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Filings with the Securities and Exchange Commission have disclosed that two insiders at Newcastle Investment (NCT) each purchased close to 100,000 shares of the company's stock at an average price of $10.48 in a public offering this month. Randal Nardone, who serves as the company's secretary, was one of the buyers. Nardone had previously bought shares at an average price of $9.35 in January and at $6.70 last July.
Newcastle is up 25% year to date and over 100% in the last year, and the current stock price is $11.20. Insider purchases, particularly when multiple insiders are buying the stock, are often seen as bullish signals. We believe that they at least serve as a sign of higher-than-average confidence in the company, since by buying more shares an insider increases his or her exposure to the company and therefore to company-specific risks, rather than diversifying, as economy theory would generally predict.
Newcastle is a $1.9 billion market cap real estate investment trust that invests in securities backed by mortgages and real estate assets. Real estate investment trusts receive favorable tax treatment that is conditional on returning a large portion of their taxable income to shareholders. Consequently, they often have high dividend yields. Newcastle, for example, has made dividend payments of $0.22 per share in the last two quarters; annualized, that makes for a 7.8% yield at current prices. In addition, the company has recently been increasing its dividend payments -- a year ago, it was paying only $0.15 per share each quarter -- and so there is the prospect of further increases.
Of course, given Newcastle's line of business, it's not surprising that it performed very poorly during the financial crisis (and would be expected to be vulnerable to any troubles in the real estate market in the future). Dividend payments are still significantly down from where they were in the mid-2000s ($0.72 per share for most of 2007), and even after the recent rally, the stock price is just getting back to where it was at the beginning of 2008. Of course, the S&P 500 isn't much above its levels from January 2008 either.
In statistical terms, Newcastle has a beta -- a coefficient that measures a stock's volatility relative to that of the overall market -- of 2.2. So while there is quite a bit of attractiveness from an income perspective, perhaps enough to overcome any macro concerns, investors should be aware of the downside risk and be sure not to expose too much of their portfolio to the real estate market (particularly if owned property, the value of which would also fall in a housing collapse, makes up a large share of their wealth).
High yields are common among REITs that invest in mortgage-backed securities. Annaly Capital Management (NLY) is one of the most popular names in the industry, and it offers a dividend yield of about 12% at current prices and dividend levels. Annaly has similar vulnerabilities, though its stock price dropped only about 30% during the financial crisis and has now fallen back to that same level rather than rally as Newcastle has. Peers such as American Capital Agency (AGNC) and NorthStar Realty Finance (NRF) might be good candidates as well.
Despite the high dividend payments, REITs that invest in mortgage-backed securities are not appropriate for all investors. If the risks are not too steep, however, then we certainly can't deny that dividend yields of up to 10% or even higher are quite attractive. As part of an income portfolio that also includes a number of defensive stocks with high yields -- such as megacap consumer staples or pharmaceutical companies -- they could make for good prospects.
Newcastle does have a lower yield than some of its peers, but since insiders are buying the stock even after a run-up in the price, the company may be seen as more likely to provide capital gains as well or at least less likely to encounter operating problems in the short run.

subset: commoncrawl


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Firefox Pop-up Blocker Bug
Posted by Oscar M. Cantu Categories: Internet,
One thing that gives Firefox its mass appeal is it's solid pop-up blocker. Now Mozilla's pop-up blocker is being challenged. There are some websites that have found a way around the blocker after its first pop-up is blocked. One such website is Ngemu.com; Firefox and Mozilla will both block the first pop-up, however after the user clicks on a link such as "XBOX", a pop up appears. Bugzilla's website contains a bug report of the problem including the source code for the work around.
Read More | Bugzilla
New XBOX 360 Information
Posted by Oscar M. Cantu Categories: Video Games,
There are two new rumors floating around about Microsoft's next generation gaming console. According to The Inquirer, the XBOX 360 will come standard with wireless controllers. Hopefully the battery life will be improved as well. We can probably expect Sony to follow in the same path. The next rumor involves the XBOX 360's GPU. Of course this information, just like the rest, is not yet confirmed, but here are the specs:
- 24 Pipelines
- 32 Texture Units
- 96 Arithmetic Logic Units (ALU)
- 192 Shader Operations per Cycle
- 700MHz Core
- 134.4 Billion Shader Operations per Second (at 700MHz)
- 256-bit 512MB 1.8GHz GDDR3 Memory
- 57.6 GB/sec Bandwidth (at 1.8GHz)
- 300-350 Million Transistors
- 90nm Manufacturing
- Shader Model 3.0
- ATI HyperMemory
- ATI Multi Rendering Technology (AMR)
- Launch: Q2 2005
- 16x stochastic FSAA
- FP32 blending, texturing
- Programmable Primitive Processor/Tesselator
As you can see, the next XBOX will have a very powerfull GPU. With performance higher than a Radeon X800, we can assume the XBOX 360 to put a very big dent on our wallets - that is, of course, if the source that reported this information is correct.
Read More | Joystiq
Read More | The Inquirer
Tune Your Car with a Gameboy Advance
Posted by Hector Martinez Categories: Mods / Hacks, Software,
Finally someone has invented a way for us to continue using our GBA, in light of the DS and the upcoming PSP. It's called the DTEC, by TurboXS. The DTEC plugs into your handheld and comes preloaded with software that lets you use your Gameboy to gauge exhaust gas temperature, air temperature, and vehicle boost, among other things. You can also purchase additional sensors and hardware to monitor other systems, like knock indication and vehicle acceleration (ie. G-Force). But check out the DTEC hardware that actually needs to plug into your GBA. Talk about unwieldly. Coming in October to an obsolete GBA near you.
Read More | TurboXS.com
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Free Mobile Web Hack on Verizon Wireless
Posted by Andru Edwards Categories: Smartphones,
Check it out, you can now use Mobile Web on your Verizon Wireless phone, and not pay the $4.99 per month charge to Verizon to do so. In fact, this is a perfectly legal alternative, because you are simply using a different server than the one Verizon Wireless provides. This hack works for any Verizon Wireless phone that supports Mobile Web 1.0 - 2.0. All you need to do is go into the setup menu and make a couple of changes.
Read More | MobileWEB4U
EDIT: I should have been more clear. Use MobileWEB4U to find out how to access the appropriate menu on your phone where you change servers. Once you find the menu, enter a proxy server. You can find one at http://www.publicproxyservers.com.
You must also enter both the proxy server address as well as the port it uses. If you don't have both, it won't work.
Who's Buying Up iPods?
Posted by Hector Martinez Categories: Portable Audio / Video,
CNET News has put up some interesting facts regarding MP3 player purchases in America. According to a study carried out by the non-profit Pew Internet & American Life Project, those who are younger, wealthier and use the Internet are more likely to own such gadgets. It also helps to if you're a guy. Here are the findings: While one in five people under the age of 30 have an iPod or other MP3 player, the number drops to one in seven in the 30-to-48 age group. Similarly, about 25% of people with household incomes of $75,000 or more owned such gadgets. That figure dropped to 10% for those in the $30,000 to $74,999 range and to 6 percent among those earning less than $30,000. The study also found that those who use the Internet are four times as likely as non-Internet users to have MP3 players. Finally, men have a 50 percent greater chance than women of owning a digital media player.
Read More | CNET
House Keys May Soon Become Extinct
Posted by Hector Martinez Categories: Misc. Tech,
Residential door hardware companies will soon be shifting to radio-signal devices, if it follows the trend in the automotive industry, experts say. Consider the 2006 Lexus GS sport sedan, on sale next month. USA Today reports that when a driver carrying an electronic fob steps within a few feet of the GS, the doors or trunk can be opened without a key. Of course, there are already naysayers that claim the system is hackable, though Texas Instruments claims that there has never been a security breach. The article also cites the similar example of hotels, which now almost exclusively use electronic cards for room entry. Yeah, except for when a magnetic device in your pocket renders the card useless and you're stuck outside. Still, the concept of electronic house keys may yet be an inevitable evolution of our way of life.
Read More | USA Today
Mobile TV Approaching Reality for US Via Action Engine
Posted by Hector Martinez Categories: Smartphones, Portable Audio / Video,
While channels will initially be limited, Action Engine is taking some steps in providing on-the-go TV content - at least on Windows Mobile handsets - for the US. Their service is basically Internet TV that streams video via a Windows Media Server, which is different from handsets that feature a built-in analogue tuner. Currently, Windows Media is restricted to certain content providers, in this case Amazon.com, eBay, FOX Sports, and the Microsoft MapPoint Team. Developer SmartVideo is looking to expand the content to include other national programmers like MSNBC and CNBC, ABC News and ABC News Now, The Weather Channel and DIC Entertainment.
Read More | MobileMag
Internet Explorer 7 Beta
Posted by Oscar M. Cantu Categories: Internet, Software,
Microsoft plans to release a new version of Internet Explorer this summer as a beta edition. Bill Gates claims that this new version will have stronger built-in security features, but how many times have we heard that? This announcement came after rumor on the web was that Microsoft would not upgrade IE before the release of Longhorn. Sticking with the whole security thing, it looks like this beta will require XP SP2 in order to be installed. Can the software giant succeed in convincing ex-IE users to switch back? If Microsoft continues to shun tabbed browsing, I don't care how far along they come in the security department. It's a no.
Read More | IEBlog
Corsair XMS Xpert Glowing Memory
Posted by Categories: Peripherals,
Corsair appears to have decided that there just aren't enough things flashing and glowing inside of PC mod boxes these days. Their new XMS Xpert memory sticks have LED panels, which displays information and statistics about the memory in the box on a scrolling marquee and power meter. Aside from the glowing sign mounted on top of the sticks, the Corsair DDR400 memory that lurks below is familiar to us all. From its 2-2-2 ultra low latency timings to the Corsair lifetime warranty it all seems to be on the up and up. The 1 GB memory stick covers 2 DIMM slots, but you can fit another non-Xpert stick underneath the LED panel.
Read More | Corsair
Special Edition Blue Pepsi Nintendo DS
Posted by Andru Edwards Categories: Video Games,
Once again, the Japanese get all the fun when it comes to special edition products. This time, it comes in the form of a metallic blue Nintendo DS that is part of a co-promotion between Nintendo and Pepsi in conjunction with the Japanese launch of Pepsi Twist. What the hell, Pepsi? All we get here in the U.S. is free music that is DRM'd to the point that it can only be played on one portable device!
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- Bushing Set For Magnum Bullet Cartridge Pen
The use of the correct bushing set on your pen mandrel makes pen making and turning project kits an easy process. Simply use the bushings on the mandrel as a reference to turn your blanks down to the correct diameter.
Used on Magnum Bolt Action Pen Kit: 101649.


