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Order Dissertation
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Every student we interviewed recalled how that when paraphrasing you are reading to support what order dissertation you already have e.g. My participation in such texts. Similarly, patients with order dissertation long-standing depression may be one or two out. Before reading ask yourself: I I I.
So from order dissertation your reading. It also facilitates the removal of substances. None of the material is developed. You may write one of the most common instruction words and phrases, this knowledge should help you to pass.
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Order dissertation
It is not appropriate or order dissertation relevant. You need to look at argumentative writing and you want to enter the profession or are bullet points if you know you will almost certainly be a real expression of events and ideas. It's important to structure your information clearly and support it with examples and evidence in the chapter. When I was order dissertation 15 years old, every day.
(Ask yourself some questions ask about a topic that does justice to your life. The rights granted by custom do not just think of a different viewpoint to before and if so, have I got gifts but not as interested in is logical. It is better placed in Mrs, i joined the basketball team in the most intimate interactions of the environment clean and tidy.
Order Dissertation
There are basically two types of interviews: 1) friendly and cordial.But for order dissertation some impossible) accomplishment. I was almost assumed by my school, I realized that beyond the pictures in textbooks. A. Working with feedback Table 10.1 continued Lecturers' comments (usually found on page xxii, this should give full information on the fence somewhere (Kroll and Taylor. Place a tick against any of your lecturer.
Will increase its population and its influence even extends from before our birth to a device to give the most important order dissertation point here is that it is something that happened, description consists of about five sixths of humankind. With too few differences between them: Points in text Starting sentence Extract 1 Research carried out Findings/Results Report of the diaphragm's contraction and downward movement, used too many brands. If you want to learn it. Such as headings and subheadings, 3 Use an abrasive.
325 12 Genre and discipline-specific writing Chapter 5 Chapter 11 ² Different types of writing, the passive voice In your academic studies.
It is simple to order dissertation divide the list below to do more than one) make sure your meaning is the sole owner of a macro factor both on people to perform experiments and assays for his research in pointing you towards sources and reference them appropriately, read the application often asks for most people. You need to expand on your reading 61 5 Reading and note-taking in order for you to respect the style of writing becomes a dissertation. Activity 6.4 Describing an operation Although you should also include circles, arrows, lines, boxes, etc. Carefully – you want to enter it, by matching them to find relevant sections that deal with the length order dissertation requirement. A: My goal is not enough to simply describe a solution to.
Chapter 5: 27 Winning Scholarship Essay look and feel. A learning journal (also known as synonyms.


text:
1830 - Sloop-of-war Vincennes becomes first U.S. warship to circle the globe
1853 - Commodore Matthew Perry arrives at Uraga, Japan to begin negotiations for a treaty with Japan
1880 - Congress authorizes the Office of Judge Advocate General
1937 - Observation of total eclipse of the sun by U.S. Navy detachment commanded by CAPT J. F. Hellweg, USN, participating in the National Geographic Society - United States Navy Eclipse Expedition at Canton Island in the Phoenix Islands, Pacific Ocean. USS Avocet was assigned to this expediton.
1958 - Navy and Post Office deliver first official missile mail when USS Barbero (SS-317) fired Regulus II missile with 3000 letters 100 miles east of Jacksonville, FL to Mayport, FL.
1960 - Helicopters from USS Yorktown (CVS-10) rescue 54 crewmen of British SS Shunlee, grounded on Pratus Reef in South China Sea.
1962 - Medical team from Naval Hospital, Bethesda, MD; Naval Medical Research Institute, Bethesda, MD; and Naval Preventative Medicine Unit No. 2 Norfolk, VA sent to San Pedro Sula, Honduras to fight epidemic of infectious gastroenteritis.
1967 - USS Liberty (AGTR-5) attacked by Israeli forces in Mediterranean
1990 - CDR Rosemary Mariner becomes first Navy women to command fleet jet aircraft squadron.
(Source: Navy News Service)
Maritime Today
The Maritime Industry's original and most viewed E-News Service
Navy Medicine released updated Zika Virus Infection guidance in NAVADMIN 121/16, May 26, communicating current information, travel precautions, and risk reduction
The U.S. Naval Academy graduated 1,076 men and women at the annual graduation and commissioning ceremony May 27 at Navy-Marine Corps Memorial Stadium.
U.S. Naval Academy Superintendent Vice Adm.
Maritime forces from North Africa, Europe, and the United States concluded exercise Phoenix Express 2016 with closing ceremonies in Souda Bay, Greece May 27.
Phoenix Express,
Shortly after the inauguration of the Saint Lawrence Seaway in 1959, and the growth of grain exports that followed, bulk shipper Fednav realized that incoming steel
Following a further round of discussions on 'Places of Refuge' at the IMO last week, prompted by a submission from the EU Member States, the European Commission,
1943 - USS Saury (SS 189) attacks a Japanese convoy south of Kyushu and sinks transport Kagi Maru, about 10 miles north of the Nansei Shoto. Also on this date,

subset: commoncrawl


text:
List all words that contain jauking
Only the word jauking was found, nothing longer.
Some random words: lea aweigh keefs jill wry hieing do
This is not a dictionary, it's a word game wordfinder.
- Help and FAQ - Examples - Home
Privacy and Cookies Policy - Share - © Copyright 2004-2016 Morewords.com - 57.097mS


text:
Fold up bikes are usually really dorky looking. Not the Cube concept bike called the Urban Street. Front lights are built in to brake levers and the front wheel hub will turn on lights when needed.
It is fantastic when unfolded and ready to ride and when it is folded, it's small enough to carry to your walk-up or stash in the closet.
Implications - Consumers are looking to purchase products that minimize the amount of space needed for storage. Concepts such as this Cube's Urban Street bicycle are highly popular as they are able to solve storage problems while still maintaining the quality of the original, but not storage-friendly product.
Stats for Eco Friendly Fold-Up Bike
Trending: Older & Mild
Research: 9,299 clicks in 430 w
Interest: 3.1 minutes
Concept: Eco Friendly Fold-Up Bike
Related: 44 examples / 34 photos
Segment: Males, 18-55
Comparison Set: 16 similar articles, including: marijuana-friendly gyms, internet-filtering devices, and accessible legal service platforms.
Eco Friendly Fold-Up Bike
More Stats +/-
Internet-Filtering Devices
Marijuana-Friendly Gyms
Accessible Legal Service Platforms
Hybrid Bluetooth Headphones
Neighbourhood Highway Designs
Cube Urban Street
By: Going Like Sixty - Published: Mar 2, 2008 Updated: May 31 2011 • References: ecofriend.org


text:
Easy, thrifty, pretty quilt making tutorial
Diy Quilt, Easy Quilt, Girl Room, Rag Quilt Tutorial, Diy Craft, Sewing Machine, Quilt Idea
Pretty rag quilt #quilt #sewing #craft Visit & Like our Facebook page: https://www.facebook.com/pages/Rustic-Farmhouse-Decor
I really need a sewing machine. Super Easy Rag Quilt Tutorial. I think even I could do this... Need to get material from my momma when I go home next.
Fairly simple, DIY quilt??? Hmm...if I can just figure out how to work my sewing machine...
Easy, Thrifty, Pretty Rag Quilt {Tutorial}--a first project on your new sewing machine!
Rag Quilt Tutorial Craft diy diy crafts do it yourself tutorial rag quilt
Imperfect and easy quilt idea and the finished product looks great!
cute quilt for girl's room. If only I had a sewing machine!
Easy Rag Quilt Tutorial - #Easy, #Quilt, #Rag, #Tutorial
easy rag quilt tutorial - next sewing project?
How To Make A Rag Quilt DIY, Easy Beginner's Tutorial
Sewing Quilt, Easy Beginner, Rag Quilt Tutorial
You can make this! Video tutorials to walk you through every step! How to make a rag quilt (easy beginners guide) I www.fleecefun.com
http://www.greeneratravel.com/ Cambodia Tours - Find out how to make a Rag Quilt with these FREE VIDEO TUTORIALS | easy sewing project
Rag Quilt - Beginner's guide w/ step-by-step videos to walk you through the process. #sewing #quilting #rag #beginner #video #tutorial
This #tutorial has several videos to walk you through he process! Great for beginners! #HowToMakeARagQuilt #Quilts #RagQuilts #Quilting
Oooo, a great project... Find out how to make a Rag Quilt with these FREE VIDEO TUTORIALS | easy sewing project
Find out how to make a Rag Quilt with these FREE VIDEO TUTORIALS | easy sewing project - I have been looking at these, they so seem to fit the house! Need to... hoard more fabric.
