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Comment Re:I picked 30% higher (Score 1) 374 374
Coincidentaly, I have an interview this afternoon for a new job that pays ~70% more than I currently get, and is more suited to my skill set. Bring it on!
Comment Re:Anite Blake (Score 1) 336 336
Comment Re:Hypercard (Score 1) 783 783
It's a pity really. I think that that programming model (or something similar) would fit the phone/tablet quite well.
Comment Re:Standing on shoulders (Score 1) 508 508
Comment Re:Backups (Score 2) 228 228
Comment Re:Doesn't Matter (Score 1) 560 560
It has already been shown that pebble bed reactors are not inherently safe designs
Do you have a reference for that? I'd really like to have a look at it.
Comment Crazy hybrid clones (Score 1) 471 471
Non-Crazy hybrid clones are obviously OK.
Comment Re:Wait, what? (Score 1) 409 409
Like many coders, I thought you were supposed to calculate Hash(password + salt).
I've never seen anyone suggest Hash(password + username + salt) as an option. Is this something that the security industry has shown to be ineffective long ago, and I have just missed it?
To me this looks like it would stop two users with the same password getting the same hash (assuming the salt is system wide, not per user) and make it harder to replace the hash with a known one and get a known password.
Comment Re:I'm not sure I like this... (Score 2) 58 58
If I'm running a mid size company and I hire an ad agency that gets paid for referrals (and it's a fly by night LLC), I'm really venerable now. I guess the anti-spam crowd will tell me not to hire a fly-by-night, but don't most successful businesses start that way? And how am I suppose to know?
If you realy were venerable then I would hope you would know better than to leave yourself vulnerable to a lawsuit by hireing dodgy contractors.
Comment Re:Now that's.... (Score 1) 233 233
Or maybe each "little death" gets you a limited time to use the software?
See http://en.wikipedia.org/wiki/Petite_Mort
Comment Re:Sure they can claim it (Score 1) 399 399
Comment Re:5th Amendment (Score 2, Informative) 767 767
Encrypting something via Public Key system is slow, so what is generally done is a random key (128bit/256bit/1024bit/whatever) is generated, and some other system like IDEA/Blowfish/etc is used to encrypt the file with this random key. Then the random key itself is encrypted using the Public Key, and included in the output file (or this may be done first).
Encrypting the same file twice with PGP/GPG will result in different encrypted files. Here is what I got when I encrypted the same file twice:
$ ls -l whycopyrightdoc.ogg*
-rw-r--r-- 1 xxxx users 444876583 2008-12-09 16:27 whycopyrightdoc.ogg
-rw-r--r-- 1 xxxx users 442961134 2009-02-27 13:38 whycopyrightdoc.ogg.gpg
-rw-r--r-- 1 xxxx users 442961133 2009-02-27 13:33 whycopyrightdoc.ogg.gpg.1
$ cksum whycopyrightdoc.ogg*
2090966688 444876583 whycopyrightdoc.ogg
909254713 442961134 whycopyrightdoc.ogg.gpg
121574791 442961133 whycopyrightdoc.ogg.gpg.1


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Today - 6:00pm
Grumpy Cat Video Premiere
Join us for one of the most-star studded cat gatherings ever assembled, headlined by world-renowned Grumpy Cat. The official Friskies® 'spokescat' is the star of the newest BuzzFeed video, Happiness Finds Grumpy Cat, and she has …
Wed, Aug 5 - 7:30pm
Mr. Holmes
1hr 44min / Rated PG / Mystery
It's 1947, and an aging Sherlock Holmes (Ian McKellen) returns from a journey to Japan where he has witnessed the devastation of nuclear warfare as he searches for a rare plant with powerful restorative qualities. ...
Sun, Aug 9 - 3:00pm
West Side Story
2hr 32min / Not Rated / Musical Drama
This modern "Romeo and Juliet" tale is set in New York's Upper West Side in the 1950s, where the area's slums are plagued by racial tensions between two rival gangs: the Puerto Rican Sharks and ...
Fri, Aug 14 - 7:30pm
The End of the Tour
1hr 46min / Rated R / Drama
In 1996, Rolling Stone reporter David Lipsky (Jesse Eisenberg) spent five days interviewing acclaimed novelist David Foster Wallace (Jason Segel) right after the 1996 publication of Wallace's groundbreaking epic novel, Infinite Jest. As the days ...
Sun, Aug 16 - 3:00pm
2hr 26m / Rated R / Crime Drama
Martin Scorsese's GOODFELLAS is the wry, violent story of Henry Hill (Ray Liotta), an aspiring criminal who ends up in witness protection after testifying against his former partners, Jimmy Conway (Robert De Niro) and Tommy ...
Sat, Aug 22 - 7:30pm
1hr 42min / Rated PG / Drama
TWO SHOW TIMES! Nightclub owner Rick Blaine (Humphrey Bogart) discovers his old flame Ilsa (Ingrid Bergman) is in town with her husband, Victor Laszlo (Paul Henreid). Torn between "love and virtue" and with the Germans ...
Sun, Aug 30 - 3:00pm
The Phantom of the Opera
1hr 33min / Not Rated / Silent Horror
At the Opera of Paris, a mysterious phantom (Lon Chaney) threatens famous lyric singer Carlotta (Virginia Pearson), forcing her to give up playing "Marguerite" in Faust and turn the coveted role over to young, unknown ...
Thu, Sep 10 - 7:30pm
WineFest Movie Under the Stars
1hr 36min / Rated PG / Comedy
NEW THIS YEAR, WineFest kicks off Thursday, Sept. 10 with a special "Movie Under the Stars" showing of the campy 2004 classic Napoleon Dynamite, presented by Sykes Enterprises. The film stars Jon Heder as a high-school ...
Fri, Sep 11 - 7:00pm
Wine Tasting
On Friday, Sept. 11, a two-tiered Wine Tasting invites you to "Eat the FOOD" from several of Tampa's most famous and flavorsome independent restaurants. Guests will have the opportunity to sample dozens of boutique wines ...
Sat, Sep 12 - 6:30pm
Wine Pairing
On Saturday, Sept. 12, the Theatre's historic stage will be expanded to seat more than 200 for the elegant Wine Pairing at 6:30 p.m. presented by The Bank of Tampa. The multi-course menu, created and catered ...
Sun, Sep 13 - 11:30am
Wine Brunch
Just like a liger is like a lion and a tiger mixed, the Wine Brunch mixes breakfast fare catered by SONO Café and Mise en Place with mimosas, bellinis and a selection of light wines ...

subset: commoncrawl


text:
posters, square posters, acrylic posters, painting posters, canvas posters, square canvas posters, square acrylic canvas posters, square acrylic canvas painting posters, yellow ochre posters, yellow green posters, orange posters
All prints ship in durable cardboard tubes.
Fine Art America is one of the largest, most-respected giclee printing companies in the world with over 40 years of experience producing museum-quality posters and prints. All of our posters are produced on state-of-the-art, professional-grade Epson printers.
We use acid-free paper with archival inks to guarantee that your posters last a lifetime without fading or loss of color. All posters include a 1" white border around the image to allow for future framing and matting, if desired.
Posters ship within 3 - 4 business days in durable cardboard tubes.
An learning abstract to see how the colors blended with each other.
A native Texan, my venture into art came when I was forced to leave my graphics design career, I first began painting abstracts and landscapes until I was exposed to photographs taken by the Hubble Space Telescope (HST) of deep outer space. The photographs had about them beauty, mystery and revelation of objects previously unseen, much less photographed. Deep outer space, once a mystery, was now being discovered with supporting documentation by HST, Chandra, other countries' space telescopes. The photos were stunningly beautiful, intriguing, addressing the artistic point of view. The scientific value of the photographs will be evaluated by the astronomers and scientists Several years ago, HST subjects became the main thrust of my work...
Our return policy is very simple:
If you're not happy with a purchase that you made on FineArtAmerica.com, for any reason, you can return it to us within 30 days of the order date. As soon as it arrives, we'll issue a full refund for the entire purchase price. Please note - Fine Art America does not reimburse the outgoing or return shipping charges unless the return is due to a defect in quality.
Fine Art America sells thousands of pieces of artwork each month - all with a 100% money-back guarantee.
If you've hesitated to purchase artwork online in the past, why not give us a try? You have nothing to lose!
We take great pride in the fact that 324,898 artists have chosen Fine Art America to fulfill their orders, and we look forward to helping you select your next piece!
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text:
Janelle Monae
Janelle Monáe Announces The EEPHUS Tour
The shows are free, but you'll need an invite.
Governors Ball 2014: A Chat About What Worked and What Didn't
Here's to Jenny Lewis' rainbow/beige pant-suit, Neko Case's skeleton pants, the Kills' leopard-print backdrop, Ezra Koenig's camo shorts, and Janelle always giving us shivers when she sings 'Given 'Em What They Love.'
Janelle Monáe Covers David Bowie's 'Heroes'
When the Electric Lady met Ziggy Stardust.
Janelle Monáe Heads to 'Rio' With New Song 'What Is Love'
The singer just dropped "What Is Love," which will also be featured on the Rio 2 soundtrack.
Pharrell, Kendrick Lamar & Janelle Monae to Play the 2014 NBA All-Star Game
The upcoming NBA All-Star Game is celebrating 63 years with a few high profile performers: Pharrell, Kendrick Lamar and Janelle Monáe.
Listen To Janelle Monae & Miguel Get Sultry On 'Primetime'
As Janelle Monae counts the days until 'The Electric Lady' arrives on Sept. 10, she's unveiled another collaboration from the album: "Primetime" featuring Miguel.
Janelle Monae Gets Remixed By Prince, Announces September 'Electric Lady' Release
"It's a beautiful thing to have a friend — someone who cares about your career, and wants to see you go far and to push boundaries and shake up the world — give whatever they possibly can to the cause," she said of Prince.
Katy Perry & John Mayer Wear Matching White To Clive Davis' Pre-GRAMMY Party
Last night at his annual pre-GRAMMY party, Clive Davis honored his friend, Whitney Houston. The music exec, whose new book about his career, The Soundtrack of My Life, comes out February 19, played a rarely […]
fun. Dominates Grammy Nominations
Cliches be damned, it was a fun. night at the GRAMMY Nominations Concert on CBS, with the band performing and getting nominations in all four major categories.
Rate Bruno Mars' "Nothin' On You" GRAMMYs Performance
[lastfm link_type="artist_info"]B.o.B.[/lastfm] with [lastfm link_type="artist_info"]Bruno Mars[/lastfm] and [lastfm link_type="artist_info"]Janelle Monae[/lastfm] took the GRAMMYs stage to perform the song you couldn't escape in 2010, "Nothin' On You."


text:
Kim Kamps of the Appleton VFW joins us in-studio to talk about the wonderful services they provide to their community, as well as the delicious fish fry's they offer on Friday nights!
Copyright 2014 Nexstar Broadcasting, Inc. All rights reserved. This material may not be published, broadcast, rewritten, or redistributed.


