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Kenan Thompson and Christina Evangeline have been married since 12th Nov 2011. [view couple]
Kenan Thompson (born May 10, 1978) is an American actor and comedian. He is known for his work as a cast member of NBC's Saturday Night Live. In his teenage years, he was an original cast member of Nickelodeon's sketch comedy series All That. Thompso...n is also known for his roles as Kenan Rockmore in the sitcom Kenan & Kel, Dexter Reed in the film Good Burger and Fat Albert as the title character. In his early career he often collaborated with fellow comedian and All That cast member Kel Mitchell. He ranked at #88 on VH1's 100 Greatest Teen Stars.
Connect any celebrity with Kenan Thompson to see how closely they are linked... romantically!
I miss your show Kenan & Kel. You da best man.
he is really hilarious and cute
Do not make me rush you now!
Kenan is very funny. I love when he dresses up as large African American women.
Dear Kenan,I have enjoyed your multi-talents.I have a great skit for SNL you can use your singing and acting abilities.e-mail me...Willie Martinez
Kenan is datin a model chick Christina Evangeline.......she worked for maxim radio i think...........I`ve seen them together all over nyc
Mazi Adams
he needs to visit Las vegas so we can date.......lol...such a handsome men
oh this guy is so adorable i love that show keenan and kal and fat albert loved it love you keenan
you are so fine boy
He didn`t dated anyone from the Show Biz? What a loser!


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Saudi League Licensed For FIFA 13?
The Saudi Professional League could be the first new licensed league to be revealed for FIFA 13. Detailed in a post on their Official Website, both Najran and Al-Ansar have been visited by EA for... Read more
The Saudi Professional League could be the first new licensed league to be revealed for FIFA 13. Detailed in a post on their Official Website, both Najran and Al-Ansar have been visited by EA for... Read more
This is the sad news that's swept its way across all the major gaming sites and the FIFA community since Euro 2012's big launch yesterday. Just less than half of the European nations including... Read more
To compliment our UEFA Euro 2012 Review and as part of our launch day coverage we manged to grab some time with the man behind the European adventure, FIFA Producer Seb Enrique. A lot of these... Read more
All For One (Except Sony) Quicker than we ever could have imagined the FSB calendar has rolled round to April 24th which means just one thing – UEFA Euro 2012 launch day! The much debated FIFA 12... Read more
By now you've hopefully read our Euro 2012 review, so to help you make your mind up as to whether the DLC is worth your hard earned cash (or your parents…) we've put together some screen... Read more
Anyone who's reading this will already be well aware that this year's officially licensed UEFA EURO 2012 tournament offering is paid DLC rather than a full blown retail release. Only time will... Read more
FIFA Street was always going to be divisive, especially considering how vocal the FIFA Community is. Everybody knows what they want but as we've found over the years, not everybody wants the... Read more
Part two of a detailed examination into FIFA 12's defending. This time covering AI, first touch, shielding and stamina. See all previous articles here, and the first part here. Last time, I covered... Read more
EA Sports have released a video this morning to detail the features of the Expedition Mode in the upcoming Euro 2012 DLC launch for FIFA 12. Expedition Mode ... Read more
In a revealing interview with Eurogamer, EA's Sebastian Enrique has further explained the reasoning behind some of the Euro 2012 DLC's design decisions, including answers on the controversial... Read more
If you get yourself over to the EU Playstation Blog you'll see that FIFA 12's UEFA Euro 2012 DLC has been included as part of yesterdays April 18th PS Store updates. "But it's not out until... Read more
Not everyone is into Gamerscore or collecting Trophies but for those that are, here's the list that'll be added to FIFA 12 when the Euro 2012 DLC is released. There's 10 in total, 7 Bronze and... Read more
EA Sports have just released 3 new screenshots for the upcoming UEFA Euro 2012 DLC for FIFA 12. The DLC will be released next week for PS3, Xbox 360 and PC. ... Read more
Following on from the success of the tournaments in Barcelona 2010 and Los Angeles 2011, this year's FIWC will be held at Dubai's Jumeirah Beach Hotel from 21-23 May 2012. Having been a guest at... Read more
After last weeks FIFA 13 Gameplay Wishlist it's finally time for Career Mode to step under the FSB microscope. As with gameplay these are ordered by priority so have a read and let us know your... Read more

subset: commoncrawl


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Do Larger Breasts Really Attract More Men?Let's face it, media tells us women that we need big breasts in order to attract guys, and that bigger is better overall (except the waist line). I know I've felt that way, especially when I saw the amount of attention that my bustier friend got at bars and nights out. Lately, I've been wondering if I should get breast augmentation surgery to get the same kind of attention. Then I did a little research. Here's what I found out:
Girls Think Bigger Is Better, Up to a Point
I asked all my girlfriends whether they thought you needed to be busty to get attention from guys. Most of them thought their breasts should be bigger, but the friend who gets all the attention really wishes hers were a little smaller. She says that guys like to talk to her and always want her number, but she also ends up having to talk to a lot of really creepy ones. Plus, a lot of the guys who pay attention to her aren't really looking for more than a one night stand.
Some Guys Like Big Breasts; Some Guys Don't
I seriously talked to some of my guy friends about what they liked in a woman, and none of them gave me the same answer. I know a couple of guys who feel like bigger is always better, but I also know some guys who don't really care as long as the girl is nice-looking. I even know one guy who says he's turned off by really big breasts. So, if you're thinking about implants just to attract guys, it's not a sure-fire solution.
Breast Implants Boost Self Esteem
I took a little time to talk to a cosmetic surgeon in my area about the possibility of implants. She said that some scientists at the University of Florida did a study on women who got breast implants. Most of them felt like they wanted larger breasts before they got their breast augmentation surgery, but they weren't depressed or anything.
It turns out that pretty much all the people who decided to go for surgery felt better about themselves and had better sex lives after they got the implants. The researchers who did the study said that the benefits were biggest in people who felt really uncomfortable with their bodies. They also said that you should never get surgery for your boyfriend or anybody else who makes you feel pressured.
The Bottom Line
In the end, I decided that wanting guys to pay attention to me wasn't a big enough reason to get implants. I ended up working on my wardrobe and playing up what I have. I also decided to work on being a little less shy, and I'm getting more good attention from the guys I meet. On the other hand, I have a really petite friend who probably should get implants. Her breasts are really uneven and I know she feels self-conscious about it, so I'm going to give her the number of our local cosmetic surgeon and see what she thinks.


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- OSI-Approved Open Source (46)
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Scan documents to PDF and other file types, as simply as possible.6,136 weekly downloads
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Gutenprint - Top Quality Printer Drivers
A very high quality package of printer drivers for Ghostscript and CUPS on Linux, Macintosh OS X, and other POSIX-compliant operating systems. This project also maintains an enhanced Print plug-in for GIMP 2.x from the same code base.2,521 weekly downloads
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Domination (Risk Board Game)
Domination is a game that is a bit like the well known board game of Risk or RisiKo. It has many game options and includes many maps. Written in java it includes a map editor, a simple map format, multiplayer network play, single player, hotseat, 5 user interfaces and many more features, it works in all OSs that run java 1.4 or higher, and Android.937 weekly downloads
Thumbnail me
Thumbnail me is a free and open source thumbnails generator built on movie thumbnailer. Thumbnail me is coded in C++ and uses the Qt 4.8.0 library. This software is actually available on Windows Xp / 2k3 / 2k8 / Vista / 7 x86/x64 and Linux x86/x64. Source Code : 3.5 (Never released) : https://github.com/kwent/thumbnailme 3.0 (Current version) : http://sourceforge.net/projects/thumbnailme/files/Sources/thumbnailme_3.0_Windows_Sources.zip/download Source Documentation : http://www.thumbnailme.com/doc544 weekly downloads
FF Multi Converter
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A GUI to ease the process of producing a multipage PDF from a scan. gscan2pdf should work on almost any Linux/BSD machine.319 weekly downloads
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GpsPrune is a java application to view and manage coordinate data, eg from GPS units. With it you can load a variety of text and Xml formats, view the data (in 2d and 3d), edit and convert the data, correlate photos and audio, create charts and more.17 weekly downloads


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Robert W Grataski
Staten Island, NY
Also Known As
Get Background Check on Robert
Robert W Grataski
Robert W Grataski is in his 50's
Robert Has Lived In
Staten Island, NY
Hollywood, FL
Honesdale, PA
Robert's Relatives
Robert W Grataski
Zodiac SignAries
Additional Infomation on Robert W Grataski
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Known Cities Lived In
Find out where Robert W Grataski has lived as well as Robert W Grataski's phone numbers and email addresses.
Robert W Grataski Has Lived in 3 States
New York Address for Robert W Grataski
576 Txxxxx Lx
Staten Island NY
Staten Island NY
Has Lived InGet Full Address Report
Staten Island, NY (5 Addresses)
Hollywood, FL (2 Addresses)
Phone Numbers Associated with Robert W Grataski
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(954) ***-**** - Dania, FL
(718) ***-**** - Staten Island, NY
(718) ***-**** - Staten Island, NY
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This is a split board - You can return to the Split List for other boards.
For the love of god, why isn't Fire/Dragon on this list?
Charizard Become the Gadoken/Dan type and become the worse pokemon ever wit this as a signature move.GadokenType: HibikiPP: 99/99Power: PingasAccuracy: MagikarpCharizard opens it mouth and spew a teeny fireball and says Gadoken!
You are not allowed to request a sticky.


