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The Barefoot Executive: The Ultimate Guide for Being Your Own Boss and Achieving Financial Freedom - eBook
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Product Information
|Format: DRM Protected ePub
Vendor: Thomas Nelson
Publication Date: 2011
Availability: In Stock
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Publisher's Description
Carrie Wilkerson offers the opportunity to live life on your terms. Want to start your workday with e-mail and coffee on the back patio? Want the flexibility of joining your fourth grader on an all-day field trip? Are you ready to take that vacation you've been planning for years? Then you have a choice to make, and The Barefoot Executive will help jump-start your transition. You'll learn:
- Your "why." The most important question. Why do you want to work for yourself?
- What type of business best suits your experience and talents.
- How to stay focused on your goal and avoid distractions.
- Where to find the support that will accelerate your success.
- How to link your business to the right market.
DISCOVER what you already have to offer, how to use it to your advantage, and where to find the people who are eager to buy it. The Barefoot Executive will pull you over the hurdle of uncertainty and get you moving, planning, doing.
What Others Are Saying:
"Carrie Wilkerson has done a great job with this book, and she's personally helped me make tons of money with my business. I highly recommend this book!" - Chris Brogan, president, Human Business Works, and publisher of chrisbrogan.com
"There has never been a better time to turn your passions into income. But just having an idea doesn't mean you're ready to order business cards just yet. Carrie Wilkerson's The Barefoot Executive walks you through the process of developing your idea, finding your audience, and setting yourself up for a lifetime of success doing the work you love for the hardest boss you'll ever have... yourself!" - Dave Ramsey, host of The Dave Ramsey Show and best-selling author of The Total Money Makeover
"One of the best ways to achieve success is to learn from someone who has already done it. If you are looking to build a viable, sustainable, and lucrative business from home- or anywhere else- Carrie Wilkerson is your example, and her new book will show you the way." - Tim Sanders, author of Today We Are Rich and former CSO at Yahoo!
"A lot of books can fire up an entrepreneur. But a lot of those books leave readers high and dry when it comes to practical application. Enthusiasm isn't enough. You need a plan and the tools to build with. Carrie Wilkerson's guidance provides just that. Combine that with her enthusiasm, warmth, and core values, and you have someone very real to learn from. As my dad says, 'a great book needs to cover the Why and the How.' This is a great book. I know that when Carrie advises Ziglar, Inc. on marketing ideas, we get results." - Tom Ziglar, CEO and proud son of Zig Ziglar
"If you're dreaming of building a business on your terms, then you'll absolutely love Carrie Wilkerson." - Tory Johnson, CEO, Women For Hire and New York Times best-selling author


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2001 Mitsubishi Eclipse Repair and Maintenance
A guide to problems, costs, maintenance and repair for your 2001 Mitsubishi Eclipse
Verified by mechanics, reported by drivers like you
Ask a mechanic in our community
Never overpay. Check prices with our estimator
2001 Mitsubishi Eclipse ProblemsThe Sunroof May Become Stuck Closed or Have Difficulty Moving
The sunroof may become stuck in the closed position or require "help" moving forward and backward. The common repair is to replace the guides but often the problem will resurface again.
The manual transmission may become difficult to shift, this is commonly caused by binding between the synchronizer and the gear surface. Adding a special friction modifier to the manual transmission fluid will often correct this condition. If the problem persists revised synchronizer kits may be available.
The Check Engine Light may illuminate due to one or more engine vacuum leaks. Our technicians tell us these leaks can be caused by damage to seals and/or vacuum hoses as a result of to much ethanol content in the gasoline. Affected hoses and seals must be replaced to correct this concern.
2001 Mitsubishi Eclipse QuestionsWhat do I change next? Car just stopped while driving (1 answer)
OK so my sone was driving this car and it just stopped. After it sat for about 2 months we finally got it home from his friends house to work on it. We first checked and the fuel pump was bad so we replaced it. Then it still would not run good so we were told that the sensor in the distributor wa...
I Don't know if its the oil pump or oil pressure switch. only help?
Prior to that the driver floor board had been wet. And the idling had been acting up.. Timing belt was recently replaced also put new radiator..
2001 Mitsubishi Eclipse RecallsPassenger Sun Visor May Detach In Collision
The passenger side sun visor may detach if an accident occurs with it in the down position, and the passenger front air bag is deployed, striking it. Dealers will install a tether strap to retain the visor free of charge to resolve the concern.

subset: commoncrawl


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CORAL GABLES (AP) — Freshman left-hander Dylan Dusek scattered four hits over eight innings as Texas Tech defeated Miami 3-0 on Saturday night in a winners' bracket game in the Coral Gables regional.
Dusek (7-0) set a career high for innings pitched while striking out three and walking one for Texas Tech (42-18). Corey Taylor pitched the ninth and earned his second save.
Chris Diaz (9-1) suffered his first loss of the season for the Hurricanes, who have scored just one run in two tournament games — on a passed ball in the ninth to beat Bethune-Cookman on Friday. Dale Carey, who came into hitting .312 on the season, went 0 for 4 and stranded seven runners against Texas Tech.
The Hurricanes will face Bethune-Cookman in an elimination game Sunday. The winner will face Texas Tech in the nightcap.
(© Copyright 2014 The Associated Press. All Rights Reserved. This material may not be published, broadcast, rewritten or redistributed.)
- Fernandez Tosses 7 Scoreless Innings In 3-1 Win
- Exclusive: Colombian Nat'l Soccer Player Arrested In Miami Beach
- Poppinga: "If You're The Dolphins, You're Excited To Get Dion Jordan Back"
- Keidel: Don't Underestimate The Warriors Like I Did
- Former Dolphins RB Ronnie Brown Speaks About Team, Teammates And More


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Draft and Trade Talk Message Board
Flash Flashley Flash Flashley Sep 25, 2012 11:22 PM Flag
Josh Beckett in 2013, What Do Y'all Think?
Is He Keeper Material Again Thanks To Landing In LA?!
I've Got Him, But Don't Know What To Think About Him And Next Season!?
Opinions?!?Sort: Newest | Oldest | Most Replied Expand all replies
BrewCrewDue BrewCrewDue Feb 5, 2013 6:57 PM Flag
I'm just going to LOL and say you must have 10 players left out of 21 on your team in a 24 team League to even consider Beckett as a 6th keeper. I can name off 5 Prospect pitchers I'd take over him:Miller,Skaggs,Bauer,Turner, and Bundy. Your team must have traded away all their mid level guys and have 5 of the top 20 players overall and no one else in the top 150 discussion. Beckett ranks in the 200s for Fantasy. Just saying.
Greenraven Greenraven Feb 5, 2013 1:15 AM Flag
Why are you even keeping a pitcher with only 6 keepers total?!?!
If you don't have a pitcher named Verlander, Kershaw, Strasburg or Price, don't keep them. Only 6 keepers there will be tons and tons of pitchers in re-draft. Everyone keeps their star position players first last and always in a keeper league. Pitchers are easily replaced. I like Fister the best of the three but no way would I ever consider him in 6 keeper territory.
As for Beckett, send him off with some beer and chicken wings and never think about him again. Ever.
Slappytheclown Slappytheclown Feb 4, 2013 8:10 PM Flag
he's not really a keeper except in dynasty leagues. He may have a year or two left in LA, have to watch his weight and velocity in spring to see how much chicken he's eaten...
3 words josh becket Sucks !! and im a dodger fan but he could turn it around and I'm 90% sure he won't
Post your team and how many keepers at least
- 1 Reply to Andre-Z
Flash Flashley Flash Flashley Sep 26, 2012 7:28 AM Flag
Well, I've already got 5 of My 6 Keepers Picked and I'm Totally Locked-In with them. BECKETT is up against J.PARKER, and D.FISTER for My 6th Spot. I'm just curious if BECKETT, with LA sucking up good players & looking to be a contender again in 2013, should even be considered for a Keeper slot, or Not.
