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Superhero Bits: Guardians of the Galaxy, Doc Savage, Avengers: Age of Ultron, X-Men: Days Of Future Past
Posted on Wednesday, September 18th, 2013 by Germain Lussier
What has Gwyneth Paltrow heard about Iron Man 4 and Avengers: Age of Ultron? When is Thor: The Dark World coming to Disneyland? Does Shane Black have an update on Doc Savage? Want to see a new behind the scenes image from X-Men: Days of Future Past? Is Michael Rooker enjoying Guardians of the Galaxy? Is that film's IMDB page accurate? Why does Chris O'Donnell have the script to Batman vs. Superman? Who is the new lead of Spider-Man: Turn Off The Dark? Read about all this and more in today's Superhero Bits. Read More »


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Pocket Timeline of Islamic Civilzations
written by Nicholas Badcott
British Museum Press | ISBN 9780714131337
Hardback – 32 pages
Member's price: $14.36
Usually ships within 2–11 business days.
At the back of the book is a 12-page foldout timeline which can be detached and displayed on a wall or noticeboard, offering an attractive quick visual reference to the key periods, events and developments of Islamic civilizations from approximately the 7th to the 19th centuries AD. The 32-page book offers introductions to each of the periods and dynasties, with short sections on particular themes and on the great achievements of Islamic art and culture over the centuries. Both book and timeline are richly illustrated throughout with colour photographs, including numerous objects from the British Museumas collections.
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subset: commoncrawl


text:
Several sixth-graders from suburban St. Louis are being disciplined for creating "Hit a Jew Day" and then hitting Jewish classmates.
Four or five students at Parkway West Middle School in Chesterfield could be suspended and undergo counseling for last week's incident, school officials told the Associated Press. Others who taunted Jewish students or encouraged others to participate face lesser punishment.
Officials said fewer than 10 of the school's 35 Jewish students were hit. One was slapped in the face and the others were hit mostly on the back of their shoulders…
It began with an unofficial "Spirit Week" among sixth-graders that started harmlessly enough with a "Hug a Friend Day." Then there was "High Five Day."
Soon, though, the days moved from friendly to silly. Next there was "Hit a Tall Person Day" and, finally, "Hit a Jew Day."
Principal Linda Lelonek told the St. Louis Post-Dispatch she learned about the incidents Monday and called an assembly Tuesday morning.
"What's tomorrow going to be? 'Hit A Principal Day?'" she asked.
Yeah. Because 'Hit a Principal Day' would be so much worse, wouldn't it, Ms. Lelonek?


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Each year's Horizon Report, the result of a collaboration between the New Media Consortium (NMC) and EDUCAUSE, "identifies and describes emerging technologies likely to have a large impact on teaching, learning, or creative inquiry on college and university campuses." The 2010 Report first identified electronic books, or ebooks, as "likely to be widely adopted in two to three years." It is on the "One Year or Less" adoption timeline in the 2011 Report.
The popularity of electronic books has risen steadily in recent years, due in part to the number of devices that can support the technology. The ubiquitousness of mobile devices, from smartphones to tablets to dedicated ebook readers, has lent itself to ebook usage in all markets, including the education sector.
Electronic books offer our patrons several benefits, such as anytime, anywhere access and better searching of text.
Electronic books have had a presence at Queen's since as long ago as 2005, when Eighteenth Century Collections Online became the first ebook acquisition of Queen's Library Systems. Since that time, the size of the collection has exploded, and as of September 2011, the ebook collection was just shy of half a million titles, with a growth of almost 12,000 titles between May and September 2011 alone. "Electronic books offer our patrons several benefits, such as anytime, anywhere access and better searching of text," notes Leslie Taylor, ebook specialist for Queen's Libraries.
However, despite these impressive numbers, there are challenges in developing an electronic book library. There is a general lack of standardization among publishers and ebook vendors in formats, platforms and licenses, making it difficult for the library to build a cohesive ebook collection. To add to the confusion, certain restrictions, such as how much electronic material can be downloaded and printed, vary from publisher to publisher. In addition, the release of an electronic version sometimes lags behind that of a new print title, making it impossible for the library to introduce the print and electronic versions of the same title concurrently. "Nonetheless, ebooks are growing in popularity among library users, and as the numbers indicate, the library is working hard to respond to the growing demand," says Taylor.
The availability of electronic books on campus is not restricted to the library system. The Campus Bookstore offers Digital Study Versions (DSVs), which are free versions of print texts. These are available at no cost, either because the titles are in the public domain, or because they are royalty-free materials authored by instructors. DSVs are available in a universal and free ebook format known as EPUB, and the Campus Bookstore currently has access to more than 200 such unique titles. In addition, this fall the Bookstore will be expanding its roster of available titles by introducing the commercial distribution of ebooks, a process that's currently in the final stages of planning and testing.
Ebooks are not the only form of electronic materials offered by the Campus Bookstore. They also sell web access codes, electronic keys to dynamic content offered by publishers to complement print books. The cost of the code is included in the purchase of the textbook, and can be purchased separately if the text is bought used. "Web access codes are by far the fastest growing area of digital support we see," says Chris Tabor, General Manager of the Campus Bookstore. "Access to supplemental material such as lab exercises, practice exams and interactive videos is highly valued by students."
The building of the Campus Bookstore's digital materials has not been a solo effort; it has been done in concert with Campus eBookstore, a North American partnership founded to develop affordable alternatives and complements to traditional course materials. "Queen's was instrumental in building this platform," states Tabor. "Currently it is being used by more than 100 institutions in Canada and the United States, and we are proud of the role we have played."
Electronic books have the potential to transform the way we interact with reading material of all kinds.
As mentioned, a number of logistic elements still need to be overcome before electronic books are widely adopted in an educational environment. However, as noted in the 2011 Horizon Report, "Audiovisual, interactive and social elements enhance the information content of [electronic] books and magazines … What makes electronic books a potentially transformative technology is the new kinds of reading experiences they make possible. Publishers are beginning to explore richly visual interfaces that include multimedia and collaborative elements … Electronic books have the potential to transform the way we interact with reading material of all kinds." The development and adoption of ebooks in educational environments will clearly be a contributing piece of the technology puzzle that continues to redefine the concepts of teaching and learning.
*PDF files can be read for free using Adobe Acrobat Reader.
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The current proposals to give block grants to the states and dismantle Medicaid by eliminating the federal-state partnership would destroy the flexible institutional framework that has been so successful. Furthermore, the proposed block grant funding formula actually rewards states that have taken advantage of flaws in the existing Medicaid program. Part II of this Article discusses the failures of the block grant proposal. Part III describes how we can achieve these goals without discarding the federal-state partnership that has served the people of our nation so well during the past thirty years and how we can continue to provide a medical safety net for poor, elderly, and disabled Americans.
Back to the Law Review home page


