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Patrick Robinson (I)
Patrick Robinson was born in November 1963 in London, England. He is an actor and director, known for Casualty (1986), The Bill (1984) and Belly of the Beast (2003). See full bio »
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Hello all! So recently I've been doing a series called "Adams Family Photo Album", which I've really enjoyed doing and has gotten some small support from the few of you that swing by this little blog site. I really do enjoy doing it, and will continue in the future, but recently I've been inspired to go back to the roots of this blog. I wanted this site to pay homage to some of the similar themes of Elena Starz's blog, and the iconic theme right before she left was the "How to be a Blonde Bimbo" series, a series about a college class that required male students to dress and act like blonde bimbos to pass. I loved this series and dreamed of a idea that many others have toyed with over on other blogs and story sites - the idea of a school that turns boys to bimbos. I wanted to do this in a high school setting, a private academy or boarding school that turns unaware/unwilling boys into bimbos, both as a homage to Elena and as a fun series to do. So here are the first two caps, to give you an idea of what its going to be about, and expect more caps about "Bimbo High" in the future! Enjoy!
Super TG Captions
Wednesday, February 25, 2015
Bimbo High #1
Labels: bimbo, Bimbo High, blonde, crossdress, forced
Song Story - A New Idea!
Hello again all! I've been really busy of late! :) I've thought of another idea that I want to play with on this blog! Like the "Bimbo High" idea, its not really original because other TG captioners/writers have done something similar to it, but its new to me and I still want to do it. What is "it", you ask? Well "it" is an abbreviated TG Cap done to the toon of a popular song! Basically, there are a lot of songs out there with lyrics that are BEGGING for a TG idea based on the song with some lyrics altered (but still in the same rhythm that you'd sing the song!). Here is my first try based on the song, "Glad You Came" by The Wanted. Check it out!
So I've discovered that it's sometimes hard to get full context for a story inside the song if the lyrics are short and repetitive (as is the case for this song), but if I get more ideas I'll do this again! Also, if you have suggestions for good songs to spoof, let me know! Ideally there is at least one or two lines in the song that would pertain to some TG aspect, but shoot me a song name in the comments below and I'll try to work with it! Also, I will be posting a video of the actual song I use too, both to share some music and give you something to listen to the see what the song is like when you're reading my lyrics. Here is a link to this song if you want to get the tune in your head while you read the cap!
Labels: brunette, forced, magic, slut, Song Story
Tuesday, February 24, 2015
Student "Body" President Sidney Davis
Hi all! I got two lovely comments from MsLaraYves and Kathryn giving me praise on my first "Bimbo High" caption, and that has really motivated me to get captioning more for this series, so thank you to both of you! These next couple of captions coming up will be explaining some general concepts, ideas, and important people/positions at the Best Institute, otherwise known as Bimbo High. However, if there are more than just two of you reading these, I would like to know if I should:
- Tell stories as an outside observer about what "might happen" at Bimbo High in 2013 (as in future tense) with some anecdotes from 'previous years' that can be more specific.
- Tell stories in real time with more dialogue between characters and/or descriptions of what actually happened to the Bimbo High Class of 2013 upon entry to the school.
- Tell stories from the perspective of one student who is attending Bimbo High for the first time as a student in the class of 2013, meaning third person descriptions with references to the narrator/the narrator's understanding as well as dialogue between the narrator and other students.
I hope I explained these possibilities well enough for the bimbos of you out there :p I could mix options and don't have to have an answer now, but if I am going to do JUST option 3 I would like to know soon so I can start developing the characteristics/personality of the student who will be narrating. Anyways, please comment below and enjoy this series!
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Use this beautiful carved wood box to store your mala to maintain its purity and potency. Fits both wrist and most full malas. The dimensions of the natural box are : 2.5"h x 7"w x 5"d. The dimensions of the brown box are : 2.25"h x 6"w x 4"d. Handmade in India.
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Red is the traditional color of the thread and tassel used to make a mala. This was traditionally used as a symbol of the bloodline of the original teacher or Guru.
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Next, you'll be asked to connect with Twitter. Rest assured, we will never send a tweet from your account
without your permission.
We will send you an email with an invite soon.
RT @Traceyspacey1: "@sotak: In Czech Republic, this is how you threat people, so they don't do bad things... " Brilliant :)
RT @IrinaGreenVoice: One of the most spectacular places in the world is under threat. Help #SaveTheArctic>>>
Rajasthan: Keoladeo National Park faces survival threat - The Times of India #Ramsar
Sri Lanka court gives green light to deport Pakistani asylum seekers: "threat to the island's security and public health" : Vatican Radio
Terai forests under threat - The Times of India #CorruptIndia
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Editorial Staff • West End • 10 Dec 2003
Actually, moral philosophy is coming back into fashion, at least in the theatre. After Tom Stoppard's Jumpers, now revived at the Piccadilly, Dinner offers another journey down the twisting avenues of philosophical thought, as some of the husband's theories are brutally put to the test.
Moira Buffini's play (directed by her sister Fiona Buffini) has lots on the menu, and I don't just mean a "primordial soup" made of algae and living organisms, an "apocalypse of lobster" in which the guests are served a live lobster and have to decide whether to let it live or die, and a dessert made up of the frozen contents from the waste bin.
It's comic as well as symbolic. And when Paige announces a party game to have her guests talk on subjects she has specially chosen for two minutes, proceedings take a savage turn that recalls the 'Get the Guests' scenario in Edward Albee's famous dinner party play, Who's Afraid of Virginia Woolf? Dinner is likewise a play of mordant wit and macabre pleasure, and it is played to the stylish hilt by a cast that includes the brilliant Harriet Walter as Paige, who goes from the heartbreak of her last role in The Deep Blue Sea (seen on a national tour) to pointed hilarity here. Nicholas Farrell is also wonderful as her husband, barely suppressing his irritation and then fury at her, while Penny Downie is very funny as his mistress Wynne, whose own partner has just walked out on her.
There's also a splendid contribution from Paul Kaye as an uninvited guest - something he's adept at playing, having created the uninvited celebrity interviewer Dennis Pennis, on television, who would aggressively doorstep stars like Demi Moore and ask questions like: "If it wasn't gratuitous in any way and it was tastefully done, would you consider keeping your clothes on in a movie?"
This play of hilarious bad taste and worse manners sometimes feels like an Orton comedy, and you may have trouble keeping your food down at any post-theatre meal afterwards!


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Connect to the catalog for a full set of search tools.
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In February of 2013, the Office of Science and Technology Policy issued a memo requiring all federal funding agencies with more than $100 million in research funds to design a Public Access Plan. Since then, several plans have been released. What does this mean for you? That largely depends on which agencies award you funding and whether the various policies and laws allow you to share your research products. However, there are some emerging trends. {read more in the Research Commons blog}
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School Library JournalGr 2-4A young Ashanti boy invites readers to visit his West African village, famous for fine kente cloth, and to share his "magic" a masterful imagination. Artistic typesetting composition is accompanied by appealing color photos that bring the lyrical text into sharp focus. Kofi is an engaging scamp whose vivid "daydreams" that transport him to other places will speak to children everywhere and present them with a clear vision of his beloved West African world. Kofi's joy in his life is reflected in both text and pictorial content and will be an eye-opener to more materialistic children in technically developed environments. A winner.
—Patricia Manning, formerly at Eastchester Public Library, NY


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Edit Page Last Edit: 3 years 4 months ago
A very common vegetable that can be found in homes, on farms (would be stealing if taken directly from land) and many other places.
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Torre Grossa
Via Costarella, San Gimignano, Italy 53037Map
Piazza del Duomo
Located on the historic Piazza del Duomo, Torre Grossa is the only tower of the fourteen existing medieval towers to be open to public. With the height of 54 meter, the tower is the tallest in the city and was constructed over a period of eleven years beginning from 1300. The walls of the tower hide a belfry which is bound by a walkway that leads you to the top of the tower. Once on top, you can enjoy breathtaking view of the town and the countryside locale.
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UW Today
This is an archived article.
November 22, 2008
Meet the mammals.
Discover the diversity of mammals, ranging from shrews to whales. Talk to mammalogists, touch bones, pelts, horns, and antlers, and see amazing specimens including enormous whale skulls! It's all part of Family Day at the Burke.
10 a.m. to 4 p.m., Burke Museum.


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The 20th sangeethanjali to Muthuswami Dikshitar is being organised on August 9, 9 a.m. to 6.30 p.m., at Sri Muthuswami Dikshitar Memorial Mandapam in Ettayapuram. Artistes from Chennai, Tiruchi, Thanjavur and Madurai will participate. Saradha Ramana will inaugurate the festival, which is jointly organised by Sri Parthasarathy Swami Sabha, Saraswathi Vaggeyakra Trust, Narada Gana Sabha Trust, Chennai, Bharatiya Sangeetha Vaibahavam and Nadha Jyothi Sri Muthuswami Dikshitar Memorial Trust, Ettyapuram.
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Samuel L. Jackson Denies Dropping F-Bomb on 'Saturday Night Live' [NSFW VIDEO]
Did Samuel L. Jackson swear twice on SNL? Watch the video and decide for yourself.
Did Samuel L. Jackson swear twice on SNL? Watch the video and decide for yourself.
In a rare departure from its comedic opening, 'Saturday Night Live' started the show with a children's choir singing "Silent Night," to pay tribute to those killed at Sandy Hook Elementary School.
As the nation absorbs the news that continues to flow from the crime scene in Newtown, Connecticut, questions about gun control and school safety are becoming top-of-mind.
Authorities have released the names of the victims of Friday's mass shooting in Newtown, Connecticut, in which Adam Lanza, 20, reportedly killed 27 people, as well as himself. Lanza's rampage began when he shot and killed his mother, Nancy, at her home before he drove to Sandy Hook Elementary School and killed six adults and 20 children before taking his own life.
Adam Sandler contributed to this week's Hurricane Sandy relief concert, with a unique take on the classic 'Hallelujah.' In a parody this is so-Sandler, Adam sings 'Sandy Screw Ya.'
NOTE: This post will be continually updated as new information comes in. Video and photos are below. All times Eastern.