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Squeezing Thor, Mike Trout and Bryce Harper into a daily lineup is no simple feat, but one of our experts managed to do it. … More »
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Girl loses her mind and starts ramming a car with hers
In front of Howiees on 4-23-12
By: drewniverse | Comments: 22 | Views: 2755 | Votes: 3 | Shared: 0
Leaked: May-3-2016 in WTF
Bulldozer goes wild on busy street
A bulldozer driver has put his heavy vehicle into malicious use, going on a rampage on the streets of Shuozhou City, north China's Shanxi Province. The incident happened on September 2015, but foota
By: Lake8737 | Comments: 54 | Views: 2670 | Votes: 12 | Shared: 0
Location: China | Leaked: May-18-2016 in WTF, Vehicles
Race Car Crashes During Race
A sportsman can race turns into a demolition derby when two drivers go at each other, with one deliberately ramming the other, almost completely wrecking both vehicles.
By: DailyPicksandFlicks | Comments: 44 | Views: 2625 | Votes: 2 | Shared: 0
Leaked: May-7-2016 in WTF, Vehicles
Angry driver rams into bus, injures 6
Two bus drivers in northern China's Tianjin municipality have been suspended from work for putting the lives of passengers at risk after a quarrel between them ended in a deliberate collision. Th
By: Lake8737 | Comments: 237 | Views: 63286 | Votes: 16 | Shared: 109
Location: China | Leaked: May-3-2016 in Other News, WTF, Vehicles
Road rage - car ramming- machete attack
Some road rage happening in Costa Rica involving car ramming, machetes. Costa Rica hoy
By: Chivalry is alive | Comments: 23 | Views: 4562 | Votes: 2 | Shared: 0
Location: Costa Rica | Leaked: Mar-5-2016 in WTF, Vehicles
Kazakhstan Two Ladies Ramming Each Other
By: LBFM | Comments: 35 | Views: 2438 | Votes: 7 | Shared: 0
Location: Kazakhstan | Leaked: Mar-17-2016 in WTF, Other Entertainment, Vehicles
Wild Chase Of Stolen Police Car Ends With Officers Ramming Cop Vehicle
The cop car thief was shot dead on scene.
By: Dmanfig | Comments: 12 | Views: 912 | Votes: 2 | Shared: 0
Location: Glendale, California, United States | Leaked: Mar-15-2016 in Other News
Radical Left artist shocks Haaretz Tel Aviv cultural event by ramming a flag into his exposed ass
Ariel Bronz causes uproar at Haaretz Tel Aviv cultural event by ramming a white flag into his exposed rear end - Israel's social media was atwitter on Sunday after controversial performance artist A
By: aydeo | Comments: 37 | Views: 3285 | Votes: 0 | Shared: 0
Location: Tel Aviv-Yafo, Tel Aviv District, Israel | Leaked: Mar-7-2016 in Other News, WTF
Palestinian woman shot dead after car ramming attack – Israeli army
Israeli forces say they have shot dead a Palestinian woman who drove a car into an Israeli soldier in the West Bank on Friday. He is not thought to be seriously injured. Israel's army says a kni
By: Euronews | Comments: 43 | Views: 2451 | Votes: 0 | Shared: 0
Leaked: Mar-4-2016 in Other News
Bulldozers battle on street in northern China
Police in northern China say an argument between construction workers escalated into a clash of heavy machinery that left at least two bulldozers flipped over in a street. This video footage shows
By: sosola | Comments: 20 | Views: 1436 | Votes: 2 | Shared: 5
Location: China | Leaked: May-1-2016 in WTF
Rival companies battle on street with bulldozers in China
Workers from two rival companies decided to settle their differences in a highly unusual way on Sunday as they used bulldozers to battle on the streets of Xingtang County in north China's Hebei Provin
By: PressTV | Comments: 21 | Views: 2054 | Votes: 5 | Shared: 4
Location: China | Leaked: Apr-19-2016 in Other News, Creative
California police shooting at rampaging utility worker
Just heard about this little incident from some friends and family still in my home town. Also, this is my first attempt at uploading a video so please accept my apologies in advance for whatever ne
By: BEASTsorrow_mad | Comments: 26 | Views: 2331 | Votes: 4 | Shared: 0
Location: Torrance, California, United States | Leaked: Apr-13-2016 in Regional News
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Half-term activities
Sales and Seals – 1st and 2nd of June
We're going seal-crazy this half-term! Design your own charter seal or animal seal out of clay. Drop in sessions, 11am – 1pm & 2pm – 4pm. Children MUST bring an adult. Usual entry fees apply.
|Opening hours
|Contact us
|Tuesdays to Saturdays
Sundays and Bank Holidays
|10am to 5pm
2 to 5pm
|Saffron Walden Museum
Museum Street
Saffron Walden
CB10 1JLTel. 01799 510333
Email: email@example.com


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Part Time Night Shift Jobs in London
PERFECT PLACEMENT - London
As a Workshop Controller you will be responsible for controlling the work flow through the workshop, acting as quality control for the technicians work and striving to achieve a prompt first time fix for... £35000 per annum
from: jobflurry.com (+4 sources) - 6 days ago
Nadler Hotels Limited - South West London, London, South East
Nadler Hotels are currently recruiting for a Night Receptionist to join their vibrant team at The Nadler Kensington. This role is a part time position, working 16 hours per week, Monday to Sunday on a...
from: caterer.com - 11 days ago
Chiltern Firehouse - Central London / West End, London, South East
Chiltern Firehouse is hotelier Andre Balazs's bespoke luxury hotel in the heart of Marylebone in central London. Sister property to the acclaimed Mercer Hotel in New York and the iconic Chateau Marmont...
from: caterer.com - 11 days ago
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As a Key Worker under the guidance of a Registered Nurse, taking responsibility for the physical and emotional well being and social needs of our client's residents. If you're passionate about providing... 6.70
from: reed.co.uk - 5 days ago
First Call Contract Services Ltd - North West London, London
This is a full time role, with various shifts available (both days and nights). You will work a minimum 12 week probationary period via the agency, before being offered permanent contract of employment... 7.20
from: reed.co.uk - 13 days ago
COREcruitment - London, South East
At COREcruitment we are experts in recruiting for the service sector. We currently have over 700 live roles across the UK, Middle East, Europe, North America, South East Asia, Africa and Australia. To... £7.20 - 7.20 per hour + tips
from: retailchoice.com (+2 sources) - 12 days ago
HCL Permanent - London
With the most advanced medical equipment and the largest private paediatric ITU in the country, it's no surprise we attract some of the finest specialist consultants from many of London's major teaching... £31086 to £39326 Per year
from: nurses.co.uk (+4 sources) - 9 days ago
Bespoke Health and Social Care - South West London, London
Bespoke Health & Social Care is a leading, specialist provider of complex care staffing services to individuals, throughout the UK. We support adults & children who have either a spinal injury, acquired... 8.00
from: reed.co.uk - 11 days ago
PERFECT PLACEMENT - London
As a night shift Technician, hours are 6pm-3am Monday to Friday. Rates of pay are up to £15.44 per hour (£36,000 Per Annum). Overtime is available at 110% of base hour rate. Training and development opportunities... £36000 per annum
from: jobflurry.com (+2 sources) - 6 days ago
JS3 Recruitment Ltd - London
Staff nurse London Permanent/Full Time Salary up to £35,000 per annum plus Benefits Our client are actively seeking an experienced Haematology Staff Nurses to complement the existing nursing team on thier... £30000 to £35000 Per year
from: nurses.co.uk (+1 source) - 9 days ago


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Latest Games
Frif Pl Gry
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Ben 10 Treasure Hunter
Ben 10 is in hot pursuit of a mythical treasure that has been passed down for centuries. Help him finish his mission and escape from the mountain.