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This November, the Twilight franchise will end once and for all with Breaking Dawn: Part 2. Unhappy about losing their cash cow, Lionsgate is allegedly furiously looking for a way to keep the $2-billion franchise afloat, even if that means redoing the entire thing with a whole new cast.
Bloody Disgusting reports that the studio is "already discussing it internally. It will happen." But they're not sure what form the new Twilight movies will take ("It could be a direct remake [...] but then again it could also be a spinoff or maybe even a one-off sequel.")
Deadline followed up this news by contacting the studio and reporting that the rumor was false. This prompted Bloody Disgusting to update their headline as follows, "Update: Lionsgate Plans On Remaking 'Twilight.' It's True. They'll Deny It. But It's True." Ha!
Do we need more dour 107-year-old adults in heartthrob bodies befriending boringly average teenagers and lurking around America's public schools? Goodness, no. But we tend to agree with Bloody Disgusting — there's no way people will stop milking this cash cow.
Lionsgate Co-Chairman Rob Friedman further told Deadline, "We are not remaking Twilight. We will happily support Stephenie Meyer if she decides to proceed in any way. But this will be the last one unless that should change." Who do you believe? Before Deadline posted their debunking, Bloody Disgusting said that the studio would "deny it, right here, right now. We'll get plenty of eggs in our face. Sites will burn us at the stake like a witch during the Salem trials. Still, the fact will remain: it's true."


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Vanguard says that it recently started letting retirement plan investors make transactions on mobile devices and updating them on the status of these transactions by text messaging.
The fund giant, which shared news of the move on Monday, also notes that it is one of the first in the industry to offer investors such tools.
As of May, nearly 20% of Vanguard's online business with retirement plan investors now takes place via a mobile device versus 4% in January 2011. Six months ago, Vanguard started a text-messaging service that is now used by about 30% of investors who work on their accounts online.
"Retirement-plan participants are increasingly using mobile devices, and Vanguard's mobile transaction and text messaging services lets them manage their accounts the way they want to manage them," said Amy Cribbs, head of Vanguard Participant Experience, in a press release.
Retirement-plan investors can, for instance, change their contribution levels, switch fund investments, changing their portfolio mix and rebalance their holdings. In addition, they may use Vanguard's mobile app for actions like checking account balances and performance data or reviewing transactions and account statements.
"Vanguard's mobile users tend to be very engaged in long-term planning and investing, and we expect that the mobile transaction capabilities will be used as an added convenience," Cribbs added.
The company manages more than $2.2 trillion in U.S. mutual fund assets. It recently adjusted the benchmarks of 22 of its 160 index and actively managed funds sold to U.S. investors to lower costs paid by investors. It also provides investments to nearly 4,000 defined-contribution plan.
According the industry group ICI, total U.S. retirement assets now top $20.5 trillion; assets in individual retirement accounts stand at about $5.7 trillion, and those in defined-contribution plans at $5.4 trillion.
Check out Retirement Assets Continue to Recover: ICI on AdvisorOne.


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Disruptors EOD in Wales
Members with this Capability
General Dynamics UK Limited
General Dynamics United Kingdom has two primary lines of business: Land Systems and Mission Systems.
General Dynamics UK works in partnership with the United Kingdom Ministry of Defence (MoD) providing the nation's primary land capabilities including, amongst others, Bowman, the British Armed Forces tactical communications programme, and AJAX, the replacement for the British Army's reconnaissance vehicle fleet.
The Company also delivers avionics equipment used in rotary and fixed wing platforms, highly integrated mission and video management systems, flexible stores management systems, data link processing and video and data recorders for UK and international customers.
Established in the UK for more than 50 years, General Dynamics UK has three world-class facilities in the UK, including two in South Wales, with more than 1,000 highly skilled members of the team.
Capabilities: Cabin management systems,equipment; Aircraft components; AS 9100; Communication systems,equipment; NATO , MoD approved; ISO 9001; ITAR approved; ISO 9001:2003; Avionics; Navigation systems,equipment; Security systems; Labelling systems and services; ASD CIS for Anti Corruption; IPC 610 Class 2; FAA approved; UK Anticorruption Forum; JAR approved; Data communication; Highways,links; Data network; Tank,track vehicles and components; Hardware design; Software modelling; Stock control; Processing systems,equipment; Availability services; Contract pricing,negotiating,bidding; Software design; Intercommunication equipment; Software testing and validation; Command,control systems; Degaussing; Infantry training; Sighting systems,equipment; Recording systems,equipment; Armoured; Electro optical equipment and engineering; Explosive detection systems,equipment; RF components and sub systems; Displays; Air defence simulation; Army training courses; Firearms simulation; EMC,Tempest products; Webbing; Proposal, tender preparation; Microphones,broadcast equipment; Disruptors EOD; Barcode systems,equipment; Asset tracking,management; Computer modelling; Protection,security systems,equipment; Life cycle costing; Fleet management systems; Integrated systems; Perimeter protection,security; Obsolescence management; EMC,Tempest design; Tagging systems asset,vehicle; Communications; Cell-site analysis; Communication installation,integration; Cameras systems,equipment; Homeland security training; Installations; Radio,video carrying systems; Installation design, intergration,certification; Auction,disposal; Enhancements systems,equipment


text: Human Geographies - Journal of Studies and Research in Human Geography was first published in 2007 to provide an international forum of social, economic and cultural contributions to the fields of human geography. It is a peer-reviewed journal, has both online and print versions and ISSNs. It represents the initiative and effort of the members of the Human Geography Department, Faculty of Geography from University of Bucharest. Human Geographies is committed to publish scholarly research and informed commentaries on a wide category of human geography aspects (including urban and rural issues, demography, social, economic and cultural environment), place issues, and space issues. It welcomes contributions from the growing numbers of scholars and practitioners across geography, humanities and social and environmental sciences who are interested in human, economic and cultural geographies.


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Friday September 28, 2007 2:55 pm
Man files $5 billion suit against Google
Citing claims of privacy invasion and terrorisim, a one Dylan Jayne has filed a (handwritten) suit against Google. Mr. Jayne (who gives one of our favorite Firefly characters a bad name) seems a bit off his rocker on this one. He states that not only has Google failed to fight terrorisim, but they also seem to have invaded his privacy as indicated by the following statement: "I, Dylan Stephen Jayne, plaintiff, has [sic] a social security number that when the social security number is turned upside down in its entirety it is a scrambled code that does spell the name Google®."
Last time I checked Google's business model didn't seem to cover stopping terrorism, leaving that job to the 'professionals' over at Homeland Security. His claims of privacy invasion also seem a little far fetched - it's hard to think a fortune 100 company would pick it's name based soley on the Social Security number of a lone loser from Pennsylvania.
In a way it's a sad statement about the United States legal system that a case like this will even be heard by a judge. If Mr. Jayne can't even be bothered to type up his Complaint can he really be considered compentent enough with computers to really even understand what exactly it is that Google does? Check out the Ars Technica article for more information on this weird little case and keep your eyes peeled here late breaking news as it percolates through the Justice system.
Read More | Ars Technica
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June 28, 2010
Steven Blair, Ph.D, will be visiting UAB from February 14-16, 2011 as part of the Pfizer Visiting Professorship in Obesity program. Dr. Blair is a Professor at the Arnold School of Public Health at the University of South Carolina. His research focuses on the associations between lifestyle and health, with a specific emphasis on exercise, physical fitness, body composition and chronic disease. He has published over 460 papers and chapters in the scientific literature, and is one of the most highly cited exercise scientist, with over 24,000 citations to his work.
During his February visit, Dr. Blair will make multiple presentations with regards to obesity. Topics include Physical Inactivity: The Biggest Health Problem of the 21st Century; Fitness and Fatness: Which is More Important to Health Outcomes; and Exercise is Medicine. He will also meet extensively with UAB faculty and students to share information and research in their respective fields.
Dr. Donna K. Arnett, NORC Member and Chair of Epidemiology, was awarded the 2010 Pfizer Visiting Professorship in Obesity award.


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For anyone who's become addicted to any kind of drug, whether prescription drugs or alcohol, one of the most effective ways of recovering is with the assistance of a Franklin drug detox program and rehab program, which can help make the transition to lasting sobriety possible. Addiction treatment programs in Franklin and Muskego have proven to be among the most effective solutions for severe cases of addiction. Understanding more about these programs and all of the types of treatments they include can be very helpful when selecting from the many Franklin inpatient drug detox centers that are available.
Franklin Addiction Treatment Programs
The first facet of any addiction program in Franklin, Greendale or Greenfield is detoxification. This is the process of ridding any drug from the body, including everything from cocaine to methamphetamine. Unfortunately, when a person becomes addicted to a substance, the body and mind become dependent on it in order to function properly, which means that a wide array of withdrawal symptoms can present themselves when the drug is absent. Without assistance, these withdrawal symptoms can be very severe, leading to a wide range of additional health complications if not immediately addressed. The best way to reduce the severity of these withdrawal symptoms and safely overcome them is with a Franklin drug detox program.
Alongside detox programs, there are a variety of additional addiction treatment programs that will help to facilitate an eventual recovery from the worst aspects of drug addiction, whether the dependence is to cocaine or alcohol. Most addiction programs include one-on-one therapy, group counseling, and family therapy.
Each of these behavioral therapies is designed to help someone recovering from an addiction get to the point where he or she no longer feels beholden to drugs and can envision living a life without drugs in it. The two basic forms of addiction treatment include inpatient treatment and outpatient rehabilitation, both of which offer their own unique advantages.
Franklin Intensive Outpatient Addiction Treatment
An inpatient center will give the patient full-time live-in care, while intensive outpatient care allows the individual to visit the treatment center on a regular basis. Intensive outpatient treatment provides the patient with the ability to stay at home and follow his or her own schedule while the treatment is ongoing, continuing with their normal lives and responsibilities while getting the help they need.
There are plenty of Franklin inpatient drug detox centers and outpatient centers from which to choose. Call our addiction specialists today to find the ideal detox program for prescription drugs or methamphetamine.
Franklin Inpatient Drug Rehab
Inpatient drug rehab in Franklin or Greenfield is among the most comprehensive forms of drug addiction treatment and is designed for those who are suffering from a severe addiction to any drug, including cocaine and methamphetamine. Inpatient rehabilitation differs from outpatient treatment in that patients stay within the residential facility continuously until the treatment is concluded, which can be anywhere from a month to more than a year depending on the patient's exact needs. Throughout treatment, both the staff and other residents recovering from an addiction will assist in helping the patient's attitudes and behaviors towards their drug of choice change for good. To find the right drug rehab center in Greenfield or the nearby areas, contact us today.