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MMA News
Free Fight Video | Chris Weidman KO's TUF 17's Uriah Hall | UFC NEWS
Watch one of the UFC's top middleweight contender take out the top prospect on this season on "The Ultimate Fighter".
21 Responses to "Free Fight Video | Chris Weidman KO's TUF 17's Uriah Hall | UFC NEWS"
And the reason for this????? Who is hall? hes got good stand up skills, i have seen alot of scary stand up fighters fail in the ufc, stop trying to hype weidman!!!!!!!!! he needs a big win before he gets silva just like bisping needed a big win give him vitor, or if bisping beats belcher, weidman vs bisping make it happen!!
Fukc that he's the #1 contender he deserves the next shot!
This so called no name will be Silvas toughest fight and his camp knows this, his fans don't!
While he does deserve a title shot, I wouldn't say he's the hugest threat to Anderson's "invinciblity" record. We seen fighters with wrestling abilities (Sonnen & Hendo), and with similar striking abilities (Bonnar & once again, Hendo) fall victim to Silva. Still… I would like to see the fight.
Weidman isn't nearly as much of a threat as silva haters are trying to portray him as. Honestly he probably gets finished in round 1 or 2 in highlight reel fashion….
That said, with Bisping and rashad's losses there is no more qualified MW contender right now and the handful of dights that are more interesting arent happening. GSP doesn't want the fight and jones has a long line of contenders, so by default Weidman is the guy.
I am sick of his "fans" and I think he blatantly ducked Vitor while talking his way into a shot, but with nothing else doin, llet him get his ass kicked. I'll buy it.
snicker…again and again, Andy needs to silence you fools. Weidman is going to get stomped by Andy and EVERYONE knows it, but you apparently. What's sad here is that Andy is not in decline right now; I'd like to see him do a superfight against Jones on GSP before he starts to lose based simply on age. This Weidman stuff just uses him up in training, lasts 5 minutes in the cage, and surprise surprise, another beat down for the GOAT. C'mon UFC get him a real fight before it's too late!
n once silva ruins weidmans career they'll all start crying that wasnt a fair match up weidmans a can a bum put him against Jones n hell lose blah blah blah, I'm over it also.. make it happen tomorrow get it over n done with…
Uriah keeps his hands DOWN.
Lol I think some people don't realize this happen a few years ago.
Worst Camera Skills ever.
I'd say this is the TUF difference. Uriah gets to fight guys who will never make it to the ufc to get into the ufc. Granted this is old & he has improved, but idk if he'll ever be a contender.
dude.. this footage is raw as hell i LOVE IT.. :D!!!
*Weidman knocks Hall down and swarms with a flurry of punches of Hall*
Dude with the camera : CHOKE HIM. CHOKE HIM!!!!!
………good job.
This WILL NOT be the guy to beat Silva.
That kick by Weidman at 3:40. Better striking than Silva alright.
Difficult to tell, but it seems to me that this fight should have been ended much earlier. Uriah may have taken significant damage here.
Well, I think this happened a few years ago, and both guys seemed to have improved leaps and bounds. Uriah's movement is so much better and Weidman seems to be more technical.
Please someone tell me why weidman deserves a title shot? He hasn't earned it yet, he needs to fight more top 10 middleweights first before he gets a title shot, if he deserves one Bisping deserved one well before the belfort fight!
i agree, chris weidman should have 1 more fight to prove hes a threat to anderson silva
idk but weidman seems like some1 silva would handle pretty quick not hating on him or anything but silva has fought guys that were bigger than him ,longer reach than him ,etc and they all got ended just sayin …..but idc give him his shot at silva
yeah….This video proves what? That Weidman deserves AS without fighting Belcher, Boetsch, Bisping, Lombard, Vitor, Const. Phil. or any in 185 for that matter?
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Posted at: 03/27/2013 10:30 PM
By: Chris Ramirez, KOB Eyewitness News 4
Government officials are advising workers to stay out of part of a nearly 80-year-old state office building in Santa Fe to avoid exposure to radon.
Attorney General Gary King said Tuesday that agency workers will not use a section of the Villagra Building, which was built in the 1930s. The building is connected to a newer complex for the attorney general's office.
A General Services Department spokesman said elevated levels of radon, including one very high reading, were detected in the building's basement and corrective measures are planned. Radon wasn't a problem in other parts of the building.
Radon is a naturally occurring radioactive gas and enters buildings through basements and foundation cracks. According to the EPA, radon is the number cause of lung cancer for non-smokers. The EPA estimates that 21,000 people die each year of radon caused lung cancer.
GSD Deputy Cabinet Secretary Mike Unthank said the department is making headway to correct the problem, although the exact way the State will do that is still unknown.
(The Associated Press contributed to this article.)


text:
Volume - GMAT Math Study Guide
Table of Contents
Rectangular Solids
A rectangular solid is a three-dimensional object composed of rectangular sides. Each of the six rectangular sides is a face. The solid and dotted lines are the edges. Opposing faces are parallel and have the same length and width. If all of the six sides are of equal length, the rectangular solid is called a cube.
Volume = lwh
Consider the following example:
Volume = lwh
Surface Area
SA = 2lw + 2hw + 2lh
In other words, the surface area is equal to the summation of the area of each of the faces. For example, if a rectangular solid had a length of 2, height of 4, and width of 3, then SA = 2(2)(3) + 2(4)(3) + 2(2)(4)
Right Cylinders
A right circular cylinder has two circular bases of equal size whose centers are both perpendicularly intersected by the same line. In the diagram below, the surface with point P and the surface with point Q are both the same size. Surface P and surface Q are both perpendicularly intersected by line PQ, making these surfaces parallel.
V = πr2h where r is the radius, which is QR in the above diagram
In other words, the volume is equal to the area of the base multiplied by the height.
Consider the following example:
V = (π32)(5) = 9π(5) = 45π
Surface Area
SA = 2(πr2) + 2πrh
In other words, the surface area is equal to the summation of the area of each of the faces. For example, if a right circular cylinder had a radius of 3 and height of 5, then SA = 2(π*9) + 2π*3*5 = 18π + 30π = 48π
Types of GMAT Problems
- Filling Problems
Often, GMAT questions will ask how long it takes to fill an object given the rate that a substance is being poured into the object. For time based problems, the volume of the object in question should be determined. Then the volume can be divided by the rate at which the substance is being poured to determine how long it will take to fill the object in the question. Another twist to the problem occurs when the time and rate are given, but one measurement of the object is left unknown. In order to calculate the length of the unknown side, calculate the volume with the given time. Then substitute the volume, V, for the corresponding volume in the corresponding function and solve for the unknown. (This probably sounds quite confusing, but an example will make it seem much simpler).If a gas tank in the shape of a right circular cylinder is 10 meters high and is being filled at a rate of 4π gallons a minute until it is filled after 10 minutes, what is the radius of the base of the cylinder?Correct Answer: A
- When the gas tank is full, the volume of gasoline in the tank will equal the volume of the cylinder.
- For each minute that elapses, another 4π gallons of gasoline occupy the tank. When the tank is full, the volume of the cylinder will be 10(min) * 4π(gal/min) = 40πgal since it took 10 minutes to fill the tank and every minute another 4π gallons is poured into the tank.
- V = πr2h (this is the formula for the volume of a cylinder)
h = 10, given in the problem
Substitute 40π in for V
40π = hπr2 = 10πr2
- Solve for r.
40π = 10πr2
4 = r2
2 = r
r = 2


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Alt.binz Review
Alt.binz is an excellent Usenet newsreader specifically designed for downloading binary content.
Alt.binz allows you to download an antiquated version for free and then they ask that you donate to upgrade. 17 Euros is the donation right now.
Usenet Search
Alt.binz does not offer their own search however you can use a wide range of public search engines such as NewsLeech, Beta.binaries, Yabse, etc
NZB Support
Alt.binz supports NZB file downloads
Platform Information
Alt.binz works on Window and Linux with wine!!
Alt.binz is an excellent Usenet Newsreader. Be sure to check out their free version and then decide if you want to donate for the upgrade
More Details
Alt.binz is a binary newsreader that allows users to download and manage articles from the Usenet. There are many different features to this software such as checking downloaded files, auto unpausing missing PAR@ blocks, repairing them and also unraring them. The newsreader is supported by various search engines for Usenet. With Alt.binz, then you can easily and quickly search for files and browse groups.
There are many different features that make this newsreader worthwhile, so we have identified what we think are the key elements.
A wide range of Usenet search engines are fully supported. Search engines such as NewsLeech, Beta.binaries, Yabse and more are all supported.
- Auto PAR and RAR " If the file that you are downloading needs par2 files, then alt.binz will automatically download and repair the files for you. It will also un-rar the files.
- It fully supports NZB files and allows a user to import into download queues. Scheduler that will manage your download queues and start them at optimum speeds.
- XPAT-server side search support.
- Multi-server support that gives you the ability to download from more than one server at any one time.
- Linux compatible " This is one of the few systems we found that actually works on Linux.
- Customize your own interface.
You can use alt.binz for all your newsgroup download needs. The software will let you download nzb files from Usenet search engines and rss feeds. You can schedule autopare and autounrar the files straight into the folder you want to store them in.
Installation of Alt.binz is easy. All you need to do is create a directory in the computer. Extract the file and then run it! The system download is an exe file, so it will do all the setting up for you. When you visit the website you can find an extremely useful link to wiki that has a page that is fully dedicated to this software newsreader. The information here will no doubt answer any question you have. Start with the ˜quick start™ guide, which will take you through all the necessary parts to starting your alt.binz.
There is also a very useful forum section at the website that allows you to ask all your questions or solve your issues with fellow users. The chances are that any issue you come across has been faced by these old hands a long time ago so you should get quick help and support. This is a great newsreader program that will quickly have you fully engrossed in the world of the Usenet. It is quick to learn, easy to install and has a wealth of resources that will help with any problems or questions you have.