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Film Hound
Entertainment news and trivia for film fans and animal lovers. Sit. Stay. Read.
Posts filtered on Tag
A Singing Gorilla Lost in Suburbia
If you've ever had to deliver a singing telegram in a gorilla suit (and who hasn't?), you're bound to enjoy some vicarious monkeying-around via the playful predicaments of some award-winning humorists. Parade.com currently features an amusing article by Michele Wojciechowski on the trials and tribulations of humorist Tracy Beckerman who left the asphalt jungle of […] [Read More]
My Funny Valentine
Looking for a fun alternative to flowers and candy for your Valentine this year? Check out the new book My Funny Valentine featuring some of America's most hilarious writers cuddled up with Cupid under one cozy cover. If love and laughter are what you're after, then look no further than this movable Valentine feast. With […] [Read More]


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November 11: What Are We Wearing Today?
What Ami Is Wearing Today
5 of 5
Details: Madewell vintage rocker jeans and scarf (new!); H&M top; Comptoir des Cotonniers booties; vintage jewelry.
Outfit Notes: I am posing "H to T" (as Tyra would say) to model my new scarf. As if I need another scarf. But oh well, scarves make me happy.


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The CentOSPlus Repository
1. What is the CentOSPlus repository?
The CentOSPlus repository contains packages that are upgrades to the packages in the CentOS base + CentOS updates repositories. These packages are not part of the upstream distribution and extend CentOS's functionality at the expense of upstream compatibility. Enabling this repository makes CentOS different from upstream. You should understand the implications of this prior to enabling CentOSPlus. You can browse the CentOSPlus directory for CentOS 5 or CentOS 6 on our mirrors for the architecture you intend to use.
The CentOSPlus repository contains a group of packages, all of which are updates. You probably do not want to enable CentOSPlus as a whole, but instead want to pick the exact packages that you want to use.
Prior to enabling the CentOSPlus repository you should read about the includepkgs= and/or exclude= options in yum. To read about these options use this command at the command line:
man yum.conf
2. Enabling the CentOSPlus repository
To enable the CentOSPlus repository, edit the file /etc/yum.repos.d/CentOS-Base.repo and look for the [centosplus] section. Here is how it looks by default:
#additional packages that extend functionality of existing packages [centosplus] name=CentOS-$releasever - Plus mirrorlist=http://mirrorlist.centos.org/?release=$releasever&arch=$basearch&repo=centosplus #baseurl=http://mirror.centos.org/centos/$releasever/centosplus/$basearch/ gpgcheck=1 enabled=0 gpgkey=http://mirror.centos.org/centos/RPM-GPG-KEY-CentOS-5 <== -CentOS-6 in CentOS-6
Example 1: We want the new CentOSPlus postfix with mysql_pgsql support. Here is how to setup /etc/yum.repos.d/CentOS-Base.repo:
#additional packages that extend functionality of existing packages [centosplus] name=CentOS-$releasever - Plus mirrorlist=http://mirrorlist.centos.org/?release=$releasever&arch=$basearch&repo=centosplus #baseurl=http://mirror.centos.org/centos/$releasever/centosplus/$basearch/ gpgcheck=1 enabled=1 gpgkey=http://mirror.centos.org/centos/RPM-GPG-KEY-centos5 includepkgs=postfix-* exclude=postfix-*plus*
You would also want to add this to both the [base] and [update] sections of /etc/yum.repos.d/CentOS-Base.repo, so as not to get postfix packages from there anymore:
Example 2: We want to use CentOSPlus kernel to be able to use the jfs or reiserfs file system and the creation tools. We would edit /etc/yum.repos.d/CentOS-Base.repo and modify the following in the [centosplus] section:
enabled=1 includepkgs=kernel* jfsutils reiserfs-utils
In the [base] and [update] section you would do the following:
exclude=kernel kernel-devel kernel-PAE-*
3. yum-plugin-priorities
Another way to protect your system from updates from the CentOSPlus repository is to use the yum-plugin-priorities plugin. This is the recommended method. Follow the instructions shown in the link and set up yum-plugin-priorites. Edit /etc/yum.conf and add this line:
You would set priorities in /etc/yum.repos.d/CentOS-Base.repo like this:
[base] exclude=foo bar priority=1 [update] exclude=foo bar priority=1 [centosplus] enable=1 priority=2
This will make the [base] and [update] repositories have higher priority over the [centosplus] repository, so the only items in CentOSPlus that will update either [base] or [update] are items that are excluded from those repositories with an exclude= setting.
Therefore, using yum-plugin-priorities allows you to skip setting up the includepkgs= for the [centosplus] section of CentOS-Base.repo, but it still only allows updates of packages that you exclude= from the [base] and [update] repositories.
4. Summary
Using the CentOSPlus repository is more dangerous than using other CentOS repositories, as it is designed to have several updated packages and it is not really designed to be completely enabled.
You can use all the packages in CentOSPlus, but normally one will pick only the packages they are looking for and use exclude= and includepkgs= (or exclude= and yum-plugin-priorities) to load only those packages from the CentOSPlus repository.
Please ensure that you understand all these concepts before you use the CentOSPlus repository.


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VW Beetle Diesel Convertible 2013. Surprise! Convertible + Manual Transmission + Turbo Diesel = 2013 VW Beetle Convertible! MotoMan finds out who was behind it and how it came to the US. MotoMan. Ordinary Car Guy. Extraordinary Adventures.
Subscribe now to experience our adventures in the car world. http://motomantv.blip.tv
Facebook - http://www.facebook.com/MotoManTV
Twitter - http://twitter.com/MotoManTV
Website - http://www.MotoMan.TV
MotoMan is an ordinary car guy on an extraordinary adventure through the car world. Everything from learning how to drift from Vaughn Gittin Jr to piloting the Goodyear Blimp.


text: Gear Video G3 Infidel Ski 5 5 Community Rating | 3 Reviews Item # GGG0173 Size? Need Help? Contact a Gearhead 24/7 with any size or fit questions. Chat Now Call: 1.800.409.4502 Men's Skis Your ski size is largely determined by both your skiing ability and your preffered style of skiing. For example, an expert skier in Vermont will ski a far different ski than an expert in British Columbia. So take a look at our chart and explanations and find your perfect fit. Your weight also plays a large factor in finding the right ski. If you are either under or over average weight for your height consider downsizing or upsizing, respectively. Size Guide Big Mountain FreerideBackcountry JibAll MountainPark and PipeAll Mountain Carve Pro 180-200cm 180-190cm 180-190cm 175-185cm 175-185cm Expert 170-180cm 175-185cm 170-180cm 160-180cm 170-185cm Intermediate 160-180cm 160-180cm 160-180cm 160-180cm 160-175cm Entry Level N/A N/A 150-170cm 150-170cm 150-170cm Skill Level Explanations:Pro:Excels on any terrain, on any snow condition. Enjoys high speeds.Expert:Comfortable on any terrain and most snow conditions.Intermediate:Comfortable on Blue trails, exploring Black trails.Entry Level:Learning to ski Green and Blue trails.Skiing Style Explanations:Big Mountain Freeride:High speeds, deep powder, steep lines, straightlining, chutes, cliffs.Backcountry Jib:Backcountry kickers, hucking, twintips, deep powder.All Mountain:From bumps to back bowls, groomers to glades; everything and anywhere on the mountain.Park and Pipe:De-tuned edges and buttery twin tips, occasionally pole-impaired.All Mountain Carve:Stiff. High-speed corduroy cutter. For those blind to SLOW signs. Quantity Add to cart View full product page Tech Specs Length: 175 cm, 180 cm, 185 cm, 190 cm Dimensions: 128 x 97 x 119 mm Turn Radius: (190cm) 24 m Profile: full rocker Construction: sandwich Core: wood Tail: raised Binding Included: no Claimed Weight: 8 lbs 3.2 oz Recommended Use: all-mountain, powder Manufacturer Warranty: 60 days Chris Wilke Posted on December 8, 2012 Little low-down on the Infadel (0) View More Details on G3 Infidel Ski


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104 PagesPDF Format
NOTE: This digital Guidebook is in PDF format. Upon completion of purchase, it will be immediately available to you in your "My On-Demand Library."
Inside Self-Storage Ownership Guidebook 2014Whether you're in-the-trenches as a hands-on self-storage owner or more removed from the day-to-day operation of your business, you no doubt have a vested interest in the financial performance of your property. To maximize the revenue generated by your self-storage business, you must focus your efforts in several key areas including profit enhancement, expense management, auditing, staffing, insurance and others.
This Guidebook provides guidance to help single- and multi-facility owners take control of and maximize their investment. Covered topics include:
To view other guidebooks in the 2014 series, click here.