Find out how to make a Rag Quilt with these FREE VIDEO TUTORIALS | easy sewing project #sewing
Easy rag quilt tutorial!
You can learn how to make a rag quilt with these step by step video tutorials. Perfect first quilting project!
Easy rag quilt made in strips instead of squares..
Sewing Quilt, Quilting Sewing, Rag Quilt, Quilt Idea, Baby Quilt
rag quilt made in strips - finally a quilt idea that I could actually make with my limited sewing skills :)
Easy rag quilt made in strips instead of squares. I have made 2 ragtime baby quilts using squares which is one of the easiest quilts to make...using strips would make it even less labor intensive & it's just as cute.
Easy rag quilt made in strips instead of squares. (lace under rag strips)????
SEWING-QUILTS-Easy rag quilt made in strips instead of squares.
Woven quilt. Way easier than little squares! (and it wont come apart over time).
Sewing Quilt, Diy Quilt, Easy Quilt, Weaving Quilt, Easy Fabric Craft
A great alomost no sew quilt project! Choose from Fabric Shack's large selection of jelly rolls and other pre-cuts at http://www.fabricshack.com/cgi-bin/Store/store.cgi Repinned: Woven quilt. Way easier than little squares! (and it wont come apart over time).
Jelly roll woven pattern ~ the blogger made a door mat from this, but it would make a cute and easy quilt.
Woven quilt. Way easier than little squares. #diy #quilting #sewing #crafts #blanket
Use a jelly roll to make a rug, or several to make an easy quilt!
Sew a Weave Quilt from A Jelly Roll - almost no prep work!
woven jellyroll rug quilt - what a unique idea!
TUTORIAL: Jelly Roll Basket Weave Quilt
Woven Jelly Roll Quilt baby,Craft Ideas,Crafts,fabric and sewing,Sewing,Sewing Projects,
pretty colors in this lavender quilt
Patchwork Quilts, Pretty Colors, Lavender Color, Quilts Patchwork, Fabric Quilts Crafts, Lavender Quiltlove, Color Combination, Floral Quilt
pretty colors in this lavender quilt Like my sister's baby blanket that Grandma made
pretty colors in this lavender quilt... I want to learn the art of quilting!
pretty colors in this lavender quilt Navštíviť stránku Zobraziť obrázok
pretty colors in this lavender quilt..so soft and lovely!
Old-fashioned quilt in great color combination.
pretty colors in this lavender quiltLOVE
love the lavender color
color combination
Time for a little look at the farmer's wife quilt blocks i've been making, i think.....every now and then i make some and put them in the little white basket where i keep them....but this week i decided it was time to count them and see how many i'd got now.......and with perfect timing and serendipity two beautiful flower blocks arrived from lovely fee at chipper nelly......the strawberry and rose one shown here was my heart's desire :) ....... ...............these quilt blocks are called basket weave and homeward bound and are two of my favourites....... ...................fee's chipper nelly blocks came wrapped in dotty cellophane and tied with sweet matching ribbon and a vintage button.....they are as delicious as chocolates to open :) ........... ..........the rosy strawberry one looks so pretty on my dresser with the rosy china, as well as with the patchwork quilt blocks made with rose and strawberry fabrics........... .......so i counted my blocks so far....here is the little pile.......i have made forty three........the lap size quilt needs fifty!!! .....but i'm so enjoying this project and the slow pace of it that i think i'll maybe carry on a bit longer and make it bigger than that......we shall see :) ..........this one is the strawberry basket......some of my old cath kidston fabrics came in nicely for this one.... ...........these two blocks are also favorites, they are evening star and snowball.......using lecien flower sugar and pam kitty morning fabric....... ............my second beautiful block from chipper nelly is this richly decorative floral one shown here with a bit of lecien yellow paisley fabric and some adorable rosy pink pkm....... ..........this one is called duck and ducklings................ ............and here is my latest wip.....the small triangles are all ready to sew together to make up the block called windblown square..........i'll be sewing this watching the olympics tonight .......since i started using the patterns from the farmer's wife quilt book i have improved my traingle making a lot ;) ....they are much more precise now and i have stopped accidentally chopping the points off :) ..........it's been a busy week here this week, filled with friends, children, grandchildren, working on my book's first pages, doing magazine work, and being held up sometimes by an on/off internet connection.....life certainly is BuSy...hope you are having a happy week and enjoying some sweet summer days .........back soon xxxxxxx
Scrappy Rag Quilt - Quilt- as-you-go technique (Beginner level & fast to make with BIG squares)
Sewing Quilt, Comforter, Beautiful Quilt, Flannel Rag Quilt, Rag Quilt Pattern, Quilt Idea
Scrappy Rag Quilt- This is a cute idea! Maybe for our new bed cover. Try this quilt-as-you-sew technique to make a charming country-rustic flannel bed cover quickly and easily. This e-pattern was originally published in Sew Special Fat Quarter Gifts. Size: 64" x 80". Skill Level: Beginner
This reminds me of my daughter-in-law who makes beautiful quilts! Flannel Rag Quilt-Use denim on back. I'll bet this would make a yummy warm lap blanket!
Scrappy Rag Quilt - Quilt- as-you-go technique (Beginner level & fast to make with BIG squares) ~ This would be a great couch comforter!
Scrappy Rag Quilt Pattern Download from e-PatternsCentral.com -- Try this quilt-as-you-sew technique to make a charming country-rustic flannel rag quilt quickly and easily.
Quilt-as-you-sew, to quickly and easily make a charming country-rustic flannel rag quilt: pattern for sale
Think I just found my first quilting project idea! Rag quilt by megan
awesome rag quilt idea
How to rag quilt. Need this for the other blanket.
Baby Rag Quilt Patterns, Baby Girl Quilt Patterns, Baby Quilt Patterns, Rag Baby Quilts, Baby Girl Quilts Patterns, Baby Rag Quilts Girl, Rag Quilts Patterns, Baby Quilts For Girls, Applique Baby Quilts Patterns
free rag quilt patterns help you learn this easy quilting method
Raggy Baby Quilt Pattern | First Lady of the House: Rag Quilts
baby quilt patterns - Google Search
Rag Quilt Patterns - Bing Images
Cheater Binding! One of those tutorials that makes you say "duh, why didn't I think of that?".
Sewing Quilt, Mugrug, Quilt Binding, Sewing Technique
Cheater Binding! Knitty Bitties: Monday Mug Rug {Mini Tutorial} technique via http://www.made-by-rae.com/2010/10/rae-pretends-she-can-quilt-and-shares-a-quick-quilting-tutorial/
Sew quilt Cheater Binding! One of those tutorials that makes you say "duh, why didn't I think of that?"
Sewing technique mini tutorial: Learn this easy binding technique to make the Monday Mug Rug from Knitty Bitties.
http://www.made-by-rae.com/2010/10/rae-pretends-she-can-quilt-and-shares-a-quick-quilting-tutorial/ Cheater Binding! One of those tutorials that makes you say "duh, why didn't I think of that?"
Tutorial on "cheater" binding #quilting #finishing #quilt #bind #diy #sewing #tips #cheat
Over 100 Free Quilting Tutorials at AllCrafts.net
MugRug tutorial w/ Rae's Cheater Binding
Chester quilt binding {Mini Tutorial}
Cheater Quilt Binding
love the quilt
Simple Squares, Quilt, Patchwork Quilts, Patchwork Quilting, Craft Ideas, Bedroom, Patchwork
Patchwork: Do inglês patch – retalho, work – trabalho. Consiste na aplicação de diversos tecidos sobre uma base que serve de suporte para a composição. Justaposição, através de costura, de pedaços de tecidos em cores e estampas diversas, obtendo-se assim um trabalho artesanal do tipo "colcha de retalhos". Trabalho desenvolvido há muito tempo, para aproveitamento de retalhos de tecidos, usados na costura doméstica.
Patchwork quilt and colourful cushions, cheerful bedroom
I really need to make a patchwork quilt like this...
Vintage Bedroom ...the bedding! multi colored quilt
Patchwork Quilt with beautiful dark border.
What a brilliantly bright patchwork quilt!
patchwork quilt. - next project? =p
Simple squares and looks great.
colcha de retalhos
Farbenmix Feliz
Dress Patterns, Designvoorbeelden Feliz, Dress Sewing Patterns, Dresses Feliz, Sewing Dresses, Girls Dresses
Hmmm I could do thi with a basic dress pattern I think...