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Fake university degrees from any University
One purveyor of early childhood
education degrees online is the University of Life. The
University has one of the most comprehensive online distance
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of academic subjects. The University offers a Master of Arts in
Education degree that contains a specialization in early childhood
education or a
university college. The Master of Arts in Education degree
focuses on the study of how young children learn and how best to
design and implement lesson plans and teaching activities that will
have the most impact.
Map of places to buy the products
Another school that offers online accounting degree programs is the University Online. Is well known and respected as a quality educational institution and it has lead the way in offering many of its course offerings online. The online learning experience at University includes streaming video lectures, chat rooms, message boards, and other internet means of communication as many paths to a fake diploma. University's online degree programs feature accelerated eight week semesters, which means that dedicated students can complete their degrees quickly. In case it is not possible for you to get enrolled there is nothing to worry about as there are many online stores that offer fake university degrees. Go ahead and check the fake transcripts university guide out today.
The industry in general for Fake Diplomas
Technical Institute also offers online accounting degree programs. As ITT is primarily focused on technology, most of the ITT accounting instruction is geared towards the use of computers in accounting and also note the correct uses for fake diploma. Of course, this is an optimum situation since the computer is an integral component of modern accounting. ITT also offers a masters of business administration (MBA) degree that allows students to focus on accounting easting the growing need for a fake college degree.
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The Lazy Gardener
Gardening with Brenda Beust Smith
Posts by Author
Most important garden view
"In the spring, at the end of the day, you should smell like dirt." — Margaret Atwood The most important window in my house is the one over the kitchen sink. That's the place I have to stand the most often where I wish I were somewhere else. Therefore, the view should be something that […] [Read More]
Drought's Silver Lining
Gaura — don't overwater! For all the bad things you can say about this drought — and there are many — several silver linings exist in my yard. One of the best is gaura. This extremely-drought tolerant bloomer, with its airy pink blooms, is actually a native of this area. But it generally thrives in […] [Read More]
Amaryllis — the wanton country maid
"I care not for these ladies that must be wooed and prayed. Give me kind Amaryllis, the wanton country maid." — from A Book of Airs, "I Care Not for These Ladies" by Thomas Campion By BRENDA BEUST SMITH Every Southern garden — and every Gulf Coast garden for sure — should include at least […] [Read More]
Hot Weather Veggies — Get Started!
IT MAY BE SNOWING UP NAWTH, but here it's time to plant those hot weather vegetables like beans, cantaloupe, corn, cucumbers, melons, peppers and okra. That's not enough? Okay, in his "Year Round Vegetables, Fruits and Flowers for Metro Houston" manual, Dr. Bob Randall also recommends planting now: Squash, arugula, celtuce, chard, cumin, fenugreek, garlic […] [Read More]
Dog-triggered blooms?
This is a clivia. (Pronounced "KLY-via" or "KLIV-ee-ya." Those in the know don't seem to agree.*) Maybe that's why these South Africa natives are also called kafir lilies. They're not usually grown here which, to Mickey and Doug January, is really strange. Theirs has been thriving and blooming like crazy for years. Normally, even here, […] [Read More]
Treasure Trove of Tropicals!
Crinum macowanii are among the unusual varieties grown in Jerry's Jungle</strong> Once upon a time there was this wonderful gardener who brought a bunch of unique ferns to a TV show I was doing for Houston PBS (Ch. 8). We had a great time looking over his collection. Then he said, "And now, I want […] [Read More]
Spring weed, thy name is @#$%^&!
Velcroweed invades a Martha Gonzales antique rose Wonder why the plant gods didn't give velcroweed a flower? At least then it would contribute something besides backaches and itchy arms to the garden. Actually, I looked it up and long about May it should produce a blue flower so tiny and insignificant it can hardly be […] [Read More]
Quit smushing the bluebonnets!
(A Chappell Hill-area bluebonnet field I photographed several years ago.) Quit smushing the bluebonnets! It boggles the mind. Here on TV is this reporter, standing in a field of obviously-sparser-than-usual bluebonnets, telling us how FEW of this treasured native flower there are this year. So why, lady, are you trampling down the precious ones we […] [Read More]
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|3D Mechanical Drawings
Perhaps the most prolific person in the last two millenniums has been Leonardo da Vinci. He was not only a painter and sculptor he was also an architect, a botanist, a mathematician, an inventor extraordinaire and to cap it all - a brilliant scientist. Whatever he did, he easily put things to paper for all to see and understand as he was such a gifted artist. And what better way to put across your ideas than in graphic descriptions. Perhaps the modern concept of wire meshes and solid modeling has been inspired by the da Vinci genius. Just like his inventions his sketches were comprehensive with all clear lines showing the depths and dimensions, in our modern wire mesh and 3D modeling we try and be as comprehensive and demonstrative as were his inventions.
3D drawings have a great role to play when it comes to engineering drawings. Designing in 3D is much faster than traditional 2D drawings which allows an engineer to devote more time to designing activities rather than spending time drafting. Using 3D solid modeling engineers can produce a geometrically accurate "virtual prototype" that is used throughout the product development cycle, manufacturing, and assembly activities. 3D models allow engineers to study cross sectional views of various machine parts and determine parametric relationships between the parts. This is very important as it helps maintain required clearances and tolerances of assembly parts at the time of assembly which if not sorted out at the design stage itself proves very costly at the time of production. Once the solid model is made further CAE experiments can be carried out by simulating these models in a real world environment. With 3D solid modeling the opportunities are enormous and the results stunning. Perhaps da Vinci's Mona Lisa can smile more broadly now!
Typically clients require number of individual 3D CAD models/assemblies/drawings which join together to form a single complex assembly. It can be very difficult to assess what even a simple assembly may look like, without a visual of it. This process can be made extremely simple by using expertise in the fields of assembly modeling thereby, helping clients to see what their assembly's would finally look like.


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Mixed polymer markets for start of April
1:18 PM MDT | April 9, 2013 | Lindsay Frost
Polymer markets were mixed through the end of March and into April, players report. In North America, polyethylene (PE) was generally stronger in both export and contract trading, but polypropylene (PP) and polystyrene (PS) were softer. In late-month March contract settlements, PE of all grades increased 2–3 cts/lb, and Dow put a 4 cts/lb increase on the table for May. PP was said to be lower by 4 cts/lb for March contracts, while PS slid 5 cts/lb. Linear low-density PE was said to be off $20/m.t., while high-density PE gained $40/m.t. for blow-molding...
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Bihar CGL Exam 2013:
Bihar Staff Selection Commission (BSSC) Conducts Combined Graduate Level (CGL) exam every year. Now the Bihar SSC CGL exam will be held on 27 January, 2013.The candidates who appeared in the Bihar SSC CGL examination are waiting for their result. The Bihar CGL result will be publish after some time of the examination and the candidates can check their result on its official web portal after declaration of the result.
Bihar SSC CGL Result 2013-
The result of Bihar CGL 2013 will be published after some time after the examination is over. The candidates are advised to keep visiting this site for latest updates regarding Bihar CGL 2013.
Important Dates-
BSSC CGL 2013 exam was held on 27 January,2013 (Sunday).
About Bihar SSC-
Bihar Staff Selection Commission (BSSC) is the Staff Selection Commission for Bihar States. It conducts main examination and recruitment exams in Bihar states and recruit new candidates for their Jobs.
Official Source-
For More Detail and latest update please visit- http://bssc.bih.nic.in/