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climate: 75/100 of 1575
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Crossing a chasm slowly, in ten small steps? Sustainable living demands big changes
Kirstie O'Neill, Adrian Friday & Adrian K. Clear
29th March 2015A new government website to promote more sustainable lifestyles is hopelessly lacking in ambition, write Kirstie O'Neill, Adrian Friday & Adrian K. Clear. We need to be re-engineering our infrastructure, re-imagining society and re-thinking the ways we live for disruptive, transformative change - not tinkering ineffectually at the margins of 'normality'. more...
Global water crisis causing failed harvests, hunger, war and terrorism
Nafeez Ahmed
27th March 2015The world is already experiencing water scarcity driven by over-use, poor land management and climate change, writes Nafeez Ahmed. It's one of the causes of wars and terrorism in the Middle East and beyond, and if we fail to respond to the warnings before us, major food and power shortages will soon afflict large parts of the globe fuelling hunger, insecurity and conflict. more...
Amazon carbon sink declines as trees grow fast, die faster
Oliver Phillips & Roel Brienen
21st March 2015To date the Amazon has been a huge carbon sink, soaking up billions of tonnes of our emissions from fossil fuels, write Oliver Phillips & Roel Brienen. But now that's changing, as trees grow faster and die younger: the sink appears to be saturating. more...
Deep in the Amazon, one tribe is beating big oil
David Goodman
30th March 2014The people of Sarayaku in Ecuador's Amazon rainforest are a leading force in 21st century indigenous resistance, writes David Goodman, resisting the incursion of oil exploration into their lands, winning legal victories, and inspiring other communities to follow their example. more...
Antarctic warmth brings more snow, reducing sea level rise
Alex Kirby & Oliver Tickell
18th March 2015Rising temperatures will result in more snow falling in Antarctica, and the build-up of ice will reduce sea level rise from other sources. But as the extra weight of ice makes Antarctica's glaciers flow faster, the continent will still be a net contributor to sea level rise. more...
College fossil fuel divestment - Yes we must!
Cutler J Cleveland
18th March 2015Univerisities' core mission is one of civilization and enlightenment, and that's incompatible with investing in fossil fuels that pose an existential threat to humanity and the planet, writes Cutler J Cleveland. It's is also financially prudent for for them to avoid sinking capital into future 'stranded assets' of unburnable carbon. more...
Let them eat carbon! The corporate plan to cook Africa in its own fossil fuels
Nnimmo Bassey & Sheila Berry
17th March 2015Mining corporations, politicians and big NGOs are meeting in London today to plan the future of extractive industries in Africa, write Nnimmo Bassey & Sheila Berry. Absent African civil society and impacted communities, delegates are setting an agenda for 'resource-led development' that will cook the continent in the greenhouse gases of its plundered oil, gas and coal. more...
Money dries up for Great Barrier Reef coal project
Marina Lou & Christine Ottery / Greenpeace Energydesk
16th March 2015Indian coal firm Adani is struggling to finance its proposed mega coal mine in Australia's Galilee Basin, write Marina Lou & Christine Ottery, as promised government support evaporates and a major investor looks set to pull out. more...
Patriarchy is killing our planet - women alone can save her
Nafeez Ahmed
13th March 2015The global epidemic of violence against women and their systematic exclusion from the power structures that rule us are integral to man's violent exploitation of Earth and her resources, writes Nafeez Ahmed. The fight to save the Earth must begin with the empowerment of women - and that means ending our complicity in their oppression, and servitude. more...
UK plans first new coal power station since 1974 - and it burns forests too!
Almuth Ernsting
17th March 2015A new coal and biomass-fired power station could soon be built at Drax in Yorkshire, already the UK's biggest coal burner, writes Almuth Ernsting. It comes with a weak promise of possible 'carbon capture and storage' - an expensive, inefficient technology shunned elsewhere. As the Government's nuclear dream fades, could this be its equally flawed replacement? more...
London Assembly votes for £5 bn fossil fuel divestment - listen up, Boris!
Divest London
12th March 2015Members of the London Assembly yesterday voted for the London Pension Fund Authority, worth £4.8 billion, to ditch all its fossil fuel investments over a 5-year period. The vote is non-binding, but the huge 15-3 margin puts strong pressure on London Mayor Boris Johnson to follow through. more...
Unlikely hero (or villain): Michael Mann, creator of the hockey stick graph
Brendan Montague / DeSmog UK
16th March 2015Michael Mann will be remembered as the creator of the 'hockey stick' graph of rising global temperatures, which has put him forever in the crosshairs of climate change sceptics. But as Brendan Montague found, he is a curiously unlikely hero, or villain: rather a dedicated scientist living the American dream, who just happened, to his own surprise, to stumble on something big. more...
climate: 75/100 of 1575
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Climate change sparked Syria's ruinous war
Alex Kirby
6th March 2015Climate change probably caused the savage drought that struck Syria nearly a decade ago, writes Alex Kirby - and helped to trigger the civil war that has so far claimed over 200,000 lives. more...
It's here, and it's growing: the self-assembling Coalition of the Radical Left
Alexander Reid Ross
6th March 2015Naomi Klein famously called for a 'grand coalition' of the progressive left to fight climate change and Earth-destroying capitalism, writes Alexander Reid Ross. And now it's happening, drawing together diverse strands that encompass the fight for social and racial justice, the right to work, health, clean air and fresh water, and our freedom to be alive and thrive on this our one planet. more...
Save the Arctic sea ice while we still can!
John Nissen
5th March 2015The Arctic Ocean is coming close to complete summer meltdown, writes John Nissen - indeed it could happen as soon as September, triggering a severe deterioration in climate across the northern hemisphere. With fast-rising temperatures predicted in the coming decade, we must act now to save the Arctic, before it's too late. more...
Coming soon: the 'Big Heat'
Nafeez Ahmed
3rd March 2015Global warming has been on vacation for a few years, writes Nafeez Ahmed. But that's only because the excess heat - two Hiroshima bombs-worth every second - has been buried in the deep ocean. But within a few years that's set to change, producing a huge decade-long warming surge, focused on the Arctic, that could overwhelm us all. more...
Without its rainforest, the Amazon will turn to desert
Peter Bunyard
2nd March 2015Mainstream climatologists predict a 15% fall in rainfall over the Amazon if it is stripped of its rainforest. But the 'biotic pump' theory, rooted in conventional physics and recently confirmed by experiment, shows that the interior of a forest-free Amazon will be as dry as the Negev desert. We must save the Amazon before it enters a permanent and irreversible dessication. more...
Keystone plankton 'go slow' as ocean acidity rises
Tim Radford
1st March 2015Increasing acidity in the Southern Ocean is slowing the growth of diatoms, reports Tim Radford. Why worry? Because these tiny plankton sustain essential marine ecosystems, and are highly effective at drawing CO2 down into the deep ocean. more...
Tar sands campaigners are Canada's new 'terrorists'
Pete Dolack
5th March 2015Canada's 'Anti-Terrorism Bill' proposes a massive increase in the power of security services, writes Pete Dolack - and in the crosshairs are campaigners against a tar sands industry that's intent on releasing 240 billion tonnes of CO2 into the atmosphere, and those fighting the pipelines needed to get the heavy crude to market. Who are the real 'extremists'? more...
Brazil's ravaged forests are taking their revenge
Robert Hunziker
2nd March 2015Thanks to massive deforestation along Brazil's Atlantic coast and the Amazon, São Paulo's reservoirs are at just 6% of their capacity and water rationing is in place. But this is just the beginning of a long term drying process that could be recreated around the world as forests are laid waste and hydrology disrupted. more...
China's fossil fuel emissions fell 3% in 2014
Lauri Myllyvirta / Greenpeace EnergyDesk
27th February 2015China has just recorded its first fall in emissions from burning fossil fuels in 15 years, writes Lauri Myllyvirta. The sharp decline has surprised analysts, and reflects the fast growing proportion of renewables in the country's power supply. more...
Survivable IPCC projections are based on science fiction - the reality is much worse
Nick Breeze
27th February 2015The IPCC's 'Representative Concentration Pathways' are based on fantasy technology that must draw massive volumes of CO2 out of the atmosphere late this century, writes Nick Breeze - an unjustified hope that conceals a very bleak future for Earth, and humanity. more...
US tax dollars must not finance $1bn Great Barrier Reef destruction!
The Ecologist
20th February 2015A powerful call has gone out the the US Export-Import Bank not to finance a massive coal mine, railway, port terminal and dredged 'canal' through Australia's Great Barrier Reef with $1 billion in loans and guarantees. more...
Fossil fuel divestment backlash forces the question: Which side are you on?
Kate Aronoff / Waging Nonviolence
18th February 2015The fossil fuel industry's big reaction to Global Divestment Day shows us something important, writes Kate Aronoff - they understand the existential danger they face better than we do. To win the battle for the world's climate, as we must, the victory must be total - and there is no place for neutrality or weak compromise. more...
Southwest USA faces long term 'megadroughts' this century
Tim Radford & Oliver Tickell
17th February 2015The same pattern of severe droughts that extinguished the Ancient Pueblo culture of the southwest US in the 13th century will come back with a vengeance later this century as climate warms and dries, writes Tim Radford. And it could have precisely the same effect on the region's modern-day residents. more...
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text:
Watch This: Alpinestars 50 Year Video
This two-minute video is part of Alpinestars' celebration of their 50-year anniversary. As epic they come, this grand A*stars commercial takes viewers on a journey from the world as it was during Alpinestars' early years through human and racing history to the present, and beyond. If you've got a heart that beats for motorsports, happy Valentine's Day. Now click on the link below and treat yourself to a little bit of that lovin' feelin' (sorry, we can't embed the video):
"In the course of 50 years, the most amazing thing that can occur is that history can be written and the future initiated." -Alpinestars


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Veteran peace processor Aaron David Miller gets it half right in today's Los Angeles Times when he dissects the apparent desire of the Obama administration to drive Israeli Prime Minister Benjamin Netanyahu from office.
Miller, a functionary who helped carry out the State Department's failed Middle East policy during the administrations of both the first president Bush and Clinton, is correct when he points out that American attempts to treat Israel as a banana republic don't always work out as Washington intends. While the elder George Bush may have successfully undermined Yitzhak Shamir's re-election in 1992, Bill Clinton's all-out effort to help Shimon Peres beat Netanyahu in 1996 was a failure that helped sour relations between the two countries. For all of the fact that the United States is Israel's only ally, not surprisingly Israelis don't enjoy being dictated to, especially when the issues at stake are their own rights and security. Obama's transparent attempt to overturn the outcome of an election that was held only a few weeks after his own inauguration doesn't sit well with the Israeli public and has increased Netanyahu's popularity. That Jerusalem is the issue over which Obama has sought to ditch Netanyahu is as wrongheaded as it is foolish. No Israeli prime minister is likely to accept Obama's demand that Jews not be allowed to build in existing Jewish neighborhoods in their own capital.
Miller is also correct when he points out that if Obama were really interested in making progress toward Middle East peace, he'd be far better off cozying up to Netanyahu than attempting to somehow impose a left-wing government on Israel. Only right-wingers or former military leaders have the standing to persuade Israelis to take risks for peace. Obama's notion that Israel's opposition leader Tzipi Livni would be more susceptible to American pressure might be true. But there's little chance that she could rally the country behind the disastrous peace plan that the administration is reportedly planning to try to impose on Israel at some point. Miller's also right when he points out, albeit reluctantly, that Bibi has in fact been far from intransigent. He has signed several peace accords, including the Hebron agreement and the Wye Plantation deal during his first term in office, and in the last year he has formally agreed to a two-state solution and a building freeze in Jewish communities in the West Bank.
But what Miller leaves out of his piece is a basic fact about Middle East peacemaking: not even the most accommodating Israeli government can make peace if the Palestinians won't take yes for an answer. Left-wing Israeli governments in the 1990s that gave all that Bill Clinton asked them to give to the Palestinians were still unable to persuade the Arabs to recognize the legitimacy of a Jewish state within any borders. Nor was the Left-leaning government in which Livni served as foreign minister just two years ago able to persuade the supposedly moderate Palestinian Authority leadership to accept a Palestinian state in Gaza, virtually all of the West Bank and half of Jerusalem.
Miller wisely counsels that where Obama is headed in the Middle East will lead only to more failure: "A no-win fight over settlements, the threat of pushing its own peace plan — or worse: too-clever-by-half meddling in Israeli politics. Such an approach will only waste time and energy the United States doesn't have, and risk failure at a time when America is trying to protect its own interests in an angry, complex and turbulent region." But what Miller leaves out of this sage lecture is that the basic premise of Obama's policies — that Israeli intransigence is the primary obstacle to peace — is itself the great myth of current American foreign policy that needs to be debunked.