UPDATE 6:30 p.m.: Originally it was thought that Adam Lanza, the gunman, shot his mother at the Sandy Hook Elementary school, where she was a teacher's aide. ABC has learned that, in fact, Nancy Lanza was killed at her home (by her son) prior to the massacre. He then drove to the school, where he killed 20 children and six adults, before killing himself.
Details are still coming in about a school shooting in Newtown, Connecticut. It happened this morning shortly after 9:40 at Sandy Hook Elementary School. A shooter was reported in the main office, and one victim has numerous gunshot wounds.
Yesterday's 12-12-12 benefit concert for Hurricane Sandy relief raised over $30 million dollars, but it wasn't all good. We're still cringing for Bobby Moynihan's awkward appearance as his 'SNL' character "Drunk Uncle," for example.
Because celebrities love nothing more than a good cause they can say they helped out with, a whole lot of them stepped out for Wednesday night's 12-12-12 concert at Madison Square Garden in New York City.
But let's not forget: It was totes about the Hurricane Sandy victims!
Hurricane Sandy effected the entire Tri-state area around New York City, leaving millions without power and displaced from their homes. The storm, which touched down around Halloween, is still at the forefront of our minds.
Pop stars did their part and performed at the largely classic rock-leaning 12-12-12 concert event that took place at New York City's Madison Square Garden on Dec. 12. Kanye West and Alicia Keys were on hand to lend their talents for good, as was Coldplay frontman Chris Martin.
Several amazing artists are joining forces tonight in Madison Square Garden for the 12-12-12 Hurricane Sandy Relief Concert. Big names like Bon Jovi, Eric Clapton, Billy Joel, Alecia Keys, The Rolling Stones, Bruce Springsteen, The Who, Roger Waters and Sir Paul McCartney are among the seemingly endless list of performers.
The evening skyline over parts of New York City has been a little dim lately, thanks to Superstorm Sandy, but this is a city that bounces back quickly. A fantastic light show on Monday evening on the Empire State Building put everyone back in a New York state of mind! Watch 16 million colors dance and dazzle to the music of Alicia Keys after the jump.


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At Dream Foundation, support of our services and programs can can come in a variety of ways. We consider every contribution — whether it's time, cash, airline miles, or membership – a tremendous gift to our organization. Dream Foundation is proud to maintain a 4-star rating by Charity Navigator for sound fiscal management, so you know your investment in dreams is put to good use.
Adopt a Dream
Introducing you to just some of the dreams currently in progress with Dream Foundation. You can make a direct impact in the lives of our dream families by adopting one of these featured dreams. Contribute to a dream with a donation in any amount or adopt a dream outright with a $1,000 contribution.
Donate Airline Miles
Give dreams the gift of flight. Our established airline partnerships allow you to contribute airline miles directly to the needs of our dream families. Whether it's a bedside reunion, a vacation with children, or a trip to the ocean, your donated miles will make dreams come true.
In-Kind Contributions
In-kind contributions come in the form of donated products or services and are critical to the mission of Dream Foundation. Whether it's travel resources that allow families to connect and create happy memories, or basic needs items that provide simple comfort in end-of-life care, these are the gifts that make dreams come true.
Dream Foundation has hundreds of volunteers serving our mission; enhancing our program efficiency and instilling the spirit of giving in the schools, neighborhoods, and communities in which they serve. Become a volunteer today, and experience the gift that is discovered in giving back.
Leave a Legacy
Make a gift now to the Dream Endowment Fund in honor or memory of a loved one or make a provision in your estate plans to leave a future gift that will carry on the work of Dream Foundation after you are gone. Building a legacy of dreams ensures that we can make dreams come true—for eternity.
Seed Card
Make a contribution in honor of someone special and Dream Foundation will send you – or a selected recipient – this plantable seed card.
Dream Team Council (DTC)
Dream Foundation's Dream Team Council (DTC) is a national committee comprised of high school student leaders who are committed to bringing Dream Foundation's mission to new generations.
Cars 4 Causes
Donate your car to Cars 4 Causes and designate Dream Foundation to receive proceeds.


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Eclipse Pressure Cooker Set (5 PC)
Please select an available size.
Please select a size.
This item is final sale and non-returnable.
Estimated Delivery: -
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Description: Eclipse Pressure Cooker Set:
- One covered pressure cooker measures 8¾ inches in diameter with 6.3 quart capacity
- One pressure cooker measures 8 .75 inches in diameter with 3.1 quart capacity
- One glass cover measures 8¾ inches in diameter
One steam basket 8 inches in diameter
Made of 18/10 stainless steel
- Black phenolic resin handles
- Cover is made of 18/10 stainless steel with silicone ring
- Working pressure: 11.6 PSI/80 KPa
- Both covers are interchangeable
- Dishwasher safe
- Lids should only be hand washed
Material: 18/10 stainless steel/ synthetic handles
Care: Body is dishwasher-proof, cover is not suited for dishwasher
Brand: BergHOFF
Origin: Imported


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Villages at Carver Apartments1453 Moury Ave, Atlanta, GA 30303 View On Map (404) 624-1226
For rates, availability, and other information fill out the availability request form and a representative from Villages at Carver Apartments will contact you shortly
Villages at Carver is located in the Atlanta Area in the 30303 zip code. View this apartment on a map.
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The ACLU says administrators at a public after-school program in Middle Tennessee have agreed to train their staff on constitutional issues after one student was told he couldn't read the Bible during free reading time.
The American Civil Liberties Union's Nashville office usually has a pretty good idea of what bills they'll need to address before they're introduced. The Religious Freedom Act was an exception.
Introduced shortly before last week's filing deadline, HB2467 and SB2566 would protect business owners from having to provide goods or services to gay couples "in furtherance of a civil union, domestic partnership, or marriage not recognized by the Tennessee Constitution."
On Nov. 4, 2014, Tennesseans will go to the polls and vote on whether the state's General Assembly should have the authority to regulate abortion. The so-called abortion amendment will appear on the ballot as "Amendment One" and if approved by voters, would add language to the state constitution that would read (in part), "Nothing in this constitution secures or protects a right to abortion."
Knoxville, Tenn. - Tennessee Governor Bill Haslam will issue the second veto of his term on a controversial bill centered on livestock abuse.
The bill would have made it illegal to video or photograph livestock abuse without turning in the evidence within 48 hours.
The American Civil Liberties Union of Tennessee submitted 34,000 signatures urging a veto earlier this month; executive director Hedy Weinburg says she commends Haslam's decision.


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Resolution: standard / high
Figure 3.
Phosphorylation of E2F4 on serines 244 and 384 promotes its transcriptional activity. A. and B. 293T cells were transfected with pCDNA3.1 empty vector (EV) or encoded for HA-tagged- human wild-type (WT) E2F4 or E2F4 mutants as indicated. After 48 h, cell lysates were analyzed for the expression of E2F4 proteins. C. 293T cells were transfected with EV or encoding for HA-E2F4 WT, HA-E2F4 S244A, HA-E2F4 S384A or HA-E2F4 S244A/S384A. After 48 h, cells were lysed and immunoprecipitated with anti-HA antibody. Kinase assays were performed by incubating beads containing HA-E2F4 immune complexes with recombinant ERK1 for 5 min. Radiolabeled proteins were separated on SDS-PAGE and autoradiographed or analyzed for the expression of E2F4. D. 293T cells were co-transfected with DP2, thymidine kinase luciferase reporter with either empty vector, HA-wtE2F4, HA-E2F4 S244E, HA-E2F4 S384E or HA-E2F4 S244/S384E. pRL-SV40 Renilla luciferase reporter control vector was also co-transfected. Forty-eight hours following transfection, luciferase activity was quantified and normalized using the Renilla reporter, with the empty vector condition set at 1. A representative experiment of three experiments is shown. *Significantly different from control at p < 0.001, **Significantly different from WT at p < 0.002, ***Significantly different from WT at p < 0.001 (Student's t test). E. HIEC grown on coverslips were transfected with either empty vector, HA-wtE2F4, HA-E2F4 S244E, HA-E2F4 S384E or HA-E2F4 S244/S384E. After 48 h, cells were analyzed by immunofluorescence for subcellular localization of HA-tagged E2F4 forms. Total cell number was determined using DAPI staining and cells exhibiting E2F4 forms into the nucleus or into the cytoplasm or in both compartments were counted. The percentage of cells exhibiting HA staining into the nucleus, into the cytoplasm or in both compartments was calculated and shown in the graph. Representative experiment is shown.
Paquin et al. BMC Cell Biology 2013 14:33 doi:10.1186/1471-2121-14-33


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Grounding on purpose
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Re: Grounding on purpose
Originally Posted by
If you are just looking to clean the bottom there is no need to careen or actually ground the boat. When I was in northwest Florida the tide was typically less than 8 inches. When I wanted to clean the bottom without donning the scuba gear and diving at the dock I would anchor fore and aft in 6-7 feet of water grab the snorkel and mask and take my time cleaning and inspecting.
This is actually probably the BEST way with warm water like is in FL. Local here in teh nw US, water is 40-42F year around, so snorkling is a dry suit affair per say.
WIth that, if you have a fin keel, there are some stilts one can get for either side of the boat, you put at the four corners and a fin keel can rest on the ground with area's of bigger tides as mentioned, ala 12-14' as we get here in the salish sea, bigger the farther north one seems to go to a point!
I've seen pics of a 40'ish foot Jeanneau with a 6.5' keel resting against a dock in the UK, with no issues before or after doing a cleaning and bottom job.
She drives me boat,
I drives me dinghy!
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Aww, Zendaya Coleman posted this photo of herself and her "Shake It Up" co-star Davis Cleveland on her Instagram account. Here's what Zendaya posted along with the picture:
"D-dogg and Z-swag"
The second season of "Shake It Up" just began on the Disney Channel. Are you a fan of the show?


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Exploring the Zend Studio 4 developer environment
PHP experts consider Zend Studio the most mature and feature-rich IDE for PHP. The latest version offers enhanced database manipulation and other improvements. We'll put the Zend Studio IDE through its paces and show you how you can use it to speed up PHP development.