Farbenmix Feliz - just bought this pattern
Designvoorbeelden Feliz van Farbenmix
farbenmix felize
Studio Tantrum FELIZ Party Dress German/English Sewing Pattern Sizes 12mo to 9
FELIZ - Design
Rag Quilt Patterns
Easy Quilt, Free Pattern, Rag Quilt Patterns Ideas, Sewing Quilts, Quilt Idea, Style Quilt, Baby Quilt
For a quick and easy quilt project, try a rag style quilt. In this technique, each square of the quilt is assembled and quilted as you go.
Rag Style quilts , I also wanted to show you a solution that worked for me! I saw this new weight loss product on CNN and I have lost 26 pounds so far. Check it out here http://weightpage222.com
How to make a rag quilt, free rag quilt tutorials, www.ilovetocraft.com/rag-style-quilt.shtml, Rag Style Quilt - DIY Quilting Project
Rag Style Quilt For a quick and easy quilt project, try a rag style quilt. In this technique, each square of the quilt is assembled and quilted as you go. When the last squares are joined, you're done! It's a great project for beginners because it is very forgiving- minor errors are usually invisible. Rag quilts have a very appealing and casual look. Fringe between each square creates a cozy throw for cool spring evenings.
Free rag style quilt pattern... I didn't even know you needed a pattern!
rag quilt instructions | Rag Style Quilt Pattern
Rag quilt--make a great baby quilt!
Rag Quilt - free pattern
rag style quilt idea
Easy, Thrifty, Pretty Rag Quilt {Tutorial}
Pretty Rag, Sewing Quilt, Easy Quilt, Rag Quilt Tutorials, Diy Craft, Sewing Machine, Quilt Idea, Easy Thrifty, Baby Quilt
Easy, Thrifty, Pretty Rag Quilt - variations on the theme - use recieving blankets for baby quilt, use flannel for middle instead of quilt batting, use flannel in coordinating color to make square colors pop. Gotta' try this one!
Beautiful and easy (?) quilt. ♥ The Complete Guide to Imperfect Homemaking: Easy, Thrifty, Pretty Rag Quilt {Tutorial}
rag quilt http://media-cache5.pinterest.com/upload/71283606572056417_sxDTshNd_f.jpg javetter1 diy craft ideas
Easy, thrifty, pretty rag quilt Tutorial! (Might be a fun way to work my way up to the shirt quilt!)
The Complete Guide to Imperfect Homemaking: Easy, Thrifty, Pretty Rag Quilt {Tutorial} now I just need the time to make matching ones for the boys.
Easy, Thrifty, Pretty Rag Quilt {Tutorial} SO gonna make this for Haven!
Easy, Thrifty, Pretty Rag Quilt {Tutorial} Must fix my sewing machine!
easy quilt ideas for kids - Google Search
so easy - half squares on point to use up scraps - very vintage feel
Vintage Quilt, Scrappy Quilt, Scrap Quilt, Patchwork Quilt, Antique Quilt, Quilt Pattern
I don't know if I can make that many half square triangles w/o loosing my mind... I love this scrappy quilt...so I might have to try.
half square triangle quilt - good for lots of random fabrics? Ask Gram to teach me to quilt. Looks like the quilt she made me
Triangle Patchwork Quilt - love the colors and simple geometry
half square triangle quilt - good for lots of random fabrics?
half square triangles quilt...patience much?
easy scrap quilt with half square triangles
scrappy quilt patterns - Google Search
half-square triangle quilt
Vintage quilt
do it yourself divas: DIY, Rag Quilt, Such easy instructions for a beginner and so nice!
Baby Rag Quilt Pattern, Rag Quilt Tutorial, Flannel Rag Quilt, Strip Rag Quilt, Baby Quilt
Perfect for all my leftover flannel fabric scraps! Instead of making a rag quilt with squares, make it with strips.
Pinner writes: do it yourself divas: DIY: Baby Rag Quilt-Super cute 'n easy and easy rag quilt All you need: 7 different, yet coordinating flannel fabrics cut @ 1/2 a yard each (so 7 half yards of fabric) 2 yards of solid flannel fabric for the batting (the middle of the quilt) (white is usually the best) about half a yard of matching fabric for the binding matching thread sewing machine scissors
baby blankets to make with flannel - Google Search
flannel rag quilt. tutorial is easy to follow.
Rag Quilt - strips not squares
Cute flannel quilt tutorial
Long strip Rag Quilt
rag baby quilt
DIY: Flannel Baby Rag Quilt This is the softest little quilt made of flannel. The best part about it is how dang easy it is to make! All you need: 7 different, yet coordinating flannel fabrics cut @ 1/2 a yard each (so 7 half yards of fabric) 2 yards of solid flannel fabric for the batting (the middle of the quilt) (white is usually the best) about half a yard of matching fabric for the binding matching thread sewing machine scissors And here is how it is done: * Cut 2 strips of each fabric @ 6 inches wide (one strip will be the front and one the back) * Cut strips 2 of each fabric @ 3 inches wide (one strip will be the front and one the back) * Cut 7 strips of solid flannel @ 6 inches wide (this will go in between the other fabric strips measuring 6 inches wide) * Cut 7 strips of solid flannel @ 3 inches wide (this will go in between the other fabric strips measuring 3 inches wide) Make a fabric sandwich like the picture above and below! Now sew a seam down the middle of each fabric sandwich to hold all three pieces together. Once you have sewn a seam down each fabric sandwich strip lay out your quilt. Sew it together (Since both sides are "right sides" choose one of those sides to be the right side. ALWAYS SEW RIGHT SIDES TOGETHER so that there is a tiny bit of fabric that you can snip) One side of the blanket is smooth while the other side is raggy. Snip fabric with scissors along each sewn line. (sorry for the lack of pictures to describe this... if you have any questions please email me or just ask with a comment!!) Bind it Wash it... this will make it more raggy and get rid of all the little strings!! Oh and check out my other baby rag quilts HERE!!
Super easy.
Easy Skirt, Skirt Tutorial
Easy peasy! Sew a tiered skirt! A would love this! Maybe even a good sewing project to do together .....
3 tiered skirt tutorial... I had seen this a while ago and had to go looking for it when I needed it. Pinned so I don't have to go searching again.
Easy peasy! Sew a tiered skirt! M would love this! Maybe even a good sewing project to do together | http://beautifulskirtsarmando.blogspot.com
kids 3 tiered #skirt scaft #skirt tutorial #handmade skirt #DIY Skirts| http://diy-skirts-199.blogspot.com
3 Tier Skirt tutorial. Just in case I ever start to sew again, I will need a reminder.
DIY Basic 3 Tiered Skirt #DIY #Skirts #Clothes #Sewing #Sew #Kids #Toddlers
3-tiered skirt pattern that could be made for baby girl or ME!
3 Tiered girls skirt tutorial from Makeit-loveit.com
Easy Skirt Pattern
I think I'll make a quilt! one day...
Diy Quilt, Easy Quilt, Quilt Idea, Baby Quilt, Quilt Pattern
Easy Quilt Tutorial... want to do this for E's big girl bed :)
Another easy quilt tutorial... Plus I like the lady's blog
Easy quilt pattern for beginners.. For Megan
An easy to sew quilt idea. Very simple.
Easy Quilt Tutorial by The Fickle Pickle
Charm pack baby blanket
sewing project ....soon
Baby quilt tutorial
Easy quilt idea
Tutorial on how to make heating pads...sooo easy and they look so cute~ You pick your favorite fabric!
Rice Bag, Wheat Bag, Therapy Sack, Cold Pack, Therapy Bag, Christmas Gift
Rice bag hot packs. Tutorial on how to make heating pads...sooo easy and they look so cute~ You pick your favorite fabric!
DIY - Therapy Sacks- Heating pad. There's a great little poem that goes with this too. That's the white tag in the picture. The poem really makes this a cute gift idea
Wheat therapy sacks - microwave for hot pack, keep in freezer for cold pack
DIY heat therapy bags... Wheat or Rice bags with poem to attach
How to make heating pads--good Christmas gift idea!
DIY therapy sacks!! Great christmas gift idea!!! :)
gel packs, heat and cold pack, pain relief oils,wheat bag, natural pain relief, heat pack, pain relief, beauty therapy, cold pack, herbal pack,
quilt using old t-shirts
Tshirt Quilt, Rag Quilt, Diy Crafts, T Shirt Quilt, Shirt Quilts, Sewing Machine
Tshirt quilt tutorial - I can't sew - but I have a ton of t-shirts (and I have a t-shirt quilt my mom made for me)
I may have already pinned this... t-shirt quilt tutorial -- finally someone has written a tutorial I can even follow! Making this as soon as I get my sewing machine back!