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Here's a Peek at some of this years entertainment!
Check out all the fun we're going to have on Friday and Saturday!
Vendor Listing and Map Below
This year we
have a great lineup of Entertainment for you with some of your old favorites and some new
exciting venues too! We also have a variety of displays and events, something for
everyone in the family.
Entertainment and Displays throughout
the Festival Grounds
Captain Cardiac
Captain Cardiac Friday Night Dance band.
(3 sets between 5:00 and 9:00 - exact times TBD)
Centennial Park Gazebo
Viper Six Band
is going to play on at the Centennial Park Gazebo
from 11:30am - 2:30pm on Saturday.
Loren Radis
Picnic Park
Saturday, Sept 27th: 11:00am - 2:00pm
"Loren Radis is a Central Coast native who has loved writing and
performing music since he first heard the Beatles at age 10. His
blend of acoustic/rock music has been compared to artists like The
Beatles, Simon & Garfunkel, Iron & Wine, and Jason Mraz. His songs
are about what's important to him; life, love, growing up, and the
importance of authenticity and honesty in music. You can hear his
songs online at music.lorenradis.com, and he thanks you for
Movie Night is back!!
Friday Night
Friday, Sept. 26th at Rotary Bandstand (in Heritage Square Park)
Movie: "ParaNorman" - In Blithe Hollow, Norman Babcock is a boy who
speaks to the dead, but no one besides his eccentric friend, Neil,
believes him. Norman's eccentric uncle tells him of an annual ritual
he must take up to protect the town from a curse cast by a witch it
condemned centuries ago. Eventually, Norman cooperates, but things
don't go according to plan. Now, a magic storm of the witch
threatens Blithe Hollow as the dead rise. Norman struggles to save
his town, only to discover the horrific truth of the curse. With
that insight, Norman must resolve the crisis for good as only he
can. **"Shrek's Swamp Stories" – Three short stories will be shown
prior to the main feature.
Suggested donation of $1 per adult or 50c per child
Anthony Roselli
Picnic Park
Saturday, Sept 27th: 2:00pm - 5:00pm
Anthony has been writing and performing original songs for over 20
years and has a unique folk-rock sound that is infectious. He has
featured and hosted Singer-Songwriter showcases and plays weekly
shows at great venues all over the Central Coast of California. Some
notable venues where you may find Anthony playing his original music
would be: Eureka Burger, Cambria Pines Lodge, Stax Wine Bar, Pour
House, Backstage Pizza, Wood Winery, Tap-It Brewery, Creative
Juices, KunFusion, Last Stage West, Pozo Saloon, Frog & Peach Pub,
and Wise Owl Cafe.
Beyond playing his original music all over the Central Coast of
California, he also can be found at Cheap Thrills Records and doing
sound and stage work with artists from Merle Haggard and Blues
Traveler to Ziggy Marley.
The Daily Special Bluegrass Band - country, folk & bluegrass
Hall Parking lot
11:30am - 4:00pm Saturday
Nipomo High School Pep Band
Saturday: 3:00 - 4:30pm
Centennial Park Gazebo
Pacific Flips
Pacific Flips are performing on
Saturday from 11:30am - 4:00pm.
On Bridge Street at the end of Olohan Alley
Demonstration with Audience Participation
Presented by Tantrum Fitness
Saturday 2:30-3:00
Centennial Park in Olohan Alley (lawn around the Gazebo)
Agriculture Pavilion
All day on Saturday on Bridge Street
Click Here for Details
Big Ditch Derby
Saturday on Nelson Street
Click Here for Details
Grande Rotary Fish Fry
Friday Night, Sept. 26th
in Olohan Alley
Grande High School Robotics Team
Sign Up at the Festival!
Ballooney the Clown
Always a favorite with the young and young at heart, Ballooney the Clown,
aka, Mike Kilton, will perform for the Harvest Festival again this year. Ballooney
has been entertaining for more than 20 years throughout the United States, the Carribean
and overseas, and has entertained in the Arroyo Grande area since 1994.
He takes
part in the morning Parade and then entertains the children in his "Kid Zone" on
the Village Green all afternoon. With hundreds of props and a wild imagination
Ballooney keeps the kids in stitches all day! Not only does he perform for the
children but he involves them in educational games and fun activities.
Click here for details
Engines Display
Spelling Bee
Sign up on Saturday at the Schoolhouse
Kids Parade
Three years ago Ballooney initiated his afternoon closing "Kid
Parade" This was a big hit and proves to be bigger and better
this year! The kids should gather with Ballooney next to the
Rotary Bandstand at 4:00pm to receive their costumes and
instructions. Once all are in costume the group will parade
around the Village Green, across the Swinging Bridge and end up
circling through the Olohan Alley. Parents are
encouraged to join their small children since Ballooney will have a
costume for them too!
Lots Lots More!
See home page for
Wiener Dog Races
Fruit, Veggie & Flower Display & Contest
Baking Contest
Lots Lots More!
See home page for
Wiener Dog Races
Fruit, Veggie & Flower Display & Contest
Baking Contest
Times Subject To Change
Handicapped Parking
is available at the City Hall parking lot located at the corner of
East Branch Street and Mason Street.
Handicapped Parking
is available at the City Hall parking lot located at the corner of
East Branch Street and Mason Street.
Copyright 2014 ©Arroyo Grande Valley Harvest Festival All Rights
Site Developed and Maintained by: Vivian Krug©


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We now offer custom made invitations. For further information, please call us at (718)810-3216.
Online order available for Queens and its surrounding areas. Please contact us at (718) 810-3216 for service within Manhattan and Long Island.
Visit our Facebook page for photos of our work: https://www.facebook.com/MetropolitanBalloon
We are proud to provide balloon services for these local schools events:
- P.S. 19Q (3 consecutive years, Grad ceremony 2012-2014)
- New Allen School (3 consecutive years, Grad ceremony 2012-2014)
- P.S. 119Q (4 consecutive years, grad ceremony and prom 2011-2014)
- P.S. 139Q (4 consecutive years, Grad ceremony 2011-2014)
- P.S. 174Q (5 consecutive years, Grad ceremony 2010-2014)
- P.S. 107 (1st Year, End of Term Party 2014)
- Bayside High School (1st Year, Prom 2014)
- Richmond Hills High School (1st Year, Graduation, prom 2014)
- High School for CTEA (1st Year, Senior Dinner 2014)
- IS 141 (1st Year Graduation, 2 events 2014)
- IS 230 (1st Year Prom 2014)
- Forest Hills High School (Various events 2014)
- The Life Skills School (1st Year, Prom 2013)
- School for Language and Communication Development (1st Year, Grad ceremony 2013)
- Village Preschool Center (1st year Grad ceremony 2013)
- LaGuardia Community College (3 consecutive years for Science events 2010-2013)
- St. Johns University (Several different events 2011-2014)
- St. Agnes Academy High School(Open house, 2nd consecutive years 2012-2014)
feature Items
Columns and Arches
Balloon Bouquets and Centerpieces
Balloon Bouquets and Centerpieces
Columns and Arches
Latex balloons
Birthday Balloons
Boy's License foil balloons
Girl's License Balloons
1st Birthday Balloons
Jumbo Foil Balloons
Number balloons
Baby Shower / New Baby Balloons
Religious Balloons
Anniversary Balloons
Bridal Balloons
Wedding Store
Sports Balloons
Love Balloons
Solid Foil Balloons
Graduation Balloons
Other Balloons
Holiday Balloons
New Year's Eve Latex Balloons
Connect to our Facebook Page
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Copyright 2006 Metropolitan Balloon. All rights reserved.


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Carhartt Girls' Fishing Is My Sport Cap Sleeve T-Shirt
Key Features
Made of 4.4-oz., 100% cotton jersey
Forward side seams for flexibility
Cap sleeves allow greater range of motion
"Fishing Is My Sport" screen print on front
Silver metallic foil fish graphic on front center
Our Price $14.00
Sale Price $9.96
Availability: Sold Out
- Please note: This item can only be shipped to U.S. addresses.
detailsback to top
Product DescriptionMade of 4.4-oz., 100% cotton jersey, the Carhartt Girls' Fishing Is My Sport Cap Sleeve T-Shirt is perfect for relaxing or adventuring in the great outdoors. Forward side seams allow for more flexibility and increased durability, while the cap sleeves provide great range of motion, as arms are not hindered by the fabric. A "Fishing Is My Sport" screen print with silver metallic foil fish graphic dominates the center front chest. This design gives the Cap Sleeve T-Shirt a unique look and ensures you will look as good as you feel. Imported. Style #CA9263.