The choice of an integrated development environment is often a matter of taste. Many PHP developers prefer text editors like Emacs or Vim. Developers who favor a more integrated approach have several choices in the Linux world. The free Quanta Plus IDE, the closed source Maguma environment, and even Eclipse (with the right set of plug-ins) are all genuine alternatives to an editor. For PHP developers, EditionZend Studio has the reputation of being one of the most mature and powerful IDEs. Zend Studio is the brainchild of Israel's Zend Software, a vendor that prefers to be known as "The PHP Company." Older versions often suffered from performance problems or instability, but the latest version, Zend Studio 4, is an extremely powerful and stable developer environment. Zend Studio is neither Open Source, nor is it free of charge, although US$ 249 is a fair asking price. You can download a trial version from the Zend website. The test version is full-featured for the 21 day trial period and then degrades to the "Zend Studio Personal Edition," a non-commercial version that disables so many useful features it is not really worth the effort (see the box titled "Zend Studio Personal Edition").
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Code.org and College Board Team Reach Out for Talented High School Coders
New partnership will bring more and better CS training to US schools
A Peek Inside TeslaCrypt Ransomware
Criminals offer online help over Tor network
Mumblehard Still Spams
Sophisticated malware is still present on Joomla and WordPress sites around the world.
Launchpad Gets Git
Future versions of Ubuntu's code service will support the popular Git version control system used with Linux and other open source projects.
AMD Posts Code for Linux GPU Driver
New release marks the arrival of AMD's unified driver strategy.
30 Percent of New Server Equipment Goes to Cloud Infrastructure
A new study by IDC charts big changes in the big hardware market.
Windows Might Go Open Source
Azure CTO says Redmond has already considered the unthinkable.
Linux Mint Will Stay with Ubuntu
Lead developer quells rumors that the Debian version is slated for center stage.
Microsoft Frees Code for .NET Build Engine
MSBuild is now just another GitHub project as Redmond continues its path to the light.
Researchers Demonstrate Hack by Heat
Malware could pass data and commands between disconnected computers without leaving a trace on the network.


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29 October 2013 09:58 [Source: ICIS news]
(adds detail of full confirmation)
LONDON (ICIS)--The European propylene contract price for November is confirmed at €1,080/tonne ($1,500/tonne), down by €30/tonne from October to reflect weaker feedstock values, contract settlers said on Tuesday.
The decrease was also in recognition that supply could lengthen through the month as planned maintenance is due to come to an end and year-end inventory concerns rise to the forefront.
To date, two producers and three consumers - two non-integrated and one integrated - have confirmed the settlement.
The contract is agreed on a free delivered (FD) northwest Europe (NWE) basis.
($1 = €0.72)
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From the Publisher"A wonderfully useful book."—William Cronon, Frederick Jackson Turner Professor of History, Geography, and Environmental Studies, University of Wisconsin-–Madison
"This atlas fills a void in the bibliography of Wisconsin history."—Margaret Beattie Bogue, professor emeritus of history, University of Wisconsin–Madison, author of Around the Shores of Lake Michigan
"[Wisconsin's Past and Present] is a first of its kind for this state and is long overdue."—Onno Brouwer, associate director, University of Wisconsin Cartography Laboratory, co-editor of the Cultural Map of Wisconsin


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A high surface area carbon nanofiber is provided. The carbon nanofiber has an outer surface on which a porous high surface area layer is formed. A method of making the high surface area carbon nanofiber includes pyrolizing a polymeric coating substance provided on the outer surface of the carbon nanofiber at a temperature below the temperature at which the polymeric coating substance melts. The polymeric coating substance used as the high surface area around the carbon nanofiber may include phenolics-formaldehyde, polyacrylonitrile, styrene, divinyl benzene, cellulosic polymers and cyclotrimerized diethynyl benzene. The high surface area polymer which covers the carbon nanofiber may be functionalized with one or more functional groups.
1. A high surface area carbon nanofiber, comprising:
a nanofiber, having an outer surface having an effective surface area; and
a high surface area layer formed onto said outer surface of said nanofiber;
wherein said high surface area layer contains pores including mesopores, macropores or micropores, and wherein at least a portion of said pores are of a sufficient size to increase the effective surface area of said nanofiber.
2. The high surface area nanofiber recited in claim 1, wherein the surface of said high surface area carbon nanofiber is substantially free of micropores.
3. The high surface area nanofiber recited in claim 1, wherein said high surface area layer is produced by pyrolyzing a polymeric coating substance onto the outer surface of said nanofiber, and wherein said polymeric coating substance is capable of carbonizing at a temperature below the temperature at which said polymeric coating substance melts.
4. The high surface area nanofiber recited in claim 1, wherein said high surface area layer is formed by pyrolyzing a polymeric coating substance selected from the group consisting of phenalics-formaldehyde, polyacrylonitrile, styrene divinyl benzene, cellulosic polymers, and cyclotrimerized diethynyl benzene.
5. The high surface area nanofibers recited in claim 1, wherein said high surface area layer is formed by chemically modifying a polymer coating substance.
6. The high surface area nanofiber recited in claim 1, wherein said high surface area layer is applied to said nanofiber by an evaporation technique.
7. The high surface area nanofiber recited in claim 1, wherein said pores have a minimum length and width of about 20 Å.
8. The high surface area nanofiber recited in claim 1, wherein said pores have a maximum depth of 200 Å.
9. The high surface area nanofiber recited in claim 1, wherein said pores have a maximum depth of 100 Å.
10. The high surface area nanofiber recited in claim 1, wherein the high surface area layer of said nanofiber is activated to form an activated surface.
11. The high surface area nanofiber recited in claim 1, wherein said high surface area nanofiber is functionalized.
12. The high surface area nanofiber recited in claim 1, wherein said high surface area nanofiber is functionalized with one or more functional groups selected from the group consisting of --SO3, --R'COX, --R'(COOH)2, --CN, --R'CH2 X, ═O, --R'CHO, --R'CN, and a graphenic analogue of one or more of ##STR5## wherein R' is a hydrocarbon radical, and wherein X is --NH2, --OH or a halogen.
13. The high surface area nanofiber recited in claim 10, wherein the surface of said activated layer is functionalized.
14. The high surface area nanofiber recited in claim 1, wherein the effective surface area is increased by 50%.
15. The coated nanofiber recited in claim 1, wherein the effective surface area is increased by 150%.
16. The high surface area nanofiber recited in claim 1, wherein the effective surface area is increased by 300%.
17. The high surface area nanofiber recited in claim 1, wherein said nanofiber comprises carbon and the carbon purity of said nanofiber is about 90% by weight.
18. The high surface area nanofiber recited in claim 1, wherein the carbon purity of said nanofiber is about 99% by weight.
19. The high surface area nanofiber as recited in claim 1, wherein when said high surface area nanofiber has a cross-section of 65 angstroms, the effective surface area of said high surface area nanofiber is greater than 400 m2 /g.
20. The high surface area nanofiber recited in claim 1, wherein when said high area nanofiber has a cross-section of 130 angstroms, the effective surface area of said high surface area nanofiber is greater than 200 m2 /g.
21. The high surface area nanofiber as recited in claim 1, wherein when said high surface area nanofiber has a cross-section of 250 angstroms, the effective surface area of said high surface area nanofiber is greater than 100 m2 /g.
This application claims benefit to U.S. Provisional Application 60/017,787 filed May 15, 1996, which is now abandoned.
The invention relates generally to high surface area nanofibers. More specifically, the invention relates to nanofibers which are coated with a substance, derived by pyrolysis of a polymer, in order to increase the surface area of the nanofibres. More specifically still, the invention relates to graphitic carbon nanofibers coated with a graphenic carbon layer derived by pyrolysis of a polymer. The graphenic layer can also be activated by known activation techniques, functionalized, or activated and then functionalized, to enhance its chemical properties.
A number of applications in the chemical arts require a substance which embodies, to the greatest extent possible, a high surface area per unit volume, typically measured in square meters per gram. These applications include, but are not limited to catalyst support, chromatography, chemical adsorption/absorption and mechanical adsorption/absorption. These applications generally require that a high degree of interaction between a liquid or gaseous phase and a solid phase; for instance, a catalyst support which requires that a maximum amout of reagents contact a catalyst in the quickest amount of time and within the smallest possible space, or a chromatagraphic technique wherein maximum separation is desired using a relatively small column.
More specifically regarding catalysts, heterogeneous catalytic reactions are widely used in chemical processes in the petroleum, petrochemical and chemical industries. Such reactions are commonly performed with the reactant(s) and product(s) in the fluid phase and the catalyst in the solid phase. In heterogeneous catalytic reactions, the reaction occurs at the interface between phases, i.e., the interface between the fluid phase of the reactant(s) and product(s) and the solid phase of the supported catalyst. Hence, the properties of the surface of a heterogeneous supported catalyst are significant factors in the effective use of that catalyst. Specifically, the surface area of the active catalyst, as supported, and the accessibility of that surface area to reactant chemisorption and product desorption are important. These factors affect the activity of the catalyst, i.e., the rate of conversion of reactants to products. The chemical purity of the catalyst and the catalyst support have an important effect on the selectivity of the catalyst, i.e., the degree to which the catalyst produces one product from among several products, and the life of the catalyst.
Generally catalytic activity is proportional to catalyst surface area. Therefore, high specific area is desirable. However, that surface area must be accessible to reactants and products as well as to heat flow. The chemisorption of a reactant by a catalyst surface is preceded by the diffusion of that reactant through the internal structure of the catalyst.
Since the active catalyst compounds are often supported on the internal structure of a support, the accessibility of the internal structure of a support material to reactant(s), product(s) and heat flow is important. Porosity and pore size distribution of the support structure are measures of that accessibility. Activated carbons and charcoals used as catalyst supports have surface areas of about 1000 square meters per gram and porosities of less than one milliliter per gram. However, much of this surface area and porosity, as much as 50%, and often more, is associated with micropores, i.e., pores with pore diameters of 2 nanometers or less. These pores can be inaccessible because of diffusion limitations. They are easily plugged and thereby deactivated. Thus, high porosity material where the pores are mainly in the mesopore (>2 nanometers) or macropore (>50 nanometers) ranges are most desirable.