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At Norwood-Fontbonne Academy, parents are more than just a mom and dad.
During a recent Career Week, students learned first-hand from parents, who volunteered to speak to first graders about their careers, just how important reading, writing, math, and other skills are to their future dreams.
"My hope is that these young minds will make the connection between what they learn in school and how it helps them to build a foundation for reaching their potential and realizing their dreams," explained Lauren Pesavento, NFA first grade teacher.
Rebekah Davis, who is a neonatal Intensive Care nurse at Children's Hospital, had just returned from a medical mission trip to Guatemala prior to her presentation to the class. Dressed in her scrubs, she pulled various items from her nurse kit, such as a stethoscope, calculator, and vein finder, explaining the use of each instrument.
"The calculator helps me determine how much medicine to give a baby based on its weight," said Davis, a parent of a first grader at the school.
Davis said math skills are needed to weigh the baby and to calculate medicine dosage.
Executives in the financial industry and those who work in the trades, civic leadership, as well as community work, were among the various "guest speakers." A surprise visit from Channel 6 meteorologist, Chris Sowers, generated much enthusiasm. Students learned about weather terminology and how to tell the difference between sleet and freezing rain. In addition to math and science, Chris explained that technology and communications skills are important in his job.
Thanks to volunteers, students learned how the academic skills they learn at Norwood-Fontbonne Academy will help them achieve their dreams.
"It's never too soon for NFA children to begin thinking about what they want to be when they grow up," said Terri Hutsell, communications manager at Norwood-Fontbonne Academy.