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DuPont strengthens presence in Bangladesh
DuPont Bangladesh set up as a wholly owned subsidiary; focus on science-based solutions that address Bangladesh growth
Dhaka, Bangladesh, February 26, 2013: DuPont recently announced setting up of its wholly owned subsidiary 'DuPont Bangladesh Ltd'. This new legal entity further strengthens DuPont presence in the high growth Bangladesh market and will enable local collaborations, especially in the areas of agriculture and food, apparel and textiles, paints and construction, graphics and packaging, infrastructure, renewable energy, safety and protection, and others. The announcement was made at a high-profile event hosted at a prominent hotel in Dhaka and attended by about 100 guests.
Speaking at the event, G M Quader, Honorable MP, Commerce Minister, Government of Bangladesh, said ''I am delighted that a prestigious company like DuPont has now fully stepped into Bangladesh''.
Congratulating DuPont on the opening of the new subsidiary, John F. Danilowicz, Charge the Affairs, US Embassy, Dhaka, said, "DuPont is one of the leading companies in the USA and it is great that the company has decided to expand its presence in Bangladesh".
In his remarks at the event, Rajeev Vaidya, president – south Asia & ASEAN, DuPont, said, "The DuPont growth strategy is focused on delivering science-powered solutions to address the key challenges of feeding the growing population, reducing dependence on fossil fuels and protecting people and the environment. In emerging economies like Bangladesh, we see a great synergy between DuPont science & technology and the needs of the local markets and consumers."
Showkat Ali Sarkar, Managing Director, DuPont Bangladesh, said "DuPont established local presence in Bangladesh through its liaison office in 2010 and today's announcement reiterates our commitment to the country. As we build and expand our presence in Bangladesh, our goal is to work closely with our local customers to better understand the unique market needs here and offer them innovative products and solutions from the global DuPont portfolio."
G M Quader MP, Commerce Minister is declaring official inauguration of DuPont Bangladesh Ltd. On the dais - from right to left : John F. Danilowicz, Charge the Affairs - US Embassy Dhaka, Rajeev Vaidya - President South Asia & ASEAN,DuPont, Showkat Sarkar - Managing Director, DuPont Bangladesh Ltd.
DuPont products have the right fit with the needs of the Bangladesh economy. For instance, DuPont offers innovative solutions for water proofing, weatherization, innovative design, energy efficiency to country's booming construction and infrastructure industry. In the textiles sector, use of DuPont™ PrimaGreen® textile enzymes can help save costs through reduced consumption of water, less use of conventional processing chemicals and better product quality. DuPont Pioneer seeds and advanced crop protection solutions can offer Bangladesh farmers higher yield per acre.
DuPont science is the foundation for the market-driven innovation that the company delivers to its customers. With the world's population projected to reach 9 billion by the year 2050, providing for the food, energy and protection needs of people everywhere presents unprecedented challenges. Over 9,500 DuPont scientists and engineers collaborate with customers, governments, and others to develop sustainable solutions to address those challenges. In 2012, DuPont launched more than 2000 new products aimed at meeting the needs of people around the world.
About DuPont
DuPont (NYSE: DD) has been bringing world-class science and engineering to the global marketplace in the form of innovative products, materials, and services since 1802. The company believes that by collaborating with customers, governments, NGOs, and thought leaders we can help find solutions to such global challenges as providing enough healthy food for people everywhere, decreasing dependence on fossil fuels, and protecting life and the environment. For additional information about DuPont and its commitment to inclusive innovation, please visit http://www.dupont.com
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Egton Medical Information Systems Ltd (EMIS) is the UK's market-leading primary care software provider with more than 39 million patient records entrusted to its systems. Its core market is the 52.2 percent of GP practices that use a mixture of LV, PCS and EMIS Web systems.
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Browse by Manufacturer: Famosa
Sort by:
- Trending
- New Review
- Special Needs
- Video Review
Feber Range Rover Sport 12-Volt Ride-On
from Famosa
Kids 3+ can ride around in their very own Range Rover with this battery-powered ride-on.
Feber Happy Caterpillar Play Tunnel
from Famosa
Multiple kids 2+ can climb, crawl, and play on this indoor/outdoor play tunnel in the shape of a caterpillar.
Pinypon Fairies
from Famosa
Kids 4+ can collect and customize these sparkly 3-inch fairy figures.
My Little Nenuco Travel with Me
from Famosa
Kids 3+ can take their baby doll with them in the car with this 14-inch baby doll and car seat that can be installed in a car like a regular car seat.
Pinypon Mermaid Friends
from Famosa
Kids 4+ can add to or start their Pinypon collection with these two mermaid dolls with mix-and-match hair and body parts, two sea creature friends, and accessories.
Feber Super Water Slide
from Famosa
Create a backyard water park for kids 3+ with this slide that you connect to a hose to create a water slide or remove the hose and use this slide as a regular slide.
Nenuco My Little Nenuco
from Famosa
The Nenuco My Little Nenuco baby dolls have soft bodies and fruity scents. There are three styles available: strawberry, orange, and apple. Each 16.5-inch doll has a soft body with squeezable plastic…
Nenuco Baby Sleeps with Me
from Famosa
Kids can sleep with their baby dolls right by their side thanks to Nenuco Baby Sleeps with Me. This unique playset includes a cradle that can attach to the side of a child's bed, keeping the baby…
Nenuco Let's Play School
from Famosa
The Nenuco Let's Play School playset comes with everything kids need to be a teacher to their Nenuco doll. A 16.5-inch vanilla-scented doll is included. One side of the playset is a desk and storage…
Nenuco Runny Nose
from Famosa
Nenuco Runny Nose is a baby doll with a runny nose. When the 16.5-inch doll gets a cold, little bubbles run out of its nose. Kids can then wipe them away with a tissue. To make the doll's nose run,…


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The essence of social commerce is nothing new.
For all of human history, our purchase decisions have been influenced by our friends, family and the zeitgeist of crowds. Harnessing social influences is the Holy Grail of marketing. It is the defining trait of all great brands: They become social movements. To harness the value of a crowd, you must start by gaining the enthusiasm of a single person – then scale it as quickly as possible. This poses three vexing problems for marketers:
- Who are the influential people that will be the evangelists that motivate crowds to buy my brand?
- How to I position my brand to attract and maintain good customer relationships?
- How do I get customers to engage with my brand so that I build lasting and valuable relationships?
Social commerce offers the right answers:
- Find influential people at the center of social networks that share common interests and values.
- Attract people with content that is relevant to their interests and values.
- Engage with social media (Facebook, LinkedIn, Twitter, blogs, YouTube, etc.)
Measuring personal influence is the single most important step: Find the right brand evangelists and they will do the selling for you — growing your business without the costs of advertising and promotions. Piss off the wrong person and your brand will suffer. Badly.
Klout's answer: Focus on people that have the greatest online influence.
Klout evaluates online reputation by evaluating the impact of your Tweets, Facebook postings and other online interactions to get others to act. Your score is proportional to the number of clicks you generate online. The theory is routed in social network analysis (SNA): A high Klout number indicates that a person can influence behavior and preferences among people in their personal network.
The most amazing thing about Klout is that it is the first wide-spread measure for person's value to social commerce. Its simplicity is genius… if it is accurate. And I think not…
Most brands fail because they forget a simple truth: The vast majority of people don't give a damn about you or message.
Most brands are irrelevant.
We live in a world filled with marketing messages that land on deaf ears. Most advertising fails. Coors wastes millions on advertising that is shown to children (who can't legally buy beer). Pfizer bombards me with commercials for drugs that treat diseases that I don't have. ATT hires movie stars to convince me that they provide great coverage yet everyone I personally know with an iPhone hates ATT's wireless service.
And yet, the spending escalates as we all grow deaf…
Social commerce is the new gold rush of marketing: Promising that it can turn any brand into a social movement. You only need to engage customers – provide them with a way to interact with your brand. Most marketers interpret this to mean they need to be friends with all 500 million people on Facebook and all 200 million people on Twitter. Again, they miss the point: Relevance.
Relevance is king. Long live relevance!
Dave Carroll's United Breaks Guitars is a great case study on how a big corporation with so-called sophisticated marketing miserably failed to understand the importance of relevance. For those of us that fly a lot, we all know that United sucks. Small seats. Employees who ignore customers. Lost luggage, etc. Thanks to Dave, we now know that United also breaks $3500 guitars – then denies any responsibility. Ignoring Dave's repeated requests to fix his guitar was a $180 million mistake for United. More than 9.4 million people watched his video as thousands of mainstream media outlets joined the blogosphere's rage against the airline's insensitivity and arrogance. Dave's message was relevant: We've all had bad experiences with United.
Klout Can't Help United
What would have happened if United paid attention to Dave's Klout score? Nothing different. As of today, Dave has a Klout score of 39 – the same as mine. We are in the top 30% of all Klout scores – hardly worth of mentioning since there are tens of millions of people with higher scores who fly on United. My guess is that Dave's score would have been far lower at the time of the incident. In short, Dave was (and still is) not a crowd mover according to Klout. However, he is a crowd mover as measured by personal influence. Just ask United's shareholders.
The Value of Personal Influence is Measured by Relevance
United failed to see Dave as an individual who mattered. He had a problem that was relevant to millions of their customers (and potential customers). Initially, United did not even see Dave. They ignored him. Then they saw him as a loss mitigation problem and denied responsibility. Next he became a public relations problem. Then a problem affecting stock price. And now, he is a case study at Harvard Business School on how to manage customer problems.
Can you afford to be inauthentic, irrelevant and lack authority?
The problem was never Dave. It was United. They did not align their business processes to the relevant needs of their customers. They gave lip service rather than real service. They said they were sorry then did nothing – providing proof they lacked authenticity. Finally, they lacked the authority in the market to counter act the wave of negative press generated by Dave. And I'd bet that no one at United lost their job over this incident.
Influence is personal… not electronic.
We all know people who refuse to participate on Facebook. And we know even more people who think Twitter is a noise generator and a fantastic waste of time. Yet many of these social media naysayers have tremendous personal influence. My doctor has no Twitter account yet I follow his advice to follow The China Study while ignoring Pfizer's commercials. My best friend (in real life) warns me about ATT service so I buy an Android phone that works with Verizon. New Belgium Brewing sponsors my favorite charity events so I'm willing to experiment with buying new beers they bring to market. None of these purchase decisions were driven by online behavior. Yet, all of these decisions were driven by social commerce. And all of them have two three things in common:
- Relevance – The brands relate to my personal values and interests.
- Authenticity – The brands do what they promise to do.
- Authority – The brands are endorsed by people I trust.


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Anarsia spartiella
(Schrank, 1802)Wingspan 12-15 mm.
Distributed throughout much of England, local in Scotland and mostly coastal in Wales and Ireland, this species is on the wing between June and August.
The wings may be relatively plain, or have darker and paler mottling. The long, upwardly curved, labial palps of the female protrude from a large tuft of scales, but the shorter palps of the male are concealed in the tuft.
In May and June, the larvae spin the shoots of gorse (Ulex), broom (Cytisus) or Dyer's greenweed (Genista tinctoria), feeding within.
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Mon June 10, 2013
Swedish Commuter Rail Engineers Get Around Dress Code
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Good morning. I'm Linda Wertheimer. In Stockholm, engineers on the Swedish commuter rail line have found a new way to skirt a dress code. The drivers were told no more shorts, even though the heat in the cab can top 95 degrees - just long pants or skirts. So many of the male engineers are now wearing skirts. Women are allowed to, so the company says it will not discriminate. Something tasteful in an A-line, or pleats, perhaps? It's MORNING EDITION. Transcript provided by NPR, Copyright NPR.