It is also important that supported catalysts not fracture or attrit during use because such fragments may become entrained in the reaction stream and must then be separated from the reaction mixture. The cost of replacing attritted catalyst, the cost of separating it from the reaction mixture and the risk of contaminating the product are all burdens upon the process. In other processes, e.g. where the solid supported catalyst is filtered from the process stream and recycled to the reaction zone, the fines may plug the filters and disrupt the process.
It is also important that a catalyst, at the very least, minimize its contribution to the chemical contamination of reactant(s) and product(s). In the case of a catalyst support, this is even more important since the support is a potential source of contamination both to the catalyst it supports and to the chemical process. Further, some catalysts are particularly sensitive to contamination that can either promote unwanted competing reactions, i.e., affect its selectivity, or render the catalyst ineffective, i.e., "poison" it. Charcoal and commercial graphites or carbons made from petroleum residues usually contain trace amounts of sulfur or nitrogen as well as metals common to biological systems and may be undesirable for that reason.
Since the 1970s nanofibers have been identified as materials of interest for such applications. Carbon nanofibers exist in a variety of forms and have been prepared through the catalytic decomposition of various carbon-containing gases at metal surfaces. Such vermicular carbon deposits have been observed almost since the advent of electron microscopy. A good early survey and reference is found in Baker and Harris, Chemistry and Physics of Carbon, Walker and Thrower ed., Vol. 14, 1978, p. 83, hereby incorporated by reference. See also, Rodriguez, N., J. Mater. Research, Vol. 8, p. 3233 (1993), hereby incorporated by reference.
Nanofibers such as fibrils, bucky tubes and nanofibers are distinguishable from continuous carbon fibers commercially available as reinforcement materials. In contrast to nanofibers, which have, desirably large, but unavoidably finite aspect ratios, continuous carbon fibers have aspect ratios (L/D) of at least 104 and often 106 or more. The diameter of continuous fibers is also far larger than that of nanofibers, being always >1.0μ and typically 5 to 7μ.
Further details regarding the formation of carbon nanofiber aggregates may be found in the disclosure of Snyder et al., U.S. patent application Ser. No. 149,573, filed Jan. 28, 1988, and PCT Application No. US89/00322, filed Jan. 28, 1989 ("Carbon Fibrils") WO 89/07163, and Moy et al., U.S. patent application Ser. No. 413,837 filed Sep. 28, 1989 and PCT Application No. US90/05498, filed Sep. 27, 1990 ("Fibril Aggregates and Method of Making Same") WO 91/05089, all of which are assigned to the same assignee as the invention here and are hereby incorporated by reference.
While activated charcoals and other carbon-containing materials have been used as catalyst supports, none have heretofore had all of the requisite qualities of porosity and pore size distribution, resistance to attrition and purity for the conduct of a variety of organic chemical reactions.
Specifically, nanofiber mats, assemblages and aggregates have been previously produced to take advantage of the increased surface area per gram achieved using extremely thin diameter fibers. These structures are typically composed of a plurality of intertwined or intermeshed fibers.
The macroscopic morphology of the aggregate is controlled by the choice of catalyst support. Spherical supports grow nanofibers in all directions leading to the formation of bird nest aggregates. Combed yarn and open nest aggregates are prepared using supports having one or more readily cleavable planar surfaces, e.g., an iron or iron-containing metal catalyst particle deposited on a support material having one or more readily cleavable surfaces and a surface area of at least 1 square meters per gram.
Moy et al., U.S. application Ser. No. 08/469,430 entitled "Improved Methods and Catalysts for the Manufacture of Carbon Fibrils", filed Jun. 6, 1995, hereby incorporated by reference, describes nanofibers prepared as aggregates having various morphologies (as determined by scanning electron microscopy) in which they are randomly entangled with each other to form entangled balls of nanofibers resembling bird nests ("BN"); or as aggregates consisting of bundles of straight to slightly bent or kinked carbon nanofibers having substantially the same relative orientation, and having the appearance of combed yarn ("CY") e.g., the longitudinal axis of each nanofiber (despite individual bends or kinks) extends in the same direction as that of the surrounding nanofibers in the bundles; or, as, aggregates consisting of straight to slightly bent or kinked nanofibers which are loosely entangled with each other to form an "open net" ("ON") structure. In open net structures the degree of nanofiber entanglement is greater than observed in the combed yarn aggregates (in which the individual nanofibers have substantially the same relative orientation) but less than that of bird nests. CY and ON aggregates are more readily dispersed than BN making them useful in composite fabrication where uniform properties throughout the structure are desired.
Nanofibers and nanofiber aggregates and assemblages described above are generally required in relatively large amounts to perform catalyst support, chromatography, or other application requiring high surface area. These large amounts of nanofibers are disadvantageously costly and space intensive. Also disadvantageously, a certain amount of contamination of the reaction or chromatography stream, and attrition of the catalyst or chromatographic support, is likely given a large number of nanofibers.
Aerogels are high surface area porous structures or foams typically formed by supercritical drying a mixture containing a polymer, followed by pyrolysis. Although the structures have high surface areas, they are disadvantageous in that they exhibit poor mechanical integrity and therefore tend to easily break down to contaminate, for instance, chromatographic and reaction streams. Further, the surface area of aerogels, while relatively high, is largely in accessible, in part due to small pore size.
The subject matter of this application, deals with reducing the number of nanofibers needed to perform applications requiring high surface area by increasing the surface area of each nanofiber. The nanofibers of this application have an increased surface area, measured in m2 /g, as compared to nanofibers known in the art. Also advantageously, even assuming that a certain number of nanofibers per gram of nanofiber will be contaminant in a given application, the fact that less nanofibers are required for performing that application will thereby reduce nanofiber contamination.
It is therefore an object of this invention to provide a nanofiber having a high surface area layer containing pores which increase the effective surface area of the nanofiber and thus increases the number of potential chemical reaction or catalytic sites on the nanofiber.
It is another object of this invention to provide a nanofiber having a high surface area layer containing pores which increase the effective surface area of the nanofiber and thus increases the number of potential chemical reaction or catalytic sites on the nanofiberand which nanofibers are capable of forming rigid structures.
It is yet another object of this invention to provide a nanofiber having a high surface area layer containing pores which increase the effective surface area of the nanofiber and thus increases the number of potential chemical reaction or catalytic sites on the nanofiber.
It is yet another object of this invention to provide a composition of matter comprising nanofibers having an activated high surface area layer containing additional pores which further increase the effective surface area of the nanofiber and thus increases the number of potential chemical reaction or catalysis sites on the nanofiber.
It is a further object of this invention to provide a nanofiber having a high surface area layer containing pores which increase the effective surface area of the nanofiber and thus increases the number of potential chemical reaction or catalysis sites on the nanofiber, which also is functionalized to enhance chemical activity.
It is further still an object of this invention to provide a composition of matter comprising nanofiber having an activated high surface area layer containing additional pores which increase the effective surface area of the nanofiber and thus increases the number of potential chemical reaction or catalysis sites on the nanofiber, which also is functionalized to enhance chemical activity.
The invention encompasses coated nanofibers, assemblages and aggregates made from coated nanofibers, functionalized coated nanofibers, including assemblages and aggregates made from functionalized coated nanofibers, and activated coated nanofibers, including activated coated nanofibers which may be functionalized. The nanofiber made according to the present inventio have increased surface areas in comparison to conventional uncoated nanofibers. The increase in surface area results from the porous coating applied to the surface of the nanofiber. The high surface nanofiber is formed by coating the fiber with a polymeric layer and pyrolyzing the layer to form a porous carbon coating on the nanofiber.
FIG. 1 is a side elevational view of a carbon fibril.
FIG. 2 is a front elevational view of a carbon fibril taken along line 1--1'.
FIG. 3 is a side elevational view of a carbon fibril coated with a polymer.
FIG. 4 is a front elevational view of a carbon fibril coated with a polymer taken along line 3--3'.
FIG. 5 is a side elevational view of a carbon fibril coated with a polymer after pyrolysis.
FIG. 6 is a front elevational view of a carbon fibril coated with a polymer after pyrolysis taken along line 5--5'.
FIG. 7 is a side elevational view of a carbon fibril coated with a polymer after pyrolysis and activation.
FIG. 8 is a front elevational view of a carbon fibril coated with a polymer after pyrolysis and activation taken along line 7--7'.
FIG. 9 is a flow diagram of the process for preparing fibrils coated with a carbonaceous thin layer.
FIG. 10 is a flow diagram of the process for preparing fibril mats coated with a carbonaceous thin layer.
The term "effective surface area" refers to that portion of the surface area of a nanofiber (see definition of surface area) which is accessible to those chemical moieties for which access would cause a chemical reaction or other interaction to progress as desired.
"Graphenic" carbon is a form of carbon whose carbon atoms are each linked to three other carbon atoms in an essentially planar layer forming hexagonal fused rings. The layers are platelets only a few rings in diameter or they may be ribbons, many rings long but only a few rings wide. There is no order in the relation between layers, few of which are parallel.
"Graphenic analogue" refers to a structure which is incorporated in a graphenic surface.
"Graphitic" carbon consists of layers which are essentially parallel to one another and no more than 3.6 angstroms apart.
The term "macroscopic" refers to structures having at least two dimensions greater than 1 micrometer.
The term "mesopore" refers to pores having a cross section greater than 2 nanometers.
The term "micropore" refers to a pore which is has a diameter of less than 2 nanometers.
The term "nanofiber" refers to elongated structures having a cross section (e.g., angular fibers having edges) or diameter (e.g., rounded) less than 1 micron. The structure may be either hollow or solid. This term is defined further below.
The term "physical property" means an inherent, measurable property of the nanofiber.
The term "pore" refers to an opening or depression in the surface of a coated or uncoated nanofiber.
The term "purity" refers to the degree to which a nanofiber, surface of a nanofiber or surface of high surface area nanofiber, as noted, is carbonaceous.
The term "pyrolysis" refers to a chemical change in a substance occasioned by the application of heat.
The term "relatively" means that ninety-five percent of the values of the physical property will be within plus or minus twenty percent of a mean value.
The term "substantially" means that ninety-five percent of the values of the physical property will be within plus or minus ten percent of a mean value.