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Melissa Dawn Taylor is a blonde bombshell. The Oregon-born Miss Taylor moved to Los Angeles with her Louis Vuitton purse filled with dreams of becoming a singer, songwriter and model. Her modeling career led her to the Playboy Mansion where she attended many parties and late...
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Ask Klaus
Ask Klaus
Klaus Knopper answers your Linux questions.
Video Woes
Klaus: I have recently installed Fedora 20 on a Pentium 4 with 1GB of RAM and a Ti4200 video card. I can't seem to get the video sorted out. Your Knoppix 7.04 works perfectly. I wonder what video drivers you are using? The best I can get out of Fedora is 1024x768, but your 7.04 gives me a perfect 1280x1024 @75Hz resolution. Xrandr in Fedora doesn't show the proper resolutions, but yours in 7.04 does. Thanks in advance for any advice you might have. Ron
Answer: You can find out which graphics card drivers Knoppix (or any other distro) uses by looking for the graphics-related kernel modules and Xorg plugins in use. Check the output of
lsmod for the "nouveau" driver and look into
/var/log/Xorg.0.log to see which driver is active in Xorg.
If Xorg cannot find or activate the proper accelerated driver for your graphics card in Fedora, it will try the generic VESA or framebuffer module. Both of these will not be able to handle changing resolution via xrandr and most likely will not even give you the perfect resolution unless an optimized framebuffer kernel module exists for your graphics card.
To get best support for your Ti4200 graphics card (NVidia code name NV25 [1]), you will need:
- A relatively new kernel (especially the
- Xorg server 7.7 (core 1.12) and the matching nouveau video module version 1.0.1 or later.
libdrm-nouveau(1a or 2) matching the above.
- The Mesa DRI package, which may be "experimental" depending on the distribution:
libgl1-mesa-dri or libgl1-mesa-dri-experimental.
It must be noted that it is crucially important that the versions of Xorg, the nouveau kernel and nouveau Xorg module, and the DRM and DRI packages play nicely together, which is usually the case if you install all of them from the same development branch (for Debian, I usually use the "unstable" and "experimental" branch for all graphics hardware support packages and drivers).
The proprietary driver also is available from NVidia, but it should not be necessary to use it if the free nouveau driver works fine on Knoppix 7.0.4.
If you find that all needed packages are in fact installed in Fedora (double-check for the newer nouveau drivers), there can still be a problem actually loading the nouveau kernel module, related to the
vesafb driver needed to display a "splash screen" in Fedora. For some accelerated kernel graphics modules, activation of the high-resolution vesafb during boot will prevent the nouveau driver from claiming the framebuffer and switch to fast mode. In this case, just kill the framebuffer splash screen by trying the kernel options:
video=vga16fb:off vga=normal
With these options, you should get plaintext messages during the startup process instead of the splash screen, but as soon as the
nouveau driver is loaded, the resolution will switch to the "native" resolution of graphics card and monitor, and Xorg should be able to use the accelerated driver again. Also, check whether
/etc/grub.conf or
/etc/default/grub includes the Fedora-specific
rhgb kernel option. If it is present, please remove this keyword and run
grub2-mkconfig as root, then reboot Fedora.
Linux on Mac
Hi Klaus, I have a question on how to install Linux on a Mac. What is an easy way to install Linux on a Mac, and what web pages will show, step by step, how to do this? Thanks, Jesus
Answer: Depending on the Mac hardware you have, different Linux distros are available. For Ubuntu, you can find an overview with links to the installation procedure for MacBook [2] and MacBook Pro [3] in the online documentation.
To just test an Intel Mac for hardware compatibility, you can use the Knoppix "boot-only" CD, which contains only the Mac-compatible "El Torito" bootloader and the Linux kernel. Hit Cmd+C after turning on the Mac for the CD boot choice (you also have to do this when you install a Linux distribution from DVD). After the kernel and initial ramdisk are loaded, in the Knoppix "boot-only" version, the system will search for and transfer control to a previously installed Knoppix USB flash disk. In this mode, there is no trouble with the Mac's EFI boot system, as opposed to directly booting from USB. Booting from the full DVD version is possible, too, of course.
The Tuxation website [4] also contains more technical in-depth information about partitioning and interoperability issues, but for a simple Linux installation on the Mac, you will probably not need this information unless you plan to run Linux in dual-boot mode, keeping the old OS X system and repartitioning the hard drive.
New Life for Old Laptop
Hi Klaus: In issue 150 [5], you dealt with my query about getting Knoppix to boot on an old laptop with faulty BIOS. There was further mention of this query in issue 157 [6].
So, here's what happened. I first followed your suggestion about installing to hard drive using the flash installation. Well, that worked fine, although it didn't really give proper warning it would delete the Windows partition. No matter – the intent was to "upgrade" to Linux anyway!
Then, I decided if you had designed Knoppix for ReiserFS, I had better install on ReiserFS. So, I repartitioned the drive, loaded Knoppix on partition 1 and then Ubuntu on partition 2 with Ubuntu's version of GRUB. The latter evidently has the necessary BIOS routines to respond to keyboard input, and I can now select Knoppix and boot successfully. (I also included a 2GB swap partition).
Knoppix is pretty nifty on the old machine (Acer Travelmate 345T with Pentium 3 CPU, 256MB RAM), but I wonder if you can recommend a lighter, faster web browser. It must still be Java enabled since my goal is suitably nerdy – i.e., play chess on chess.com! Opera (which I downloaded) seems to work pretty reasonably for ordinary browsing but more or less dies when I select "play live" on chess.com. I don't know what the system overheads are for this type of gaming client and all the ads that accompany it.
Finally, in respect to clock sync on reboot (because of the faulty BIOS), I discovered the client
ntpdate, which works fine. It was just a mission to install – may I suggest that you include it as a standard part of the Knoppix distro? I did actually buy a new battery (as your reader suggested in issue 157) but that doesn't solve the BIOS problem – BIOS is dependent on the CMOS battery, which has died and seems impossible to replace.
Many thanks for your response to my query – I look forward to further use of my old laptop with Knoppix installed.
Regards, Neil
Answer: Congratulations on giving your laptop a new life with Linux. Concerning the overwritten Windows installation: I'm quite sure that the Knoppix flash installer warns you before repartitioning and formatting the drive and tells you that "all data will be lost."
Anyway, about the CMOS battery: That one is actually the one I would replace. On some boards it is just a CR2032 "button cell," which is inserted into a special socket or soldered onto the board [7]. In the first case, it is easy to replace the battery after you found it, but in the second case, it is more dangerous to remove it and set a new one in place.
If you want to start
ntpdate <time server> automatically in Knoppix, you can add the command at the end of
/etc/rc.local before the final
exit statement; it will then be called as root during system startup.
About web browsers: Yes, Firefox tends to consume a lot of RAM, but using the Knoppix zRAM feature, it might not be too heavy, even for old computers. However, the browsers Midori [8] and Epiphany (built in to the Gnome 0 desktop) might consume somewhat less memory, and they support the IcedTea Java plugin for running applets, although not every version may be compatible.
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Android Bug Threatens Millions of Users
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Lenovo and Canonical Announce Laptop Deal
PC vendor will pre-install Ubuntu on portables in India.
Mozilla Firefox Blocks Flash
More embarrassment for Adobe's embattled multimedia tool
Security Problem in Firefox's NoScript Add-On
Mozilla's script blocker add-on could be putting malware sites on the whitelist.
RIP SSLv3
The Internet community officially banishes the notoriously unsafe Secure Sockets Layer protocol.
Mate 1.1 Arrives
Popular desktop environment continues the Gnome 2 legacy – with new support for the Gnome 3 toolkit.
US Government Requires HTTPS
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text:
Kauffmann, Stanley, 1916-2013
From Library of Congress Name Authority File
Kauffmann, Stanley, 1916-2013
Instance Of
Scheme Membership(s)
Collection Membership(s)
Use For
Exact Matching Concepts from Other Schemes
- found: LCCN 40019614: Close courting, c1940 (hdg.: Kauffmann, Stanley, 1916- ; usage: Sprangler Barry)
- found: New York times (online), viewed Oct. 17, 2013 (in obituary published Oct. 9: Stanley Kauffmann; b. Stanley Jules Kauffmann, Apr. 24, 1916, Manhattan; d. there Wednesday [Oct. 9, 2013], aged 97; his literate, tightly constructed movie reviews appeared in The new republic for more than a half-century and set a standard for critical ease and erudition)
- found: LCCN 42006219: Play ball!, 1940 (hdg.: Kauffmann, Stanley, 1916- ; usage: Spranger Barry)
LC Classification
Change Notes
- 1979-03-29: new
- 2013-10-17: revised
Alternate Formats


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Like much of the world, John Legend and his girlfriend Chrissy Teigen are obsessed with Pippa – but not the one you might think! This couple is infatuated with Pippa, their new French bulldog puppy.
Teigen went to pick up the female pup from a breeder in Gainesville, Fla., over the holiday weekend and has been overjoyed since.
"On the plane! Headed home. Stopping in Charlotte again. She is worth it. I'm in love," the model Tweeted on July 2. "Flight delay. Our little friend is sound asleep. And mark exactly 3pm as the time of her first fart with me."
The noisy little pooch, who weighed in at 4-lbs. on June 30, seems to be settling into her new life very well. "Pippa whines and hollers for a minute, pees, whines again for another minute, then goes to bed. she is me," Teigen wrote.
And like Teigen, Pippa is getting along swell with Legend's bulldog, Puddy, who has been the only child in the household for several years. The two dogs' first meeting on Independence Day went well.
"Puddy is beyond patient with pippa," Teigen wrote. "She is so rough on the guy. Poor pudds."
Click here to see a video of Pippa in action!
Can't get enough pet news? See more on PEOPLE Pets:
Kellie Pickler Rescues a Pit Bull on July 4th
Look Out Below! Squirrel Gets Stuck in Manhole Cover
Courtesy John Legend; Inset: Frank Micelotta/PictureGroup