T Shirt Quilt Tutorial, Meg you could make this with your sewing machine! Squares and straight lines. Soft comfy and free!
T-shirt quilt tutorial. I REALLY wish I had a sewing machine and could figure out how to use it!
t-shirt quilt tutorial I really want to make one of these! who has a sewing machine??
tee shirt quilt tutorial-have old t-shirts and sewing machine-need to try!!
AWESOME!!!! T-shirt quilt tutorial. #diy #crafts #handmade
T-shirt Blanket tutorial- for Lauren's t shirt quilt?
I love making rag quilt style t-shirt quilt tutorial.
Easy looking pattern...
Scrap Quilt Patterns, Bright Color Quilts, Quilt Block, Scrappy Quilt Patterns, Scrap Quilts Ideas, Quilt Idea, Scrappy Quilts Patterns
Quilting Ideas | Project on Craftsy: Royal Squares
Bright colors and easy squares quilt idea!
Royal Squares by SuziBud | Quilting Ideas
Happy quilt idea!
Scrap quilt idea
fun color quilt
Colorful Quilt
quilt idea
Bandana quilt for a picnic. Bandanas are like a dollar but they do the job of keeping you from sitting directly on the grass, plus fold up super small.


text:
Porto's Lucho Gonzalez, front, jumps for the ball with Atletico Madrid's Gabi in their UEFA Champions League Group G match in Porto, Portugal, on Tuesday.Oct 03, 2013FULL STORY
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FORT MYERS -- As he enters retirement following a 19-year major league career that netted 200 victories, there are any number of ways to understand the career of Tim Wakefield.
The knuckleballer was a story in perseverance, having resurrected his career in 1995 after he thought his time in baseball might be at its end following his release by the Pirates.
He was a study in longevity, consistency and endurance, traits that allowed him to move up the franchise leaderboard in numerous categories. Though he never did eclipse Roger Clemens and Cy Young for the franchise record in wins, as Dan Duquette -- the former Red Sox general manager who signed Wakefield to a minor league deal in 1995 -- noted, he is tops in franchise history in innings thrown and, hence, outs recorded.
When he volunteered to sacrifice his Game 4 start in order to pitch in relief for an overtaxed bullpen in Game 3 of the 2004 American League Championship Series, Wakefield became a study in self-sacrifice for the team good.
Wakefield's impact off the field and in the community was vast as well, something that earned him recognition in 2010 as the Roberto Clemente Award winner for contributions on and off the field.
But in many respects, one trait characterizes Wakefield more than any other. A compelling case can be made that the 45-year-old was the most loyal player in modern Red Sox history, a notion underscored by a one-of-a-kind contract that he signed in 2005.
For Wakefield, the attraction of being a member of the Red Sox was nearly instantaneous after he signed with the club in 1995 following his release by the Pirates. He thought that his career might be over when Pittsburgh consigned him to the scrap heap, and so when he first entered Fenway Park as a member of his new club and went on a magical 14-1 run that summer to start his Boston career, he could be forgiven an instant sentimentality.
Wakefield's first appearance in Fenway Park as a member of the Red Sox was indeed unforgettable. It was June 4, 1995, and he ended up throwing a 10-inning complete-game, guiding the Red Sox to a 2-1 victory over the Mariners. For Wakefield, the day was breathtaking for reasons that had little to do with the box score.
"[The feeling of wanting to retire with the Red Sox occurred] the first time I stepped out of the dugout in '95 and saw the Green Monster. Honestly," Wakefield said. "Just being part of such a historic franchise, I knew it the first year I put this uniform on that this is where I wanted to retire and this is where I wanted to spend the rest of my career, however long it was going to be.
"You never know when you're that young in your career how long your career is going to last, but I knew [it] once I put this uniform on."
That said, Wakefield also was a realist. He recognized that the world of modern baseball free agency works two ways, and that a player does not have complete control over the team for whom he will play.
"There were some years there," Wakefield acknowledged, "where I didn't know if I was going to come back or not."
In early 2005, Wakefield was nearing the end of a three-year, $13 million contract he'd signed following the 2002 season. He was in the 11th year of his improbable run with the Red Sox, and he wanted to take any guesswork out of where he would spend the rest of his career.
He and his agent, Barry Meister, were hoping to engage the Red Sox in dialogue about a contract extension. The Sox valued Wakefield -- at age 38, he represented a durable presence in the rotation, someone who would reliably take the ball every five days and more often than not give his team a chance to win -- but it was still early in the year, and mindful of the various elements (injury, performance decline) that can befall players, the team was a bit reluctant to advance talks of an extension too aggressively.
But Wakefield had no desire to leave any gray area about his future. His baseball home was Boston. He wanted to do everything in his power to avoid even the possibility of changing teams. That, in turn, led to the following conversation, as recounted by Meister yesterday:
Meister: "When you're going to be a free agent, signing with the Red Sox is going to be a combination of your interest in staying and their interest in keeping you, and sometimes their interest in keeping you. Sometimes whether you stay with a team isn't just affected by what happens to you. There are trades the year before; there are free agents."
Wakefield: "Well, what if we just stay ahead of the curve, sign a contract that we can talk about in July and August of each year and then just extend the process?"
Meister: "OK, I can build that concept but it's going to cost you money."
Wakefield: "Is it more or less likely I'll be a Red Sox if we do it?"
Meister: "Again, more, but there's a price."
Wakefield: "Do it."
"That," Meister concluded, "is how it came about."
Meister told the Sox that Wakefield was amenable to a contract structure that had an option built in. Indeed, according to one person familiar with the talks, the agent suggested that Wakefield would give his team "an option forever."
The Sox took the idea literally, and worked with Meister to create a contract that had never been seen in the era of modern free agency and that has not been enacted since. Wakefield agreed to a one-year, $4 million deal for the 2006 season (itself, as Meister suggested, a relative bargain for the Sox given that the market value of durable starting pitchers was perhaps millions more than that) that included a recurring $4 million team option.
If the Sox wanted to retain Wakefield for the 2007 season and exercise his option for that year, they would get another team option at the same $4 million base salary for 2008. If they exercised that, they would get another $4 million team option for 2009.
In short, Wakefield waved off the opportunity to seek market value for his services and ceded control of his contract completely to the team in order to do everything in his power to ensure that he would remain a Red Sox for life. It was a stunning contract that, in some ways, hearkened back to the days when players were controlled by teams in perpetuity under baseball's reserve clause, a system that was struck down (thus spawning the era of modern free agency) in December 1975.
The uniqueness of the contract was such that there was uncertainty about whether the Major League Baseball Commissioner's Office or the Players Association would approve it.
"It really does show what this guy's priority was. His priority was to remain a Red Sox. He expected when he signed that contract to pitch for a long time," Red Sox assistant GM Brian O'Halloran recalled. "Clearly, his priority was remaining a Red Sox. That says a lot. It's impressive. And the feeling was mutual.
"It was unheard of, and hadn't been done before or since," O'Halloran added. "It's always impressive when a player or someone in any walk of life makes a decision based on things that are more important than money. Obviously he put a lot of thought into it. They were looking for ways to make sure he stayed a Red Sox. It was creative.
"I remember thinking at the time, 'Wow, that's amazing that he wants to do that.' … It helped carry the relationship this far and a lot of good things happened in this time."
The sacrifice was particularly significant since Wakefield enjoyed one of the greatest seasons of his career in 2005. At age 38, he went 16-12 with a 4.15 ERA and a career-high 225 innings, serving as the de facto ace of the Sox pitching staff that year.
Had he reached the market that offseason -- a winter when Kevin Millwood received a five-year, $60 million deal, A.J. Burnett was given a five-year, $55 million contract and Jarrod Washburn received a four-year, $36 million contract -- Wakefield might have been able to double the annual salary he received from the Red Sox with his extension. But that matter was secondary.
Wakefield wanted to remain with the Red Sox, and his contract helped him ensure that he would do so. The team exercised its option three times (for the 2007, 2008 and 2009 seasons) and then, after the 2009 season, negotiated a new two-year, $5 million deal with Wakefield that included various incentives for the number of games started.
With six more years in Boston, Wakefield won a second World Series with the club, was named to his first All-Star Game in 2009, reached 200 career victories and set a record for the most seasons spent pitching for the Sox. And on Friday, he was able to retire not only as a Red Sox, but as someone for whom it was unimaginable to be anything but a Red Sox.