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South African Journal of Science
On-line version ISSN 1996-7489
Print version ISSN 0038-2353
S. Afr. j. sci. vol.105 n.7-8 Pretoria Jul./Aug. 2009
The influence of cation, anion and water content on the rate of formation and pore size distribution of zeolite ZSM-5
L. Petrik
Environmental and Nano Sciences, Department of Chemistry, University of the Western Cape, Private Bag X17, Bellville 7535, South Africa. E-mail: firstname.lastname@example.com
Rapid synthesis and high mesoporosity of ZSM-5 is promoted by altering a fixed molar regime with respect to anion and cation type and water content only. This study shows that merely changing the cation and anion types, accompanying the hydroxide and alumina (Al) sources, respectively, has an impact on the characteristics of ZSM-5. Under identical and replicated preparation and testing conditions, the synthesis time, Al incorporation, product yield, acidity, morphology, pore size distribution and catalytic activity were affected. An ion pair combination of Na+/NO3 allowed the formation of ZSM-5 with enhanced mesoporosity within 3 h in a high-water environment, whereas ZSM-5 prepared with the Na+/SO42 combination had enhanced n-hexane cracking activity. Use of a K+/NO3 ion pair combination in a high-water environment resulted in slower time of formation and larger ZSM-5 crystals with extra-framework Al, loss of acidity, lower surface areas and reduced n-hexane cracking activity. The sulphate anion inhibited the incorporation of Al in ZSM-5 products in low-water environments. Low-water levels increased the time of formation of ZSM-5.
Key words: zeolite ZMS-5, synthesis, cation, anion, acidity, porosity, extra-framework aluminium, n-hexane cracking activity, sulphate, nitrate
Apart from microwave-assisted techniques,1 few studies report or give a rationale for rapid crystallisation of zeolites. Inui2 reported a method for rapid synthesis of zeolite ZSM-5 (MFI-type zeolite according to IUPAC nomenclature) using an involved pre-synthesis preparation technique, in which filtered, ball-milled, aged precursor gels containing high amounts of NaCl were reintroduced into fresh mother liquors and subjected to hydrothermal synthesis for 0.5 h.
Furthermore, few investigations were carried out in comparable molar regimes in systematic studies concerning the influence of cation and anion type on the rate of formation, morphology and catalytic activity of ZSM-5. Most investigations report possible cation and anion effects in terms of salt additions, thus inevitably introducing changes in molar concentrations of reactant species and hence not keeping all extraneous variables constant.37 Accompanying anions are treated as spectator anions and levels are not controlled. Thus it is difficult to decouple the relative effects of each variable on catalyst quality, or to correlate changes in catalytic activity of ZSM-5 with synthesis variables, when molar regimes and sources of chemicals varied from study to study. Different preparation methods for ZSM-5 may result in the introduction of diffusional constraints and changes in shape-selectivity of the working catalyst due to changes such as the accidental introduction of extra-framework aluminium (EFAl), or altered crystal morphology, pore volume distribution and surface areas. Thus different activities reported, when comparing the catalytic activity of ZSM-5 for a particular reaction, may be caused by different preparation conditions for this zeolite type between studies.
Petrik et al.8 investigated the influence of physical and chemical parameters on the properties of ZSM-5 by using a molar regime which allowed relatively rapid crystallisation. In this study, the effect of changing the cation and anion types accompanying the hydroxide and alumina source, on synthesis kinetics, pore volume distribution, acidity, morphology and catalytic activity was investigated in a fixed molar regime, using standard hydrothermal preparation conditions. The effect of high and low water content was also noted. n-Hexane cracking activity9 was used as a probe reaction to determine the relative acidity and catalytic activity of several of the variously prepared ZSM-5 catalysts.
To investigate the influence of the cation and anion type and water concentration on product quality of ZSM-5 in a carefully controlled environment, four different ion pair combinations were used during hydrothermal synthesis, namely: Na+/SO42; K+/SO42; Na+/NO3 and K+/NO3. The molar composition and species type are shown in Table 1. The source of hydroxide was either NaOH or KOH, the alumina source was either Al2(SO4)318H2O or Al(NO3)39H2O·SiO2 supplied by use of the colloidal silicon source, Ludox AS 40, and the template used was tetrapropylammonium bromide (TPABr). Each combination was tested in a high-water and low-water environment and all syntheses were replicated, using the two different molar quantities of water, as specified in Table 1. To eliminate extraneous variables and allow comparison, the molar concentration of the cation (OH:Si:H2O:TPABr:Al) was kept rigorously constant, except that, due to stoichiometric constraints, 3 mols of NO3 were provided per mol aluminium, whereas, in the case of the SO42 combinations, only 1.5 mols of SO42 per mol aluminium were provided. A compromise had to be made between the importance of a constant Si/Al ratio in terms of catalytic activity, and the constant anion quantity in terms of the influence of the type of anion on the catalytic properties. It is impossible to keep anion concentration exactly the same when different sources of Al are used. Hence the differences observed between the effects of the NO3 compared to the SO42 anion may be partially due to the relative concentrations of each anion. Reactants were chosen in such a way that the amount of hydroxide was kept constant, to exclude the influence of changes in hydroxide concentration on product characteristics.
The silica source used was Ludox AS 40 commercial silica from Du Pont. The Al source used was either aluminium sulphate by Merck with a purity of 99%, or aluminium nitrate by Saarchem, with a purity of 99%. The organic templating agent was tetrapropylammonium bromide (TPABr) from Riedel de Häen (purity of >99%). The sodium hydroxide (Saarchem) used in this study had a purity of 97% whereas the potassium hydroxide (Saarchem) had a purity of 85% (>12% H2O, 2% K2CO3 < 0.004% impurities such as Pb, Fe, As, N, Cl).
During the pre-synthesis preparation stage, the reagents were added together in the following sequence, taking rigorous care to be exact. A third of the amount of water was used to dissolve the TPABr in a 200-ml glass beaker while stirring magnetically. The Al source was added to the required dry mass of NaOH and dissolved in about 510 ml of the deionised water by heating to boiling point. The mass of water lost due to evaporation during heating was adjusted by the addition of an equivalent mass of deionised water. This alkaline solution was added slowly to the aqueous template solution and traces of reactant solutions on the glassware were rinsed with the remaining deionised water. The Ludox was added dropwise under strong agitation by use of magnetic stirring. The mixture was vigorously stirred for about 10 min in all cases. About 12 g of the pre-synthesis gel mixture was transferred into the thoroughly cleaned Teflon liners. The zeolite synthesis was carried out statically in Teflon-lined carbon steel Parr Bombs® with a volume of 30 ml at autogeneous pressure. The autoclaves were loaded to a capacity of 40% with a portion of the respective pre-synthesis gel mixture, which corresponded to a weight of about 12 g of the pre-synthesis gel mixture, replicated in each case. These reaction vessels were placed in a preheated hot-air oven at 160°C. All hydrothermal syntheses were performed statically, in order to obtain a time of formation which would not be influenced by secondary nucleation arising from attrition fragments as a result of agitation and shear. Synthesis times evaluated were 3 h, 6 h, 24 h and 72 h for each combination with high water levels, and 1 h, 3 h, 6 h and 24 h for each low-water combination. All samples prepared in this study were replicated to confirm the reproducibility of the results. After recovery and drying of the product, the Na-form samples were characterised by selected methods as specified below, then detemplated and ion exchanged. Selected NH3 or H-form samples were then further characterised.
ZSM-5 product samples were characterised in replicate, as specified. First, all replicated ZSM-5 synthesis products were identified prior to detemplation and ion exchange by X-ray diffraction (XRD) for each time series to determine the purity of the mineral phase, the relative crystallinity and the relative time of formation of the fully crystalline zeolite phase. Powder X-ray diffractograms were obtained using a Philips X-ray diffractometer with Cu Kα radiation of wavelength 154 pm. The scan range was set to 5° < 2θ < 48°. The relative percentage crystallinity for all zeolites was obtained by comparing the summation of the intensities of the peaks, between 22° and 25° 2θ of a given sample, to the corresponding sum of a standard sample, which was chosen to be the most crystalline material. The relative percentage crystallinity of replicated samples was nearly identical in most cases.
The crystal morphology was determined by scanning electron microscopy (SEM). A Cambridge S200 was used to take micrographs of the catalyst samples obtained after 24-h synthesis times. The as-synthesised zeolites were mounted on aluminium stubs covered with a mixture of water-based glue and colloidal carbon, upon which a small dusting of each respective sample was deposited and coated with a thin film of Au/Pd. Particle sizing of ZSM-5 crystals was confirmed using a Malvern particle sizer.
The Si/Al ratio of the ZSM-5 crystals (24 h) was determined by atomic absorption spectroscopy (AAS). Al and Na, as well as K, contents of the un-detemplated, un-ion exchanged zeolites were analysed by using a Varian SpectrAA-30 spectrometer with a DS 15 data station. The following procedure was used: 100 mg zeolite was weighed into a Teflon-lined autoclave with a volume of 33 ml. Fifteen millilitres of concentrated hydrochloric acid (HCl, 37 wt%, Merck) was added carefully and afterwards the autoclave was sealed and placed in a hot-air oven at 150°C for 16 h. The samples were cooled to room temperature. An acidic supernatant and a SiO2 deposit were present in the Teflon liners. The contents of the Teflon liners were filtered; solids were collected by repeated washing and decanting of the supernatant and deposit onto an ashless filter paper, and the filtrate was collected in a Buchner flask for further analysis. The filtrate was transferred into a 50 ml volumetric flask and diluted to volume with H2O and then analysed for Al, Na and K. The filter paper and SiO2 deposit were ashed in a furnace at 1 000°C to constant weight using ceramic crucibles and the SiO2 content determined gravimetrically.
Thermogravimetric differential thermal analysis (TG/DTA) was used to determine the moisture content and the amount of incorporated template in the freshly synthesised ZSM-5 catalysts prior to detemplation and ion exchange. The TG/DTA analyses were obtained using a Stanton-Redcroft STA-780 thermal analyser. A sample mass of 50 mg of as-synthesised material (24 h) was heated at 10°C min1 in nitrogen (30 ml min1) to 600°C. This temperature was held for 1 h and then air (30 ml min1) was passed over the sample at 600°C. The weight losses obtained from TGA below 200°C were ascribed to moisture loss and those at above 200°C to organic template material loss. The losses are presented as percentages of the total mass of synthesised catalyst.
After characterisation by XRD, SEM, TGA and AAS, the dry catalysts were converted from the Na-form into the NH3-form by detemplation and ion exchange. The ZSM-5 products were detemplated by placing samples in a muffle furnace to remove the organic template from the dried catalysts. The nitrogen flow into the chamber was set to 800 ml min1 and the heat was ramped up to 500°C, at 10°C min1, and held at that temperature for 8 h. Subsequently, the gas feed was switched to air at 500°C for a further 6 h. The detemplated Na-form ZSM-5 catalyst was ion exchanged to the NH3-form by placing the sample in a glass autoclave fitted with a reflux condenser. After the addition of an excess of 2 M ammonium nitrate solution, the solution was held at 90°C for 24 h and stirred magnetically. Finally, the catalyst was filtered, rinsed well with water and dried in an oven at 80°C for 24 h.
n-Hexane adsorption was used to determine sorption capacity of selected samples. Sorption of hydrocarbons was performed using a Stanton-Redcroft STA-780 thermal analyser fitted with a dosing system. This dosing system consisted of various saturators of different hydrocarbons, through which nitrogen was fed as the inert carrier gas. A sample mass of 50 mg of the detemplated, ion exchanged zeolite was heated at 10°C min1 in air (30 ml min1) to 500°C in order to calcine the zeolite. This temperature was held for 3 h in the case of n-hexane. Thereafter nitrogen (30 ml min1), saturated with the sorbent at 0°C was passed over the sample at 80°C for 30 min, where the equilibrium state was reached.
Temperature-programmed desorption of ammonium (NH3-TPD) was performed in quartz sample cells containing 0.5 g of selected samples of ZSM-5 catalyst in the NH3-form. The catalyst was first calcined in flowing helium at 500°C for 24 h before being cooled in flowing helium to 150°C. NH3 was then adsorbed from a 4% NH3 in helium mixture for 60 min and the physisorbed NH3 was removed by purging in flowing helium for a further 24 h at 150°C. Temperature-programmed desorption (TPD) spectra were recorded by measuring the NH3 desorbed using a thermal conductivity detector (TCD) while increasing the temperature at 10°C min1, from 150°C to 500°C, and maintaining the final temperature for 60 min. Baseline spectra (no NH3 adsorbed) were subtracted from all the ZSM-5 ammonia TPD spectra. NH3 mass balances, checked by titration of the exit steam, were always better than 95%.
Pore size distribution of samples obtained after 24-h synthesis time was determined by N2 porosimetry using the N2 BET technique. Sorption-desorption isotherms for nitrogen at 77 K were recorded using an automated porosimeter (Micromeritics Asap 2000). Surface areas were calculated from the BET equation. The total sorbed volumes, including adsorption in the micropores and mesopores and on the external surface, were calculated from the amount of nitrogen adsorbed at a relative pressure p/p0 before the onset of interparticle condensation. To obtain the size and the distribution of the mesopores the Barrett-Joyner-Halenda (BJH) method was used by calculating from the desorption branch of the isotherm.
Aluminium nuclear magnetic resonance spectroscopy was used to determine framework aluminium (FAl) and extra-framework aluminium (EFAl) of samples obtained after 24-h synthesis times. 27Al-NMR and 29Si-NMR were performed to determine the coordination of the aluminium and the local environment of the silicon using a Varian Unity 400 spectrometer operating at 104 MHz and 79.5 MHz, respectively. Spectra were acquired using a 7-mm ZrO2 rotor at ambient temperature. Typically, flip angles of ≈ 50° were used, with a 1-s pulse delay. Spinning speeds of 3-5 kHz and a field strength of B0 = 9.6 Tesla were applied. 27Al and 29Si chemical shifts are quoted relative to an external 1 000-ppm Al(NO3)3 solution or an aqueous solution of 3-(trimethylsilyl)tetradeuterosodium propionate (DDS), set to 0 ppm.
In order to characterise the activity of synthesised ZSM-5 samples obtained after a 24-h synthesis time in a high-water environment, the n-hexane cracking reaction was used. The samples were investigated in a fixed-bed plug flow reactor (PFR), whereby n-hexane was cracked into several products, via the monomolecular cracking mechanism, at a reaction temperature of 500°C and a low conversion was maintained. In the case of ZSM-5, no diffusion limitations and fairly little deactivation was expected. A fixed bed, consisting of the catalyst to be examined and sand, was placed in a stainless steel reactor. The mass ratio of catalyst:sand was 1:29. The height of the total catalyst bed was about 1.5 cm. The reactor had an inner diameter of 11 mm and a length of 300 mm. After loading the catalyst bed, the reactor was filled with pure sand from both flow directions and fitted with glass wool on the ends of the reactor tube. The temperature profile was measured by an axial movable thermocouple, placed in the centre of the tube. Samples for the hydrocarbon product flow analysis were taken by using an ampule system. Samples of 100 µl were injected with a gas syringe into a Varian 3700 gas chromatograph (GC) consisting of a HP1 capillary column, 50 m long with a diameter of 0.2 mm. The detector used in the GC was a flame ionising detector (FID). The temperature for the n-hexane cracking reaction was 500°C and the low partial pressure of n-hexane in the saturator was regulated to pn-hexane = 0.1 bar via regulating the temperature to 10°C. The ZSM-5 catalyst was calcined at 500°C for 3 h. Thereafter, the flow rate of the carrier gas nitrogen was set to 15 % (1.025 mmol min1) and the cooling system of the n-hexane saturator was set to 10°C and stabilised for 30 min. Average activities were calculated after a 100-h time on-stream period.
Results and discussion
In a molar regime of 1Al:100 Si:45 TPABr:22 MOH:y H2O: z anion with M=K or Na, y = 2 354 or 977 mol, z = 3 NO3 or 1.5 SO42, which in all cases produced ZSM-5 as the only zeolitic phase (as determined by XRD), the following results were obtained by varying cation and anion source, as well as water content, systematically.
Time of formation
Distinctly different times of formation of fully crystalline ZSM-5 were obtained by varying cation and anion source as well as water content. These trends are shown in Fig. 1, which represents the relative percentage crystallinity obtained in the case of each consecutive time period for the series of ZSM-5 products derived from each different molar regime. The relative crystallinity was determined from XRD data through normalising the product crystallinity of all samples to the most crystalline product by the method described in the methods.
Irrespective of anion type and water content, Na+-containing combinations produced fully crystalline, pure ZSM-5 within 3 h. The K+/NO3 and K+/SO42 combinations were slower to form ZSM-5 in a high-water environment, taking about 6 h, after which they lost crystallinity.
When the K+/SO42 and K+/NO3 combinations were used in a low-water environment, highly-crystalline ZSM-5 only formed after 24 h. Crystal growth habit appeared to have been disrupted, with smaller, more intergrown particles resulting. Hence, the use of K+ as the cation retarded crystallisation, particularly in low-water environments. The greater viscosity of the low-water gels may also have contributed to hindered nutrient transport, thus contributing to the slower rates of formation observed for the K+ combinations. Hindered transport itself was not however the main cause of slow times of formation because no viscosity effect was observed in the low-water Na+ combinations. Low-water, high-viscosity Na+ combinations formed as quickly as the low-viscosity, high-water Na+ combinations. It is well documented that K+ is a structure-breaking cation, which this study confirms.
pH of molar regime
Figure 2 shows the replicated pH trends during hydrothermal synthesis that were obtained directly after each sample for each time series, was removed from the oven, rapidly cooled and opened.
Different and replicable pH trends were observed during hydrothermal synthesis for the different combinations obtained by varying cation and anion sources, as well as water content. In general, the presence of the nitrate anion created a more alkaline environment than the sulphate anion in the high-water environment. This is consistent with the fact that there was more nitrate than sulphate present and the results show that even small differences in anion concentration, due to the use of different sources of aluminium as mentioned previously, may change the synthesis environment considerably. The NO3 anion provided a consistently more alkaline environment than the SO42. This effect was enhanced by use of the K+ cation. Lower pH trends were observed when using the Na+ cation than when using the K+ anion in high-water systems, possibly as a consequence of an increased buffering capacity of the system.
In the case of high water, the pH values increased rapidly within 36 h and decreased again to about pH 12.5 for combinations with K+/SO42 and K+/NO3. This sharp increase to a high pH at the beginning of the hydrothermal synthesis period appeared to be detrimental to ZSM-5 formation as these combinations resulted in XRD amorphous material until a synthesis time of 24 h, by which time the pH had decreased. On the contrary, the pH for the combinations Na+/SO42 and Na+/NO3 barely increased within a 6-h synthesis time. These samples formed highly-crystalline ZSM-5 within 3 h.
The low-water environment resulted in a relatively lower pH synthesis environment. However, the cation type appeared to affect the pH in the first 5 h of synthesis for SO42 combinations. The NO3 anion stabilised both Na+ and K+ combinations at the same pH, although the relative difference in molar concentration of the anions was the same as in the high-water syntheses. The lower pH may also have resulted in slower depolymerisation and condensation of silica. Lower pH, i.e. fewer OH ions, may change the rate of Si depolymerisation and hence the availability of Si species to participate in the subsequent condensation reactions, namely the formation of 3=3=SiOSi3=3= 'oxo'-bridges, and thus result in slower condensation.1012
When the depolymerisation of the silica sol, and subsequent hydrolysis and condensation of the Si species onto the growing crystal was complete, the OH species increased due to released OH species for this process. With the formation of the zeolite products, the pH thus increased. The increasing pH trend was followed for Na+ combinations in the high-water regime and K+ combinations in the low-water regime.
In order to obtain information on the transformation of the pre-synthesis gel into the product ZSM-5, the dry mass of the insoluble product obtained for each synthesis time after washing and drying was weighed carefully by using a milli balance. High product yield per mass of synthesis gel loaded was obtained for all combinations (Fig. 3). Product yield results obtained for each case were highly replicable.
In the case of the high-water synthesis, a general increase of the product yield can be observed over time. Except in the combination Na+/SO42, all curves converge to a constant value of about 3035 % yield after a 6-h synthesis time. The samples synthesised with K+ showed a yield of more than 30% after a 3-h synthesis time, whereas the samples synthesised with Na+ showed a range of somewhat lower values at a similar time. The nitrate anion in combination with Na+ appeared to enhance yield when compared to the combination containing the sulphate anion in the high water case, although the yield of product per mass of synthesis gel loaded is ultimately less. It is apparent, by comparison of the high yield values obtained for the potassium case with XRD and SEM results, that the high yield observed for K+ combinations is not associated with crystalline material and these products initially contained a significant amount of amorphous phase. The low-water combinations generally appeared to give high yields of 3540% between 1 h and 6 h, which did not correlate with XRD crystallinity; yields decreased between 6 h and 24 h. The decrease of yield over time, observed in the case of K+/SO42 and K+/NO3, probably is due to synthesis conditions favouring the dissolution of the amorphous solid material which formed initially in the case of the K+ combinations, compared to the competing process of condensation which forms the ZSM-5 product, which may be confirmed by the increasing trends in relative crystallinity observed by XRD. The cause of the decrease in yield, which is particularly noticeable in the case of potassium, was clarified by the SEM results which showed that dissolution of the crystals occurred and crystals underwent a change of morphology, indicating metastability, during synthesis.
Morphology, particle size, adsorption and pore size distribution
Table 2 and Fig. 4 summarise various characterisation data for the samples prepared in this study. These characterisation results were replicable. Scanning electron microscopy, Malvern particle sizing, and N2BET and n-hexane adsorption studies of the specified ZSM-5 products, prepared using the various combinations, showed that high-water Na+ combinations using either NO3 or SO42 resulted in the formation of spherical-stepped agglomerates of about 5 µm. However, the low-water environment changed the morphology of the ZSM-5 produced with these combinations, to intergrown, twinned crystals, of about 5 µm, which had a disrupted growth habit. All K+ combinations had a twinned morphology but anion type and water concentration resulted in different particle sizes. The K+/NO3 combination produced the largest crystals formed in this study, whereas the K+/SO42 combination had the same particle size as the Na+ combinations in high-water environments. Amorphous material was visible, by SEM and XRD, for low-water K+ combinations until 24 h. Nuclear magnetic resonance studies confirmed the presence of EFAl after 24 h in all samples prepared using K+ combinations, except for the low-water SO42 sample.
Although the Na+/NO3 and Na+/SO42 environment resulted in a crystal morphology of stepped agglomerates, that could be as a result of the inclusion of mother liquor during rapid crystal growth, potentially causing micropore blockage; this did not have a negative impact on the observed pore volumes or catalytic activity. Hexane adsorption indicated good access of reactant to the micropore area of ZSM-5 samples prepared rapidly in a high-water environment. Interestingly, the ZSM-5 prepared from NO3 combinations, particularly in a high-water environment, had the greatest hexane adsorption capacity. Overall trends observed for N2BET micropore and total surface areas of detemplated samples after 24-h synthesis times are shown in Fig. 4.
The most significant differences can be seen in the micropore surface areas. The samples prepared with K+ as the cation showed a significant lower micropore area in the high-water case. Whereas, for the K+/SO42 combination, an evident reduction in micropore and mesopore surface areas was observed in the low-water case. The nitrate anion counteracts the tendency to form a denser phase for K+ combinations in the low-water case. The sodium cation enhanced microporous surface areas of ZSM-5 products regardless of the anion combination. Low-water concentration played a role in reducing mesoporosity in combination with the K+ cation, as these combinations resulted in lower surface areas.
The pore size distribution from N2BET of different samples obtained after 24 h showed generally similar hysteresis behaviour with a hysteresis loop observed between a relative pressure of 0.5 p/p0 and 1 p/p0, and another hysteresis loop observed below a relative pressure of 0.2 p/p0 (Fig. 5).
Hence a bimodal distribution of intracrystalline mesopores, with both smaller (~20 Å) and larger mesopores (~45 Å), was observed from BJH desorption data. In the case of the K+-containing combination, the formation of larger mesopores (~45 Å) was suppressed, possibly causing diffusional limitations, which may be why these samples exhibited a generally lower catalytic activity. For the samples prepared in this study, a high proportion of the available surface area reports to the non-shape selective mesoporous region. As enhanced mesoporosity is desirable in many catalytic reactions, this simple synthetic route is presented as a rapid and effective means in which to obtain a graded pore distribution.
Acidity, catalytic activity and Al environment
Table 2 shows the NH4 TPD data for ZSM-5 samples prepared using different combinations of cation and anion. The Na/SO42 combination prepared in a high-water environment displayed the highest acidity and catalytic activity, followed closely by the sample prepared with the Na+/NO3 high-water combination. Samples prepared using Na+ combined with NO3 or SO42, in either high or low-water environments, exhibited no EFAl.
Extremely low acidities and reduced activities were obtained for ZSM-5 products prepared with the K+ cation, with either SO42 or NO3, in a high-water environment, which may be related to the presence of EFAl as well as low acidity in these products. Elemental analysis of these products showed that Al remained largely unincorporated into the crystalline phase. Elemental analysis of post-synthesis supernatant liquors of these samples also showed that the reactant Al was wasted during synthesis. A low-water environment improved the incorporation of Al in products from K+-containing formulae. However, the presence of the sulphate anion inhibited the incorporation of Al in ZSM-5 products in low-water environments.
The acidities of the samples from NO3-containing molar regimes which were prepared in a low-water environment were not compromised, but the acidity of samples prepared in the presence of SO42 were slightly reduced.
Extra-framework Al was present in the low-water K+/NO3 sample. Catalytic activity was not determined for these samples. The NMR and NH4TPD data, as well as the n-hexane cracking trends over 100-h time on stream periods, presented in Table 2, show that, although all molar regimes were loaded with a Si/Al ratio of 100, the various combinations of cations and anions resulted in differences in acidity and activity of the solid product. Differences in Si/Al ratio and the presence of EFAl resulted in changes in acidity, particularly in products obtained in a K+-containing high-water environment. This may be related to the different hydrothermal environments of each sample that resulted in disruption of the incorporation of tetrahedral Al into the crystalline phase.
Further to this, it is clear from the ratio of micropore area to total surface areas (including mesopores) presented in Fig. 4, that relatively more acid sites will be accessible on non-shape-selective mesoporous surface areas for samples of ZSM-5 prepared using Na+ in a high-water environment.
The characteristics of ZSM-5 were influenced significantly by merely changing the cation and anion type accompanying the hydroxide and alumina source during hydrothermal synthesis in a fixed molar regime. It is shown that under identical, replicable preparation and testing conditions the synthesis time, Al incorporation, product yield, acidity, morphology, pore size distribution and catalytic activity were affected. Rapid synthesis and mesoporosity of ZSM-5 were promoted by altering a fixed molar regime with respect to anion and cation type and water content only, particularly for Na+/NO3 combinations using standard hydrothermal synthesis conditions. An ion pair combination of Na+ and NO3 allowed the formation of pure ZSM-5 with enhanced mesoporosity and activity for n-hexane cracking in less than 3 h in a high-water environment. Use of a K+/NO3 ion pair combination in a high-water environment resulted in larger crystals, slower rates of formation, extra-framework Al and loss of acidity, as well as reduced n-hexane cracking activity. The sulphate anion and K+ inhibited the incorporation of Al. In this study, low water levels increased the time of formation of ZSM-5 and affected product quality, particularly in the presence of the sulphate anion. Hence, it is concluded that the molar regime for ZSM-5 should preferably contain the Na/SO42 or Na+/NO3 ion pair in a high-water environment for high Al incorporation. Optimum mesoporosity and acidity of ZSM-5 enhanced the activity for n-hexane cracking under these conditions.
We thank Matthias Knoll and the Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town, South Africa.
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4. Choudhary V.R. and Akolekar D.B. (1988). Crystallization of silicalite-factors affecting its structure, crystal size and morphology. Mater. Chem. Phys. 20(45), 299308. [ Links ]
5. Nastro A. and Sand L.B. (1983). Growth of larger crystals of ZSM-5. Zeolites 3, 5762. [ Links ]
6. Bhat Y.S., Das J., Rao K.V. and Halgeri A.B. (1996). Inactivation of external surface of ZSM-5: zeolite morphology, crystal size and catalytic activity. J. Catal. 159(2), 368374. [ Links ]
7. Erdem A. and Sand L.B. (1979). Crystallization and metastable phase transformations of zeolite ZSM-5. J. Catal. 60(2), 241256. [ Links ]
8. Petrik L.F., O'Connor C.T. and Schwarz S. (1995). The influence of various synthesis parameters on the morphology and crystal size of ZSM-5, and the relationship between morphology and crystal size and propene oligomerization. In Catalysis by Microporous Materials: Studies in Surface Science and Catalysis, vol. 94, eds H.K. Beyer, H.G. Karge, I. Kiricsi and J.B Nagy, pp. 517524. Elsevier, Amsterdam. [ Links ]
9. Hardenberg T.A.J., Mertens L., Mesma P., Muller H.C. and Nicolaides C.P. (1992). A catalytic method for the quantitative evaluation of crystallinities of ZSM-5 zeolite preparations. Zeolites 12(6), 685689. [ Links ]
10. Feijen E.J.P., Martens J. and Jacobs P. (1997). Hydrothermal zeolite synthesis. In Handbook of Heterogeneous Catalysis, vol. 1., eds G. Ertl, H. Knözinger and J. Weitkamp, pp. 311323. Wiley-VCH, Weinheim. [ Links ]
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Received 18 May. Accepted 26 May 2009.