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Luis Suarez finished off a marvellous team move to net the opening goal against Tottenham on Sunday, and LFC TV Online subscribers can now watch his strike in seven different angles.
The move started with some samba flair from Brazilian Philippe Coutinho who produced a majestic flick and then set up the rampaging Jose Enrique down the left wing.
The Spaniard then found Suarez who did the rest to fire his 29th goal of the season.
Click play below to watch the clip.
You can get audio commentary, goals, highlights and analysis of all first-team matches, live press conferences, LFC TV, top 100 features, live youth football, exclusive interviews from Melwood and loads more from just £2.99 per month with an LFC TV Online subscription. Sign up or find out more>>
Tagged: Luis Suarez , Suarez , spurs , tottenham , tottenham Hotspur
Submit your views in the box below. Alternatively, you can debate these issues with fellow fans on our Message Boards or blog about them on The Kop
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Papa Roach is an American rock band formed in 1993. At first, the band was influenced by punk and rap music, and over the years became a hard rock ensemble. Currently, the group consists of Coby Dick, Jerry Horton, Tony Palermo, and Tobin Esperance. Their album "Infest", released in 2000, was certified triple Platinum. Their latest album, Metamorphosis (2009), includes the singles "Hollywood Whore", "Lifeline", and "I Almost Told You That I Loved You".
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text:
This invention relates to polyolefin compositions. In particular, the invention pertains to elastic polymer compositions that can be more easily processed on cast film lines, extrusion lamination or coating lines due to improved resistance to draw resonance. The compositions of the present invention comprise an elastomeric polyolefin resin and a high pressure low density type resin. The preferred compositions of the present invention comprise from 88 to 99 percent elastomer or plastomer and from 1 to 12 percent by weight of a high pressure low density type resin.
1. A composition comprising:
a. about 88 to about 99 percent by weight of the composition of a linear and/or substantially linear ethylene/alpha olefin copolymer plastomer and/or elastomer having a density of less than about 0.885 g/cm3 and a melt index (I2) of less than about 20 g/10 min; and
b. from about 1 to about 12 percent by weight of the composition of a high pressure low density resin
wherein the heat of melting of the composition (measured by integrating the area under the melting endotherm of a differential scanning calorimetry (DSC) curve from the beginning of melting to the end of melting by using a linear baseline) is less than about 60 J/g; and wherein the partial area above 80° C. for the composition is less than about 25% of the total heat of melting; and wherein the cumulative detector fraction (CDF) for the composition having molecular weights greater than 1,150,000 is in a range of from greater than about 0.02 to about 0.167, where the CDF of the LALLS chromatogram (CDFLS) is calculated based on its baseline-subtracted peak height (H) from high to low molecular weight (low to high retention volume (RV)) at each data slice (i) according to the following equation:
where i is between the LowestRVindex and the HighestRVindex.
2. The composition of
3. The composition of
4. The composition of
5. The composition of
6. The composition of
7. The composition of
8. The composition of
9. The composition of
10. The composition of
This application is a non-provisional 371 national phase patent application of International Patent Application No. PCT/US2005/047172, filed on Dec. 23, 2005, entitled "ELASTOMERIC RESIN COMPOSITIONS WITH IMPROVED RESISTANCE TO DRAW RESONANCE, which claims priority from the U.S. Provisional Patent Application No. 60/641,093, filed on Jan. 3, 2005, entitled "ELASTOMERIC RESIN COMPOSITIONS WITH IMPROVED RESISTANCE TO DRAW RESONANCE," the teachings of which are incorporated by reference herein, as if reproduced in full hereinbelow.
This invention relates to polyolefin compositions. In particular, the invention pertains to elastic polymer compositions that can be more easily processed on cast film lines, extrusion lamination or coating lines due to improved resistance to draw resonance. The compositions of the present invention comprise an elastomeric polyolefin resin and a high pressure low density type resin. The preferred compositions of the present invention comprise from 88 to 99 percent elastomer or plastomer and from 1 to 12 percent by weight of a high pressure low density type resin.
Elastic films made from elastomeric polymers have found use in laminates with nonwoven fabrics as a way to impart elasticity to the nonwoven laminates. Such elastic nonwoven laminate materials have found use in the hygiene and medical market particularly in such applications as elastic diaper tabs, side panels of training pants, leg gathers, feminine hygiene articles, swim pants, incontinent wear, veterinary products, bandages, items of health care such as surgeon's gowns, surgical drapes, sterilization wrap, wipes, and the like. These materials may also find use in other nonwoven applications including but are not limited to filters (gas and liquid), automotive and marine protective covers, home furnishing such as bedding, carpet underpaddings, wall coverings, floor coverings, window shades, scrims etc. These elastic films can be incorporated into laminate designs such as those described in WO9003464A2, U.S. Pat. No. 4,116,892, U.S. Pat. No. 5,156,793.
Such elastic films are often prepared using cast film processes. In a typical cast film process the molten polymer is extruded through a die and then the molten film is drawn to the nip/chill rolls where it is rapidly cooled on the chill roll. Particularly as the speed of the production increases, a phenomenon known as draw resonance can occur under particular extrusion conditions especially when a nip is used. Draw resonance is the name given to periodic fluctuations in the thickness of the film in the machine direction (MD) which corresponds to periodic variations in the film width in the cross direction (CD). Draw resonance results in film instability which can restrict the productivity of commercial processes. Draw resonance is known to be a particular problem for polyolefin elastomers, particularly linear polyolefins. Accordingly, it is a goal to reduce or eliminate draw resonance in the production of films, particularly in the production of elastic films. This phenomenon has been described previously in the scientific literature. The following are some examples:
It has been discovered that when using polyolefin elastomers or plastomers in an extrusion lamination/coating application, the addition of a minor amount of a material with high levels of long chain branching, reduces the occurrence and/or severity of draw resonance. This enables higher productions rates. The preferred branched material will have a broad molecular weight distribution and sufficiently high melt strength. It is known however that the addition of such material negatively affects the elastic properties of the films or coatings. Surprisingly, however, it has been discovered that over certain optimal compositional ranges, the draw resonance is improved without the concurrent significant degradation in elastic performance.
Accordingly, one aspect of the invention is a composition of matter suitable for use in extrusion coating and/or extrusion lamination applications comprising:
In a particular aspect of the present invention, at least one ethylene-based elastomer is used. The ethylene content comprises the majority of the monomers by weight with the remainder comprising one other comonomer with C3-C22. The preferred polymer has a density of 0.855-0.885 g/cm3 (ASTM D792) and has a MI less than about 20 g/10 min (ASTM D1238 for polyethylenes). In this aspect, it may be advantageous to use an ethylene containing highly branched polymer for the second component. It should be understood that more than one ethylene based elastomer may be used.
In another aspect of the present invention, a propylene-based elastomer is used. The preferred polymer comprises at most 89 mol percent propylene with the remainder comprised of at least one other monomer type and has a MFR less than about 25 g/10 min (ASTM D1238 for polypropylenes). In one case, the copolymer is propylene-ethylene. Some polymers fitting this description include VERSIFY™ plastomers and elastomers from The Dow Chemical Company and VISTAMAXX™ polymers from the Exxon-Mobil Corporation. When using a propylene based elastomer, it may be advantageous to use a propylene containing highly branched polymer for the second component. Also, more than one propylene based elastomer may be used.
Another aspect of the present invention is a method to improve the extrusion coating and/or extrusion lamination of polyolefin elastomeric or plastomeric materials comprising adding up to 12 percent by weight of a high pressure low density type resin as the second component. Also, more than one second component may be used.
Elastic laminates and coatings made from the compositions of the present invention are another aspect of the present invention.
The following terms shall have the given meaning for the purposes of this invention:
For purposes of this invention, a film is considered to be "elastic" if it has a permanent set of less than 40 percent as determined according to the following procedure: the samples is loaded into a Sintech mechanical testing device fitted with pneumatically activated line-contact grips with an initial separation of 4 inches. Then, the sample is stretched to 80 percent strain at 500 mm/min and returned to 0 percent strain at the same speed. The strain at 10 g load upon retraction was taken as the permanent set.
"Linear" means a polymer having a CDF less than about 0.02.
"Density" is tested in accordance with ASTM D792.
"Melt Index (I2)" is determined according to ASTM D1238 using a weight of 2.16 kg at 190° C. for polymers comprising ethylene as the major component in the polymer.
"Melt Flow Rate (MFR)" is determined for according to ASTM D1238 using a weight of 2.16 kg at 230° C. for polymers comprising propylene as the major component in the polymer.
"Molecular weight distribution" or MWD is measured by conventional GPC per the procedure described by Williams, T.; Ward, I. M. Journal of polymer Science, Polymer Letters Edition (1968), 6(9), 621-624. Coefficient B is 1. Coefficient A is 0.4316.
With recent advances in technology, new lower density ethylene-based and propylene-based polymers have become available. Some classification schemes divide these materials into subgroups of "elastomers" and "plastomers." As many of these polymers are linear, they are ideally suited to be used in this invention, however they should exhibit elastic properties as defined earlier.
The term "polymer", as used herein, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term "homopolymer", usually employed to refer to polymers prepared from only one type of monomer as well as "copolymer" which refers to polymers prepared from two or more different monomers.
The term high pressure low density type resin is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides (see for example, U.S. Pat. No. 4,599,392, herein incorporated by reference) and includes "LDPE" which may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". The CDF of these materials is greater than about 0.02.
The term "high pressure low density type resin" also includes branched polypropylene materials (both homopolymer and copolymer). For the purposes of the present invention, "branched polypropylene materials" means the type of branched polypropylene materials disclosed in WO2003/082971, hereby incorporated by reference in its entirety.
Description of the Composition
The composition of matter of the present invention comprises at least two components. The first component is a polyolefin based plastomer and/or elastomer. Polyolefin based elastomers and plastomers/polymers include copolymers of ethylene with at least one other alpha olefin (C3-C22), as well as copolymers of propylene with at least one other alpha olefin (C2, C4-C22). Preferred polyethylene based materials for the first component include linear and substantially linear polyethylene/alpha olefin copolymers. Propylene/ethylene polymeric materials can also be used where the ethylene content is from 9 to 15 percent by weight. If the first component is an ethylene based polymer, it can be characterized as having a density of less than about 0.885 g/cm3, more preferably less than about 0.88 g/cm3, most preferably less than about 0.875 g/cm3 The first component will also have a melt index (I2) of less than about 20, more preferably less than about 15, and most preferably less than about 12.
In the case the first component comprises a propylene-based polymer, it should have at most 89 mol percent propylene, preferably at most 85 mol percent propylene. In one embodiment of the invention, the remaining copolymer is comprised of ethylene polymerized using metallocene or non-metallocene catalysts. The polymers in this invention are not method specific and can be made using gas phase, solution, or slurry processes. The first component will also have a MFR of less than about 50, more preferably less than about 25, and most preferably less than about 10.
The first component of the present invention may also include blocked or multi-blocked polymers, as described for example, in WO 2005/090427, WO 2005/090426 and WO 2005/090425, each claiming priority to U.S. Ser. No. 60/553,906 filed Mar. 17, 2004, the disclosures of each of which is incorporated herein by reference. Multi-blocked ethylene based polymers and interpolymers (including, for example, ethylene/C3-C20 alpha-olefin interpolymers) are especially preferred.