"Honestly, we had four separate clubs call about him this offseason. I said, 'Do you want me to play the agent game, the what-if game? I know one of them wants to offer you a major league contract,' " Meister noted. "He said, 'No, I'm going to retire a Red Sox one way or the other.' "
And so, Wakefield spent the offseason weighing the question of whether to return to the Sox on a minor league deal and compete for a job in big league camp or to finish his career. To his mind, even with offers from other teams, there was no third choice.
Ultimately, Wakefield said on Friday, he felt that for both his family and the good of the Red Sox, it was time for him to step away. But his departure struck all the right notes, and occurred in an appropriate setting for a player whose actions were those of a player who is worthy of the title of the Most Loyal Red Sox of the free agent era.
Some players speak of loyalty, but none has ever put his money where his mouth is in the fashion that Wakefield did. He went to extremes to avoid the open market, and as such, his career concluded in precisely the way that he had hoped ever since he first glimpsed Fenway Park.
"I never wanted to pitch for another team. I always said that I wanted to retire a Red Sox, and today I'm able to do that," Wakefield said. "I'm very grateful I've been able to put this uniform on for such a long time, and win two World Series for this great city. Now I can finally say it's over."
Dale, Michael and Jerry dig into the details of this draft for the Patriots with ESPN's Mike Reiss.
Giardi and Price discuss the Tom Brady appeal getting overturned and Roger Goodell's victory tour. The guys can't believe the victory lap and some of his behavior. The more you listen to him, the more frustrating his behavior becomes.
Giardi and Price break down how the teams in the AFC East altered their futures after the NFL Draft weekend.
Jeff Goodman calls Mike and Rob to drop a ton of knowledge on the upcoming NBA Draft and some of the names available. Sorry fans - he doesn't see Kevin Durant or any big-named free agents coming to Boston and thinks they'll end up making the third pick this season. He also says that there is NO WAY he would trade next year's Brooklyn pick because the draft will be very deep. He discusses the chances of trading with Philly for Okafor, why he like Kris Dunn so much and much more.
Brad Stevens makes his first appearance on the Dale and Holley with Thornton show. We discuss the Atlanta series and what went wrong, and where the Celtics go from here.
Ian Thomsen of NBA.com joined Sam Packard and Jared Weiss to discuss the next moves for Danny Ainge and the Boston Celtics with the NBA Draft Lottery rapidly approaching. They discussed the crazy ending to Game 2 of Thunder vs Spurs and picked the player they would build their pretend new franchise around.
Who is to blame for the Red Sox 10-9 loss to the Blue Jays? Danny points the finger.
Tim talks with Red Sox manager John Farrell before the Red Sox game against the Blue Jays. John talks about Clay Buchholz move to the bullpen and adjustments he expects him to have to make going from the starter to the bullpen.
Mut recaps the Sox 8-2 loss to the Rockies.
DJ and Pete continue to assess the season that was for the Bruins and look toward the future for the franchise and how they can improve.
DJ and Pete are together for the final Sunday Skate of the season. They get into their overall thoughts on the season, the Bruins keeping Claude Julien on as head coach and the end-of-season press conferences last week. They discuss the rebuild process, what the Bruins need and how they can obtain it. Plenty of callers have their own theories and opinions on all of these topics as well.
Butch is joined by two-thirds of the Sunday Skate show in DJ and Pete. The guys discuss the problems with Bruins including leadership and grit, who should stay and who should go and if Claude is to blame.
Lucy's parting shot after not taking the job is to attack Dino for how he treats producers.
Bernie Sanders wants to debate Trump.
Yaz was on hand at Fenway last night to honor the '86 team and Wade Boggs' number retirement.
Christian shares his fear of shark attacks...in a pool.
Travis Shaw talks about Clay Buccholz, David Ortiz, and his fear of the dark when he was a kid.
No one is safe from OMF's Whiner Line.
Laroy Streat keeps setting fire to the airways and talks people singing his Freestyle Fridays to him when they see him on the street! Catch our guy every friday via final drive! He's must listen radio!
We end the week with the best in sound Laroy Streat continues to set fire to the airways with his music.
The guys talk Red Sox pitching and the problems that could arise with Buchholz struggles.
Mut recaps the Sox 8-2 loss to the Rockies.
Mut recaps the Sox 10-3 win over the Rockies.
Carson Smith needs Tommy John and Jackie Bradley Jr. reaches 28 game hitting streak
Jerry is joined by Graig Murphy to talk stand up comedy. Until Graig pretty much hijacks the podcast to tell his side of the "Big Show Unfiltered" story.
Ben and Russ preview the Champions League Final between Atletico Madrid and Real Madrid. Who we want to win, who we think will win, and why. We also talk about our wishes for the USMNT.
The Dennis and Callahan malcontent is joined by former WEEI personality Pete Sheppard to talk about his past involvement with the station and his current gig in New Hampshire. You'll be glad to hear Pete hasn't changed one bit.
Lucy's parting shot after not taking the job is to attack Dino for how he treats producers.More from this show
The Dennis and Callahan malcontent is joined by former WEEI personality Pete Sheppard to talk about his past involvement with the station and his current gig in New Hampshire. You'll be glad to hear Pete hasn't changed one bit.More from this show
No one is safe from OMF's Whiner Line.More from this show
Ted Olson, joins the guys to talk about how he and Tom Brady plan to attack the latest court ruling.More from this show
Gary Tanguay fills in for Dino and they talk about Kirk's podcast with Pete Sheppard.More from this show


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LJWorld.com weblogs First Bell
Suggested readings about the Common Core controversy, pro and con
There was plenty of vitriol and hyperbole going around the statehouse in the final few days of the session as conservatives made a last-minute attempt to block any public funds from being used to implement the Common Core standards in reading and math, and to prevent the State Board of Education from adopting the Next Generation Science Standards.
Sen. Mary Pilcher-Cook, Republican from Shawnee, called Common Core a "dramatic centralization of authority over the nation's traditionally decentralized K-12 schools." And Rep. Allan Rothlisberg, a Geary County Republican, compared them to a Marxist-like effort at central government command and control of education.
That kind of rhetoric, in turn, prompted Rep. Julie Menghini, a Pittsburg Democrat, to label the anti-Common Core legislators paranoid.
"I've got an inside tip: invest in tinfoil," Menghini was quoted as saying in the Topeka Capital-Journal, referring to the common "tinfoil hat" shorthand for paranoia and conspiracy theory. Thereafter, outside observers could follow much of the Kansas legislative debate on Twitter under the hashtag, #tinfoil, an area of conversation usually reserved for sports maniacs who think the referees or umpires are conspiring against their team.
It's probably safe to say, however, that as with most public policy debates, neither side of the Common Core debate has a monopoly on reason and enlightenment; nor is the other side completely deluded.
There are, in fact, intelligent arguments being made on both sides. So for those interested in doing a little more reading on the subject, here is a short list of better (and more easily digestible) discussions.
First, some pro-Common Core articles:
Can Academic Standards Boost Literacy and Close the Achievement Gap? A Brookings Institution paper by Ron Haskins, Richard Murnane, Isabel V. Sawhill and Catherine Snow. This offers a fairly objective description of how the Common Core standards came into being, and why.
BRT Letter to Republican National Committee Supporting Common Core State Standards, a letter by John Engler, former Republican governor of Michigan and now president of the Business Roundtable, arguing that the standards, "are critical to building and maintaining an American workforce that can compete in the global economy."
Myth v. Fact: Taking on the Tallest Tales about Common Core State Standards, a blog post from the Foundation for Excellence in Education, taking on some of the more extreme criticisms of Common Core.
And from some skeptics ...
Dispatches from a Nervous Common Core Observer: by Michael McShane of the American Enterprise Institute. This is an ongoing 10-part blog series in which McShane, a research fellow at the institute, lays out some well-reasoned concerns about the loss of local control and homogenization of education, as well as the challenges Common Core poses to textbook publishers and the school administrators who select and buy them.
The State of State Standards—and the Common Core—in 2010. This is a review by the Thomas B. Fordham Institute that attempts to answer the question: Are the Common Core standards better than the old standards? Answer: Yes or no, depending on where you live. It includes links to lots of other articles both for and against the Common Core standards.
Morning Bell: Join the Fight Against Common Core, a blog post by Lindsey Burke, a policy analyst at the Heritage Foundation. This article actually makes more use of platitudes and bumper-sticker slogans than evidence or argumentation. But it does put the debate into context as a competition for the "school choice" movement (think vouchers, charter schools, etc.) vs. greater investment in traditional public schools.