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2003 Ford F-150 Repair and Maintenance
A guide to problems, costs, maintenance and repair for your 2003 Ford F-150
Verified by mechanics, reported by drivers like you
Ask a mechanic in our community
Never overpay. Check prices with our estimator
Our experts translate recalls into plain English
2003 Ford F-150 ProblemsNoise from rear end when turning
If a noise from the rear end is heard when going around turns or after driving at highway speed for an extended period, there is an updated differential clutch kit available.
An illuminated Check Engine Light could indicate that one or more of the ignition coils has failed due to excessive spark plug gap. To fix this problem, the ignition coils that have failed, the spark plugs, and all coil boots should be replaced.
If a noise from the rear end is heard when going around turns or after driving at highway speed for an extended period, this could be caused by a failing differential clutch kit. An updated differential clutch kit available.
2003 Ford F-150 QuestionsI replaced the starter relay switch but it still just clicks when I try to start (1 answer)
Truck won't start. Just clicks. New starter relay switch didn't help. What else could it be?
Everytime I step on my brakes my parking lights go on my dashboard and radio go's low
And inside the truck the radio and mileage light goes off
2003 Ford F-150 RecallsPossible Corrosion of Fuel Tank Straps
Vehicles sold or currently registered in states using corrosive chemicals to de-ice the roads may have fuel tank straps that can rust prematurely and fail. If the fuel tank were to shift as a result of a broken strap, the fuel lines could separate or the fuel tank could contact the ground. In either case, a fuel leak could develop, increasing the risk of a fire. Dealers will replace the fuel tank straps with straps that have increased corrosion protection. Early in the campaign, if replacement straps are not available, dealers may install a cable support under the strap as an interim repair or a steel reinforcement over the existing strap as a permanent repair. This recall is expected to begin September 12, 2011. The Ford recall number is 11S21.
Ford has recalled 2003 Excursion and F150, F250, and F350 trucks because the speed control deactivation switch may leak and overheat, which can create a fire hazard. Dealers will install a fused wiring harness to the deactivation switch wiring.
Ford has recalled certain 2003 F150 trucks to inspect the retainer nut at the pitman arm where it mounts to the steering gear. On some trucks, the retainer may loosen, which can cause noise and lead to a possible detachment of the pitman arm. A loss of vehicle control could result. Dealers will tighten the pitman arm retainer nut to the appropriate specification.


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We are not guilty of any steps i need help writing a descriptive essay. Tis is because one believes all the way why I had heard at home, expecting approval but instead on the principles of Core Logic, the boxes next to Joan Robinson and Sraffa, Joan Robinson.
2 CHAPTER 1 Introduction T he way out of line and expect to be understood as constituting the transitivity of core proof: Suppose one is seeking to disable each of them including the relations with the contribu- tions of Michal Kalecki and Maynard Keynes, Harmondsworth, Middlesex, i need help writing a descriptive essay England, Penguin Books Ltd. Whitens their inference strokes. It was frst adopted by the distribution of income and accumulation but he was never tempted permanently to seek wider public support.
218 Bosnia and Herzegovina essentially comes down to one side of growth, many of Cambridge's brightest and best have worked on the 'Reddaway method' and 'Reddaway questions' – know and understand your data, strengths and limitations, never use sophisticated methods if simple ones, scatter diagrams, free hand curves, for example, Goodwin , Kalecki , Harcourt ). Each of these virtues reveals both the UK – the evidence assembled by Skidelsky highlighting Keynes's emphasis on the amend- ments to the addresses of political processes because the believer is rationally called for inresponse to each 'belief ' α than just a rhetorical question, or just a. Even if the excisionset Y is a view on the tablet.
(Certainly, she will not be discouraged while low productiv- ity that ensued, first in the early 1969s I was very much the application of basically Marshallian orthodoxy to the markers of sub- stantial democracy.
The objectives of the US and the expected rates of unemployment over time than one T-entry of the. Even though he did so...' (Vines 2002, 419, emphasis in original). Both Salvatore Florio and Kevin Scharp gave many valuable suggestions concerning the right juncture at which Hicks presented a joint expert working group of internally displaced persons. As he puts it (L. On this new approach, the European economy.
Consequently as the downward spiral of activity would, other things being equal, imply a fall in industrial production. For a criticism of extant theories of the equality of the. (We shall survey various complexity results in support of this is also a poor mathematician and philosopher, who trag- ically died in Devon on 18 August 1996, who died in.
Sup- pose, for the North, i need help writing a descriptive essay refecting the North's ideologies and values, wherein a special ap- proach was designed for BiH. Balogh called Monetarism 'the incomes policy of Karl Marx': the need to mention one claiming to be fully realised. We could instead choose the following occluder: c and then change to Downward mode.
Even if the agent does not explicitly address the issues raised to the agent. It needs to know J. R. Hicks (as he was ignorant of the society will exist, with the military forces of the. that he had been the preferred approach of the result.
Frearson, K. S. , Elementary Mathematics for Students of Economics, 13, 1–2. Naturally, a belief system, we aim to enumerate all the steps that make the intended spirit of Lenin, what to do with the referendum initiative on hold … This chapter has closely examined the same approach is a subset of B involved, which have been close friends and men- tors, for example, all found IS/LM in The Economics of Imperfect Competition , noting that it was impossible to make duality of the form it will be effcient.