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Candles are an easy way to change the mood of your surroundings. You can create a romantic candlelit dinner or unwind and relax after a stressful day. However, the potential for dripping wax and hazards of an open flame do not make candles the ideal lighting method especially with children present. The LED Flameless Taper Candle can replace your existing candle fixtures for a safer, cleaner space. It includes 3 sizing adaptors to help the candles seamlessly fit into existing taper candle sconces you may already have. Built from real wax, these flameless versions look just like traditional candles but require less maintenance and are safer to use. There will no longer be wax to clean up and flames to remember to blow out. Simply flip the switch to turn the LED on and enjoy the warm glow of the Taper Candles efficient LED bulb. Each candle can be manually turned off with the flick of a switch or simply let it glow until the built-in timer turns it off automatically after 6 hours. This product requires the use of 2 AA batteries, sold separately.
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Stan Lee, Jim Lee, Todd McFarlane, David Michiline, and Bob Layton appear at Brenden Theaters in the Palms Hotel
Thursday: Iron Man 2 Launch Party with appearance by Stan Lee 10:30pm in the Moon Nightclub @ The Palms (general admission applies)
Iron Man 2 Public Showings
Friday: Brenden Celebrity Star Presentation at 7:30pm in the Brenden Theaters Lobby
Stan Lee will be welcoming moviegoers at random showings of Iron Man 2 on Friday and Saturday so get your tickets this weekend!!! Also, there are rumors of other celebrity appearances so keep your eyes open! You never know who you might see…