Kamikaze Blocks 2
There are more hungry Sky Creatures in Kamikaze Blocks 2 now with Antigravity! Test your puzzle solving skills with the power of advanced physics by...
Iron Man 2
Help Iron Man survive the tunnels, fight against a metal army. Then, kill the boss!
Kissing at the Mall
Stay on guard while these two teen lovebirds are having their romantic kissing sessions at the mall and see that they don't get spied!
Metal Slug Flash
This is an awesome "Metal Slug" clone, shooting game, where you've to infiltrate into the enemy territory and shoot down all the hostile guards that...
MegaMind Pinball
Funny little pinball flash game which is promoting the new movie Megamind 3D. Use arrows to launch the ball and trigger the paddles.
Bond 007 Agent Attack
Shoot the enemies as they pop up. Careful you can scroll left and right.
Age of War 2
Age of War 2 is a mix between a defense game and a strategy game. The goal is to destroy the enemy base while defending yours. You can build turrets...


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10 Steps to Pick the Right Doctor
Whether you need a primary care doctor or a specialist, these 10 steps will ensure you find the right doctor for you. View Slideshow
Dr. Mayer's Experience
- Gastroenterology
Board Certifications
- Gastroenterology
- Capsule Endoscopy
- Colonoscopy
- Colonoscopy, Proctosigmoidoscopy, and Sigmoidoscopy
- Colorectal Cancer Screening
- Endoscopy (Esophagus, Stomach, Small Intestine)
- ERCP (Endoscopic Retrograde Cholangiopancreatography)
- Esophageal pH Monitoring
- Gastroenterology Procedures
Conditions Dr. Mayer Treats
Dr. Mayer does not have any conditions listed. If you are Dr. Mayer and would like to add conditions you treat, please update your free profile.
Background Check for Dr. Mayer
0 Malpractice Claims
- No malpractice history found for California.
- No sanctions history found for the years that Healthgrades collects data.
0 Board Actions
- No board actions found for the years that Healthgrades collects data.
Awards & Recognitions
Education & Training
Medical School
- State University of New York At Buffalo
- Graduated in 2000
Internship Hospital
- Cedars Sinai Med Center
- Complete in 2001
Residency Hospital
- Cedars Sinai Med Center
- Complete in 2003
Fellowship Hospital
- University Of New Mexico Hospital
- Complete in 2006
Undergraduate Schools
- Williams College
- Graduated in 1993
Languages Spoken by Dr. Mayer & Staff
- English
- Spanish


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Senior Project Engineer
GM Powertrain
Ph. D.
University of Iowa
Meet the Contributors
www.powertrain-intl.com [cached]
Banks Chen
Inventec Corporation
Jed Chen
Ivory Capital Asia
Tsute Chen
International Association for Biological and Medical Research Inc
Suria Chen
Reggio Emilia Inspired School
Melody Chen
Vantage Point


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- 2-hour small-group walking tour of Kensington Market and Chinatown
- Learn about these two eclectic neighborhoods from your professional local guide
- Explore unique shops; visit historical sites; and admire stunning graffiti and street art
- Small-group size with a maximum of 12 people ensures a personalized experience
Recent Photos of This Tour
What You Can Expect
Customer Reviews
May 2016
Ask for Ted. He's THE BEST!!! Great tour...as simple as that!!!
April 2016
Mike was a great tour guide. He was very informative and knowledgeable about the area and its history. I would highly recommend this tour with Mike.
November 2015
We had a small 4 persons but very interesting group with an excellent tour guide: Mike. Mike lives in one of the neighborhoods we visited and knew the area history, local architecture, and many of the store owners. I can highly recommend this tour and Mike as a tour guide.
October 2015
I Very much enjoyed the tour of Kensington, and Chinatown, it was nice to have a small group o people.
the tour guide mike had a great deal of historical knowledge. learned a lot of local history and colour
well worth the time and money invested.
August 2015
Our tour guide Mike was very interesting! He gave us a lot of cultural and historical information about Chinatown and Kensington Market as well as fun commentary. Mike answered all of our questions and took whatever time we needed to fully investigate the sites on the tour. Wish we would have had more time to take additional tours.
July 2015
Our tour guide Michael was knowledgeable and very entertaining! We enjoyed the tour and would definitely recommend it to others.
June 2015
The tour guide did a very good job. It was interesting
August 2014
Me niece and I both enjoyed the tour! Interesting, fun, and well paced! Tour guide was friendly, well-spoken and informative.
July 2013
Very fun and knowledgable guide. Great area
September 2015
Good guide. Well informed, pleasant, good sense of humor, gave enough information without overload, very enjoyable


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A design pattern is a general reusable solution to a commonly occurring problem within a given context in software design. A design pattern is not a finished design that can be transformed directly into code. It is a description or template for how to solve a problem that can be used in many different situations. So patterns are formalized best practices that you must implement yourself in your application.


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All Posts Tagged Tag: 'Recipes'
Quinoa Tabbouleh: a Beautiful Fresh Herb Salad
Fresh herbs are the star in this fresh and tasty take on Tabbouleh made with quinoa and a splash of lime. Quinoa tabbouleh is simple to make and a great way to use the abundance of herbs that grow in the summer. It's a fresh side dish that gets better after it marinates for a few hours. Pick the herbs in the …Read More
Natural & Homemade Common Cold Remedies
These tried and true cold remedies really work! I have an adverse reaction to cold medication and some of the symptoms can really be a pain without some sort of relief. Many of them I have been using for years to get through cold and flu season, and I have honed them to help with the varied symptoms brought on …Read More
Low Carb & Gluten Free Zucchini Noodle Lasagna
The beauty of this lasagna is not just that it uses up all those extra zucchini that you are harvesting from the garden. It's not the nutty flavor the zucchini imparts, or the gorgeous colour. No, it's that this lasagna is grain-free and low carb, and you don't miss the noodles one bit! Zucchini noodles, aka zoodles, are my new …Read More
Olive and Fig Tapanade
Do you like the combination of salty a sweet? The addictive combination is incredibly popular for a reason. There is research to show that there are certain sweet taste receptors on our tongues that are activated only when sodium is also present. Whatever the reason, sweet and salty are SO FREAKING GOOD TOGETHER! While I'm not adverse to salted caramel …Read More
Garlicky Spinach and Kale Butter
Warning, this garlic bread made with spinach and kale butter is dangerously tasty! Gluten-haters don't be afraid, you can easily make this gluten-free by swapping out the bread with your preferred brand. No matter what bread you choose, you can pack in the greens and makes a new favorite side for dinner, especially when entertaining! This recipe isn't just to get …Read More
Mason Jar Recipes: Awesome Food in Jars
Remember way back when I wrote that I was addicted to mason jars? I showed this round up of 20+ Mason Jar Crafts and Gardening in Jars. That was just the first installment of my mason jar posts. If you thought that one had a lot of unique ideas for using mason jars, check out this list of recipes made in …Read More


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Click here to print the obituary below
J. Pittman JERNIGAN
JERNIGAN, J. Pittman, age 86, a lifelong resident Brooksville, Fla., passed from this life to his Eternal Home on February 12, 2013. Pittman graduated from Hernando High School and attended the
University of Florida
. Pittman was a
U.S. Navy
veteran of