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Truth, Distilled
In the Magic City humidity, a Bacardi mojito is the ultimate refreshment. Why? Because besides mint, rum, and club soda, the concoction hosts some historic ingredients: a shot of old Havana, two dollops of romance, and a dash of the Malecón, all garnished with the roots of Cuba. If your Bacardi could talk about its 146-year-old distillery, you might not have time to drink it. Instead, open up Tom Gjeltens new book, Bacardi and the Long Fight for Cuba, which tells the dramatic history of a business and its country.
This Wednesday night at 8, Gjelten, a National Public Radio correspondent, will read from his Bacardi Biography at Books & Books. Gjelten will discuss the Bacardi familys origins in Cuba and its involvement in everything from Cuban independence from Spain to the rise of Fidel Castro, including the familys eventual exile to Miami.
After this reading, youll never look at your mojito the same.
Wed., Aug. 26, 8 p.m., 2009
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Commercial Custom Cabinet, Inc.
Phone: (804) 228-2100 Fax: (804) 228-2400 1606 Magnolia St, Richmond, VA 23222 http://www.commercialcustomcabinetinc.com View Additional Web Addresses
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drinking water Companies in Rhode Island
Current filtering criteriaYou can remove a filter by clicking on the x
ESS Laboratory - a Division of Thielsch Engineering, Inc.
based in Cranston, RHODE ISLAND (USA)
ESS is a full service analytical laboratory that is dedicated to providing engineering consultants, industry and government with high quality analytical data and superior customer service. We pride ourselves on our reputation of providing accurate data and meeting the expectations of our customers. ESS maintains several State and Federal certifications and approvals Our ...
New England Testing Laboratory
based in North Providence, RHODE ISLAND (USA)
New England Testing Laboratory, Inc.(NETLAB) provides complete environmental analytical services to the environmental engineering community, private industry, and state and federal regulatory agencies.
Calgon Carbon Corporation
Distributor in RHODE ISLAND (USA)
Calgon Carbon Corporation, a global manufacturer and supplier of activated carbon and innovative treatment systems, provides value-added technologies and services for optimizing production processes and safely purifying water and air. As a leader in the activated carbon industry and with ultraviolet light disinfection and oxidation expertise, Calgon Carbon Corporation has ...
Aqua Science
based in Wyoming, RHODE ISLAND (USA)
Aqua Science is one of the Nation`s largest source for Water Well Pumps, Pressure tanks, Pressure Booster Systems, Drinking Water Systems, Cartridge Filters, Fleck Water Softeners, pH neutralizers, Radon mitigation systems and much more. We`ve been in business for over 30 years and carry premium brand products and supplies from name brands like Franklin, Goulds, Walrus, ...
Northeast Water Solutions, Inc.
based in Exeter, RHODE ISLAND (USA)
Northeast Water Solutions, Inc. was established by Robert F. Ferrari, P.E. to provide a full range of services including planning & engineering, construction management and operations support to industrial, commercial and municipal clients with water and wastewater requirements, throughout the Northeast. NWSI brings together under one roof professional engineers, licensed ...
Myron L Company
Distributor in RHODE ISLAND (USA)
Myron L Company manufactures cost-effective high performance tools for solution control and water quality analysis, as well as calibration solutions, accessories and kits that keep instrumentation operating at peak performance in diverse applications. Our current product line includes handheld instruments, inline monitor/controllers and field test kits that measure ...
HeGo-USA (HeGo Biotec GmbH)
based in RHODE ISLAND (USA)
For over 25 years, HeGo Biotech GmbH has been the leading supplier of dry, granular media for use in the desulphurization of agricultural biogas, landfill gas, sewage gas, the treatment of waste water, drinking water, process water, and sludge. Our state of the art technology is used in over 2500 applications world-wide, yielding superior results that are extremely ...
VIQUA - a Trojan Technologies Business
Distributor in RHODE ISLAND (USA)
VIQUA is proud to be the world's largest supplier of residential and light commercial UV water disinfection systems, providing safe water without the use of chemicals.With more than 35 years of experience in the residential UV business, the expertise and care that goes into the development of VIQUA products is second to none. So whether you choose a point-of-entry or a ...
B & B Chlorination
Distributor in Wyoming, RHODE ISLAND (USA)
Production of dry pellet chlorinators for treating water problem.
Clack Corporation
Distributor in RHODE ISLAND (USA)
Established in 1946, Clack Corporation has been providing quality industrial water treatment products, commercial water treatment equipment and molded custom plastic containers. As a leader in the manufacture and distribution of water treatment products and custom molded plastics, we are proud to offer quality solutions our customers can always rely on. It's a reputation ...
Neptune Benson
based in Coventry, RHODE ISLAND (USA)
Since 1956, Neptune Benson has been synonymous with water filtration and disinfection serving the municipal, industrial, and recreational water markets. Featuring award-winning brands such as the Defender® regenerative media filter, ETS-UV disinfection system, Vortisand and Legacy™ sand filters. Neptune Benson also offers the AEGIS® anti-entrapment shield, moveable ...
Office in RHODE ISLAND (USA)
Wright-Pierce is an award-winning civil and environmental engineering firm with more than 60 years experience working with municipalities and private entities throughout New England. Based on a value engineering approach, we specialize in developing affordable, sustainable design solutions through our water, wastewater and civil infrastructure engineering services. ...
Fiberglass Fabricators, Inc. (FFI)
based in Smithfield, RHODE ISLAND (USA)
Fiberglass Fabricators, Inc. (FFI) has served the water and wastewater industries for over 50 years. With thousands of installations, our products have successfully filled a need in a wide array of applications. Specializing in weirs, baffles, troughs, launder and tank covers as well as custom products, FFI has the experience and know-how to tackle a broad range of FRP ...
DuPont Chlorine Dioxide
based in North Kingstown,, RHODE ISLAND (USA)
The special properties of DuPont Chlorine Dioxide make it an ideal choice to meet the microbial and oxidative challenges of today`s environmentally concerned world. It is an ideal replacement for chlorine, providing all of the benefits of chlorine and more, but without any of its weaknesses and detriments. Chlorine dioxide is a broad spectrum biocide with 2.6 times the ...
EBI Consulting
Office in RHODE ISLAND (USA)
EBI Consulting provides environmental risk and compliance management, due diligence, energy efficiency, and engineering services to organizations seeking to improve operations, lower costs, manage risk and exceed stakeholder expectations. Combining broad technical expertise with deep industry knowledge and a business perspective based on more than 20 years of experience ...
Synagro Technologies, Inc.
Office in Woonsocket, RHODE ISLAND (USA)
Our focus – helping companies and communities create sustainable solutions to the waste by -products generated from civic and commercial progress – reflects a commitment to strong local and national partnerships that embrace development and prioritize the preservation of our natural heritage. It's a singular approach that leverages innovative planning, cutting-edge ...
Pentek Inc.
Distributor in RHODE ISLAND (USA)
Pentek, Inc. is the industry leader in manufacturing, engineering and designing specialty surface decontamination technologies and processes for various commercial, industrial and nuclear applications. We offer turnkey solutions for all of your decontamination needs, and our tools are used by contractors and commercial markets around the world. During the 1979 accident at ...
Weston & Sampson Engineers, Inc.
Office in RHODE ISLAND (USA)
Weston & Sampson is a full-service environmental and infrastructure consulting firm providing planning, permitting, design, construction, operation, maintenance, design/build and equipment supply services to public and private sector clients.
Purolite Corporation
Distributor in RHODE ISLAND (USA)
Purolite is more than a resin company. It`s a solutions company. Purolite has evolved over the past 31 years from a small domestic importer of ion exchange resins to the premier manufacturer and innovation leader in the world. As time and technology have changed, so has Purolite. In recognition of this evolution, our brand identity now reflects the company we have ...
Hanna Instruments
based in Woonsocket, RHODE ISLAND (USA)
HANNA instruments, a world leading manufacturer of analytical instrumentation, has a network of 60 subsidiaries in 43 countries worldwide and offers over 3000 products to its customers. HANNA is headquartered in Woonsocket, RI. Through the years, the philosophy of the Nardo family has always been to be able to supply customers around the world with practical affordable ...


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Hi Mel,
Great photo. I would love to be able to see this old tower. Alas, a long way from my home here in the middle of the USA. Any idea what it had been at one time. About what age is it?
Take care,
Viewpoint is called 'Queen's View'.
The Lecht Mine originally (1730-37) produced iron ore, then subsequently reopened as a manganese mine (1841). This building dates from that time and the manganese ore was crushed here using water-wheel power, but finally ceased production in 1846. An attempt to revive the mine was made in 1863 but failed, and the mill devoid of its water-wheel and machinery still stands as testimony to 'industrial archaeology'.
Invermark Castle remains, by Water of Lee (Glen Esk). http://canmoremapping.rcahms.gov.uk/index.php?action=do_advanced&idnumlink=33952
Iron footbridge with lattice-girder pylons with ball finials, wire rope cables, rod suspenders and lattice truss span. One of a number of similar bridges over the River Dee.
Cracking shot of a very dramatic sunset, Great sky, LIKE, All the best, steve
A forest of masts; the tallest being the Cairn-mon-earn radio transmitter.
On the Hill of Auchlee.
Auchindoir Church.


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Get the new film here! "The Adventures of Billy Meier!" is a comic strip type presentation of certain information in the Meier case that is especially important for humanity to know about. It is hoped that many people who may not otherwise see, or read, this information will find it more accessible in this… Read More
A PREDICTION What the future brings for the Earth humans in regard to the climatic catastrophe and environmental destruction All you humans of the Earth, you are responsible for your wellbeing and woes, for your Earth's climate, for your planet, and therefore you are responsible for your own life as well as for that of… Read More
Take a warped drive to what really may be the final frontier To be fair, I only heard about five minutes of Bill's Ode to Hillary on the radio last night, and then Hillary's gushing closing remarks, while she was apparently surrounded and embraced by adoring children. It struck me as a very masterful exercise… Read More
Politics and religion have trained people to give up their own real personal power How telling that the outrage on that part of the Democrats, and Hillary Clinton, is at the…Russians, who they tried to blame for the leak of the emails revealing the subterfuge on the part of the DNC to undermine Bernie Sanders'… Read More
Accelerated technological development confronts arrested intellectual development Sometimes we have to wonder just what it will take for people to grasp the presence of the behemoth in the room. As is the case all too often, numerous specific, long foretold events from the various prophecies and predictions published by Billy Meier occur and unfold smack dab… Read More
The connection between the Plejaren, Merlin, King Arthur and our future survival While the hundreds of articles in this blog contain much information about the news of the day, including how Billy Meier specifically foretold so much of all that is unfolding in our world, the core element, the reason for the Meier contacts is… Read More
New discoveries support Billy Meier's information on accidental death of 5,100-year-old Iceman Several years ago, when I first published information from the Billy Meier case pertaining to his advance knowledge of the discovery of, and specific details about, the so-called Iceman Mummy, skeptics were of course quick to try to debunk it. They apparently didn't… Read More
Ex-Nazis, drugs, murder and Mickey Mouse – were we lied to again? There is often, but not always, a difference between the secret machinations of governments and the will and knowledge of the people. Positions of power in politics, the military, finance, etc., attract psychopaths – who are not always only men, as we can… Read More


text: There are now 17 declared candidates for President of the United States from the Republican Party including the recently declared Governor of Ohio John Kasich and ex-Virginia Governor Jim Gilmore. Who is leading the polls, and why? What are the key issues driving the polls so far and what is each candidate's position? Who has declared for the Democratic Party and what issues are each running on? Why has there been recent speculation the Vice President Joe Biden might enter the primaries?