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Happy birthday, Jonny! 'Rent' composer's story comes to CroswellWritten by Mary Petrides | | email@example.com
Time is running out for Jonathan Larson, a starving artist in New York City: it's 1990 and his 30th birthday is fast approaching.
He's been waiting tables and writing his musical Superbia for five years, and at almost 30, he's come to a crossroads: should he pursue his passion for musical theater or should he find a steady corporate job (like his childhood friend Michael did) and settle down with a family (like his girlfriend Susan wants)?
Performances of Tick Tick… Boom! continue at 8 p.m. July 30-31 and Aug. 1 at 3 p.m. at Croswell Opera House in Adrian, less than an hour's drive from Toledo. The show, which runs about 90 minutes, contains adult themes and language that may not be appropriate for children.
The musical is effectively an autobiography of Larson, creator of the Broadway musical Rent, said Michael Yuen, who plays Jon. In the musical, Jon is both character and narrator, often describing the scene before or in between dialogue with other characters.
"Telling this side of a story is interesting to me as an actor because I've always seen it from the performance [side]," Yuen said. "Watching and learning about this side of the process has been very enlightening."
Jon takes his musical to a workshop and sees in the audience "St— S—," a composer so great Jon won't pronounce his name. This composer's opinion of the work could make or break Jon's career.
Jere Righter, artistic director at Croswell, said Tick Tick… Boom! was discovered by accident after Larson's death. Larson's family hired a lawyer to go through his files and prove that he had written Rent, since some people were filing lawsuits claiming authorship after Larson died. While searching, the lawyer found most of Tick Tick… Boom! in Larson's files. A writer was hired to complete it.
The musical isn't performed often and hasn't been performed before in the area, Righter said, and it required some extra creativity.
The cast comprises three actors (Nicholas Fuqua and Kyrie Bristle play 10 or 15 characters between them) and the acting could take place in a smaller area than would be needed for a large cast. Croswell workers arranged 158 chairs on the stage around three sides of the area where the actors performed. During the performance, audience members are as close as three or four feet away from the actors.
Yuen said acting in close setting is similar to acting on film because the audience can see little things, like a small exhalation or smile, that they wouldn't be able to see form 20 feet away.
"Being in a more intimate setting … it allows me to be more natural," Bristle said.
"It's more relaxed," Fuqua said. "There's no bells and whistles in your acting."
Righter said the smaller stage area helped to tell Larson's story.
"The show is enough on its own," she said. "It stands without that over-the-top kind of stuff."
"You feel like you know Jonathan Larson when it's over: who he was and what he struggled with," she said. "It's a really great story."
Damn Yankees opens Aug. 20 at Croswell.


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2012: Named to Athletic Director's Honor Roll for 2011 fall semester...Has played and started in all 62 games this season, with 57 starts coming at third base...Bat .273 with 24 runs, 44 hits, 21 RBI, seven doubles and five home runs...Led the team with a .333 average over six games during the postseason...Went 3-for-3 against Coastal Carolina in the Athens Regional with two doubles...Went 2-for-2 with a run scored against Kentucky at the SEC Tournament...Went 1-for-2, including a solo home run, with two runs and a RBI in regular-season finale against Arkansas...Had two hits with two RBI in game two at No. 23 LSU...Notched a hit with a RBI in game one versus No. 2 Alabama...Posted a hit with a run and RBI in game two against No. 4 Florida...Went a perfect 3-for-3 with two runs versus Georgia State...Had a five-game hit streak starting on March 4 against Mercer and ending in game three at Mississippi State that included going 2-for-2 with a double and home run while posting two runs and two RBI in win over Furman...Earned a hit and run in each game at Mississippi State...Tallied a solo home run against No. 15 Arizona in Cathedral City Classic...Made debut at third base against Connecticut...Made college debut at shortstop against Army where she went 2-for-2 with two runs and three RBI.
High School/Club: Lettered three years at Cactus Shadows as a shortstop...Three-year First Team All-Region selection...As a senior, earned Louisville Slugger/NFCA All-America honors after helping the Falcons reach the state quarterfinals as she hit .667 with a 1.075 slugging percentage, a .767 on-base percentage, seven home runs, 50 runs, 33 RBI and 46 stolen bases...Also earned her All-Arizona recognition and East Valley Tribune Player of the Year honors following senior season...Earned Defensive Player of the Year and Scholar-Athlete recognition as a freshman...Also played two seasons of varsity basketball earning First Team All-Region and Honorable Mention All-Arizona as a sophomore and Second Team All-Region as a freshman...Played travel ball for the Arizona Suncats, Arizona Storm and Arizona Hotshots...Served as President of Best Buddies.
Personal: Born: Sept. 25, 1992...Daughter of Andy and Charlie Goulder...Has four brothers who all play or played collegiate baseball, Albie (Louisiana Tech), Ollie (Western Carolina), Jake (Pacific) and Jackson (Utah)...Major: Special Education.


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Quiet protests at an Iowa Board of Regents meeting Thursday turned boisterous at a news conference where demonstrators peppered officials with shouted questions and comments.
More than 150 students, faculty and parents first amassed outdoors at the University of Northern Iowa's Maucker Union for a rally. When they then moved inside to the meeting, some regents looked up to observe them as they quietly held signs saying "Board of Betrayal" and "Regents of Mass Destruction."
It was the first board meeting on the UNI campus since a series of academic cuts and faculty buyouts were announced earlier this year. The planned closure of UNI's Malcolm Price Laboratory School, the elimination of about one-fifth of academic programs and buyouts of more than 40 tenured faculty have drawn steady public criticism.
University officials have said the measures are necessary to close a $5 million budget gap. On Thursday, though, they said details on the savings won't be available for several weeks.