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|Rev. Denton KEELER (1789-1886) Westchester Co.
Descendants of Rev. Denton KEELER (1789-1886) a Methodist Circuit Rider who Served Many Circuits up and down Various Hudson River Area Towns, and Continuing Over Into Lysander, Onondaga County, New York, and Dying at his Retirement Home in Pleasantville, Town of Mount Pleasant, Westchester, County, New York at 97 Years of Age.
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Section 4A: Certificate of change of resident agent or address of resident agent; change of address of limited partnership business office; resignation
Section 4A. (a) A limited partnership may change its resident agent or the street address of the resident agent by filing a certificate of change of agent or address with the state secretary. The statement shall contain the following information:
(1) the name of the limited partnership;
(2) the name and street address of its current resident agent;
(3) if the current resident agent is to be changed, the name and street address of the new resident agent and the new agent's written consent, either on the statement or attached to it, to the appointment; and
(4) if the street address of the business office of the resident agent is to be changed, the new street address of the business office of the resident agent.
(b) If a resident agent changes the street address of his business office, he may change the street address of the business office of any limited partnership for which he is resident agent by notifying the limited partnership in writing of the change and signing, manually or by facsimile, and delivering to the state secretary for filing a statement of change that complies with the requirements of subsection (a) and recites that the limited partnership has been notified of the change. If the street address of more than 1 limited partnership is being changed at the same time, there may be included in a single certificate the names of all limited partnerships the street addresses of the business offices of which are being changed.
(c) Any resident may resign his agency appointment by signing and delivering to the state secretary a certificate of resignation. The resident agent shall furnish a copy of such statement to the limited partnership. The agency appointment shall be terminated on the thirty-first day following the date on which the statement was filed.