and later was employed at Florida Rock and Hernando Concrete. He was a member of Eden Baptist Church for 75 years where he served as deacon and on the Eden Christian School Board, taught Sunday school and was a song leader for the choir. He was a family man, churchgoer and church leader and along with his wife Shirley, he volunteered with the Alachua Baptist Association. He dabbled in golf and hunting. He is preceded in death by his parents, Jay and Mary Snow Jernigan and sister, Leona Jernigan Sellers. He is survived by his sweetheart and loving wife: Shirley Jones Jernigan; daughter and son-in-law: Gege Jernigan and James Gornto; sons and daughters-in-law: Charles Pittman and Mahalley Jernigan; James Roy and Terrie Jernigan; siblings: Charlotte Jernigan Hypes, Max Jernigan, Nell Jernigan Austin, Mallory Jernigan and Patricia Jernigan McQuaig. He is Poppa to 5 grandchildren, Jensie Gornto Chetelat and her husband, Steven, Amber Jernigan Cameron and her husband Eric, Ashley Jernigan Gomes and her husband, John, Justin Roy Jernigan and his wife Alicia, Kevin Allen Jernigan. He has 9 great- grandchildren, Faithlyn, James and Carys Chetelat, Mackenzie Natale, Reagan and Noah Cameron, Johnny and Halley Gomes and Makenzie Jernigan; and many loving nieces and nephews. He was a faithful husband, loving father and doting grandfather. His great-grandchildren have brought him much joy. Pittman lived every day of his life as a testimony to his faith in the Lord Jesus Christ and would desire most to be remembered as a Christian in name and service. A celebration of his life will take place at 11:00 a.m., Tuesday, February 19, 2013 at Eden Baptist Church. Interment will follow at Lake Lindsey Cemetery. In lieu of flowers, donations may be made to Hernando-Pasco Hospice. Arrangements by Merritt Funeral Home, Brooksville Florida (352) 796-6699 "Family Owned and Operated" www.merrittfuneral.com
Funeral Home
Merritt Funeral Home and Crematory Brooksville Chapel
2 South Lemon Avenue
Brooksville, FL 34601
(352) 796-6699
Published in TBO.com on Feb. 17, 2013


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Dianshan Lake Winter Match Racing Regatta- An Uncalled-for Penalty
by China Boating Intelligence (CBI) on 29 Nov 2013
Briefing on the alternative rules of Match Racing. Mr Liu rearranges the Rules for the Dianshan Lake event China Boating Intelligence (CBI)
With the Monsoon Cup presently running in Kuala Terengganu, Asian sailors are getting an eyeful of match racing at the moment. And on that subject, here's a question from one of the spectators at the recent Dianshan Lake Winter Match Racing Regatta, 23-24 November: When is a penalty not a penalty?
'In one of the early matches, one boat sailed to leeward of the other, no room asked or given, and certainly no 'Y' flag from either team. This was confirmed by one of the other people on the umpire boat. So imagine this viewer's surprise when suddenly a blue flag shot up on the umpire boat.
(The Dianshan Lake Regatta organisers claimed that the rules were the same as the China Club Challenge Match (CCCM) run just two weeks earlier, with the event 'managed by a referee (sic) from the CCCM').
On coming ashore a rightly aggrieved Shanghai Airport team asked 'why the penalty when there was no Y flag?' to be told by Mr Liu QiDong that 'If neither boat raises a flag in a boat-on-boat situation then the umpires can give a penalty if they think there should be one.' When it was suggested that this wasn't the case, Mr Liu informed the team that the rules had changed with the 2013 update'.
Sorry, Mr Liu, but as one of the bloggers suggested on Chinese Weibo social media site, you must have a cheap Chinese copy of the Racing Rules of Sailing! The RRS 2013-2016, Appendix C Rule C6.5(A) clearly states 'After flag Y is displayed, the umpires shall decide whether to penalize any boat.' In other words the umpires cannot penalize a boat-on-boat incident without a 'Y' flag. We checked with an America's Cup jury member, as well as a former member of the ISAF Rules Committee, both of whom agree that this is a very basic error and is clearly in conflict with the fundamental umpiring concept of 'No Flag – No Foul'.
They also clarified that an umpire can give a penalty on certain occasions, including contact with a mark (Rule 31), illegal propulsion (Rule 42), starting errors (in other words being in the box early or not over the start line at two minutes to go), and finally non-compliance with either a second existing penalty or a red flag penalty. In all other cases the aggrieved boat must fly a 'Y' flag before a penalty can be given.
Background info: Race Management was led by Lu QiDong, know in English as 'Tony, who had indeed been a Race Officer of the CCCM in the past, which involved him setting the course and raising and lowering flags - but at no time had he umpired a match in the event.
In fact, such was his performance at the Club Cup that, as the event grew, he was not up to the task and a number of years ago he was replaced even in his relatively minor role. This replacement roughly coincided with Lu QiDong being 'dropped' by the CYA (Chinese Yachting Association) after a 470 sailor died during an event at which he was Principal Race Officer.
At the Dianshan Regatta skipper's briefing Mr Lu declared that no boat was allowed into the 'box' before four minutes – the actual rule states that they must be 'outside the box AT four minutes' which any match racer knows is more than a small difference.
We would like to believe that the organizers simply believed what they were told by Lu QiDong, but when they were informed that his claim of experience was clearly untrue they declined to issue a correction to potential competitors.
It is sad that someone who obviously doesn't understand the rules to a basic level should use the name of China's top match racing event (the China Club Challenge) to further their own ends at the expense of competitors who entered this local event in good faith.
Alistair Skinner, who has been part of the umpire team of the China Club Challenge Match for each of the past seven years, confirmed that Mr Lu QiDong has never umpired any match at this event (which next year reaches its 10th birthday). Additionally, Mr. Skinner resents the reputation for accuracy and fair play that the Club Cup has built up over the years being abused for personal gain by an individual in this manner, and is concerned by the potential damage to the Club Cup's reputation by such a poorly policed event claiming to be run by the same team, which it clearly wasn't.
On the other hand, perhaps when sailors sit back and compare the two events it will only serve to further boost the already high reputation of the China Club Challenge Match.
[For the record, the author of this story was NOT part of the team incorrectly penalised. Ed]
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|Publication number
|Publication type
|Application number
|Publication date
|Jul 13, 2004
|Filing date
|Oct 9, 2001
|Priority date
|Oct 9, 2001
|Fee status
|Also published as
|Publication number
|David J. Chaiko
|Original Assignee
|The University Of Chicago
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (24), Non-Patent Citations (6), Referenced by (11), Classifications (11), Legal Events (9)
|External Links: USPTO, USPTO Assignment, Espacenet
The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the United States Department of Energy and the University of Chicago representing Argonne National Laboratory.
This invention relates to liquid crystalline compositions comprised of phyllosilicates and polymers. More particularly, this invention relates to liquid crystalline compositions for use in barrier applications.
It is common practice to blend materials such as mica, talc, kaolin, precipitated calcium carbonate, precipitated silica, fumed silica, barite, zinc oxide, carbon black, etc. into elastomeric, thermoset, and thermoplastic polymers. Inorganic fillers are added as high as 40 to 50 weight percent. The addition of minerals to polymers can improve properties such as strength, stiffness, temperature and impact resistance, dimensional stability, and scratch resistance. In conventional mineral/polymer composite materials, the mineral phases are dispersed within the polymer matrix at the micrometer scale.