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Reinforced copolymers formed from a functionalized copolymer that undergoes a reactive extrusion process with an inorganic component to form the reinforced copolymer. The functionalized copolymer in the form of a block and/or graft copolymer includes hard segments and soft segments, where the soft segments are covalently bonded with a coupling agent either before or after copolymerization with the hard segments. The reinforced copolymer of the present disclosure can be suitable for use as a biomaterial and/or in medical devices.
1. A reinforced copolymer comprising:
a copolymer having soft segments and hard segments;
a coupling agent covalently coupled to the soft segments, where the coupling agent is not covalently coupled to the hard segments;
an inorganic component coupled to the soft segments of the copolymer to form the reinforced copolymer.
2. The reinforced copolymer of
3. The reinforced copolymer of
4. The reinforced copolymer of
5. The reinforced copolymer of
6. The reinforced copolymer of
7. The reinforced copolymer of
8. The reinforced copolymer of
9. The reinforced copolymer of
10. The reinforced copolymer of
11. The reinforced copolymer of
12. The reinforcement copolymer of
13. The reinforcement copolymer of
14. A medical device prepared from the reinforced copolymer of
Dilation catheters are used for opening blood vessels or other passageways in the body that may be blocked by obstructions or stenosis. Dilatation catheters are generally formed from thin, flexible tubing having an inflatable balloon at or near a distal tip of the catheter that can be inflated with fluid pressure communicated to the balloon through a lumen of the catheter. In a typical angioplasty procedure, the balloon dilatation catheter is passed through the vasculature to the location of a stenosis in an artery, and the balloon is inflated to a predetermined size and shape to open the blocked artery.
It is desirable for balloons of balloon dilatation catheters to be capable of inflating to a diameter of typically many times their uninflated diameter in order to be able to open an obstructed vessel. Other desirable properties of balloons for such balloon dilatation catheters include strength, softness, flexibility and a thin, low profile which are important for achieving the performance characteristics of folding in an uninflated state, tracking, crossing and recrossing the area of the obstruction or stenosis in a vessel in an uninflated state. In addition, properties of burst strength, compliance, and fatigue have been increasingly important in the continuing effort to create thinner, lower profile balloons for dilatation catheters with an ability to track, cross and recross increasingly narrow passages in obstructed vessels.
Polymeric materials that have been used for making medical devices, catheters, dilatation catheters, and balloons for dilatation catheters include polyethylene, polyolefins, polyvinyl chloride, polyester, polyamide, polyethylene terephthalate (PET), polyamides, polyurethane, and the like. Balloons made of soft polyolefin or ethylene copolymers materials are typically foldable, and track and cross well, so that they can often be used more than once, and can be used to cross multiple lesions. However, such balloons also commonly have high balloon compliance and low burst strengths. Balloons made from polyethylene terephthalate (PET) are commonly stronger, with a higher rated burst pressure. However, dilatation catheter balloons made of PET are generally stiff, not readily foldable and refoldable, and are susceptible to acquiring defects from mechanical handling.
It would be desirable to provide a polymeric blend for balloons of balloon dilatation catheters with a combination of the best features of the softer balloon materials and the stronger balloon materials, including good flexibility, folding, track, cross and recross, with a thin, low profile, high resistance to fatigue, low compliance, and high burst strength.
The present disclosure relates to catheters and balloons for medical catheters formed from a reinforced copolymer having certain characteristics generally desirable in medical devices. The reinforced copolymer described herein is particularly suitable for use in forming medical products such as catheters, dilatation catheters, and balloons of dilatation catheters.
The reinforced copolymer of the present disclosure is formed from a functionalized copolymer that undergoes a reactive extrusion process with an inorganic component to form the reinforced copolymer. The functionalized copolymer in the form of a block and/or graft copolymer includes hard segments and soft segments, where the soft segments are covalently bonded with a coupling agent either before or after copolymerization with the hard segments. In one embodiment, the coupling agent can covalently bond with the inorganic component during the reactive extrusion process to form the reinforced copolymer. Alternatively, the functionalized copolymer can act as a compatilibizer to facilitate blending the functionalized copolymer with other polymers.
The reinforced copolymer of the present disclosure can be suitable for use as a biomaterial and/or in medical devices. The reinforced copolymer display excellent performance in many characteristics important for medical device use, including compressive strength, diametral tensile strength, flexural strength, fracture toughness, puncture resistance, hardness, changes in hydrophobicity, adhesion, non-adhesion, friction, patency or biointegration of the device with one or more tissue surfaces of a body of a patient depending on the particular application of the device, resistance to wear (e.g., characterized by compressive strength and diametral tensile strength), durability, thermal expansion, visual opacity, x-ray opacity, impact strength, chemical durability, electrical conductivity, biocompatibility, modulus, shelf life, patient comfort, ease-of-use, and structural integrity relative to a polymer without the inorganic component that is used in forming the reinforced copolymer.
In addition, the reinforced copolymer of the present disclosure can be further characterized in that it can be substantially insoluble in body fluids and tissues and that is designed and constructed to be placed in or onto the body or to contact fluid or tissue of the body. Ideally, the reinforced copolymer will be biostable, biocompatible, and will not induce reactions in the body such as blood clotting, tissue death, tumor formation, allergic reaction, foreign body reaction (rejection) or inflammatory reaction; will have the physical properties such as strength, elasticity, permeability and flexibility required to function for the intended purpose; can be purified, fabricated and sterilized; and will substantially maintain its physical properties and function during the time that it remains implanted in or in contact with the body. A "biostable" material is one that is not broken down by the body, whereas a "biocompatible" material is one that is not rejected by the body.
As used herein, a "medical device" can be defined as a device that has surfaces that contact blood or other body fluids and/or tissues in the course of their operation. This can include, for example, extracorporeal devices for use in surgery such as blood oxygenators, blood pumps, blood sensors, tubing used to carry blood and the like which contact blood which is then returned to the patient. This can also include devices such as vascular grafts, stents, electrical stimulation leads, valves for use in the cardiac system (e.g., heart valves), orthopedic devices, intracorporeal or extracorporeal devices (e.g., catheters), catheter shaft components, filters, guide wires, shunts, clamps, sensors, membranes, balloons (e.g., dilatation balloons), anastomotic devices, aneurysm repair devices, embolic devices, implantable devices (e.g., orthopedic implants), replacement devices for nucleus pulposus, cochlear or middle ear implants, intraocular lenses, coatings for such devices, and the like that comprise reinforced copolymers.
Reinforced copolymers of the present disclosure can be used in medical devices as well as nonmedical devices. As discussed, they can be used in medical devices and are suitable as biomaterials. Examples of medical devices are listed herein. Examples of nonmedical devices include foams, insulation, clothing, footwear, paints, coatings, adhesives, and building construction materials, besides others.
As used herein, the terms "a," "an," "the," "one or more," and "at least one" are used interchangeably and include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, all scientific and technical terms are understood to have the same meaning as commonly used in the art to which they pertain. For the purpose of the present disclosure, additional specific terms are defined throughout.
As used herein, a "reinforced copolymer" refers to a functionalized copolymer that includes, at least in part, an inorganic component covalently bonded thereto and any desired filler and/or adjuvants. In one embodiment, the copolymer used to form the functionalized copolymer is a thermoplastic having a block copolymer and/or a graft copolymer configuration. The copolymer can include one or more each of an A-Block and a B-Block for either of the block copolymer and/or graft copolymer configurations, as discussed herein.
For the present disclosure, the A-Block is a soft-segment polymer and the B-Block is a hard-segment polymer as compared to the A-Block. Each "block" or segment of the copolymer may be a homopolymer, or a random or block copolymer itself. As used herein, a "hard-segment" polymer is one that includes a majority of either crystalline domains (i.e., has ordered domains) at use temperature or amorphous domains with a glass transition temperature above use temperature (i.e., glassy), and a "soft-segment" polymer is one that includes a majority of amorphous domains with a glass transition temperature below use temperature (i.e., rubbery). Typically, hard segments add considerable strength and higher modulus to the copolymer. Similarly, soft segment adds flexibility and lower modulus, but may add strength particularly if it undergoes strain crystallization, for example. The copolymers can vary from hard and rigid to soft and flexible. In one example, the copolymers can be elastomers. An "elastomer" is a polymer that is capable of being stretched to approximately twice its original length and retracting to approximately its original length upon release.
Soft-segment polymers for the A-Block can be selected from the group consisting of polyoxyalkene glycols such as polyoxyethylene (PEO) and/or polytetramethylene ether glycol (PTMEG, Terathane�), polyethylene octene elastomer (POE), poly(oxypropylene) (POP), and polyethylene butene elastomer or other suitable aliphatic soft polymer moieties, optionally polymerized with other monomers. Combinations of the soft-segment polymers are also possible. Other soft-segment polymers are also possible.
Examples of hard-segment polymers for the B-Block can be selected from polyamide, polyimide, polyethylene terephthalate (PET), polyesters, polypropylene, or other suitable aliphatic hard polymer long-chain organic units that includes urethane groups, urea groups, ether groups, ester groups, or combinations thereof (e.g., polyurethanes, polyureas, or polyurethane-ureas) in the B-Block. Other hard-segment polymers are also possible.
As used herein, "long-chain" refers to an organic connecting unit (i.e., connecting the A-Blocks) containing 20 atoms or more (preferably, 20 carbon atoms or more). As used herein, the term "organic unit" refers to a hydrocarbyl group (aliphatic and/or aromatic) optionally including other atoms (e.g., heteroatoms) or groups (e.g., functional groups) replacing the carbon and/or hydrogen atoms. The term "aliphatic group" means a saturated or unsaturated linear (i.e., straight chain), cyclic, or branched hydrocarbon group. This term is used to encompass alkyl (e.g., —CH3) (or alkylene if within a chain such as —CH2—), alkenyl (or alkenylene if within a chain), and alkynyl (or alkynylene if within a chain) groups, for example. The term "alkyl group" means a saturated linear or branched hydrocarbon group including, for example, methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like. The term "alkenyl group" means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon double bonds, such as a vinyl group. The term "alkynyl group" means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon triple bonds. The term "aromatic group" or "aryl group" means a mono- or polynuclear aromatic hydrocarbon group. These hydrocarbon groups may be substituted with heteroatoms, which can be in the form of functional groups. The term "heteroatom" means an element other than carbon (e.g., nitrogen, oxygen, sulfur, chlorine, etc.).