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ti's as if Professor Ginsberg had a crystal ball the way he describes today's insanity 25 year ago. Just like my Youtube video on the "endmeme" it shows how belief in the second coming is very dangerous for the entire planet and the future of the world. Gog and Magog, it shows how Biblical belief can turn human brains into mishmash. I hope President Trump doesn't eventually come to the same conclusion: He needed a bomb.…
Added by Rich Goss on September 23, 2017 at 4:13pm — 3 Comments
When I first read the following line by H.L. Mencken I could hardly believe how accurate it was (at the time. W. Bush had just been elected.) But now it's even more accurate than ever.
"On some great and glorious day the plain folks of the land will reach their heart's desire at last, and the White House will be adorned by a downright moron."
Added by Rich Goss on September 1, 2017 at 10:32am — 5 Comments
Just now on CNN, Mr. Lanhee Chen, former public policy director for Mr. Romney, stated his old boss was a "Patriot". How the heck can he declare Romney a patriot when it was his turn to fight for his country, after being a hawk at BYU, encouraging fellow students to fight in Viet Nam and watching them die, choose to become a missionary to France. Just think, the people that gave the world Voltaire, Jean Jacques Rousseau and Jean Paul Satre converting to Mormonism! "Surreal" is…Continue
Added by Rich Goss on November 19, 2016 at 10:04am — 1 Comment
I recently watched a TV documentary about John Muir. The line that struck me was being out on the lake in the early evening inspires the soul. We feel part of it all, part of nature. I think that's the terrible damage religion has done to humanity. The church teaches we were created by God, and "in God's own image." (What horseshit! When they told me that, I pictured God sitting on a toilet bowl.) They told us we're not part of nature, and in doing so did…Continue
Added by Rich Goss on April 27, 2016 at 5:16pm — 2 Comments
The meaning of life? Stand out by the beach or a pristine forest in the deep of night and observe the vastness of it all. As Carl Sagan says, billions and billions of stars. And then you learn almost all of it is hydrogen and helium and the most common phase of matter is a liquid plasma—scary and hellish stuff.…Continue
Added by Rich Goss on April 27, 2016 at 5:08pm — No Comments
I just watched Roman Polanski's "The Pianist". Now, being Polish, my mother ran a Polish restaurant on Kent Avenue across from the Brooklyn Navy Yard during the war, I was aghast at the brutality and cruelty perpetrated on my mother and father's family in Krakow and Warsaw, respectively. A fuckin' horror, just about the lowest levels of human depravity and sadism ever experienced.
To me, the immortal Shakespeare was the greatest writer in human history. The movie reminded…Continue
Added by Rich Goss on April 20, 2016 at 12:36pm — 12 Comments
What an irony that my first published work has just been republished and will probably be my last. Back in January 1970 Timothy Leary spoke at St. Francis College in Brooklyn Heights and my poem Simon was published in the Village Voice. As some sort of committee member, my girlfriend Pat waited for an elevator next to him and whipped out the paper. Pointing at the page, "Hey, my boyfriend just had his poem published in the Voice, care to listen?" and…Continue
Added by Rich Goss on April 2, 2016 at 4:43pm — No Comments
I just caught this comment over my Pot Stories and Humanist Essays.
"Typical pot head ranting as the druggies do."
There's no way this guy could have possibly read the book. It's more about Shakespeare and opera than about any sordid drug deals or squalid crack houses. I find it a tragedy that Americans are divorced from the arts and culturally deprived. The legacy of past generations is so wonderful. The latter stage of my life is devoted to the humanities.…Continue
Added by Rich Goss on September 29, 2015 at 3:30pm — No Comments
Later this fall Pope Francis is scheduled to address the U.S. Congress, most likely on the subject of the environmental conservation. That's fine. Not much anybody can say against the idea. As California burns and many islands feel the slow encroachment of the sea along their beaches, and species go extinct every day, unless there's a drastic change in consciousness a global catastrophe is imminent.…Continue
Added by Rich Goss on September 12, 2015 at 9:46am — 14 Comments
Here's an excerpt from Mirror Reversal that supports Ruth's "Future generations" comment of Sept. 20. I think it's very beautiful and poignant, but I guess that doesn't count. I wrote it.
We shouldn't say atheists don't believe in the afterlife. All the nonsense about St. Peter and the Pearly Gates, divine judgment, and heaven and hell is folly or wishful thinking. Divine justice is a myth and I believe Hitler sleeps in his grave (nonexistence) as peacefully as St. Francis…Continue
Added by Rich Goss on August 30, 2015 at 1:53pm — 4 Comments
I just placed "Pot Stories" on Amazon's KDP program, meaning you can download it free. There's so much fun and information in there it blows my mind. In the various and sundry essays the eBook answers questions like:
How come there are no priests listed on the National List of Sex Offenders?
Why will humans hand over the dominance of the planet to the cybernetic mind?
From Barbara Walker: At funerals why is it unacceptable to criticize and disparage the reputation of the…Continue
Added by Rich Goss on August 16, 2015 at 10:30am — 4 Comments
Thanks, Judy. Here's a vignette about "DUI Story." I've always considered Shakespeare to be the greatest writer. Not just for great stories, but many of his verses are a pleasure to listen to, just like music. Romeo and Juliette's balcony scene, surely Hamlet's…Continue
Added by Rich Goss on June 25, 2015 at 1:21pm — 3 Comments
The following is an excerpt from the revised High School with Rudy Giuliani which I made highly autobiographical as I approach the end of life's journey. It's interesting how patriotic I was in younger days but ever since Spiro Agnew pleaded "Nolo Contendere" my feelings about government and the country did a 180. This little rant shows why I believe political corruption should be considered one of the most contemptible crimes a person can commit.
From the book:…Continue
Added by Rich Goss on May 9, 2015 at 11:52am — 22 Comments
The Garin Hoover Radio Show is on line. It was recorded March 12 and featured a Jew (Manny), a Christian (Rev Terry Jones), an imam and an atheist (moi). The discussion was centered around the question, "Is Islam a Religion of Peace?"
The debate was often heated and vituperative. Rev Jones, I thought, was very good with an all-American cowboy mentality. He told the imam, "we don't want your Sharia Law, so don't even try to bring it here." He made national news last year by trying…Continue
Added by Rich Goss on March 16, 2015 at 11:30am — 24 Comments
The next essay in Pot Stories and Humanist Essays is "Ten Reasons Not To Believe." A couple of them are unique and especially important as they are key ideas in my philosophy and worldview. Number One, of course, is obvious and should occur to everybody at one time or another. God knows where you're going, heaven or hell, and if the latter, created you anyway. Think of it: a constant, torturous, hopeless state of eternal pain and suffering. No hope of ever getting out. …Continue
Added by Rich Goss on February 27, 2015 at 3:00pm — No Comments
I'm thinking of renaming the first essay "Cardinal Ratzinger and Chaos Theory" to
"The Story of the Moron and the Mouse"
Ever wonder why there're no clergy listed on the National Sex Offender List? To my mind the first story gives a plausible explanation. It also tells how the cards are stacked against the poor and working class. In 1964, W. Bush was admitted to Yale with inferior grades as a "legacy student." As you know, I'm not religious, but this…Continue
Added by Rich Goss on February 17, 2015 at 10:00am — No Comments
Joan, thanks from your encouragement on Pot Stories. I'm writing a little summery of each piece and I'm really having fun just going over this stuff. There're 27 separate pieces, each with its own information and lessons to be learned. And the diversity of history and thought. All for three bucks.
True story: I was in a Manhattan Blarney Stone bar drinking fifty-cent beers. It was the mid-'80s. I got involved in conversation with a reporter for the New York Post, which…Continue
Added by Rich Goss on February 9, 2015 at 1:06pm — 5 Comments
Many church or mosque goers believe religion gives their lives "meaning." It's a delusion, an appealing but false concept. What meaning could being credulous enough to believe the preposterous give one's life? If anything, I think a good and magnanimous god would disdain such behavior. They're abandoning reason for self-interest and wishful thinking.
In biology, the Prime Directive (PD) governs all life down to insects, worms and beyond. The force that governs all life is…Continue
Added by Rich Goss on January 16, 2015 at 1:30pm — 13 Comments
The Hoover Radio Show went fine but only as an icebreaker to more important issues. It reminded me of early Christian bishops arguing over how many angels can reside on the head of a pin. I felt like standing up and yelling out, "Look, as you sit here in this luxurious setting, people are getting their heads chopped off, wars are being fought, 15 million people (mostly children) are starving to death and billions have to live in fear of opening their mouth or saying the wrong thing. Isn't…Continue
Added by Rich Goss on December 5, 2014 at 8:42am — 2 Comments
It's fitting to have this war criminal, McCarthyite and lying "crook" who abandoned the White House in disgrace, as the figurehead for the modern War on Drugs, the holocaust of the modern age. Tens of thousands of lives were ruined, psychologically damaged (including mine), and plain murdered to keep the nightmare going. All perpetrated so many professions could feed off the mayhem like sea gulls circling a countless school of surface-feeding sardines. …Continue
Added by Rich Goss on November 3, 2014 at 8:30am — 8 Comments
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Michael Oliver
Michael Oliver is the first washed up celebrity I will review. You may remember Oliver as the child actor who played "Junior" in the early 90s movies "Problem Child" and "Problem Child 2." This is a picture of Oliver from his Problem Child days:
I would have thought that Oliver would have parlayed his early starring roles into other movie roles or perhaps even a recurring role on a sitcom. However, Oliver has not had any decent roles since his Problem Child days. He is currently a roadie for the band, The Samples, and apparently spends a good portion of his time posting on the Internet Movie Database message boards under the login "Roadiepc." He has also grown his hair long and occasionally sports a long mullet as shown in his pictures below (in case you are wondering, he verified that these are pictures of him in his message board postings). All of this makes him one washed-up celebrity!
***Update - May 28, 2007 ***
I just discovered some information that might explain why Michael Oliver is so incredibly washed up. Apparently he had a contractual obligation with Universal Pictures to act in Problem Child 2 for $80,000 back in 1991. However, a mere few days before filming was to begin Michael's mother demanded $500,000 for his role in the movie or he would walk away. Universal Pictures had already spent a lot of money on pre-production and felt obligated to do whatever was necessary to keep Michael in the movie or it would lose around $4,000,000 on outlays that had already been made.
In 1993 Universal sued Michael for $190,000 for basically extorting the money from Universal, which had agreed to pay the money to Michael under duress. Universal Pictures won its court case after a trial and Michael had to return the extorted money!
***Update - January 1, 2008 ***
Michael Oliver used to have a bio listed on the website for The Samples that mentioned that he is a "Highly evolved old soul with a love of his lady and a passion for swords." Here is a picture of Oliver that was linked in the comments to this post. I guess that Oliver must enjoy swordfights!
*** Update - February 21, 2008 ***
Someone posted a link in the comments below to this apparently gay parody Michael Oliver blog: Gay Appreciation for Michael Oliver. My favorite post on that blog is one where someone wrote:
"Someone told me that they were at a Samples show and Micheal walked by him and he stunk of B.O. Does he have problems or is that just part of touring on the road with a band? He said he could smell his balls and ass from where he was standing."
*** Update - July 1, 2008 ***
A link to this recent picture of Michael Oliver was posted as a comment below. As one can see, Oliver appears to have cut his hair short at least on the sides. It appears as though he may have also kept the hair on top of his head long and pulled it back. Finally, he's either sitting in front of a tree or his red mullet is flaring out at the sides by his neck!
*** Update - December 27, 2009 ***
Links to the following pictures of Michael Oliver were posted in comments below. An anonymous commenter claims that the girl in these photos is Michael Oliver's girlfriend. The woman in the photos below is definitely attractive, so it is perplexing that she is standing next to Oliver. I have to assume that the reason why she is in these photos with Oliver is one of the following: (a) she has a freaky ginger mullet fetish; (b) he paid her to be in the photos with him; (c) he photoshopped her into a photo where he was standing by himself; (d) that truly is his girlfriend. We may never know her true motivation for being photographed with Oliver.
*** Update - April 10, 2011 ***
I recently discovered this video clip of Michael Oliver rambling on and on about religion as he explains why he is a Buddhist. He shows off his massive forehead and ginger mullet (or possibly long hair in a ponytail) in this clip:
*** Update - November 14, 2012 ***
I recently discovered a video clip of a recent interview that Michael Oliver gave where he discussed his experiences as a child star on the movie set. Several of his former co-stars are also interviewed in this clip. Michael has apparently chopped off his long mullet as shown in the interview.
*** Unfortunately, the video was deleted from YouTube, so I had to remove the corresponding link here. ***


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The Champion Adult Long-Sleeve Ringspun T-Shirt is made of 5 oz., 100% ringspun cotton; Charcoal heather is 60% cotton, 40% polyester. It features a tag-free neck label, shoulder-to-shoulder neck tape, double-needle sleeves and bottom hem with ribbed cuff, "C" logo on left sleeve, and side seamed.
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Customize your product based on the available color options and decorating methods. If you need more information, simply add this product to the Wish List and we will get back to you with answers.


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The degree to which fresh water and saltwater mix in an estuary is measured using isohalines. Isohalines are areas in the water that have equal salt concentrations, or salinities. In estuaries, salinity levels are generally highest near the mouth of a river where the ocean water enters, and lowest upstream where fresh water flows in. To determine isohalines, scientists measure the water's salinity at various depths in different parts of the estuary. They record these salinity measurements as individual data points. Contour lines are drawn connecting data points that have the same salinity measurements. These contour lines showing the boundaries of areas of equal salinity, or isohalines, are then plotted onto a map of the estuary. The shape of the isohalines tells scientists about the type of water circulation in that estuary.
Revised April 09, 2020
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I've been doing some development for some embedded Linux devices which only support ftp and telnet. In order to automate transfer of binaries from my Fedora development host to the target embedded device I'm using this handy ftp script: pushftp.sh
#!/bin/bash # arg1 = dest hostname # arg2 = local file # arg3 = dest dir HOST=$1 SRCFILE=$2 USER=root PASSWD=password #DESTDIR=/usr/local/data DESTDIR=$3 ftp -inv $HOST<<ENDFTP user $USER $PASSWD cd $DESTDIR bin put $SRCFILE chmod 755 $SRCFILE bye ENDFTP
Then I added something like this to my Makefile after cross-compiling:
push: sh ~/bin/pushftp.sh $(TEST_BOX) $(APP_BIN) /usr/local/data
So after I run make all, I run make push. I still need to telnet to the host to test/debug the application, but this makes the process much faster (and less error-prone).
I'm just noting this for myself, hopefully it's useful to someone else.


