sloppily run through a group of mobs), but when I get jumped while fighting. Should the same penalty apply when a single add jumps me from behind? And while we're at it, shouldn't being mounted lower the chance of getting dazed as well? Having a flying mount has made serious dazing tragedies much less common, but for characters still on ground mounts, shouldn't being mounted protect them a little more than being on foot?


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GYMNASIUM. - Men who wish to take the strength test before the comparative lists are published must come to the Gymnasium between 9 and 12 or 2 and 5 on Monday, Tuesday or Wednesday, November 26, 27, 28.
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