The terms "substantially isotropic" or "relatively isotropic" correspond to the ranges of variability in the values of a physical property set forth above.
The term "surface area" refers to the total surface area of a substance measurable by the BET technique.
The term "thin coating layer" refers to the layer of substance which is deposited on the nanofiber. Typically, the thin coating layer is a carbon layer which is deposited by the application of a polymer coating substance followed by pyrolysis of the polymer.
Nanofibers are various types of carbon fibers having very small diameters including fibrils, whiskers, nanotubes, bucky tubes, etc. Such structures provide significant surface area when incorporated into macroscopic structures because of their size. Moreover, such structures can be made with high purity and uniformity.
Preferably, the nanofiber used in the present invention has a diameter less than 1 micron, preferably less than about 0.5 micron, and even more preferably less than 0.1 micron and most preferably less than 0.05 micron.
The fibrils, buckytubes, nanotubes and whiskers that are referred to in this application are distinguishable from continuous carbon fibers commercially available as reinforcement materials. In contrast to nanofibers, which have desirably large, but unavoidably finite aspect ratios, continuous carbon fibers have aspect ratios (L/D) of at least 104 and often 106 or more. The diameter of continuous fibers is also far larger than that of fibrils, being always >1.0 μm and typically 5 to 7 μm.
Continuous carbon fibers are made by the pyrolysis of organic precursor fibers, usually rayon, polyacrylonitrile (PAN) and pitch. Thus, they may include heteroatoms within their structure. The graphenic nature of "as made" continuous carbon fibers varies, but they may be subjected to a subsequent graphenation step. Differences in degree of graphenation, orientation and crystallinity of graphite planes, if they are present, the potential presence of heteroatoms and even the absolute difference in substrate diameter make experience with continuous fibers poor predictors of nanofiber chemistry.
The various types of nanofibers suitable for the polymer coating process are discussed below.
Carbon fibrils are vermicular carbon deposits having diameters less than 1.0 μ, preferably less than 0.5 μ, even more preferably less than 0.2 μ and most preferably less than 0.05 μ. They exist in a variety of forms and have been prepared through the catalytic decomposition of various carbon-containing gases at metal surfaces. Such vermicular carbon deposits have been observed almost since the advent of electron microscopy. A good early survey and reference is found in Baker and Harris, Chemistry and Physics of Carbon, Walker and Thrower ed., Vol. 14, 1978, p. 83 and Rodriguez, N., J. Mater. Research, Vol. 8, p. 3233 (1993), each of which are hereby incorporated by reference. (see also, Obelin, A. and Endo, M., J. of Crvstal Growth, Vol. 32 (1976), pp. 335-349, hereby incorporated by reference).
U.S. Pat No. 4,663,230 to Tennent, hereby incorporated by reference, describes carbon fibrils that are free of a continuous thermal carbon overcoat and have multiple ordered graphenic outer layers that are substantially parallel to the fibril axis. As such they may be characterized as having their c-axes, the axes which are perpendicular to the tangents of the curved layers of graphite, substantially perpendicular to their cylindrical axes. They generally have diameters no greater than 0.1 μ and length to diameter ratios of at least 5. Desirably they are substantially free of a continuous thermal carbon overcoat, i.e., pyrolytically deposited carbon resulting from thermal cracking of the gas feed used to prepare them. The Tennent invention provided access to smaller diameter fibrils, typically 35 to 700 Å (0.0035 to 0.070μ) and to an ordered, "as grown" graphenic surface. Fibrillar carbons of less perfect structure, but also without a pyrolytic carbon outer layer have also been grown.
U.S. Pat. No. 5,171,560 to Tennent et al., hereby incorporated by reference, describes carbon fibrils free of thermal overcoat and having graphitic layers substantially parallel to the fibril axes such that the projection of said layers on said fibril axes extends for a distance of at least two fibril diameters. Typically, such fibrils are substantially cylindrical, graphitic nanotubes of substantially constant diameter and comprise cylindrical graphitic sheets whose c-axes are substantially perpendicular to their cylindrical axis. They are substantially free of pyrolytically deposited carbon, have a diameter less than 0.1μ and a length to diameter ratio of greater than 5.
These carbon fibrils free of thermal overcoat are of primary interest as starting materials in the present invention.
When the projection of the graphenic layers on the fibril axis extends for a distance of less than two fibril diameters, the carbon planes of the graphenic nanofiber, in cross section, take on a herring bone appearance. These are termed fishbone fibrils. Geus, U.S. Pat. No. 4,855,091, hereby incorporated by reference, provides a procedure for preparation of fishbone fibrils substantially free of a pyrolytic overcoat. These fibrils are also useful in the practice of the invention.
Carbon nanotubes of a morphology similar to the 4-catalytically grown fibrils described above have been grown in a high temperature carbon arc (Iijima, Nature 354 56 1991, hereby incorporated by reference). It is now generally accepted (Weaver, Science 265 1994, hereby incorporated by reference) that these arc-grown nanofibers have the same morphology as the earlier catalytically grown fibrils of Tennent. Arc grown carbon nanofibers are also useful in the invention.
High surface area nanofibers may be used in the formation of nanofiber aggregates and assemblages having properties and morphologies similar to those of aggregates of "as made" nanofibers, but with enhanced surface area. Aggregates of high surface area nanofibers, when present, are generally of the bird's nest, combed yarn or open net morphologies. The more "entangled" the aggregates are, the more processing will be required to achieve a suitable composition if a high porosity is desired. This means that the selection of combed yarn or open net aggregates is most preferable for the majority of applications. However, bird's nest aggregates will generally suffice.
The assemblage is another nanofiber structure suitable for use with the high surface area nanofibers of the present invention. An assemblage is a composition of matter comprising a three-dimensional rigid porous assemblage of a multiplicity of randomly oriented carbon nanofibers. An assemblage typically has a bulk density of from 0.001 to 0.50 gm/cc.
The general area of this invention relates to nanofibers which are treated so as to increases the effective surface area of the nanofiber, and a process for making same.
Generally, a nanofiber having an increased surface area is produced by treating nanofiber in such a way that an extremely thin high surface area layer is formed. These increases the surface area, measured in m2 /g, of the nanofiber surface configuration by 50 to 300%. One method of making this type of coating is by application of a polymer to the surface of a nanofiber, then applying heat to the polymer layer to pyrolyze non-carbon constituents of the polymer, resulting a porous layer at the nanofiber surface. The pores resulting from the pyrolysis of the non-carbon polymer constituents effectively create increased surface area.
A more detailed procedure for preparation of a nanofiber having increased surface area is illustrated at FIG. 9. The procedure consists of preparing a dispersion containing typically graphenic nanofibers and a suitable solvent, preparing a monomer solution, mixing the nanofiber dispersion with the monomer solution, adding a catalyst to the mixture, polymerizing the monomer to obtain a nanofiber coated with a polymeric coating substance and drying the polymeric coating substance. Finally, the coating substance can be pyrolyzed to result in a porous high surface area layer, preferably integral with nanofiber, thereby forming a nanofiber having a high surface area.
A preferred way to ensure that the polymer forms at the fibril surface is to initiate polymerization of the monomers at that surface. This can be done by adsorbing thereon conventional free radical, anionic, cationic, or organometallic (Ziegler) initiators or catalysts. Alternatively, anionoc and cationic polymerizations can be initiated electrochemically by applying appropriate potentials to the fibril surfaces. Finally, the coating substance can be pyrolyzed to result in a porous high surface area layer, preferably integral with nanofiber, thereby forming a nanofiber having a high surface area. Suitable technologies for preparation of such pyrolyzable polymers are given in U.S. Pat. No. 5,334,668, U.S. Pat. No. 5,236,686 and U.S. Pat. No. 5,169,929.
The resulting high surface area nanofiber preferably has a surface area greater than about 100 m2 /g, more preferably greater than about 200 m2 /g, even more preferably greater than about 300 m2 /g, and most preferably greater than about 400 m2 /g. The resulting high surface area nanofiber preferably has a carbon purity of 50%, more preferably 75%, even more preferably 90%, more preferably still 99%.
A procedure for the preparation of nanofiber mats with increased surface area is illustrated at FIG. 10. This procedure includes the steps of preparing a nanofiber mat, preparing a monomer solution, saturating the nanofiber mat with monomer solution under vacuum, polymerizing the monomers to obtain the a nanofiber mat coated with a polymeric coating substance, and pyrolyzing the polymer coating substance to obtain a high surface area nanofiber mat.
As used above, a "coating substance" refers to a substance with which a nanofiber is coated, and particularly to such a substance before it is subjected to a chemically altering step such as pyrolysis. For purposes of electrochemical applications of this invention, it is generally advantageous to select a coating substance which, when subjected to pyrolysis, forms a conductive nonmetallic thin coating layer. Typically, a coating substance is a polymer. Such a polymer deposits a high surface area layer of carbon on the nanofiber upon pyrolysis. Polymer coating substances typically used with this invention include, but are not limited to, phenalic-formaldehyde, polyacrylonitrile, styrene divinyl benzene, cellulosic, cyclotrimerized diethynyl benzene.
In addition to the methods of activation described in the "Methods of Functionalizing Section herein", the term "activation" also refers to a process for treating carbon, including carbon surfaces, to enhance or open an enormous number of pores, most of which have diameters ranging from 2-20 nanometers, although some micropores having diameters in the 1.2-2 range, and some pores with diameters up to 100 nanometers, may be formed by activation.
More specifically, a typical thin coating layer made of carbon may be activated by a number of methods, including (1) selective oxidation of carbon with steam, carbon dioxide, flue gas or air, and (2) treatment of carbonaceous matter with metal chlorides (particularly zinc chloride) or sulfides or phosphates, potassium sulfide, potassium thiocyanate or phosphoric acid.
Activation of the layer of a nanofiber is possible without diminishing the surface area enhancing effects of the high surface area layer resulting from pyrolysis. Rather, activation serves to further enhance already formed pores and create new pores on the thin coating layer.
A discussion is activation is found at Patrick, J. W. ed. Porosity in Carbons: Characterization and Applications, Halsted 1995.