Polymers used to form the A-Blocks and B-Blocks can be prepared using a variety of techniques from polymerizable compounds (e.g., monomers, oligomers, or polymers). Such compounds include diols, diamines, diacids, diiscocyantes, or combinations thereof, for example. The method to prepare the block and/or graft copolymer can be by any of the methods generally known for block and/or graft polymerizations. Embodiments of the copolymer can include a di-block, tri-block or multi-block copolymer. In the case of the tri-block or multi-block copolymer, different configurations of block order are included in the present disclosure. In addition, the molecular weight (i.e., average molecular weights) of the various blocks can be modified and adjusted to help determine processing characteristics and end-use performance properties of the copolymer used in the present disclosure. The molecular weights of the block copolymers can be controlled by well-known synthetic techniques, where the molecular weights of the copolymer used for the reinforced copolymer may vary depending on the desired properties and use.
Typically, the A-B block copolymers are prepared from precursor polymers (i.e., prepolymers), although other methods can be used to build polymers with the same block architecture. In one embodiment, the B-Block is formed from an acidic functional precopolymer (e.g., a monofunctional and/or difunctional carboxylic acid polyamide (HOOC—PA-COOH) or polyimide (HOOC—PI—COOH)) and the A-Block is formed from a hydroxyl functional precopolymer (e.g., a monofunctional and/or difunctional polyoxyethylene (HO—PEO—OH)), where the copolymerization reaction is carried out under vacuum and with tetraalkylorthotitante as a catalyst, as discussed in U.S. Pat. Nos. 4,230,838, 4,331,786 and 4,332,920 all to Foy et al., which are incorporated herein by reference in their entirety.
Alternatively, the B-Block is formed from an acidic functional precopolymer (e.g., a monofunctional and/or difunctional carboxylic acid polyamide (HOOC—PA-COOH) or polyimide (HOOC—PI—COOH)) and the A-Block can be formed from an amine functional precopolymer (e.g., a monofunctional and/or difunctional polymethylenediamine (H2N—(CH2)n—NH2)), where n is in the polymeric range. In an additional embodiment, the B-Block is formed from an isocyanate functional precopolymer (e.g., a monofunctional and/or difunctional isocyanate polyamide (OCN—PA-NCO) or polyimide (OCN—PI—NCO)) and the A-Block is formed from a hydroxyl functional precopolymer (e.g., a monofunctional and/or difunctional polyoxyethylene (HO—PEO—OH)).
Although certain polymers are described herein, the polymers used to form the B-Blocks of the A-B Block copolymers for the present disclosure can be from a wide variety of polymers that include polyamide groups, polyimide groups, or combinations thereof. Such polymers are prepared from acid-containing compounds, such as polycarboxylic acids (e.g., dicarboxylics), and compounds having at least two hydrogen atoms reactive with the acid groups, such as polyamines (e.g., diamines).
Each of the individual A-Blocks and B-Blocks, as well as the resultant copolymer, may be linear or branched, although not so significantly branched that the resultant polymer is not thermoplastic. Because the B-Block can be branched, it is envisioned that the A-B block copolymer could be a star block copolymer, for example.
The copolymer according to the present disclosure can be obtainable by reactive processing of a mixture comprising the A-Block polymer and the B-Block polymer, as discussed herein, in a melt-mixing process, i.e., reactive processing the polymers together in an internal mixer, a single screw extruder, a co- or counter rotating twin-screw extruder, an open mill or any other type of equipment suitable and known in the art. Preferred conditions for forming the A-B Block copolymer include the use of an inert atmosphere (e.g., nitrogen or argon), temperatures of about 20� C. to about 150� C., and reaction times of about 1 hour to about 3 days. The A-Block and B-Block precursors are typically combined under such conditions to form the A-B Block copolymers of the present disclosure. Other reaction schemes are also possible.
In an additional embodiment, additional block copolymers suitable for use in the present disclosure include, but are not limited to, polyamide/polyether block copolymers such as those sold under the trade name "PEBAX" by Elf Atochem.
The present disclosure further provides that the soft segment polymers forming the A-Block can be functionalized with a coupling agent. In one embodiment, the A-Block polymers can be functionalized with the coupling agent in a number of ways. For example, the A-Block polymers can be functionalized by reacting the A-Block polymers with a coupling agent such as a cyclic anhydride, or other suitable like materials. In addition, the coupling agent is not covalently coupled to the B-Block polymer hard segments. The resulting functionalized copolymer (i.e., the copolymer of the B-Block and A-Block polymer having the covalently bonded coupling agent) can then react with the inorganic component during a reactive extrusion process to form the reinforced copolymer of the present disclosure.
Alternatively, the functionalized copolymer of the present disclosure can be used as a compatibilizer for blending and/or reacting with one or more additional polymers. When used as a compatibilizer the functionalized copolymer can be used to blend, for example, polar with non-polar polymers selected from polar/non-polar thermoplastic elastomers, non-polar polyolefins/polar thermoplastic elastomers and non-polar thermoplastic elastomers/engineering resins.
According to the present disclosure, the A-Block polymers can be functionalized with the coupling agent prior to being copolymerized with the B-Block polymers. Alternatively, functionalization with the coupling agent can take place after copolymerization of the A-Block and B-Blocks. The functionalized copolymer of the present disclosure can then be modified with the inorganic component, as will be discussed herein, by reacting the functionalized copolymer with the inorganic component in a reactive extrusion process to form the reinforced copolymer of the present disclosure. The reactive extrusion process can be carried out in conventional polymer processing equipment such as a single screw extruder, a twin screw extruder, a two roll mill, or a Henschel type of mixer, and the like.
Typically, the coupling agent(s) can be added to the A-Block polymer after the polymers (e.g., the A-Block alone, or the A-B Block copolymer) have been molten and blended. The reaction temperature depends on the melting-point of the polymer and is typically 150� C. to 250� C. Free radical source suitable for use in the process of the present disclosure are those materials typically used for the A-Block polymers provided herein that exhibit free radical generation in the melt processing range typically used for such polymers. Specific examples include acyl peroxides, such as benzoyl peroxide; dibenzoyl peroxide, dialkyl, diaryl, or aralkyl peroxide, such as di-t-butyl peroxide; dicumyl peroxide; cumyl butyl peroxide; 1,1-di-t-butyl peroxy-3,5,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; 2,5-dimethyl-2,5-bis-(t-butylperoxy) hexyne-3 and bis(a-t-butyl peroxyisopropylbenzene); peroxyesters such as t-butyl peroxypivalate; t-butyl peroctoate; t-butyl perbenzoate; 2,5-dimethylhexyl-2,5-di(perbenzoate) t-butyl di(perphthalate); dialkyl peroxymonocarbonates and peroxydicarbonates; hydroperoxides, such as t-butyl hydroperoxide, p-methane hydroperoxide, pinane hydroperoxide and cumene hydroperoxide and ketone peroxides, such as cyclohexanone peroxide, methyl ethyl ketone peroxide, and the like.
The free radical source is generally used in the process according to the present disclosure in a sufficient quantity to make it possible to effect the coupling of the coupling agent. Furthermore, it is desirable that the quantity should not exceed the minimum quantity needed because any excess of radical-generator may results in a degradation of the copolymer and/or may create undesirable cross-linking of the copolymer.
Examples of cyclic anhydrides useful for making the functionalized copolymer for the reinforced copolymer according to the present disclosure are selected from the group consisting of maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecylsuccinic anhydride, phthalic anhydride, nadic anhydride, pyromellitic anhydride, and mixtures thereof. A cyclic anhydride, which is particularly useful in certain embodiments of the disclosure, is maleic anhydride. The molecular weights of the cyclic anhydrides useful for making the reinforced copolymer may vary depending on the desired properties and use.
As used herein, the inorganic component servers as a reinforcement in the reinforced copolymer. A reinforcement may be defined simply as the material that is added to the functionalized copolymer of the present disclosure to improve the strength of the copolymer. As is appreciated, the relative amounts of the various ingredients will depend in part upon the particular end use and on the particular reinforced copolymer that is selected for the particular end use.
Most of the reinforcing materials are inorganic products of high molecular weight. Various examples include glass fibers, boron fibers, carbon and graphite fibers, whiskers, quartz and silica fibers, ceramic fibers, and metal fibers. It is also possible to use organic reinforcements with the functionalized copolymer, such as natural organic fibers, and synthetic organic fibers.
A useful reinforcement for the reinforced copolymer of the present disclosure is inorganic components formed from sol-gel preparations of at least one silicon alkoxide. The resulting sol-gel preparations can be bonded to the functionalized copolymer through reacting with the coupling agent in the reactive extrusion process. In one embodiment, the sol-gel preparations are formed from at least one silicon alkoxide of the formula (Formula I):
wherein R is an organic group. Examples of such organic groups include a straight chain or branched alkyl group, a straight chain or branched alkylene group, where R optionally includes heteroatoms that may be in the chain of the organic group or pendant therefrom as in a functional group.
As used herein, the term "organic group" is used for the purpose of this disclosure to mean a hydrocarbon group that is classified as an aliphatic group. In the context of the present disclosure, suitable organic groups for the silicon alkoxide of this disclosure are those that do not interfere with the formation of sol-gel preparations.
In one embodiment, each R is independently a straight chain or branched alkyl group optionally including heteroatoms, such as nitrogen, oxygen, phosphorus, sulfur, and halogen. The heteroatoms can be in the backbone of R or pendant therefrom, and they can form functional groups such as heteroatom-containing groups (e.g., functional groups) include, for example, an alcohol, carbonyl, ether, acetoxy, ester, aldehyde, acrylate, amine, amide, imine, imide, and nitrile, whether they be protected or unprotected. In one embodiment, R does not include heteroatoms. In an additional embodiment, each R is independently a straight chain or branched alkyl group includes 18 carbon atoms or less. In a further embodiment, each R is independently a straight chain or branched (C2-C8) alkyl group. In other embodiments, each R is independently a straight chain or branched (C2-C4) alkyl group (e.g., ethyl, n-propyl, isopropyl, or butyl). In one example, R is a C2 alkyl group.
As will be appreciated, for Formula I, R can vary within any one of the sol-gel preparations. For example, in addition to each R being the same or different within each Si(OR)4, the OR groups can be the same or different in any one sol-gel preparation.