Much interest has been created by the more recent advance of producing nanocomposites. Nanocomposites—nanometer sized dispersions of organophilic clays in polymers to form polymeric hybrids—have been demonstrated to produce dramatic improvements in mechanical properties, heat resistance, thermal stability, and reduced gas permeability of the base polymer without loss of impact strength. Due to their enhanced barrier properties and clarity, nanocomposites are well suited for use as gas transport barriers in packaging applications. Examples include nylon-based nanocomposites for food and beverage packaging which incorporate the nanocomposite layer within single or multi-layer films. Reduction in gas diffusion is attributed to the presence of the clay particles which act to increase diffusion path length. Current nanocomposites characteristically contain small amounts of phyllosilicates dispersed in the base polymer, typically six percent or less, producing overall improvements in reduction of gas transfer that can be calculated from simple diffusion theory and which depend on the generation of a tortuous diffusion path originating from the presence of the dispersed organoclay. A major impediment to the commercial development of nanocomposites has been the difficulty of producing homogenous dispersions of organoclays within the polymer matrix. To improve the affinity between the hydrophilic clay surface and organic polymers, clays are treated by cation exchange with high-molecular-weight onium salts (e.g., ammonium, phosphonium, and sulfonium). However, even with surface treatment, phyllosilicates can still only be dispersed at the nanoscale into polymers that contain polar functional groups. The presence of these polar functional groups makes high barrier polymers, such as PET, EVOH, and Nylon, sensitive to water, thus requiring their use as multiplayer laminates which contain an external, water-barrier layer. The requirement of multiplayer laminates thus increases manufacturing costs of flexible packaging films.
Accordingly, there is a continuing need to provide low cost materials which provide superior barriers against gas transport and diffusion.
One embodiment of the present invention provides a phyllosilicate-polymer composition comprised of a phyllosilicate and a polymer layer adsorbed onto the basal surface of the phyllosilicate providing a phyllosilicate-polymer composition. In the phyllosilicate-polymer composition the phyllosilicate-polymer composition is present as a single phyllosilicate-polymer phase and exhibits an anomalous basal spacing. Preferably a sufficient proportion of exchange sites on the basal surface of the phyllosilicate are substantially occupied by protons. In other embodiments of the invention the polymer has at least one hydroxyl group and can be selected from the group consisting of polyethylene glycol, polypropylene glycol and their monoalkyl ether derivatives. Still other embodiments of the invention provide phyllosilicate-polymer compositions wherein the polymer comprises greater than 27 weight percent of the phyllosilicate-polymer composition, the basal surface of the phyllosilicate is bound substantially with hydrogen ions or the basal spacing of the phyllosilicate-polymer composition increases as the molecular weight of the polymer increases. In yet another embodiment, the basal spacing of the phyllosilicate-polymer composition is equal to or greater than 17.8 Å.
Still another embodiment of the present invention provides an anisotropic liquid crystalline composite comprising a phyllosilicate-polymer composite made of at least a phyllosilicate, and a polymer adsorbed onto the basal surface of the phyllosilicate. In this embodiment the phyllosilicate-polymer composite has a highly ordered, well-defined basal spacing and the phyllosilicate-polymer composition is birefringent. Other aspects of this embodiment of the invention include a nematically oriented phyllosilicate in the phyllosilicate-polymer composition. In this embodiment, the phyllosilicate can make up greater than 10 percent of the phyllosilicate-polymer composite. Typically, the phyllosilicate is selected from the group consisting of kaolins, talcs and montmorillonites and the polymer is water soluble. In another embodiment the polymer can be hydrophobic, such as polyethylene. The anisotropic liquid crystalline composite of this embodiment can further comprise an antioxidant. In still another embodiment of the invention the anisotropic liquid crystalline comprises a barrier layer such that the barrier layer provides a gas permeability below the gas permeability of the polymer alone.
The present invention also provides methods for producing an anisotropic liquid crystalline composite from a phyllosilicate and a polymer. The method can include the steps of suspending a phyllosilicate in a compatible solvent, dissolving a polymer that is soluble in the compatible solvent, and removing a sufficient amount of the compatible solvent to produce an anisotropic liquid crystalline composite. In the method the solvent can be water and the polymer polyethylene glycol. The method can further include the step of purifying the phyllosilicate prior to suspending the phyllosilicate in the compatible solvent. The method can provide an anisotropic liquid crystalline composition comprising between about 10 and 70 percent phyllosilicate. The method also provides composites which are extrudable and useful as gas barrier layers.
In yet another embodiment of the present invention, a barrier film for use in packaging and coating applications is provided having reduced gas permeability. The barrier film comprises an anisotropic liquid crystalline composite layer having a gas permeability below the permeability of the polymer alone. Typically the film is transparent and is comprised of a phyllosilicate and a polymer or a combination of polymers. The phyllosilicate can make up greater than ten percent by weight of the liquid crystalline composite layer. The barrier film of the present invention can also be incorporated into other films as a barrier layer to form a multilayer film. As a non-limiting example, the liquid crystal composite can be blended with polyethylene to impart water barrier properties and improve extrusion properties.
The above described embodiments are set forth in more detail in the following description and illustrated in the drawings described hereinbelow.
The preferred exemplary embodiment of the invention will hereinafter be described in conjunction with the appended drawings, wherein like numerals denote like elements and:
FIG. 1. Basal spacing as a function of polymer loading in liquid crystal composites containing polyethylene glycol.
FIG. 2. X-ray diffraction pattern of sodium exchanged saponite admixed with polyethylene glycol at a ratio of 1 g polymer per 1 g of clay.
FIG. 3. X-ray diffraction pattern of a liquid crystalline composite containing 50 weight percent polyethylene glycol.
FIG. 4. A differential scanning calorimetry plot of a liquid crystalline composite containing 27 weight percent polyethylene glycol and a basal spacing of 17.3 Å.
FIG. 5. A differential scanning calorimetry plot of a liquid crystalline composite containing 50 weight percent polyethylene glycol and showing a melt transition at approximately 50� C. and a freezing transition at approximately 15� C.
FIG. 6. X-ray diffraction pattern of a liquid crystalline composite containing 50 weight percent LAPONITE� clay and 50 weight percent polyethylene-block-polyethylene glycol.
The present invention provides liquid crystal composites comprised of phyllosilicate-polymer compositions and methods of making the liquid crystal composites. Liquid crystal composites of the present invention can contain minimal amounts of on the order of one percent or less by weight, up to about 70% phyllosilicate by weight. The technique utilized in the present invention involves intercalating a polymer within the galleries of a phyllosilicate which is preferably a purified clay material. Examples of suitable clay minerals include: kaolins, talcs, saponites and montmorillonites as non-limiting examples. Intercalation of the polymer within the phyllosilicate can occur according to several methods. As will be well understood by one skilled in the art, phyllosilicates inherently have basal surfaces and are arranged in layers of phyllosilicate particles which are stacked on top of one another. The stacking of the phyllosilicates provides interlayers or galleries between the phyllosilicate layers. These galleries are normally occupied by cations, typically comprising sodium, potassium, lithium, calcium, magnesium ions and combinations thereof, that balance the charge deficiency generated by the isomorphous substitution within the phyllosilicate layers. Typically, water is also present in the galleries and tends to associate with the cations. The distance between the basal surfaces of adjacent phyllosilicate layers is referred to as the basal spacing.
A preferred method involves dispersing the phyllosilicate in a compatible solvent, dispersing or dissolving the polymer in the compatible solvent and then removing enough of the solvent to produce a liquid crystalline composite of phyllosilicate and polymer. Compatible solvents as used in the present invention mean solvents, either neat or in admixtures, in which the phyllosilicate and polymer is capable of being dispersed or suspended and preferably solvents in which the polymer is soluble. The preferred solvent according to the present invention is water, although other solvents in which phyllosilicates and polymers can be dispersed are suitable for use in the present invention. Accordingly, preferred polymers can be water soluble or not soluble in water. Preferred polymers also have at least one hydroxyl group. After the solvent is removed, the phyllosilicate-polymer mixtures produce a self-assembled liquid crystal structure. Typically, the phyllosilicate is nematically ordered within the liquid crystalline composite. Surprisingly and unexpectedly, liquid crystalline composites provide excellent resistance to gas transport. With proper modification, the liquid crystalline compositions of the present invention can be made to be extrudable, their water sensitivity can be adjusted, and by incorporating the proper functionality, can be made to function as both a barrier layer and as an adhesive material for multilayer laminates and films.