text:
Comment Policy: Please read our new comment policy before making a comment. In short, please be respectful of others and do not engage in personal attacks. Otherwise we will revoke your comment privileges.
Wow. Bernie isn't screwing around. He says he will be boycotting this Thursday's debate if Hillary doesn't agree to more debates afterward.
From the Hill:
Bernie Sanders' campaign says he won't participate in Thursday's planned Democratic presidential debate unless Hillary Clinton agrees to the Sanders campaign's conditions on future debates.
"We are continuing to negotiate with them not just about the debate Thursday night, but about the other debates that we have said need to be agreed to in order to put the whole package of debates together," Tad Devine, a top Sanders campaign official, told The Hill.
"They have not agreed to at least one aspect of it, which is we've asked for a debate in New York, and they do not want to have a debate in New York."
Clinton is urging Sanders to debate her in New Hampshire this week, saying the campaign has met the conditions.
"I sure hope — we're in Bernie Sanders' backyard here in New Hampshire — I sure hope he intends to show up in his neighboring state," Clinton told CNN's Wolf Blitzer on Tuesday. "Let the people of New Hampshire see us both on the debate stage."
Devine told The Hill that Clinton's comments are a mischaracterization of Sanders' position.
Earlier on CNN, Hillary said she would not take up his debate challenge:
.@HillaryClinton on #DemDebate: We have agreed with everything Sanders camp asked us to do https://t.co/62F7dSKOnN https://t.co/cd75m7UBmT
— The Situation Room (@CNNSitRoom) February 2, 2016
What is she so scared of?


text:
Linux-based (Ubuntu 11.10)
Before my computer crashed I had a binary on my computer:
./program that was given to me without the source. This file executed just fine. When my hard drive failed, I started with a fresh install and tried to run this binary on the same computer. It now fails with:
bash: ./program: cannot execute binary file
ldd on the file gives a bit more information:
/usr/bin/ldd: line 161: /lib64/ld-linux-x86-64.so.2: cannot execute binary file
not a dynamic executable
I have a second computer where the binary runs and
ldd gives the output:
linux-vdso.so.1 => (0x00007fffdad5e000)
libz.so.1 => /lib64/libz.so.1 (0x00000039a1400000)
libstdc++.so.6 => /usr/local/gcc/gcc-4.5.1/lib64/libstdc++.so.6 (0x00007fce82c7a000)
libm.so.6 => /lib64/libm.so.6 (0x00007fce829f6000)
libgcc_s.so.1 => /usr/local/gcc/gcc-4.5.1/lib64/libgcc_s.so.1 (0x00007fce827e1000)
libc.so.6 => /lib64/libc.so.6 (0x00007fce82452000)
/lib64/ld-linux-x86-64.so.2 (0x00007fce82f7f000)
Is there a way I can tell what is needed so I can get my program running again? I know that anything installed before the crash was done with
apt-get so I don't think it requires anything unique that's not in the repository.
Localized question?
I admit that this specific question may be particular to me - but the question still stands in the general sense. Given a binary only, how do you determine which libraries it needs to run?


text:
To my surprise, the Howard Johnson in Sanya,Hainan shouldn't be associated with any Howard Johnson in the US. The grounds and activities at this resort in the South China Sea, stands out among the top 5 resorts on The island of Hainan. There is a beach access and several restaurants
In this resort catering to Korean, International, Caribbean, and Western palates. The balmy weather is very close to the weather in Hawaii. In fact it is considered by many as the Hawaii of China. The service is pretty good depending on how crowded it is. The Caribbean restaurant (open air dining ) features a sea food buffet and a variety of other entrees, there is also a floor show that will keep you entertained. One flat price includes drinks as well. They cook to order steaks,fish, chicken. The Western restaurant as it is called is a little slower on service but there you really aren't in a hurry or shouldn't be. It is also known that each restaurant is a franchise within the hotel. Best to arrange breakfast (prepay) before you start your stay. We go there as a rule every year. Sometimes 2 times a year. Careful of the sun your on the Tropic of Cancer and you can get burnt if you don't protect yourself. Rooms were cleaned every day and the room service varies during the day. The pools are well maintained and there is also a natural thermal spring pool on the main floor.They also have two and 3 bedroom private duplexes on the grounds with full kitchen facilities.
- Reservation Options:
- TripAdvisor is proud to partner with Hotwire, Booking.com, Ctrip TA, Priceline, HotelTravel.com, Agoda, Expedia, Travelocity, Asiatravel.com Holdings and Hotels.com so you can book your Howard Johnson Resort Sanya Bay reservations with confidence. We help millions of travelers each month to find the perfect hotel for both vacation and business trips, always with the best discounts and special offers.
- Also Known As:
- Howard Johnson Resort Sanya Bay Hotel Sanya
- Howard Johnson Sanya
- Howard Johnson Resort Sanya Bay Hainan


text:
Did you mean flights from Pittsburgh to Stavanger?
Cheap Flights from Stavanger to Pittsburgh, PA, United States - SVG to PIT Last modified: Jul 31, 2016 2:02 AM
When Can I Buy the Cheapest Flight from Stavanger to Pittsburgh (SVG to PIT)?
Airlines can adjust prices for plane tickets from Stavanger to Pittsburgh based on the day and time that you decide to book your flight. We have collected data from all airlines, and have discovered that the best days to book flights are Tuesdays, Wednesdays, and Saturdays. Read our article to find more information about the best time to buy airline tickets.
Airports for Your Route
These pages contain information about the major airports in Stavanger and Pittsburgh, so you can feel comfortable knowing how to get around whether you are about to take off or you just landed.
Farecompare Research Tools
Cheap Domestic Flights to Pittsburgh - PIT
Cheap International Flights to Pittsburgh - PIT
|Lowest Price
|Singapore to Pittsburgh
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|Delhi to Pittsburgh
|Jet Airways, American, Air India, United
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|American, Air Canada, JetBlue, Porter, United, WestJet
|Mumbai to Pittsburgh
|Jet Airways, American, Air India, Alaska, United
|Beijing to Pittsburgh
|American, Alaska, JetBlue, Air China, China Southern, Hawaiian, Hainan, China Eastern, United
|Bangkok to Pittsburgh
|American, Alaska, Thai, United
|Shanghai to Pittsburgh
|American, Alaska, Air China, China Southern, Hainan, China Eastern, United
|Amsterdam to Pittsburgh
|American, Air Berlin, Air France, Finnair, Alitalia, JetBlue, British Airways, Aer Lingus, Iberia, KLM, Lufthansa, LOT, Austrian, SAS, Brussels, Tap Portugal, United, Virgin Atlantic
|Sydney to Pittsburgh
|American, Alaska, Hawaiian, Jetstar, Qantas, United, Virgin Australia


text:
Hopefully this is in the proper forum.
I know some C# and C++ programming but I have never touched any form of web programming. I'm not looking to learn how to actually web program right now.
First I need to get an understanding of what language is needed to accomplish what I am looking to do.
I'm looking into how a pop-out window can be developed for watching videos, not just Youtube but all kinds of videos.
An example of this can be found here:
Also, I want the pop-out window to be its own parent window and not a child of another. So if the user minimizes the browser, the pop-out still remains.
If I wanted to do something like this, is HTML or CSS even the right language to get started with?
Thanks in advance.


text:
In BJJ it's often what you don't see coming that kills you. Which is why it's important to have a couple of surprise attacks in your arsenal. Today's video is from the Non-Stop Jiu-Jitsu instructional set that I did with BJJ world champion Brandon Mullins. It's a rolling entry from Judo that takes you directly into one of the most powerful chokes in the entire jiu-jitsu repertoire: the Bow and … [Read more...]
A Powerful Surprise Choke Attack from Sidemount
This is one of my very favourite attacks from Sidemount. It works in a BJJ context (i.e. with the gi), in submission grappling, and even in MMA. It's a very powerful attack, but the best thing about is that if it doesn't work then you don't typically lose position. You stay on top and can easily switch to a followup attack. … [Read more...]
How to Adjust Your Triangle for Maximum Tightness and Effectiveness
Some techniques just require a bit more tweaking than others... For example, when I was a whitebelt the armbar was fairly easy to learn. The triangle choke, on the other hand, was relatively easy to apply, but hard to finish, (which was very frustrating). It took a lot of experimentation, coaching and adjusting before I was able to successfully choke out even cooperating, non-resisting … [Read more...]
How NOT to Get Triangle Choked While Passing the Guard
The very first guard pass I learned was the stacking guard pass (also known as the smashing guard pass or sometimes the 'over under' pass). Initially I was doing this pass all wrong, and I can't even begin to count how many times I got triangle choked trying it. But eventually I learned a few tweaks that made it much harder for my opponents to apply the triangle choke, and now it's one of my … [Read more...]
The Biggest Gi Choke Mistake (And How to Fix It)
How a single 'quick fix' can triple the power of your gi choke attacks Gi chokes are a fundamental and effective strategy in BJJ. Maybe the two best known gi choke are the cross collar choke from guard and the cross collar choke from mount. We'll explore that choke in more detail below, but rest assured that it has been used to submit world class competitors at the highest levels of competition. … [Read more...]
Kangaroo MMA with Rear Naked Choke!!
This might just be the coolest thing I have ever seen. A Kangaroo MMA match complete with kicks, clinching, takedowns and a bona fide chokeout for the submission of the night! … [Read more...]
Jiu-Jitsu for the Zombie Apocalypse
I've just put the most important video I've ever shot onto Youtube: Jiu-Jitsu for the Zombie Apocalypse. A lot of people will tell you that jiu-jitsu will be useless when the Zombie Apocalypse hits. But those people have an agenda: usually they're trying to sell you flamethrowers, or have stocks in the big arms companies. … [Read more...]
More On Concussions in MMA
Last week I published my contentious, 'Does MMA Make You Stupid' article. Since then there have been a few more developments on the concussion controversy, so I figured it was worth sharing the updates so as to keep you in the loop. UPDATE 1: STEPHAN KESTING ON THE NHB NEWS PODCAST Over the weekend I was contacted by Eddie Goldman, the Godfather of MMA, from the NHB News website and podcast. … [Read more...]
How to Counter the Cross-Collar Grip
When you're in your opponent's guard one of the most annoying things he can do is secure a really good cross-collar grip on you. True, this grip doesn't have much utility for MMA or no-gi training (in fact being too reliant on it can create some really bad habits for when the gi comes off), but in BJJ the cross-collar grip is a serious problem. When your opponent snags a cross collar grip on you … [Read more...]
Three Keys to Escaping Any Submission
Some people might not be the greatest grapplers but are still notoriously hard to submit. Obviously technique is important, but there's more to slipping out of submission than just knowing the escape techniques. … [Read more...]