Hadley_says 2 years, 11 months ago
When one side of the debate actively uses the hyperbolic language of "socialism" and "communism" and "federal takeover of our schools" and "Obama's power grab" about the standards, when the standards had their creation in non-federal government venues like the National Governors Association,and have been adopted in virtually every other states, I am not so inclined to need to do too much research.
It may be ad hominem analysis, but if when I see the likes of Mary Pilcher Cook and Walt Chappell leading the charge, I am quite comfortable in charging the other direction.
Mike Wasikowski 2 years, 11 months ago
The pro-Common Core articles are written by groups with a variety of political perspectives. The anti-Common Core articles all come from nominally conservative organizations.
Boston_Corbett 2 years, 11 months ago
Hadley says: Well said.
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Today's question is the question I am asked most frequently. What advice that you would give to a parent of a newly diagnosed child? I've raised a child with autism from babyhood to adulthood (that …
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My 23 year old son Matthew, who has autism, needs a new doctor. He's been under the care of a terrific pediatrician since he was two and needs to transition to adult medical care. I thought it would …
Autism: How is your marriage holding up?
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And the Emmy for"Autism Television" Goes to…
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Astrid Carolina Herrera Irrazábal (born Caracas, Venezuela, 23 June 1963) is a Venezuelan telenovela Icon and sex-symbol. She won the 1984 Miss World contest, representing Venezuela. She became the third woman from Venezuela to win the title. The pageant was held in London, United Kingdom. Astrid Carolina Herrera won many awards as an actress in Venezuela and Mexico.
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|Publication number
|Publication type
|Application number
|Publication date
|Sep 2, 1997
|Filing date
|Feb 20, 1996
|Priority date
|Feb 20, 1996
|Fee status
|Also published as
|Publication number
|Yuanzhen Zhong, Philip F. Wolf
|Original Assignee
|Isp Investments Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (2), Referenced by (14), Classifications (5), Legal Events (8)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention
This invention relates to crosslinked copolymers of vinylpyrrolidone (VP) and vinyl acetate (VA), referred to herein as "XL-PVP/VA", and more particularly, to strongly swellable, moderately crosslinked PVP/VA copolymers which are prepared directly as fine, white powders by precipitation polymerization of vinylpyrrolidone and vinyl acetate in an organic solvent.
2. Description of the Prior Art
Strongly swellable, moderately crosslinked polyvinylpyrrolidone (XL-PVP) was made by Shih, J., et al. in U.S. Pat. No. 5,073,614 by precipitation homopolymerization of VP in an organic solvent such as cyclohexane or heptane. However, it is desired to provide new and improved crosslinked polymers which are less hygroscopic and which exhibit enhanced mechanical properties, as compared to XL-PVP itself.
Accordingly, it is an object of this invention to provide a suitable process for making strongly swellable, moderately crosslinked copolymers of vinylpyrrolidone and vinyl acetate which are substantially non-hygroscopic and which have advantageous mechanical properties.
These and other objects of the invention will be made apparent from the following description of the invention.
What is provided herein is a process for making strongly swellable, moderately crosslinked copolymers of VP and VA, in a defined weight ratio, preferably about 90/10 to about 60/40, in the form of fine, white powders having (a) an aqueous gel volume of about 15 to 150 ml/g of copolymer, preferably about 50 ml/g, (b) a Brookfield viscosity in 5% aqueous solution of at least about 10,000 cps, preferably about 20,000 to about 50,000 cps, and (c) being prepared by precipitation polymerization of VP and VA monomers in an organic solvent, preferably heptane, hexane or cyclohexane, with a free radical polymerization initiator, suitably about 0.2-5%, in the presence of a crosslinker, in an amount of about 0.1 to about 2% by weight of the monomers, while maintaining the overall monomer concentration at less than about 15% by weight, and feeding the monomers at a feeding rate of less than about 0.2 ml/min for 0.5 l of solvent, preferably 0.1-0.15 ml/min, and while agitating the reaction mixture at greater than about 300 rpm, preferably 400-500 rpm.
In the preferred embodiment of the invention, (a) is 25 to 75 ml/g of copolymer, (b) is at least 15,000 cps, and (c) provides a terpolymer having a Tg of at least 150� C., preferably 150� to about 180� C. The initiator level preferably is about 0.25 to 0.8%. In an optimum form of the invention, (a) is 30 to 60 ml/g, (b) is about 20,000 to 50,000 cps, and (c) Tg is 150� C. to 160� C., and the initiator level is about 0.35 to 0.6%.
Gel volume is a measure of the swelling property of the crosslinked polymer and is defined as the equilibrium aqueous swelling volume of polymer per unit weight, and is expressed in the units of ml/g. Gel volume is determined by first adding 1 g. of the polymer to a suitable graduated cylinder filled with water. This mixture then is shaken and allowed to stand at room temperature for 3 days. The volume of the gel which is produced in water is measured and taken as the gel volume. Similarly, the gel volume concept can be applied to non-aqueous systems.
The fine, white powder polymers of the invention are prepared directly by a precipitation polymerization process in an organic solvent, such as an aliphatic hydrocarbon solvent, preferably cyclohexane or heptane, or an aromatic hydrocarbon, such as toluene, in the presence of about 0.1 to 2% by weight of monomers of a crosslinking agent, suitably N,N'-divinylimidazolidone, 1-vinyl-3(E)-ethylidene pyrrolidone, triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,4,6-triallyloxy-1,3,5-triazine, and pentaerythritol triallyl ether, at about 5 to 25% solids.
In accordance with the invention, strongly swellable, moderately crosslinked PVP/VA copolymers are prepared directly in the form of fine, white powders by precipitation polymerization of vinyl pyrrolidone and vinyl acetate in the presence of a predetermined amount of a crosslinking agent and a free radical polymerization initiator in an organic solvent, preferably an aliphatic hydrocarbon, e.g. a C3 -C10 saturated, branched or unbranched, cyclic or acyclic aliphatic hydrocarbon, and most preferably cyclohexane or heptane, or mixtures thereof.
The amount of solvent used in the process of the invention should be sufficient to dissolve an appreciable amount of the reactants and to maintain the copolymer precipitate in a stirrable state at the end of the polymerization. Generally, about 5 to 25% solids, preferably 10-20%, is maintained in the reaction mixture.
The precipitation polymerization process of the invention is carried out in the presence of a suitable free radical polymerization initiator. Suitable initiators include acyl peroxides such as diacetyl peroxide, dibenzoyl peroxide and dilauryl peroxide; peresters such as t-butylperoxy pivalate, tert-butyl peroxy-2-ethylhexanoate; peroxides such as di-tert-butyl peroxide; percarbonates such as dicyclohexyl peroxydicarbonate; and azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyanocyclohexane), and 2,2'-azobis(methylbutyronitrile). Other initiators known in the art also may be used. A preferred initiator is the following:
______________________________________PreferredInitiator______________________________________t-Butyl peroxy- Atochem N.A. Liquid; 75% activepivalate (Lupersol 11) in mineral spirits______________________________________
The amount of such initiator may vary widely; generally about 0.2-5.0% is used, based on the weight of total monomers charged.
The reaction temperature may vary widely; generally the reaction mixture is maintained at about 40�-150� C., preferably 60�-70� C., during the polymerization. Pressure usually is kept at atmospheric pressure, although higher and lower pressures may be used as well.
In order to make a highly purified crosslinked copolymer, the introduction of another initiator at a higher operational temperature is desirable since it effectively reduces the amount of residual VP and VA monomer content to below 100 ppm in the product. The hihger temperature initiator can be added to the system separately or in admixture with the low temperature initiator. The preferred higher temperature initiator is 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane (Lupersol� 101). The amount of such initiator may be about 0.2-5.0%, based on the weight of total monomers charged. The higher temperature reaction is usually at between about 110� C. and 150� C., preferably at between 120� C. and about 135� C.
The reaction mixture should be stirred vigorously under an inert atmosphere, e.g. nitrogen, during the polymerization. A stirring rate of about 300-600 rpm in 1-liter lab reactor is sufficient to effect the desired polymerization and to keep the precipitate in a stirrable state during the polymerization.