As understood by one skilled in the art, in general, the lower the density of the first component, the more elastic the polymer will be. The first component can be made using a gas, slurry or solution phase reactors. Likewise, it may be heterogeneous (for example, as prepared by chrome or Ziegler-Natta catalysts) or homogeneous (for example, as prepared by single site or metallocene catalysts) or of intermediate composition distribution. Possible configurations by which the first polymer component can be made include using one reactor or multiple reactors arranged in series or parallel or combinations thereof.
Although polymers that have varied molecular weight distributions are suitable for use with this invention, narrower molecular weight distributions are preferred such as those made using metallocene catalysts to minimize effects of draw resonance.
The first component may comprise from 85 to 99 percent of the total composition with greater than 88 percent or even greater than 90 percent being more preferred.
The second component is a high pressure low density type resin Possible materials for use as the second component include LDPE (homopolymer); ethylene copolymerized with one or more α-olefins, for example, propylene or butene; and ethylene copolymerized with at least one α,β-ethylenically unsaturated comonomer, for example, acrylic acid, methacrylic acid, methyl acrylate and vinyl acetate; branched polypropylene and blends thereof. A suitable technique for preparing useful high pressure ethylene copolymer compositions is described by McKinney et al. in U.S. Pat. No. 4,599,392, the disclosure of which is incorporated herein by reference.
LDPE (homopolymer) is generally the most preferred material for use as the second component with an ethylene-based first component, however, if the first component includes propylene (for example, if the first component is a propylene/ethylene copolymer) then it may be advantageous for the second component to also include propylene as a comonomer. Though not limited by theory, it is hypothesized that inclusion of propylene in the second component is thought to increase compatibility and miscibility if the first component also comprises propylene. Likewise, the theory of increased compatibility through increased miscibility of like components is thought to explain the preference of ethylene-based elastomers to be used with ethylene based species with high levels of long chain branching.
When propylene based polymers are desired for use as the second component, the preferred materials are the branched polypropylene materials (both homopolymer and copolymer) of the type disclosed in WO2003/082971. The Coupled Impact Polypropylene Polymers disclosed in that reference are particularly preferred propylene-based materials. Such polymers and their manufacture are disclosed in U.S. Pat. No. 6,359,073, and in WO 2000/78858, which are hereby incorporated by reference in their entirety.
The preferred high pressure low density polyethylene material (LDPE) has a melt index MI (I2) of less than about 20, more preferably less than about 5, most preferably less than 1, and greater than about 0.2, more preferably greater than about 0.25, most preferably more than 0.3 g/10 min. The preferred LDPE will have a density between 0.915 g/cm3 and 0.930 g/cm3, with less than 0.920 g/cm3 being more preferred.
The second component will ideally be added in an amount such that it makes up at least about 1 percent, more preferably at least about 5 percent, and most preferably about 6 percent by weight of the final composition. Preferably, the second component will not comprise more than 12 percent, preferably not more than 10, still more preferably not more than about 8 percent and most preferably between 4 and 7 percent by weight of the final composition. It should be understood that the total amount of the first and second components does not necessarily have to equal 100 percent as other materials may be present.
In yet another embodiment of this invention, a third polymer component may be used to improve compatibility, miscibility, dispersion, or other characteristics among the polymer components as is generally known in the art.
The second component may be made in any autoclave or tubular reactors capable of running at pressures above 14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides, but it is preferred that this component be made in an autoclave reactor (optionally configured with a series tube reactor) with chilled ethylene feed below 35° C. operating in single phase mode with three or more zones. The reactor is preferably run above the transition point (phase boundary between a two-phase and a single-phase system) at an average reactor temperature of approximately 240° C.
The composition of the present invention may also include LDPE/LDPE blends where one of the LDPE resins has a relatively higher melt index and the other has a lower melt index and is more highly branched. The component with the higher melt index can be obtained from a tubular reactor, and a lower MI, higher branched, component of the blend may be added in a separate extrusion step or using a parallel tubular/autoclave reactor in combination with special methods to control the melt index of each reactor, such as recovery of telomer in the recycle stream or adding fresh ethylene to the autoclave (AC) reactor, or any other methods known in the art.
For additional attributes, any of the polymer components may be functionalized or modified at any stage. Examples include but are not limited to grafting, crosslinking, or other methods of functionalization.
Preparation of the Blends
The preferred blends for making the polymer extrusion compositions of this invention can be prepared by any suitable means known in the art including tumble dry-blending, weigh feeding, solvent blending, melt blending via compound or side-arm extrusion, or the like as well as combinations thereof.
The compositions of the present invention can also be blended with other polymer materials, such as polypropylene and ethylene-styrene interpolymers. The other polymer materials can be blended with the inventive composition to modify processing, film strength, heat seal, or adhesion characteristics as is generally known in the art.
Both of the required components of the blends of the current invention can be used in a chemically and/or physically modified form to prepare the inventive composition. Such modifications can be accomplished by any known technique such as, for example, by ionomerization and extrusion grafting.
Additives such as antioxidants (for example, hindered phenolics such as Irganox® 1010 or Irganox® 1076 supplied by Ciba Geigy), phosphites (for example, Irgafos® 168 also supplied by Ciba Geigy), cling additives (for example, PIB), Standostab PEPQ™ (supplied by Sandoz), pigments, colorants, fillers, and the like can also be included in the ethylene polymer extrusion composition of the present invention, to the extent that they do not interfere with the reduced draw resonance discovered by Applicants. The article made from or using the inventive composition may also contain additives to enhance antiblocking and coefficient of friction characteristics including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate, and clay, as well as primary, secondary and substituted fatty acid amides, chill roll release agents, silicone coatings, etc. Other additives may also be added to enhance the anti-fogging characteristics of, for example, transparent cast films, as described, for example, by Niemann in U.S. Pat. No. 4,486,552, the disclosure of which is incorporated herein by reference. Still other additives, such as quaternary ammonium compounds alone or in combination with ethylene-acrylic acid (EAA) copolymers or other functional polymers, may also be added to enhance the antistatic characteristics of coatings, profiles and films of this invention and allow, for example, the packaging or making of electronically sensitive goods. Other functional polymers such as maleic anhydride grafted polyethylene may also be added to enhance adhesion, especially to polar substrates.
Alternatively, the polymeric and non-polymeric components may be combined with steps that include solution blending (also known as solvent blending) or a combination of melt and solution methods. Solution blending methods include but are not limited to multiple reactors in series, parallel, or combinations thereof. As solution methods can sometimes result in better dispersion of the components, greater efficacy of the second component is anticipated. Benefits may include using less second component to achieve comparable improvements in resistance to draw resonance with maintenance of greater elastic properties such as reduced set strain and less hysteresis.
Multilayered constructions comprising the inventive composition can be prepared by any means known including coextrusion, laminations and the like and combinations thereof. When the inventive composition is used in multilayered constructions, substrates or adjacent material layers can be polar or nonpolar including for example, but not limited to, paper products, metals, ceramics, glass and various polymers, particularly other polyolefins, and combinations thereof. If a polymer substrate is used, it may take a variety of forms including but not limited to webs, foams, fabrics, nonwovens, films etc.
Test Procedures
Molecular Architecture Determination
In order to determine the molecular architecture of various polymer compositions, the following procedure is used:
The chromatographic system consists of a Waters (Millford, Mass.) 150° C. high temperature chromatograph equipped with a Precision Detectors (Amherst, Mass.) 2-angle laser light scattering detector Model 2040. The 15-degree angle of the light scattering detector is used for calculation purposes. Data collection is performed using Viscotek TriSEC software version 3 and a 4-channel Viscotek Data Manager DM400. The system is equipped with an on-line solvent degas device from Polymer Laboratories.
The carousel compartment was operated at 140° C. and the column compartment is operated at 150° C. The columns used are 4 Shodex HT 806M 30 cm 13-micron columns and 1 Shodex HT803 15 cm 13-micron column. The solvent used is 1,2,4 trichlorobenzene. The samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent contain 200 ppm of butylated hydroxytoluene (BHT). Both solvent sources are nitrogen sparged. Polyethylene samples are stirred gently at 160 degrees Celsius for 4 hours. The injection volume used is 200 microliters and the flow rate is 0.67 milliliters/minute.
Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 and are arranged in 6 "cocktail" mixtures with at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80° C. with gentle agitation for 30 minutes. The narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).:
A fourth order polynomial is used to fit the respective polyethylene-equivalent calibration points. Deviation between the polynomial fit and the calibration points is minimized.
The total plate count of the GPC column set is performed with Eicosane (prepared at 0.04 g in 50 milliliters of TCB and dissolves for 20 minutes with gentle agitation.) The plate count and symmetry are measured on a 200 microliter injection according to the following equations:
The Systematic Approach for the determination of multi-detector offsets is done in a manner consistent with that published by Balke, Mourey, et. al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), optimizing dual detector log results from Dow broad polystyrene 1683 to the narrow standard column calibration results from the narrow standards calibration curve using in-house software. The molecular weight data for off-set determination is obtained in a manner consistent with that published by Zimm (Zimm, B. H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, N.Y. (1987)). The overall injected concentration used for the determination of the molecular weight is obtained from the sample refractive index area and the refractive index detector calibration from a linear polyethylene homopolymer of 115,000 molecular weight. The chromatographic concentrations are assumed low enough to eliminate addressing 2nd Virial coefficient effects (concentration effects on molecular weight).
In order to monitor the deviations over time, which may contain an elution component (caused by chromatographic changes) and a flow rate component (caused by pump changes), a late eluting narrow peak is generally used as a "marker peak". A flow rate marker is therefore established based on the air peak mismatch between the degassed chromatographic system solvent and the elution sample on one of the polystyrene cocktail mixtures. This flow rate marker is used to linearly correct the flow rate for all samples by alignment of the air peaks. Any changes in the time of the marker peak are then assumed to be related to a linear shift in both flow rate and chromatographic slope.
To facilitate the highest accuracy of a RV measurement of the flow marker peak, a least-squares fitting routine is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on a flow marker peak, the effective flow rate (as a measurement of the calibration slope) is calculated as Equation 1. In a high-temperature SEC system, an antioxidant mismatch peak or an air peak (if the mobile phase is sufficiently degassed) can be used as an effective flow marker. The primary features of an effective flow rate marker are as follows: the flow marker should be mono-dispersed. The flow marker should elute close to the total column permeation volume. The flow marker should not interfere with the chromatographic integration window of the sample.