After pyrolysis, or after pyrolysis and subsequent activation, the increased effective surface area of the nanofiber may be functionalized, producing nanofibers whose surface has been reacted or contacted with one or more substances to provide active sites thereon for chemical substitution, physical adsorption or other intermolecular or intramolecular interaction among different chemical species.
Although the high surface area nanofibers of this invention are not limited in the type of chemical groups with which they may be functionalized, the high surface area nanofibers of this invention may, by way of example, be functionalized with chemical groups such as those described below.
According to one embodiment of the invention, the nanofibers are functionalized and have the formula
[Cn HL .paren close-st.Rm
where n is an integer, L is a number less than 0.1 n, m is a number less than 0.5 n,
each of R is the same and is selected from SO3 H, COOH, NH2, OH, O, CHO, CN, COCl, halide, COSH, SH, R', COOR', SR', SiR'3, Si.paren open-st.OR'.paren close-st.y R'3-y, Si.paren open-st.O--SiR'2 .paren close-st.OR', R", Li, AlR'2, Hg--X, TlZ2 and Mg-X,
y is an integer equal to or less than 3,
R' is alkyl, aryl, heteroaryl, cycloalkyl, aralkyl or heteroaralkyl,
R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl,
X is halide, and
Z is carboxylate or trifluoroacetate.
The carbon atoms, Cn, are surface carbons of of the nanofiber or of the porous coating on the nanofiber. These compositions may be uniform in that each of R is the same or non-uniformly functionalized.
Also included as particles in the invention are functionalized nanotubes having the formula
[Cn HL .paren close-st.[R'--R]m
where n, L, m, R' and R have the same meaning as above.
In both uniformly and non-uniformly substituted nanotubes, the surface atoms Cn are reacted. Most carbon atoms in the surface layer of a graphitic material, as in graphite, are basal plane carbons. Basal plane carbons are relatively inert to chemical attack. At defect sites, where, for example, the graphitic plane fails to extend fully around the surface, there are carbon atoms analogous to the edge carbon atoms of a graphite plane (See Urry, Elementary Equilibrium Chemistry of Carbon, Wiley, N.Y. 1989.) for a discussion of edge and basal plane carbons).
At defect sites, edge or basal plane carbons of lower, interior layers of the nanotube or coating may be exposed. The term surface carbon includes all the carbons, basal plane and edge, of the outermost layer of the nanotube or coating, as well as carbons, both basal plane and/or edge, of lower layers that may be exposed at defect sites of the outermost layer. The edge carbons are reactive and must contain some heteroatom or group to satisfy carbon valency.
The substituted nanotubes described above may advantageously be further functionalized. Such compositions include compositions of the formula
[Cn HL .paren close-st.Am
where the carbons are surface carbons of a nanofiber or coating, n, L and m are as described above,
A is selected from ##STR1##
Y is an appropriate functional group of a protein, a peptide, an enzyme, an antibody, a nucleotide, an oligonucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analog of an enzyme substrate or is selected from R'--OH, R'--NH2, R'SH, R'CHO, R'CN, R'X, R'SiR'3, R'Si.paren open-st.OR'.paren close-st.y R'3-y, R'Si.paren open-st.O--SiR'2 .paren close-st.OR', R'--R", R'--N--CO, (C2 H4 O.paren close-st.w H, .paren open-st.C3 H6 O.paren close-st.w H, .paren open-st.C2 H4 O)w --R', (C3 H6 O)w --R' and R', and w is an integer greater than one and less than 200.
The functional nanotubes of structure
[Cn HL .brket open-st.[R'--R]m
may also be functionalized to produce compositions having the formula
[Cn HL .brket open-st.[R'--A]m
where n, L, m, R' and A are as defined above.
The nanofibers of the invention also include nanotubes upon which certain cyclic compounds are adsorbed. These include compositions of matter of the formula
[Cn HL .brket open-st.[X--Ra ]m
where n is an integer, L is a number less than 0.1 n, m is less than 0.5 n, a is zero or a number less than 10, X is a polynuclear aromatic, polyheteronuclear aromatic or metallopolyheteronuclear aromatic moiety and R is as recited above.
Preferred cyclic compounds are planar macrocycles as described on p. 76 of Cotton and Wilkinson, Advanced Organic Chemistry. More preferred cyclic compounds for adsorption are porphyrins and phthalocyanines.
The adsorbed cyclic compounds may be functionalized. Such compositions include compounds of the formula
[Cn HL .brket open-st.[X--Aa ]m
where m, n, L, a, X and A are as defined above and the carbons are surface carbons of a substantially cylindrical graphitic nanotube as described above.
The functionalized nanofibers of the invention can be directly prepared by sulfonation, cycloaddition to deoxygenated nanofiber surfaces, metallation and other techniques. When arc grown nanofibers are used, they may require extensive purification prior to functionalization. Ebbesen et al. (Nature 367 519 (1994)) give a procedure for such purification.
A functional group is a group of atoms that give the compound or substance to which they are linked characteristic chemical and physical properties. A functionalized surface refers to a carbon surface onto which such chemical groups are adsorbed or chemically attached so as to be available for electron transfer with the carbon, interaction with ions in the electrolyte or for other chemical interactions. Functional groups typically associated with this invention include, but are not limited to, functional groups selected from the group consisting of an alkalai metal, --SO3, --R'COX, --R'(COOH)2, --CN, --R'CH2 X, ═O, --R'CHO, --R'CN, where R' is a hydrocarbon radical and X is --NH2, -OH or a halogen. Methods of preparing surfaces functionalized with these and other groups are outlined below.
The nanofibers must be processed prior to contacting them with the functionalizing agent. Such processing must include either increasing surface area of the nanofibers by deposition on the nanofibers of a porous conducting nonmetallic thin coating layer, typically carbon or activation of this surface carbon, or both.
Although several of the following examples and preparations were performed using aggregated nanofibers, it is believed that the same examples and preparations may be performed with non-aggregated nanofibers or other nanofibers.
Background techniques are described in March, J. P., Advanced Organic Chemistry, 3rd Ed. Wiley, New York 1985; House, H., Modern Synthetic Reactions, 2nd Ed., Benjamin/Cummings, Menlo Park, Calif. 1972.
Activated C-H (including aromatic C-H) bonds can be sulfonated using fuming sulfuric acid (oleum), which is a solution of conc. sulfuric acid containing up to 20% SO3. The conventional method is via liquid phase at T˜80� C. using oleum; however, activated C-H bonds can also be sulfonated using SO3 in inert, aprotic solvents, or SO3 in the vapor phase. The reaction is:
Over-reaction results in formation of sulfones, according to the reaction:
Background techniques are described in Urry, G., Elementary Equilibrium Chemistry of Carbon, Wiley, N.Y. 1989.
The surface carbons in nanofibers behave like graphite, i.e., they are arranged in hexagonal sheets containing both basal plane and edge carbons. While basal plane carbons are relatively inert to chemical attack, edge carbons are reactive and must contain some heteroatom or group to satisfy carbon valency. Nanofibers also have surface defect sites which are basically edge carbons and contain heteroatoms or groups.
The most common heteroatoms attached to surface carbons of nanofibers are hydrogen, the predominant gaseous component during manufacture; oxygen, due to its high reactivity and because traces of it are very difficult to avoid; and H2 O, which is always present due to the catalyst. Pyrolysis at -1000� C. in a vacuum will deoxygenate the surface in a complex reaction with an unknown mechanism. The resulting nanofiber surface contains radicals in a C1 -C4 alignment which are very reactive to activated olefins. The surface is stable in a vacuum or in the presence of an inert gas, but retains its high reactivity until exposed to a reactive gas. Thus, nanofibers can be pyrolyzed at -1000� C. in vacuum or inert atmosphere, cooled under these same conditions and reacted with an appropriate molecule at lower temperature to give a stable functional group. Typical examples are: ##STR2## RNS+Maleic anhydride→Nanofiber-R'(COOH)2 RNS+Cyanogen→Nanofiber--CN
RNS+CH2 ═CH--CH2 X→Nanofiber-R'CH2 X X∇--NH2,--OH, -Halogen
RNS+H2 O→Nanofiber═O (quinoidal)
RNS+O2 →Nanofiber═O (quinoidal)
RNS+CH2 ═CHCHO→Nanofiber-R'CHO (aldehydic)
RNS+CH2 ═CH--CN→Nanofiber-R'CN
RNS+N2 →Nanofiber-(aromatic nitrogen)
where R' is a hydrocarbon radical (alkyl, cycloalkyl, etc.)
Background techniques are given in March, Advanced Organic Chemistry, 3rd ed., p. 545.
Aromatic C-H bonds can be metallated with a variety of organometallic reagents to produce carbon-metal bonds (C-M). M is usually Li, Be, Mg, Al, or Tl; however, other metals can also be used. The simplest reaction is by direct displacement of hydrogen in activated aromatics:
1. Nanofiber-H+R-Li→Nanofiber-Li+RH
The reaction may require additionally, a strong base, such as potassium t-butoxide or chelating diamines. Aprotic solvents are necessary (paraffins, benzene).
2. Nanofiber-H+AlR3 →Nanofiber-AlR2 +RH
3. Nanofiber-H+Tl(TFA)3 →Nanofiber-Tl(TFA)2 +HTFA TFA=Trifluoroacetate HTFA=Trifluoroacetic acid
The metallated derivatives are examples of primary singly-functionalized nanofibers. However, they can be reacted further to give other primary singly-functionalized nanofibers. Some reactions can be carried out sequentially in the same apparatus without isolation of intermediates. ##STR3##
A nanofiber can also be metallated by pyrolysis of the coated nanofiber in an inert environment followed by exposure to alkalai metal vapors:
Nanofiber+pyrolysis→Nanofiber (with "dangling"
orbitals)+alkalai metal vapor (M)→Nanofiber-M
The graphenic surfaces of nanofibers allow for physical adsorption of aromatic compounds. The attraction is through van der Waals forces. These forces are considerable between multi-ring heteronuclear aromatic compounds and the basal plane carbons of graphenic surfaces. Desorption may occur under conditions where competitive surface adsorption is possible or where the adsorbate has high solubility.