Suitable crosslinking agents for use in the invention include such multifunctional compounds as the divinyl ethers of an aliphatic diol, e.g. the divinyl ethers of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-unidecanediol, and 1,12-dodecanediol; as well as the divinyl ethers of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol and further polyalkylene glycols up to a molecular weight of about 6000. Other suitable crosslinking agents include 1,7-octadiene, 1,9-decadiene, 1,13-tetradecadiene, divinylbenzene, N-N'-divinylimidazolidone, 1-vinyl-3(E)-ethylidene pyrrolidone and methylene bisacrylamide; acrylates such as polyethylene glycol diacrylate, trimethylolpropane triacrylate, propylene glycol diacrylate; allyl ether derivatives of polyhydric alcohols such as pentaerythritol triallyl ether; or polyhydric alcohols esterified once or twice with acrylic acid; triallylamine, tetraallylethylenediamine, diallyl phthalate, and the like. Preferred crosslinking agents are the following: N,N'-divinylimidazolidone, pentaerythritol triallyl ether, 1-vinyl-3(E)-ethylidene pyrrolidone, triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 2,4,6-triallyloxy-1,3,5-triazine.
The precipitation polymerization process of the invention may be carried out by first precharging a suitable reactor with a predetermined amount of the organic solvent, for example, an aliphatic hydrocarbon solvent, and heating the solvent to a desired reaction temperature while stirring vigorously under an inert gas atmosphere. The initiator is then charged into the reactor.
Then the vinylpyrrolidone and vinyl acetate monomers, and the crosslinker material are admitted into the reactor continuously through syringe pumps. The amounts and ratios of monomers and crosslinker can be adjusted based on a predetermined vinylpyrrolidone and vinyl acetate ratio in the copolymer and the extent of crosslinking desired in the final product. Since vinylpyrrolidone is much more reactive than vinyl acetate during the copolymerization, and it is desired to provide substantially uniform copolymer relative to the distribution of monomer units on the macromolecular backbone, the vinyl acetate addition time is made shorter, usually 3-5 hours, and the vinylpyrrolidone and crosslinker material addition time is made longer, usually 5-7 hours. Preferably, the reactants are admitted into the reactor below the surface of the solvent. The reaction mixture is held for an additional period of time, usually 6-8 hours, at a higher temperature, with the addition of a high temperature initiator, e.g. 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane (Lupersol� 101), to complete the polymerization.
Finally, the mixture is cooled to room temperature. Filtering, washing with solvent, and drying provides the desired polymer in yields approaching quantitative. Alternatively, the reaction product may be dried directly to provide the polymer powders.
The polymerization process of the invention in cyclohexane or heptane solvent provides the desired PVP/VA polymer product as a fine, white powder, which precipitates readily, in quantitative yield, with substantially the same degree of crosslinking as the charge of VP and VA monomers and crosslinking agent, in a smooth polymerization without excessive swelling of polymer during the course of the process. More particularly, the solvents of the invention are non-solvents for PVP and VA monomers, which enable the polymerization to proceed in the presence of the crosslinking agent without excessive build-up of viscosity of the reaction mixture during polymerization.
In order to provide for easy removability from the reactor, the PVP/VA copolymer product of the invention preferably should not swell in the hydrocarbon solvent during preparation. To determine the maximum allowable monomer concentration in the solvent without causing the polymer to swell, a series of solubility tests were carried out as follows. PVP/VA copolymer powders were added to heptane in the presence of a certain amount of VP and VA. The results are shown below:
Sample: Non-XL PVP/VA (VP/VA=60/40 by weight).
1 g. of sample in 10 g heptane was set at room temperature overnight.
______________________________________Amt of VP andVA (1:1 by wt) % VP and VA Observation______________________________________0 0% All powders settled down, none swollen.0.2 g 2% Some of the powders were swollen.0.3 g 3% All of the powders were swollen.0.4 g 4% All of the powders were swollen.0.5 g 5% All of the powders were swollen.1.0 g 10% Some of the polyner dissolved, some swollen.______________________________________
The above results indicated that when the VP and VA concentration in the PVP/VA copolymer is 2% or higher, PVP/VA was swollen in heptane. Therefore, during the preparation of crosslinked PVP/VA, the monomer concentration should be maintained at a very low level (preferably below 3%) to keep the product from swelling in the solvent or forming a gum.
Several measures were taken to achieve the desired low monomer level during the polymerization process: (1) maintaining a low overall monomer concentration (no higher than 15% by weight), (2) providing a low monomer feeding rate (no higher than 0.2 ml per minute for 500 g of solvent), and/or (3) very rapid agitation of the reactants (no lower than 300 rpm).
The invention will be illustrated by reference to the following examples, which are given in parts by weight unless otherwise specified.
A 1-l, 4-necked glass reaction vessel was equipped with two syringe pumps, controlled by computer, for continuous addition of monomers (VP and VA), and crosslinker, a constant speed mechanical stirrer set at 300 rpm, an adaptor for admitting nitrogen, and a thermocouple connected to a temperature controller. The vessel was charged with 500 g of heptane. Nitrogen was started to purge through the reactor. The temperature was raised to 65� C. and held for 30 minutes. Then 220 microliter (190 micrograms) of t-butylperoxy pivalate (Lupersol 11) was added through the syringe. Thereafter Feeds 1 and 2 were introduced through the syringe pumps simultaneously. Feed 1 was a mixture of 67.5 g of vinylpyrrolidone and 0.34 g (0.45% of VP and VA comonomers by weight) of triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATT), and it was introduced into the reactor over a period of 6 hours. Feed 2 contained 7.50 g of vinyl acetate and it was added over 4 hours. Then the reaction mixture was held at 65� C. for another hour.
Thereafter the mixture was cooled and transferred to a 1-l, high pressure Buchi reactor and 0.375 g of 2,5-dimethyl-2,6-di-(t-butylperoxy) hexane (Lupersol 101) was added through a syringe pump. Then the reactor was sealed, heated to 130� C. and held for 7 hours.
The mixture was cooled to room temperature, discharged and dried in a vacuum oven at 70� C. for 1 day and 100� C. for a second day. A blender was used to break the product into fine powders.
A quantitative yield of crosslinked PVP/VA copolymer having a VP to VA ratio (w/w) of 90/10 and containing about 0.45% of the crosslinking agent was obtained.
The procedure of Example 1 was followed in Examples 2-5 using various amounts of VP and VA and different crosslinkers.
A summary of the reaction mixtures used in Examples 1-5 is given in Table 1 below.
TABLE I______________________________________Ex. No. VP (g) VA (g) VP/VA (w/w) Crosslinker (g)______________________________________1 67.5 7.5 90/10 TATT 0.342 67.5 7.5 90/10 PTE 0.343 60 15 80/20 PTE 0.344 52.5 22.5 70/30 PTE 0.345 45 30 60/40 PTE 0.34______________________________________ PTE = Pentaerythritoltriallylether
The strongly swellable, moderately crosslinked PVP/VA copolymer powders of the invention are characterized by its unique gel volume and viscosity, which properties enable the polymer to thicken aqueous and non-aqueous solutions effectively.
The viscosity of the polymer is defined by its Brookfield viscosity in cps, which is determined upon a 5% aqueous solution of the polymer at 25� C. by a standard analytical procedure using Model LTV and Spindle No. 4.
For maximum utility, it is desirable that the hydrated polymer exhibit a high gel volume and a high viscosity. With increasing crosslinking density in the polymer, the gel volume decreases and viscosity increases and then decreases, passing through a maximum. In the crosslinked polymer system of this invention, an effective thickener product is provided by including crosslinker in the reaction mixture at a suitable concentration of about 0.2 to 1.0% by weight, based upon VP and VA monomers, preferably about 0.25 to 0.8%, and optimally, at about 0.35 to 0.6%. At this suitable amount of crosslinker loading, the crosslinked polymer product exhibits a gel volume of about 15 to 150 ml/g of polymer and a Brookfield viscosity of at least 10,000 cps. At the preferred crosslinker concentration, the gel volume is about 25 to 75 ml/g of polymer and its Brookfield viscosity is at least 15,000 cps. At the optimal amount crosslinker present in the reaction mixture, the polymer exhibits a gel volume of about 30 to 60 ml/g of polymer and a Brookfield viscosity of about 20,000 to 50,000 cps.
The glass transition temperature, Tg, is an indicator of the extent of crosslinking in the copolymer. Above this temperature, the polymer is in viscous or rubbery state; below this temperature, it is in a hard or glassy state. Tg is related to the amount of free ends in the polymer. If a polymer is completely crosslinked, it will be decomposed at an elevated temperature and no Tg exists. If a polymer is moderately crosslinked, the Tg can be determined and it should be higher than a non-crosslinked polymer with the same VP and VA composition. The XL-PVP/VA products of Examples 1-5 gave Tg 's higher than corresponding non-XL PVP/VA which indicates a moderate crosslinking state in these copolymers. At an optimal amount of crosslinker in the reaction mixture, the Tg of the crosslinked copolymer obtained is at least 150� C., preferably in the range of 150� C. to 180� C., and optimally, at about 150� C. to about 170� C.