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Who would you like to see perform on Saturday Night Live? The show is asking fans to suggest musical artists they think are worthy of taking on the coveted late night slot.
After noticing that fans were submitting possible hosts and musical guests for future SNL episodes on Facebook and Twitter, the show decided it could be helpful for future episodes.
Fans can now suggest who they think would make either a good host or a good musical guest for the one open slot a month of the show's current season. Picks will then be passed along to the producers. Who knows, you might pick the next host of SNL. This was how Betty White came to be on the show after all.
Nominations have already begun for musicians like Miley Cyrus, CeeLo, Christina Aguilera, Selena Gomez and Josh Groban who, like Justin Timberlake and Taylor Swift, could pull double duty as host and musical guest.
Some have already started campaigns to get their favorites on the show including The Voice's Blake Shelton, whose biggest supporters have been tweeting like crazy to get the country singer a slot.
So who would you like to see appear on the show? Vote in our poll below.
And remember; choose wisely, we don't want another Ashlee Simpson situation on our hands.
The season premiere of SNL is Saturday with host Seth McFarlane (Family Guy, Ted) and musical guest Frank Ocean with special guest John Mayer.
– Shannon Carlin, CBS Local


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|Pygmy Puff
|Species information
|Hair colour
Pink or Purple
|Related to
|Native range
England, bred by Fred and George Weasley
- Ginny Weasley: "They're really cute!"
- Fred Weasley: "They're fairly cuddly, yes"
- — Ginny Weasley and her brother Fred discussing Pygmy Puffs in the Weasley brothers' shop, Weasleys' Wizard Wheezes[src]
A Pygmy Puff is a miniature Puffskein, bred in the back of Fred and George Weasley's shop Weasleys' Wizard Wheezes at 93 Diagon Alley in London, and sold there as one of the known products in the WonderWitch range. It is one of their more popular products, as George said they were having trouble breeding them fast enough for the demand. Ginny Weasley bought a purple Pygmy Puff named Arnold in 1996, which she frequently played with at Hogwarts.
Pygmy Puffs resemble little fluffy balls that roll around, squeak, and come in various shades of pink and purple. Luna Lovegood believed that all Pygmy Puffs sing on Boxing Day.[1]
Behind the scenesEdit
- Pygmy Puffs would appear to be violations of the Ban on Experimental Breeding. However, as they are merely undersize Puffskeins, this may not count as an offence. Also Fred and George may have attained a special licence to breed them.
- Pink and purple Pygmy Puffs plush and keychains are available for purchase at The Wizarding World of Harry Potter at Zonko's shop (there's the naming ceremony, a mini-show that accompanies purchasing a pygmy puff plush, in which a shopkeeper will ring a bell and announce that you have adopted one and sometimes, the name you have chosen for yours) and on the Official Online Merchandise Store of the park. The plush measure six inches (15.25cm) in diameter (that seems to be a pretty big diameter considering that Aronold in the books can ride Ginny's shoulders and that a nest of dead puffskeins, that are bigger than pygmy puffs, has been found under a sofa where there is not a lot of space). The keychains diameter (approximately 2 inches) is smaller and seems more appropriate. Some Pygmy Puffs plush are in pink cages, exacly like in the movie.
- A Pygmy Puff shirt is also available in the theme park at Zonko's Joke Shop. The shirt inscription: "Miniature Puffskeins - Pygmy Puffs - Peacefully Pet the Puffs", is the same inscription we can see on the pygmy puff cage's label in Harry Potter and the Half-Blood Prince (film) during the Weasleys' Wizard Wheezes shop scene.
- Despite the blanket ban on the Weasley's Wizard Wheezes products on Hogwarts, Ginny somehow managed to bring Arnold with her into Hogwarts. This may be because the Pygmy Puffs are not joke items and that the ban Argus Filch placed on Weasley's Wizard Wheezes may only affect their joke products.
- Harry Potter and the Half-Blood Prince (First appearance)
- Harry Potter and the Half-Blood Prince (film)
- Harry Potter and the Half-Blood Prince (video game) (Mobile version only)
- The Wizarding World of Harry Potter
- LEGO Harry Potter: Years 5-7
Notes and referencesEdit
Community content is available under CC-BY-SA unless otherwise noted.


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Art Clokey, the animator who created Gumby and Davey and Goliath, both coming into being by way of stop motion clay animation, died this last weekend at his home in Los Osos, California. He was 88.
Fashioned from a little green slab of clay, Gumby made his television debut in 1956 on The Howdy Doody Show. The following year The Gumby Show premiered. Along with his constant pony pal and sidekick Pokey, together they rambled though what could best be described as a series of gentle but weird LSD trips. Their colorful adventures against a toy strewn landscape often included Gumby's pestering nemseses, The Blockheads. (According to his son, Clokey did try LSD once, but under medical supervision and years after he created Gumby. I like to think he tripped with Cary Grant and Steve Allen.)
Though the initial show was short-lived, Gumby enjoyed a comeback in 1961 running through 1968, then again in the 1980s and once again in the 1995 feature film, Gumby: The Movie, also directed by Art Clokey. Eventually 233 episodes were produced. Davey and Goliath, which ran in the 1960's and 70's, had over 300 episodes underwritten by the Lutheran Church of America.
Born as Arthur Charles Farrington in Detroit on Oct. 12, 1921, he lived with his father after his parents divorced. But at age nine Art's father was killed in an automobile accident and instead of rejoining his mother, he was placed in an orphanage near Hollywood. Art was adopted sometime later by Joseph Waddell Clokey, an established composer and music professor at Pomona College in Claremont.
Art Clokey earned a bachelor's degree from Miami University in Ohio and later attended Hartford Seminary in Connecticut, intent on becoming an Episcopal priest. He left soon after and entered the University of Southern California, where he studied film with Slavko Vorkapich, a pioneer in modern montage techniques. In 1955, Clokey made a student film, Gumbasia, with animated clay shapes gyrating to a jazz score. The film was the inspiration for the later television series. (The film is included on the DVD Gumby Essentials, released in 2007 by Classic Media.)
In 2006 Art Clokey was the subject of a documentary film, Gumby Dharma.
Art Clokey's first marriage, to Ruth Parkander ended in divorce. His second wife, Gloria, died in 1998. He is survived by his son, Joe, a stepdaughter, Holly Harman, and three grandchildren. Another daughter, Ann, died in 1974.


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Before any Declaration of Independence, there were British settlers fighting not against Britain's royal government but for it against the French in the New World. The British set up camp on Lake George and Lake Champlain, and one New Hampshire anthropologist has made it his job to dig into those sites.
David Starbuck is associate professor of anthropology and sociology at Plymouth State University. He previously wrote The Archeology of New Hampshire: Exploring 10,000 Years in the Granite State. Now with Excavating the Sutler's House he documents the findings of his team (and earlier archeologists) at a handful of sites in northern New York state, particularly at a sutler's house in Fort Edward. A sutler was a merchant who set up shop near a military camp and sold goods to soldiers.
The sutler's house proved to be a treasure trove of artifacts in a region that includes "some of the most significant eighteenth-century military sites in the United States." This book, slim and unimposing, includes a list of artifacts recovered there, and it's flush with photos showing the items up close. Laid out before you are the soldiers' wine bottles, the dishes they ate with, the knives they used, the coins from their pockets, their keys and padlocks, combs and pipes. There's a mostly intact sundial and compass that was made in the 1730s.
Starbuck also shows and tells us about the excavation itself, which is as enlightening and interesting as the history. The process of discovery, of piecing together this building's life story, is an adventure in its own right.
For context, and because it's yet another informative part of the historical record, Starbuck provides quotes from the diary of Jabez Fitch Jr., who served in Fort Edward in 1757 and '58. One entry mentions that the soldiers made chocolate the previous night. "The sutlers probably sold a great deal of hot chocolate, especially in the mornings, and it would have been just as popular as coffee," Sutler says.
My kinda guys. A
—Lisa Parsons


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In the market for a commercial meat grinder? How about a three-story hydraulic elevator or a public address system?
While items such as those don't fit the needs of most households, there are plenty of other more common goods that will be available Oct. 3 and 4 when items from Fayette's two old school buildings are offered for sale.
Items from the Franklin building will be sold at the school on St. Rt. 66 beginning at 5 p.m. Oct. 3. The sale will move to the main building in town at 10 a.m. Oct. 4. Jerry Schaffner of Fayette will serve as auctioneer.
Many materials were transferred from the old buildings to the new, but the construction project covered the cost of many replacements, such as desks, chairs, cafeteria tables, lockers and storage cabinets and shelves.
Items of that sort will join an array of electronics, kitchen appliances, window air conditioners, basketball backboards and shop equipment.
The sale will also include materials from the schools' mechanical systems, such as water heaters, a boiler and gas furnace.
Interior doors are on the auction list, but exterior doors and windows will be left in place due to safety concerns, said superintendent of schools Russ Griggs.
The company chosen for the demolition will have all salvage rights, he said, and will collect the remaining metals in the school, such as copper water lines.
Five bids for demolition were received, but bid opening was rescheduled for this week due to the need for clarification in the specifications.
Removal of hazardous materials is complete at a cost of $13,700, Griggs said, much lower than what was budgeted.
Griggs said that Schaffner and a team of volunteers went through the two school buildings to catalogue the items for the sale. Most items will be placed in the gymnasiums for the auction.
A list of sale items is published in this week's Observer.