Literature on the oxidation of graphite by strong oxidants such as potassium chlorate in conc. sulfuric acid or nitric acid, includes R. N. Smith, Ouarterly Review 13, 287 (1959); M. J. D. Low, Chem. Rev. 60, 267 (1960)). Generally, edge carbons (including defect sites) are attacked to give mixtures of carboxylic acids, phenols and other oxygenated groups. The mechanism is complex involving radical reactions.
The number of secondary derivatives which can be prepared from just carboxylic acid is essentially limitless. Alcohols or amines are easily linked to acid to give stable esters or amides. If the alcohol or amine is part of a di- or poly-functional molecule, then linkage through the O- or NH-leaves the other functionalities as pendant groups. Typical examples of secondary reagents are:
______________________________________ PEN- DANTGENERAL FORMULA GROUP EXAMPLES______________________________________HO--R, R = alkyl, aralkyl, R-- Methanol, phenol, tri-aryl, fluoroethanol, fluorocarbon, OH-terminatedpolymer, SiR'3 Polyester, silanolsH2 N--R = same as above R-- Amines, anilines, fluorinated amines, silylamines, amine terminated polyamidesCl--SiR3 SiR3 -- ChlorosilanesHO--R--OH, R = alkyl, HO-- Ethyleneglycol, PEG, Penta-aralkyl, CH2 O-- erythritol, bis-Phenol AH2 N--R--NH2, R = alkyl, H2 N-- Ethylenediamine, polyethyl-aralkyl eneaminesX--R--Y, R = alkyl, etc; Y-- Polyamine amides,X = OH or NH2 ; Y = SH, CN, MercaptoethanolC═O, CHO, alkene,alkyne, aromatic,heterocycles______________________________________
The reactions can be carried out using any of the methods developed for esterifying or aminating carboxylic acids with alcohols or amines. Of these, the methods of H. A. Staab, Angew. Chem. Internat. Edit., (1), 351 (1962) using N,N'-carbonyl diimidazole (CDI) as the acylating agent for esters or amides, and of G. W. Anderson, et al., J. Amer. Chem. Soc. 86, 1839 (1964), using N-Hydroxysuccinimide (NHS) to activate carboxylic acids for amidation were used.
N,N'-Carbonyl Diimidazole
1. R-COOH+Im-CO-Im→R-CO-Im+Him+CO2, Im=Imidazolide, Him=Imidazole ##STR4##
Amidation of amines occurs uncatalyzed at RT. The first step in the procedure is the same. After evolution of CO2, a stoichiometric amount of amine is added at RT and reacted for 1-2 hours. The reaction is quantitative. The reaction is:
3. R-CO-Im+R'NH2 →R--CO--NHR+Him
Activation of carboxylic acids for amination with primary amines occurs through the N-hydroxysuccinamyl ester; carbodiimide is used to tie up the water released as a substituted urea. The NHS ester is then converted at RT to the amide by reaction with primary amine. The reactions are:
1. R-COOH+NHS+CDI→R-CONHS+Subst. Urea
Trialkylsilylchlorides or trialkylsilanols react immediately with acidic H according to:
R-COOH+Cl-SiR'3 →R-CO-SiR'3 +Hcl
Small amounts of Diaza-1,1,1-bicyclooctane (DABCO) are used as catalysts. Suitable solvents are dioxane and toluene.
Sulfonic Acid-Functionalized Nanofibers
Aryl sulfonic acids, as prepared in Preparation A can be further reacted to yield secondary derivatives. Sulfonic acids can be reduced to mercaptans by LiAlH4 or the combination of triphenyl phosphine and iodine (March, J. P., p. 1107). They can also be converted to sulfonate esters by reaction with dialkyl ethers, i.e.,
Nanofiber--SO3 H+R--O--R→Nanofiber--SO2 OR+ROH
Nanofibers Functionalized by Electrophillic Addition to Oxygen-Free Nanofiber Surfaces or by Metallization
The primary products obtainable by addition of activated electrophiles to oxygen-free nanofiber surfaces have pendant --COOH, --COCl, --CN, --CH2 NH2, --CH2 OH, --CH2 -Halogen, or HC═O. These can be converted to secondary derivatives by the following:
Nanofiber-COOH→see above.
Nanofiber-COCl (acid chloride)+HO-R-Y→F-COO-R-Y (Sec. 4/5)
Nanofiber-COCl+NH2 -R-Y→F-CONH-R-Y
Nanofiber-CN+H2 →F-CH2 -NH2
Nanofiber-CH2 NH2 +HOOC-R-Y→F-CH2 NHCO-R-Y
Nanofiber-CH2 NH2 +O═CR-R'Y→F-CH2 N═CR-R'-Y
Nanofiber-CH2 H+O(COR-Y)2 →F-CH2 OR-Y
Nanofiber-CH2 OH+HOOC-R-Y→F-CH2 OCOR-Y
Nanofiber-CH2 -Halogen+Y→F-CH2 -Y+X- Y=NCO-, --OR-
Nanofiber-C═O+H2 N-R-Y→F-C═N-R-Y
Nanofibers Functionalized by Adsorption of Polynuclear or Polyheteronuclear Aromatic or Planar Macrocyclic Compounds
Dilithium phthalocyanine: In general, the two Li+ ions are displaced from the phthalocyanine (Pc) group by most metal (particularly multi-valent) complexes. Therefore, displacement of the Li+ ions with a metal ion bonded with non-labile ligands is a method of putting stable functional groups onto nanofiber surfaces. Nearly all transition metal complexes will displace Li+ from Pc to form a stable, non-labile chelate. The point is then to couple this metal with a suitable ligand.
Cobalt (II) Phthalocyanine
Cobalt (II) complexes are particularly suited for this. Co++ ion can be substituted for the two Li+ ions to form a very stable chelate. The Co++ ion can then be coordinated to a ligand such as nicotinic acid, which contains a pyridine ring with a pendant carboxylic acid group and which is known to bond preferentially to the pyridine group. In the presence of excess nicotinic acid, Co(II)Pc can be electrochemically oxidized to Co(III)Pc, forming a non-labile complex with the pyridine moiety of nicotinic acid. Thus, the free carboxylic acid group of the nicotinic acid ligand is firmly attached to the nanofiber surface.
Other suitable ligands are the aminopyridines or ethylenediamine (pendant NH2), mercaptopyridine (SH), or other polyfunctional ligands containing either an amino- or pyridyl-moiety on one end, and any desirable function on the other.
Further detailed methods of functionalizing nanofibers are described at U.S. patent application Ser. No. 08/352400 filed on Dec. 8, 1994 for FUNCTIONALIZED NANOTUBES, incorporated herein by reference.
The coated nanofibers of this invention can be incorporated into three-dimensional catalyst support structures (see U.S. patent application for RIGID POROUS CARBON STRUCTURES, METHODS OF MAKING, METHODS OF USING AND PRODUCTS CONTAINING SAME, filed concurrently with this application, the disclosure of which is hereby incorporated by reference).
High surface area nanofibers or nanofiber aggregates or assemblages may be used for any purpose for which porous media are known to be useful. These include filtration, electrodes, catalyst supports, chromatography media, etc. For some applications unmodified nanofibers or nanofiber aggregates or assemblages can be used. For other applications, nanofibers or nanofiber aggregates or assemblages are a component of a more complex material, i.e. they are part of a composite. Examples of such composites are polymer molding compounds, chromatography media, electrodes for fuel cells and batteries, nanofiber supported catalyst and ceramic composites, including bioceramics like artificial bone.
Various carbon coating structures have also been used in the manufactutre of batteries. Currently available lithium ion batteries use an intercalatable carbon as the anode. The maximum energy density of such batteries corresponds to the intercalation compound C5 Li, with a specific capacity of 372 A-hours/kg. A recent report by Sato, et al. (Sato, K., et al., A Mechanism of Lithium Storage in Disordered Carbons, Science, 264, 556 (1994) describes a new mode of Li storage in carbon that offers the potential for significant increases in specific capacity. Sato, et al. have shown that a polymer derived disordered carbon is capable of storing lithium at nearly three times the density of intercalate, i.e., C2 Li, and appears to have measured capacities of 1000 A-hours/kg.
These electrodes are made by carbonization of polyparaphenylene (PPP). PPP polymers have been previously synthesized and studied both because they are conducting and because they form very rigid, straight chain polymers interesting as components of dual polymers self reinforced systems. NMR data suggests that the resulting carbon is mainly condensed aromatic sheets, but x-ray diffraction data suggests very little order in the structure. The intrinsic formula is C2 H.
Although possibly useful, the reference is insufficient data to compute all the key parameters of this electrode. Additionally, one suspects from the synthesis and from the published electron micrographs that the electrodes so produced are quite dense with little porosity or microstructure. If so, one would anticipate a rather poor power density, which cannot be deduced directly from the paper.
Finally, it is clear that at least two modes of Li storage are operative, and one is the classic intercalate C6 Li. The net achieved is about C4 Li. Depending on what one postulates is the way of alternative structures and how trusting one is of the deconvolution, different ratios of C6 Li and the denser storage species can be calculated. Clearly, however, a more selective storage of the desired species would lead to a higher energy density.
Another aspect of the invention relates to electrodes for both the anode and cathode of the lithium ion battery. Ideally, both electrodes will be made from the same starting material--electrically conductive pyrolized polymer crystals in a porous fibril web. By imposing the high surface area of the fibrils on the system, of higher power density associated with increased surface is achievable.
The anode chemistry would be along the lines described by Sato, et al. Cathode chemistry would be either conventional via entrapped or supported spinel or by a redox polymer. Thus, preparation of both electrodes may begin with a polymerization.
According to one embodiment, the electrodes would be produced by electropolymerization of PPP on a preformed fibril electrode. PPP was first grown electrochemically on graphite by Jasinski. (Jasinski, R. and Brilmyer, G., The Electrochemistry of Hydrocarbons in Hydrogen Fluoride/Antimony (V) fluroide: some mechanistic conclusoins concerning the super acid "catalyzed" condensation of hydrocarbons, J. Electrochem. Soc. 129 (9) 1950 (1982). Other conductive polymers like polypyrrole and polyaniline can be similarly grown. Given the uncertainty as to the optimum disordered carbon structure described by Sato, et al., and considering redox polymer cathodes, this invention embodies making and pyrolizing a number of materials and compare their carbonization products to. pyrolized PPP.