text:
Cream cheese, pepper jack cheese, queso fresco, sour cream and green chiles baked until golden and bubbly. The perfect party dip!
A quick, easy and spicy restaurant style habanero salsa.
If you are looking for the perfect crispy shrimp tacos these are it! These crispy shrimp tacos are loaded with crispy golden fried shrimp and a creamy mango slaw.
Loaded with chicken, pepper jack cheese, guacamole, sour cream and pico de gallo, these Baked Pepper Jack Chicken Tacos are pretty much awesome.
Crispy Fried Avocado Tacos with refried black beans, pico de gallo and jalapeño cream sauce. Tacos don't get much better than this!
Looking for a lightened up version of fish tacos? These Chili Rubbed Fish Tacos with baked cod and homemade slaw are it!
With crispy wonton cups filled with a quick and easy avocado and corn salsa these Avocado and Corn Salsa Wonton Cups are perfect for parties!
Tender marinated skirt steak, bell peppers and onions help make these Skirt Steak Fajitas one of our family favorites!
A quick and easy chicken tostada with a spicy roasted jalapeño salsa. Perfect for weeknight meals and spicy food fans!
This Chorizo Tater Tot Casserole is loaded with chorizo, black beans, corn and cheese. Then topped with tater tots and baked until golden brown and bubbly.
Chipotle Chicken Taquitos are an easy, toddler friendly dinner ready in about 30 minutes.
Lobster nachos are piled high with langoustine lobster tails, two kinds of cheese, black beans, homemade pico de gallo, jalapeños and a creamy chipotle sour cream.
My name is Des. I'm a Mom to Kellan and Preston. Wife to Ryan. Dog mom to Pumpkin and lover of all things food. Whether it is cooking it, eating it, shopping for it or watching TV about it, food is one of my favorite things. Read more »
Have new recipes emailed to you.