Without limiting the scope of the invention, it has been surprisingly found that polymer intercalation to levels sufficient to increase the gallery spacing to at least 19 Å produces composites that are extrudable. Water sensitivity of the liquid crystalline composite can be reduced by co-adsorption of ethylene-co-acrylic acid polymers. Ethylene-co-acrylic acid polymers with at least 15-20% acrylic acid content are water soluble and under low pH conditions bond directly to the phyllosilicate surface. A high degree of water resistance can be achieved by inhibiting the neutralization of the acid functionality to less than about 3%.
Another method for intercalating a polymer within the galleries of the phyllosilicate involves mixing the phyllosilicate and the polymer together and then heating the phyllosilicate-polymer mixture to a temperature above the melting temperature of the polymer. According to this method the polymer intercalates into the galleries of the phyllosilicate thus producing a liquid crystalline composite.
The liquid crystalline composite formed by the intercalation of the phyllosilicate with the polymer can itself be intercalated with a second polymer, such as polyethylene or modified polyethylene, to form a liquid crystalline composite comprising more than one polymer intercalated within the galleries of the phyllosilicate. Alternatively, two or more polymers can be mixed with the phyllosilicate in the initial step of forming the liquid crystalline composite and then heated to a temperature above the melting temperature of the polymer. Utilizing additional polymers in the liquid crystalline composite can impart desirable properties to the liquid crystalline composite including water resistance, extrudability and adhesive properties.
The present phyllosilicate-polymer liquid crystal composites can be used as ultra-high-barrier films for packaging and coatings applications in the form of either extrudable liquid crystalline composites or as cast, thin-film liquid crystalline composite applied to a substrate, preferably a polymeric substrate (e.g. PET). Liquid crystalline composites, preferably exhibiting a nematic structure and containing high concentrations of clays, offer greater resistance to gas diffusion due to very high concentrations of overlapping, impermeable clay platelets. The clay concentrations within the liquid crystalline composite are in one embodiment in the range of 10 to 70 weight percent, and in other embodiments 10 to 30, 30 to 50 or 50 to 70 weight percent depending upon the application in which the liquid crystalline composite is used. The barrier layers of the present invention provide resistance to gas permeability which is greater than the gas resistance of the base polymer alone. Preferably, the barrier layers of the present invention provide gas resistance which is 1.5 times or more than the base polymer. More preferably, the barrier layers provide resistance to gas diffusion ranging from about ten times greater and up than the base polymer. Most preferably, the barrier layers provide gas resistance that is from about 1,000 to about 1,000,000 times greater when compared to barrier layers made of the base polymer without the phyllosilicate.
A particularly interesting class of liquid crystalline composites can be prepared from purified smectites onto which low-molecular-weight polyethylene glycols are adsorbed at concentrations in excess of 27 weight percent, although the present invention is not limited to such compositions. These liquid crystalline composites are synthesized by adding water-soluble polymers to an aqueous suspension of a phyllosilicate. Removal of the water to less than about 2 weight percent moisture produces self-assembled nematic liquid crystalline composites. Surprisingly and unexpectedly, a liquid crystalline composite containing greater than 27 weight percent polymer, and in particular polyethylene glycol, can be produced which exhibits a single phyllosilicate-polymer phase and is a liquid crystalline composite. This is in contrast to published studies in which polymer loading in excess of 27 weight percent produced two phases—a simple admixture of a polymer-phyllosilicate phase and a crystalline polymer phase. As described below, the single-phase liquid crystalline composites of the present invention containing about 30 to 70 weight percent polymer exhibit unique properties which make them prime candidates for the manufacture of cast and extruded films. Liquid crystalline composites for use in the production of cast and extruded films include those composites which contain 30 to 40 weight percent polymer, 40 to 50 weight percent polymer, 50 to 60 weight percent polymer and 60 to 70 weight percent polymer. Because of their ordered structure, these liquid crystalline composite materials are expected to exhibit excellent resistance to the transport of gases, and in particular oxygen and carbon dioxide, making them good candidates for barrier and packaging applications. In order to mitigate their sensitivity to water vapor, the liquid crystalline composites would be preferably be incorporated as a thin, barrier layer within multi-layer films. These multi-layer films can be produced by attaching a cast film to other polymeric layers or through coextrusion. In an alternative embodiment of the present invention, hydrophobic polymers, such as polyolefins, can be intercalated into the liquid crystal composite to produce a composite which is water resistant. The polyolefin is preferably used in combination with water-soluble polymers and/or coupling agents such as PEG-based surfactants. Preferred hydrophobic polymers include polyolefins, and in particular polyethylene and modified polyethylene. Intercalating a hydrophobic polymer into the galleries of the phyllosilicate can produce a liquid crystalline composite which is hydrophobic and extrudable.
Without limiting the scope of the present invention, it is believed that a single phyllosilicate-polymer phase can be achieved by loading greater than 27 weight percent polyethylene glycol onto a basal surface of the phyllosilicate through adsorbtion the polymer as an oxonium cation. However, the phyllosilicate-polymer compositions of the present invention do not depend upon the proposition that the polymer is adsorbed onto the phyllosilicate as an oxonium ion.
The attachment of polyethylene glycol according to the present invention, theorized to be through oxonium ion exchange, offers a unique method of achieving higher than normal polyethylene glycol loading. A comparison of x-ray diffraction patterns in FIGS. 2 and 3 illustrate the difference between polymer adsorption via ion dipole interaction and the proposed oxonium cation exchange. FIG. 2 shows the x-ray diffraction pattern of a sodium-exchanged saponite admixed with 50 weight percent polyethylene glycol. It displays the expected d(001) spacing of 17.8 Å. However, the diffraction pattern also shows diffraction peaks at 4.63 and 3.83 Å which correspond to a crystalline polyethylene glycol phase. In other words, the admixture is comprised of two discrete phases—a clay/polymer intercalate containing 27 weight percent polymer and a separate crystalline polymer phase not associated with the clay. The x-ray diffraction pattern of the oxonium-exchanged clay containing 50 weight percent polyethylene glycol is shown in FIG. 3. Aside from basal reflections, it does not show diffraction peaks for a crystalline polymer phase. This indicates the existence of only one phase—a clay/polymer intercalate containing 50 weight percent polyethylene glycol.
Published x-ray data indicate that a complete monolayer of polyethylene glycol expands the basal spacing of sodium exchanged smectite clays from 9.5 Å to 17.8 Å. This 8.3 Å increase corresponds to the formation of a double layer structure residing between adjacent clay platelets and thereby indicating a monolayer depth of approximately 4 Å. The 4.0 Å spacing is in agreement with the width of a hydrocarbon chain. Therefore, the intercalates with greater than 17.8 Å spacing contain polyethylene glycol in excess of a monolayer. Without limiting the scope of the invention, the unusually high adsorption density is believed to be driven by solvation of the adsorbed hydrogen ion by polyethylene glycol via formation of oxonium cations at the clay surface. An ion exchange mechanism would produce basal spacings that are dependent upon the molecular weight of the polymer in agreement with experimental data.