Although certain sol-gel preparations are described herein, the sol-gel preparations used in the present disclosure can be formed in a cross-linking process from a wide variety of silicon alkoxides of Formula I. For example, a method of preparing the sol-gel preparations involves the combining of at least one silicon alkoxide of the Formula I under sol-gel reaction conditions to form a reaction mixture allowing the sol-gel preparations to form in the reaction mixture.
The Sol-gel processes is generally described, for example, in "Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing" (Brinker et al., Academic Press, 1990). As used herein, "sol-gel" refers to any method of synthesizing the sol-gel preparations that comprises a step wherein at least one of the precursors is an aqueous or organic dispersion, sol, or solution.
Three reactions are generally used to describe the sol-gel process: hydrolysis, alcohol condensation, and water condensation. The characteristics and properties of the sol-gel preparations formed through the sol-gel process with compounds of Formula I can be related to a number of factors that affect the rate of hydrolysis and condensation reactions, such as, pH, temperature and time of reaction, reagent concentrations, catalyst nature and concentration, aging temperature and time, and drying. Controlling these factors allow for the structure and properties of the sol-gel preparations to be varied as desired.
A method for preparing the sol-gel preparations for the present disclosure through a sol-gel process involves the combining of (1) the mixture of the compound(s) of Formula I and (2) an aqueous or organic dispersion or sol of reagents that include at least one alcohol and a catalyst provided under conditions for the sol-gel reaction to take place. Examples of silicon alkoxides of Formula I include normal and branched butoxides, propoxides, ethoxides, and methoxides of silicon (Si) and mixtures thereof. Specific examples of suitable silicon alkoxide of Formula I include tetraethoxysilane (TEOS), and the like.
Examples of suitable catalysts include mineral acids such as hydrochloric acid (HCl), ammonia, acetic acid, potassium hydroxide (KOH), titanium alkoxides, vandium alkoxides, amines, KF, and HF. Additionally, it has been observed that the rate and extent of the hydrolysis reaction is most influenced by the strength and concentration of the acid- or base catalyst. In one embodiment, the concentration of the acid- or base-catalyst can be from 0.01 M to 7M. In addition, the nature of the sol-gel reaction can be influenced by the selection of an acid or base catalyst, where under acid-catalyzed conditions the sol-gel reaction yields primarily linear or randomly branched polymers which entangle and form additional branches resulting in gelation. On the other hand, the sol-gel reaction yields derived under base-catalyzed conditions can yield more highly branched clusters which behave more like discrete clusters.
Examples of suitable alcohols include anhydrous alcohol such as methanol, ethanol, propanol, butanol, pentanol, and mixtures thereof. Suitable alcohols have a water content of less than about 1% by weight, especially less than about 0.5% by weight or less than about 0.1% by weight. Other organic solvent (or mixtures of solvents) may also be used that are miscible with the other components.
Examples of suitable alcohols include anhydrous alcohol such as methanol, ethanol, propanol, butanol, pentanol, and mixtures thereof. Suitable alcohols have a water content of less than about 1% by weight, especially less than about 0.5% by weight or less than about 0.1% by weight. Other organic solvent (or mixtures of solvents) can also be used that are miscible with the other components.
According to the present disclosure, the sol-gel reaction can take place with the reagents in either a liquid phase and/or a gas phase. Typical reaction conditions for the sol-gel reaction can occur in a temperature range of 20� C. to 100� C. Other temperature ranges are also possible.
The method of forming the medical device and/or medical device component can then include (1) preparing the reinforced copolymer in the reactive extrusion process with the functionalized copolymer and the sol-gel preparation, and (2) forming the reinforced copolymer prepared from the extrusion into the predetermined shape of the medical device component. As discussed herein, preparing the reinforced copolymer in the reactive extrusion process includes combining the sol-gel preparations with the functionalized copolymer during the melt process to form the reinforced copolymer. The reinforced copolymer may contain a sufficient amount by weight percent of the sol-gel preparations that do not interfere with either the sol-gel preparations and/or the processing of the reinforced polymer.
The reinforced copolymer of the present disclosure can be utilized in several different ways: 1) on its own, (2) combined with one or more additional thermoplastics (co-block polymers—PEBAX�, polyamides), PET, etc. to alter the final properties of the reinforced copolymer. Furthermore, other components known in the art may be added to the graft polymers of this disclosure to further enhance the properties of the final material. All of these additives are generally used in relatively small amounts as compared to the weight percent of the final composition. Applications for the reactive extruded reinforced copolymer produced according to the present disclosure include films, injection molded articles (e.g., dilatation balloons), extruded profiles, fiber additives, and barrier containers.
The present disclosure provides for a reactive extrusion process of the functionalized copolymer and inorganic components to form the reinforced copolymer. As used herein, a "reactive extrusion process" is the use of chemical reactions during a polymer extrusion process to form desired products. Specifically, the present disclosure provides for coupling of a cyclic anhydride onto the A-Block polymer of the A-B Block copolymer followed by covalently coupling the inorganic components through the coupling agent during the reactive extrusion process.
Free radical initiators, crosslinking agents, and other reactive additives can be injected into the reactive extrusion process to cause and/or promote the coupling reactions discussed herein. In addition, while the reactive extrusion process may result in production of a homogeneous product, a somewhat heterogeneous product is within the scope of this disclosure. Examples of such processes and/or techniques include, but are not limited to, mixing process that include screw extrusion (single or twin barrel), among others.
The melt extruder used in the reactive extrusion process of the present disclosure is designed to conduct several operations during the preparation of the melt reactive extrusion. The reinforced copolymers of the present disclosure are produced in the reactive extrusion process. In one embodiment, it is desired according to the present disclosure to blend or mix the A-B Block copolymer, the coupling agent (e.g., the cyclic anhydride), a free radical source, and the sol-gel preparations in an extruder, such as a single-screw or twin-screw extruder under appropriate temperature and shear/pressure conditions to ensure mixing.
A particularly desirable reaction device is an extruder having one or more ports. For example, the reaction device is a co-rotating, twin-screw extruder, that allows multiple feeding and venting ports and provides high intensity distributive and dispersive mixing that is essential to produce functionalized copolymers of uniform composition and homogeneous distribution of the sol-gel preparations in the functionalized copolymer. The reactions are desirably conducted in the polymer melt phase; i.e., in the absence of bulk solvent. This is an effective process since the solvent removal step is not needed in the process.
In one embodiment, the A-B Block copolymer is fed into and melted in the melt extruder. After melting the A-B Block copolymer, the coupling agent (e.g., the cyclic anhydride) is fed into and melt blended in the melt extruder and, further down the extruder barrel, the free radical source, such as a peroxide, is fed to the extruder to yield improved coupling efficiency of the coupling agent to form the functionalized copolymer. After a length of extrusion sufficient to accomplish coupling of the coupling agent, i.e., sufficient time, the sol-gel preparations are fed to the molten, functionalized copolymer stream either as pellets or powder through an open throat to the extruder or as a molten stream fed through a side stream extruder. After melt consolidation of the functionalized copolymer and the sol-gel preparations, a vacuum port can optionally be used to remove ungrafted or unreacted coupling agent (e.g., cyclic anhydride).
By coupling the coupling agent onto the A-B Block copolymer, the resulting functionalized copolymer is more compatible with and reactive to the sol-gel preparations. The compatibility of the functionalized copolymer of the present disclosure with the sol-gel preparations can be controlled by the selection of the coupling agent, the level of coupling and the blending process conditions. Tailoring the compatibility of the functionalized copolymer with the sol-gel preparations leads to better processability and improved physical properties of the resulting reinforced copolymer.
The resulting reinforced copolymer can then be processed in a number of ways into a predetermined shape. Processes useful with the reinforced copolymer include, but are not limited to, injection molding, compression molding, over molding, dipping, extrusion, roto-molding, slush molding, fiber spinning, blow molding, polymer modification, cast film making, blown film making and foaming. In addition, the resulting reinforced copolymer can also be coated onto or coextruded with a substrate in forming the medical device component.
Included with the predetermined shapes are both balloon dilatation catheters and the dilatation balloons, as are known. The reinforced copolymer of the present invention can be used to form dilatation balloons by known techniques such as free-blowing or through molding techniques. As is known, the molding techniques can include positioning tubing formed from the reinforced copolymer of the present disclosure in a blow molding apparatus. One end of the tubing can then be connected to a source of pressurized gas, while the other end of the tubing extending beyond the mold can be clamped, or otherwise sealed, during pressurization of the tubing. The tubing can also be affixed to a tensioning device. The tubing within the mold is then heated to a desired temperature below the crystalline melting point of the tubing, such as until the material deforms, for example. During heating, or optionally after heating, pressurized gas is applied to the tubing, and optionally tension is also applied to the tubing, until the balloon is formed, filling the desired interior shape of the mold. The balloon and tubing are then cooled to room temperature. The balloon is then removed from the mold, and can be further processed to construct a dilatation catheter.
The reinforced copolymers of the present disclosure can be compounded with other components not adversely affecting the reinforced copolymer properties. Exemplary materials that could be used as additional components would include, without limitation, pigments, antioxidants, stabilizers, surfactants, processing lubricants, imaging enhancers, fillers, and the like.
The disclosure has been described with reference to various embodiments. It is understood, however, that there are many extensions, variations, and modification on the basic theme of the present disclosure beyond those discussed in the detailed description that are within the spirit and scope of the present disclosure.
The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of this disclosure. It should be understood that this disclosure is not intended to be unduly limited by the illustrative embodiments set forth herein and that such embodiments are presented by way of example only with the scope of the disclosure intended to be limited only by the claims set forth herein as follows.
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