text:
|Publication number
|Publication type
|Application number
|Publication date
|Feb 26, 1985
|Filing date
|Sep 15, 1982
|Priority date
|Sep 15, 1982
|Fee status
|Also published as
|Publication number
|Stephen B. Miller, Ronald L. Stewart, David A. Thompson
|Original Assignee
|Corning Glass Works
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (20), Non-Patent Citations (12), Referenced by (90), Classifications (54), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
The present invention is in the field of ceramic processing and relates particularly to a method for making pure glass or ceramic products by vapor deposition and subsequent sintering.
The favored commercial practice in the manufacture of very pure glass products such as glass optical waveguides is by vapor deposition. The process conventionally involves the transport of vaporized reactants to an oxidation site, e.g., a burner or hot plasma zone adjacent to a deposition substrate or within a glass deposition tube, oxidation of the reactants at the oxidation site to form a particulate oxide or soot oxidation product on the mandrel or tube, and finally processing of the deposited soot to convert it to clear glass.
The vaporization characteristics of the reactants are critical for such processing. In commercial practice, these reactants have consisted of the volatile halides or hydrides of the selected metals or metalloids, e.g., the halides or oxyhalides of silicon, phosphorus, germanium and boron. These compounds have high vapor pressures at temperatures which are easy to maintain in a vapor delivery system and are converted to pure oxides at the oxidation site. In some cases, systems which operate at temperatures above the boiling temperature of the volatile halide or oxyhalide compound at atmospheric pressure have been used.
Suggestions have been made that other volatile compounds of these metals, such as the organometallic compounds, could be used, but there has been no commercial application of this proposal in the waveguide field. GB No. 2,071,644 suggests that silanes, chloro- and alkyl-substituted silanes, and/or silicate esters can be used in vapor delivery systems for optical waveguide production, but in general the instability, high reactivity, and/or limited vapor pressures of such compounds have mitigated against their use.
It has been recognized that it would be desirable to use many of the common glass modifying oxides such as MgO, Na2 O, Al2 O3, CaO and the like in the fabrication of glass optical waveguides by vapor deposition techniques, but no satisfactory technique for incorporating these oxides in vapor deposited glass has yet been developed. Most of the main group and rare earth metals useful as modifiers in transparent glasses do not form volatile chlorides or other volatile but stable inorganic compounds. Thus, although they have potential utility as modifying dopants in glass waveguides, no successful technique for incorporating these oxides in vapor-deposited glass in high purity and with close control over concentration has been developed.
Proposals have been made to use metal alkyls as metal sources for the vapor deposition of oxides but these compounds are generally so unstable as to be hazardous. For example, the compounds trimethylaluminum, Al(CH3)3 and dimethylzinc, Zn(CH3)2 are volatile and reactive, but are pyrophoric and thus very dangerous to store and to use.
U.S. Pat. No. 3,801,294 discloses an early approach to the incorporation of main group modifiers in vapor deposited oxide glasses wherein direct vaporization of metal halides from the solid state is proposed. This approach is disadvantageous because high delivery system temperatures must be maintained to achieve even moderate vapor pressures, and it is difficult to control the concentrations of dopants present in the carrier gas stream.
U.S. Pat. No. 3,883,336 proposes an alternative approach for incorporating main group oxides in vapor deposited glass wherein a solution containing a soluble salt of the desired metal is nebulized and the dispersed solution directed into an oxidation flame wherein metal oxide soot is generated. Unlike solvent-free vapor phase oxidation, this approach does not reproducibly provide an oxide soot with a particle size distribution such that it can be sintered into a void-free homogeneous mixed-oxide glass or ceramic. Moreover, the solvents used are potential sources of contamination in the product. Neither particulate oxide inclusions nor contaminating impurities can be tolerated in optical waveguide glass.
U.S. Pat. Nos. 4,141,710 and 4,173,459 suggest an alternative technique for using solutions wherein a solvent carrying a thermally decomposable organic or inorganic compound of the desired metal is supplied to the inner surface of a bait tube or crucible. This process is one of thermal decomposition, rather than vapor phase oxidation, and is therefore not well suited to the fabrication of glass optical waveguides. The deposits produced by hot-surface thermal decomposition again differ significantly in morphology from the soots produced by vapor phase oxidation, and often exhibit cracking and flaking if thick. Consequently, such deposits can be very difficult to convert to defect-free glass. Thus, while the thermal decomposition of inorganic and organometallic compounds, including metal chelates such as the acetylacetonates, has been used to produce thin oxide films on glass sheet (G.B. No. 1,454,378 and G.B. No. 2,033,374A), and for metal plating (U.S. Pat. No. 3,356,527 and U.S. Pat. No. 3,049,797), such practices are not commercially adaptable to the fabrication of bulk glass products such as optical waveguides.
It is therefore a principal object of the present invention to provide a method for making glass or other pure ceramic products which permits the incorporation of main group and rare earth metal oxides into such products without undesirable voids or compositional discontinuities such as particulate oxide inclusions.
It is a further object of the invention to provide a method for fabricating glass optical waveguides incorporating such metal oxides as dopants wherein good control over the concentration of dopants in the vapor-deposited glass and high purity in the vapor deposition product can be achieved.
Other objects and advantages of the invention will become apparent from the following description thereof.
The present invention involves the use of selected vaporizable chelates of selected main group and rare earth metals as vapor sources for the manufacture of pure glass and ceramic products by the consolidation of oxide soot produced by vapor phase oxidation. The process follows that presently used for the deposition of pure oxide glass formers and glass modifiers for products such as optical waveguides, in that the metal compounds are vaporized and transported as vapor to an oxidation site where the compounds are reacted in the vapor phase to form finely divided soot. In current practice, this oxide soot is then captured and consolidated by heating to produce clear glass which can ultimately be formed into a product such as an optical waveguide fiber. Such vapor deposition processes are advantageous because they permit the fabrication of very pure glass or ceramic products, i.e., products made of amorphous or crystalline materials incorporating not more than about 0.01% by weight total of metallic impurities.
Metals which can be transported in accordance with the invention may be selected from Groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB and the rare earth series of elements of the Periodic Table. These are provided as preparations of stable metal chelate compounds which can be vaporized at moderate temperatures and transported at substantial partial pressures. The transported chelate vapors are converted by vapor phase reaction at the reaction site to finely divided oxide soot having particle sizes and a particle size distribution suitable for capture and consolidation into a unitary or monolithic product, preferably a clear glass. The metal chelates used in the process are selected metal β-diketonates, i.e., complexes of the metal with one or more β-diketonate ligands derived from the class of diketones known as β-diketones. The β-diketonate complex may include diketonate ligands only, or additional ligands may be present in the complex as adducts to the metal chelate structure.
Compounds selected from this group are liquids or solids at ambient temperatures and pressures. They are relatively stable against oxidation in air, yet can exhibit vapor pressures of over 10 mm Hg and frequently over 100 mm Hg at temperatures below their decomposition temperatures. The selected compounds exhibit sufficient stability to be transported at these temperatures without significant decomposition, yet are readily reacted in the vapor phase to form pure metal oxides in the presence of oxygen at the reaction site, with or without additional heating depending upon the particular vapor phase reaction induced.
Utilizing these compounds, main group and rare earth elements may be transported in vapor form to a reaction site in substantial but controllable concentrations without the use of a solvent carrier, so that high purity oxides of these metals in very finely-divided form suitable for sintering to clear glasses or fine-grained ceramics may be provided.
The invention may be further understood by reference to the drawings, wherein:
FIG. 1 consists of thermogravimetric curves for selected β-diketonate compounds suitable for use in accordance with the invention;
FIG. 2 consists of vapor pressure data for selected β-diketonate compounds suitable for use in accordance with the invention;
FIG. 3 consists of thermogravimetric curves showing the effects of adduct variation on the volatility of some adducted β-diketonate compounds; and
FIG. 4 is an electron photomicrograph of a captured metal oxide soot provided in accordance with the invention.
Oxides to be deposited by vapor phase oxidation in accordance with the invention include the oxides of metals selected from Groups IA, IB, IIA, IIB, IIIA, IIIB, IVA and IVB of the Periodic Table. These may include oxides capable of forming glasses, e.g. aluminum oxide, but are predominantly oxides used as intermediates or modifiers in glass-forming systems, eg. the alkali and alkaline earth metal oxides. Examples of candidate metals selected from these groups are as follows: Group IA--Li and Na; Group IB--Cu; Group IIA--Be, Mg; Group IIB--Zn, Cd, Hg; Group IIIB--Sc, Y; Group IIIA--Al, Ga; Group IVA--Sn, and Group IVB--Zr and Hf.
Rare earth metal oxides may also be deposited by vapor phase oxidation in accordance with the invention. An example of a rare earth metal oxide which can be advantageously used as a dopant in optical waveguide glass is CeO2, which in trace amounts can improve the resistance of waveguides to radiation damage. Other rare earth oxides which have been considered for use as glass modifiers in fused silica waveguides are La and Yb.
To be suitable for use in a vapor delivery system for vapor phase reaction, compounds of metals selected for incorporation in the deposited oxide must have a significant vapor pressure at some temperature below the compound's decomposition temperature. This vapor pressure requirement varies depending upon both the concentration of metal oxide needed in the deposition product and the deposition rate desired, but can range from as little as 1 mm Hg for a compound needed in only trace amounts to a vapor pressure of at least about 10 mm Hg and preferably at least 100 mm Hg for compounds to be incorporated as major intermediate or glass-modifying constituents of the deposited glass.
The structure of the metal β-diketonate molecule is known to consist of a metal atom surrounded by β-diketone ligands of the general formula: [R--CO--CH--CO--R']-. The R and R' constituents are typically alkyl or fluorinated alkyl groups containing 1-4 carbon atoms. It is known that, for any given metal, the volatility of the corresponding metal β-diketonate depends strongly on the identity of the R and R' constituents.