Differential scanning calorimetry (DSC) measurements of liquid crystalline composites containing 27, 34, and 50 weight percent polyethylene glycol were conducted to gain further insight into the physicochemical properties of the liquid crystalline composites. FIG. 4 shows the DSC scan for the liquid crystalline composite exhibiting a d(001) spacing of 17.3 Å and produced by oxonium exchange. A melting transition at 43 to 45� C. for the polyethylene glycol (molecular weight of 1500) is notably absent, indicating that the adsorbed polymer is distinctly different from a discrete bulk phase. The scan does, however, show a decomposition endotherm at approximately 215� C. For reference, the decomposition temperature for polyethylene oxide/clay intercalates in an inert atmosphere is approximately 360� C. Without limiting the scope of the invention, the lower decomposition temperature for the liquid crystalline composite is believed to be due to the enhanced molecular motion of the polymer chains that occurs upon melting of the two-dimensional crystal phase located within the clay galleries. This clay, when sodium exchanged and containing 27 weight percent polyethylene glycol, showed the expected decomposition temperature of 360� C.
The DSC data for the liquid crystalline composites containing 32 and 50 weight percent polymer were identical and displayed a reproducible melting transition at approximately 50� C. (the DSC profile for the liquid crystalline composite containing 50 weight percent polymer loading is shown in FIG. 5). These data indicate that the polymer in excess of a monolayer behaves like a discrete, two-dimensional crystalline polymer phase (i.e., displays a melting transition) but the x-ray data indicate that all of the polymer is attached to the basal surface of the clay and therefore does not display a 3-dimensional x-ray diffraction pattern. Note that the observed melt transition of 50� C. is approximately 5-7� C. higher than that of pure polyethylene glycol with identical molecular weight (e.g., 1500). This increase in melt transition has been observed with other polymer systems in confined geometries. Accordingly, the polymer chain segments which undergo a melting transition could produce a lubricating zone thereby enabling the clay platelets to slide past one another under pressure. This would permit extrusion of liquid crystalline composites at temperatures above the melting point (i.e., 50� C.) but below the decomposition point. The decomposition temperature can be increased by extruding in an inert atmosphere and/or by adding an antioxidant to the liquid crystalline composite. Typical antioxidants used to prevent polymer degradation are phenols (e.g., 2,4-Di-t-butyl-4-methylphenol) and aromatic amines (e.g., N,N′-Bis(1-methylheptyl)-p-phenylenediamine).
The film extrusion temperatures of typical packaging polymers such as polyolefins (e.g., polyethylene and polypropylene) and polyethylene terephthalate (PET) are 190� and 280� C., respectively. With the addition of an antioxidant to the liquid crystalline composite it should be possible to co-extrude laminates with polyolefins and PET.
Alternatively, with incorporation of polyethylene glycol based surfactants (e.g., polyethylene-block-polyethylene glycol or polypropylene-block-polyethylene glycol), it is possible to produce extrudable liquid crystalline composites with reduced water sensitivity. Because of their superior characteristics, these materials could be used in single-film barrier applications. The liquid crystalline composites of the present invention are also dispersible in polyolefins making it possible to produce conventional nanocomposites with clay contents of 3-10 weight percent.
Another unexpected feature of the liquid crystalline composites of the present invention is that these phyllosilicate-polymer composites, which have relatively high, typically greater than ten weight percent, phyllosilicate content are transparent. Thus, the liquid crystalline composites of the present invention (provided the resin itself is transparent) are highly desirable in packaging applications. Until now, it has not been possible to produce transparent liquid crystalline composites containing clay minerals at concentrations of ten weight percent or more, especially with extrusion processes.
All references cited herein are hereby incorporated by reference.
Non-limiting examples which further illustrate the properties of the clay-based liquid crystalline composites are provided below.
This example demonstrates that polyethylene glycol polymer can be loaded at greater than 27 weight percent and still exhibit a single phyllosilicate-polymer phase. Using a Ca-saponite, twenty-seven percent by weight (i.e., 0.27 g of polyethylene glycol per g of clay) was adsorbed onto the basal surface of the saponite by suspending the saponite particles in water, dissolving the PEG in the water and substantially removing the water to form the phyllosilicate-polymer composition. This clay-PEG composition showed an anomalous basal spacing [d(001)], exhibiting a d(001) spacing of 13.6 Å instead of the expected 17.8 Å. As used in the present invention, the phrase "anomalous basal spacing" is used to mean a basal spacing which substantially differs from the basal spacing exhibited by a Wyoming montmorillonite coated with a monolayer, 27 to 30 weight percent, of polyethylene oxide. The polymer loading was verified by Loss on Ignition measurements. The fact that the dried organoclay did not readily disperse in water suggests that the polymer coating was actually less than a monolayer despite the 27 weight percent loading. Sodium exchange improved the colloidal stability of the clay and increased the d(001) spacing to near the expected 17.8 Å. Based on these results it is believed that the presence of hydrogen ions in the exchange sites of the clay caused some of the polyethylene glycol to adsorb onto the clay surface as an oxonium cation rather than through normal ion-dipole interactions between the polymer and the exchangeable cations at the clay surface. This hypothesis is supported by observations that oxonium cation formation by polyethylene glycols has been reported in the solvent extraction literature (J. Rais, E. Sebestova, and M. Kyrs, "Synergistic Effect of Polyethylene Glycols in Extraction of Alkaline Earth Cations by Nitrobenzene," J. Inorg. Nucl. Chem., 38, (1976) pp. 1742-1744). This mechanism of adsorption also offers a plausible explanation for the anomalous d(001) spacing. Without limiting the scope of the invention, it is believed the oxonium cation is produced by protonation of the terminal hydroxyl groups of the polyethylene glycol which are stabilized by formation of a five member ring through hydrogen bonding to the terminal ether oxygen. Loss of hydrated metal ions in the exchange positions on the clay surface would explain the anomalous basal spacing since the volume that would otherwise be occupied by the metal cations now becomes unoccupied.
To test the hypothesis of oxonium cation adsorption, a different saponite was purified using the pseudophasic extraction process described in U.S. patent application Ser. No. 09/532,728 filed on Mar. 22, 2000, incorporated herein by reference. The purified clay was then treated with a cation-exchange resin in the H+ form to replace the Na+ and Ca++ on the clay surface with H+. Varying amounts of polyethylene glycol were then added to aliquots of the clay slurry as described above. The samples were dried overnight at 100� C. producing translucent, birefringent liquid crystalline composite films. The x-ray diffraction patterns were measured to determine the d(001) spacing as a function of polymer loading. The data in FIG. 1 show a plateau in d(001) values at about 19.2 Å and correspond to a polymer loading of about 50 weight percent. This is in contrast to literature data showing a maximum d(001) spacing of 17.8 Å at 27 weight percent polyethylene glycol loading. The 17.8 Å spacing at a polymer loading of 27 to 30 weight percent has been reported in the literature to be independent of polymer molecular weight for all smectites that have been studied. In contrast, oxonium ion exchange produces a basal spacing that increases with increasing polymer molecular weight. These results clearly indicate the importance of hydrogen ion concentration in the clay exchange positions on polymer adsorption behavior. Thus, phyllosilicates which have either a naturally high hydrogen ion concentration in the exchange positions or which have been altered through cation exchange to provide a high hydrogen ion concentration are useful in the present invention.
This example demonstrates the excellent oxygen barrier properties of a cast liquid crystalline composite film. A cast liquid crystalline composite film was prepared by drying an aqueous slurry containing approximately 3 weight percent sodium montmorillonite having a monolayer coating of polyethylene glycol (molecular weight 1500) at the ratio 0.27 g polymer per g of clay. The slurry was dried at room temperature producing a flexible film approximately 50 μm thick. Oxygen transport across the film was measured at a relative humidity of zero percent. Oxygen permeability was below detection (i.e. 3�10−20 mol/msPa).