The verification of adequate column separation and appropriate shear rate can be made by viewing the low angle (less than 20 degrees) of the on-line light scattering detector on an NBS 1476 high pressure low density polyethylene standard. The appropriate light scattering chromatogram should appear bimodal (very high MW peak and moderate molecular weight peak) as shown in the
The calculation of the cumulative detector fractions (CDF) for the refractometer ("CDF RI") and the low angle laser light scattering detector ("CDF LS") are accomplished by the following steps:
1) Linearly flow correct the chromatogram based on the relative retention volume ratio of the air peak between the sample and that of a consistent narrow standards cocktail mixture.
2) Correct the light scattering detector offset relative to the refractometer as described in the calibration section.
3) Subtract baselines from the light scattering and refractometer chromatograms and set integration windows making certain to integrate all of the low molecular weight retention volume range in the light scattering chromatogram that is observable from the refractometer chromatogram.
The ethylene based compositions of the present invention have a CDF for the molecular weights greater than 1,150,000 of greater than about 0.02, more preferably in the range of from greater than 0.03 to less than about 0.12, and still more preferably in the range of from greater than about 0.04 to less than about 0.09.
Compression Molding
Compression molded films were prepared by weighing out the necessary amount of polymer to fill a 9 inch long by 6 inch wide by 0.1-0.5 millimeter mold. This polymer and the mold were lined with Mylar film and placed between chrome coated metal sheets and then the ensemble was placed into a PHI laminating press model PW-L425 (City of Industry, California) preheated to 190° C. for ethylene-based elastomers and to 210° C. for propylene-based elastomers. The polymer was allowed to melt for 5 minutes under minimal pressure. Then a force of 10000 pounds was applied for 5 minutes. Next, the force was increased to 20000 pounds and 1 minute was allowed to elapse. Afterwards, the ensemble was placed between 25° C. water-cooled platens and cooled for 5 minutes. The polymer sheet was then removed from the mold and allowed to age at ambient conditions (about 25° C.) for at least 24 hours before testing for ethylene-based elastomers and for at least 48 hours before testing for propylene-based elastomers. 6 inch long by 1 inch wide strips were cut from the compression molded film using a punch press.
Specimen Preparation for Mechanical Testing
Specimen (6 inches long and 1 inch wide) cut from compression molded films. For extruded film, the specimens were cut with the length parallel to the cross direction (CD). CD is defined as the direction perpendicular to extrusion. Specimens were extracted from areas of the film that were as uniformly thick as possible. Typically, the edges of the extruded film were avoided.
To qualify a material as elastomeric and thus suitable for the first component, a 1-cycle hysteresis test to 80 percent strain was used. For this test, the specimens were then loaded into a Sintech type mechanical testing device fitted with pneumatically activated line-contact grips with an initial separation of 4 inches. Then the sample was stretched to 80 percent strain at 500 mm/min, and returned to 0 percent strain at the same speed. The strain at 10 g load upon retraction was taken as the set. Upon immediate and subsequent extension, the onset of positive tensile force was taken as the set strain. The hysteresis loss is defined as the energy difference between the extension and retraction cycle. The load down was the retractive force at 50 percent strain. In all cases, the samples were measured green or unaged.
Strain is defined as the percent change in sample length divided by the original sample length (22.25 mm) equal to the original grip separation. Stress is defined as the force divided by the initial cross sectional area.
DSC Method
Differential scanning calorimetry (DSC) is a common technique that can be used to examine the melting and crystallization of semi-crystalline polymers. General principles of DSC measurements and applications of DSC to studying semi-crystalline polymers are described in standard texts (for example, E. A. Turi, ed., Thermal Characterization of Polymeric Materials, Academic Press, 1981).
Differential Scanning Calorimetry (DSC) analysis is determined using a model Q1000 DSC from TA Instruments, Inc. Calibration of the DSC is done as follows. First, a baseline is obtained by running the DSC from −90° C. to 290° C. without any sample in the aluminum DSC pan. Then 7 milligrams of a fresh indium sample is analyzed by heating the sample to 180° C., cooling the sample to 140° C. at a cooling rate of 10° C./min followed by keeping the sample isothermally at 140° C. for 1 minute, followed by heating the sample from 140° C. to 180° C. at a heating rate of 10° C./min. The heat of fusion and the onset of melting of the indium sample are determined and checked to be within 0.5° C. from 156.6° C. for the onset of melting and within 0.5 J/g from 28.71 J/g for the heat of fusion. Then deionized water is analyzed by cooling a small drop of fresh sample in the DSC pan from 25° C. to −30° C. at a cooling rate of 101° C./min. The sample is kept isothermally at −30° C. for 2 minutes and heated to 60° C. at a heating rate of 10° C./min. The onset of melting is determined and checked to be within 0.5° C. from 0° C.
The polymer samples are pressed into a thin film at a temperature of 190° C. About 5 to 8 mg of sample is weighed out and placed in the DSC pan. The lid is crimped on the pan to ensure a closed atmosphere. The sample pan is placed in the DSC cell and heated at a high rate of about 100° C./min to a temperature of about 30° C. above the melt temperature. The sample is kept at this temperature for about 3 minutes. Then the sample is cooled at a rate of 10° C./min to −40° C., and kept isothermally at that temperature for 3 minutes. Consequently the sample is heated at a rate of 10° C./min until complete melting. This step is designated as the 2nd heating. The resulting enthalpy curves are analyzed for peak melt temperature, onset and peak crystallization temperatures, total heat of fusion (also known as heat of melting) (ΔH), the heat of fusion (melting) above 80° C. (ΔHPA(80° C.) or "PA"). The total heat of fusion was measured by integrating the area under the melting endotherm from the beginning of melting to the end of melting by using a linear baseline. The heat of fusion (melting) above 80° C. was defined as the partial area of the total heat of fusion above 80° C. This is typically measured by dropping a perpendicular at 80° C. using standard DSC software.
For ethylene based system, the heat of melting of the composition is less than about 60 J/g, and the partial area above 80° C. for the composition is less than about 25 percent of the total heat of melting, preferably greater than about 4 percent and less than about 20 percent, more preferably greater than about 7 percent and less than about 17 percent of the total heat of melting.
For propylene based systems, the heat of melting of the composition is less than about 57 J/g; and the partial area above, 80° C. for the composition is less than about 65% of the total heat of melting, preferably greater than about 20 percent and less than about 60 percent of the total heat of melting.
DSC Method for Extruded Films
For extruded film, the equipment, calibration procedures, sample preparation, and data analysis were nearly the same as used for compression molded film. The difference was that extruded film was used. Calculation of heat of melting and partial area is the same as previously described.
Inventive and comparative blends used for compression molding (Table II) were also formulated by weighing out the dry blend components. They were then introduced to a Haake mixer preheated to 190° C. and set at 40 rpm rotor speed. After torque reached steady state (typically three to five minutes), the sample was then removed and allowed to cool. The blends were then molded in the same way as the individual resins.
100 Percent Cycle Test
For the 100 percent cycle test, an Instron 5564 (Canton, Mass.) equipped with pneumatic grips and fitted with a 20 pound tension load cell was used. After proper calibration of the load cell, the specimen is oriented parallel to the displacement direction of the crosshead and then gripped with a separation of 3 inches. The sample was stretched to 100 percent strain at a rate of 10 inches per minute. The crosshead direction was immediately reversed at then returned to the starting grip separation of 3 inches. The crosshead direction was again reversed such that the sample was then extended at the same speed until a positive tensile force was measured. The strain corresponding to the onset of positive tensile force was taken as the immediate set. Extension and retraction stress were measured at 30 percent strain.
Strain measured as a percentage is defined as the crosshead displacement divided by the original grip separation of three inches and then multiplied by 100. Stress is defined as force divided by the original cross sectional area. To measure film thickness, the weight of the sample is divided by its density and surface area (6 in2 for the sample geometry used).
A description of all of the resins used in the Examples is presented in Table 1.
A critical aspect necessary for describing draw resonance (DR) is two fixed points that anchor the molten web. The die serves as one of the anchors. The nip roll/chill roll serves as the second anchor on the web. The flow from the die to the nip roll is drawn down in planar extension. The draw down ratio (DDR) is a dimensionless number that describes the extension imparted to the film from the die to the chill roll. The DDR is shown in Equation-1.
Vf=M/(h0·Wf·ρs)=Haul-off speed
Vo=M/(h0·W0·ρm)=Die Exit velocity
M=Mass output rate
hx=Film thickness at location x
Wx=Film width at location x
ρx=Polymer density at the temperature at location x
The draw down ratio at which draw resonance starts will be called the critical draw down ratio (DDRc,). This can be determined by increasing the haul off speed until the onset of edge weave draw resonance. Draw resonance is described by periodic film thickness and/or web width variations.
For the examples in the present invention the following extrusion coating line was used to determine the DDRc. A Black Clawson extrusion coating line equipped with 3.5 inch 30 L/D extruder driven by a 150 HP drive was used. The line has a 36 inch Cloeren die. The die is deckled to 24 inches. The air gap was set at 5.7-inches. Thus, the aspect ratio (A) (which is the ratio of air gap length to one half of the die width) was 0.475. The haul-off speed was capable of running as high as 2500 feet per minute. The die gap was set to 0.023 inches. For this study 40-lb Kraft paper was the substrate coated. The melt temperature was targeted for 420° F. (215° C.). The output rate was limited by amps on the screw drive motor to 60 rpm (200 lb/hr) when running with the 3.5-inch extruder.
Dry blends of the materials indicated in Tables II, III, IV were then prepared. These blends were then processed on the extrusion coater at 60 rpm screw speed (˜190-200 lb/hr). Film samples were isolated during extrusion coating inserting pieces of Mylar film on top of the Kraft paper prior to coating with polymer. They were collected at approximately 1.8 mil film thickness for testing of elastic properties, then the haul-off speed was increased until draw resonance (DR) was encountered. The line speed was then reduced to get out of DR, and increased up to just before DR was observed. The process conditions were recorded and the DDRc, calculated. The DDRc for each blend is reported in Table II, III, IV. Later, the polymer film was removed from the mylar film for testing.
A plot of DDRc, vs. percent second component was prepared for Examples 1-1 to 1-5 and. This plot appears as
Mechanical Properties
The extrusion coated film samples were then evaluated for elastic properties. Six inch long and one inch wide strips of the films were cut in the CD. For compression molded film samples, direction was not specific. The precise thickness for the films was calculated by dividing the weight of the film (as determined using a microbalance) by density and area. An Instron 5564 testing frame was then used to determine extension and retractive forces as well as set. Specimens were gripped with either pneumatic or roller grips. The spacing between grips taken as the gauge length was 3 inches. Crosshead speed was set at 10 inches per minute. Hysteresis behavior was measured in three steps:
1. The crosshead was displaced to provide a strain of 100 percent.
2. The crosshead was then returned to 0 percent strain.
3. The crosshead was then increased again until a positive tensile load was measured.
This test was performed for selected compression molded ("comp") and extrusion coated ("ext") samples (Table V). Extension and retraction forces were measured at 30 percent strain of extension and retraction during the first cycle. The onset of positive load in the third cycle was taken as the immediate set strain. Stress was calculated in the megapascals (MPa).
Extension and retraction stresses are plotted for 2/1, 2/2, 2/3 blends and corresponding controls in
DSC and CDF analysis was performed according to the previous descriptions. Table VI summarizes the results for the inventive examples (number designation in example column) and comparative examples (C designation in example column).
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