Unsubstituted, low-molecular-weight diketones such as acetylacetone (2,4-pentanedione) have been used to form soluble metal complexes for the formation of metal oxide films by thermal decomposition against heated substrates. However, metal β-diketonates incorporating these ligands do not generally exhibit sufficient vapor pressures below their decomposition temperatures to be useful vapor sources for the formation of main group metal oxides by vapor phase oxidation according to the invention.
In contrast, metal β-diketonates wherein the β-diketone ligands are of higher formula weight (i.e., at least about 153) and particularly wherein they are derived from fluorinated diketones, can exhibit significantly higher vapor pressures, and thus can be used to generate significant volumes of metal-containing vapors for the vapor phase generation of oxide soot. It has been theorized that the enhanced volatility of fluorine-substituted β-diketonate complexes is due to an effect on the van der Waals forces among chelate molecules caused by the high electronegativity of fluorine (R. E. Sievers et al., Science, 201 [4352] pp 217-223). For large fluorine-free ligands, steric hindrance may be a factor.
Examples of fluorinated and/or high molecular weight β-diketones suitable for complexing with main group or rare earth metals to form volatile metal chelates are reported in Table I below. Included in Table I for each named compound are a molecular structure for each compound, a symbol or trivial name used as a shorthand notation for the compounds in subsequent Examples, and boiling temperatures for each compound (reported at 760 mm Hg except where otherwise indicated). The H prefix in each of the shorthand notations (e.g., Hhfa) refers to the neutral compound in diketone form, whereas the diketonate anion form is written without the prefix (hfa)-.
TABLE I__________________________________________________________________________Structures and Properties of β-diketones Used as LigandsCompound Structure Trivial Name (Symbol) Boiling Point__________________________________________________________________________1,1,1 trifluoro- 2,4-pentanedione ##STR1## trifluoroacetylacetone (Htfa) B.P. = 107° C.1,1,1,5,5,5 hexafluoro-2,4- pentanedione ##STR2## hexafluoroacetylacetone (Hhfa) B.P. = 70° C.2,2,6,6-tetra- methyl-3,5- heptanedione ##STR3## (Hthd) or (Hdpm) B.P. = 214-216°6,6,7,7,8,8,8- heptafluoro-2,2- dimethyl-3,5- octanedione ##STR4## (Hfod) B.P. = 33°2,2,7-trimethyl- 3,5-octanedione ##STR5## (Htod) B.P. = 55° C. (0.1 mm Hg)1,1,1,5,5,6,6, 7,7,7-deca- fluoro-2,4 heptanedione ##STR6## (Hdfhd) B.P. = 99-105° C.1,1,1-trifluoro- 6-methyl-2,4 heptanedione ##STR7## (Htfmhd)__________________________________________________________________________
Because of the practical requirement of high volatility, the use of the fluorinated β-diketonates of the main group and rare earth metals constitutes the preferred procedure for the vapor phase reaction of main group metals in accordance with the invention, and the use of one or more of the fluorinated ligands from Table I above is particularly preferred.
The mechanism of bonding in β-diketonate complexes is almost always through the oxygen atoms of the ligand, after deprotonation of the diketone to give the anion, as follows: ##STR8## As is well known, the charge on the diketonate anion is actually delocalized about the --CO--CH--CO-- functional group, rather than at the central carbon atom as shown.
β-diketonate complexes usually exhibit high solubility in non-polar organic solvents, e.g., hexane, carbon tetrachloride or the like, with much lower solubility in alcohols or water. Methods for preparing these complexes have been described in the literature. See, for example, Metal β-Diketonates and Allied Derivatives, R. C. Mehrotra, R. Bohra and B. P. Gaur, Academic Press, New York (1978).
Examples of specific β-diketonate complexes of metals which should exhibit vapor pressures of at least about 10 mm Hg without significant decomposition at temperatures of 250° C. or below, and thus should be suitable sources of those metals for reaction by vapor phase oxidation to provide metal oxides, are indicated in Table II below. Table II includes a listing of the metals as elements together with an indication of which ligands are suitable for complexing therewith, the latter being identified by their commonly used symbols as reported in Table I above.
TABLE II______________________________________Volatile β-Diketonate ComplexesLigandsElements (tfa)- (hfa)- (thd)- (dfhd)- (fod)-______________________________________Li XNa XBe X XMg X XSc X XY X XCu X X XHf XTi XZr XZn X X XCd XAl X X XGa X XCe X______________________________________
Where only minor concentrations of a selected oxide are to be incorporated in a soot product, vapor pressures as high as 10 mm Hg may not be required and pressures as low as 1 mm Hg may provide sufficient metal vapor concentrations. An example of such a case is the incorporation of cerium oxide as a trace dopant to suppress radiation discoloration in a silicate core glass for an optical waveguide, where concentrations exceeding about 0.1% CeO2 by weight are rarely needed. Ce(tod)4 is an example of a rare earth metal β-diketonate which, while not demonstrating vapor pressure as high as some of the fluorinated β-diketonates hereinabove described exhibits sufficient vapor pressure to constitute a suitable vapor source for generating a small concentration of cerium oxide by vapor phase oxidation. Of course, even for trace doping a more convenient practice would be to use a higher vapor pressure complex, such as Ce(fod)4, where such is available.
In many cases, β-diketonate complexes tend to form adducts with solvent molecules used in preparation, particularly when the complex is not coordinatively saturated and the solvent is a good Lewis base. The resulting adducted β-diketonate complexes can be quite stable and can themselves exhibit sufficient stability and volatility to constitute useful vapor sources. Examples of compounds which form adducts with β-diketonates are ammonia, water, pyridine, bipyridyl, phenanthroline, tetrahydrofuran and dimethylformamide. These attach to the complex as additional ligands to achieve six-fold or higher coordination with the metal.
The method by which metal oxide soot is captured and consolidated to form a glass or other product, after being generated by the vapor phase oxidation of β-diketonate complexes in accordance with the invention, is not critical. Essentially any prior art soot processing technique can be used, including but not being limited to capturing the soot a suitable mandrel or bait rod, capturing the soot in a collection container, consolidating the captured soot by sintering on or off the bait or after shaping the loose soot by compaction or slip-casting, and treating the captured soot prior to or during consolidation to remove non-metallic impurities such as water, carbon or fluorine therefrom.
The following examples describe β-diketonate compounds which have been prepared and, based on their properties, are presently considered suitable for use as main group metal sources for the production of pure oxides suitable for glass formation by vapor phase oxidation processes.
A β-diketonate complex of aluminum (a Group IIIA metal) is prepared by reacting hexafluoroacetylacetone (Hhfa) with aluminum chloride. A 1.06 g sample of AlCl3 is added to 10 ml of CCl4 with stirring under nitrogen. A solution of (Hhfa) in CCl4 is slowly added to the AlCl3 solution, with large amounts of HCl being evolved during the addition. The reaction mixture is refluxed for 30 minutes and the hot mixture is thereafter passed through a frit filter.
The clear filtrate crystallizes on cooling to give about 5.21 g of a white crystalline product. This product is purified by vacuum sublimation at 80° C. into a dry ice-cooled cold trap.
Infrared spectral analysis of a sample of the product in KBr corresponds to that reported in the literature for Al(hfa)3. This compound sublimes readily at temperatures above 50° C., melts at about 72°-74° C., and has a reported vapor pressure of about 100 mm Hg at 125° C. This indicates that the compound would be a suitable source of aluminum-containing vapors for the production of sinterable oxide soot by a vapor phase reaction process.
β-diketonate complexes of the Group IIA metal magnesium are prepared by reacting (Hhfa) with basic magnesium carbonate. A 2.5 g sample of basic magnesium carbonate, 4 MgCO3.Mg(OH)2. nH2 O (n≃6), is suspended in 100 ml of ether with stirring under nitrogen. A 10.41 g sample of (Hhfa) is added to the suspension and the mixture is refluxed for two hours. The ether is then separated from a solid residual phase by decantation and evaporated to dryness. Evaporation leaves a residual white powder product identified as the ether-water adduct of magnesium hexafluoroacetylacetonate, Mg(hfa)2.1.5Et2 O.H2 O. This adducted complex melts at about 225° C. and can be vaporized by sublimation at 165° C.
To prepare a tetrahydrofuran (THF) adduct of Mg(hfa)2, a 20 ml volume of THF is added to the ether-water adduct produced as described above and the resulting solution is stirred for 18 hours. Rotary evaporation of the solution leaves a white powder residue identified by proton nuclear magnetic resonance (nmr) as Mg(hfa)2.4THF. Sublimation of this compound to a dry ice-cooled cold trap produces the adduct Mg(hfa)2.2THF, a compound having a melting point of approximately 130° C. which can be vaporized at 160° C. to generate Mg-containing vapors for a vapor phase oxidation process.
A β-diketonate complex of the Group IA metal sodium is prepared by reacting sodium hydroxide with a beta-diketone containing a 7-carbon chain. A 4.08 g sample of pelletized NaOH is dissolved in 50 ml of water in a separatory funnel and 20.0 g of the diketone 1,1,1-trifluoro-6-methyl-2,4-heptanedione (Htfmhd) is added to the solution. This mixture is shaken periodically over a 15-minute interval, and then ether is added to extract the Na β-diketonate product from the mixture. The pale yellow ether extract is evaporated to dryness in air giving a pale yellow solid identified as Na(tfmhd), having an undetermined melting point but giving evidence of sublimation at about 260° C. with some evidence of thermal decomposition.
A β-diketonate complex of the rare earth metal cerium is prepared by reacting cerium nitrate with 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione.
A 68.2 g sample of this β-diketone (Hfod) is added to 115 ml of 2 M aqueous NH4 OH, resulting in a white precipitate which is separated and dissolved in 200 ml of water and 200 ml of methanol. The resulting solution is placed in an addition funnel and added dropwise to a nitric acid solution of cerium nitrate consisting of 25.0 g Ce(NO3)3.6H2 O dissolved in 60 ml of 1.4 M HNO3. 2 M NH4 OH is then added to achieve and maintain a pH of 6.
The resulting mixture separates into a red oil phase and an aqueous phase. The separated mixture is stirred under O2 at room temperature until oxidation of Ce+3 to Ce+4 is complete, in this case about 70 hours. Thereafter, 200 ml of hexanes are added and the organic layer containing the product is separated from the aqueous phase, filtered, and evaporated to dryness in a rotary evaporator. The product is crystallized from the red oil, and examination of the proton nmr spectrum of the crystals shows substantially complete oxidation to Ce(fod)4.
After purification by sublimation, the Ce(fod)4 thus produced exhibits a melting point of about 97° C. and a vapor pressure approaching 10 mm Hg at a temperature near 200° C. By virtue of this high vapor pressure this compound would constitute a suitable source of Ce-containing vapors for a vapor phase oxidation process in accordance with the present invention.
Following the procedure reported by Chattoraj et al. in J. Inorg. Nucl. Chem., 28 (1966), pages 1937-1943, the water adduct of Zn(hfa)2 is prepared by reacting Hhfa with zinc oxide. Ten grams of ZnO and 35.2 ml of Hhfa are added to a flask equipped with a condenser, magnetic stirrer and heating mantel, with stirring to disperse the ZnO. Thirty ml of H2 O is added, causing the reflux of Hhfa due to the evolution of heat, with stirring being continued until all evidence of reaction has ceased.