The enhanced barrier performance is significantly greater than that expected if the clay platelets merely increased the tortuosity factor and hence the total path length of diffusing oxygen. The reported oxygen permeability for polyethylene oxide is 2�10−14 mol/msPa. While the estimated tortuosity factor of the liquid crystalline composite is 20-40 the oxygen permeability in the liquid crystalline composite is reduced by more than 650,000 fold over that of polyethylene oxide.
This example illustrates the preparation of an extrudable liquid crystalline composite by using a surfactant to plasticize the polyethylene glycol/clay composite. A commercial hectorite (Bentone MA) was purified using the pseudophasic extraction technique. The aqueous slurry, containing approximately 3 weight percent organoclay, was treated with a cation exchange resin to convert the organoclay into the H+ form. The treated slurry was combined with polyethylene-block-polyethylene glycol and heated to 120� C. for 1-5 h to remove water. The final product contained approximately 5 weight percent clay, 2 weight percent polyethylene glycol, and 93 weight percent polyethylene-block-polyethylene glycol. The extremely large amount of surfactant (polyethylene glycol/polyethylene copolymer) used in this example illustrates the ability of the water-dispersed organoclay to adsorb the polymeric surfactant to levels that are well beyond a monolayer coating and to maintain the clay platelet spacing greater than 17.8 Å even after water removal. This is in contrast to the polyethylene glycol (similar molecular weight to the polymeric surfactant) liquid crystalline composites of FIG. 1 which exhibit a plateau in the d(001) spacing of about 19 Å. X-ray analysis of the product showed an absence of basal reflection. The birefringent solid was extrudable at 120� C., producing a clear, colorless film. The birefringence is evidence of a liquid crystal structure, however, the spacing between the clay platelets is beyond the resolution of the laboratory defractometer (i.e., −35 Å).
This example illustrates the direct production of a liquid crystal film from a highly concentrated aqueous suspension. A Wyoming montmorillonite was purified according the pseudophasic extraction process as follows The clay feed was dispersed in hot tap water at 40� C. for 15 min., and the ammonium salt of the dispersant Dequest 2010 (a product of Solutia) was added to complete the dispersion of the ore. The amount of dispersant added was 3 wt % relative to the weight of the clay. Poly(ethylene glycol) with a molecular weight of 1500 was added to the aqueous dispersion at a concentration of 30 wt % relative to the weight of the clay. The amount of poly(ethylene glycol) added was sufficient to produce a monolayer coating on the basal surfaces of the exfoliated clay particles. After mixing for 30 min., the slurry was passed through a decanting centrifuge to remove mineral impurities and unexfoliated clay. The surface of the hydrophilic clay composite was further modified to reduce the surface HLB by adding a sufficient amount of the ammonium salt of an ethylene acrylic acid copolymer (Michem� Prime 4990R) to produce a final clay/polymer ratio of 60/40. After mixing for 30 min., an amount of poly(ethylene oxide) with a molecular weight of approximately 6,000,000 was dispersed in deionized water and added to the slurry at a concentration sufficient to produce a final concentration of 1 wt % relative to the weight of the clay. The solids were flocculated by reduction of the slurry pH to about 3 with concentrated sulfuric acid. The excess water was decanted and the clay/polymer composite was washed with fresh tap water. When the material was rapidly dried in the form of a sheet with a hot air dryer it produced a flexible, transparent, and colorless liquid crystal composite that was hydrophobic and which could be folded and creased without breaking. This is an example of polymer adsorption through an oxonium ion that was generated by an ion exchange process after the polymer had already been adsorbed to a clay surface which was originally in the sodium form.
This example illustrates the preparation of an extrudable liquid crystalline composite containing approximately 50 weight percent clay. The purified H-ion exchanged saponite slurry of Example 2 was combined with polyethylene-block-polyethylene glycol (melting point 106� C.) and heated to 120� C. in a sealed Teflon vessel for 1.5 h. The product slurry was then dried at 100� C. yielding an liquid crystalline composite composition of 50.9 weight percent clay, 18.3 weight percent, polyethylene glycol, 30.8 weight percent polyethylene-block-polyethylene glycol. The liquid crystalline composite produced a clear, colorless film when pressed at 120� C. and 10,000 psi.
This example illustrates the preparation of a liquid crystal composite whose surface HLB value is modified by adsorption of a polymeric surfactant thereby making it extrudable when dispersed in hydrophobic polymeric systems such as poly(ethylene), poly(propylene) and various copolymers containing a polyolefin. A Wyoming montmorillonite was purified using the pseudophasic extraction method. The clay was dispersed in hot tap water at 40� C. for 15 min., and the ammonium salt of the dispersant Dequest� 2010 (a product of Solutia) was added to complete the dispersion of the montmorillonite. The amount of dispersant added was 3 wt % relative to the weight of the clay. Poly(ethylene glycol) with a molecular weight of 1500 was added to the aqueous dispersion at a concentration of 30 wt % relative to the weight of the clay. The amount of poly(ethylene glycol) added was sufficient to produce a monolayer coating on the basal surfaces of the exfoliated clay particles. After mixing for 30 min., the slurry was passed through a decanting centrifuge to remove mineral impurities and unexfoliated clay. The surface of the hydrophilic clay composite was further modified to enable dispersion in hydrophobic systems by adding a sufficient amount of the ammonium salt of an ethylene acrylic acid copolymer (Michem� Prime 4990R) to produce a final clay/polymer ratio of 60/40. A dry product was obtained by spray drying the slurry to a final moisture content of less than 2 wt %. The solids content of the slurry fed to the spray dryer was approximately 9.5 wt %. The highly purified state of the clay was demonstrated by the fact that the material produced a transparent film when dried.
This example illustrates the direct intercalation of polyethylene-block-polyethylene glycol (mw=1400) melt in a synthetic hectorite (i.e., LAPONITE� clay). The LAPONITE� clay and surfactant were blended at a 1:1 weight ratio, pressed into a pellet at 10,000 psi and heated to 125� C. for 1 h. This temperature is above the melting point of the surfactant which is 106� C. Expansion of the clay layers due to intercalation of the surfactant caused the monolith to crumble. The powder was repressed at 10,000 psi and heated to 125� C. for 16 h. The X-ray diffraction pattern shown in FIG. 6 exhibits a diffuse band of d(001) spacings beginning at approximately 17 Å and extending beyond the resolution of the defractometer (i.e., −38 Å). The X-ray diffraction pattern of the liquid crystalline composite of this example is shown in FIG. 6.
The intercalation of the organic coating in examples 7 and 8 probably do not involve the proposed oxonium ion formation since the clay was in the sodium form. Accordingly, the present invention is not limited to phyllosilicate-polymer compositions which exhibit anomalous basal spacing. Intercalation of smectites with polymeric surfactants provides a direct route to the production of polyolefin-clay nanocomposites without the use of amine-based surfactants. Unlike the quaternary amine-based surfactants, which readily decompose via Hofmann elimination at 125� C. or higher, the polyethylene glycol-based surfactants exhibit melting points well below their decomposition points. Under anoxic conditions, the decomposition of polyethylene glycol, when intercalated within clay galleries, does not occur until approximately 360� C. In addition, the polyethylene glycol-based surfactants produce colorless intercalates and composites even at clay concentrations as high as 50-70 weight percent as opposed to quaternary amine-based materials which are generally yellow to brown due to amine degradation.
As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as "up to," "at least," "greater than," "less than," and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above.
While preferred embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the invention in its broader aspects as defined in the following claims.
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|Citing Patent
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|U.S. Classification
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|International Classification
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|European Classification
|Feb 8, 2002
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