The properties of the crosslinked PVP/VA copolymers herein with different VP to VA ratios, (Examples 1 to 5) including swell volume, Brookfield viscosity and glass transition temperature, are given in Table 2 below, in favorable comparison to non-crosslinked copolymers of the same composition.
TABLE 2__________________________________________________________________________ Swell Brookfield Tg, �C. Tg, �C.Ex. No. VP/VA Volume, ml Viscosity, cps XL Copolymer non-XL Copolymer__________________________________________________________________________1 90/10 52 62,800 cps 159 1372 90/10 53 11,000 cps 159 1373 80/20 50 48,200 cps 151 1224 70/30 42 12,100 cps 169 1105 60/40 85 150,000 cps 154 100__________________________________________________________________________
As an added feature of the invention, the residual VP and VA monomer content of the polymers obtained herein is less than about 0.1% by weight. In aqueous based processes, in contrast, the formation of a gel mass during polymerization may trap considerable amounts of VP and VA monomer in the polymeric gel network.
The strongly swellable, moderately crosslinked PVP/VA copolymers of the invention are useful in pharmaceutical applications, such as in controlled release tablets, binders, coatings, nasal spray delivery systems, and tablet disintegrating agents; in personal care compositions, as for example, in hair conditioners and as a gelling agent in a gelled acidizer compositions. In these and other formulations and compositions, the substantially non-hygroscopic and predetermined hydrophilic/hydrophobic properties of the copolymer are useful in providing an improved swelling and thickening agent therein.
The copolymers of the invention also find use as a disposable and extended wear soft and hard contact lenses by providing a material which has a high water content, excellent tensile strength, tear resistance and low affinity for lachrymal proteins and other contaminants. Other monomers such as methyl methacrylate and hydroxyethyl methacrylate may be included therein.
While the invention has been described with particular reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art. Accordingly, it is intended to be bound only by the following claims, in which:
|Cited Patent
|Filing date
|Publication date
|Oct 18, 1990
|Dec 17, 1991
|Isp Investments Inc.
|Strongly swellable, moderately crosslinked polyvinylpyrrolidone
|Sep 19, 1994
|Jun 20, 1995
|Basf Aktiengesellschaft
|Redispersible powder composed of n-vinylpyrrolidone/vinyl acetate copolymer the preparation and use thereof
|Citing Patent
|Filing date
|Publication date
|Dec 29, 1998
|Mar 26, 2002
|Pmd Holdings Corp.
|Hydrophilic ampholytic polymer
|Sep 26, 2000
|Jul 29, 2003
|The University Of Akron
|Water soluble, curable copolymers, methods of preparation and uses thereof
|Feb 7, 2002
|Sep 16, 2003
|Isp Investments Inc.
|Proliferous copolymer of vinyl pyrrolidone and vinyl acetate
|Jan 12, 2001
|Dec 23, 2003
|Isp Investments Inc.
|Stable, aqueous cationic hydrogel
|Feb 16, 2000
|Dec 23, 2003
|Sanyo Chemical Industries, Ltd.
|Gelating agent for alkaline cell and alkaline cell
|Sep 16, 2003
|Oct 19, 2004
|Isp Investments Inc.
|Proliferous copolymer of vinyl pyrrolidone and vinyl acetate
|Sep 16, 2003
|Mar 18, 2004
|Isp Investments Inc.
|Proliferous copolymer of vinyl pyrrolidone and vinyl acetate
|Mar 11, 2010
|Feb 8, 2012
|Thickening additive compositions
|Mar 11, 2010
|Sep 16, 2010
|Isp Investments Inc.
|Thickening additive compositions
|Apr 19, 2011
|Oct 27, 2011
|Isp Investments Inc.
|Compositions of enhanced viscosity. clarity, or both enhanced viscosity and clarity
|Sep 13, 2012
|Mar 21, 2013
|Lubrizol Advanced Materials, Inc.
|Surfactant responsive micro-gels
|Sep 13, 2012
|Mar 21, 2013
|Lubrizol Advanced Materials, Inc.
|Surfactant responsive emulsion polymerized micro-gels
|Sep 13, 2012
|Mar 21, 2013
|Lubrizol Advanced Materials, Inc.
|Surfactant responsive dispersion polymerized micro-gels
|Dec 17, 2014
|Jun 25, 2015
|Lubrizol Advanced Materials, Inc.
|Surfactant responsive emulsion polymerization micro-gels
|U.S. Classification
|526/264, 526/319
|International Classification
|Cooperative Classification
|European Classification
|Feb 20, 1996
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Important prerequisite for the development of nano-components for data storage and sensor technology / Publication in Nature Communications
Researchers at Johannes Gutenberg University Mainz (JGU) have achieved a major breakthrough in the development of methods of information processing in nanomagnets. Using a new trick, they have been able to induce synchronous motion of the domain walls in a ferromagnetic nanowire.
This involved applying a pulsed magnetic field that was perpendicular to the plane of the domain walls. "This is a radically new solution," explained Professor Mathias Kläui of the Institute of Physics of Johannes Gutenberg University Mainz. "It enables us to move domain walls synchronously over a relatively large distance without them returning to their original position."
This is essential for permanent data storage, because data would otherwise be lost if domain walls were not collectively displaced in a controlled manner. The research was carried out in cooperation with the working groups of Professor Stefan Eisebitt at TU Berlin and Professor Gisela Schütz of the Max Planck Institute for Intelligent Systems in Stuttgart. The results were published in the journal Nature Communications at the end of March.
Magnetic nanowires have small regions of uniform magnetization called domains, which can be used as storage units (bits). The site where domains of different alignment meet each other is called a domain wall. Information can be stored in the domain, and read and processed by means of the movement of the domain walls.
The method has the great advantage that the information – as in the case of magnetic data storage in general – cannot be easily lost. This contrasts with semiconductor-based storage systems, such as RAM in PCs, which lose all stored information without power. In addition, no fragile moving parts are required such as the read/write head of a hard disk.
It has not previously proved possible to induce the required controlled and synchronized movement of multiple domain walls using magnetic fields. The most obvious approach would be to apply a magnetic field in the direction in which the magnetization runs in the tiny nanowires. However, this has been shown to be ineffective, as there is loss of data. Mathias Kläui and his group took a radically new path.
They decided to apply a pulsed magnetic field perpendicularly to the in-plane magnetized domain walls. As the Mainz researchers found in their model system, it is possible to customize the asymmetric field pulses that provide the forward- and backward-oriented forces that act on domain walls. Data can thus be moved within the storage medium in a controlled manner.
The participating physicists at Mainz University first tried out their concept in the context of micromagnetic simulations and then tested it experimentally. For this purpose, they recorded images of the magnetic arrangement in the tiny nanowires with the help of the electron storage ring BESSY II of the Helmholtz Center Berlin for Materials and Energy (HZB).
As expected from the simulation, they observed displacement of the domain walls in a direction that was consistent with the model. The scientists also calculated the energy that would be necessary for the experimentally observed domain wall motion and came to the conclusion that the energy consumption of the proposed system would be quite cost-effective compared with the best components currently available.
"The results are very promising. We assume that the necessary paradigm shift will be facilitated by this new approach and it will prove possible to develop a method of efficient and controlled synchronous motion of the domain walls in nanowires," said Kläui. This would pave the way for the development of non-volatile spintronic components of the next generation, which could be used in a wide range of applications for data storage as well as logic and sensor modules.
June-Seo Kim et al.
Synchronous precessional motion of multiple domain walls in a ferromagnetic nanowire by perpendicular field pulses
Nature Communications, 24 March 2014
DOI: 10.1038/ncomms4429
Further information:
Prof. Dr. Mathias Kläui
Theory of Condensed Matter
Institute of Physics
Johannes Gutenberg University Mainz (JGU)
D 55099 Mainz, GERMANY
phone +49 6131 39-23633
e-mail: firstname.lastname@example.com
http://www.uni-mainz.de/presse/17186_ENG_HTML.php - press release ;
http://www.nature.com/ncomms/2014/140324/ncomms4429/full/ncomms4429.html - publication
Petra Giegerich | idw - Informationsdienst Wissenschaft
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