It is possible to electropolymerized pyrrole in situ in performed fibril mat electrodes to form fibril/polypyrrole polymer composites. The polypyrrole becomes permanently bound to the fibril mat, although the uniformity of coverage is not known. Electrochemical measurements do demonstrate that electrode porosity is maintained, even at high levels of polypyrrole deposition. Importantly, both the amount and rate of deposition can be controlled electrochemically.
Beside conductive polymers that can be electropolymerized, other high C/H polymers are also of interest. One candidate family, of particular interest as cathode materials, can be formed by oxidative coupling of acetylene by cupric amines. The coupling has usually been used to make diacetylene from substitute acetylene:
Acetylene itself reacts to uncharacterized intractable "carbons". The first reaction product must be butadiyne, HC═C--C═CH which can both polymerize and loose more hydrogen by further oxidative coupling. Systematic study of the effect of reaction variables could lead to conductive hydrocarbon with high H/C ratios for the cathode material. It may be possible to make products with high content of the ladder polymer, (C4 H2). Cyanogen, N═C--C═N, for example, readily polymerizes to intractable solids believed to consist mostly of the analogous ladder. Syntheses via organometallic precursors are also available.
Like the pyrolyzed conductive polymers, these acetylenics may be pyrolized and evaluated against pyrolized PPP, but primary interest in this family of materials is oxidation to high O/C cathode materials.
The structural features in Sato et al.'s pyrolized PP which make possible lithium loadings as high as C2 Li are not known. There is some evidence that the extra lithium beyond C6 Li is stored in small cavities in the carbon or some could be bound to the edge carbons already carrying hydrogens in C4 H.
It is possible to vary both polymerization and pyrolysis conditions on PPP and to screen other pyrolized conductive polymer/fibril composites for ability to store lithium. A more controlled polymerization could result in a greater selectivity for C2 Li. The preferable embodiment is a host carbon which forms C2 Li on charging with minimum diffusional distance and hence high charge and discharge rates.
Pyrolysis variables include; time, temperature and atmosphere and the crystal dimension of the starting PPP or other polymer. Fibrils are inert to mild pyrolysis conditions.
There are two distinct paths to nanotube based cathodes consistent with increased power density: redox polymer cathodes, which have the potential to further improve energy density as well as power density and conventional spinel chemistry carried out on a nanoscale on small "islands" of electroactive material inside a fibril mat electrode.
To form the cathode, the PPP may be oxidized anodically in strong acid containing small amounts of water using conditions which form graphite oxide without breaking carbon-carbon bonds. The preferred embodiment outcome would be conversion of PPP molecules to (C6 O4)n where n is the number of phenylene rings in the original polyphenylene.
If the single carbon-carbon bonds in the PPP are broken in the oxidation, it will be necessary to find the minimum conditions for carbonization of the PPP which permits the anodic oxidation without destroying the carbon-carbon network.
Sato, et al. describe a pyrolysis product whose composition was (C4 H2)n. This may not be optimum for the cathode where the goal is maximizing the number of oxides which replace H in the anodic oxidation because these will be quinonic oxygens. The potential of analogous quinone/hydroquinone complexes is ca. one volt--comparable to the Mn+3 /Mn+4 couple in spinels.
The coated nanofibers of this invention can be incorporated into capacitors (see U.S. patent application for GRAPHITIC NANOTUBES IN ELECTROCHEMICAL CAPACITORS, filed concurrently with this application, the disclosure of which is hereby incorporated by reference).
The coated nanofibers of this invention can be incorporated into rigid structures (see U.S. patent application for RIGID POROUS CARBON STRUCTURES, METHODS OF MAKING, METHODS OF USING AND PRODUCTS CONTAINING SAME, filed concurrently with this application, the disclosure of which is hereby incorporated by reference).
The terms and expressions which have been employed are used as terms of description and not of limitations, and there is no intention in the use of such terms or expressions of excluding any equivalents of the features shown and described as portions thereof, its being recognized that various modifications are possible within the scope of the invention.
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19 May 2015Worldwide there is a population flow from the countryside into cities. Huge new urban agglomerations arise, slums grow in the remaining open spaces.Megacities merge into megaregions with over 100 million inhabitants.
08 May 2015DFD in Neustrelitz was the first station worldwide outside the ESA core ground segment to acquire and process Sentinel-1 data.The radar data from this Copernicus satellite are being processed in near-real-time and used by DLR's Maritime Safety Research Department in Neustrelitz and Bremen for such purposes as the automatic detection of ships and oil leaks and to derive wind, wave and ice parameters. The undergirding development work is being co-financed by the Federal Ministry of Economic Affairs and Energy and the State of Mecklenburg-Western Pomerania.
06 May 2015EOC scientist Dr. Xiaoxiang Zhu has been awarded the DFG's Heinz Maier-Leibnitz Prize for 2015 in Berlin on 5 May 2015.
30 April 2015EOC scientists have used data acquired by Sentinel-1 satellite to calculate the ground displacements caused by the earthquake. The analysis shows surface displacements of several meters for a more than 90-kilometre-long and 30-kilometre-wide area around Kathmandu.
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I've been trying to implement a function in C that deletes a node in a binary tree that should (theoretically) take care of three all cases, i.e.:
- Node is a leaf
- Node has one child
- Node has two children
Is there a way to handle the whole deletion function without checking separately each case? As a commenter below noted I do check for a lot of cases and perhaps the whole problem can be addressed recursively by checking for one fundamental case.
I'm particularly interested in the case where I delete a node within the tree that has a parent and itself is a parent of two children nodes.
Both answers below have been useful but I don't think they address the problem in its entirety.
Here's what I have:
typedef struct Node
int key;
int data;
struct Node *left;
struct Node *right;
struct Node *parent;
} Node;
/* functions that take care of inserting and finding a node and also traversing and freeing the tree */
void delete(Node *root, int key)
Node *target = find(root, key); // find will return the node to be deleted
Node *parent = target->parent; // parent of node to be deleted
// no children
if (target->left == NULL && target->right == NULL)
// is it a right child
if (target->key > parent->key)
parent->right = NULL;
// must be a left child
parent->left = NULL;
// one child
else if ((target->left == NULL && target->right != NULL) || (target->left != NULL && target->right == NULL))
// here we swap the target and the child of that target, then delete the target
Node *child = (target->left == NULL) ? target->right : target->left;
child->parent = parent;
if (parent->left == target) parent->left = child;
else if (parent->right == target) parent->right = child;
// two children
// find the largest node in the left subtree, this will be the node
// that will take the place of the node to be deleted
Node *toBeRepl = max(target->left);
// assign the data of the second largest node
target->key = toBeRepl->key;
target->data = toBeRepl->data;
// if new node immediately to the left of target
if (toBeRepl == target->left)
target->left = toBeRepl->left;
Node *newLeft = target->left;
if (newLeft != NULL) newLeft->parent = target;
delete(target->left, toBeRepl->key);
// Node *replParent = toBeRepl->parent;
// replParent->right = NULL;
I would greatly appreciate your feedback.
Many thanks in advance!
edit: Just to clarify, I'm trying to delete a particular node without touching its subtrees (if there are any). They should remain intact (which I've handled by swapping the values of the node to be deleted and (depending on the case) one of the nodes of its substrees).
edit: I've used as a reference the following wikipedia article:
Which is where I got the idea for swapping the nodes values in case of two children, particularly the quote:
Call the node to be deleted N. Do not delete N. Instead, choose either its in-order successor node or its in-order predecessor node, R. Replace the value of N with the value of R, then delete R.
There is some interesting code in C++ there for the above case, however I'm not sure how exactly the swap happens:
else //2 children
temp = ptr->RightChild;
Node<T> *parent = nullptr;
parent = temp;
temp = temp->LeftChild;
ptr->data = temp->data;
if (parent!=nullptr)
Could somebody please explain what's going on in that section? I'm assuming that the recursion is of a similar approach as to the users comments' here.


text:
Originally written on BlackSportsOnline | Last updated 11/13/14
I thought Devin Hester was a decent wide receiver, I have seen worst in the NFL, but new coach Marc Trestman wants him to concentrate on special teams. I think that is a mistake, because Hester is a playmaker, so limiting his touches, isn't going to help the Bears any. Pro Football Zone has the details. Trestman said at the league meeting today that he views Hester as a return man, not a wide receiver. As a result, Trestman said, Hester will be spending his time in practice working with the special teams. Although Trestman hasn't totally ruled out Hester playing some receiver, he said he's not even sure if Hester will practice with the wide receivers this season, let alone play with them.
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text: Clinical Trials Search Results Initial search results include only NCI-sponsored clinical trials. To search all trials, click the "REFINE SEARCH" button, scroll down to the Trial ID/Sponsor section and select the "All" check box in the Sponsor of Trial section. View Content for: Patients Health Professionals Display: Title Description with: Locations Eligibility Full Trial Description Custom ? Hide Search Criteria Show Search Criteria Drug: sphingosine kinase-2 inhibitor ABC294640Find trials that include: Any drugs shownTrial Status: Active Results 1-1 of 1 for your search: Start Over Select All on Page Sort by: Phase of Trial Title Type of Trial Status of Trial Age Range Sponsor of Trial Protocol IDs Show 10 25 50 100 200 Results per Page 1. An Early-Phase Clinical Trial Evaluating ABC294640 in Patients With Refractory/Relapsed Diffuse Large B-cell Lymphoma Phase: Phase II, Phase IType: Biomarker/Laboratory analysis, TreatmentStatus: Approved-not yet activeAge: 18 and overSponsor: Pharmaceutical / IndustryProtocol IDs: ABC-102, NCT02229981 Select All on Page Start Over


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Finally, a different picture is emerging of the former New York City mayor.
Imagine a camera aimed at a human face forever.
Talking heads like former General Jack Keane are all over the news media fanning fears of IS. Shouldn't the public know about their links to Pentagon contractors?
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As the online behemoth strengthens its monopoly over the marketplace, publishers, like bookstores, are in a fight for survival.