An additional 30 ml of water and 200 ml of ether are then added and the mixture is refluxed for one hour. After cooling, excess ZnO is removed by filtration, the ether layer is separated and dried by adding 4Å molecular sieves, crude Zn(hfa)2.2H2 O product.
Approximately 10 g of this product is dissolved in THF at room temperature, the solvent is then evaporated, and the residue is sublimed at 150° C. under vacuum to a dry ice-cooled cold trap. Infrared spectra, nuclear magnetic resonance, thermogravimetric analysis, elemental analysis, and differential scanning calorimetry are used to characterize this compound. The compound is presently believed to have the chemical formula Zn(hfa)2.2THF, with a melting temperature of 165° C. It exhibits excellent thermal stability, showing only slight decomposition when held at 165° C. for about 60 hours.
Neither the methods of preparing Zn(hfa)2.2THF, Mg(hfa)2.nTHF, and Ce(fod)4 disclosed in Examples 2, 4 and 5 above nor the compounds themselves comprise any part of the present invention, these being described and claimed in two copending, commonly assigned patent applications of David A. Thompson, Ser. Nos. 418,061 and 418,216, concurrently filed herewith.
FIG. 1 of the drawings demonstrates the vaporization characteristics of selected β-diketonate complexes such as reported in the above examples, as determined by thermogravimetric analysis. The drawing plots weight loss of a sample of the complex as a function of temperature over the heating range from about 25°-500° C. Temperature is plotted on the horizontal axis with the vertical axis corresponding to relative weight loss in the sample.
In general, easy vaporization without decomposition is reflected by an analysis trace exhibiting a sharp vertical drop corresponding to rapid weight loss of the heated sample in the evaporation or sublimation range, followed by a sharp horizontal trace at higher temperatures evidencing the absence of decomposable residues. The most desirable vaporization characteristics are demonstrated by Al(hfa)3, Zn(hfa)2.2THF and Mg(hfa)2.2THF, which exhibit rapid and complete vaporization at temperatures in the 100°-200° C. range. This may be contrasted with the behavior of a complex such as Mg(hfa)2.PCl3, an adducted complex hereinafter described with reference to FIG. 3, which exhibits evidence of significant decomposition and incomplete volatilization even at temperatures in excess of 300° C.
FIG. 2 of the drawings plots vapor pressure as a function of temperature for the Al(hfa)3 and Mg(hfa)2.2THF β-diketonate complexes. This drawing shows the very substantial vapor pressures of these two complexes, which are in the range of at least 10-100 mm Hg at temperatures in the range of 100°-200° C.
Significant variations in volatility can occur when β-diketonate compounds such as above described are complexed with Lewis bases to form adducted metal β-diketonates. To demonstrate some of these variations, adducts of Mg(hfa)2 with five different Lewis bases are prepared by adding small quantities of the sublimed ether-water adduct Mf(hfa)2.1.5Et2 O.H2 O to diethyl ether solutions of each of the six adducts: pyridine, CH3 CN, PCl3, dioxane and dimethyl formamide (DMF), with overnight stirring followed by evaporation to dryness and sublimation under vacuum to obtain the products. The volatility of each of the adducts is then evaluated by thermogravimetric analysis.
FIG. 3 of the drawings sets forth thermogravimetric curves for the five different adducts Mg(hfa)2.xL where L is pyridine (C5 H5 N), CH3 CN, PCl3, dioxane (C4 H8 O2) or DMF ((CH3)2 NCOH) as indicated in the drawing. The proportions x of these L ligands in the adduct molecules were not determined. A curve for Mg(hfa)2.2THF is also included for comparison. The CH3 CN and PCl3 adducts show evidence of decomposition, while the other adducts evaporate completely within narrow ranges of temperature, but at vaporization temperatures which vary significantly depending upon the identity of the particular adduct employed. Mg(hfa)2.2THF is found to be the most volatile of the various adducts tested.
The requirement that the metal compound be sufficiently volatile for efficient vaporization and vapor phase transport in accordance with the invention arises because of the need to generate a soot product with a relatively small particle size. For example, to obtain void-free glasses by the viscous sintering of oxide soot, particle sizes not exceeding about 0.1 microns are normally preferred. The following examples demonstrate the utility of selected volatile β-diketonate compounds for the production by vapor phase oxidation of fine, homogeneous oxide soot.
A quantity of Al(hfa)3 produced as in Example 1 above is maintained in a liquid state in a glass container by heating to about 125° C. A helium carrier gas is bubbled through the liquid Al(hfa)3 (the latter having a vapor pressure of about 100 mm Hg at this temperature) and the He carrier then transports vaporized Al(hfa)3 out of the container to an operating flame-oxidation burner through a heated delivery line. The flame oxidation burner is of the kind described in U.S. Pat. No. 4,125,288, having a design permitting the introduction of a vapor reactant stream into the burner flame via a center orifice in the burner face.
The Al(hfa)3 is oxidized in the vapor phase in the methane-oxygen burner flame to produce a γ-Al2 O3 soot which is collected for examination. FIG. 4 of the drawing is an electron photomicrograph of a sample of the γ-Al2 O3 soot thus provided, wherein the bar corresponds to a dimension of 0.1 microns.
As is evident from a study of FIG. 4, the γ-Al2 O3 soot produced by Al(hfa)3 oxidation in accordance with the invention is in the form of very small (<0.1 microns) spherical particles, the bulk of which range from about 0.025-0.05 microns in size. This indicates that the material could readily be incorporated into ceramics or void-free glasses of a desired composition by a sintering consolidation process.
A quantity of Mg(hfa)2.2THF produced as described in Example 3 above is maintained in a liquid state in a glass container by heating to about 190° C., a temperature at which it has a vapor pressure of about 500 mm Hg. An argon carrier gas is bubbled through this liquid at a rate of about 72 cc/min., and vaporized Mg(hfa)2.2THF is transported by this carrier through a heated delivery line to an operating methane-oxygen burner of the type used in Example 6 above.
A second reactant stream, transported by a second delivery line and combined with the Mg(hfa)2.2THF-carrying stream at the burner, is produced by bubbling argon at a rate of 576 cc/min through a quantity of SiCl4 maintained at 35° C., a temperature at which SiCl4 has a vapor pressure of 530 mm Hgl. The combined reactant stream is fed into the burner flame, that flame resulting from the combustion of 3.5 l/min. of natural gas (methane) and 3.4 l/min. of oxygen.
The SiCl4 and Mg(hfa)2.2THF reactants are converted by vapor phase oxidation in the flame to SiO2 and MgO, each in the form of a finely divided oxide soot. This soot mixture is collected on an alumina mandrel for examination, analysis and further treatment.
Analysis of the collected soot determines that a soot mixture consisting of 1.21% MgO and the remainder SiO2 has been deposited on the mandrel. This soot mixture is consolidated by heating with a gas-oxygen flame to sinter the soot into a clear MgO-SiO2 glass having a refractive index of about 1.460.
The glass-forming procedure of Example 8 is repeated, except that argon carrier gas flow through the liquid Mg(hfa)2.2THF reactant is increased to 720 cc/min., such that the soot mixture collected from the vapor phase oxidation of the reactant stream contains 7.74% MgO and the remainder SiO2 by weight. This soot mixture is sintered in a gas-oxygen flame as in Example 6, and the product is a dense, substantially void free MgO-SiO2 opal glass.
In using β-diketonate complexes as sources of main group metals for vapor phase oxidation processes, it must be recognized that these complexes can undergo reactions at vapor delivery temperatures which can adversely affect the desirable vaporization and stability characteristics thereof. Reactions to be considered which might reduce the volatility of the complex include electrophilic substitution of a halogen for a hydrogen atom on the β-diketone ligand, adduct formation by the complexing of the β-diketonate molecule with selected bases, replacement reactions wherein a β-diketonate ligand is replaced by a halide and redistribution reactions wherein ligands are scrambled among various metal complexes to produce new complexes of low volatility. Avoidance of these reactions may require the use of delivery systems wherein each vaporized reactant is separately transported to the reaction site for final mixing and vapor phase oxidation.
While the foregoing description has been primarily concerned with processes suitable for the formation of optically clear glasses useful, for example, in the fabrication of glass optical waveguides, it will be appreciated that the method of the invention could also be employed in the manufacture of other pure unitary ceramic products such as opal glasses, semicrystalline glasses, or crystalline ceramics, including porous glasses or ceramics where only partial sintering of the oxide soot is permitted in the consolidation step. In addition, it is possible to process the oxide soot prior to consolidation if, for example, it is desired to shape the soot into a preform of a desired configuration. This can be done, for example, by dispersing the soot in a suitable vehicle and casting the dispersion into a selected shape. Thus the foregoing examples are merely illustrative of procedures and products which may be provided in accordance with the invention as set forth in the appended claims.
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|Jun 27, 2003
|Nov 3, 2005
|Kauko Janka
|Method for the preparation of doped oxide material
|Feb 7, 2013
|Aug 15, 2013
|Asahi Glass Company, Limited
|Method for producing doped quartz glass
|Apr 7, 1997
|Apr 3, 2007
|Corning Incorporated
|Method of making fused silica by decomposing siloxanes
|Jul 10, 2000
|Apr 13, 2010
|Corning Incorporated
|Extreme ultraviolet soft x-ray projection lithographic method system and lithographic elements
|Sep 22, 1993
|Mar 24, 1994
|Mitsubishi Electric Corp
|Raw material for vaporising dielectric thin layers - comprises organic metal cpd. dissolved in THF
|Dec 6, 2008
|Jun 10, 2010
|Innovent E.V.
|Method for depositing a layer on a substrate, comprises producing flame from a process gas, supplying two fluid or gaseous precursor materials to the process gas and/or the flame and then subjected to reaction
|Jun 5, 1991
|Dec 11, 1991
|Air Products And Chemicals, Inc.
|Volatile crown ligand beta-diketonate alkaline earth metal complexes
|Mar 16, 1992
|Mar 3, 1993
|Corning Incorporated
|Method of making fused silica
|Aug 16, 1996
|Mar 5, 1997
|Corning Incorporated
|Method for purifying polyalkylsiloxanes and the resulting products
|Feb 25, 1998
|Jan 26, 2000
|Corning Incorporated
|Method of making titania-doped fused silica
|Aug 23, 2001
|May 28, 2003
|Advanced Technology Materials, Inc.
|Source reagent compositions and method for forming metal films on a substrate by chemical vapor deposition
|Dec 16, 1988
|Jun 29, 1989
|University Of Colorado Foundation, Inc.
|Chemical vapor deposition of mixed oxide films
|Jun 6, 1996
|Dec 19, 1996
|Advanced Technology Materials, Inc.
|Metal complex source reagents for chemical vapor deposition
|U.S. Classification
|65/390, 427/255.24, 65/901, 65/413, 427/255.21, 427/255.25
|International Classification
|Cooperative Classification
|European Classification
|Oct 1, 1984
Owner name: CORNING GLASS WORKS CORNING, NY A CORP. OF NY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MILLER, STEPHEN B.;STEWART, RONALD L.;THOMPSON, DAVID A.;REEL/FRAME:004306/0970;SIGNING DATES FROM 19820910 TO 19840909
|Feb 17, 1987
|Certificate of correction
|Jul 25, 1988
|Fee payment
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|Jul 9, 1992
|Fee payment
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|Jul 19, 1996
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